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Proceedings of the

First International

Symposium on

Water Desalination

WASHINGTON, D.C.

OCTOBER 3-9, 1 965

U.S. DEPARTMENT OF THE INTERIOR

Office of Saline Water
WATER RESOURCES
CENTER
ARCHIVES
OF
THE UNIVERSITY
OF CALIFORNIA
RETURN WATER RESOURCES CENTER ARCHIVES
" North Gate Hall 642-2666
r_
 Proceedings of the

First International

Symposium on

Water Desalination

WASHINGTON, D.C.

OCTOBER 3-9, 1965

U.S. DEPARTMENT OF THE INTERIOR

STEWART L. UDALL, Secretory

Kenneth Holum, Assistant Secretary

For Water and Power Development
Frank C. Di Luzio, Director
Office of Saline Water
For sale by the Superintendent of Documents, U.S. Government Printing Office
Washington, D.C., 20402 - Price $4
 INTRODUCTION

This volume includes all the papers pertaining to engineering

development. Most of these papers were presented at the Symposium,
however, a few were submitted for publication only and are so designated.
After each paper presented at the Symposium is a summary of the dis
cussion period held following their presentation. Each of the papers is
followed by abstracts in French, Russian, and Spanish languages.
 CONTENTS

Page

Some Problems and Research in the Multistage

Flash Distillation Process 1
Influence of Membrane Phenomena on
Electrodialysis Operation 13
Scale Control in Sea Water Distillation 25
Saline Water Distillation—Scale Prevention
by Polymer Additives 39
Heat and Mass Transfer in Flash Distillation
without Metallic Interfaces 57
A New Ion-Exchange Desalination Technique 69
Survey of Water Desalination in Israel 87
The "Sirotherm" Demineralization Process 103
An Appraisal of Scale Control Methods at the O.S.W.
Flash Evaporator Plant in San Diego, California 139
s. Improvement in Fabrication Techniques for
Reverse Osmosis Desalination Membranes 159
Vapor Compression Evaporation with Direct
Contact Heat Transfer 181
Evaporation of Sea Water in Solar Stills and
Its Development for Desalination 193
Thin Film Distillation 205
Some Phenomena Associated with Concentration
Polarization in Electrodialysis 219
Desalination by Liquid-Liquid Extraction 239
Ion-Exchange Pretreatment 251
Aspects of Two-Phase Flow and Heat Transfer
in Distillation Type Conversion Processes 275
General Review of the Work of the Sea Water Conversion
Laboratory of the University of California 301
Methods for Scale Control in Flash Systems 317
An Engineering Evaluation of the Vertical
Tube Falling-Film Distillation Process 337
Design Criteria for Reverse Osmosis Desalination Plants 367
A Survey of Electrodialysis Developments
in the United States 389
Some British Achievements in Desalination 407
A Simple Calculation Method for the Vapor Reheat Process 415
 Solar Powered Humidification Cycle Desalination 429
The Limitations of Electrodialytic Water Desalting
with Permselective Membranes and the
Requirements for Electrodialytic Equipment 461
Utilization of Desalinated Water in Japan 475
Conversion of Sea Water by Evaporation 481
Objectives of the United Kingdom Research
and Development Programs 493
—' Low Capacity Nuclear Desalination Plants 499
Desalination of Saline Water by Electrodialysis 511
Intensification of Heat Exchange in Evaporator Installations 523
Slit and Point Corrosion (Pitting) of Stainless Steel in
Chloride Solutions at Temperatures up to 100°C 531
Prevention of Scale Formation in Distillation
Desalination Plants by Means of Seeding 539
Corrosion Resistance of Materials in Sea Water 549
Use of Ion-Exchange Membranes for Water Desalination 561
Water Desalination by the Ion-Exchange Method 575
Dropwise Condensation 589
Solar Distillation—A Review of the Battelle Experience 609
Solar Distillation in Greece 627
The Freezing Processes for Water Conversion
in the United States 641
Operational and Future Aspects of Vapor
Compression Distillation 659
Removal of Scale Formers with Byproduct Recovery 697
A Pilot Plant Design Based upon a Direct Contact Flash
Distillation Process with Liquid-Liquid Heat Exchange 717
The Multiple-Phase Ejector as a Vapor Compressor
in Distillation Desalination Systems 735
On the Freezing Process 753
The Koppers Hydrate Process 771
\ Multieffect/Multistage Flash Distillation 781
Desalination in Spain 799
"Las Marinas" Solar Conversion Pilot Plant (Spain) 819
Index 829

vi
Some Problems and Research in the
Multistage Flash Distillation Process
R. S. Silver, M.A., D.Sc., M.I. Mech.E., F.Inst.P., F.R.S.E.
Scotland
INTRODUCTION
First of all let me express my thanks to
the VS. Office of Saline Water for its invita
tion to give a paper at this Symposium, and
to the U.K. authorities for sponsoring me as
a member of the British Delegation.
Some will be familiar with my previous
papers on desalination. Many of these have
been primarily concerned with economic
aspects and hence with overall system de
sign: some have been review papers. At the
First European Symposium in Athens in
1962. a brief discussion was given (ref. 1)
or characteristic problems in distillation but
no precise scientific development was pre
sented. The object of this paper is to fill
that blank in some respects. It will have
special reference to the research work being
done in the Mechanical Engineering De
partment of Heriot-Watt College, Edin
burgh, Scotland.
This work was initially sponsored by the
Department of Scientific and Industrial Re
search, by a grant commencing in 1964. and
is being continued under the Ministry of
BASIC CHARACTERISTICS OF FLASH DISTILLATION
The distinguishable parts of the flash dis
tillation process as such are:
1. Heat transfer from tube walls to
liquid brine in heat input and recov
ery sections and to sea water in heat
rejection sections.
2. Heat transfer, usually from steam, to
tube walls in the heat input section.
3. Heat transfer, by condensation of prod
uct vapor, to tube walls in the heat
recovery and heat rejection sections.
Technology by the arrangements which
came into force in April 1965.
The range of work considered in this
paper excludes many aspects which are
important in the realization of multistage
flash distillation in practice. It is limited to
what may be termed the hydrodynamic and
thermodynamic aspects of sea water distilla
tion. Hence, we shall not discuss in detail
the construction materials in which such
processes must be made to occur or the cor
rosive and erosive actions to which mate
rials are prone. Moreover, we shall ignore
the presence of scale-forming constituents
in the sea water—unless they alter its ther
modynamic properties—and omit reference
to scale deposition or its prevention. Some
arbitrary selection is needed to delimit a
paper, and in justification of our particular
choice it can be urged that discussions of
scale, materials, and corrosion are already
abundant in desalination literature. But the
basic science of distillation itself is nowhere
in great evidence. It is to this that the
Heriot-Watt program is directed.
4. Free level flow of brine and of product
distillate, at near saturation tempera
ture and pressure conditions, from
stage to stage.
5. Flashing of vapor from brine, and
from product distillate, in the stages
and perhaps also in interstage passages.
6. Flow of flashed vapor to and through
condensing regions.
7. Entrainment and disentrainment of
brine droplets in the vapor flow.
 8. Pumping of brine with suction condi
tions near saturation temperature and
pressure.
While these characteristic events are dis
tinguishable and are suitable for separate
and independent scientific study, it should
be emphasized here that their interaction
and interdependence in an actual flash dis
tillation plant is incredibly complex.
The pressure in the r" stage counting
from the highest pressure, is determined by
the rate of brine flow into it and by the
performance of the condensing surface alio
cated to it. The rate of brine inflow is
determined by the pressure of the (r — l),b
stage and by the pressure of the r,h stage
itself, and by the design of interstate passage
and extent of flash occurring therein. The
performance of the condensing surface is
determined not only by the heat transfer
characteristics of the kind considered in
items 1 and 3 above, but by the inlet
temperature of the circulated brine, and
that depends on the whole behavior of the
(r -)- l),h stage. The theory of that inter
dependence has already been published
(ref. 2).
The energy consumption of a flash distilla
tion plant is critically dependent upon all
the design saturation temperatures in all
the stages being satisfactorily obtained. The
capital cost depends critically upon the
amount and disposition of heat transfer
surface and the provision of the equipment
in which the phenomena have to occur.
The object of a research program concerned
with items 1 to 8 is, therefore, to establish,
if possible (where it does not already exist) ,
sufficient understanding of each item so that
CONDENSATION
In 1964 a paper was published on "An
Approach to a General Theory of Sur
face Condensers" (ref. 3) . The chief new
feature of this work was the exploitation
of the concept of Reynolds Flux to discuss
the behavior of the steam side flow friction
and heat transfer. Two important predic
tions were made.
The first was that the occurrence of con
densation should modify the frictional re
sistance, reducing it below that which would
occur in a noncondensing fluid of the same
physical properties at the same velocity in
the same configuration of tubes. It was
shown that the amount of this reduction
should be sufficient to give a net pressure
rise, instead of a pressure drop. The origin
of the rise is of course in the Bernoulli
recovery of kinetic energy due to the reduc
proper design and minimization of capital
cost for a given energy consumption may
be achieved. (N.B. The optimization of
water cost is a separate issue, dealt with
in general economic studies, where overall
cost is minimized by an appropriate choice
of energy and capital costs. Lowering of
water cost must ultimately depend however
on getting the lowest capital cost for any
given energy consumption.)
In the above list, item 1 can be consid
ered well understood, since the brine is kept
under sufficient pressure to avoid any vapor
formation. The literature and practical ex
perience regarding heat transfer to liquids
flowing inside tubes is sufficient to provide
accurate and reliable heat transfer and flow
resistance data.
When we turn to items 2 and 3, however,
we are concerned with condensation heat
transfer, and this is by no means in such a
satisfactory state. Multistage flash distilla
tion can ill afford pressure drop across con
densing surfaces and is particularly subject
to the presence of noncondensable gases.
Neither of these correlates of condensation
heat transfer is well understood. Hence, the
condensation process was chosen as one of
our specific fields of research activity.
Our other field of research is obvious.
Items 4 to 8 inclusive are all dependent on
a knowledge of flow of equilibration be
havior of saturated liquid and liquid vapor
mixtures.
In the following sections an account is
presented of some of our work under the
two headings of "Condensation" and "Flash
ing Flow and Equilibration".
tion of velocity as mass flow rate is reduced
by condensation. Clearly, just as the recov
ery of kinetic energy to pressure in a dif
fuser depends on the rate of enlargement,
it is to be expected that equivalent criteria
will exist to determine the actual recovery
with condensation over tube banks. Silver's
theory (ref. 3) showed that critical condi
tions should exist which would determine
whether or not the reduction of frictional
resistance combined with reduction of vel
ocity (both due to condensation) would
give a pressure rise. The deduction was that
pressure rise should occur provided m>efm.
where m is the condensation rate per unit
surface area and efm is the Reynolds Flux,
in the presence of condensation at rate m.
A theory was also offered to describe the
functional relationship between ttm, m, and
 íf„ where efo is the normal Reynolds Flux
without condensation. The relationship de
rived was rather complicated but had the
characteristic that m = «,„ when m = 0.61
€,„. Since «,„ is easily obtained from noncon-
densing flow over the same configuration,
the conclusion could be tested.
The second important prediction was that
the effect of noncondensable gases present
in condensing vapor could also be under
stood in terms of the m and ef(> relation
ships. According to the theory developed,
if m tended to 2<(> the back diffusion of
noncondensable gases from the surface
would become impossible, and gas blanket
ing would occur. Hence in fact m would
be reduced and must stop below the value
2«f.. Thus condensation at a rate greater
than 2eto was predicted as impossible-
whatever the temperature difference avail
able—and the detailed effects of noncon
densable gases were, in principle, calculable.
Again it was possible to test these conclu
sions.
Since «t„ is primarily a function of the
Reynolds Number of the flow and the tube
configuration, these arguments were obvi
ously of potential importance to the design
of condensing plants. They are of even
greater potential importance to the con
densers in flash distillation, because of the
considerable temperature and heat exchange
value of even a small pressure recovery in
relation to the total temperature difference
available in a plant with a large number
of stages. Moreover noncondensable gases
are unavoidably present in greater propor
tion in sea water distillation plants than
in condensers for the very pure water of
a steam power cycle. Hence the first objec
tives of our research program at Heriot-
VVatt College were to test the validity of
these conclusions.
The first experiments were done by Wallis
(réf. 4), while assigned to Heriot-Watt as
Senior Visiting Fellow from Dartmouth Col
lege, New Hampshire. He set out to check
the behavior with minimal form drag. One
of the problems discussed by Silver (ref. 3)
was that in a bank of tubes, the total drag
consists not only of friction but also of form
drag. The Reynolds Flux theory applied
only to the former, and while some argu
ments suggest that form drag would also
be reduced, their validity was not obvious.
Wallis, therefore, tested the axial flow
along the inside of a straight tube since,
apart from entrance loss, form drag is neg
ligible. All his experiments were with air
instead of steam, condensation being simu
lated by extraction of air through a porous
wall. A wide range of velocities was covered,
and it was established that pressure recovery
did in fact occur to a degree which was
dependent on rate of mass extraction, and
that frictional resistance was reduced. The
criterion for positive pressure recovery over
a wide range of velocities was found to be,
with small scatter,
m > OJW «,. (S.l)
This compares surprisingly well with Silver's
predicted value of 0.61 ef0 mentioned above.
Wallis showed that a possible deduction
from his results is that the relationship be
tween tim. m, and Cf„ is the very simple one.
ft. = ft. — 0.7m (3.2)
from which efm = m when m =
1.7
m
i.e., when — — 0.59.
fro
Hence the condition for pressure recovery
agrees with Silver's general formula, m >
et„, although this occurs at a different value
of m/cf.-
Clearlv Equation (3.2) would have e,m
becoming zero at -Ш— — 1.43 as against
Cf.
Silver's prediction of Ш — 2. In view of
(fa
the effect on noncondensable gases, this
difference is potentially important.
In view of this. Silver and Wallis (ref. 5)
made another attack on the theoretical
problem. It was first shown that a very
crude approach, assuming that the Rey
nolds Flux had a uniform lateral velocity,
gave
f(m = «fo — 0.5 m (3.3)
This linear expression is much simpler than
Silver's original form, but has the same
limit at m =2. It would give the pressure
ft*
recovery criterion as m = 0.66. Silver and
Wallis (loe. cit.) then took a more sophis
ticated approach allowing for a turbulent
velocity distribution in the Reynolds Flux.
This led to -m/2«f.
tfm = ио e (3.4)
This solution is more satisfactory in prin
ciple since efm does not actually become
zero and m/ef0 may increase indefinitely.
The effect on noncondensable gases is that
their concentration at the condensing sur
face is increased over that in the main
stream by a factor which does not now
become infinite unless m/t(0 also becomes
infinite. This factor is
m/2ef„
-^--1 + — e (3.5)
t-io «Го
 From Equation (4) the critical condition
for pressure recovery occurs when m =
0.748. ITT
The net result of Wallis' experiments
was to confirm that effects of the kind sug
gested by Silver probably exist. Work has
therefore gone ahead on banks of tubes.
Drummond (ref. 6) operated a porous tube
air analog on the same basis as Wallis but
used air flow external to banks of porous
tubes. His conditions are therefore closer
to actual condensing practice, and form
drag becomes important. This work is still
in progress, but it has already been con
firmed that both form drag and friction
drag are reduced by extraction for certain
tube configurations. It has yet to be found
whether or not a net pressure recovery is
obtainable, but certainly pressure drop can
be reduced. It will be understood that since
form drag enters the problem, results are
bound to be related to tube arrangements
and this work will necessarily be more
protracted.
Simultaneously, we have constructed a
test section for actual steam condensation
experiments. The intention here is to check
in actual condensation tests such arrange
ments as are indicated as the most promis
ing from the air analogs.
One of the most important aspects of this
work in relation to desalination is as fol
lows. The distillation plant designer is
faced with the problem of an inevitable
pressure reduction due to vapor velocity
increase on entering a bank of tubes. Trying
to keep this velocity low requires a wide
tube plate. If this velocity can be increased
and the kinetic energy recovered as pressure,
this can not only help maintain the tem
perature difference but also introduce new
possibilities of tube plate dimensioning. The
higher entrance velocity will of course mean
FLASHING FLOW AND EQUILIBRATION
When a mass of liquid at temperature
T„ is reduced to a pressure p, at which the
saturation temperature T, is less than T0.
a proportion of it must eventually become
vapor. The final equilibrium proportions
q. of vapor and 1 — q, of liquid are gov
erned by the relationship
Hwo = (1 -q,)Hwl + q. H.,
= Hwl + q, L, (4.1)
Since the volume of the liquid is
not appreciably affected by small pressure
changes, we have essentially
C. (T. - TQ + V. (p. - p.)
q, -
a lower pressure and, therefore, a lower
temperature difference on the first rows of
tubes. Clearly an optimization is needed,
and for this purpose, information of the
type we are studying is essential.
The magnitude of the effects can be
shown from the following simple theory.
Ideally, the pressure change is related to
I he velocity change by the basic relations
'«■)- = - V dp (3.6)
If we are dealing with saturated steam
we may substitute for dp in terms of dT,
the change in saturation temperature, via
the Clapeyron equation. Hence
(3.7)
For the flow of saturated vapor during
condensation (assuming that the condensed
liquid has been separated to the tube walls
or is falling under its own dynamics) , we
can put V = V.; and, since the pressure
with which we are concerned is Vw «V„
we have to a good approximation
(3.8)
Over our range, L and T (its absolute
value) are nearly constant at values of the
order 1,000 Btu/lb and 660° R, respec
tively. Hence every degree Fahrenheit of
temperature fall corresponds to about 1.5
Btu/lb of velocity energy increment, and
vice versa. Starting from zero velocity, this
corresponds to about 270 ft/sec for 1° F,
and the relationship is then proportional
to V A T. For multistage flash distillation
with high performance ratio, we need so
many stages that nominal terminal tempera
ture differences may be below 5° F. Hence,
these velocity and pressure relationships
cannot be neglected.
The term V» (p„ — p,) is always much
less than Cw (T. — T,) in the range
with which we are concerned. The ratio
V. (P. - P.)
C (T. - TO
varies from order 10-' at 270°F to 10"' at
100°F.
q r~f t\
Hence effectively q, = "" ° .
La (4 .a)
Manv of the characteristic problems of the
flash distillation process are related to the
word "eventually" in the above enunciation.
The formation of the vapor cannot occur
instantaneously. It requires that heat flow
occur from zones still liquid to zones of be the causes of the difference. Hence the
evaporation and that the vapor be cooled by previous work of Benjamin and Miller
this heat flow to the new equilibrium tem gives very little guidance on the large flows
perature. The zones of evaporation require occurring in multistage flash distillation.
an interface surface between liquid and More recently, Simpson and Silver (ref.
vapor; and if such a surface does not exist, 9, 1962) gave a more sophisticated account
it must be created as bubbles or drops. of flashing flow theory, but this is exceed
The equilibrium value of q is usually ingly complex and is unlikely to be suitable
small in multistage flash distillation. For a for the scale of events in flash distillation.
4"F drop between stages, it is only of order What is required is a fairly simple theoreti
0.004. But at a temperature in the normal cal scheme, defining concepts and param
flash range, say 150°F, the ratio of V. to eters which may be measured in experiments,
Vw is 6,000. Hence that small proportion in pilot plants, and in actual plants and
of flash vapor has a volume of 24 times the whose trends may be established so that
liquid from which it has come. This ratio, new designs can be improved or made
for a 4°F drop, varies from i2 at 250°F larger. The following is a brief development
to 88 at 100°F. In flash distillation the showing the ideas which we believe will be
reduction of pressure on the liquid has to useful and which will be the subject of
be used to cause brine flow through some experimental investigation at Heriot-Watt
control area or passage between stages. College.
Hence even a small proportion of flash Equations (4.1) and (4.2) discuss even
vapor occurring in that area or passage is tual isenthalpic equilibrium. Under ideal
liable to occupy a substantial proportion velocity generating conditions we should be
of the area. These control areas cannot be concerned instead with isentropic equili
designed to allow the correct quantity ol brium. This would be obtained from
brine to flow with the correct pressure dif S„„ = (1 - q) Swl + q S„
ference unless the extent of flash in the
passage can be predicted. -S^ + qi?. (4.3)
It might be thought that there is one
easy way. If the control area is in the form Since Swo — SWJ — C. log —1- T we have
of a sharp-edged orifice, there should be no
time for flash to occur, and even saturated q= C. log -li- (4.4)
liquid flow rates through such an orifice
should be the same as cold water flow. That Now with T. — T, of order 4°F and T,
this is nearly true for pure water and for T
small circular sharp orifices at fairly high of order 600°R,-=^-is of order 1.007. Hence
pressures where the volume change is small Ti
was proved in 1941 by Benjamin and log-=^-is T to a very good approximation equal
Miller (ref. 7) . But sea water brine in a Ti
distillation plant unavoidably has minute to —- f f from which
solid particles in it which promote nucle-
ation to some extent, and the scale of
flow is such that the orifices must be large
and noncircular. The approach flow even Hence in the range with which we are
to a sharp-edged orifice is, therefore, almost dealing, we see by comparing Equations
certain to be disturbed; and there is good (4.5) and (4.2) that q is not distinguishable
evidence to indicate that flashing may com from q„ i.e., the isentropic equilibrium q
mence in front of such an orifice and cause for any pressure drop is not appreciably
restriction. Silver (ref. 8) confirmed the different from the isenthalpic q..
results of Benjamin and Miller but ex However, we have to consider the isen
tended the experiments to include short tropic change from another point of view
nozzles. A theory based on surface evapora
tion from the interface created by the inner if we want to evaluate the maximum vel
ocity energy which is available—because of
nozzle wall was found to correspond reason
ably well to experimental results for nozzles course
ocity
isenthalpic conditions give zero vel
energy. The equation for horizontal
or orifices below i/2 inch diameter, but flow of any fluid, excluding frictional re
above that size it was apparent that more
flashing was occurring than could be ac sistance, is
counted for on that surface basis. Preflash d = - V dp (4.6)
in the nozzle entrance and nucleation
within the body of liquid were presumed to For a mixture of liquid and vapor in
the respective proportions, 1 — x and x Now while Equation (4.14) is the end
thus become result of this analysis, it is instructive to
consider it in a slightly different form. If
d (-^-) = - V. dp _ x(V. _ V.) dp we multiply the third term above and
g (4-7) below by L., we obtain
ftC. (T. - T,) ■ u
Vw dp is the term which would be found
for the liquid alone, i.e., it is the increment 2L, T.
of velocity energy which cold water would which is equal to
have. MT.-TQ
x (V. - Vw) dp 2T„
We saw in discussing Equation (S.8) that,
(4.8) for a small range of integration over which
We may again use Clapeyron's equation L and T may be regarded as nearly constant,
to substitute for dp in terms of dT and L(T.-TQ
obtain T.
d(£)=dG?)-x*-dT (49) is the velocity energy which would be
obtained by saturated vapor alone in the
Now if the flow had started from satu pressure fall from p„ to p.. Moreover /3q is
rated liquid at T„ and the temperature of the actual amount of vapor formed. Hence
the liquid had reached T, the value of x the term has the simple significance of the
would be q. We now introduce the fact product of the total actual vapor quantity
that equilibrium is not always achieved by and the velocity energy obtainable from
using a concept of the "fraction of equili half the pressure drop. This is effectively
bration". This we shall define as follows. the average kinetic energy obtainable from
The pressure of the system has now the vapor.
reached p, for which T is the saturation This fact allows us to regard Equation
temperature. But if equilibration is nol (4.14) in a different light. It indicates that
complete, the mean liquid temperature will the total kinetic energy per unit weight
have some value T1 which is higher than T. obtainable in isentropic expansion can be
The "fraction of equilibration" will be simply expressed as the "cold water" kin
termed p and is defined as etic energy, plus the mean kinetic energy
_ T„ - T available from the actual vapor formed
by the end of the expansion. This appar
T„ (4.10) ently simple and satisfying conclusion has
Then we have important consequences which may now be
x _ C. (T„ - T») pointed out. As is well-known, much of the
L difficulty in discussing two-phase flow phen
= 0q omena is associated with the problem of
C. (T. - T) determining how the actual velocity is dis
= P (4.11) tributed between the two phases. The earl
ier work of Benjamin and Miller, Silver,
and Simpson and Silver all assumed homog
- 0CW V* ~ ^ dT eneous flow—i.e., that the velocity of each
(4.12) phase was the same and was given by an
analysis of the same type as Equation (4.14)
Integration of Equation (4.12) for the —while fully conscious of the probable limi
starting condition p„, T„ and finishing at tations of that assumption. Many other in
p., T„ gives vestigators of two-phase flow have discussed
v* v* T separate velocities in terms of "slip factors",
- = ^+,C.T0.og- and correlations of experimental results of
-pC„ (T. - TO (4.13) nonadiabatic flow are known on such a
basis. The interpretation we have given of
In discussing Equation (4.4) we noted Equation (4.14) now becomes helpful be
that T„ — T_ is small compared with T„ cause we need not be committed to inter
or T,. Hence we can expand log T. preting v as a homogeneous velocity, but
T, v»
in this case to the second difference term instead think only of —— as the kinetic
to give, after manipulation, 2g
energy available for distribution between
^,= y peer. -tq' the phases. Writing it. therefore, as E» we
2g 2g T 2T„ 1 ' have
 2îl ßCw (T. - TQ» and hence dissipation cannot make any
(4.15) appreciable difference to the value of q.
2g 2 T.
v«' PqLÇr.-TQ This is important in considering Equations
2 T. (4.14) and (4.15) . Although the direct
thermal effect of dissipation does not pro
In general we may assume that the actual duce appreciably more vapor, since q il
liquid phase velocity is v. and that of the unaffected, its indirect effect can in prin
vapor is v.. Then ciple be important. Dissipation may well
E*=J^ (»-л)+ -^-/sq (<-16) produce more interfacial surface and more
nucleation, and hence may give a higher
value of ß. Under dissipation conditions, we
The cross-sectional area occupied by liquid would have to write for the actual available
°— ■ WV (1 — 0q) while that occupied energy for flow
v. U=I¿. gC(T.-T,)>
WffqV.
by vapor How is Thus the total 2g + 2T. "*
(4.15)1
cross-sectional area is
WV, (l-0q)
„ ,+—
WV. Thus we have the interesting situation
A= — that if dissipation increases the value of ß
(4.17) sufficiently, the extra energy made available
may more than offset the dissipation itself,
Now for a given pressure drop in a given and hence the actual kinetic energy of flow
passage we may regard Л and q as fixed. If may be higher with dissipation than with
we assume ß constant, we also have ¥.t fixed out it. There is no contradiction with any
from Equation (4.15) . Hence vw and v. basic thermodynamic law in this conclusion
become, in principle, determinable from because the situation arises essentially from
Equations (4.16) and (4.17). A quarlic equa the lack of equilibrium.
tion has to be solved and this can be done Among the items of our experimental re
for various values of ß. Hence, the flow rate search is the investigation of dissipative de
per unit area—which is the essential thing vices with the goal of obtaining more rapid
to know for design purposes—can be investi equilibration and perhaps also improving
gated. Actual values of ß. which are un flow. The possible importance of such stud
known, may be determined by experiment. ies is indicated by considering the order of
Another interesting aspect to which atten magnitude of the terms in Equation (4.15)
tion should be drawn concerns the effect of for some typical flash distillation tempera
dissipation by turbulence and by frictional tures as shown in Table I. We see that the
forces generally. These are always present in coefficient of ß is usually much larger than
practice. But as we have seen, the value of *Л
q is negligibly different from that of q., 2R
TABLE I. Typical Hash Distillation Temperatures
Ti'F 100 160 200
(T. — Ti)'F 1 S 6 1 8 6 1 2 «
Vc1 ft lb 0.072 0.216 0.431 1.386 0.6 8.61
0.281 0.693 1.81
"¡7 л
C.(T. - Ti)» ft lb 0.68 6.11 24.7 0.68 6.69 22.76 0.68 6.26 21
2 T. lb

In the present flash distillation plant, it entrainment and of separation. Separators

is probable that the values of ß in the
actual flow control areas or passages do not
exceed 0.1 and hence the bulk of the avail
able kinetic energy from the subsequent
equilibration is released in the actual flash
chamber and is dissipated in agitation of
the brine. Such agitation undoubtedly as
sists the completion of equilibration but is
also a primary cause of ejection of droplets
of brine, giving rise to the problems- of
introduce pressure drop with loss of avail
able temperature difference. Our studies are
concerned with the possibility of obtaining
utility from the available energy shown in
Table 00. The starting point is work done
some years ago under the auspices of G. &
J. Weir, Ltd. (ref. 10) . In these experiments
flashing water was made to flow upward in
a vertical passage, in which was placed a
three-dimensional grid. Such grids could be
tried in various forms. The intention was
to use frictional dissipation and the me
chanical creation of interfacial surface
caused by such a grid to increase the value
of p, and yet prevent the available kinetic
energy from causing undue agitation. The
experiments were fairly promising but at
CONCLUSION
The grant to Heriot-Watt College for
desalination studies provides not only for
the work on condensation and two-phase
Sow but also for basic investigations on the
thermoeconomic aspects. These are impor
tant in relation to ultimate judgments and
evaluations. The objective here is funda
mental studies and not the direct economic
appraisal of particular installations, al
though these must be used as applications
of any general theory which may be devel
oped. The lines of work are those cited in
the early studies by Tribus (ref. 11) and
by Simpson and Silver (ref. 12) . It is
pleasant to record a further example of
trans-Atlantic cooperation, in that Dean
Tribus not only agreed to have Dr. Wallis
of his staff at Dartmouth come to Heriot-
Watt last year to assist in our condensation
work, but has himself participated in our
work as Senior Visiting Fellow for the
month of September 1965. In this capacity
he has not only examined, supervised, and
given advice on our activities, but has also
given a series of lectures which were open
ACKNOWLEDGEMENTS
My thanks are due to the Department of
Scientific and Industrial Research, the
Science Research Council, and the United
Kingdom Atomic Energy Authority, for
initial sponsoring and continued support
of the desalination research at Heriot-Watt
College. I am also indebted to the Gov
REFERENCES
1. Silver, R. S.: "Review of distillation
processes for fresh water production
from the sea," First European Sym
posium on Fresh Water from the Sea,
(Athens, 1962) Dechema Monographien
no. 47, pp. 19-42.
2. Silver, R. S.: Nominated Lecture, Ptoc.
l.Mech.E. no. 179, p. 1S5, (1964-65) .
3. Silver, R. S.: "An approach to a gen
eral theory of surface condensers." Ptoc.
l.Mech.E. no. 178, p. 539, (1965-64) .
4. Wallis, G. B.: "Pressure gradients for
the time it was possible to meet design re
quirements without such devices and the
work was discontinued. In the context of
today it is well worth following up and is.
therefore, included in our work at Heriot-
Watt.
to other interested parties. Moreover, one
of his former students is working with us
on thermoeconomics of steam power plant.
None of our work in this field except the
point made by Silver (ref. 2) regarding ex
traction steam temperature in mixed power
and water installations is yet ready for
publication.
It is also well-known that Tribus has
made important contributions to the de
velopment of engineering statistics. We be
lieve that some of these techniques will be
of considerable value in dealing with our
condensation and two-phase flow studies,
and in particular with entrainment investi
gation.
I hope that this account of what we have
done and are doing proves of interest. I
think that it shows that there are many
matters in distillation technology which
provide scope for good scientific engineer
ing research, the results of which may main
tain the position of distillation as a viable
method of desalination.
ernors and Principal H. B. Nisbet of the
College for enthusiastic support and en
couragement. Finally, I wish to acknowledge
the permission granted by G. & J. Weir,
Ltd., to refer to some work done on their
behalf.
air flowing in porous tubes with uni
form extraction at the walls," J.Mech.
Eng.Sc. in press (probably Sept. 1965) .
5. Silver, R. S.; Wallis, G. B.: "A simple
theory of condensation pressure drop,"
J.Mech.Eng.Sc. in press (probably Sept.
1965).
6. Drummond, G.: Heriot-Watt Fellowship
thesis (in preparation).
7. Benjamin, M. W.; Miller, J. G.: Trans.
A.S.M.E., no. 65, p. 419, (1941) .
 8. Silver, R. S.: "Temperature and pres
sure phenomena in the flow of saturated
fluids," Proc. Roy. Soc. A. no. 194, p.
464. (1948).
9. Simpson, H. C: Silver, R. S.: "Theory
of one dimensional two-phase homoge
nous non-equilibrium flow," /. Mech. E.
Symp. on Two-Phase Flow, London,
(Teb. 1962) .
10. Silver, R. S.: Internal report, G. & J.
Weir, Ltd. (1957).
ALPHABETICAL LIST OF SYMBOLS
A cross-sectional flow area
Cm concentration of noncondensable gas at
the surface of condensation
concentration of noncondensable gas in
the main stream
specific heat of saturated water
E. specific energy dissipated in flow
E, specific kinetic energy of flow
H specific enthalpy
L latent heat of evaporation
m condensation rate weight per unit time
per unit surface area
SUFFIXES
w saturated liquid phase
GREEK
ß Fraction of equilibration
if. Frictional Reynolds Flux in absence of
condensation
SUMMARY OF DISCUSSION
It was asked whether fully introduced
hydrophobic areas can be used and whether
the use of these areas has been studied. The
reply was that nothing of interest has been
found concerning this. When asked if geom-
etrv of flash chambers has been studied, the
author stated that it is hoped that geometry
can be put into practice; high water has
been studied, however, the main objective
is to get knowledge first and then to deter
mine how to use it.
11. Tribus. M.: "Therraoeconomic con
siderations in the preparation of fresh
water from sea water," First European
Symposium on Fresh Water from the
Sea, (Athens. 1962) Dechema Mono
graphien no. 47, pp. 45-70.
12. Simpson. H. C; Silver, R. S.: "Tech
nology of sea water desalination," paper
given to American National Academy
of Söence/O.S.W. Conference, Wood's
Hole, Massachusetts (June 1961).
P absolute pressure
isentropic equilibrium vapor weight
fraction
isenthalpic equilibrium vapor weight
fraction
S specific entropy
T absolute temperature
velocity of flow
velocity of flow of cold water for same
pressure difference
V specific volume
w rate of flow, weight per unit time
general vapor weight fraction
s saturated vapor phase
»r- Frictional Reynolds Flux with conden-
sation at rate m.
It was commented that a new concept in
engineering is being developed and that
engineers are looking to the possibility of
obtaining utility of kinetic energy from
flashing steam. Another comment was that
reduction in friction in the condensation
phenomenon is being studied and that if
mass flux is increased, the momentum flux
with small amounts of liquid on the wall
will be increased.
 Quelques Problèmes
Recherche Concernant le Procède de
Distillation Instantanée
Multiples
R. S. Silver, M.A., D.Sc., M.I. Mech.E., F. Inst.P., F.R.S.E.
Ecosse
La présente communication se borne à
examiner les aspects scientifiques fonda
mentaux du procédé de distillation et, dans
ce cadre, les caractères particuliers des
aspects hydrodynamiques et thermody
namiques. Les travaux dont nous indiquons
les grandes lignes sont effectués par le
bureau d'études industrielles du Heriot-
Watt College d'Edimbourg, Ecosse, au titre
d'une subvention accordée par le Conseil
de la Recherche scientifique du Royaume-
Uni.
Les résultats expérimentaux mentionnés
confirment quelques travaux récents sur la
théorie de la condensation. Ils permettent
d'espérer que l'on pourra mettre au point
du matériel de condensation pour le procédé
de distillation instantanée permettant d'at
10
et Travaux de
en Etages
ténuer la chute de pression ou même de
rétablir la pression et d'augmenter ainsi
l'efficacité de l'échange de chaleur. On ob
tient également une notion plus claire des
effets produits par les gaz non conden-
sables, ce qui devrait contribuer à une
amélioration utile de la conception de ces
installations.
L'auteur présente une analyse de la
circulation adiabatique instantanée fonda
mentale qui définit certains concepts utili
sables pour des études expérimentales et
utilisables comme paramètres pour les
ingénieurs d'étude. On démontre qu'il
existe des possibilités d'utilisation de l'éner
gie libérée au cours de la vaporisation
instantanée et on indique quelques direc
tives sur la marche à suivre.
 Некоторые Проблемы и Исследовательская

Работа в Области Многоступенчатого

Процесса Мгновенной Дистилляции

Р. С. Силвер, Магистр искусств, Доктор наук, Член Института инженер-

механиков, Член Пет. Института, Член Эдинбургского королевского
общества

Шотландия

Эта статья ограничивается рассмо пад давления или даже приведет к ре

трением основной теории дистилляци-
онного процесса и входящих в нее спе
цифических характеристик гидродина
мических и термодинамических сторон.
Описанная в общих чертах работа ве
дется в Инженерно-механическом от
деле университетского колледжа им.
Гериот-Уатт в г. Эдинбурге, Шотландия,
с помощью субсидии со стороны На
учно-исследовательского совета Соеди
ненного Королевства.
В доклад входят результаты опытов,
которые служат вспомогательным осно
ванием для некоторых последних до
стижений теории конденсации. Они
дают надежду на возможность скон
струировать такое конденсационное
оборудование для процесса мгновенной
дистилляции, которое уменьшит пере
генерации давления, благодаря чему
повысится коэффициент полезного дей
ствия теплопередачи. Понимание дей
ствия газов, не поддающихся конден
сации, тоже возросло, а это должно
привести к усовершенствованию кон
струкции.
Представлен анализ основного пото
ка с адиабатическим мгновенным вски
панием, уточняющий полезные идеи
для экспериментальных исследований,
применимые в качестве параметров
проектирования. Отмечено, что суще
ствуют возможности использовать
энергию, освобождаемую во время
мгновенного вскипания, и намечены
пути, по которым должно идти экспе
риментирование.

11
 Algunos Problemas e Investigaciones
Sobre el Proceso
Instantánea de Etapas Multiples
R. S. Silver, M.A., D.Se., M.I.Mech.E., F.Inst.P., F.R.S.E.
Escocia
Este trabajo se limita a considerar la
ciencia básica del proceso de destilación y
dentro de ella, los rasgos particulares de los
aspectos hidrodinámicos y termodinámicos.
El trabajo señalado se desarrolla en el De
partamento de Ingeniería Mecánica del
Colegio Heriot-Watt, Edinburgo, Escocia,
bajo una donación del Consejo de Investiga
ciones Científicas del Reino Unido.
Se informa sobre los resultados experi
mentales que ofrecen pruebas en apoyo de
algunos desarrollos recientes de la teoría de
condensación. Estos resultados dan lugar a
la esperanza de lograr el diseño de equipo
de condensación para el proceso de destila
ción instantánea (flash distillation) de tal
12
de Destilación
modo de reducir la caída de presión o aun
lograr recuperación de presión y de esa
manera mejorar la eficiencia de la transfe
rencia de calor. El conocimiento de los
efectos de los gases no condensables también
se ha visto profundizado y esto debería
conducir a beneficiosas mejoras de diseño.
Se presenta un análisis del flujo instan
táneo básico adiabático en el que se definen
conceptos adecuados para trabajos experi
mentales y para ser usados como parámetros
de diseño. Se muestra que existen posibili
dades para utilizar la energía liberada en el
proceso de destilación instantánea y se
indican vías de experimentación.
Influence of Membrane Phenomena

on Electrodialysis Operation

G. S. Solt, B.Sc., A.M.I.Chem.E.

United Kingdom

GENERAL
On paper the electrodialysis process of de
salination is an elegant and simple concept
and its economics are highly favorable in
the lower salinity ranges. While economic
limitations generally restrict electrodialysis
to the conversion of brackish waters below
10,000 or even 5,000 ppm, there are many
cases where electrodialysis has an apparent
economic place for treating sea water when
used in conjunction with one of the other
processes (réf. 1) . Now that reverse osmosis
is receiving so much publicity, it may be of
interest to point out in passing that reverse
osmosis of sea water yields an intermediate
product at about 2.000 ppm level, and that
it may well prove more economical to pro
duce potable water by electrodialysis than
by a second reverse osmosis stage.
So far. however, the process has not reallv
fulfilled these high expectations. In prac
tice, these have been two obstacles to their
realization. The first is that the process has
brought novel engineering problems which
could only be solved with time and experi
ence. It is fair to say that 15 years ago the
general level of engineering technology, was
simply inadequate to meet the stringent and
manifold demands made by the process. For
instance, neither plastics fabrications for
slack internals nor suitable materials for
electrodes were available at that time. In
deed there is still room for progress in such
matters, and the development effort along
these lines must continue.
Much more serious than the engineering
difficulty was the fact that, in spite of a vast
literature on membrane phenomena, one
vital aspect was very imperfectly under
stood. The dynamic performance of the
membrane is the essential core of the proc
ess, and the behavior of the membrane-
solution interface is an important factor in
this performance. If a membrane fails to
meet design requirements, the failure is
basic; unlikç engineering failure, it cannot
be overcome by ad hoc means.
We have come to realize that quite differ
ent membrane properties are required for
different applications. The electrodialysis
process is being used for three major types
of applications. In Japan the process has
been developed for the enrichment of sea
water to yield strong brine. For this pur
pose the membrane resistance and selec
tivity are by far the most important criteria.
Another group of purposes is found in vari
ous process applications, and in these the
problems are manifold. Most commonly,
however, it will be found that the tempera
ture and chemical resistance of a membrane
are of prominent importance. At this Sym
posium we are concerned only with desalin
ation of brackish water to yield potable
water. For this purpose we have found that
the kinetic properties of a membrane are
frequently the controlling factor.

THE PROPERTIES OF ION-EXCHANGE MEMBRANES

Membranes of widely differing types are properties. These include such parameters
hieing marketed by various manufacturers as ion-exchange capacity, selectivity, water
who specify a large number of membrane permeability, electrical resistance, and vari
ous mechanical properties such as burst and
tensile strength. Unfortunately the desirable
properties of these parameters are no guar
antee that a membrane will give good per
formance in actual operation. Indeed, this
stricture applies to an exhaustive list of 27
tests summarized by the Office of Saline
Water (ref. 2) . None of these tests measure
the kinetic properties which provide the
basis for the behavior of membranes on
polarization. Since we conclude that at sal
inities below 100 meq/1. the economic de
sign of a plant, even with kinetically good
membranes, is controlled by polarization
criteria, this is a serious lacuna (ref. 3) .
Before passing on to a discussion of polari
zation experience, which is the major pur
pose of this paper, it can be stated that
except in this respect most commercially
available membranes would be adequate for
brackish water work. The membrane resist
ance properties and the selectivity of mem
branes are not overcritical in the brackish
POLARIZATION THEORY AND PRACTICE
The more fundamental aspects of this
subject have been dealt with in Dr. Cooke's
paper at this Symposium (ref. 4) to which
the present paper is in part a sequel. Dr.
Cooke has drawn attention to the fact that
even in the most idealized compartment,
the local conditions for mass transfer are
not uniform. The situation is especially
complex when liquid flows through narrow
compartments which are provided with
spacers to support the membranes and to
promote mixing (refs. 6, 7).
In order to obtain an overall estimate of
polarization phenomena for practical pur
poses, we have devised a simple kinetic test.
The test uses a small laboratory stack
usually composed of about 20 cell pairs,
nominal size 25 cms x 10 cms- Platinum
electrodes are inserted to monitor the volt
age drop across 10 cell pairs in the center
of the experimental stack. A batch of brack
ish water is recirculated through this appa
ratus at constant potential across the 10 test
cell pairs. The concentration of the diluate
stream and the current density are allowed
to vary while all other parameters are kept
constant. The current flowing and the dilu
ate conductivity are recorded at frequent
intervals. The values thus obtained, cor
rected for leakage currents if necessary (ref.
5), are used to calculate the cell pair re
sistivity (in ohms cm") . When this is plotted
against the diluate resistivity (in ohms cm) ,
the resulting graph is a straight line of the
general form shown in Figure 1. The inter
water field; all available membranes are at
least good enough for a workable plant.
On the other hand, the physical prop
erties of most nonreinforced membranes are
not really adequate for satisfactory opera
tion on a large scale. Ion-exchange resins
are essentially gel structures. As such, they
are bound to show dimensional change be
tween different ionic forms and concentra
tions. On a membrane length of 150 cms,
changes of 2 per cent or over are difficult to
accommodate. We have also found a tend
ency toward plastic deformation under com
pression which is probably inherent to this
type of material. These mechanical short
comings can certainly be tolerated if no
alternative reinforced membrane is avail
able, but they inevitably increase the rate
of membrane writeoff. This rate is already
one of the major running cost factors in
any realistic pricing, hence the mechanical
properties of membranes are extremely
important.
cept "X" at zero diluate resistivity is equiva
lent to the total resistance (in ohms cm*)
of two membranes and of the concentrate
cell, all of which are held constant in this
experiment. The slope of the line repre
sented by the angle 8 is, from dimensional
analysis, in units of cms. In fact it repre
sents the equivalent thickness of the diluate
cell. Our normal apparatus has a 1.3 milli
meter cell, so that the theoretical value for
tan 0 is 0.13. This is the value which would
be obtained from an otherwise empty cell
containing diluate at the recorded concen
tration, without any of the factors which
normally add to the resistance of the cell.
In practice there is the additional effect
of the separator mesh which lies within the
cell and directly obscures a part of the
membrane area. This effect can lie meas
ured directly by determination of the a-c
resistance of the cell, which in our design
is found to be 20 to 40 per cent higher than
the theoretical value. The d-c resistance,
i.e., the resistance which results when ion
transport actually takes place, is greater
again because of the diffusion films on the
membrane surfaces. In this context the non
uniform mass transfer conditions mentioned
above must again be borne in mind. Be
cause the value of this resistance component
varies with the degree of depletion of the
films, it is meaningful only in the context
of known conditions of liquid flow and
applied emf.
In practice, we find that in good opera-
 CELL PAIR
RESISTANCE
II cm2/ CELL
INTERCEPT X
DILUATE RESISTIVITY -ft cm.
FIGURE 1. DILUTE RESISTIVITY-CELL PAIR
RESISTIVITY GRAPH.
tion we expect tan © to be of the order of
02 to 022. Bearing in mind that the test is
carried out on a small-scale electrodialysis
apparatus, the result is an overall average
over what we suppose are quite widely vari
able conditions at different points within
the stack. Identical results are obtained
from full size stacks, which confirms that
this test is of practical value for scaling-up
of results.
Where the test shows an anomalously
high intercept, this indicates a fault either
in the membranes or in the concentrate
ANION MEMBRANE POLARIZATION
Theory leads us to expect that, all other
things being equal, the limiting condition
of polarization would set in on the cation
membranes before the anion membranes. In
practice, this effect is not experienced. Even
when polarization of a cation membrane is
deliberately induced, no significant trans
port of hydrogen ions results. This is very
unfortunate, as such an effect could be used
to lower the concentrate pH and provide an
alternative to acid-dosing for scale suppres
sion. Dr. Cooke has discussed some aspects
of this phenomenon (ref. 4) , for which a
satisfactory explanation is still lacking.
In practice we are therefore concerned
only with polarization at the anion mem
brane. This results in copious transport of
OH' ions which enter the concentrate cell
through a stagnant layer of water on the
MEMBRANE PROPERTIES
Dr. Cooke has pointed out that some
anion membranes are kinetically unsound
even when new and has associated their be
havior with the presence of additional dif
system. This type of experience is rare. Very
commonly, however, we have found slopes
far in excess of 02 and these are almost
invariably ascribed to polarization.
The empirical test technique described
above is cumbersome and time-consuming.
It is our belief that the overpotential test
devised by Dr. Cooke is of theoretical sig
nificance as well as being simpler in prac
tice. On the other hand, the kinetic test has
the advantage of actually simulating plant
operation.
anion membrane surface. The resulting pH
within this stagnant layer can be appre
ciably higher than the pH of the bulk
liquid of the concentrate cell. Conditions
for scale precipitation are thus set up at the
membrane surface. To avoid actual pre
cipitation, it is necessary to maintain the
bulk concentrate pH well below the precipi
tation level. This expedient is reflected in a
substantial acid consumption. Economically,
therefore, a mild degree of polarization
(actual or threatened) affects the running
costs more by the need to suppress scale
deposition than by increases of stack re
sistance or of coulomb losses. Where polari
zation is severe, on the other hand, the stack
resistance and/or the inability of the mem
brane to pass more than a small useful cur
rent density become the controlling factors.
fusion films at their surfaces. The failure of
actual installations led to the intensive re
search effort reported in Dr. Cooke's paper
and in this one. The symptoms were a fall
of diluate pH, sharp increase in stack re
sistance above the expected value, and in
extreme cases, a total suspension of Ohm's
Law reflected in a limiting current density
which was all but indifferent to an increase
of applied voltage. We have found that
these effects appear with greater severity in
high sulphate waters than on test solutions
of sodium chloride. This fact (which has
been confirmed by Dr. Cooke) provided a
major red herring in a problem which was
already confused enough.
These phenomena were first observed
about four years ago in plants using mem
branes of types 'A' and 'T mentioned by
Dr. Cooke. The manufacturer of these mem
branes (an American company) at first re
fused to believe that their membranes,
which met all their specified requirements,
could fail to function satisfactorily. They
insisted that bad flow distribution, reten
tion of air bubbles in the stack, and various
other mechanical and hydraulic reasons
must be responsible for the failure. At last
it was recognized that the fault was in
trinsic to the membranes. The -membrane
manufacturers and their associates tried to
characterize and so avoid the fault; but,
though costly, this work was unfruitful. We
feel compelled to regard membranes from
EFFECT OF TEMPERATURE
In the course of one of our pilot investi
gations we were faced with an anomalous
set of results which we were eventually able
to correlate successfully to the temperature
of the incoming raw water, which in this
case varied rapidly and over an unusually
wide range. Hitherto our temperature al
lowance in calculating stack resistance had
been 2 per cent per degree centigrade, cor
responding to the increase in conductivity
of electrolyte solutions. As long as polariza
EFFECT ON LEAKAGE CURRENTS
Further difficulty resulted from the non-
uniformity of these polarization-prone mem
branes. We discovered that their charac
teristics differ widely between small areas
on a single roll of material. The resistance
of an individual membrane sheet would,
therefore, represent a summation of the
characteristics of the total surface exposed.
As a result the effective resistance of indi
vidual membrane sheets varies widely about
a statistical mean.
The flow of nonproductive leakage cur
rents in electrodialysis apparatus has been
described by the author in a recent paper
this source as intrinsically unsound and,
because membranes of the same chemical
class free of this defect (e.g., those de
veloped by I.C.I., Ltd.) are not commer
cially available, we now prefer to use mem
branes of the random copolymer type
reinforced with a fabric backing.
The symptoms described were observed
on brand new membranes which had been
exposed only to synthetic brackish waters
made with distilled water and analytical
reagants. Simultaneously we began to ex
perience trouble with natural waters con
taminated with organic matter. In the light
of the present state of experience in ion-
exchange treatment of organically contam
inated waters, this is not surprising. We
found that as a general rule, fouling was
particularly severe on membranes which
already possessed an external polarizable
film. In such conditions our kinetic test re
ported equivalent cell thicknesses of up to
10 cms, i.e., an increase of 8,000 per cent.
This does not necessarily mean an eighty-
fold increase of stack resistance; at high
diluate concentrations the resistance of the
stack is barely affected, but at low concen
tration the increase would approach this
factor.
tion is not a major factor, this figure is
reasonably accurate. Where it is a major
factor, we found a 4 per cent increase per
degree centigrade. Qualitatively, this is not
unexpected since the increased temperature
will increase diffusion rates and so decrease
the degree of polarization. In the absence
of theoretical confirmation, we would not
wish to put this factor forward as having
general validity.
(ref. 5) . The major leakage path available
to the current actually passing through a
stack is through the concentrate feed system
to each cell, and may be represented by a
schematic wiring diagram as shown in Fig
ure 2a. We confirmed experimentally that
the major electrical leakage path runs from
the concentrate cells at the extreme end of
the stack, through the concentrate entry
ports, along the concentrate feed duct, and
back into the concentrate cells at the other
end of the stack. With good design this
leakage is harmless and economically insig
nificant.
 <y ALL CELL PAIRS SHOWING LOW RESISTANCE

MAIN PATH OF CURRENT

b/ ONE HIGH RESISTANCE CELL PAIR.

MAIN PATH OF CURRENT

OC - CELL PAIR RESISTANCE. /3 - ENTRY PORT RESISTANCE.
5 - MAIN FLOW DUCT RESISTANCE.
FIGURE 2. LEAKAGE PATH THROUGH THE CONCENTRATE
FEED SYSTEM.

Figure 2b shows the network of a stack
in which one "rogue" membrane with a
very high resistance is placed between other
membranes with much lower resistances.
Large currents are bound to be diverted
through the concentrate system immedi
ately adjacent to such a membrane. These
large leakage currents have been known to
cause local overheating in the flow ports,
resulting in their physical collapse.

CONCLUSIONS
Our conclusions therefore are these. The
membranes offered for sale to the public
are generally adequate with respect to the
normally recognized parameters. Membranes
which are not mechanically reinforced can
be used, but the additional cost of rein
forcement tends to be less than the in
creased running cost resulting from
frequent dismantling and replacement of
torn membranes.
No manufacturer at present offering
membranes for sale offers in his specifica
tion any measure of the kinetic charac
teristics of his membranes. In the desalting
range in which electrodialysis is accepted
as an economical proposition, the polari
zation criterion generally controls plant de
sign. It is therefore important to the suc
cess of the electrodialysis process that a
universally acceptable test technique be
developed and kinetic characteristics in
cluded in the membrane specification. Dr.
Cooke's work is the only approach to this
problem of which the author is aware,
though perhaps other workers have also
produced suitable techniques.
Although a large proportion of the
world's brackish waters occurs in arid zones
where organic matter is absent, there is
increasing interest in the process from tem
perate regions where waters tend to be
contaminated with organic foulants. For
such waters, pretreatment by coagulation
and possibly even ion -exchange scavenging

17
may be necessary to avoid membrane foul
ing, though pretreatment adds substantially
to the total cost of the process. Membranes
vary considerably in their ability to with
stand organic fouling. Ideally the dynamic
test should cover this property also. Dr.
Cooke has measured overpotential charac
teristics of membranes after exposure to
polystyrene sulphonate and other "poison
ing" anions, and his findings are quali
tatively in good agreement with our own
practical experience using different types of
membrane. On the other hand, there is a
similar problem of organic fouling in ion-
exchange. Manufacturers have produced
varieties of exchange resins specifically for
high fouling resistance, but they have failed
signally to produce a reliable test method
by which this property can be accurately
predicted. The problem lies largely in the
complexity and variety of poisoning anions,
both natural and manmade, which can
occur in waters. This experience in the ion-
exchange field does not, therefore, give rise
to much optimism in the analogous prob
lem of electrodialysis.

SOME EXAMPLES
The instances recorded below (which are of cation membrane fouling (membranes
not drawn from our experience alone) serve type 'A' and type T—150 cms x 50 cms) .
to illustrate the points made in this paper. Example 3: A very large installation was
They are given in chronological order of built at a refinery in Holland to pretreat
occurrence, and show the improved grip on River Rhine water before demineralization.
the subject which we have acquired over The design predicted a 40 per cent removal
the years. During this period, not all plants of incoming salinity. This water is heavily
had these difficulties. contaminated with organic matter, mostly
Example 1: A skid-mounted plant was built of an industrial origin, and partially chlo
for delivery to a location behind the Iron rinated at the municipal waterworks. It is
Curtain. The purchaser was very secretive a notoriously difficult water to demineralize
and we suspected that the plant was re by ion-exchange. At the low influent con
quired for paramilitary purposes. We tested centration (600 ppm) the plant design was
this plant in our own works, using chemi already approaching the limiting current
cals to make up synthetic brackish waters. density criteria for normal desalination.
While the plant fulfilled our own re Within a few hours, performance of the
quirements on all-sodium chloride solu plant had fallen to a removal of 20 per
tion, a high sulphate content reduced the cent and subsequently fell further to a
output by about half. In the absence of removal of only 10 per cent. The initial
customer information regarding the water type 'T' membranes were partially replaced
to be treated, we shipped the plant and by type 'A' membranes but without im
never heard of it again (membranes type provement. Heterogeneous membranes gave
T—100 cms X 40 cms) . a better performance, but their poor physi
Example 2: A brackish water treatment cal properties made them unworkable. This
plant was built at a British military base plant was a total failure and had to be
in North Africa and was commissioned dismantled (membranes type 'A' and type
without process difficulty. The same plant T'—100 cms x 40 cms) •
house also contained an evaporation plant Example 4: A series of trials on the labo
which had been provided with inhibited ratory scale was set up by the Central
hydrochloric acid for tube descaling. The Technical Institute (C.T.I.) -T.N.O. in
electrodialysis plant utilized commercial Holland. The experiment consisted of pass
hydrochloric acid for dosing the concen ing River Rhine water similar to that in
trate. Site staff confused the two grades of example 3 through a laboratory stack. The
acid and used the inhibited acid on the stack was made up of groups of cell pairs
electrodialysis plant. The inhibitor is a comprising most of the world's commer
long chain polyamine which, one may well cially available membranes. A parallel test
imagine, is not good for cation membranes. was set up similar in all respects except that
The resultant erratic resistance rise within the incoming water was pretreated by means
the 400-membrane stack led to the local of a highly porous anion-exchanger in the
heating effects referred to in the body of chloride form (ref. 8) . The voltage drop
the paper, and the plant became unwork at set current densities was observed for
able. Following a complete membrane re each group of cells.
placement, this plant was given a 6-months' As the effects of organic fouling became
test run and has given no further difficulty. apparent, the voltage drop across these
This is probably the only recorded case groups began to rise. In order to maintain
the desired current densities, it became
necessary to remove highly fouled groups.
The fouling behavior of individual groups
was quite clearly shown to be dependent
on the anion membrane component and
independent of the cation membranes. The
test on untreated water clearly established
the relative ability of definite types of
membranes to resist organic fouling. Mem
branes of the type 'A' and T' proved to
be among the worst. At the end of the test,
only three types of membrane remained in
reasonable working condition. One of these
was a pilot sample prepared by Dr. Cooke.
The parallel test on scavenged water
showed a slower onset of fouling in all
cases, but the same relative order of per
formance between types of membranes. The
better grades remained substantially un
affected throughout the test.
Electrical polarity was reversed in the
course of these tests but this was not shown
to have any long-term beneficial effect.
Example 5: A small plant was running on
a duty similar to that in example 3. The
SUMMARY
The electrodialysis process has had set
backs due to engineering difficulties and
membrane failure. Of these, membrane
failure has been far more serious and has
shown that some important operating fac
tors have been largely ignored in the past.
Unless and until membrane manufacturers
are fully conversant with these problems
their measurement, and their cure, the in
stallation of electrodialysis plants in mam
REFERENCES
1. Hitchcock, A.; Minken. A. A. L.; Min-
ken, J. W.: "Nuclear powered electro-
dialvsis for desalination," Euronuclear
(Feb. 1965) .
2. U.S. Office of Saline Water: "Test
manual for permselective membranes,"
R. & D. Progress Report No. 77 (Jan.
1964).
3. Solt, C. S.; Wegelin, E.; Chapman.
C. V. G.: "Electrodialysis as a unit
operation," British Chem. Engineering
(July 196S) .
4. Cooke, B. A.: "Some phenomena asso
ciated with concentration polarization
in electrodialysis," First International
water supply feeding this plant could be
taken at will:
(a) Directly from the river
(b) From a partial cold lime softening
plant
(c) From the water in (b) passed
through a porous ion-exchange
scavenger.
Two of the three best types of mem
branes shown up by the C.T.I.-T.N.O. test
were used. We found that over a very long
time, the performance of the membranes
in case (c) was fully up to normal design
expectations. In case (b) the maximum
current density would be reduced by about
one-quarter and in case (a) by about one-
half.
In this as in many other installations,
we have found a rapid accumulation of
colloidal material electroprecipitated onto
the membrane surfaces. Despite sand filters
this was particularly serious in case (a) .
The inference is that coagulation pretreat-
ment is essential if the water is turbid
(membranes 100 cms x 40 cms)
individual cases will remain fraught with
uncertainty. Exploratory work done in the
laboratories of I.C.I., Ltd., in England has
provided a straightforward basis for investi
gating these matters. C.T.I.-T.N.O. in Hol
land has also continued work along these
lines. It would be highly beneficial if gen
eral international agreement on the validity
of this work could be reached.
Symposium on Water Desalination,
Washington, D.C. (Oct. 1965) .
5. Solt, G. S.: "Leakage currents in elec
trodialysis," A.I.Ch.E./I.Chem.E. Meet
ing, London (June 1965) .
6. Cooke, B. A.: Electrochimica Acta
No. /, (1961) , p. 179.
7. Cooke, B. A.; van der Walt, S. J.:
Electrochimica Acta No. 5, (1961) .
p. 216.
8. Downing, D.; Hetherington, R.: "Mac-
roreticular anion-exchange resins,"
International Water Conference, Pitts
burgh, Pa. (Oct. 1963) .
19
 SUMMARY OF DISCUSSION
It was commented that in addition to was stated that experience in Israel has
attributing polarization to the quality of shown that the cell configuration has a
the water, it is also important to consider pronounced effect on polarization and that
stack geometry, velocity, and flow distribu any scaling tends to occur in or near stag
tion within the cell compartment itself. It nant flow areas.

Influence Des Phénomènes de Mem

brane Sur le Fonctionnement de

L'Electrodialyse

G. S. Soit, B.Sc. A.M.I.Chem.E.

Royaume-Uni

Le procédé d'élcctrodialyse n'a pas ré On peut s'attendre à ce que divers facteurs

pondu aux espérances du début. Les diffi
cultés techniques ont été progressivement
surmontées avec le temps, mais un aspect
important du comportement des membranes
dans le procédé d'électrodialyse a été
jusqu'ici largement méconnu. Il s'agit de la
faculté que possède la membrane d'y laisser
passer les ions et de permettre leur diffu
sion. Cette faculté peut être mesurée comme
étant la résistance ohmique de la mem
brane à diverses densités de courant con
tinu, mais elle n'est pas déterminée par la
mesure de la résistance utilisant le courant
alternatif.
Les critères retenus à l'heure actuelle
pour déterminer la qualité des membranes
sont incomplets. Et c'est précisément à cette
insuffisance qu'il s'agit de remédier.
Ce document fait en partie suite à la
note communiquée au présent Symposium
par le Dr B. A. Cooke. laquelle traite des
aspects plus fondamentaux du problème. Il
décrit également une simple technique de
laboratoire pour examiner les propriétés
cinétiques des membranes. La présente com
munication décrit comment des expériences
d'électrodialyse effectuées à l'échelle réduite
en laboratoire peuvent être utilisées pour
parvenir au même but. Par un contrôle
approprié des paramètres, on peut obtenir
un graphique de résistance d'une paire de
cellules par rapport à la résistivité de la
solution diluée. C'est une ligne droite dont
la pente est théoriquement équivalent à
l'épaisseur de la cellule de solution diluée.
contribuent en pratique à renforcer cette
valeur théorique d'environ 50%. Les va
leurs de la pente notablement au-dessus de
150% de l'épaisseur de la cellule, peuvent
être attribuées à la polarisation, c'est à
dire au défaut de permettre le transport
normal par diffusion d'ions en quantité suf
fisante pour supporter la densité du
courant prévue.
Cet essai empirique quelque peu encom
brant peut être amplifié avec d'excellents
résultats et par conséquent se révèle d'une
utilité immédiate.
Il se peut que la polarisation, lorsqu'elle
se produit, résulte de la densité du courant
dépassant le transport d'ions permis par les
conditions hydrauliques de l'expérience.
Lorsque ce facteur ne constitue pas la cause
de ce phénomène, la polarisation "anor
male" peut être attribuée aux propriétés
cinétiques de la membrane. Nous avons
trouvé que la surface de certains types de
membranes anioniques présente une pelli
cule inerte même lorsque les membranes
sont neuves, ce qui retarde la diffusion a
un point tel qu'une polarisation anormale
s'ensuit.
Nous avons en outre trouvé que les eaux
contenant des matières organiques sont sus
ceptibles de former des pellicules inertes
sur la surface des membranes avec des
résultats similaires.
Nous avons également constaté que les
membranes qui, à l'origine, possèdent des
propriétés anormales sont bien plus prédis
 posées aux dépôts organiques que celles
qui ne sont pas ainsi affectées. L'effet con
jugué de ces deux facteurs peut donc avoir
des conséquences fort désastreuses. Une
installation réelle dont le fonctionnement
serait soumis à ces effets non seulement
consommerait une énergie électrique exces
sive, mais pourrait se révéler absolument
incapable de produire de l'eau traitée ayant
la salinité requise. En outre, l'installation
est plus exposée au dépôt de tartre dans
les cellules du concentrât.
Nous avons noté que chacune des feuilles
des membranes faisant partie du même
envoi avait un comportement très différent
lors de sa mise en service effective, et la
disparité entre les cellules voisines pouvait
conduire à d'ennuyeux phénomènes de
pertes électriques.
Nous avons aussi trouvé que lorsque la
Влияние Явлений, Происходящих
в Мембранах, на Работу Электродиализа
Г. С. С о л т , Бакалавр наук, Член-корреспондент Института инжене
ров-химиков
Соединенное Королевство
Процесс электродиализа не выполнил
своих ранних обещаний. С течением
времени технические трудности были
превзойдены, но до сих пор совершен
но игнорировалась одна из важных сто
рон поведения мембраны, относящаяся
к работе электродиализа. Этим явля
ется способность мембраны во время
электродиализа диффундировать через
себя ионы. Диффузию можно замерить,
как омическое сопротивление мембра
ны, при меняющихся плотностях посто
янного тока, но при переменном токе
ее нельзя определить измерением со
противления. Многие трудности и не
удачи, возникающие на установках,
объясняются аномалиями этого пове
дения.
Сейчас критерии, которыми пользу
ются для специфицирования качеств
мембраны, неполны и подобный недо
статок должен быть исправлен.
Этот доклад частично служит про
должением доклада, даваемого докто
ром Б. А. Куком на Симпозиуме и от
polarisation joue un rôle majeur, le rende
ment de l'installation est beaucoup plus
sensible aux variations de température en
comparaison avec le fonctionnement dans
des conditions normales. La variation du
rendement atteint environ le double de ce
qui se produirait normalement.
La communication se termine par un
argument en faveur d'une recherche accrue
destinée à parvenir à une parfaite compré
hension du comportement cinétique des
membranes, et propose qu'un accord inter
national se fasse sur une technique d'essai
permettant d'évaluer cette propriété. La
méthode du Dr Cooke parait prometteuse.
Ce document est accompagné d'un certain
nombre d'exemples illustrant sur la base
de l'expérience acquise les divers points
traités dans cette communication.
носящегося к более фундаментальным
сторонам указанной проблемы. Он там
тоже описывает простые лабораторные
приемы для исследования кинетических
свойств мембран. Настоящий доклад
касается вопроса, как применить лабо
раторные опыты малого масштаба в
области электродиализа для достиже
ния той же самой цели. Посредством
соответственного регулирования пара
метров можно получить диаграмму со
противления пары ячеек по отношению
к удельному сопротивлению соленого
раствора. Она представляет собой пря
мую линию, наклон которой теорети
чески эквивалентен толщине ячейки,
через которую проходит раствор. Бла
годаря различным способствующим
факторам, эта теоретическая величина
вероятно возрастет на практике при
мерно на 50%. Величины наклона, зна
чительно превышающие 150% толщины
стенки ячейки, могут быть приписаны
поляризации, т.е. нарушению нормаль
ного диффузионного переноса доста
 точного количества ионов при ожидае
мой плотности тока.
Это несколько громоздкое эмпири
ческое испытание можно успешно про
водить в большом масштабе, а потому
оно полезно для чисто практических
целей.
Поляризация возникает, когда плот
ность тока превышает перенос ионов,
который допускают гидравлические
условия, существующие во время опы
та. Если этот фактор не является при
чиной, то сабнормальную» поляризацию
можно приписать кинетическим свой
ствам мембраны. Мы нашли, что неко
торые типы даже совершенно новых
мембран, имеют инертные поверхност
ные пленки, которые настолько тормо
зят диффузию, что за ней следует аб-
нормальная поляризация.
Далее мы обнаружили, что воды, со
держащие органические вещества, спо
собствуют образованию инертных пле
нок на поверхностях мембран, что при
водит к аналогичным результатам.
Мы также нашли, что мембраны, об
ладающие с самого начала аномальны
ми свойствами, гораздо более подвер
жены органическому загрязнению, чем
те, которые их не имеют. Поэтому сов
местное воздействие этих двух факто
ров может оказаться весьма вредным.
Им на работе подверженная установка
не только будет расходывать избыточ
Influencia de los Fenómenos de las
Membranas Sobre el Funcionamiento
de la Electrodialisis
G. S. Solí, B.Sc, Ingeniero Químico A.M.I.
Reino Unido
El Proceso de Electrodiálisis no ha cum
plido su promesa inicial. Las dificultades
técnicas han sido solucionadas gradualmente
con el tiempo, pero un importante aspecto
del comportamiento de las membranas en el
funcionamiento de la Electrodiálisis ha sido
mayormente ignorado hasta el presente.
Este se refiere a la capacidad de la mem
brana de permitir la difusión iónica a
través de sí misma durante el funciona
22
ную электрическую энергию, но вооб
ще сможет потерять способность про
изводить опресненную воду с желае
мым солесодержанием. Кроме того, на
установке повысится образование на
кипи в ячейках концентрата.
Мы нашли, что отдельные листы мем
бран, выбранные из одной общей пар
тии, сильно отличались в функциональ
ном отношении, а несоответствие меж
ду прилегающими ячейками способ
ствовало неприятным явлениям утечки
электрического тока.
Мы далее открыли, что в условиях
сильной поляризации, производитель
ность установки гораздо более чув
ствительна к переменам температуры,
чем это бывает на работе в нормаль
ных условиях. Колебания производи
тельности превосходят почти в два ра
за нормальный уровень.
Доклад заканчивается просьбой на-
пречь исследовательские усилия для
полного понимания кинетического по
ведения мембран, и выработать меж
дународное соглашение по вопросу
технических испытаний, предназначен
ных для определения этого свойства.
Метод доктора Кука выглядит много
обещающим.
Приложен ряд наглядных примеров,
которые иллюстрируют на основании
пройденного опыта различные пункты
доклада.
miento. Puede medirse como la resistencia
óhmica de la membrana a distintas densi
dades de corrientes continua pero no se
puede determinar mediciones de resistencia
utilizando corriente alterna. Muchas dificul
tades y fallas en las plantas pueden atri
buirse a anomalías en este comportamiento.
Los criterios empleados en el momento
para especificar la calidad de las membra
nas son incompletos, y esta situación debe
 remediarse.
Este trabajo es, en parte, una continuación
del presentado por el Dr. B. A. Cooke en este
Simposium, el cual trata los aspectos más
fundamentales de este problema. También
describe él una técnica de laboratorio sen
cilla para examinar las propiedades cinéticas
de las membranas. El presente trabajo des
cribe la forma en que puede lograrse el
mismo objeto mediante experimentos de
Electrodiálisis en pequeña escala realizados
en el laboratorio. Mediante el adecuado
ajuste de los parámetros, se puede obtener
una gráfica de la resistencia del par de
células en función de la resistividad del
diluto. Este es una recta cuya pendiente es
teóricamente equivalente al espesor de la
célula de diluto. En la práctica, hay varios
factores aditivos que pueden aumentar este
valor teórico en alrededor de un 50%. Los
valores de la pendiente que excedan al
espesor celular en más de un 150% pueden
atribuirse a la polarización—es decir, a no
haber permitido el transporte por difusión
normal de suficiente cantidad de iones para
llevar la densidad de corriente esperada.
Esta prueba empírica, en cierto modo en
gorrosa, reproduce las condiciones de trabajo
en mayor escala con considerable éxito y
por esto resulta de utilidad práctica in
mediata.
Cuando se experimenta polarización, ello
puede deberse a que la densidad de corrien
te excede al transporte iónico que permiten
las condiciones hidráulicas del experimento.
Cuando este factor no es la causa, la polari
zación "anómala" puede atribuirse a las
propiedades cinéticas de la membrana.
Hemos descubierto que ciertos tipos de
membranas aniónicas poseen películas su
perficiales inertes aun cuando son nuevas,
las cuales retardan la difusión en grado tal
que provocan polarización anómala.
También hemos observado que las aguas
que contienen materia orgánica poseen ten
dencia a formar películas inertes sobre la
superficie de las membranas con resultados
análogos.
Además, hemos descubierto que las mem
branas que poseen propiedades anómalas
tienen una tendencia mucho mayor al
"envenenamiento" por materia orgánica que
aquéllas cuyas propiedades son normales.
El efecto combinado de estos dos factores
puede ser, por consiguiente, completamente
desastroso. En la práctica, una planta cuyo
rendimiento estuviera menguado por estos
efectos, no sólo consumiría excesiva energía
eléctrica sino que podría ser totalmente in
capaz de producir agua tratada de la salini
dad deseada. La planta, además, posee una
mayor tendencia a la formación de costra
en las células de concentrado.
Hemos encontrado grandes diferencias de
funcionamiento entre láminas de membrana
individuales tomadas de la misma partida.
De producirse esta disparidad entre células
adyacentes, podría originar pérdidas eléc
tricas desconcertantes.
También hemos descubierto que, cuando
la polarización constituye un factor de im
portancia, el rendimiento de la planta es
mucho más sensible a los cambios de tempe
ratura que lo que sería de esperar en condi
ciones normales de funcionamiento. La
variación en el rendimiento es aproximada
mente el doble que la que se experimentaría
normalmente.
La presentación del trabajo concluye pi
diendo se realice más investigación dirigida
hacia el alcance de una completa compren
sión del comportamiento cinético de las
membranas y solicitando un acuerdo inter
nacional sobre un método de prueba para
evaluar esta propiedad. El método del
Dr. Cooke parece ser promisorio.
Se agrega un número de ejemplos descrip
tivos tomados de experiencias reales, los
cuales demuestran los puntos expuestos en
el texto del trabajo.
23
Scale Control in Sea WaterDistillation
Toshihiko Matsuda, Shinkitchi Akimoto, and Yoshio Taniguchi
Japan
INTRODUCTION
Distillation has been widely used for
obtaining potable water from the sea. The
major troubles encountered in sea water
distillation are scale formation and corro
sion. The deposition of scale on heat trans
fer surfaces and prevention of such deposits
hive been of interest for many years, both
from a scientific and an economic stand
point. Scale brings undesirable effects: that
is, it increases resistance to heat transfer.
In general, three types of scale form in
sea water distillation: calcium sulfate, cal
cium carbonate, and magnesium hydroxide.
Occurrence of these deposits depends on
temperature, brine concentration, pH of
brine, and so on. Sulfate scale is usually
formed in the concentration of brine above
the solubility of calcium sulfate. The de
position of calcium carbonate and mag
nesium hydroxide is primarily attributed
to chemical equilibrium observed between
bicarbonate and carbonate ions in the brine
(ref. 1) . When sea water is heated, the bi
carbonate ion decomposes into the carbonate
ion and carbon dioxide. The decrease in
solubility of carbon dioxide caused by in
crease in temperature tends to drive this
reaction. The carbonate ion (formed as ex
plained above) may react with the calcium
ion to precipitate calcium carbonate or may
decompose with further evolution of carbon
dioxide and formation of hydroxide ions.
The hydroxide ion may react with the
magnesium ion to precipitate a form of
magnesium hydroxide. Temperature level
primarily determines whether calcium car
bonate or magnesium hydroxide predom
inates in the deposited scale.
In general, two methods are used for
scale control.
The first is addition of arid (such as
sulfuric acid or acid salt) to feed water
to control the rise of alkalinity. If kept
under reasonably careful control, this
method seems to minimize scale deposition.
It is reported that successful operation of
a large-scale sea water distillation unit is
achieved by addition of acid for pH con
trol. However, acid treatment of feed water
usually leads to unavoidable corrosion in
all parts of the evaporator. There is a risk
of serious corrosion if control is not careful.
The second is a physical method in con
trast to the chemical method (addition of
acid) . The principle of this method is to
control scale-forming constituents so that
the deposit occurs on a surface other than
the heating surface. An example of this
method is the contact stabilization process
proposed by Langelier (ref. 2) and his co
workers, in which brine from the evapora
tor is continuously circulated through a
bed of granular particles, such as sand or
limestone. Many seed-recycle processes (ref.
3) , in which fine crystals of scale-forming
constituents (such as Mg (OH) „ CaCO„ or
CaSO,) are kept suspended in the evapora
tor, attempt to prevent scale deposition on
heating surfaces. In Japan, many plants for
recovering salt from sea water have been
running for many years without serious
scaling troubles. In these plants, scale is
prevented by mixing the feed sea water
with the highly concentrated mother liquid
(ref. 4) .
The authors have developed a new scale
control method which combines chemical
and physical features. With the new meth
od, scale control can be easily carried out
by adding a given amount of a scale-
preventing agent to feed water and keeping
it in suspension in brine. The additive
(commercially named "Kuriverter" by the
authors) consists mainly of a kind of clay.
The additive is fine enough to remain in
suspension. The particles of the scale
preventing agent accelerate the deposition
of scale-forming constituents on particles of
the additive rather than on heating sur
faces. The additive seems to act as an acid
in the distillation of sea water. It should
be noted that a careful control is not
critical for addition of the additive.
The present study was made to observe
how the additive suppresses scale formation
in sea water distillation and how operating
conditions (i.e., brine velocity, pressure,
and temperature difference) influence the
action of the additive. In the experiment, a
forced circulation evaporator was used;
distillation capacity of the evaporator was
30 to 50 liters per hour. Brine concentra
tion for the series of experiments was
maintained at 8° to 9°B£ (s.g. 1.058 to
1.066 at 15°C) to avoid formation of cal
cium sulfate scale. The brine was kept at
about 105°C. The flash evaporator was
operated at atmospheric pressure.
The study revealed an appreciable pos
sibility for use of "Kuriverter" as a scale-
preventing agent.

EXPERIMENTAL
DESCRIPTION OF EQUIPMENT
AND OPERATION shown in Figure 3 and Table II. The
A multitube forced circulation evapora- plant consisted mainly of a brine heater,
tor with auxiliary equipment was used as a furnace, a flash tank, and a condenser.

TABLE II. Construction Features of the Evaporation Plant

Vertical coil of tube: 700 mm D. x 2,300 mm

Heat transfer medium heater Diameter of tube: 32 mm O.D.
Type of heater: one through
Heat transfer area: 6.8 m-
Type: special gear Head: 30 m
Heat transfer medium pump Delivery pipe: 50 mm Capacity: 180 l./min
Revolution: 400 rpm Motor power: 3.7 kw
Type: multitube heat exchanger, four through
Brine heater Shell: 150 mm I D. x 1.100 mm length
Tube: 13.4 mm I.D. 810 mm length
Material of tube: aluminum-brass
Heat transfer area: 0.58 m2 (16 tubes)
Evaporator Top: cylindrical 600 mm I.D. x 700 mm
Bottom : conical
Head: 20 m Capacity: 0.33 m'/min
Brine pump Delivery pipe: 80 mm Motor power: 3.7 kw
Revolution: 1.450 rpm
Type: multitube heat exchanger, one through
Condenser Shell: 160 mm I.D. x 300 mm
Material of tube: aluminum-brass

TABLE III. Properties of Chlorinated condenser was immediately mixed with

Diphenyl Used as Transfer Medium brine in the flash tank and heated to the
temperature of the brine. Chlorinated
diphenyl was used as a heat transfer me
Temperature CO 100. 200. dium. Properties of the chlorinated diphenyl
Specific gravity 1.38 1.28 are shown in Table III. The heat transfer
Viscosity C. P. 5.7 1.0 medium was circulated through the circu
lating gear pump from the heating coil in
Specific heat Kcal/kg °C 0.293 0.326 the furnace to the brine heater. Heat was
Thermal transferred to the brine from the heat
conductivity Kcal/m-hr °C 0.083 0.079 transfer medium in the brine heater. Heated
Steam pressure mmHg 0.16 18.0 brine was evaporated in the flash tank.
The concentrated brine was returned from
Remarks: Colorless and uncorrosive the flash tank to the brine heater through
against metal at high temperature the brine pump. Part of the concentrated
brine was continuously blown down, main
Sea water was fed to the condenser. Some taining the concentration at 8°Be and a
of the feed water passing through the fixed level in the flash tank. Vapor formed
 in the flash tank was cooled with the feed
water to condense in the condenser shell
and collect in the fresh water tank.
The brine heater consisted of 16 tubes,
having a total heating surface of 0.58
square meters. The tubes were divided into
four groups, each group having a heating
surface of 0.145 square meters. A pressure
gage, valve, and flow meter were fitted to
the pipeline serving each group. Brine ve
locity and pressure in each group could be
controlled by valves. The brine heater
could easily be separated from the flash
tank. The method of tube installation sim
plified removal of tubes for inspection and
sampling of deposited scale on internal
27
 surfaces of the tubes. The temperature of
!he heat transfer medium could be con
trolled by the fuel feed to the furnace.
Liquid level in the flash tank was automati
cally controlled by a solenoid valve de
signed to govern the flow of feed water.
The valve responds only to a change in
liquid level of the flash tank. Any slight
variation in brine velocity, brine concentra
tion, or temperature of the heat transfer
medium was corrected as soon as it occurred.
The operating procedures in each run
were:
1. Fill the flash tank with sea water to
a fixed level;
2. Drive the brine pump and the heat
transfer medium pump;
3. Ignite the burner in the furnace;
4. Gradually raise the temperature of
the circulating heat transfer medium
to a definite degree.
The additive was periodically supplied
in the form of 0.4 per cent suspension to
the flash tank by a slurry pump. The ex
periments were conducted at the concentra
tion of 100, 160, and 200 mg per liter of
feed water.
During continuous operation, the follow
ing were measured once an hour:
1. Fuel consumption (1/h)
2. Temperature of heat transfer
medium (°C)
3. Brine velocity (m/s)
4. Feed rate of sea water (1/h)
5. Distilled water (1/h)
6. Blow down of brine (1/h)
7. Brine concentration (°B£)
8. Brine temperature (°C)
9. Brine pressure (kg/cm2)
10. Added amount of the additive (g/h)
11. Liquid level in the evaporator
Every 3 to 6 hours, the following data
were taken:
12. pH of brine
13. Content of total iron ion
14. Brine concentration (chloride)
15. Content of the additive
Since thermal conductivity of chlorinated
diphenyl used as a heat transfer medium
is low (Table III) , its coefficient is also low.
Therefore, the difference between the tem
perature of the medium and the tube wall
is large. Temperature difference is usually
expressed as the difference between the
temperature of a warmer fluid (such as
steam) and that of a colder fluid (such as
sea water) ; in the present paper, it is
expressed as the difference between brine
temperature, tc, and temperature of tube
wall, tw, which is calculated by the follow
28
ing equation (ref. 5) so as to be comparable
with operations utilizing steam as a heat
transfer medium.
tw = tc H >H/ *H (Tc - tc) (1)
T»H/0H + »L/0Ll ' 1 ;
where:
tc = temperature of colder fluid (brine)
(°C)
"H — film coefficient of heat transfer for
warmer fluid (Kcal/hr m'°C)
hL — film coefficient of heat transfer for
colder fluid (Kcal/hr mJ°C)
= viscosity correction factor for
warmer fluid
^L = viscosity correction factor for
colder fluid
Tc = temperature of warmer fluid (°C)
DETERMINATION OF DEPOSITED SCALE
The brine was drained from the evapora
tor after testing. Inlet and outlet side
headers of the brine heater were removed,
then the tubes of the heater were washed
with water. One of these tubes was taken
out for complete inspection and analysis of
the scale. A new tube of the same kind
was used as a replacement. To prepare the
tubes for the next trial, 5 per cent hydro
chloric acid solution was circulated in the
heater tube. The removed test tube was
treated for the determination of the scale
by the following method:
1. Determination of Adhered Scale. Scale
was analyzed as follows: The two 10-cm
long pieces, of which heat transfer area
was 0.48 dra!, were cut off from the ends of
the tube for determination of the deposited
scale. The total weight of these cut-off
tubes was measured after cleaning the ex
ternal surfaces of the tubes and drying at
100° to I10°C in a hot air bath. The scale
was removed with 50 ml of one normal
nitric acid. Next, the tube was washed with
water, dried, and weighed. The difference
between tube weights before and after acid
cleaning was represented as the weight of
the scale. Thickness of the scale was calcu
lated from the density of the adhered scale,
regarded as about two, and the total weight
of the scale.
2. Scale Analysis. The nitric acid solution
was heated to dissolve the collected scale.
The acid insoluble portion of the scale was
filtered, washed, ignited, and weighed. The
filtrate was analyzed for magnesium, cal
cium, chloride, and sulfate ion. Kach ion
was determined by the following method:
Mg and Ca : titration with EDTA
CI : Mohr's method
SO, precipitation as BaSO,
 pH TZ- Tistinn^lyZed da>^The ** ThC diStillate COn,ained 5 '° 'S mg of
P Шс dl"'»ate ranged from 5.4 to chloride ions per liter.

RESULTS AND DISCUSSION

SCALE FORMATION WITHOUT ADDITIVE TABLE V. Hours of Operation and Amount
A large amount of white glossy scale was of Scale Deposited on Heating Surface
observed on the surfaces of the brine heater
tube. A photograph of tubes after testing is Time-hours in
shown in Figure 4. Tubes from the inlet operation
side in the brine heater are shown in the 88 139 241
middle of each photograph, tubes from the Total distillate m" 2.71 4.37 7.10
outlet side at the right, and a new tube Amount of scale mit/dm- 1820 3020 5620
before test run at the left. The deposited Thickness of scale mm 0.091 0.151 0.281
scale appeared thicker on the outlet side of Scale constituent r/c
the tube than on the inlet side as shown in % %
Ms 39.2 38.Б 39.3
Figure 4. Analysis of the feed sea water (Mk(OH)j)
and the concentrated brine are shown in (94.1) (92.5) (94.3)
Ca 0.4 0.6 0.3
Table IV. Operating results are shown In CI 1.0
Table V. 1.5 1.1
SO, 3.1 2.2
Fe 0.4 0.4
Operating condition:
No addition of the additive
Brine concentration: 8eBé
Brine pressure in the heater: 0.4 кг/cm'
Brine velocity: 1.6 m/s
Temperature difference: 9.9°C
Total heat transfer area: 0.29 mJ

As seen from Table V, the scale in

creased in proportion to the lime of opera
tion. In the range of scale thickness below
0.28 mm, the amount of scale was approxi
mately proportional to the total volume of
distillate under the experimental condi
FIGURE 4. TUBES AFTER TEST tions. These results lend some support to
the hypothesis derived by McC.abe and
RUN NO. 5 ON SCALING Robinson (ref. 6), in which thickness of
POTENTIAL. adhered scale is proportional to total heal
Operating condition without addition of flux. The pH of the brine was 9.2 on the
the additive average and kept a nearly constant value
Brine velocity: 1.6 m/s during operation.
Temperature différencie: 9.9 С
Hours of operation; a: 88 b: 139 a 241 The deposited scale consisted mainly of
Brine pressure: 0.4 kg/cm* magnesium hydroxide as shown in Table
Brine concentration: 8°Bé V. It contained about 0.5 per cent of cal
cium. Small amounts of chlorides and
TABLE IV. Analysis of Sea Water and sulfates were also present in the scale.
Brine (g/I.) The fact that the scale consists pre
dominantly of magnesium hydroxide agrees
Sea Water Brine closely with results obtained by Miyogawa
CI 18.900 44.000 (ref. 7) in recovering salt from sea water.
Мя 1.265 2.850
Ca 0.395 0.940
SO. 2.500 6.010 EFFECT OF ADDITIVE
HCO* 0.136 0.030 A continuous test was made to study the
CO» 0.080 behavior of the additive as a scale-
pH 8.30 9.25
Concentration CBé) 3.4 preventing agent. The results arc shown in
7.9 Table VI. Figure 5 shows an apparent
Condition in sea water evaporation decrease of scale deposition. Figure 6 shows
Temperature difference: 9.9°C the relationship between the thickness of
Brine velocity: 1.6 m/s
No addition of the additive the scale and the operating time.

29
FIGURE 5. COMPARISON WITH
TUBES OPERATED IN ADDI
TION OF THE ADDITIVE
AND IN NO ADDITION.
Operating
Condition
Concen Tempera rao во
tration ture TIME ■ HOUM IN 0НМТЮМ
of the Hours of differ FIGURE 6. HOURS OF OPERA
Tube additives operation ence TION VS THICKNESS OF
5-b 0 ppm 139 hrs 9.9°C
4-b 200 ppm 155 hrs 9.9°C SCALE.
Brine Brine Operating Condition
Tube velocity pressure Brine velocity: 1.6 m/s
5-b 1.6 m/s 0.4 kg/cm3 Brine pressure: 0.4 kg/cms
4-b 1.6 m/s 0.4 kg/cm3 Temperature difference: 9.9°C
TABLE VI. Operating Results in Addition of the Additive

Added amount of the additive ppm

0 100 200
Hours of operation hr 88 86 168
Amount of scale ml/dm1 1,820 76 87
Adjusted to 30 days operation mg/dm- 14.900 637 397
Analysis of brine (в/1.)
„H 9.25 9.10 8.7Б
CI 14.0 4Б.0 41.0
Mg 2.85 8.04 2.71
Ca 0.94 0.96 0.87
SO, 6.01 6.26 5.Б6
HCC-3 0 030 0.040 0.026
COj 0.080 0.080 0.027
Operating condition
Brine concentration: 8°Bé
Brine velocity: 1.6 m/s
Temperature difference: 9.9°C
Temperature of chlorinated diphenyl: 170°C
Brine pressure: 0.4 kg/cm2
When 200 mg of the additive per liter per liter of feed water was added as a
of feed water was added, the pH of the seeding material to prevent scale formation.
brine was lowered from 9.25 to 8.75, and The additive was sufficient for concentra
the amount of the deposited scale was tions of 0.2 grams per liter of feed water
reduced to one-fortieth of the amount and was more effective in preventing scale
observed in tests without additive. On ad deposition than magnesium hydroxide
ding 100 mg of the additive per liter of seeding.
feed water, the pH of the brine did not Furthermore, no great change of pH in
appear to change, remaining as high as that the brine occurred with excessive amounts
in the case of no additive. The thickness of of additive. No corrosion of metal parts of
the adhered scale was considerably less the evaporator was observed. Therefore,
than that without additive. Under the test careful control was not always necessary
conditions, there was usually no accumula in the additive tests. The results indicate
tion of the additive in the system. that the additive can easily be applied in
According to Shimizu and his coworkers practice.
(ref. 8) , 20 grams of magnesium hydroxide
 EFFECT OF TEST CONDITIONS
ON THE ADDITIVE
Scale deposition usually depends on the
operating conditions of sea water distilla
tion (i.e., brine velocity, temperature dif
ference, pressure, etc.) . The effect of the
test conditions on the additive was observed
to be as follows:
I. Temperature Difference. The effect of
the temperature difference, tw — tc, on scale
deposition was investigated by the follow
ing method: the amount of the additive is
200 mg per liter of feed water, brine ve
locity 1.6 meters per second, temperature
difference, tw—tc, 4.6° to 16.2°C brine
concentration 8°Be, and pressure in the
brine heater 0.4 kg per cm* gage. Figure 7
shows the relationship between the tem
perature difference and the thickness of
the deposited scale,
The alkaline scale as Mg(OH) , or CaCO,
is mainly attributed to decomposition of
the bicarbonate ion in sea water. There
fore, the decomposition rate depends on the
temperature difference, as well as on the
temperature of brine. The temperature
difference had a considerable effect on scale
formation as shown in Figure 7. The scale
thickness was approximately proportional
to this difference.
Miyauchi and Moriyama (ref. 9) reported
that the deposition rate of hard scale as
calcium sulfate was governed by the degree
of supersatuTation on CaSO,. The scaling
potential in the present operation was con
sidered in terms of the degree of super-

5.0 - A THICKNESS OF SCALE WITH 200ppm OF THE ADDITIVE

5 XIO-6
0 ADOED AMOUNT OF THE ADDITIVE /
:20oppm *
_ X "0 ADDITION OF THE ADDITIVE .

8 20| 2 XIO-6

2
10 I X I0"6 fi-i
CO
to he

CM
0L5 8X»-7 5

02 2 XIO-7
J I ' ■ ■ ■ I J l_
S 10 20 60
TEMPERATURE DIFFERENCE, ^-tg.^C)

FIGURE 7. TEMPERATURE DIFFERENCE VS AMOUNT OF SCALE

DEGREE OF SUPERSATURATION OF Mg(OH)2 IN THE BRINE.
tw: Tube wall temperature in the brine heater
tB: Brine temperature in the brine heater
Kk Solubility product constant of Mg(OH), = 10-" • at 100°C boiling (ref. 5)
Operating Condition
Brine velocity: 1.6 m/t
0.4 kg/cm1
 saturation, according to their study. The
degree of supersaturation, Ds, on magne
sium hydroxide was calculated by the fol
lowing equation:
Ds = C« (C + a) - Ks (2)
where:
C = concentration of OH" in evap
orator solution (mol/1)
C a = concentration of Mg"* in evap
orator solution (mol/1)
Ks = solubility product constant of
Mg (OH), in saturated so
lution.
As shown in Figure 7, the plotted curve
of the degree of supersaturation against FIGURE 8. TUBES AFTER
the temperature difference has a similar TEST RUN NO. 4 ON BRINE
shape to the curve of the scale thickness VELOCITY.
versus temperature difference. Therefore, Operating Condition
the scale thickness is linear to the degree Concentration of the additive: 200 ppm
of supersaturation and would work as a Hours of operation: 155 hrs
driving force of the scale deposition under Temperature difference: 9.9°C
these experimental conditions. The degree Brine velocity, a: 1.2 b: 1.6 c- 2.0 m/j
of supersaturation of magnesium hydroxide Brine pressure: 0.4 kg/cm'
was observed to be higher in the operation Brine concentration: 8° Be
without the additive than with the additive.
The lowering of the degree of supersatura
tion might occur as a result of the seeding
action and the acid behavior action of the
additive.
The degree of supersaturation on calcium
carbonate calculated by the above equation
was found to be larger than that for mag
nesium hydroxide. This fact is in accord
with conclusions reported by Langelier
(ref. 2) , in which calcium carbonate does
not deposit ion, as long as it is kept in a
supersaturated state for a longer period
than magnesium hydroxide.
2. Brine Velocity. The tests were made
to determine the influence of brine velocity
on scale prevention. Results are shown in
Figures 8 and 9. It was found that scale
thickness depended to a large extent on MINE VELOCITY (nvfc)
brine velocity in the brine heater tube.
The effect of brine velocity was influenced
to a certain degree by brine temperature. FIGURE 9. BRINE VELOCITY
In the range of brine velocity, V, below 2.0 VS THICKNESS OF SCALE.
meters per second, the thickness of the Operating Condition
adhered scale was proportional to V"* 1 in Hours of operation: 130-155 hrs
the pressure above the saturation pressure Added amount of the additive: 160-200 ppm
corresponding to the wall temperature of Brine pressure: 0.4 kg/cm2
the brine heater tube, and to below Brine concentration: 8°Be
the saturation pressure. It is supposed that
this difference is due to bubble formation
in the brine heater. The operation was mainly attributed to the decomposition of
carried out at a brine velocity below 2.0 the bicarbonate ion; it is influenced by
meters per second because of economic partial pressure of carbon dioxide gas in
considerations. vapor phase. It is presumed that deposited
3. Brine Pressure in the Brine Heater scale should decrease with an increase of
Tube. Soft scale in sea water distillation is pressure in the heater tube to suppress

32
 evolution of carbon dioxide gas and for
mation of vapor bubbles on the heating
surface.
The experimental results are shown in
Table VII and Figure 10. The higher the
pressure in the brine heater, the less was
the scale deposited. However, the effect of
the brine pressure was not as large in
comparison with that of temperature dif
ference and brine velocity in the experi
mental range. It is presumed that increas
ing pressure in the tubes may be more
effective in preventing scale under condi
tions where bubble formation will occur.
The most suitable tube pressure for distil
lation must be determined by the economic
factors.

TABLE VII. Influence of Brine Pressure

in Heater Tube

Brine pressure kg/cm^

0.4 0.8 1.2
Amount of scale lmy/dm3)
Inlet-side of heater tube 18 10 7
Outlet-side of heater tube 22 23 19
Average 20 17 13
FIGURE 10. TUBES AFTER
Operating condition TEST RUN NO. I ON BRINE
Temperature difference: 4.1°C
Added amount of the additive: 200 ppm PRESSURE.
Hours of operation: 137 hrs
Heat transfer area: 0.58 m* Operating Condition
Brine velocity : 1.6 m/s Concentration of the additive: 200 ppm
Total distillate: 3.75 m*
Hours of operation: 133 hrs
Temperature difference: 9.9°C
Further investigation will be required Brine concentration: 8 Ik-
for effective application of the additive as abed
a scale-preventing agent in a large-scale Brine velocity m/s: 1.6 1.6 1.6 0.8
sea water distillation unit. Brine pressure kg/cm2: 1.2 0.8 0.4 0.4

SUMMARY
Experiments were carried out in a 30 to
50 liter/hr forced circulation evaporator to
investigate the effect of the additive "Kuri-
verter" on scale prevention.
The results are summarized as follows:
1. Without the additive, a large amount
of scale was found on the surfaces of the
brine heater tube after a short run. The
scale consisted mainly of magnesium hydro
xide resulting from decomposition of bi
carbonate in sea water. The amount of the
scale was proportional to the period of
operation.
2. When 200 mg of the additive per liter
of feed sea water was added, the pH of the
brine dropped from 9.25 to 8.75 and the
scale was one-fortieth of the amount ob
served in the operation without the addi
tive. On adding 100 mg of the additive
per liter of feed water, no change of pH
in the brine was observed. While the
thickness of the adhered scale was less than
that without the additive, it was found by
analysis of the brine that the additive-
acted to reduce the degree of supersatura-
tion of the Mg(OH). in the brine. These
observations indicate two actions of the
additive on scale control: the first is an
acid behavior action and the second a
seeding action.
3. The operating conditions had a re
markable effect on scale deposition. The
thickness of the scale as well as the degree
of supersaturation on Mg(OH), in the
brine increased in proportion to tempera
ture difference, tw—tc, in the operating
conditions. In the range of brine velocity,
V, below 2.0 meters per second, the thick
ness of the scale was proportional to about
V-*-* to V-*T. The higher pressure in the
brine heater gave a desirable result, but the
REFERENCES
1. Badger, W. L.:R & D Process, Report
No. 25, U.S. Department of the Interior,
Office of Saline Water (July 1959) .
2. Langelier, W. F.; Caldwell, D. H.; Law
rence, W. F.: Ind. Eng. Chem. no. 42
(1950) . pp. 126-30.
3. Brit. Patent No. 131 (1920) . p. 279.
4. Sugi, J.: SekkO-to-sekkai [Gypsum and
Lime] no. 18, (1955) p. 65-69.
5. Murakami, K.; Shinagawa, J.: KOjo
Sdsa, p. 20, Kagakukôgyô sha, Japan,
SUMMARY OF DISCUSSION
There was no discussion.
Contrôle de L'Entartrage Dans la
Distillation de L'Eau de Mer
Toshihiko Matsuda, Shinkitchi Akimoto et Yoshio Taniguchi
Japon
Les principaux ennuis rencontrés dans la
distillation de l'eau de mer sont la forma
tion du tartre et la corrosion. Le tartre sur
les surfaces d'échange de chaleur résiste à
l'échange de chaleur. Il se forme en général
trois genres de tartres dans la distillation de
l'eau de mer: le sulfate de calcium, le car
bonate de calcium et l'hydroxide de magné
sium. Deux méthodes ont principalement
été utilisées pour contrôler la formation du
tartre. La première est le traitement à
l'acide de l'eau d'alimentation pour em
pêcher l'élévation du pH; la seconde est
une sorte de méthode physique similaire à
l'ensemencement de cristaux dans les sys
tèmes pour diriger le dépôt du tartre à un
emplacement autre que la surface de
chauffage.
Les auteurs de cet exposé ont mis au
point une nouvelle méthode de contrôle de
effect of the pressure on scale prevention
was not so large.
The above results prove that the additive
is effective as a scale-preventing agent in
sea water distillation. In using it, care
must be taken in the distillation operations.
(Sept. 1960) .
6. McCabe, W. L.; Robinson, T.: Ind.
Eng. Chem., no. 16 (1924) , pp. 478-9.
7. Miyogawa, S.: Shio (Salt) no. 8 (1955) ,
pp. 3-5.
8. Shimizu, K.; Sakurai, T.; Sugita, S.:
Rept. of Central Lab., pp. 102-107.
Japan Monopoly Corp., Japan (1959) .
9. Miyauchi, T.; Moriyama, T.: Kagaku
Kogaku (Chemical Engineering, Japan)
no. 25 (1961) , pp. 531-537.
l'entartrage que combine les caractéristiques
des méthodes sus-mentionnées. Avec la
nouvelle méthode, le contrôle de l'entar
trage peut se faire facilement par l'addition
d'un agent de prévention de l'entartrage
à l'eau de mer d'alimentation. Cet additif,
dont le nom commercial est "Kuriverter",
se compose principalement d'une sorte
d'argile. Les particules de l'additif sont
assez fines pour rester en suspension dans
l'eau. L'additif accélère le dépôt des élé
ments de formation du tartre sur les sur
faces des particules de l'additif plutôt que
sur les surfaces de chauffage. L'additif
semble agir de la même manière qu'un
acide en supprimant l'élévation du pH
dans la distillation de l'eau de mer. Un
contrôle précis n'est pas critique dans
l'utilisation de l'additif.
Cet exposé indique comment l'additif
 empêche le dépôt du tartre et comment
les conditions de fonctionnement (c'est-à-
dire la vélocité de la saumure, la pression
et la différence de température entre la
température de la paroi du tube de chauf
fage de la saumure, tw, et la température
de la saumure, te) influence l'action de
l'additif. Un évaporateur à circulation
forcée (capacité de distillation: 30 à 50
litres par heure) a été utilisé au cours de
l'étude. La concentration de la saumure au
cours des essais a été maintenue de 8 à 9
Bé (poids spécifique de 1,058 à 1,066 à
15°C) pour éviter la formation de tartre
de sulfate de calcium. Du diphényl chloré
utilisé comme véhicule d'échange de chaleur
dans le réchauffeur de saumure a été
chauffé aux temperatures de 130, 170 et
200°C. La saumure a été maintenue à
environ ÎOS'C. L'évaporateur à action
instantanée (vaporisation par détente)
fonctionnait à la pression atmosphérique.
Les résultats obtenus furent les suivants:
1. Entartrage sans le nouveau additif.
On a trouvé une grande quantité de tartre
sur les surfaces des tubes de chauffage de
la saumure après un court fonctionnement.
Le tartre déposé se composait principale
ment d'hydroxide de magnésium attribué à
la décomposition du bicarbonate dans l'eau
de mer. Dans la gamme d'épaisseur de
tartre inférieure à 0.28 mm., le montant de
tartre était approximativement proportion
nel au temps de fonctionnement.
2. Effet de l'additif en tant qu'agent
anti-tartre. Après l'addition de 200 mg.
d'additif par litre d'eau de mer d'alimenta
tion, le pH de la saumure est tombé de
955 à 8,75 et le montant de tartre déposé
était d'un quarantième du montant observé
dans l'essai sans additif. En ajoutant 100
mg. d'additif par litre d'eau d'alimentation,
aucun changement de pH dans la saumure
n'est apparu, le maintenant aussi élevé que
dans le cas sans additif. L'épaisseur du tartre
adhérent était considérablement moindre
que dans les essais sans additif. Il a été
également trouvé par l'analyse de la sau
mure que l'additif agissait pour réduire le
degré de super-saturation de l'élément de
formation du tartre dans la saumure.
Les résultats indiquent deux actions de
l'additif sur le contrôle de l'entartrage: la
première est l'action de comportement
d'acide que supprime une élévation dans le
pH de la saumure provenant de la décom
position des ions bicarbonates; la seconde
est une action d'ensemencement, trouvée
dans les procédés usuels de recirculation
d'ensemencement, qui accélère le dépôt des
éléments de formation de tartre sur les par
ticules en suspens de l'additif plutôt que
sur les surfaces de chauffage. On n'a pas
trouvé de changement remarquable du pH
dans la saumure après une addition exces
sive de l'additif. Il semble donc que l'appli
cation de l'additif pour le contrôle de l'en
tartrage aille facilement en fonctionnement.
S. Effets des conditions de fonctionne
ment de l'additif sur l'action de prévention
du tartre.
Le dépôt du tartre dépend généralement
des conditions de fonctionnement de la
distillation.
Premièrement, l'effet de la différence de
température, tw-tc, sur le dépôt du tartre a
été étudié dans les conditions suivantes: le
montant ajouté de l'additif était de 200 mg.
par litre d'eau d'alimentation, la vélocité
de la saumure de l,6m/seconde et la diffé
rence de température, tw-tc, de 4,1 à
16,2°C. L'épaisseur du tartre adhérent ainsi
que le degré de super-saturation de Mg(OH)5
dans la saumure, augmentait en proportion
avec la différence de température dans les
conditions expérimentales.
Deuxièmement, des expériences furent
effectuées sur l'effet de la vélocité de la
saumure dans le réchauffeur de saumure.
Il a été observé que la vélocité de la
saumure a un effet remarquable sur le
dépôt du tartre. Dans la gamme de vélocité
de saumure, V, au-dessous de 2m./seconde,
l'épaisseur du tartre adhérent était propor-
tionelle à envion V-1'7 dans les opé
rations actuelles.
Enfin, la pression plus élevée de la sau
mure dans le Téchauffeur de saumure a
donné un résultat désirable, mais l'effet de
la pression sur la prévention du tartre n'a
pas été aussi importante que la différence
de température et la vélocité de la saumure.
Les résultats ci-dessus prouvent que l'ad
ditif a une action importante en tant
qu'agent anti-tartre dans la distillation de
l'eau de mer. Cependant, dans l'utilisation
de l'additif il faut surveiller les conditions de
fonctionnement du procédé de distillation.
35
 Борьба с Накипью при Опреснении
Морской Воды
Тошихико Матсуда, Шинкитчи Акимото и Йошио Танигучи
Япония
Главными затруднениями при опре
снении морской воды являются обра
зование накипи и коррозия. Накипь на
теплообменных поверхностях задержи
вает теплопередачу. При дистилляции
морской воды встречаются вообще три
типа накипи: сульфат кальция, карбо
нат кальция и гидроокись магния. Для
борьбы с накипью преимущественно
пользовались двумя методами. Первый
состоит из обработки исходной воды
кислотой для предотвращения повы
шения pH; второй является физическим
методом затравки кристаллами, чтобы
отводить осаждение накипи с поверх
ности нагрева на другое место.
Авторы настоящего доклада усовер
шенствовали новый способ борьбы с
накипью, который сочетает особенно
сти двух вышеупомянутых. При новом
методе без труда достигается предот
вращение образования накипи с по
мощью добавления к исходной воде
специального реактива. Он имеет тор
говое название «Куривертер» и глав
ным образом состоит из глинистой по
роды. Частицы его настолько тонко по
молоты, что остаются взвешенными в
воде. Добавка способствует отложению
накипи не на поверхностях нагрева, а
на поверхности частиц самого реакти
ва. «Куривертер» видимо действует при
дистилляции морской воды, как кисло
та, задерживающая повышение pH.
При пользовании добавкой не требует
ся внимательного за ней наблюдения.
В настоящем докладе указано, как
добавка предотвращает отложение на
кипи, и как рабочие условия (т.е. ско
рость потока раствора, давление, пере
пад между температурой стенки трубы
подогревателя раствора и температу
рой самого раствора и т.п.) влияют на
действие реактива. При исследованиях
пользовались испарителем с принуди
тельной циркуляцией (дистилляционная
производительность 30-50 литров/час).
Для предотвращения образования на
кипи сульфата кальция, во время опы
тов поддерживалась концентрация ра
створа при 8-9 градусах Бомэ/удель-
ный вес 1,058-1,066 при 15вС). В ка
честве теплоносителя в подогревателе
рассола был использован хлорирован
ный дифенил, температура которого до
водилась в подогревателе раствора до
130, 170 и 200°С. Раствор имел пример
но 105°С. Испаритель со мгновенным
вскипанием работал при атмосферном
давлении.
Были получены следующие резуль
таты :
1. Когда реактив не употреблялся, от
лагалась накипь. После короткого опы
та было обнаружено большое количе
ство накипи на поверхностях трубы
подогревателя раствора. Она преиму
щественно состояла из гидроокиси маг
ния, возникавшей вследствие разложе
ния бикарбоната в морской воде. При
толщине накипи менее 0,28 мм, ее ко
личество было почти пропорционально
продолжительности работы.
2. Воздействие добавки реактива для
предотвращения образования накипи.
При добавлении 200 мг «Куривертера»
на литр исходной воды, показатель pH
раствора снижался с 9,25 до 8,75, а
количество отлагавшейся накипи со
ставляло одну сороковую часть того,
что замечалось при опытах без его
добавления. При добавке 100 мг реак
тива на литр исходной воды, в раство
ре не происходило изменения pH, ко
торый оставался на прежнем уровне.
Толщина сцеплявшейся накипи была
значительно меньше, чем при опытах
без реактива. При анализе раствора
было также обнаружено, что добавка
уменьшала степень пресыщения со
ставной части раствора, способствовав
шей образованию накипи.
Результаты указывают на два дей
ствия реактива: первое является ки
слотным, которое сдерживает повыше
ние pH раствора, получающееся вслед
 стене разложения бикарбонатного ио
на; второе служит затравкой, встречаю
щейся в обычном затравочном рецир
куляционном процессе, которая способ
ствует отложению составных частиц,
образующих накипь, не на поверхно
стях нагрева, а на самой взвеси «Кури-
вертера». При чрезмерном добавлении
реактива не было найдено в растворе
значительного изменения pH. Поэтому
применение добавки для борьбы с на
кипью повидимому не представляет во
время работы никаких трудностей.
3. Влияние рабочих условий на дей
ствие добавки для предотвращения
образования накипи. Отложение наки
пи обычно зависит от рабочих условий
перегонки.
Во-первых, было обследовано воз
действие перепада между температу
рой стенки трубы (т.е.) подогревателя
раствора и температурой самого раст
вора (т.р.) на образование накипи при
следующих условиях: количество до
бавляемого реактива — 200 мг на литр
исходной воды; скорость потока раст
вора — 1,6 м/сек; температурный пе
репад т.с.-т.р. — 4,1°С- 16,2°С. Толщи
на отлагавшейся накипи, а также и сте
El Control de las
la Destilación del Agua de
Toshihiko Matsuda, Shinkitchi Akimoto y Yorhio Taniguchi
Japon
La causa principal de las dificultades que
sobrevienen en la destilación del agua de
mar son: la formación de incrustaciones y
la corrosión. Las incrustaciones que se for
man en las superficies de transmisión caló
rica oponen resistencia a dicha transmisión.
En la destilación del agua de mar se
forman, por lo general, tres tipos de incrus
taciones a saber: las de sulfato de calcio,
carbonato de calcio e hidróxido de magne
sio. Para el control de las incrustaciones se
han empleado principalmente dos métodos.
El primero consiste en el tratamiento del
agua de alimentación con ácido para evitar
la elevación del pH; el segundo es una
especie de método fisico, tal como el espar
cimiento de cristales de "semilla" en los
пень пересыщения Mg(OH)2 в раство
ре увеличивались пропорционально
температурному перепаду, имевшему
место в условиях опыта.
Во-вторых, были произведены опыты,
относившиеся к воздействию скорости
потока в подогревателе раствора. Бы
ло обнаружено, что скорость потока
раствора оказывает заметное влияние
на отложение накипи. При скорости
потока раствора V < 2,0 м/сек, тол
щина сцеплявшейся накипи во время
этих опытов была приблизительно про
порциональна v-*,--v-*,T.
Наконец, повышение давления раст
вора в его подогревателе давало поло
жительные результаты, но воздействие
давления на предотвращение образо
вания накипи было менее, чем эффект,
производимый температурным перепа
дом и скоростью потока раствора.
Вышеуказанные результаты подтвер
ждают, что при опреснении морской
воды добавка играет видную роль в
борьбе с накипью. Однако, при ее при
менении надо тщательно следить за
рабочими условиями дистилляционного
процесса.
Incrustaciones en
Mar
sistemas para que las incrustaciones se
formen en un sitio que no sea la superficie
de calentamiento.
Los autores de este trabajo han perfeccio
nado un nuevo método en que se combinan
los rasgos característicos de los métodos ya
mencionados. Gracias al nuevo método, la
prevención de las incrustaciones puede efec
tuarse fácilmente agregando al agua salada
de alimentación un agente protector contra
incrustaciones. El aditivo, denominado co-
mercialmente "Kuriverter" por los autores,
consiste principalmente en una especie de
arcilla. Las partículas del aditivo son lo
suficientemente finas para permanecer sus
pensas en el agua. El aditivo acelera la
precipitación de los constituyentes formado
res de incrustaciones sobre la superficie del
aditivo y no en las de calentamiento. £1 adi
tivo parece actuar como un ácido al impedir
el ascenso del pH en la destilación del agua
de mar. Cuando se emplea el aditivo no
es indispensable mantener un control
cuidadoso.
Este trabajo indica cómo el aditivo evita
la formación de incrustaciones y cómo las
condiciones de trabajo (v.g., la velocidad de
la salmuera, la presión, y la diferencia entre
la temperatura de las paredes del tubo de
calentamiento de la salmuera, tw, y la tem
peratura de la salmuera, te), influyen en la
acción del aditivo. En los trabajos de inves
tigación se empleó un evaporador tie circu
lación forzada (capacidad de destilación:
de SO a 50 litros por hora). Durante las
pruebas, la concentración de agua salobre
se mantuvo entre 8 y 9 Baumé (peso espe
cifico: 1.058 a 1.066 a 15° C.) para evitar la
formación de incrustaciones de sulfato de
calcio. El difenilo clorinado que se empleó
como medio de transmisión térmica en el
califactor de salmuera, fué calentado a
temperaturas de 130, 170 y 200° C. La sal
muera se mantuvo a una temperatura de
más o menos 105° C. El evaporador instan
táneo trabajó a la presión atmosférica.
Se obtuvieron los siguientes resultados:
1. La formación de las incrustaciones sin
el nuevo aditivo. Se encontraron muchas
incrustaciones en las superficies del tubo
calentador de salmuera después de un breve
período de funcionamiento. La costra depo
sitada consistió principalmente en hidróxido
de magnesio, lo cual se atribuyó a la des
composición de bicarbonato en el agua de
mar. En las incrustaciones con espesor infe
rior a 0,28 mm., la cantidad de incrustacio
nes fué más o menos proporcional al periodo
de funcionamiento.
2. El efecto del aditivo como agente pro
tector contra incrustaciones. Cuando se
agregaron 200 mg. del aditivo por cada
litro de agua de mar de alimentación, el pH
de la salmuera bajó de 925 a 8,75 y la can
tidad de incrustaciones depositadas fué de
un cuadragésimo de la que se observó en la
prueba sin el aditivo. Cuando se agregaron
100 mg. del aditivo para cada litro de agua
de alimentación, no ocurrió ningún cambio
en el pH de la salmuera, manteniéndose
tan alto como sin el aditivo. El espesor de
la costra adherida fué considerablemente
menor que en las pruebas sin el aditivo.
También se comprobó por medio del aná
lisis de la salmuera que la acción del aditivo
redujo el grado de sobresaturación en el
constituyente formador de incrustaciones en
la salmuera.
Los resultados indican que el aditivo
ejerce dos acciones en el control de las in
crustaciones, a saber: la primera es una
acción ácida que suspende el ascenso del pH
de la salmuera que resulta de la descompo
sición del ion bicarbonato; la segunda es
una acción de sembrado de "semilla" que
ocurre en el procedimiento común de recir
culación de "semillas" que acelera la preci
pitación de los constituyentes formadores de
incrustaciones en las partículas suspendidas
del aditivo y no en las superficies de calen
tamiento. Al agregarse una cantidad exce
siva de aditivo no se observó un cambio
grande de pH en la salmuera. Por lo tanto,
parece que la aplicación del aditivo para
el control de las incrustaciones se lleva a
cabo fácilmente.
3. El efecto de las condiciones de trabajo
en la acción protectora contra incrustaciones
del aditivo. La formación de incrustaciones
depende, por lo general, de las condiciones
de trabajo de la destilación.
En primer lugar, se investigó el efecto de
la diferencia de temperaturas, tw-tc, en la
formación de incrustaciones, en las siguien
tes condiciones: La cantidad adicional del
aditivo es de 200 mg. por litro de agua de
alimentación, la velocidad de la salmuera es
de 1,6 metros por segundo y la diferencia de
temperaturas, tw-tc, es de 4,1 a 162° C.
Tanto el espesor de la incrustación adhe
rida como el grado de sobresaturación de
Mg(OH)2 en la salmuera, aumentaron pro-
porcionalmente a la diferencia de tempera
turas en las condiciones de prueba.
En segundo lugar, se condujeron experi
mentos para determinar el efecto de la velo
cidad de salmuera en el calentador de esta
última. Se observó que la velocidad de la
salmuera ejercía un efecto grande en la for
mación de incrustaciones. En los límites de
velocidad del agua salobre, V, inferiores a
2,0 metros por segundo, el espesor de las
incrustaciones adheridas era proporcional
a entre V-*'* y V"*'T en las operaciones
actuales.
Finalmente, la presión más alta de la
salmuera en el calentador de esta última
produjo el resultado deseado, aunque el
efecto de la presión en la prevención de
incrustaciones no fué tan notable como el
de la diferencia de temperaturas y la veloci
dad del agua salobre.
Los resultados obtenidos demuestran que
el aditivo ejerce una acción notable como
agente de protección contra incrustaciones
en la destilación del agua de mar. Sin em
bargo, al emplearse el aditivo debe tenerse
cuidado en lo que toca a las condiciones de
trabajo en el procedimiento de destilación.
 Saline Water Distillation
Prevention by Polymer Additives
L. S. Herbert, P. F. Rolfe and U. J. Sterns
Australia
INTRODUCTION
Distillation of sea water and other natu
rally occurring saline waters gives rise to
the formation of scale deposits of low ther
mal conductivity on the heat transfer sur
faces of the distillation plant. The heat
transfer coefficients are thereby reduced,
leading to deterioration of plant perform
ance and necessitating the eventual shut
down of the plant for cleaning. Although
•several methods are in use for the control
of "alkaline" scales, scaling considerations
still set an upper limit on the brine boiling
temperature and concentration factor, and
hence on plant performance.
In work recently reported (réf. 1) , it was
found that the addition of small amounts
of certain polymeric acids of selected molec
ular weight range to the sea water feed of
an experimental spray evaporator had a
remarkable effect in reducing the adverse
effects of scale formation on the heat trans
fer surfaces. Of the materials tested, poly-
acrylic acid of mean molecular weight
20,000, added to the extent of 3 ppm to the
sea water feed, proved to be particularly
effective during evaporation at 240°F. Over
all heat transfer coefficients in excess of
2300 Btu/sq ft hr°F were maintained over
a period of 50 hours, whereas evaporation
of untreated sea water resulted in a rapid de
crease of the coefficient to about 800 Btu/sq
ft hr"F after only 6 hours.
The mechanism of protective action was
not clear, but there was evidence of the
formation of a thin film of the polyacid or
a related salt on the heating surface. The
scale-forming components then appeared to
deposit on the film, which stripped from the
wall, possibly as a result of stresses set up
in the film by temperature differentials.
— Scale
The protective film then reformed on the
exposed surface and the process was re
peated. Such a "regenerating film" mech
anism is of general interest, and techniques
based on it may find extensive practical
application in saline water distillation
plants and in other plants where the prob
lem of scale formation is encountered. The
work reported below was carried out in an
attempt to establish the limits of applic
ability of the scale prevention method and
to elucidate the mechanism of the protec
tive action by experiments with both the
experimental evaporator and small-scale
beaker tests.
PREPARATION AND CHARACTERIZATION
OF POLYMERS
The polyacrylic acid used in the earlier
experiments (réf. 1) was supplied by Can
adian Industries, Ltd., (C.I.L.) who also
provided details of a method of preparation
for low molecular weight polyacrylic acids
(Appendix 1A) . Several batches of homo-
polymer—designated Rl through R8—were
made by this method. Since a partially
csterified polyacrylic acid might be expected
to possess improved surface activity com
pared with the homopolymer, a 10 per cent
ethyl acrylate/acrylic acid copolymer, desig
nated R9, was made by the method detailed
in Appendix IB.
In attempts to produce homopolymers of
differing molecular weights, the propor
tions of monomer, initiator and chain trans
fer reagent given in the preparative method
were varied.
Weight average molecular weights of sev
eral polymers were determined by equilib
 TABLE VIII. Characterization of Polymers by Equilibrium Ultracentrifugation
Polymer Type
C.I.L. Homopolynoer
K2 Homopolymer
R6 Homopolymer
R6 Homopolymer
R9 10% ethyl acrylate—
90% acrylic acid copolymer
rium ultracentrifugation using a Spinco
Model E Ultracentrifuge. using the method
outlined in Appendix 2. Typical results are
presented in Table VIII.
It can be seen that the effect of variation
of reactant proportions in the homopolymer
EXPERIMENTAL
SPRAY EVAPORATION AND CLIMBING FILM
EVAPORATION TESTS
Figure 11 shows a simplified flow diagram
for the test apparatus. It was essentially the
same as the "spray" evaporation rig de
scribed in detail in a previous publication
(ref. 1) . Preheated sea water was intimately
mixed with steam in a venturi and the re
sulting two phase mixture passed upwards
at high velocity through a steam jacketed
copper tube of i/s inch internal diameter
which was 2 feet long. Transfer of heat
from the higher pressure jacket steam
caused evaporation of the sea water drop
lets. The resultant mixture of brine and
steam was separated, the steam condensed,
and both product liquid streams metered.
In tests with untreated sea water, the rate
of scale formation was rapid and repro
ducible and, on these grounds, the method
was selected for a detailed appraisal of
scale-prevention techniques. The rate of
heat transfer was measured by weighing the
jacket condensate produced in selected time
intervals.
For the work previously reported, polymer
additions were made to 240 gallon batches
of sea water stored in a stirred tank at some
distance from the evaporator. Adsorption
of polymer on the inside tank and pipe sur
faces during runs at high polymer concen
tration followed by desorption into the feed
water during the succeeding low concentra
tion runs contributed to poor reproduci
bility of heat transfer data. To overcome
Method No. of runs Av. m. wt.
Long 1 19,000
Long 2 22.000
column
Long 1 16.000
column
Short 3 18.000
column
Short 1 13.000
column
preparative method had relatively little
effect on molecular weights, which were in
the range 16,000 to 26,000. A study of molec
ular weight distributions revealed that the
C.I.L. polymer possessed a somewhat broader
distribution than polymers R2 and R6.
this effect the apparatus was modified so
that a strong polymer solution was added
continuously by a metering pump feeding
a small mixing chamber in the preheated
feed water line, and positioned as near as
possible to the steam-water venturi mixer.
A further advantage was that longer runs
could be made. As an additional modifica
tion, a manual throttling valve was installed
in the pipeline between the separator and
the condenser to permit the use of increased
pressures, and hence increased tempera
tures, within the evaporator tube.
The values of flowrates and jacket steam
temperature, e.g.. 300 lb/hr water, 96 lb/hr
steam and 40 psig jacket steam pressure
(287°F) , found to be most suitable in the
previous work, were used as "standard"
evaporation conditions in the present work.
F.vaporation temperature changed along the
tube length due to the pressure drop and
averaged 240°F, with a 45°F difference be
tween heating steam and evaporating fluid
temperatures. The concentration factor ob
tained (i.e., the ratio of feed water rate to
residual brine rate) was approximately 1.3.
At the end of any test the inside tube sur
face and any adhering scale could be ex
amined by cutting the tube in half along
its axis.
CALCULATION OF EFFECTIVENESS
OF SCALE PREVENTION
Instantaneous readings of pressure, tem
perature, and rate of condensate production

JocAet
1
Grotfuotect
Ton*
—2
Po/ymer
Feect water
0
Preneoter
I 5Г—^ '
1 J Steo.n/ Voter Aftxer
FIGURE 11. SIMPLIFIED FLOW DIAGRAM
FOR SPRAY EVAPORATOR.
were subject to considerable fluctuations
during any run. Consequently the heat
transfer coefficient at the end of a fixed
operating time, or the rate of decrease of
heat transfer at any selected time measured
from the start of the run, were unsatisfac
tory criteria of effectiveness of scale preven
tion. It was decided that the quantity of
jacket condensate collected during the first
6i/i hours of any test was a reasonable basis
for comparison of different runs. This was
incorporated in an arbitrary "Improvement
Ratio" defined as
m = ±f* x loo (i)
where A = weight of jacket condensate col
lected in ву2 hours using the
given polymer addition;
В — weight of jacket condensate col
lected in hours with un
treated sea water.
Due to the accumulation of deposits in
side pipelines to and from the evaporator
tube, the pressure and consequently the
temperature inside the system were subject
Condenser
Diati/lote
JocAet Com/ensote
to minor variations from test to test. Small
proportional corrections were made to the
weight "A" to compensate for the changes
in the heat transfer driving force.
LABORATORY BEAKER TESTS
A single run in the pilot plant evaporator
took 61/4 hours and consumed approxi
mately 200 gallons of sea water. Only one
set of conditions could be investigated in
the period. A study was made of simple
laboratory evaporation tests with the aim
of developing a small-scale, quick method
of evaluating different polymeric compounds
for effectiveness as scale-prevention agents.
In one such method, natural sea water
samples containing various concentrations of
copolymer R9 were evaporated on a hot
plate at a closely controlled boiling rate in
pyrex glass beakers covered with watch
glasses. The evaporation was continued until
a predetermined weight of brine remained,
corresponding to a concentration factor of
1.3 similar to that obtained in spray evap
oration "standard" tests. Every beaker and
watch glass was carefully cleaned before
each test, using a combination of hot acid
and alkali washes.
The residual brine was allowed to cool
overnight and any precipitates formed were
collected on sintered glass filter crucibles,
EFFECT OF POLYMER CONCENTRATION
SPRAY EVAPORATION
Data from preliminary tests are plotted
in Figure 12 as Improvement Ratio versus
polymer concentration (ppm). Several batches
of sea water were used as feed with vari
ous concentrations of several different
batches of polymer additives. The polymers
were all polyacrylic acids, estimated to be
in the molecular weight range 16,000-26,000
and made by the methods described in
Appendix 1A. An optimum polymer con
centration, corresponding to a maximum
Improvement Ratio, is shown quite clearh
although there is a considerable scatter of
data around the optimum concentration.
Data for single batches of sea water using
various concentrations of a single polymer,
O
loo r
FIGURE 12. VARIATION OF IMPROVEMENT RATIO WITH
POLYMER CONCENTRATION 7 BATCHES OF SEA WATER,
POLYMERS OTHER THAN R9, "STANDARD" CONDITIONS.
washed with a measured volume of nitrate,
then dried and weighed. A correction was
made for any suspended solids in the orig
inal sea water by means of a blank deter
mined on untreated sea water.
R9, the ethyl acrylate/acrylic acid copoly
mer, are plotted in Figure IS. An optimum
polymer concentration at approximately 2
ppm is indicated for sea water batches 103
and 107 while it appears that an optimum
has not been reached at 3 ppm for batch
106. Differences in optimum polymer con
centration in the range 1.0-4.0 ppm have
been observed for different batches of sea
water and may be accounted for by differ
ences in the dissolved solids or suspended
matter content of the different batches of
sea water. Analyses of each batch showed
no gross differences in total dissolved solids
or total alkalinity, but traces of oil con
tamination or variations in the amount of
organic matter could lead to variable re
sults with the very small quantities of poly
mer added.

2 * 6 8
Po/ymer Concentrator* -ppm
FIGURE 13. VARIATION OF IMPROVEMENT RATIO WITH
POLYMER CONCENTRATION POLYMER R9, "STANDARD"
CONDITIONS.
The optimum polymer concentration of
2 ppm of R9 was set as the additive con
centration for a 50-hour evaporation test
on sea water batch 103. Due to operating
difficulties, the addition rate varied from
2.0 ppm at the start of the run, down to
less than 1.5 ppm at the end of the run,
the average corresponding to 1.6 ppm. The
variation of overall heat transfer coefficient
with time is plotted in Figure 14, together
with typical results obtained for spray evap
oration of an untreated sea water for com
parison. Figure 14 also shows the effect of
a momentary interruption of the flow of
sea water feed after 30 hours of operation.
The immediate recovery of the overall heat
transfer coefficient to the "clean tube" value
indicates that the deposit formed up to that
time was attached only loosely to the tube
surface and was easily removed by the in
terruption of water flow.
—°— Sea Voter Botch /OS
—X—
O Seo Sea
Voter
Mooter
Batch
Botch
/Otf07
W 12
EFFECT OF POLYMER CONCENTRATION
CLIMBING FILM
Climbing film evaporation tests were
made using the apparatus of Figure 11, fed
with preheated sea water feed and no en-
trainment steam. The evaporation tempera
ture was adjusted to approximately 240°F,
with an overall temperature difference be
tween jacket steam and evaporating fluid
of approximately 45°F.
The results for two batches of sea water-
batches 108 and 110—are plotted in Figure
15. An optimum polymer concentration is
evident in both curves, between 1 and 2
ppm of polymer. At polymer concentrations
higher than 5 ppm, a negative Improvement
Ratio resulted, i.e., the scale deposits formed
with excess polymer present were more dele
terious to heat transfer than those resulting
from untreated sea water.
43
 5.000

10 20 30 40 50 60
f/oara of operot/on
FIGURE 14. VARIATION OF OVERALL HEAT TRANSFER
COEFFICIENT WITH TIME AT "STANDARD" CONDITIONS.

— •— Sea woter botch /Og

*— Seo water batch //O

\ G 8 tO 12
\ Po/ymer Concenirotton -pp m

FIGURE 15. VARIATION OF IMPROVEMENT RATIO WITH

POLYMER CONCENTRATION POLYMER R9, CLIMBING FILM
EVAPORATION AT 240°F.

44
 EFFECT OF POLYMER CONCENTRATION—
LABORATORY TESTS ON
NATURAL SEA WATER
In laboratory tests on a given batch of
sea wateT. polymer additions were made to
samples of the water in several beakers to
give a different polymer concentration in
each sample, in the range 0 to 10 ppm.
Beakers and contents were then subjected to
the standard test procedure outlined in a
previous section.
Examination of the contents of the beak
ers after boiling showed that the amount
of visible precipitate varied with polymer
concentration. There was generally one
beaker, corresponding to a particular poh
mer concentration (in the range 1 to 4
ppm for different batches of sea water) in
which the amount of visible precipitate was
a minimum.
cent probability that the three low precipi
tate weights at polymer concentration 3.4
ppm were simply random fluctuations from
a smooth curve through the remaining
points. In a similar series of tests with sea
water batch 103. minimum amounts of pre
cipitate resulted at a polymer concentration
of 1.8 ppm (cf. optimum polymer concen
tration of 2.0 ppm obtained in spray evap
oration tests—Fig. 13.
EFFECT OF POLYMER CONCENTRATION—
LABORATORY TESTS ON
SYNTHETIC SEA WATER
Synthetic sea water was made up accord
ing to a formula of Lyman and Fleming
(ref. 3) . Special precautions taken to avoid
contamination with surface active materials
included chemical cleaning of vessels, use of
the purest available chemicals, and prcven-

I 2 3 4-5 6 7
Po/ymer Concentrat/on -ppm

FIGURE 16. VARIATION OF PRECIPITATE WEIGHTS WITH

POLYMER CONCENTRATION SEA WATER BATCH 104, POLY
MER R9, BEAKER TESTS.

By careful filtration and weighing it tion of ingress of airborne materials. Beaker

proved possible to determine the very small
weights of the individual precipitates. Typi
cal data for sea water batch 104 are plotted
in Figure 16. The previous visual observa
tion that a minimum amount of precipitate
resulted from the addition of about 3.4 ppm
of polymer was confirmed by the weights
of precipitate actually measured. Statistical
examination, using student's "t" tests,
showed that there was less than a 2 per
tests indicated scale deposition behavior
similar to that in natural sea waters, with
a minimum precipitate occurring at a polv
mer (R9) concentration of 0.6 ppm.
Modifications of the synthetic sea water
formula were made in order to obtain mag
nesium -deficient "sea water" (producing
largely calcium carbonate scale on boiling)
and calcium-deficient "sea water" Cproduc
ing largely magnesium hydroxide scale).
The variation of precipitate weights with
|>olymer concentration is shown in Figure
17 from which it is seen that at small poly
mer concentrations, the effect of polymer
addition is most marked where Mg(OH),
is being deposited, giving a minimum pre-
cipitate weight at a polymer concentration
of 0.4 to 0.5 ppm. Where CaCO, is being
deposited, there is a steady decrease in
precipitate weight up to 3 ppm polymer
concentration, with no evidence of a mini
mum weight.

40 r

FIGURE 17. VARIATION OF PRECIPITATE WEIGHTS WITH

POLYMER CONCENTRATION SYNTHETIC SEA WATER, POLY
MER R9, BEAKER TESTS.

FIGURE 18. EFFECT OF VARIOUS CONCENTRATIONS OF POLY-

MER R6 ON AMOUNT OF CaCO, PRECIPITATED FROM SEA
WATER.
 An interesting related effect is illustrated
in Figure 18, which shows the results of
increasing polymer additions to natural sea
water treated with excess sodium carbonate
in order to give a precipitate of calcium
carbonate but with no concentration by
evaporation. The amount of precipitate col
lected at the bottom of the centrifuge tubes
is seen to decrease steadily with increased
polymer concentration and the amount of
material still dispersed is obviously greater
for the 5 and 9 ppm polymer concentrations.
EFFECT OF TEMPERATURE OF EVAPORATION
—SPRAY EVAPORATION
Several tests were made using increased
pressure inside the evaporator tube, corres
ponding to an evaporation temperature of
about 270°F compared to 240°F at "stand
ard" conditions. Overall temperature differ
OBSERVATIONS ON THE NATURE OF THE DEPOSITS
Scale deposits were examined by cutting
the heat transfer tube in half along its
length at the end of a run. It was important
not to allow the deposits to dry out before
cutting the tube since they dried very rapid
ly in air and could be lost during the
cutting operation.
DEPOSITS FORMED UNDER "STANDARD"
EVAPORATION CONDITIONS
The appearance and extent of adherence
of deposits were observed to change mark
edly with polymer concentration. In "stand
ard" spray evaporation tests at a tempera
ture of 240°F, the use of the optimum
polymer concentration resulted in complete
coverage of the heat transfer surface with a
thin film of a deposit which was transpar
ent when wet. On immediate examination,
therefore, the inside surface of the tube
appeared perfectly clean, but after a few
seconds exposure to the air, the film became
blue colored and began to strip from the
copper surface to form curled "whiskers"
of a self-stripping plastic film. The drying
and stripping action was often quite violent
and resulted in parts of the dried film being
thrown from the surface. Figure 19 shows
a series of photographs taken at given time
intervals after commencement of the first
signs of stripping.
At polymer concentrations lower than the
optimum, the self-stripping film was con
fined to the lower parts of the tube, merg
ing into an increasingly adherent film of
crystalline appearance in the upper parts of
the tube. At polymer concentrations higher
than the optimum, an adherent deposit
ence was maintained at about 40°F by in
creasing the jacket steam pressure from 40
to about 65 psig. Operating difficulties were
encountered using these conditions and scal
ing behavior lacked reproducibility even on
untreated sea water. The scales from un
treated sea water were coarse crystalline
deposits, in contrast to the gelatinous de
posits typical for standard conditions.
Tests with polymer additions gave vari
able results with the Improvement Ratio
fluctuating between small negative and
small positive values throughout the range
of polymer concentration. Although the
scale deposits were considerably modified
by the higher polymer concentrations there
was no evidence of significant improvement
at any polymer concentration up to 10 ppm
or of an optimum concentration.
formed at the lower end of the tube, with
the self-stripping film being observed only
at the upper ends of the tube. At the higher
polymer concentrations—above about 5 ppm
of R9—the self-stripping plastic film was
not observed anywhere in the tube. In gen
eral, deposits were colored light blue, indi
cating the probable presence of copper
polyacrylate.
The change of appearance of the deposit
with polymer concentration was character
istic and could be used as a satisfactory
qualitative guide as to whether polymer
concentration was above or below the opti
mum for scale prevention. Quantitative
analysis was made of the deposits which
were approximately midway along the heat
ed section of the tubes used in the variable
polymer concentration series on sea water
batch 103 reported in Figure 13. The values
for percentage total organic material and
percentage MgO obtained from these analy
ses are plotted against polymer concentra
tion in Figure 20. Stoichiometric magnesium
polyacrylate would be analyzed as 22 per
cent MgO, 78 per cent organic material
(ratio 1 MgO to 3.5 polyacrylic acid) . Fig
ure 20 shows that, even at a polymer con
centration of 10 ppm, there is insufficient
organic material for the scale to be stoichio
metric magnesium polyacrylate.
DEPOSITS FORMED DURING CLIMBING FILM
AND HIGH TEMPERATURE RUNS
Observations for these runs are based on
the examination of relatively few tubes com
pared with those from runs at "standard"
conditions. The self-stripping film was not
 observed in any part of the tubes used for
the climbing film tests, although the effect
of polymer addition on the appearance of
the deposits formed was quite marked. In
general, at the higher polymer concentra
tions, a continuous, green colored film of
glazed appearance covered all the heated
section: at concentrations near the optimum,
a similar type of scale was formed, but it
was patchy and considerably thinner than
at higher concentrations.
START
FIGURE 19. "PLASTIC" SCALE STRIPPING FROM
HEAT TRANSFER SURFACE.
48
The deposits formed during the high
temperature evaporation tests did not con
form to any general pattern although lhe\
were invariably heavier than those formed
at "standard" evaporation conditions. There
appeared to be much less alteration in ap
pearance due to the action of the added
polymer, even at a polymer concentration
of 2 ppm, although there was occasional
evidence of the formation of the self-strip
ping type of plastic film.
40 SECS
 60г
4Z В 8 Ю t2
Po/ymer cor/centrot/osi - pp m
FIGURE 20. VARIATION IN SCALE ANALYSIS WITH POLYMER
CONCENTRATION SEA WATER BATCH 103, POLYMER R9,
"STANDARD" CONDITIONS.
DISCUSSION
Both polyacrylic acid and a 10 per cent
ethyl acrylate/acrylic acid copolymer hav
ing molecular weights of approximately
20,000 have been shown to be effective as
scale-prevention additives in sea water dis
tillation. Л polymer concentration of about
2 ppm of the weight of sea water feed gave
optimum results under standard test condi
tions, corresponding to a maximum Im
provement Ratio of 70 to 80 per cent in
spray evaporation tests and of 40 to 50 per
cent in climbing 61m evaporation tests. The
use of polymer concentrations lower or
higher than the optimum gives lower values
of Improvement Ratio. Varations -in the
value of the optimum polymer concentra
tion for different batches of sea water may
be due to variations in the content of sus
pended solids and of surface active materials
in the sea water as collected. At polymer
concentrations considerably higher than the
optimum, scale deposits can be formed
Orçan/c moíer/о/
which may have a more deleterious effect
on heat transfer rate than those formed
from untreated sea water.
An earlier tentative explanation (réf. 1)
of the scale prevention mechanism postu
lated the formation of a brittle magnesium
polyacrylate film at the heat transfer sur
face. Thermal stresses set up in the film
caused it to strip from the surface, on which
a new film was formed which, in turn,
subsequently stripped. In the present work,
the film remaining on the tube surface at
the end of a run was found to be largely
magnesium polyacrylate and it is considered
that such a "regenerating film" mechanism
has important potential in scale prevention -
However, there is clear evidence of a de
pendence on polymer concentration of both
Improvement Ratio and the nature of the
deposits formed. Laboratory beaker tests
indicated that there was also a dependence
on polymer concentration of the total
weight of precipitate formed during the
evaporation of sea water and that there
was some agreement between the polymer
concentration required to give minimum
precipitate weights in beaker tests and that
required to give maximum Improvement
Ratio in spray evaporation tests.
It is common practice to use surface
active materials in the treatment of super
saturated aqueous solutions to modify or
inhibit scale deposition (refs. 4-6). Polyac-
rylic acid and polyacrylamide additives have
recently become available commercially for
such applications and at least one of these
is believed to have proved effective in pre
venting adherent scale in a sea water dis
tillation plant (ref. 7) .
Such systems are undoubtedly extremely
complex as the surface active materials may
modify the nucleation and growth stages of
precipitate formation, as well as affect the
final state of dispersion of particles in the
liquid phase. The few fundamental investi
gations reported have generally been limited
to studies of specific agents in simple solu
tions (refs. 8,9) . Modifications of settling
and filtration characteristics of slimes by
the flocculation/deflocculation action of
polyelectrolytes are of great importance in
metallurgical milling operations, and con
sequently considerably more work has been
done on the simpler systems of suspended
solids in water used in the mineral indus
try. In recent work (refs. 10,11) such vari
ables as polymer concentration, molecular
weight, and pH of the liquid environment
have been examined and physicochemical
mechanisms suggested for the observed
action of the polyelectrolytes on the sus
pended solids.
There is strong evidence from the beaker
tests that the polymers used in the present
work act as dispersing or, more correctly,
(ref. 12) deflocculating agents. Concepts
similar to those proposed to explain the
flocculation/deflocculation action of poly
electrolytes on mineral slimes may be rele
vant to scale prevention. At polymer con
centrations below optimum, it may be
assumed that polymer molecules are ad
sorbed at the scale particle surface with a
high proportion of the carboxyl groups
attached. Higher polymer concentrations, up
lo the optimum, lead to more complete
surface coverage, with increasing mutual
repulsion between particles. Above the op
timum polymer concentration, there would
be an increasing probability of adsorption
of molecules with fewer carboxyl group
attachments per molecule. ■ The large un
attached portions could then participate in
"bridging" interactions, leading to adher
ence and particle growth.
Scale prevention during spray evaporation
tests at "standard" conditions may, there
fore, involve two different mechanisms: first,
the deflocculating action of the polymer
which, in the region of optimum polymer
concentration, is able to prevent the growth
and adherence of most of the precipitate;
and second, the "regenerating film" action
which removes the small amount of precipi
tate which is deposited on the heat transfer
surface. The latter mechanism appears to
provide scale protection only when the
quantity of precipitate has been substanti
ally diminished by deflocculation.
With this assumed mechanism, it might
be expected that the use of a higher molecu
lar weight polymer would result in a lower
effectiveness of scale prevention, since the
larger molecules are likely to be adsorbed
with a lower proportion of surface-attached
carboxyl groups and a high probability of
the occurrence of "bridging" interactions.
Preliminary experiments indicate that high
molecular weight polymers are of little use
for scale prevention.
There are many implications of the pro
posed scale-prevention mechanism which still
need to be tested—for example, there is no
indication of a minimum precipitate weight
when CaCO, is precipitating (Fig. 17) . In
order to facilitate further testing, a small
spray evaporation test apparatus has been
developed which uses only one-twentieth of
the material flow rates of the spray evapora
tor used in the present work. It will there
fore be practicable to use synthetic feed
waters as well as sea water so that, for ex
ample, the effect of polymer addition on
CaSO, and CaCO, precipitation can be
studied.
The variation of Improvement Ratio with
polymer concentration for climbing film
evaporation (Fig. 15) can be explained by
the deflocculating action of the polymer.
It appears from experimental observations
that the self-stripping film is not formed
under the climbing film test conditions.
Spray evaporation results for higher evap
oration temperatures indicate that the poly
mers used were ineffective in scale preven
tion at temperatures above about 260"F.
Changes in the composition of the solid
phase deposited and an increase in the
amount deposited at higher temperatures
may account for the poor results, although
modifications of the polymer configuration
may also be responsible.
 CONCLUSIONS
1. Small concentrations of low molecular
weight polyacrylic acid or 10 per cent ethyl
acrylate/acrylic acid copolymer have been
found to be effective in preventing scale
deposition during sea water evaporation.
Significant improvements in heat transferred
over a standard period were noted during
tests carried out in experimental climbing
film and "spray" evaporators, evaporating
sea water at 240°F.
2. The extent of scale prevention in the
experimental evaporators was found to be
dependent on polymer concentration. An
optimum polymer concentration of about
2 ppm was observed to be most effective.
Lower and higher polymer concentrations
were less effective and, at concentrations
considerably higher than optimum, scale
deposits in the climbing film tests proved
to be more deleterious to heat transfer than
those from untreated sea water.
3. Laboratory beaker distillation tests
showed that polymers acted as deflocculating
or dispersing agents and that the extent of
deflocculating action was dependent on poly
ACKNOWLEDGEMENTS
The authors wish to thank Dr. H. R. C.
Pratt and Mr. D. F. Kelsall for continued
support during this work. The assistance of
Dr. D. H. Solomon and Professor A. E. Alex
REFERENCES
1. Herbert, L. S.: Sterns, U. J.: Saline
Water Conversion II, A.C.S. Series No.
38 (1963) p. 52.
2. Yphantis, D. A.: Annals New York
Academy of Sciences, no. 88 (1960) p.
586.
3. Harvey, H. W.: "The chemistry and
fertility of sea waters," Cambridge Uni
versity Press (1957) p. 137.
4. Zeleny, R. A.; Vithani, K.: "Combus
tion" (Feb. 1963) p. 47.
5. Badger and Associates Inc.: Ann Arbor.
Michigan, "Critical review of literature
on formation and prevention of scale,"
Office of Saline Water, Rep. no. 25
(July 1959).
6. Ireland, G. H.: "Corrosion prevention
and control" (Oct. 1958) p. 57.
7. Derrick, A.: Imperial Chemical Indus
mer concentration. For the same batch of
sea water, there was fair agreement between
polymer concentration required to produce
maximum deflocculation and the optimum
polymer concentration corresponding to
maximum scale prevention.
4. An explanation for the observed scale
prevention postulates the simultaneous op
eration of two physical mechanisms. First,
at or near the optimum polymer concen
tration, the adherence and growth of scale
particles is suppressed due to adsorption of
polymer molecules at their surface, thereby
substantially reducing the amount of scale
deposited. Second, the small amount of
scale deposited has a high content of mag
nesium polyacrylate and, under conditions
of evaporation in the spray evaporator,
this scale is capable of self-stripping from
the surface by the "regenerating film"
mechanism.
5. The beneficial effect of the polymers
studied to date has been so marked that
the phenomenon justifies further and more
detailed investigations.
ander in helpful discussions on polymer
chemistry and of Dr. B. Harrop and Dr.
P. Plackett in molecular weight measure
ment is gratefully acknowledged.
tries (A.N.Z.), Ltd., Melbourne, Private
communication.
8. McCartney, E. R.; Alexander, A. E.:
/. Colloid Sci., no. li (Aug. 1958) p. 383.
9. Blackadder, D. A.: Industrial Research
Fellow Rep. no. 3, The Chemical Engi
neer, Institution of Chemical Engineers,
CE303 (Dec. 1964) .
10. Linke, W. F.; Booth, R. B.: Tram.
A.I.M.E., no. 217 (1960) p. 364.
11. La Mer. V. K.; Healy, T. W.: Rev. Pure
and Appl. Chem., no. 13 (Sept. 1963)
p. 112.
12. Moiliet, J. L.; Collie, B.; Black, W.:
Surface Activity, Spon Press. (1961)
p. 160.
13. Jirgensons, B.; Straumanis, M. E.: A
Short Textbook of Colloid Chemistry,
Pergamon Press, Ltd. (1962).
51
 APPENDIX 1A
THE METHOD OF PREPARATION OF
LOW MOLECULAR WEIGHT
POLYACRYLIC ACID
Isopropanol (200 gm) was placed in a
one liter flask equipped with stirrer, ther
mometer, reflux condenser, and addition
funnel. The stirred isopropanol was heated
to reflux. Then a solution of benzoyl perox
ide (6 gm) in acrylic acid (300 gm) was
added dropwise during hours. After
approximately one-half hour the reaction
became exothermic, the heat was removed.
and a cold water bath was applied. The
temperature in the flask was controlled
close to 87°C. After monomer addition was
complete, the reaction moderated and steam
heating was used again. The stirrer was
stopped and the mixture left heating over
night on the steam bath. A water-white very
viscous solution of approximately 60 per
cent solids was obtained.
Some batches of polymer were made using
variations in the weights detailed above, in
an attempt to produce polymers having a
range of molecular weights.

APPENDIX IB
THE METHOD OF PREPARATION OF
A LOW MOLECULAR WEIGHT
10 PER CENT ETHYL ACRYLATE—
90 PER CENT ACRYLIC ACID COPOLYMER
The method was similar to that given in
Appendix 1A, except that azo di-iso butyro
nitrite initiator was used in preference to
benzoyl peroxide to insure the production
of essentially linear polymers.
Isopropanol (200 gm) was placed in a
one liter flask equipped with stirrer, ther
mometer, reflux condenser, and addition
funnel. The stirred isopropanol was healed
to reflux. Then a solution of azo di-iso
butyro nitrile (7.8 gm) in acrylic acid
(270 gm) and ethyl acrylate (30 gm) was
added dropwise during \\/2 hours.

APPENDIX 2
EQUILIBRIUM ULTRACENTRIFUGATION
METHOD FOR
MOLECULAR WEIGHT DETERMINATION
Determinations were made in the Spinco
Model E Ultracentrifuge (réf. 13) at speeds
of about 25,000 rpm. Initial determinations
made at 20°C. using isopropanol as solvent
in conventional long (12 mm) columns, re
quired sedimentation times of about 20
hours. There was no evidence of a depend
ence of results on polymer concentration
in the range 0.5 to 1.5 per cent.
To reduce the time required for deter
minations, the rapid short (1 mm) column
method of Yphantis (ref. 2) was adopted.
Sedimentation times were reduced to about
3 hours at speeds of about 20,000 rpm, using
isopropanol as solvent at a temperature of
20°C.

SUMMARY OF DISCUSSION
There was no discussion.

52
Distillation Des
Protection Contre
L'Addition de Polymères
L. S. Herbert, P. F. Rolfe et U. J. Stems
Australie
Toute nouvelle amélioration du rende
ment des usines de distillation d'eau saline
doit attendre la mise au point de procédés
efficaces et peu coûteux permettant d'em
pêcher la formation de tartre sur les sur
faces d'échange de chaleur, particulièrement
lorsqu'il s'agit de saumures d'une tempé
rature et d'une concentration plus élevées
que celles employées actuellement. Lei
travaux antérieurs ont indiqué que l'acide
polyacrylique, d'un poids moléculaire d'en
viron 20.000, ajouté à l'eau de mer alimen
tant un évaporateur expérimental à pulvé
risation, à une concentration de 3 ppm,
prévient très efficacement la formation de
tartre pendant l'évaporation à 115°C.
Le présent document porte sur de nou
velles études de ce phénomène. Plusieurs
lots d'acides polyacryliques de faible poids
moléculaire et un lot d'un copolymère,
composé de 10% d'acrylate d'éthyle et de
90% d'acide acrylique, ont été préparés et
mis à l'essai comme additifs contre l'entar
trage. Le copolymère a été choisi pour les
études plus poussées au moyen d'essais d'é-
vaporation par pulvérisation et par la
méthode à longs tubes verticaux à écoule
ment laminaire ascendant.
Les auteurs ont constaté que la protec
tion la plus efficace contre l'entartrage se
manifestait à une concentration optimale
de polymère se situant entre 1 et 4 ppm
pour différents lots d'eau de mer. Les con
centrations plus faibles ou plus fortes
étaient moins efficaces et, aux concentra
tions beaucoup plus élevées que la concen
tration optimale, on a constaté que les
dépôts de tartre formés dans les essais
d'évaporation à écoulement laminaire as
cendant s'opposaient plus fortement aux
échanges de chaleur que ceux de l'eau de
mer non traitée. On a constaté que les
caractéristiques physiques et la composition
chimique des dépôts formés sur les surfaces
d'échange de chaleur, examinées en fendant
Eaux Salines —
L'Entartrage Par
les tubes en fin de marche, variaient selon
la concentration de polymère employée
dans l'essai. A la concentration optimale
de polymère, on a observé notamment qu'il
ne se formait qu'une mince pellicule de
matière "plastique" qui, par séchage au
contact de l'air, se détachait rapidement de
la surface d'échange de chaleur. L'analyse
a indiqué que cette pellicule était princi
palement composée de polyacrylate de
magnésium.
Au cours de recherches parallèles en la
boratoire, des essais d'évaporation en vase
ont été mis au point et les résultats ont
indiqué qu'une certaine concentration de
polymère, s'établissant entre 1 et 4 ppm
selon les différentes eaux de mer, produi
saient une diminution marquée du préci
pité formé au cours de l'évaporation. Avec
le même lot d'eau de mer, on a constaté
qu'il existait une certaine correspondance
entre la concentration de polymère donnant
la précipitation la plus faible dans les
essais en vase et la concentration optimale
de polymère donnant la meilleure protec
tion contre l'entartrage dans les essais
d'évaporation par pulvérisation.
Pour tenter d'expliquer le mécanisme de
protection des polymères contre l'entartrage,
les auteurs offrent des théories analogues à
celles qui ont été avancées pour expliquer
l'effet de floculation et de défloculation des
polyélectrolytes sur les boues minérales.
Deux mécanismes simultanés sont énoncés.
A la concentration optimale de polymère,
l'effet de dispersion ou de défloculation du
polymère empêche le dépôt d'une partie
importante des éléments d'entartrage; l'accu
mulation de la partie restante est prévenue
par la formation, à la surface d'échange
de chaleur, d'une mince pellicule, composée
principalement de polyacrylate de magné
sium, qui est capable de se dépouiller et
de se reconstituer spontanément et à
maintes reprises au cours de l'évaporation.
 Дистилляция Соленой Воды —
Предотвращение Образования Накипи
Посредством Добавки Полимеров
Л. С Герберт, П. Ф. Ролфе и Ю. Дж. Стерне
Австралия
Для дальнейшего повышения произ
водительности установок, опресняю
щих соленую воду, требуется развитие
дешевых и эффективных методов для
предотвращения образования накипи
на теплопередаточных поверхностях,
особенно при высоких температурах
соленого концентрата и при более вы
соких коэффициентах концентрации,
чем те, которые применяются в насто
ящее время. Прежние исследования по
казали, что добавление полиакриловой
кислоты с молекулярным весом около
20.000 (при концентрации 3 мг/л.) к
морской исходной воде, было весьма
эффективным в смысле предотвращения
образования накипи на эксперименталь
ном испарителе с распылением при
температуре выпаривания 240°F.
Настоящий доклад связан с дальней
шим исследованием этого явления. Бы
ло произведено несколько загрузок по
лиакриловой кислоты с низким молеку
лярным весом и одна загрузка сополи
мера 10% этилакрилата — 90% акри
ловой кислоты, которые испытывались,
как добавка для предотвращения обра
зования накипи. Сополимер был выбран
для более широкого обследования вы
парки «с разбрызгиванием) и испыта
ния испарения с ползучей пленкой.
Максимальная эффективность в смы
сле предотвращения образования на
кипи имела место при оптимальной по
лимерной концентрации, которая ко
лебалась в пределах от 1 до 4 мг/л
для отдельных загрузок морской воды.
Более низкие и более высокие концен
трации оказались менее эффективны
ми, а при концентрациях значительно
превышавших оптимальные, отложение
накипи при испытаниях на выпарку с
ползучей пленкой оказалось более
вредным для теплопередачи, чем от
необработанной морской воды. Физи
ческие характеристики и химический
состав отложений, образовавшихся на
теплообменных поверхностях, которые
по окончании опыта были обследованы
с помощью разрезания трубы, оказа
лись неоднородными и зависящими от
концентрации полимера, примененного
во время испытания. Следует отметить,
что при оптимальной концентрации по
лимера была обнаружена только тон
кая пленка из «пластичного» материала,
которая по высыхании на воздухе бы
стро отделялась от теплопередаточной
поверхности. Анализ показал, что она
главным образом состояла из поли-
акрилата магния.
При параллельных исследованиях в
лабораторном масштабе был проведен
ряд выпарочных испытаний в химиче
ской посуде, результаты которых по
казали, что имеется концентрация по
лимера, колеблющаяся в пределах от
1 до 4 мг/л для различной морской
воды, которая явно уменьшает коли
чество осадка, образуемого во время
процесса испарения. При одинаковом
составе морской воды было обнаруже
но известное соответствие между кон
центрацией полимера, дающей мини
мальный осадок при испытаниях в хи
мической посуде, и оптимальной кон
центрацией полимера, максимально пре
дотвращающей образование накипи при
испытании выпарки «с разбрызгива
нием».
В настоящем докладе, пытающемся
объяснить противодействие полимеров
образованию накипи, были использова
ны идеи подобные тем, которые были
предложены для объяснения флокку
лирования — дефлоккулирования, про
изводимых полиэлектролитами на ми
неральный шламм. Считается, что од
новременно существуют два механиз
ма. Благодаря диспергирующему или
дефлоккулирующему действию полиме
ра при его оптимальной концентрации
предотвращается отложение значитель
ного количества составных частей на
кипи. С другой стороны, предотвраще
ние накопления остальной накипи до
Destilación del
Evitación de la
Incrustaciones Mediante
de Polimeros
L. S. Herbert, P. F. Rolfe у U. J. Sterns
Australia
La ulterior mejora del rendimiento de las
plantas de destilación de agua salina depen
derá del establecimiento de métodos econó
micos y eficaces para evitar la formación
de incrustaciones en las superficies transmi
soras de calor, especialmente cuando las
temperaturas de la salmuera son más ele
vadas y los factores de concentración mayo
res que los utilizados en la actualidad. En
investigaciones anteriores se había demos
trado que el ácido poliacrflico de peso
molecular aproximado a 20.000, añadido en
concentración de 3 ppm al agua de mar
con que se alimentaba un evaporador expe
rimental por rociamiento, resultaba muy
eficaz para evitar la formación de incrusta
ciones durante la evaporación a 240°F.
El presente trabajo trata de las investiga
ciones ulteriores relativas a este fenómeno.
Varias partidas de ácidos poüacrflicos de
peso molecular bajo y una partida de un
determinado copollmero, compuesto de 10%
de acrilato de etilo y 90% de ácido acrilico,
fueron preparadas y sometidas a prueba
como substancias aditivas evitadores de in
crustaciones. El copolfmetro fue seleccio
nado para una investigación más extensa en
las pruebas de evaporación por "rociamien
to" y por capa ascendente (LTV) .
La máxima eficacia en la evitación de
incrustaciones se produjo a una concentra
ción óptima de polímero, la cual varió de 1
a 4 ppm para las distintas partidas de
agua de mar. Las concentraciones inferiores
y superiores resultaron menos eficaces y, a
стигается образованием на теплообмен-
ной поверхности тонкой пленки, пре
имущественно состоящей из полиакри-
лата магния, которая сама собой пери
одически отваливается и регенерирует
во время процесса выпариавния.
Agua Salina —
Formación de
la Adición
concentraciones considerablemente mayores
que la óptima, las incrustaciones deposita
das en las pruebas de evaporación por capa
ascendente resultaron ser más perjudiciales
con respecto a la transmisión térmica que
las procedentes de agua de mar no sometida
a tratamiento. Las características físicas y
composición química de los sedimentos for
mados en las superficies de transmisión
térmica, examinados después de abrir el
tubo al final del curso de cada prueba,
resultó que variaban según la concentración
de polímero utilizada en la prueba. En
particular, a concentraciones óptimas de
polímero, se observó tan sólo una película
delgada de una materia "plástica" que, al
secarse al aire, se desprendía rápidamente
de la superficie de transmisión térmica. El
oportuno análisis indicó que se trataba prin
cipalmente de poliacrilato de magnesio.
En una investigación de laboratorio simi
lar a la anterior, se llevaron a cabo pruebas
de evaporación en vaso de precipitados y
los resultados indicaron la existencia de una
determinada concentración de polímeros,
que variaba de 1 a 4 ppm según las dis
tintas aguas de mar, lo cual producía una
notable reducción en la cantidad de preci
pitado formado durante la evaporación. Con
respecto a la misma partida de agua marina
se observó cierta armonía entre la concen
tración de polímero que produda un míni
mo de precipitado en las pruebas efectuadas
en vaso de precipitados y la concentración
óptima de polímero con la que se obtenía
 el grado máximo de evitación de incrusta
ciones en las pruebas de vaporación por
rociamiento.
En el trabajo que nos ocupa, se aplican
conceptos similares a los expuestos para
explicar la actividad de floculación-desflocu-
lación de los polielectrólitos en los fangos
de origen mineral, en una aclaración tenta
tiva de la eficacia de los polímeros para
evitar la formación de incrustaciones. Se da
por supuesta la existencia de dos meca
nismos simultáneos. Con la concentración
56
óptima de polímero se evita la sedimenta
ción de una parte importante de los ele
mentos constituyentes de las incrustaciones
mediante la acción dispersante o desflocu
lante del polímero, y se impide la acumula
ción del resto por medio de la formación,
en la superficie de transmisión térmica, de
una capa delgada constituida principal
mente por poliacrilato de magnesio, la cual
es capaz de desprenderse y reaparecer, es
pontánea y repetidamente, en el curso de
la evaporación.
 Heat and Mass Transfer in Flash
Distillation Without Metallic
Interfaces
Abraham Kogan
Israel
Methods of sea water desalination based
on distillation are today practically the
only ones that have reached an industrial
production scale application. On the basis
of the considerable amount of theoretical
and experimental work that went into the
development of these desalination systems,
it is possible to estimate with fair accuracy
the minimum cost of water which they can
achieve.
Such estimates (ref. 1) have shown that
for optimized plants of one mgd capacity,
the energy cost of desalination is still larger
by an order of magnitude than the theoret
ical minimum energy necessary for the
removal of salts from solution. These large
thermodynamic losses are explained by the
need to maintain considerable temperature
differences across metal heat exchanger
surfaces which would otherwise become
exceedingly large.
A distillation process which avoids the
use of metallic interfaces (ref. 2) for heat
transfer holds promise for a real break
through in desalination technology. In such
a process a stream of heated sea water is
cascaded through a series of flash stages
RATE OF PRODUCTION
Figure 21 is a schematic representation
of temperature distribution in the distilla
tion system.
GB1 and GCi represent the rates of saline
water and converted water, respectively,
leaving stage i and Xi —the rate of transfer
of vapor from saline water stream to con
verted water stream in this stage.
It is obviously impractical to allow
and the amounts of vapor flashed off in
each stage are condensed by direct contact
with the surface of a converted water
stream. This stream flows through the
stages in a countercurrent direction and
emerges from the hottest stage at an in
creased rate of flow and temperature. It is
passed through a liquid-liquid-liquid heat
exchanger, where it surrenders heat to the
makeup sea water stream. A product stream
is diverted from the plant and the remain
ing stream of cold converted water is
recirculated through the flashing stages.
The performance of the multiple-flash
evaporator can be evaluated by setting up
material and heat balance equations for
each stage and solving them successively
with the aid of an automatic computer.
An alternative analytic solution would be
more advantageous for design and optimi
zation studies, since it would exhibit explic
itly the influence of the various parameters
upon performance of the system. It is the
purpose of this paper to develop such an
analytic approach to calculation of the
performance of a multiple-flash evaporator
without metallic interfaces.
widely different values for the two water
stream rates passing through the stage,
since a great difference in heat capacity
rate of the two streams would be incom
patible with small terminal temperature
differences at both ends of the cascade. It
is, therefore, reasonable to consider the
case in which the rate of sea water entering
the hottest stage is equal to the rate of
 converted water leaving it: in conjunction with Equation (1) , we
G.W = Ge. (1) obtain:
Using recursively the material balance G„U1 = GCl = G„ (i = 1,2.3 ...,..) (3)
equation for stage i An energy balance between rate of en
"i 1 GHui — CiH, = GC| thalpy loss by saline water stream passing
-С (2) through stage i and rate of enthalpy

z
о
"H
H
S3
03
5
h

M
S
■H

58
 investment into production of stream gives Observe that since (Ih,.! — tH|) is of the
(Get) Blrt - (Get) h, = X, (hUV4 + ctBl) order of 1°F. ai is of the order of 0.001.
(4) Terms of second order in ai may, there
where fore, be neglected for engineering purposes.
, = i/2 (h, + hul) (5) Equation (10) gives, to a second order of
is a mean value of latent heat of saline approximation,
water in the system at temperature tH) and
G. i=i i=i hUii (П)
We shall define a relative production rate Approximating the variation of heat of
a, as the ratio of the rate of converted vaporization with temperature over the tem
water production in stage i to the rate of perature range of interest by a straight line.
converted water outflow from stage i. As h=a(l— bt) (12)
suming a constant value с for specific heat we can write
and writing
GHl = GH|<1 — X, (6) ¿-=| {l + b(.„m -.„,)}
in Equation (4) , we obtain neglecting terms of order (bt) '.
X, _c(tH|,1_ t,„) Equation (11) becomes:
<7) X с , - tHl)V + —
G, be (t',.tI - fHl)
g-= -(tHn.I
Equation (7) for the n stages of the cas
cade forms a linear system in X,. Indeed, = К (t^,. tHl) (IS)
substituting Thus the total production rate of the
G i =; G„ — 2 XK cascade is, to a high degree of approxima
we obtain tion, independent of the detailed tempera
ture distribution in the intermediary stages.
2 XK-a,G„,(i = 12.3, . -n) It is determined by the terminal tempera
(8) tures of the saline water stream only.
with the solution Figure 2 represents the variation of heat
X| — G„ ai nil - aK) (9) of vaporization h with temperature. Substi
tuting in Equation (12)
The total production rate X is obtained a = 1090 Btu/lb, b = 0.54Я . 10"* ("F) -1
by summation: the values of h differ from the linear ap
proximation by less than 0.3 per cent in the
X
Л Ы
2 ] (10) range
П (1 - ok)
G. G„ 32°F < t < 280°F

EXACT CURVE

60 IM 200
100 260 300
t CF)
FIGURE 22. VARIATION OF HEAT OF VAPORIZATION WITH
TEMPERATURE.

59
 Based on these values of a and b, the
variation of relative production X/G„ has
been calculated and plotted in Figure 23
as a function of hot sea water inlet tempera
ture tH„.,, with brine outlet temperature
150
FIGURE 23. VARIATION OF RELATIVE PRODUCTION WITH
BRINE INLET TEMPERATURE.
Heat consumption
The rate of heat input necessary to com
pensate for the thermodynamic irreversibili
ties of the cascade is given by
H = G.c(tHM-tO (14)
It should be emphasized that Equation
(14) does not represent the entire heat con
sumption of the process. Heat recovery from
converted water leaving the hottest stage to
sea water entering it must be accomplished
by some kind of heat exchanger. Part of the
total heat consumption is due to the irre
versibilities in the heat exchanger. But we
shall limit ourselves in this discussion to the
t„, as a parameter. The relative production
is roughly proportional to the difference
between inlet and outlet temperatures of
saline water stream.
200 250 300
Wl <°F)
analysis of heat consumption in the cascade
proper.
Define a stage heat transfer efficiency 1,:
I tc' — ten
' _ tHl - ten <15>
In a completely inefficient cascade there
would be no temperature rise in the con
verted water stream, i.e.. I , = 0. Conversely,
in an ideally efficient cascade the converted
water would leave the stage at the tempera
ture of saline water in the stage, tc, =tH,,
i.e., I, — 1. This ideal condition can, of
course, only be approached in a very large
and completely deaerated stage, carrying
 two water streams of equal salt concentra ditions and stage efficiencies, the relative
tion. The actual value of 1, is determined production rates n in Equation (22) must
by stage geometry, by flow characteristics of be evaluated in terms of I , , (i — 1 2fi, . . . , n) .
the two water streams and, to a great ex The relationships between aK and I, are
tent, by the degree of water deaeration. An defined implicitly by the nonlinear system
upper limit to 1 1, is set by the boiling of Equations (15), (16), and (17). Neg
point elevation of brine. For given geom lecting second order terms, it is possible to
etry, flow pattern, deaeration conditions, eliminate the temperatures from these equa
and salt concentration, it may be consid tions. Indeed, by Equations (15) and (16) ,
ered as a constant parameter that may be tHU1 — tH, = (tH,„ — tCl) +
determined by experiment.
(tc, - tc,.,) - (t„, - tc, J =
A second relationship between tempera (I, - a,) (t„, - tc,_,)
tures in stage i is given by an energy balance
between the two water streams: Hence, by Equations (7) and (16) ,
Gbu, tH,., — GH, tH, = Gc, tc, — GCl., tc,_, a, + i = -rh, + ^ • I, +; i — a, ♦ i • 0 — a,).
or, making use of Equations (3) , (6) , and at n, t щ i, — a,
(7). (23)
lHlrt - tCl = (1 - c) (tHl - t0l.,) (16) Again, neglecting second order terms,
Then, by recursion, £LLi = ÍLti.(l_ei) (24)
ai t.
'■«i — tc. = (t*,- te*)' П (1-a,)
(17) Equation (24) gives bj multiplication
Similarly, by Equations (15) and (16) П (1 - o») = a,/m„ (i = 23 n)
lc, - tcu, = (Ih, + tc.) • I, • П (1 - o«) (25)
(18) or, to a second approximation,
and, hence i-i
1 — 2aK : : a,/m,,(i = 2,S n)
tc. - tCo = 2 (tc, - tCUl) = K=l (26)
with
(tHl-tc„) -2 1|П (1 -аж)
1=1 *=* (19) m,= * I,
Ii
Inserting the Equations (17) and (19) This is a linear system of (n — 1) equa
into the relationship tions defining ai, a» • • • , a. in terms of a,
'я»»! — tH, — (tH„„ — tc„) -+- and the stage efficiencies I„ I I„. Its
(tc„ - tc) - (tHl - tc.) solution is given by
and eliminating (t„, — tc.) between the re i-i
o, = (1 — ai) m, П (I — Oi) ■
sulting equation and Equation (17) , we
obtain by Equation (14) (1 = 2А.".1.п) (27)
П (1 _«,,)• О (t„„ The value of «, can now be determined
H tBl) by substituting Equation (27) into the total
production expression, Equations (11) and
2 1, П (1 _aK) -I- II (1 _ai) _ 1 (13) . We obtain
1=1 K=l 1=1
(20) К = 2 a,
Also 1:1 n 1-1
X _ X/G. = oi + (1 — ai) 2 m, П (1 — m»)
H — H/G„ 1 = 3 к=з
(1 - a,)} {2 I, П (1 _aK) = ai+ (l-o.) {l-П (1-m,)
1=1 Izl K=l i=а
+ i=_i
П (1-a,) -1} =i-)rî (i
1=1 h
П (1 -a,) -C • <t„„,t — tBl) (21) = ^-21,
•i , = i +0 (a,")
1= i
or, neglecting second order terms in aK and Thus, to the second order of approxima
in bt, tion.
—={2 I. П (l_a,)-K}. 2 I,
Ii. i=i
H , .1 к l
К 1 Ol К (28)
1_ K -C(tHo>1-tHl) í22) To complete the calculation of steam
In order to obtain the cascade steam economy, we don't have to substitute ex
economy in terms of end temperature con plicitly for all values of aK in Equation
 (22) . Making use of Equation (25) , we tion in the cascade by
obtain
(32)
2» I. П (1 - oK) = —I, 2» «■ = К • -i-
I,
i^i K=i at isi a, Equation (31) may then be put into the
(29) form of a steam economy expression:
hX 2 I, - К
and Equation (22) takes on the simple form i= i
_x_/_L__i) _í! i H 1-K <">
The dependence of steam economy on
H a, * 1 - К * С (tB.„ - t„,) saline water temperature drop in the cas
(30) cade and on stage efficiencies is exhibited
separately by this formula. Observing that
The last stage production rate en may
finally be eliminated from Equation (30) by 2n 1 1 is much larger than K, it is seen that
Equation (28) : 1=1
an increase in temperature range, i.e., an
— -ill П K 1 increase in relative production K, also has
a beneficent effect upon steam economy.
(31) For constant terminal temperatures, steam
economy increases linearly with the sum of
Define a mean value for heat of vaporiza all the stage efficiencies.

OPTIMUM NUMBER OF STAGES

The optimum number of stages of a de
salination plant is determined by capital
investment in equipment and specific heat
consumption. The capital investment per
stage will depend much upon the charac
teristics of stage design. It will increase with
stage efficiency. But it seems that there arc
no conclusive results concerning this param
eter at present. It will have to be determined
by experiment.
Interesting conclusions can be drawn,
however, from Equation (33) by assuming
numerical values for the minimum tem
perature difference.
a, = t„, _ tci (34)
is attained in each stage. Expressed in terms
of Si the stage efficiency becomes
I, = 1 *!
Ih, — tcUl
(35)
Using Equations (15) and (16) , the dif-
erence tH, — tci _ , may be put into the
form
tH, — t C|-l —
П (1 - ok) • (Ih«, - tHl)
(36)
2 I, ПО -aK) + П (1 _„,) _ 1
1=1 K=l 1=1
In order to obtain an insight into the
■ 150°F and 200°F, respectively) do not vary
dependence of 2 I| upon the number of
1= 1
stages n, we shall consider the particular
case where
ai = as — ■ . . — an = a (37)
Making this assumption in Equation (36)
and also substituting a mean value I for I,
in that equation and a mean value î for g,
in Equation (35) , we obtain after some
algebraic calculations:
2 1 1 = n —A n2 (38)
i=i
with
A —. . L (39)
1 — К tH„, — tHl
Equation (38) shows that even from the
point of view of heat consumption alone
there is no advantage in increasing the
number of stages indefinitely. The number
of stages which gives maximum steam
economy is expressed by
n.„ = - =' -K . - '"' (40)
2A 21 Í
and the corresponding value of steam
economy is
(41)
4I*
Figure 24 is a diagram of steam economy
as a function of a number of stages, with К
and i/ (t„nil — tH,) as parameters. The
straight lines through the origin connecting
all optimal points for К = 0.15 and К —
0.20 (i.e., approximately for tHluI — tH, =
much in inclination. But the optimal
points corresponding to the same value of J
lie quite far away. The great advantage of
a high temperature drop of saline water
through the cascade and of a small mean
minimum temperature difference S is quite
evident.
 X«leF

FIGURE 24. VARIATION OF STEAM ECONOMY WITH NUMBER

OF STAGES.

REFERENCES
1. Fluor Corp.: U. S. Office of Saline Water landris, G. C.: Chem. Eng. Prog. vol.
Rcpt. no. 34 (1959) . 57 (1961), p. 47.
2. Othmer. D. F.; Benenati, R. F.; Gou

SUMMARY OF DISCUSSION
There was no discussion.

63
Transfert de Masse
Dans la Distillation Spontanée
Interfaces Métalliques
Abraham Kogan
Israel
Les trois méthodes de distillation pour
le dessalement de l'eau de mer qui sont
en utilisation sur une grande échelle—la
distillation à effets multiples à faible ten
sion de vapeur, la distillation spontanée à
étages multiples et la thermocompression—
ont toutes une caractéristique commune:
elles utilisent toutes des échangeurs de
chaleur métalliques pour le transfert de la
chaleur de la vapeur de condensation à
l'eau saline. Dans la conception de ces
installations, une diminution des dimen
sions de l'équipement de transfert de
chaleur a pour résultat une augmentation
dans la différence de température à travers
les parois de l'échangeur de chaleur pour
une capacité donnée de l'installation. Les
conceptions optimums, dans lesquelles on
effectue un compromis entre le coût de la
vapeur et l'amortissement de l'investisse
ment en biens d'équipement, pour arriver
à un coût minimum de l'eau convertie,
ont pour résultat une consommation rela
tivement élevée de chaleur spécifique.
Une méthode alternative de distillation
a été proposée par Othmer dans laquelle
on évite complètement la condensation sur
des surfaces métalliques. Dans cette mé
thode, un courant d'eau saline et un
courant d'eau convertie passent à contre-
courant à travers une série d'étages à vapo
risation spontanée. Dans chaque étage, une
certaine quantité de vapeur est dégagée
spontanément du courant d'eau saline et
condensée par contact direct avec le courant
d'eau convertie qui est un peu plus froid.
La saumure concentrée est déchargée de
l'étage à la plus faible température en
tant que résidu, tandis que le courant
d'eau convertie émergeant de l'étage le plus
chaud abandonne sa chaleur au courant
d'entrée de l'eau de mer dans un échangeur
de chaleur liquide-liquide-liquide. Une
partie de l'eau convertie refroidie est dé
et de Chaleur
Sans
tournée du système en tant que produit
de la distillation, tandis que la plus grande
partie circule à nouveau à travers les étages
de vaporisation spontanée.
Comme la condensation par contact
direct avec l'eau convertie peut se faire
avec des coefficients de transfert beaucoup
plus élevés que ceux obtenus dans la con
densation pelliculaire normale, cette mé
thode semble offrir des possibilités pour
arriver à une réduction importante des
frais de dessalement.
Ce document porte sur le traitement
analytique du système à vaporisation spon
tanée à étages multiples par contact direct.
On peut décrire la performance de trans
fert de chaleur et de masse entre les deux
courants d'eau, d'un seul étage d'un tel
système, par un paramètre d'efficacité
d'étage:
I, = (t., - t,ul)/(tHI - UUJ
donnant l'élévation de température du
courant froid en tant que pourcentage de
la différence maximum de température
dans cet étage. I, dépend de la géométrie
de l'étage, des caractéristiques de débit, de
la concentration en sel et du degré de
désaération de l'eau. On peut le déterminer
de façon empirique.
En supposant des taux égaux d'entrée
d'eau saline et de sortie d'eau convertie
dans un étage, l'équilibre énergétique de
l'étage devient:
'■M — l«l = (' — ('hi —
où tH| et t,., sont respectivement les tem
pératures des courants chauds (H) et froids
(c) quittant l'étage i, tandis que «, est le
taux de production relatif de l'étage:
ai = X,/G, = c (t„ui — tH1)/h, 4. i/2
Les trois équations ci-dessus forment un
système non linéaire en tHul, tCl et ai.
En observant que ai est de l'ordre de
0.001 et que la variation de la chaleur de
 vaporisation avec la température peut très
bien s'exprimer en approximation par une
ligne droite ce système se simplifie en négli
geant les terms de second ordre. On obtient
alors les résultats significatifs suivants:
1. Le taux relatif de production d'en
semble ne dépend pas des efficacités des
étages séparés. Il est déterminé par les
températures terminales du courant d'eau
saline:
X/Gn = K(tHlul_tHl) = (c/a)
[(tiw - tHl) +b(tH.%, - t„',)]
2. Considérant seulement la consomma
tion de chaleur provoquée par les irréver
sibilités dans la cascade des étages de vapo
risation spontanée, l'économie de vapeur
dépend du taux de production et de la
somme de toutes les efficacités de chaque
étage:
hX/H = ^| I,-K^/(l-K)
3- La consommation de chaleur spéci
fique ne diminue pas indéfiniment avec
l'augmentation du nombre des étages. Pour
une différence de température minimum
Перенос Тепла и Массы при Дистилляции
со Вскипанием без Металлических
Поверхностей Раздела
Абрахам Коган
Израиль
Три метода дистилляции для опрес
нения морской воды, достигших широ
кого применения — 1) Многоступен
чатая дистилляция с длиннотрубным
вертикальным испарителем; 2) Много
ступенчатая дистилляция со вскипани
ем; и 3) Со сжатием пара — имеют
одну общую черту: они все применяют
металлические теплообменники для пе
реноса тепла от конденсируемого пара
к соленой воде. В проектах таких уста
новок заданной производительности,
уменьшение размеров теплообменного
оборудования сопровождается увели
чением перепада температур у стен
теплообменников. В оптимизированных
проектах, где стоимость пара идет на
moyenne donnée entre les deux courants
d'eau dans un étage I, on obtient l'écono
mie de vapeur la plus élevée lorsque:
nOI>t = {(1-K) / 21}. {(tBlwl _ t„,)/a}
L'économie maximum de vapeur corres
pondante est donnée par:
(hX/H),1I = (l„„-g/4Ie
En contraste avec les méthodes normales
de distillation, dans lesquelles l'entartrage
limite fortement la température la plus
élevée de l'eau de mer, on peut, dans la
méthode à distillation par contact direct,
tolérer des températures d'eau de mer
beaucoup plus élevées, ce qui a pour résul
tat à la fois une plus grande économie de
vapeur et une augmentation du taux de
production.
La dernière équation montre également
l'importance d'une faible valeur de la
différence de température terminale d'étage
i. Dans la méthode à distillation par con
tact direct, on devrait pouvoir obtenir des
valeurs très faibles de J, ayant pour résultat
une plus grande économie de vapeur.
компромисс с амортизацией капитало
вложения, чтобы снизить до минимума
стоимость опресненной воды, получа
ется относительно высокое потребле
ние удельной теплоты.
бттмер предложил альтернативный
метод дистилляции, при котором совер
шенно не применяется конденсация на
металлических поверхностях. При этом
методе поток соленой воды и поток
опресненной воды движутся во взаим
но-противоположных направлениях че
рез ряд ступеней вскипания. В каждой
ступени мгновенно отводится из потока
соленой воды некоторое количество
пара, который конденсируется при со
прикосновении с несколько более хо
 лодным потоком опресненной воды.
Концентрированный раствор сбрасыва
ется в виде продувки из ступени с са
мой низкой температурой, в то время
как поток опресненной воды, выходя
щий из самой горячей ступени, отдает
в жидкостно-жидкостно-жидкостном те
плообменнике свое тепло исходному
потоку морской воды. Часть охлажден
ной опресненной воды отводится из
системы в качестве конечного продук
та, в то время как ее большая часть
рециркулируется обратно через ступе
ни вскипания.
Так как при конденсации путем пря
мого контакта с опресненной водой
коэффициенты теплопередачи гораздо
выше, чем при обычной пленочной кон
денсации, то с помощью этого метода
видимо удастся значительно снизить
стоимость опреснения.
Этот доклад аналитически разбирает
многоступенчатую прямо-контактную
систему вскипания.
Производительность одной ступени
такой системы, при переносе тепла и
массы между двумя потоками воды,
может быть изображена параметром
эффективности ступени
I, — tC| ~ tc'-i
'и, - te,.,
где повышение температуры холодно
го потока выражено в процентах мак
симального температурного перепада
ступени. Ii — эффективность теплопе
редачи ступени зависит от геометриче
ской формы ступени, характеристик
потока, концентрации соли и степени
деаэрации воды. Она может быть опре
делена эмпирически.
Считая, что в одной ступени вток
соленой воды и истечение опресненной
воды имеют одинаковую скорость,
энергетический баланс ступени выра
зится в виде
'"1*1 — tci = 0 — «i) ('и, — te,.,)
aïïj tB, и te, являются температурами
горячего и холодного потока, соответ
ственно выходящих из ступени, в то
время как а, представляет собой отно
сительную скорость продукции ступени
X, C(t„ul-t„)
0,1 - G, - h, + v4 :
Вышеуказанные три уравнения пред
ставляют собой не-линейную систему
в tHl.,, te, и m- Принимая во внима
G6
ние, что ai является величиной поряд
ка 0,001, и что колебания тепла паро
образования в зависимости от темпера
туры близко приближаются к прямой
линии, эта система может быть упро
щена, отбросив члены второго поряд
ка. Тогда получатся следующие суще
ственные результаты:
1. Общая относительная скорость
продукции не зависит от эффективно
сти отдельных ступеней. Она опреде
ляется конечными температурами со
леного потока
А = - { (Ч,., -tHl) + 0(t,M _ tHl)}
1 a =K(tHM:tHl)
2. Принимая во внимание только по
требление тепла, вызываемое необра-
тимостями в каскаде ступеней вскипа
ния, экономия пара зависит от скоро
сти продукции и от суммы эффектив-
ностей всех отдельных ступеней:
в
fix £ !|-к
н - 1 _к
3. Потребление удельной теплоты не
ограниченно не уменьшается с увели
чением числа ступеней. При заданном
среднем минимальном температурном
перепаде § между двумя потоками во
ды в ступени, максимальная экономия
пара получается, когда
_ 1 — К >н„., — tHi
-~2Г~' i
Соответственная максимальная эко
номия пара выражается в виде
(ш\ _ t«.ti - tu,
\Н/"
N BU 41«
В противовес обычным методам ди
стилляции, при которых отложение на
кипи сильно ограничивает температуры
морской воды, метод прямо-контактной
дистилляции допускает применение го
раздо более высоких температур мор
ской воды, благодаря чему снижается
потребление пара и возрастает ско
рость производства.
Последнее уравнение указывает так
же на важность иметь в ступени малый
конечный температурный перепад §.
При прямо-контактной дистилляции
можно получить весьма низкие значе
ния §, что улучшает паровое хозяй
ство.
La Trasmisión Térmica y de Masas

en la Destilación Instantánea Sin

Interfaces Metálicas

Abraham Kogan

brad

Los tres métodos de destilación usados como producto, si bien la mayor parte del
para la desalinización de agua de mar que agua vuelve a circular a través de las etapas
han llegado a aplicarse en gran escala— de evaporación instantánea.
destilación con evaporadores verticales de Como la condensación por contacto di
tubos largos (VTL) de efecto múltiple, recto con el agua transformada puede lo
destilación instantánea en etapa múltiple y grarse con coeficientes de transmisión tér
compresión de vapor—tienen una caracter mica mucho más altos que los obtenidos en
ística en común: la utilización de intercam la condensación convencional por formación
biadores térmicos metálicos para trasmitir, de película, el método que nos ocupa ofrece,
al agua salina, el calor procedente de la al parecer, la posibilidad de reducciones
condensación del vapor. En el diseño de importantes en el costo de la desalinización.
tales instalaciones, la reducción de las di En el presente trabajo, se expone el trata
mensiones del equipo trasmisor de calor miento analítico del sistema de destilación
resulta en un aumento de la diferencia de instantánea en etapa múltiple por contacto
temperatura a través de las paredes del directo.
intercambiador térmico, para una capaci El rendimiento de una etapa de tal
dad determinada de la planta. En los di sistema, en cuanto a la trasmisión de calor
seños calculados para un rendimiento y masa entre ambas corrientes de agua,
óptimo, en los que se establece un equili puede determinarse mediante un parámetro
brio entre el costo de la producción de de la eficiencia de etapa.
vapor y la amortización del capital inver
tido, a fin de conseguir un costo mínimo I, = (tc.-tc,.,) /(t,, - tc.J
de agua transformada, se obtiene como re considerando el aumento de temperatura
sultado un consumo específico de calor de la corriente fría como porcentaje de la
relativamente elevado. máxima diferencia de temperatura habida
Como método alternativo de destilación en la etapa. El valor I, depende de la
Othmer ha propuesto uno mediante el cual estructura geométrica de la etapa, caracter
se evita por entero la condensación sobre ística de la corriente, concentración de sal
superficies metálicas. En este método, una y grado de desaireación del agua. Puede
corriente de agua salada y otra de agua determinarse empíricamente.
transformada fluyen en contracorriente a Dando por supuesta la igualdad del flujo
través de una serie de etapas de evaporación de entrada de agua salada y de salida de
instantánea. En cada etapa de la corriente agua transformada, en una etapa, el equili
de agua salada se evapora instantáneamente brio de energía de la etapa es
una cantidad de vapor, que se condensa por
contacto directo en la corriente, algo más t„m - t,., = (1 - ct) (tw, - te, - 1)
Ma, de agua transformada. La salmuera donde tHl y tc, son. respectivamente, Ы
concentrada es eliminada como descarga de temperaturas de las corrientes caliente y
la etapa de menor temperatura, mientras fría que salen de la etapa i, mientras que
que la corriente de agua transformada que ai es un índice relativo de la producción
surge de la etapa más caliente entrega de la etapa
calor a la corriente de entrada de agua de a, = X,/G, = c (tw, + 1 - tw,)/h, + i/2
mar, en un intercambiador térmico líquido-
líquido-líquido. Parte del agua transforma Las tres ecuaciones anteriores constitu
da, ya fría, es desviada fuera del sistema, yen un sistema no lineal en tWui, tr¡ y ai
Teniendo en cuenta ai es del orden de
0,001 y que la variación del calor de vapo
rización con la temperatura puede repre
sentarse aproximadamente por una recta
este sistema se simplifica despreciando los
términos de segundo orden. De esta forma,
se obtienen los resultados significativos
siguientes:
1. £1 índice relativo total de producción
no depende de la eficiencia de cada una de
las etapas. Se determina mediante las tem
peraturas finales de la corriente de agua
salada
X/Gr = К (t.M = (ca) { (tw>il _ twi)
+ b (tfj-tw,1) }
2. Considerando únicamente el consumo
de calor ocasionado por las irreversibili-
dades existentes en la catarata de etapas in
stantáneas, la economía de vapor depende
del Indice de producción y de la suma de
todos los valores de la eficiencia de cada
una de las etapas:
■ etapa. En el método de destilación por con
EX/H = (S I, - K)/(l - K)
3. El consumo específico de calor no dis
minuye indefinidamente con el aumento del
número de etapas. Para un determinado
promedio de diferencia mínima de tempera
tura entre ambas corrientes de agua en la
etapa, la mayor economía de calor se logra
cuando
n„pt = { (1 - R) /21} - { (t.M - tWl) ¡i }
La correspondiente economía maxima de
vapor se calcula mediante
(ïïx/H) = (tw..t _ tWl) /4ia
En contraste con los métodos de destila
ción convencionales, en los que la forma
ción de costra limita considerablemente la
temperatura máxima del agua del mar, en
el método de destilación por contacto di
recto pueden admitirse temperaturas de
agua de mar mucho más elevadas, lo cual
da por resultado una economía de vapor
mejorada y un índice de producción mayor.
La última ecuación indica asimismo la
importancia de un valor pequeño de la
diferencia mínima de temperatura de la
tacto directo es posible obtener valores de
muy reducidos, lo cual da origen al mejora
miento de la economía del vapor.
A New Ion -Exchange
Technique
Robert Kunin
United States of America
INTRODUCTION
The various programs throughout the
world, geared to the development of brack
ish and sea waters as well as sewage efflu
ents as sources of water for domestic,
agricultural, and industrial uses, have re
sulted in studies of new techniques for the
desalination of such supplies. These tech
niques include various evaporative, freezing,
membrane, ion-exchange, and extraction
processes. Although ion-exchange has been
widely used for many years in various water
treatment practices, including softening, de-
ionization, and dealkalization, the principle
has been ignored as a desalination tech
nique to a considerable degree in recent
years. Ion-exchange processes have been
limited primarily to concentrations below
1,000 ppm; however, in some instances, 500
ppm has been an upper limit. Although
some ion-exchange deionization plants are
built for operation above this concentration
level, the number is quite small and re
stricted to unusual conditions.
One of the problems associated with the
use of ion-exchange resins for the desalina
tion of water is the fact that a minimum
of equivalents of a base and an acid must
be used for each equivalent of salt re
moved. Although this fact has limited the
use of ion-exchange heretofore to salini
ties below 500 ppm, it is most important
to reassess the virtues of ion -exchange in
terms of the technology that has been de
veloped in recent years. In comparison with
other desalination techniques, ion-exchange
is often neglected in many desalination
programs because of this obvious salinity-
cost relationship. However, the other tech
niques such as distillation, membrane proc
esses, freezing, etc., although fundamentally
less sensitive to salinity, are plagued with
Desalination
some practical problems that require re
agents for amelioration. Whereas these
problems may not appear to be funda
mental to these processes, they are, for all
practical purposes, fundamental when one
considers operation of the processes under
field conditions. Too often, cost estimates
are made for processes operating on a
sparkling clear solution of NaCl instead
of a turbid saline water containing such
troublesome constituents as CaSO,, organic
acids (humic and fulvic acids) , iron, and
manganese. For example, all evaporative
processes operating on saline waters require
chemicals to prevent scaling, foaming, and
corrosion. Electrodialysis cannot be effec
tively accomplished without extensive water
pretreatment. If the water is not effectively
pretreated, the membranes will foul with
organic matter and scale rapidly on many
raw waters. The same action may be antici
pated for other osmotic membrane proc
esses. The "shutdowns" created by these
scaling and fouling problems are quite
costly and have been grossly underesti
mated in many evaluations. Their severity,
however, must be considered when the
processes are compared with ion-exchange.
The limitations of ion-exchange in treat
ing waters of high concentrations are based
upon two factors: the ion-exchange resin
regeneration costs and the rinse require
ment. The first factor is quite obvious and
has already been discussed. The relation
ship between the second factor and influent
concentration, however, is not usually real
ized by investigators. When the feed con
centration is low, the rinse requirement is
not a serious problem since there is usually
ample deionized product available for rin
sing, or raw water can be used for rinse
 without appreciably exhausting the resins.
At high concentrations, the problem be
comes quite serious since sufficient product
is not available and the use of raw water
for rinse exhausts an appreciable fraction
of the capacity of the exchangers.
The simplicity and flexibility of ion-
exchange as a unit operation has resulted
in the worldwide acceptance of ion-exchange
techniques for normal water treatment prac
tices. Of considerable significance in this
respect are the high flow rates that one
can achieve with small units and the ease
with which one can operate such equip
ment continuously and intermittently with
but minimum degrees of difficulty. Recent
developments in ion-exchange engineering,
resulting in practical means for conducting
ion-exchange in continuous, countercurrent
fashion coupled with the development of
new ion-exchange resins of high capacity
and regeneration efficiency, have extended
the limits of ion-exchange methods to in
clude the desalination of waters of higher
salinity than before.
The key to extension of ion-exchange
deionization techniques to waters of higher
CONVENTIONAL
Before considering the extension of ion-
exchange to brackish waters, some aspects
of the deionization of water with a conven
tional ion-exchange resin system must be
considered.
In conventional deionization the water
may first be passed through a column of
a strong acid cation-exchange resin in the
hydrogen cycle in order to remove the
cations in exchange for hydrogen ions,
RSO.H + NaCl ï± RSO.Na + HCl (la)
The effluent from this operation must then
be passed through a column of anion-
exchange resin in the hydroxide form to
remove the acid formed in the first step,
ROH + HCl -> R-Cl + H.O (lb)
In contrast to the above procedure, the
water may first be passed through a strong
base anion-exchange resin in order to re
move the anions in exchange for hydroxide
ions,
R OH + NaCl ;± R-Cl + NaOH (2a)
The effluent from this step must then be
passed through the column of the hydrogen
form of the cation-exchange resin,
RSO.H + NaOH -> RSO.Na + H.O (2b)
Л third technique is to pass the water
through a single bed containing an inti
mate mixture (Monobed) of the above
anion- and cation-exchange resins.
70
salinity such as brackish water is the de
velopment of ion-exchange resins of high
capacity and high regeneration efficiency
using régénérants of low cost, and the de
velopment of techniques for employing
such resins in a desalination process. This
is not a novel thought; the literature is
replete with the description of such efforts.
In previous publications, the author and
his associates (refs. I. 2) have described the
nature and properties of such ion-exchange
resins and their use in deionization systems.
It becomes quite obvious that for efficient
regeneration with either acid or base, the
ion-exchange resin must essentially be a
weak electrolyte, i.e., a carboxylic acid
cation-exchange resin (R-COOH) or an
amine-based anion-exchange resin (R-NH,) .
These structures are in contrast to the
strong electrolyte ion-exchange resins such
as the sulfonic acid cation-exchange resin
(R-SO,H) and the quaternary ammonium
anion-echange resin,
CH,
R-N CH^OH"
CH,
ION-EXCHANGE
RSO.H + R-OH + NaCI -»
RSOjNa + R-Cl + НгО (3)
In most conventional deionization systems,
the water is first passed through the cation-
exchange resin to remove cations in ex
change for hydrogen ions. The efficiency of
this operation depends upon the selectivity
of the cation-exchange resin for the various
cations to be removed as compared with
the hydrogen ions in the regenerated form
of the cation-exchange resin, normally a
sulfonic acid exchanger. It is quite obvious
that, if the exchanger is not very selective
for a particular cation, leakage of this
cation will readily occur, resulting in poor
effluent quality. Table IX summarizes the
selectivities of the various cations normally
encountered in the deionization of water.
It is readily evident from these data that
leakage problems in the hydrogen cycle
operation will depend upon the amount
of monovalent ions (Li, Na, and K) pres
ent in the influent.
It is also quite obvious that the divalent
(Ca, Mg) or hardness-contributing ions do
not pose leakage problems. It is quite in
teresting to note that most natural waters
used for domestic and industrial purposes
are low in monovalent ions as compared to
divalent ions. This fact has contributed
significantly to the success of ion-exchange
as a deionizacion technique. If the salts in
most waters now being treated by ion-
exchange were primarily sodium chloride,
deionization by means of ion-exchange
would not be as popular as it now is.
TABLE IX. Selectivity of Cations in the
Hydrogen Cycle of a Sulfonic Acid
Cation-Exchange Resin
W 0.8
H«« 2.0
K* S.0
NH<* S.0
Mr" 20
Ca» 42
Leakage of monovalent ions during the
hydrogen cycle can best be understood by
tracing the course of the resin using the
sodium ion (Na*) as the model. In most
waters encountered, the sodium is present
as the sulfate, chloride, bicarbonate, or
carbonate salt. The possible exchange re
actions involved are:
RSO,H + NaCl ^ RSO.Na + HCl (1)
2 RSO.H + Na,SO, -> 2 RSO.Na + H.O (4)
RSO.H + NaHCO, ;±
RSO,Na -f. CO, + H,0 (5)
2 RSO.H + Na,CO. —
2 RSO,Na + CO, +H.O (6)
In the case of NaCl and Na,SO„ the
hydrogen ions liberated during the ex
change process are present as hydrochloric
or sulfuric acid (reactions 1 and 4) . This
acidity limits the extent to which the re
actions can proceed. In the case of NaHCO,
and Na,CO„ the products of the exchange
reaction are CO, and H,0 and, therefore,
the reactions (5 and 6) proceed to com
pletion. Even though the selectivity coeffi
cient for the sodium ion is low, efficient
removal (low leakage) can be achieved if
the sodium ion is present as alkalinity
(NaHCO,, Na,CO„ and NaOH) . Leakage
of sodium ions is, therefore, only encoun
tered in waters high in chlorides and sul
fates.
It is quite interesting to note that if one
reversed the order of the two ion-exchange
resins and passed the water first through
the hydroxide form of the anion-exchange
resin (strong base, quaternary ammonium
anion-exchange resin) and then through
the hydrogen form of the sulfonic acid
cation-exchange resin, the leakage would
be determined by the anion-exchange selcc-
tivities. Table X compares the anion-
exchange selectivities of those ions com
monly found in water supplies with those
of the hydroxide ion. It is evident from
these data that the leakage would be consid
erably less if this procedure were followed.
There are, however, practical problems that
discourage the use of this technique. These
include the precipitation of CaCO, and
Mg(OH) , in the anion-exchange column
and the extra expense of removing CO,
and НСО,- by ion-exchange rather than by
mechanical means.
TABLE X. Selectivity of Anions in the
Hydroxide Cycle of a Quaternary Anion-
Exchange Resin
Selectivity coefficient
Anion vs hydroxide Ion
HCOi- 4
ГЛ- 11
NOr 40
80.= 60
The economics and the effluent quality
which can be achieved with any of the
above techniques depend to a large degree
upon the choice of both the ion-exchange
resins and the technique as well as the
regeneration levels. In the multiple bed
techniques, the economics and quality that
can be achieved usually depend upon the
leading column of ion-exchange resin. The
leakage characteristics of an NaCl water
and the excess regeneration requirements
of the leading column in each of the above
two methods are summarized in Tables XI
and XII. These data depict the excessive
quantities of régénérants required if NaCl
salinity is present and if good quality of
water is required. Countercurrent operation
reduces the leakage and improves the eco
nomics of the regeneration.
There are, however, various ion-exchange
techniques, developed over the last several
years, which have improved the economics
of ion-exchange as a deionization tech
nique. Some of these, although rather
obvious, have been ignored in various de
salination programs. None of these tech
niques is of any great importance by itself,
but they become significant when used as
a group. For example, one would not gen
erally employ a strong base resin following
the sulfonic acid exchanger in the conven
tional deionization technique. Unless one
wished to remove CO, and SiO„ a weak
base anion-exchange resin would be used
since it usually exhibits a much higher
capacity than the strong base anion-ex
change resins and since it can be regener
ated with base at high efficiency. It is,
however, possible to regenerate such resins
TABLE XI. Leakage and Regenerant Efficiency of a Sulfonic Acid Cation-Exchanger
Operated in the Hydrogen Cycle on an NaCl Water
Pounds HtSOt (66° Be) True capacity,
per cu ft kgr per cu ft
tJt 10.4
6.0 17.0
7.5 24.5
10.0 27.8
15.0 32.1
20.0 S4.0
25.0 84.9
TABLE XII. Leakage and Regenerant Efficiency of a Quaternary Ammonium Anion-
Exchange Resin Operated in the Hydroxide Cycle on an NaCl Water
Pounds. NaOH per True capacity.
cu ft kg-r per cu ft
1 6.0
1 6.1
1 8.8
4 9.7
( 11.8
8 18.8
with lime slurries or with NH, using lime
to recover the ammonia from the waste
regenerant. The same is true for the com
bined use of strong and weak acid cation-
exchange resins. This approach has not re
ceived proper attention although it would
WEAK ELECTROLYTE ION-EXCHANGE RESIN SYSTEMS
The quest for an ion-exchange process,
based solely upon weak electrolyte ion-
exchange resins, is predicated upon the as
sumption that the ion-exchange desalina
tion process involves the overall removal
of electrolyte from water by exchanging the
anions and cations for hydrogen and hy
droxide ions and that an acid and a base
are required for regeneration. Thus, the
author has rejected all techniques which
employ ion-exchange resins for removing
electrolytes with water, electrical energy,
or steam as a regenerant. Experience has
shown that such techniques are ineffective,
resulting in poor utilization of the ion-
exchanger's capacity. An ideal ion-exchange
system is one in which the exchangers can
be regenerated by an equivalent of cheap
acid and base for each equivalent of salt
removed. In addition, the exchangers must
be capable of effectively removing salt from
water at high degrees of utilization of the
ultimate capacity of the ion-exchange resins.
Unless these requirements are met, ion-
exchange cannot be used economically for
the desalination of brackish or saline waters.
The use of weak electrolyte ion-exchange
Leakage Excess acid
percent reQuired, per cent
68 58
45 95
80 104
22 148
10 210
6 290
8 875
Leakage Excess caustic
per cent required, per cent
12 74
8 186
6.5 215
8.7 260
1.5 818
0.7 595
cut the cost of regeneration significantly.
If these approaches were coupled with the
use of countercurrent and continuous mov
ing bed techniques, ion-exchange could be
even more useful as a desalination process.
resins in deionization systems is not new.
In fact, both carboxylic acid cation-exchange
resins and weak base anion-exchange resins
have been used to increase the efficiency of
deionization systems; however, in these cases
the weak electrolyte ion-exchange resins
were always used in conjunction with strong
electrolyte ion-exchange resins. It is impor
tant to note, however, that when such resins
were used in deionization systems, they were
regenerated at approximately 100 per cent
efficiency with inexpensive regenerants.
When used without strong electrolyte ion-
exchange resins, the nature of the equili
bria involved limited their use to a mixed
bed or Monobed system, i.e., an intimate
mixture of the two weak electrolyte ion-
exchange resins. Several years ago, the au
thor and his associates (ref. 1, 2) investi
gated the properties of a weak electrolyte
mixed bed for dionizing brackish waters
using the ion-exchangers then available and
concluded that the system was poor from
a kinetic point of view, requiring finely
divided material. A comparison of the de
ionization efficiency of Monobeds of normal
particle size and of finely divided material
 70
ELECTROLYTE TREATED, Equiv /Liter
FIGURE 25. PERFORMANCE OF A WEAK ELECTROLYTE
ION-EXCHANGE MONOBED.
is given in Figure 25. The author and his
associates found such mixed beds to be
difficult to handle in cyclic processes since
the two ion-exchange resin components
were difficult to separate for the purpose
of regeneration.
The authors also investigated the use of
finely divided exchangers employing super
heated water as a regenerant. Although
some success was achieved, the quality of
the water was poor and the method of re
A NEW ION-EXCHANGE DESALINATION TECHNIQUE
Quite recently, the author (ref. 4) and
his associates (ref. 5) developed a new ion-
exchange desalination technique for em
ploying weak electrolyte ion-exchange resins
without the use of the mixed bed principle.
This technique is based upon the discovery
that certain anion-exchange structures of a
weakly basic nature can form the bicarbon
ate salt with solutions of carbon dioxide
and that the chloride-bicarbonate selectivity
coefficient, CI" , is favorable. This dis-
KHCOa-
covery suggested the possibility of employ
ing weak electrolyte ion-exchange resins in
generation was ineffective, particularly if
divalent ions were present in the feed. A
system (ref. 3) has been developed for
regenerating such exhausted mixed beds
without separation of the ion-exchange
resin components, using ammonia followed
by water saturated with CO,. The method
has not been sufficiently economic to be
useful for treating brackish waters, although
it does hold promise in chemical processing.
a reverse deionization system (anion-ex-
changer followed by cation-exchanger)
based upon the following reactions:
[R-N] + H,0 + CO,-»
[R-NH] HCO,
(carbonation) (1)
[R-NH] HCO, + NaCl ->
[R-NH] CI + NaHCO,
(alkalization) (2)
R-COOH + NaHCO, -»
R-COONa + CO, + HsO
(dealkalization) (3)
[R-NH] CI + NH.OH-*
[R-N] + NH.C1 + HsO
(anion-exchanger regeneration) (4)
 or TABLE Xin. K hco^ Selectivities of
2 [R-NH] CI + CaO-»
[R-N] + CaCl, +H.O (4a) Anion-Exchange Resins
2 RCOONa + H.SO. -»
2 RCOOH + Na^O. Amberlite K Cl« Degree of chloride
(cation-exchanger regeneration) (5) resin HCO» saturation, per cent
Since (he equilibria for these ion-exchange IRA 68 60 26
reactions were favorable, the basic aspects IRA-68 20 60
of these reactions and the deionization sys IR-45 1 9
tem were studied in detail both in the IRA-9S 4 28
laboratory and in the field. IRA-400* 2 40
■ Measured at 0.02N concentration.
LABORATORY STUDIES b A strong base anion-exchange resin.

The key factors in the new process are
the unusual characteristics of the weak base
anion-exchange resin, Amberlite IRA-68.
This weak exchange resin is not onh
capable of absorbing CO, to form the bicar
bonate salt, but also the bicarbonate-
mineral acidity selectivity is such that the
salts present in brackish water and even
sea water can be converted to alkalinity
with negligible leakage. The unusual
Khcoj- of Amberlite IRA-68, as compared
with other anion-exchangc resins, is illus
trated in Table XIII.
Because of this, one may select a weak acid
cation-exchange resin for removing the
alkalinity. However, since the alkalinity
would normally be present as sodium al
kalinity, not all weak acid cation-exchange
resins are useful and Amberlite IRC-84 is
unique in this application. The properties
of these two resins as compared with other
weak electrolyte ion-exchange resins are
summarized in Table XIV. By selecting the
proper weak electrolyte ion-exchange resins,
it is possible to employ them in a de
salination technique at high regeneration
efficiencies at capacities corresponding to a
high degree of utilization of the ion-ex
change resins' theoretical capacities.
The new cyclic deionization process in-

TABLE XIV. Properties of Weak Electrolyte Ion Exchange Resins

Ion-exchange resin Moisture Capacity pK"

per cent Meq/g Meq/ml or "pKb
Cation-exchangers :
Amberlite IRC -60 60 10.1 S.6 6.1
Amberlite IRC-84 66 11.5 8.6 5.8
Anion-exchangers :
Amberlite IRA-68 60 6.6 1.6 8.6
Amberlite IR-45 46 6.0 2.0 9.2
Amberlite IRA 93 67 6.2 1.4 9.0
Note: "Apparent pK« ( cation-exchange resins ) and pKh (anion-exchange resins) values measured by
Henderson-Hasselbach equation.

volves a series of three columns: Amberlite
IRA-68 (HCOa) -* Amberlite IRC-84 (hy
drogen form) -» Amberlite IRA-68 (free
base) . Saline water passing through the
first column undergoes the alkalization re
action in which the anions are exchanged
for bicarbonate ions, e.g., NaCl is converted
to NaHCCv Passage of the NaHCO, through
the second column results in the exchange
of Na* for H* (dealkalization) , with the
effluent containing merely CO, and H,0.
The effluent from the second column is
passed through the third column with the
resultant recovery of the CO, forming the
bicarbonate salt of the Amberlite IRA-68
(carbonation) . The first column is regen
erated with base to convert the resin to the
free base and the second column is already
in the bicarbonate form. The deionization
is now accomplished by passage of the
saline water in the opposite direction i.e.,
through the third column first. In other
words, the first and third column contain
ing the Amberlite IRA-68 alternate with
each other as the alkalization or the car
bonation (CO, recovery) column. To start
the operation, the leading column is first
conditioned with CO,-saturated water. Since
the CO, is recovered by the third column,
CO, is only employed to make up for losses
due to leakage. A flow sheet is shown in
Figure 26.
 NoCI

A A A
M M M
B B B
E E E
R R R
L L L
I I I
T T T
E E E

IRA -68 IRC-84 IRA-68

I ;
ALKALIZATION DEALKALIZATION CARBONATION
(COg RECOVERY)
« * *
NaHC03 H2O+ C02 H2O
FIGURE 26. NEW DEIONIZATION FLOW SHEET.

The regeneration efficiency is excellent ous methods of regeneration studied, it has

for a system of this type, since weak elec
trolyte ion-exchange resins are employed,
permitting regeneration with cheap acids
and bases at regeneration levels approach
ing 100 per cent efficiency. The regenera
tion of resins described in this study, in
cluding the recovery of the ammonia from
the waste regenerant using lime, has al
ready been discussed in detail. A study em
ploying a lime slurry directly as a regenerant
was of considerable success. From the vari
become apparent that regeneration costs
can be reduced to approximately the use
of one equivalent each of H.SO, and CaO
per equivalent of NaCl removed.
The effectiveness of the new desalination
technique is described in Figures 27. 28. and
29 using a synthetic water containing 1,000
ppm. It is quite obvious that the new tech
nique yields excellent quality water and
excellent capacities.

75
 eOr

l_

tu
о Со' 1000 рря
и ■ 2 gal /ftVmln
< h • 24"

10

10 2030 40 50 60 70 80 90
BED VOLUMES, THROUGHPUT
FIGURE 27. EFFECT OF THE TEMPERATURE ON THE PER
FORMANCE OF AMBERLITE IRA-68 IN THE NEW DEIONIZA-
TION PROCESS.

60i—

0 10 20 30 40 50 60 70 80 90
BED VOLUMES, THROUGHPUT

FIGURE 28. EFFECT OF REGENERANT AND RINSE WATER

QUALITY ON NEW DEIONIZATION TECHNIQUE.
 50,

Со ■ 1000 ppm
(9 и » 2 gal / ft5/ min
4 h » 24"
at го!
< T » RT*

10

10 20 30 40 50 60 90
MEQ THROUGHPUT
FIGURE 29. EFFECT OF C02 RECOVERY ON NEW DEIONIZA
TION TECHNIQUE.

PILOT PLANT TESTS Sturla (ref. 6) , of Direzione Construzioni

In view of the encouraging laboratory
results, it was deemed advisable to study
the new desalination process on a pilot
plant scale in the field. This study was
conducted in cooperation with Dr. Piero
Termiche E Nucleari (ENEL) , Rome, Italy,
at the Laboratorio Centrale in Piazenca,
Italy, using a brackish water of approxi
mately 2,300 ppm in salinity and having
the composition described in Table XV.

TABLE XV. Typical Analysis of the Brackish Water

Calcium — 230 ppm pH — 7.8

Magnesium — 490 ppm Chlorides — 1,823 ppm
Sodium — 1.574 ppm Sulphates — 180 ppm
Total solids — 2.294 ppm Nitrates — 21 ppm
Organice — 8.5 ppm as KMnOi Bicarbonates — 270 ppm
Note:—The above amounts are expressed as ppm of CaCOa.

Conventional ion-exchange equipment also the same, i.e., Amberlite IRA-68 -»

was employed, and was slightly modified to
accommodate the use of CO, to saturate
water for replacing CO, losses from the
system. The ion-exchange resins used were
the same as those used in the laboratory
study; the arrangement of columns was
Amberlite IRC-84 -» Amberlite IRA-68.
Each column, 30.7 cm in diameter and 190
cm high, contained 60 liters of ion-exchange
resin at a depth of approximately 80 cm.
Figure 30 describes the pilot plant in detail.
 SO.
TRIALS.
FIGURE
BPILOT
FOR
SKETCH
WATER
PLANT
RACKISH

00
 The pilot plant was operated for approxi and regenerant efficiency were achieved.
mately one year during which period 105 Table XVI summarizes the operating data
cycles were completed. During the course including effluent quality, regenerant con
of this study, consistent effluent quality sumption, and exchange capacity.

TABLE XVI. Summary of Operating Data

Flow rate:
Exhaustion — 1-2 gal/cu ft/mln
Regeneration — 0.5 gal/cu ft/mln
Regeneration levele:
Amberlite IRA-68 — 110% theory (4% NHi or CaO slurry)
Amberlite IRC-84 — 110% theory (4% HC1 or HsSOt)
Capacity:
Amberlite IRC-84 — 20 Kgr/cu ft
Amberlite IRC-68 — 18 Kgr/cu ft
Effluent quality: — 10-20 micromhoa

At the conclusion of the study, samples cu ft of ion-exchange resins in each of the

of each ion-exchange resin were removed three units. This involves a capital cost for
and evaluated in the laboratory to deter the ion-exchange equipment installed of
mine if any changes in the properties of approximately $300,000 and an operating
the exchangers had occurred during the cost of 11 to 22 cents per 1,000 gallons,
course of the study. A comparison of the depending on the availability and cost of
properties of the ion-exchange resins before the regenerant chemicals. It is quite evident
and after the pilot plant study is sum that the installation and operating costs
marized in Table XVII. This illustrates the compare favorably with other desalination
fact that both the exchangers changed only techniques.
slightly and appear quite stable in this
application. Included in the pilot plant was TABLE XVII. Properties of Ion-Exchange
a series of runs in which the anion-exchange Resins Before and After Use.
resin, Amberlite IRA-68, was successfully
regenerated, using a slurry of lime in place Amberlite IRA-68: Used Fresh
of the ammonia. According to the results
of this field study, the cost for treating the Moisture (%) 62.8 61.6
water in question was significantly less than Total anion-exchange capacity
(meq/gm) 5.68 S.70
that of evaporative processes at concentra Carboxyl capacity
tions less than 3,000 ppm. A modest-sized (meq/gm) 0.62 0.48
plant based upon the described process is Net adsorbed organic matter
(meq/gm) 0.82
now being erected for treating brackish Whole bead content ( % ) 98.0 98.0
wateT to be used by a power utility.
Using the data of Peak (ref. 7) , an esti Amberlite IKC-li:
Moisture (%) 49.6 49.8
mate has been made of the cost of a large Cation-exchange capacity
installation based upon the new process. (meq/gm) 10.68 10.62
To treat 1,000.000 gallons of brackish water Whole bead content (%) 98.0 98.0
(1,100 ppm) per day would require 400

CONCLUSIONS
As a result of the laboratory and pilot
plant studies, it is quite apparent that weak
electrolyte ion-exchange resins can be used
efficiently to deionize brackish waters, em
ploying regenerants such as lime and
HjSO, at efficiencies close to 100 per cent.
In addition, the new technique utilizes the
capacities of the ion-exchange resins most
efficiently when employed with conventional
equipment.
It is apparent from these studies that
ion-exchange resins can now be employed
economically so as to extend the range of
ion-exchange to brackish waters. One may
speculate in terms of future developments.
For example, further economies may be
possible if it becomes possibe to adapt the
newer moving bed, countercurrent engineer
ing designs to the above-described desal
ination process. In addition to the use
of lime as a regenerant for the anion-
exchange resin, the possibility of using C02
as a regenerant for the carboxylic cation -
exchanger.
 RCOONa + CO, ^ RCOOH + NaHCO,
and the resulting NaHCO, as the regen-
erant for the anion-exchange resin, as sug
gested in a previous paper (ref. 5) , has
potential merit in certain situations. In
practice, the less acidic cation-exchanger,
Amberlite IRC-50, would be required lo
achieve efficient use of the CO, and obtain
a high concentration of NaHCO,. A pre
liminary study has revealed that the utility
of this system would be limited to situ
ations permitting modest amounts of leak
age. In addition, about one-half to
three-fourths of the required base necessary
for regeneration could be recovered in this
manner.
The direct use of lime as a regenerant
for the anion-exchange resins is most at
tractive and has been used with success in
the pilot plant studies. The economic gains
are most encouraging if one considers that
a pound equivalent of CaO costs only $0.11
as compared with NH, at $0.74 and NaOH
at SI.20.
The weak base anion-exchange resin, Am
REFERENCES
1. Kunin, R.; Barry, R. E.: Ind. and Eng.
Chem., no. 41 (1949) p. 1269.
2. Kunin, R.; McGarvey, F. X.: Ind. and
Eng. Chept., no. 43 (1951) p. 734.
3. Kunin, R.: U.S. Patent 3,111,485 (Nov.
11. 1963).
4. Kunin, R.: U.S. Patent 3,156,644 (Nov.
10, 1964).
SUMMARY OF
Further comment was requested concern
ing the technique of backwash flow rate.
The reply stated that backwashing the resin
bed is the conventional procedure when
berlite IRA-68, possessing a high K
HCO,"
selectivity coefficient and the carboxylic
cation-exchange resin, Amberlite IRC-84,
with improved kinetic and equilibrium be
havior when employed with the new de-
ionization technique, extend the economic
utility of ion-exchange resins to the range
of many brackish waters (at least to 2,000
or 3,000 ppm) . Some of the advantages of
the new process over the older ion-exchange
methods are:
1. High regeneration efficiency, ap
proaching 100 per cent utilization of
regenerants, can be achieved.
2. Low cost regenerants can be used.
3. Raw water can be used for rinse
and regeneration without notable losses
in capacity and quality.
4. Very low leakages are noted at effici
ent regenerant levels.
5. The system can be readily integrated
with other ion-exchange resin deioniza-
tion systems.
5. Kunin, R.; Vassiliou, B.: Ind. and Eng.
Chem. Prod. Res. Develop., no. 2
(1963) p. 1.
6. Sturla, P.: 25th Meeting Int. Water
Conf. Eng. Soc, Western Pennsylvania
(Sept. 30. 1964) .
7. Peak, R. F.: Univ. of Washington,
Ph.D. Dissertation (1955).
DISCUSSIONS
the resin bed is exhausted and that normal
backwash is employed. Actual backwash
rates were not given.
Nouvelle Technique de Dessalement
Par Echange DTons
Robert Kunin
Etats-Unis D'Amérique
D'une manière générale, la désionisation
économique de l'eau par des résines échan
geuses d'ions s'est limitée aux eaux con
tenant moins de 500 ppm de solides dissous.
En général, la désionisation des eaux sau-
mâtres par les techniques normales à ré
sines échangeuses d'ions ne peut pas con
currencer les procédés par distillation et
par membranes, principalement à cause
des frais de régénérateurs et la nécessité
d'utiliser de l'eau désionisée pour l'opéra
tion de rinçage. Pour les eaux à faibles
teneurs en solides, ces facteurs sont
d'une importance secondaire; à une con
centration supérieure à 500 ppm, ils de
viennent d'une importance primordiale. On
a étudié une nouvelle technique de désio
nisation par des résines échangeuses d'ions
faiblement électrolytiques dans lesquelles
l'échangeur anionique à base faible est
utilisé dans le cycle du bicarbonate pour
convertir l'acidité minérale de l'eau en
alcalinité et la résine à acide faible dans le
cycle d'hydrogène pour éliminer l'alcalinité.
Grâce à ce système on peut désioniser des
eaux saumâtres avec très peu de pertes et
à une haute efficacité de régénération. Le
nouveau procédé de dessalement peut se
résumer par les réactions suivantes:
[R-N] + HsO-f CO,-> (1)
[R-NH] HCO,
(carbonatation)
[R-NH] HCO, + NaCl -> (2)
[R-NH] Cl + NaHCO,
(alcalinisation)
R-COOH + NaHCO, -> (S)
R-COONa -f CO, + H20
(désalcalinisation)
[R-NH] Cl + NH.OH -» (4)
[R-N] + NH.C1 + H,0
(régénération de
l'échangeur
anionique)
ou
2 [R-NH] Cl + CaO -> (4a)
[R-N] + CaCl, -I- H,0
2 RCOONa + HjSO, -» (5)
2 RCOOH + Na,SO,
(régénération de
l'échangeur
cationique)
Le nouveau procédé de désionisation
cyclique comporte une série de trois co
lonnes: Amberlite IRA-68 (HCO,) —Am-
berlite IRC-84 (hydrogène) — Amberlite
IRA-68 (base à l'état libre) . Les deux
résines échangeuses d'ions, Amberlite IRA-
68 (résine échangeuse anionique à base
faible) et Amberlite IRC-84 (résine
échangeuse cationique à acide faible) , sont
des résines échangeuses d'ions faiblement
électrolytiques et conviennent particulière
ment bien pour ce procédé. L'eau saline
passant à travers la première colonne subit
la réaction d'alcalinisation, dans laquelle
les anions sont échangés pour des ions bi
carbonate—par exemple NaCl est trans
formé en NaHCO,. Le passage de NaHCO,
à travers la seconde colonne a pour résultat
l'échange de Na* pour H* (désalcalinisa
tion) , avec l'cffluent contenant seulement
CO, et HsO. L'effluent de la deuxième co
lonne passe à travers la troisième colonne
avec pour résultat la récupération du CO,
formant le sel bicarbonate de l'Amberlite
IRA-68 (carbonatation) . La première co
lonne est régénérée avec NH, (NH,OH) ou
bouillie de chaux pour transformer la
résine à l'état de base libre, et la seconde
colonne avec HrSO, pour transformer la
résine à la forme acide. La troisième co
lonne est déjà sous forme bicarbonate. La
désionisation se fait alors par le passage de
l'eau saline dans la direction opposée, c'est-
à-dire à travers la troisième colonne en
premier. En d'autres termes, les première et
troisième colonnes, contenant l'Amberlite
IRA-68, alternent l'une avec l'autre en tant
que colonne d'alcalinisation ou de carbona
tation (récupération de CO,) .
L'efficacité de régénération est excellente
pour un système de ce genre, car on utilise
des résines échangeuses d'ions faiblement
électrolytiques permettant de les régénérer
avec des acides on des bases bon marché
(HjSO, et chaux ou ammoniac) à des
faibles niveaux de régénération.
Lorsqu'on utilise des résines échangeuses
d'ions pour la désionisation de l'eau dans
la gamme de 500 à 3.000 ppm, les régénéra
teurs, même les meilleur marché, utilisés à
leur efficacité théorique, représentent la
proportion la plus importante du prix de
revient du système de désionisation. L'utili
sation d'ammoniac, en tant que régénérateur
pour la résine échangeuse anionique, as
sociée avec sa récupération en utilisant de
la chaux
2 NH.C1 + CaO -> 2 NH, + CaCl, + H.O
peut constituer une importante réduction
du prix de revient. L'ammoniac est récu
péré de cette manière dans les industries
du sucre et de la soude.
L'utilisation directe de la chaux en tant
que régénérateur pour les résines échan
geuses anioniques est très attrayante et a
Новый Метод Ионообменной Техники
Обессоливания
Роберт Кунин
Соединенные Штаты Америки
Экономичная деионизация воды по
средством ионообменных смол обычно
ограничивалась водами, которые со
держали менее 500 ч/миллион раство
ренных твердых частиц. Деионизация
солоноватых вод путем обыкновенного
применения ионообменных смол, вооб
ще не может конкурировать с мембран
ным и перегонным методом, главным
образом вследствие высокой стоимо
сти регенераторов и потребности в де-
ионизированной воде для промывания.
Эти факторы менее важны для вод с
низким содержанием твердых веществ;
но они имеют очень большое значение
при концентрациях свыше 500 ч/мил
лион. Теперь выработана новая техника
деионизации, которая основана на ио
нообменных смолах для слабых элек
тролитов, причем слабоосновной ани-
онит применяется в бикарбонатном цик
ле, чтобы превратить минеральную ки
слотность воды в щелочность, а слабо
été réalisée avec un certain succès dans des
études d'installations pilotes. Les gains éco
nomiques sont des plus encourageants si
l'on considère que l'équivalent d'une livre
(452 g) de CaO ne coûte que $0,11, com
paré avec le NH, à $0,74 et le NaOH à
$1,20.
Le procédé a fait l'objet d'essais pra
tiques satisfaisants dans une installation
pilote de grande échelle, avec de l'eau
saumâtre d'une salinité de 2.000 ppm. Le
coût des produits chimiques pour l'exploi
tation de l'installation pilote a été de 22
cents par mille gallons (environ $0,058 par
m') , en se servant de chaux pour l'un des
régénérateurs, et la qualité de l'eau était
en moyenne de 10 à 20 micromhos.
Une installation de dimension modeste,
basée sur le procédé décrit, est actuellement
en cours de construction pour le traitement
d'une eau saumâtre destinée à être utilisée
par une centrale électrique.
кислотной смолой пользуются в водо
родном цикле для удаления щелочно
сти. Эта система позволяет деионизи-
ровать солоноватые воды с лишь не
большой утечкой и с высокой эффек
тивностью регенерации. Новый про
цесс обессоливания может быть пред
ставлен схематически в следующих ре
акциях:
/R-N/ + Н,0 + СОг —
/R-NH/HCO,
(карбонизация) (1)
/R-NH/НСО, + NaCl
/R-NH/C1 -I- NaHCO,
(алкализация) (2)
R-COOH + NaHCO, —
R-COONa -f С02 + Н30
(деалкализация) (3)
/R-NH/C1 + NH,OH —
/R-N/ + NH.Cl + Н20
(регенерация анионита) (4)
или
2/R-NH/Cl + CaO —
/R-N/ + CaCl, -(- H,0 (4a)
2 RCOONa + H,SO. —
2 RCOOH + Na^O,
(регенерация катионита) (5)
В новом циклическом процессе деио-
низации пользуются серией трех коло
нок: Amberlite IRA-68 (НС03) — Ат-
berlite IRC-84 (водородная форма),
Amberlite IRA-68 (свободное основа
ние). Две ионообменные смолы, Am
berlite IRA-68 (слабо-основной ани-
онит) и Amberlite IRC-84 (слабо-ки
слотный катионит) представляют собой
ионообменные смолы для слабых элек
тролитов и особенно подходят для про
цесса. Соленая вода, проходящая че
рез первую колонну подвергается ще
лочной реакции, при которой анионы
заменяются бикарбонатными ионами,
например NaCl превращается
NaHCOg. Прохождение NaHCOs через
вторую колонну приводит к замене
Na+ на Н+ (расщелачивание), причем
вытекающий раствор содержит лишь
С02 и Н20. Раствор, вытекающий из
второй колонны, проходит через тре
тью, где С02 извлекается, образуя дву
углекислую соль Amberlite IRA-68
(карбонизация). Первая колонна реге
нерируется посредством NH3(NH4OH)
или известковым шламмом для того,
чтобы дать смоле свободное осно
вание, а вторая колонна регенерирует
ся посредством H2S04 чтобы превра
тить смолу в ее кислотную форму.
Третья колонна уже принадлежит к
двууглекислой форме. Деионизация до
стигается прохождением соленой воды
в противоположном направлении — т.е.
сначала через третью колонну. Иными
словами, первая и третья колонны, со
держащие Амберлит IRA-68 действуют
поочередно как подщелачивающая или
карбонизирующая (извлечение С02)
колонка.
Эффективность регенерации в системе
этого типа превосходна, так как ионо
обменные смолы для слабых электроли
тов поддаются регенерации на низких
уровнях дешевыми кислотами и щело
чами (H2S04 и известь или аммиак).
Применяя ионообменные смолы для
деионизации воды в диапазоне 500 до
3000 ч/миллион даже самые дешевые
восстановители при полной их теоре
тической эффективности, представляют
самую значительную статью в себесто
имости деионизационной системы. При
менение аммиака в качестве регенера
тора для анионита, связанное с его из
влечением посредством извести
2 NH.C1 + CaO -> 2NH, + CaCl, + Н,0
может значительно уменьшить себе
стоимость. Аммиак таким образом ре
куперируется в сахарной и содовой
в промышленности.
Непосредственное использование из
вести в качестве регенератора весьма
выгодно, и оно удачно применялось при
исследованиях на опытных установках.
Экономические выгоды очень привле
кательны если принять во внимание,
что фунт СаО стоит только 11 центов,
по сравнению с 74 центами для NH, и
120 центами для NaOH.
Процесс был успешно испытан на
практике в большом масштабе на опыт
ной установке, перерабатывавшей со
лоноватую воду с соленостью в 2.000
ч/миллион. Стоимость химических ве
ществ при работе опытного завода до
стигала приблизительно 22 цента за
1.000 галлонов, причем в качестве од
ного из регенераторов употреблялась
известь, а качество воды достигало в
среднем 10-20 микроомов.
Небольшой завод, основанный на
вышеописанном процессе, строится в
настоящее время для обработки соло
новатой воды, употребляемой для пи
тания энергетической установки.
Una Nueva Técnica
cion por Intercambio Iónico
Robert Kunin
Estados Unidos de Norteamérica
La desionización de agua mediante resi
nas de intercambio iónico, en forma eco
nómica, ha estado generalmente limitada
a aguas que contienen menos de 500 ppm
de total de sólidos disueltos. En general,
la desionización de aguas salobres mediante
técnicas convencionales por medio de resinas
de intercambio iónico, no puede competir
con los métodos por medio de membranas
y por destilación debido principalmente al
costo de los regenerantes y a la necesidad
de emplear agua ionizada para la opera
ción de enjuague. En el caso de aguas de
bajo contenido de sólidos, estos factores son
de menor importancia; por sobre una con
centración de 500 ppm, éstos pasan a ser
de mayor importancia. Se ha desarrollado
una nueva técnica de desionización me
diante el empleo de resinas de intercambio
iónico débilmente electrolíticas en que el
permutador aniónico de base débil es em
pleado en el ciclo del bicarbonato para
convertir la acidez mineral del agua a alca
linidad, y la resina de ácido débil es em
pleada en el ciclo del hidrógeno para
extraer la alcalinidad. Este sistema permite
desionizar aguas salobres con poca pérdida
y a una alta eficiencia en la regeneración.
El nuevo proceso de desalinización se puede
resumir mediante las siguientes reacciones:
[R-N]+ H.O + CO,-> [R-NH] HCO,
(carbonatación) (1)
[R-NH] HCO, + NaCl ->
[R-NH] Cl + NaHCO,
(alcalinización) (2)
R-COOH + NaHCO, ->
R-COONa + CO, H.O
(desalcalinización) (3)
[R-NH] C1 + NH.OH-»
[R-N] + NH4C1 + H20
(regeneración del permutador (4)
aniónico)
° 2 [R-NH] Cl + CaO ->
[R-N] + CaCl, + H,0 (4a)
de Desaliniza-
2 RCOONa + H.SO. -»
2 RCOOH -f Na,SO,
(regeneración del permutador (5)
catiónico)
El nuevo proceso cíclico de desionización
emplea una serie de tres columnas. Amber-
lite IRA-68 (HCO,) — Amberlite IRC-84
(forma de hidrógeno) — Amberlite IRA-68
(base libre). Las dos resinas de intercambio
iónico, Amberlite IRA-68 (resina de inter
cambio aniónico base débil) y Amberlite
IRC-84 (resina de intercambio catiónico
ácido débil), son resinas de intercambio
iónico débilmente electrolíticas que se adap
tan singularmente para el proceso. El agua
salada que pasa a través de la primera
columna es sometida a la reacción de alca
linización en la cual los aniones son inter
cambiados por iones bicarbonato — por
ejemplo, el NaCI es convertido a NaHCO,.
El pasaje del NaHCO, a través de la se
gunda columna resulta en el intercambio
de Na + por H -\- (desalcalinización), con
teniendo el liquido que sale simplemente
CO, y H,0. El liquido proveniente de la
segunda columna pasa a través de la tercera
columna recuperándose, como resultado, el
CO, el cual forma la sal bicarbonatada de
la resina Amberlite IRA-68 (carbonatación).
La primera columna es regenerada con NH,
(NH,OH) o suspensión de cal para conver
tir la resina a la base libre mientras que
la segunda columna es regenerada con
H,S04 para convertir la resina a la forma
ácida. La tercera columna ya se encuentra
en la forma bicarbonatada. La desionización
se logra ahora mediante el pasaje del agua
salada en sentido contrario—es decir, co
menzando por la tercera columna. En otras
palabras, la primera y la tercera columnas
conteniendo Amberlite IRA-68 se turnan
entre sí en la función de columna de alcali
nización o carbonatación (recuperación del
CO,).
La eficiencia en la regeneración es ex
celente para un sistema de este tipo, dado
que se emplean resinas de intercambio
 iónico débilmente electrolíticas permitiendo
las regeneraciones con ácidos y bases bara
tos (H,SC), y cal o amoniaco) a bajos niveles
de regeneración.
Cuando se emplean resinas de intercam
bio iónico para la desionización de aguas
con contenido de sólidos entre 500 y 3000
ppm, aún los regenerantes más baratos,
usados a eficiencia teórica, representan la
contribución principal al costo del sistema
de desionización. El empleo de amoniaco
como regenerante de la resina de inter
cambio aniónico, junto con su recuperación
por medio de cal
2 NH«C1 + CaO -> 2 NH, -f CaCl, + H20
puede disminuir el costo en forma significa
tiva. El amoniaco es recuperado de esta
manera en las industrias del azúcar y de la
soda Solvay.
El empleo directo de cal como regene
rante para las resinas de intercambio
aniónico es sumamente atractivo y ha sido
ensayado con cierto éxito en los estudios de
planta piloto. Las ganancias económicas
son sumamente alentadoras si se considera
que una libra equivalente de CaO cuesta
sólo $0.11 comparado con amoniaco a $0.74
y NaOH a $1.20.
El proceso ha sido probado con éxito, en
forma práctica, en planta piloto en gran
escala, con un agua salobre con un con
tenido salino de más de 2000 ppm. El costo
de productos químicos para el funciona
miento de la planta piloto fue de aproxi
madamente 22 centavos de dólar por mil
galones, empleando cal como uno de los
regenerantes y la calidad del agua promedió
entre 10 y 20 micromhos.
Actualmente se está construyendo una
planta de modesta envergadura, basada en
en proceso descrito, para el tratamiento de
agua salobre destinada a ser utilizada por
una planta de energía eléctrica.
 Survey of Water
Israel
I. Vilentchuk
GENERAL INFORMATION
The State of Israel lies between the lati
tudes of 29°30' and S3" 15' north, its total
area being 21,000 sq km (about 8,000 sq
miles). Its total border is 1,215 km (770
miles) long, 190 km (120 miles) of which
is formed by the Mediterranean. Israel's
total population was, at the end of 1963,
2.430,000. (In 1948, the year in which Israel
became a sovereign state, the total popu
lation was 915,000. Almost 75 per cent of
the population is concentrated along the
Mediterranean coastal plain where the
largest towns are located. The citrus planta
tions, as well as the country's main indus
trial plants, are also situated in this area.
The climate in the northern part of the
country is characteristic of the eastern
Mediterranean region, whereas the southern
part—comprising the area known as the
Negev and the Arava—is for the most part
an arid desert region. This represents over
half the total area of the country and
tapers off at its southern extremity to an
11 -km (7 -mile) point at the Gulf of Akaba.
The Red Sea port town of Eilat is located
here.
WATER SUPPLY
The total fresh water resources of Israel
are estimated at about 1,500 million eu m
(330 billion gals) per year. It is expected
that these resources will be fully developed
by the early 'seventies. About 55 per cent
of these resources is groundwater (wells
and springs) , 31 per cent Jordan River
basin, 5 per cent intermittent floods (irreg
ular flow during a few winter rainstorms) ,
and 9 per cent reclaimed sewage effluent.
Development of the last two of these
Desalination in
Rainfall decreases from north to south.
In the north it is about 20 inches on the
Mediterranean coast, increasing to 24 to 30
inches in the mountainous region to the
east; further south, the rainfall diminishes
to about 8 inches in Beersheba, which lies
at the northern border of the Negev, and
declines to li/£ to 2 inches in the southern
Arava and Eilat. Rainfall occurs only dur
ing the winter months (November to Feb
ruary) , and the variations between dry and
wet years are considerable. The relative
geographical distribution of water resources
and water demand is extremely unfavor
able; whereas about two-thirds of the avail
able water resources are to be found in the
north, the greater part of the irrigated and
irrigable land, as well as a considerable
part of the industrial and municipal con
sumption, lies in the central part of the
country. The additional agricultural devel
opment of land in the nothern Negev
planned for the future will further aggra
vate the situation.
sources is still in its beginnings.
During the period 1963-64, the total
water consumption in Israel was 1,290
million eu m, which represents 85 per cent
of the total fresh water resources. As the
national water carrier (diversion of Jordan
River) with its proposed 320 million eu m
per year supply was not then in operation,
the deficits created by water demand dur
ing 1963-64, as well as during preceding
years, were covered by temporary over
pumping from wells, primarily in the gradually discontinued before 1970.
coastal area. To prevent lowering of the The increase in water consumption dur
water table beyond the planned safe levels, ing the years 1948-63 may be seen from
the temporary overdraft will have to be the following table.

TABLE XVIII. Increase in Water Consumption from 1948 to 1963

(Million eu m per year)
1954-56» 1966-57 1958-69 1960-61 1962-68 1963-64
Agriculture 760 830 990 1,150 1,160 1,040
Municipal and
industrial 200 280 240 250 280 260
Total 960 1,060 1,280 1,400 1,430 1,290
* In the present report, wherever a year is designated by two figures, e.g., 1964-55, it denotes the
fiscal year beginning April 1st and ending March 31st of the following year. This division coincides
closely with the agricultural year.
Administrative measures, including the age reservoir in lieu of the originally pro
adoption of an appropriate pricing policy, posed diversion of the upper Jordan. The
have been taken to arrest the growing con salinity of Lake Tiberias is relatively high
sumption of water because of several con (1,000 ppm tds of which chloride ions
secutive years of severe drought. These account for about 365 ppm) , owing to the
measures have been supplemented by an discharge of a number of saline springs
educational campaign through press and rising along the shores and at the bottom
radio. of the lake. A number of remedial works
It is difficult to forecast the water con are under construction or have been pro
sumption of agriculture since this depends posed for early execution; these are de
on the quality and the cost of water. Tak signed to gradually reduce the salinity of
ing into account the municipal and indus the lake's water.
trial demand for water for the rapidly It is proposed that most of the projects
growing population and the agricultural for the reclamation of sewage—regarded as
water demand primarily for the existing part of the national water resources (9
citrus and other plantations, the anticipated per cent) —should operate on the principle
rise in general water demand in Israel will of discharging the treated effluent into the
be as follows: aquifer and subsequently withdrawing it
from the underground storage by means of
TABLE XIX. Anticipated Water shallow wells. The sewage effluents have a
Consumption tds about 200 ppm higher than that of the
incoming water; consequently, this form of
Million eu m sewage utilization will gradually raise the
Fiscal year per year Population salinity of the underground resources in
the coastal plain.
1963-64 1,290 2.480,000 The country's most important source of
••1970-71 1,415 8,020,000
••1976-76 1.670 water—the aquifer in the coastal plain—is
••1980-81 1,900 undergoing a process of constant increase
of its mineral content as a result of the
•• Forecast. gradual accumulation of salts accruing from
industrial, municipal, and agricultural use.
A comparison of these figures with the This process of mineralization is further
estimated total safe yield of the total intensified by the diminishing discharge of
natural water resources after their full de water fand salts) into the sea by the aqui
velopment indicates the significant role that fer as a result of its excessive utilization.
desalination must assume in Israel. Almost all the salinity problems reviewed
The anticipated shortage of water from occur in the central and southern parts of
natural resources, especially for agricultural the coastal plain where, out of the total
use, is further aggravated by the excessive supply of 800 million eu m anticipated for
salinity of this water. The chief salinity 1975, about 280 million eu m, which will
problem derives principally from the na be used mainly for agriculture, will contain
tional water carrier project and is due to about 300 ppm of chloride ions. A figure
the selection of Lake Tiberias as the stor of 170 ppm of chloride ions has been pro
visionally adopted as the ceiling for such
salt-sensitive crops as citrus.
In the early "seventies, salinity problems
will become acute and an improvement of
the mineral quality of the irrigation water
will be necessary to prevent a possibly sig
nificant drop in crop yields of the citrus
plantations. It should be noted that citrus
represents the main export item of the
country.
About 125 to 150 million cu m per year
(100 to 125 mgd) of extremely high quality-
converted sea water will thus be required
at that time in order to reduce the chloride
POWER DEVELOPMENT
At present, dual-purpose (power genera
tion with flash evaporation conversion)
plants would seem to offer the most eco
nomical solution. Hence, a brief review of
the power development situation in Israel
is given below.
The Israel Electric Corporation, Ltd.
(I.E.C.) , is the only power utility in the
country, supplying virtually its entire elec
tric energy. Steam turbine power plants are
situated in Haifa (Northern District) , Tel
Aviv (Central District) , and Ashdod
(Southern District) . The total nominal
rating capacity of the system, including two
125 Mw units now under construction in
Haifa, is 965 Mw. Of these, 840 Mw were
installed after March 31, 1954. All the
power plants are situated on the seashore
and use sea water for their condensers. The
supply system consists of an interconnected
grid covering the whole country except,
temporarily, the Eilat region. The main
transmission lines operate at 110 kv, gradu
ally being changed to 150 kv.
According to the forecast of the I.E.C.',
the total annual electric sales will increase
from 2,700 million kwh in 1963-64 to 5,600
million kwh in 1970-71 —a total increase,
of 110 per cent. The sales are about 85
per cent of generation. For the period 197 1—
72 to 1975-76 the forecast is based on an
THE SEA WATER CONVERSION COMMISSION
In 1959 the Government of Israel ap
pointed the Sea Water Conversion Com
mission whose principal function is advising
the Government on the possible expansion
* The I.E.C. prepares an annual sales and de
mand forecast for five to six years based on a
detailed analysis of the expected consumption
pattern of the main consumer groups.
"* Maximum demand as measured at power
plants, including powerhouses' own use.
ion content of irrigation water to the de
sired level of 170 ppm. Incidentally, this
quantity will also be adequate to meet the
water deficit as indicated above. This quan
tity of desalted water required to meet both
the shortage and excess salinity is con
tingent on the cost of conversion.
There is also about 150 million cu m
per year of brackish water containing be
tween 500 to 1,200 ppm of chloride ions,
one-half of which could be utilized for
agriculture, if economic methods of desalt
ing were found.
extrapolation in accordance with the gen
eral trend observed up to 1970-71. The
annual electric generation will, by the end
of this period, reach over 9,000 million
kwh per year. The maximum demand
(MD) will increase from 560 Mw in
1963-64 to 1,110 Mw in 1971-72 and to
about 1,650 Mw by 1975-76. The system
load factor will remain high—over 65 per
cent.
Since the dual-purpose plants can oper
ate most economically at base load, it is
important to note that the base load of
the power system was 27 per cent of MD
in 1963 and is expected to reach about
35 per cent in 1971; it will gradually de
crease to 31 per cent by 1975 and stay at
30 per cent during the following years. The
base load in 1971 would be approximately
20 Mw and would increase by 35 Mw each
year during the following period (1971-80) .
The largest power unit now under con
struction is of 125 Mw nominal rating
capacity. For future extension of the sys
tem up to the year 1975, units of 175 to
200 Mw will be used. Units of 6 Mw to
30 Mw capacity installed before 1953-54
will be used for peak hours and as standby.
Some of them may be subsequently inte
grated with sea water conversion.
of the country's absorptive capacity and the
strengthening of its economy by the aug
mentation of known water resources through
the conversion of sea water. The Commis
sion was also instructed to advise the
Government on efficient methods for achiev
ing the above objective, either independ
ently or in conjunction with electric power.
The water situation in the country is
 periodically reviewed by the Commission
on the basis of reports presented by govern
ment and public agencies. It also keeps
abreast of the technological development of
saline water conversion in Israel and else
where. The Commission reports periodically
to the Government on related questions
and submits its recommendations.
In the course of its activities, the Com
mission advised the Government to erect
a dual-purpose plant in Eilat which, while
serving the needs of the town, would func
U.S.-ISRAEL JOINT SEA WATER DESALTING PROJECT
A project at present under consideration
is a 175 to 200 Mw salable electric power
unit integrated with a conversion plant
(most probably using multistage flash type
evaporators) of 375,000 to 475,000 cu m
per day (about 100 to 125 mgd) capacity
to be put into operation by 1971-72.
This scheme has been studied by a Joint
U.S.- Israel Desalting and Power Team. A
preliminary report was submitted in Octo
ber 1964. Two alternative sources of heat
had been examined: (1) a boiler fired by
fossil fuel and (2) a nuclear reactor. The
plant would be designed for base load
operation of water and power and would
use a back pressure steam turbine. A pre
liminary analysis indicates that a nuclear
heat source would produce the quantities
of water considered in this project at lower
cost than a fossil -fired heat source. How
ever, the cost of water converted by heat
from a nuclear reactor has now shown a
striking difference and depends on the
capital charges. The cost of generated
power has been taken at 5.3 (dollar) mills
—which, according to the Israel Electric
Corporation, will equal the cost of the
large power units to be erected by the
I.E.C. in the early 'seventies.
The reactor considered by the joint team
would be rated at 1200 to 1,300 Mw ther
mal, which is larger than any power reactor
now operating in the United States but of
a type and size now being constructed by
electric utilities.
A multistage flash type conversion plant
of the proposed capacities would, however,
be many times larger than any plant in
operation elsewhere and the risk factors—
reliability, cost, and performance—appear
to be high.
A Consulting Engineer appointed by a
Joint Board (the latter nominated by both
governments) is now preparing a feasibility
study of the project. The question of the
tion as a demonstration plant in connection
with future plans for large-scale water con
version in Israel. It was upon this recom
mendation that the Government allocated
the funds for the clectrodialysis demonstra
tion plant at the settlement of T'zeelim.
The Commission has systematically dis
seminated information on sea and brackish
water conversion development among in
terested circles in Israel. It has also accu
mulated an extensive library.
heat source—fossil or nuclear fuel—will be
one of many problems to be studied by the
Consulting Engineer whose report is ex
pected to be submitted by December 1965.
In an interim report to be ready by July
1965, the Consulting Engineer will make
his recommendations with regard to the
development program which will precede
the actual design of the conversion plant.
According to the preliminary schedule
adopted by the Joint Board, the plant
should be operating at full capacity by
April 1972. This timetable provides for a
certain lag of intensive technological devel
opment of the conversion plant with regard
to unit sizes, temperatures, materials, scal
ing control, and constructional details,
which will be undertaken upon the recom
mendation of the Consulting Engineer.
This development work will be conducted
in coordination with the Office of Saline
Water, U.S. Department of the Interior.
A paper on this subject is being pre
sented to this Symposium.
Taking into account that only relatively
small conversion units (up to 1.7 mgd)
have hitherto been built elsewhere, the
Israel Sea Water Conversion Commission
considers the construction of an intermedi
ate size prototype unit extremely important.
All the converted water will be used in
the coastal plain and consequently the
cross-country water delivery will be rela
tively inexpensive. The existing country
wide water supply system forms, to all
intents and purposes, an interconnected
water grid. The latter, together with the
countrywide power grid, considerably sim
plifies the selection of the sites for the
integrated power and water conversion
plants. The base load of the power system,
which is and will remain a considerable
part of the maximum demand, creates fa
vorable operating conditions for integrated
plants.
 CONVERSION OF SEA WATER—WATER SUPPLY FOR TOWN OF EILAT
The town of Eilat is situated in the the town until 1968. As a result of the
southernmost part of the country on the admixing, the chloride ion and Fluor con
Gulf of Akaba (Red Sea) . In the summer tents will be reduced to a lower ratio than
the maximum temperature is higher than those stipulated by the Ministry of Health.
40°C (104°F) , and the lowest mean relative The sulfate content, however, will remain
humidity is about 25 per cent. Water con higher during a considerable part of the
sumption is relatively high, mainly because year.
of the widespread use of desert coolers.
The maximum daily consumption in 1964, EILAT CONVERSION PLANTS
for a population of over 11,000, was about 1. Dual-Purpose Plant. This plant was
9.000 cu m. The estimated maximum con started in April 1965 and is now under
sumption for 1967—68 is 14,500 cu m. going the acceptance tests.
At present, the town's water comes from Data on the Flash Type Evaporation Unit
wells situated about 45 km (28 miles) to
the north. The water is of inferior quality, Net capacity 3,800 cu m per
containing more than 2,300 ppm tds. An day (1 mgd)
excessive amount of water is used to con No. of stages 30
trol scale in the coolers. According to a Performance ratio
1960 study, demineralization of the water (cu m of water per
would cut the amount used in the coolers ton of steam) 8
by half. Top operating
The Israeli health authorities have estab temperature 93°C (200°F)
lished the following stipulatons for Eilat's
drinking water: Concentration factor 1.7*
(1) The chloride ion content must not Guaranteed quality of
exceed 500 ppm (desirable limit) . distillate 25 ppm tds
(2) The yearly average Fluor (F) con Chemicals for scale 2 to 5 ppm of
tent must not exceed 0.8 ppm. control (additional "Hagevap"
(3) The sulfate (SO,) content must not arrangements for
exceed 250 ppm (desirable limit) . periodic acid treat
In 1959, a 40 cu m per day ion-exchange ment)
plant was built. It is now close to its Manufacturers Baldwin-Lima-
maximum capacity; increased water con Hamilton, U.S.A.
sumption would necessitate additional in
vestment (mostly in mains and pumps) . The power plant consists of one 6,000 kw
The quality of the water would not be capacity back pressure steam turbine inte
changed. grated with the conversion plant and three
Eilat has two conversion plants. One is a portable 1,200 kw capacity diesels as a
dual-purpose plant with a flash type evap standby. The latter supplied the power
orator of 3,800 cu m per day capacity (1 until the turbine generator was built.
mgd) ; the other is a vacuum freezing plant Data on the Back Pressure Power Turbine
of 1 ,000 cu m per day (250,000 gpd) . Two boilers at 30 metric tons of steam
The Mekorot Water Company, Ltd., per hour**
which supplies the town's water, has recom Throttle steam pressure 43.2 abs (614 psia)
mended ordering a second flash type evap
oration unit, with approximately the same Back pressure turbine 15 stages; 3,000 rpm
capacity as the first, to be put in operation Exhaust steam to sea water heater 1.02 abs
in the spring of 1968. The recommendation (14.5 psia)
has been endorsed by the Sea Water Con Net salable power:
version Commission. The construction of a First construction stage \ _ .
second conversion unit is included in the 2,170 kw / °Pt,mum
original design of the dual-purpose plant. Second construction stage ( "sage
It is estimated that the increased amount 5,230 kw ) °fsteam
of converted water available from these Manufacturer: International General Elec
two plants will meet the requirements of tric. U.S.A.
• The sea water at Eilat baa 41.500 tds. For flow chart and heat balance diagram
" The third boiler of about the same capacity of the integrated plant, see Appendix A.
will be erected together with the second conversion The conversion plant is jointly owned by
unit. One of the three boilers will serve as a
the Israel Electric Corporation, Ltd. and
the Mekorot Water Company, Ltd. (The
major part of their equity is owned by the
government.) The water company will be
responsible for the converted water. The
fixed charges and operating costs of con
verting water will be calculated on the
basis of marginal expenses as compared
with those of an independent power plant
of similar capacity with a full condensing
turbine. The costs will be determined in
the near future. The plant includes ar
rangements for taking steam from the
boiler through a pressure reducing valve
for conversion in case of an outage of the
turbine and for using one of the two sea
water heaters as a dump condenser in case
of an outage of the distillation unit.
A general view of the plant and the sea
water conversion unit will be found in
Appendix B.
The plant will not only improve the
water supply of the town but also serve as
a demonstration plant for the current study
of large flash type conversion plants and
help train personnel. A research program
for the plant has been worked out. Last
year, the owners delegated three men to
visit several conversion plants on islands in
the Caribbean and gather information on
the operation and maintenance of flash
type evaporators.
It has also been considered advisable to
use the second conversion unit as much as
CONVERSION OF BRACKIS
A well containing brackish water at the
agricultural settlement of T'zeelim in the
Negev yields about 80 eu m per hour
(350 gpm) , the water level being 120
meters. The water is highly mineralized,
containing about 2,400 ppm tds. An electro-
dialysis plant of 500 eu m per dav (125.000
gpd) capacity is at present being erected
and will be commissioned during June
1965. The plant was designed and the
stacks constructed by the F.lectrodialvsis
Research Laboratory of the Negev Institute
for Arid Zone Research at Beersheba.
The product water will contain about
500 ppm tds. The reject water will contain
about 10,000 ppm and amounts to 20 per
cent of the feed; it will be discharged for
evaporation into an open, shallow earth
reservoir covering an area of about 10
dunams (2.5 acres) .
The plant consists of three desalination
stages in series in a single closing frame,
with the possibility of adding a fourth
stage. Each stage contains 100 membrane
pairs of 1.0 m by 0.6 m. The membranes
possible without impairing safe operation
to test advances in distillation technology
which may be beneficial in implementing
the larger Joint Israeli-United States De
salting Project now under study.
2. Vacuum Freezing Plant (Zarchin
Process). The desalination plant at Eilat,
employing the vacuum freezing vapor com
pression process, was commissioned at the
beginning of 1964. This was the first field
plant of its kind to be erected anywhere in
the world. A prototype test unit has been
in operation at Beloit, Wisconsin, since
1962.
Various improvements and modifications
have been made in the operation of these
units to improve efficiency, production, and
stability of operation.
The Eilat plant consists of four desalina
tion modules, each nominally rated at 250
eu m per day (65,000 gpd) . Power con-
sumplion for the nominal production rate
was initially 22 kwh per eu m (85 kwh/
1 ,000 gals) .
The Eilat plant, as well as the Beloit
unit, was developed and is owned and
operated by Desalination Plants (Developers
of Zarchin Process) , Ltd., of Tel Aviv, a
joint venture of the Government of Israel
and Colt Industries (formerly Fairbanks
Whitney Corp.) .
A paper on this plant is being sub
milted to this Symposium.
WATER—T'ZEELIM PLANT
for the stacks came from various makers
and were, in part, manufactured at the
laboratory.
A full report on the T'zeelim plant is
given in a special paper presented to this
Symposium.
The Beersheba Laboratory is at present
cooperating with the Mekorot Water Com
pany on the design of a plant of 4,800 eu m
per day (1.25 mgd) for another Negev
settlement, Mashabei Sadeh, whose brackish
water contains about 2,500 ppm tds. This
is to be reduced to about 500 ppm. The
decision with regard to the erection of the
Mashabei Sadeh plant has been deferred
pending the results of the operation of the
T'zeelim plant.
It is believed that within the next decade
Israel's industry will prove capable of
undertaking the construction of electro-
dialysis plants for the demineralization of
some 75 million eu m per year (about
60 mgd) of brackish water, a quantity
which is considered worthwhile for desalting.
 RESEARCH IN SALINE WATER CONVERSION
The upsurge of interest in the problems
of saline water conversion in Israel has led
to the intensification of research and devel
opment work. This research is being con
ducted at the Negev Institute for Arid Zone
Research in Beersheba, at the Technion
(Israel Institute of Technology) in Haifa,
at the laboratories of Desalination Plants
(Developers of Zarchin Process) , Ltd. at
Tel Baruch (in the vicinity of Tel Aviv) ,
at the Weizmann Institute of Science in
Rehovot, at the Hebrew University in
Jerusalem, and at the Petach-Tikvah pilot
plant iOsdor's process) . Measures have
recently been taken toward closer coordina
tion in research among all these institu
tions. Part of the research work deals with
specific problems that have arisen in the
course of the construction of conversion
units (freezing method and electrodialysis) .
The remainder represents general research
in various fields of saline water conversion.
A brief description of some of the re
search work being carried out in the above-
mentioned institutions follows.
ELECTRODIALYSIS
Research work in electrodialysis is being
carried out at the Electrodialysis Research
Laboratory of the Negev Institute for Arid
Zone Research.
1. Work has been proceeding on polari
zation phenomena and the electrical resist
ance components associated with them.
This has necessitated some fundamental
research on the construction and function
of the membrane. Research is being done
on microstructure of permselective mem
branes by electron micrography and X-ray
diffraction in order to gain an insight into
the microporous structure of permselective
membranes. Preliminary experiments have
shown that, under certain conditions, it is
possible to introduce a silver deposit into
the porous structure of membranes and in
this way obtain a better picture of its
internal structure. This research was sug
gested by Dr. F. de Korosy, a member of
the laboratory staff. The Office of Saline
Water has awarded a $15,500 contract for
this research.
2. The preliminary work carried out
during 1963 showed that a considerable
saving in power can be achieved when the
process is carried out at a temperature
above 80°C. The Office of Saline Water
has awarded the Negev Institute a $37,000
contract for this research. The work is
directed toward the determination of mem
brane characteristics and the development
of suitable membranes. This research was
suggested by Mr. Г.. Forgash, a member of
the laboratory staff. A paper dealing with
this research is being submitted to this
Symposium.
HEAT AND MASS TRANSFER PROBLEMS
The research workers of the Department
of Chemical Engineering of the Technion
have paid considerable attention to heat
transfer problems and scaling in the distil
lation and freezing processes.
1. The object of the research conducted
by Dr. S. Sideman and his associates was
to study the basic phenomena associated
with the problem of direct contact heat
transfer between two immiscible fluids.
Heat transfer coefficients, as well as other
data, have been determined for conditions
both with and without change of phase.
The study was inspired by the freezing
process. Theoretical and empirical corre
lations have been suggested, broadening the
scope of the study for any temperature
level.
Studies of a single organic drop (such as
butane and pentane) evaporating in sea
water showed the heat transfer coefficient
to be larger by at least one order of mag
nitude than that for noncvaporating drops.
Studies of condensing vapors indicated simi
larity to the mechanism of transfer to the
evaporating drops.
The behavior of populations of drops
evaporating in a spray column in counter-
current flow was found to be different from
that of a single drop. The temperature
driving force between the two fluids and
the volatile phase flow rate were found to
be the controlling factors.
In another study, the effect of mechanical
mixing on the transfer characteristics of a
volatile liquid evaporating in contact with
another immiscible liquid was investigated.
A general correlation relating to power
input, temperature driving force between
the two fluids, and heat flow rates was
derived. Experimental data with a pentane-
water system confirmed the validity of this
correlation. Data from a pilot plant oper
ated by Desalination Plants (Developers of
Zarchin Process), Ltd. also confirmed the
correlation.
2. The work of Dr. E. Kehat and Mrs. R.
Letan indicated the uniqueness of mechan
ism of heal transfer in a spray column
operated as a heat exchanger between two
immiscible liquids, such as kerosene and
 water. These features are important for
proper scale-up.
Two modes of operation of a spray
column are possible: (I) dense packing
and (2) dispersed packing. Dense packing
is broken up when the coalescence rate is
increased at the kerosene-water interface as
Kerosene
Inlet
Water
Outlet
Bottom
Length of Spray Column
FIGURE 31. TEMPERATURE PROFILES IN A SPRAY COLUMN
HEAT EXCHANGER (DISPERSED PACKING).
The use of overall heat transfer coeffi
cients will, therefore, lead to poor scale-up
of laboratory data, particularly for dis
persed packing. It is preferable to operate
the column with dense packing, and drain
age of the interface will be required.
The optimum ratio of the flow rates of
kerosene to those of water required for
the establishment of full dense packing in
the column may not be the desired ratio
of flow rates for heat balance. Additional
work is required to study the conditions
for optimum operation and scale-up of
heat exchange spray columns.
3. Heat transfer in the direct contact
condensation of steam on a water jet has
been studied by Dr. D. Hasson and his
associates. This method of condensation is
particularly important for the "vapor re
heat flash process", which is based entirely
on the principle of direct contact heat
transfer between water vapor and water jets.
Theoretical analyses of steam condensa
tion on various types of jets have been
01
a result of accumulated scale at the
interface.
A temperature jump observed at the
water inlet for dispersed packing prevents
close approach of the temperatures of the
two liquids at the top of the column
(Fig. 31) .
Kerosene
Outlet
Water
Inlet
Top
carried out, with the assumption that the
system is free of air contamination. The
validity of these analyses has been con
firmed by experimental data, under condi
tions of airfree steam and water.
Experimental results show that, under
normal water supply conditions, i.e. tap
water containing about 100 cm* free air
per liter of water but without air in the
steam, the local Nu (Nusselt Number) and,
consequently, the heat transfer coefficient,
are half of the theoretical value calculated
above.
A correlation was obtained on the reduc
tion in the heat transfer coefficient with
increasing air content of steam with normal
tap water. This was measured at steam
pressures 133 Hg and 850 Hg, which pro
duced very similar results. The correlation
Nu, — 4.8e-°•«•
c = % vol. air in steam,
so by 1 per cent of air the Nu. will de
crease by 2.
4. Dr. D. Hasson and Dr. W. Resnik
95
96
have studied the mechanism of scale dep
osition on heat transfer surfaces.
The object of this research is to elucidate
basic scaling mechanisms and determine
quantitative relationships for predicting
rates of scale deposition. So far, work has
been restricted to nonboiling conditions
under which CaCO, scale is deposited.
A practical method has been developed
for correlating the variations of thermal
resistance with time in steam heat
exchangers.
A fundamental analysis of processes tak
ing part in scale deposition has been
proposed and the rates of some of these
processes have been determined.
A noteworthy achievement is the devel
opment of a constant heat flux electrical
exchanger for scale investigations.
5. Within the Department of Aeronau
tical Engineering of the Haifa Technion,
Professor A. Kogan is experimenting with
a single-stage direct contact evaporation-
condensation unit. The influence of stage
geometry and inert gas content upon per
formance is being investigated. A paper on
this subject has been submitted to this
Symposium.
OTHER RESEARCH WORK
1. Professor A. Katchalsky of the Weiz-
mann Institute of Science and Dr. Margaret
Wickson Ginzburg and Dr. B. Z. Ginzburg
COORDINATION OF RESEARCH ACTIVITY
Following the recommendations of the
Joint U.S.-Israel Desalting and Power Team
on coordination between the development
programs of the Governments of the United
States and Israel, the Israel National
Council for Research and Development is
actively engaged in the preparation of a
comprehensive coordinated research pro
gram. It is estimated that about fifty sci
entists in the institutions of higher learning
and research institutions of Israel are pre
pared to work in the field of saline water
conversion. Such a group of research
workers will require a yearly expenditure
of SI,000,000, as compared with the $150,000
being spent on conversion research during
the current year.
In view of the fact that Israel still lacks
SUMMARY OF DISCUSSION
In response to questions concerning the
solar ponds being worked on at Beersheba
and the progress being made in solving
of the Hebrew University in Jerusalem are
studying the ion transport in Dead Sea
bacteria as a possible means of biological
desalination. This study is being carried
out under a contract with the Office of
Saline Water. A paper on this subject is
being submitted to this Symposium.
2. A study sponsored by the Interna
tional Atomic Energy Agency (Vienna) on
"The Feasibility of Nuclear Reactors for Sea
Water Distillation in Israel" is being con
ducted by Dr. S. Yiftah and Dr. F. S.
Aschner and associates of the Department
of Nuclear Science of the Haifa Technion.
3. A pilot desalination plant for opera
tion in the vicinity of the critical point of
water is at present being erected in the
town of Petach Tikvah. The process has
been suggested by an Israeli engineer, A.
Osdor, and its development is privately
financed. The incoming sea water is heated
and compressed by means of direct contact
heat exchangers and pressure exchangers
respectively. Hydrocarbon and nitrogen gas
are used as heat transfer agents. After
separation at the critical point, the product
steam is further compressed. Consequently,
the raising of the temperature proceeds at
a lower specific heat; the cooling cycle is
effected at a higher pressure than the heat
ing cycle, securing a 10°C temperature dif
ference between the fluids.
industrial enterprises equipped for the
production of such items as large heat
exchangers, large pumps, boilers, etc., it is
expected that research work in the future
will perforce be primarily devoted to more
basic aspects, such as scale deposition, cor
rosion, membrane structure and function.
At Israel's present stage of development,
her scientists can contribute in the fields
of heat and mass transfer and membrane
processes. Work in these fields is being
carried out at the Technion, the Negev
Institute for Arid Zone Research, and the
Weizmann Institute. In time, other institu
tions, such as the universities in Jerusalem
and Tel Aviv, may become active in this
work.
the problem of wind stirring the water and
dirt settling in, it was stated that the
answer would be given by representatives
 bom the Negev Institute.
The question of which process is of in
terest to serve irrigation water purposes
was raised. In answer, it was stated that
rate of interest on money and years of
writeoff on capita! and operating costs
determine the cost of desalinated water,
and that the price of this water, in turn,
is related to these costs and to the value
Aperçu Sur le Dessalement de L'Eau
en Israel
I. Vilentchuk
La consommation de l'eau en Israël ap
proche de 85% de la totalité des ressources
naturelles en eau du pays, si bien qu'après
1970 le pays souffrira d'une pénurie aiguë
d'eau. Une proportion appréciable de ces
ressources sont minéralisées, les rendant
impropres à l'agriculture, à moins d'être
mélangées à de l'eau de qualité très élevée.
Vers 1970, il faudra un appoint d'environ
475.000 m3 par jour d'eau de mer convertie.
Une installation à double usage, produisant
200.000 kW d'énergie et 380.000 m'/jour
d'eau de mer convertie, est actuellement à
l'étude de la part d'une équipe conjointe
Etats-Unis/Israël, se spécialisant dans la
déminéralisation.
Une installation à double usage, de 6.000
kW d'énergie, intégrée avec un ensemble
de conversion du type à évaporâtion instan
tanée de 3.800 m'/jour, a récemment été
construite dans la ville d'Eilat, dans la
partie la plus méridionale d'Israël, ce qui
augmentera les approvisionnements exis
tants en eau saumâtre. Cette installation
est considérée comme une installation de
démonstration dans le cadre de l'important
projet de conversion mentionné ci-dessus.
of the water when put to bénéficiai use.
The speaker stated further that if the
water could be obtained for 7 cents per
eu m (equivalent to about 30 cents per
thousand gallons) , and if the water were of
high quality and blended with brackish
water to improve the quality of the mix
ture for agricultural purposes, this would
be acceptable for agricultural use in Israel.
Une seconde installation d'une capacité
similaire est envisagée pour le début de
1968.
Une installation de congélation sous vide
de 1.000 m*/jour a également été construite
à Eilat. Une installation d'électrodialyse est
en cours de construction dans un kibboutz
du sud et, selon les résultats de son fonc
tionnement, une installation de 4.800 m'/
jour est à l'étude pour une autre commu
nauté agricole dans la même région aride.
Des travaux de recherche sur les diffé
rents aspects du dessalement sont effectués
dans les hautes écoles et dans des labora
toires spéciaux en Israël. Il convient de
noter tout particulièrement les travaux de
recherche portant sur les problèmes de
transfert de chaleur et de masse dans les
procédés de distillation et de congélation
au Technion (Institut de Technologie d'Is
raël à Haifa) , et sur l'électrodialyse à
l'Institut du Neguev pour les recherches sur
la zone aride, à Beersheba. Des mesures
sont prises en vue d'assurer une coordina
tion plus étroite de la recherche effectuée
par toutes ces institutions.
90
 Обзор Опреснения Воды в Израиле
И. Виленчук
Израиль
Потребление воды в Израиле прибли
жается к 85% суммы всех естественных
водных ресурсов страны, так что в на
чале семидесятых годов наступит
острый недостаток воды. Значительная
часть этих ресурсов содержит в себе
минералы, делая их непригодными для
земледелия без смешения с водой
очень высокого качества. В начале се
мидесятых годов потребуется выраба
тывать 125 миллионов талонов опре
сненной морской воды в день. Сейчас
объединенная американо-израильская
группа по опреснению изучает вопрос
постройки завода двойного назначения,
производящего 200 мегаватт электри
ческой энергии и 100 миллионов галло
нов опресненной морской воды в сутки.
Установка двойного назначения на
6.000 киловатт электроэнергии с сов
местным опреснительным агрегатом,
типа мгновенного испарения, на 1 мил
лион галлонов воды в сутки была не
давно построена в городе Эйлате, в
самой южной части Израиля, что уве
личит существующее снабжение соло
новатой водой. Этот завод считается
показательным в связи с вышеупомя
нутой крупной схемой опреснения. В
100
начале 1968 года предполагается по
строить второй агрегат такой же про
изводительности.
В Эйлате была также построена ва
куумная холодильная установка на
250.000 галлонов в сутки. Агрегат на
125.000 галлонов в сутки строится в
одном южном поселке, а по выяснении
его эксплуатационных качеств намеча
ется постройка завода на 1,25 миллиона
галлонов в день для другого земледель
ческого поселка в том же пустынном
районе.
В высших учебных заведениях и спе
циальных лабораториях Израиля иссле
дуются различные вопросы, касающие
ся опреснения. Заслуживает особого
внимания исследование проблем пере
носа тепла и вещества при процессах
дистилляции и замораживания, которое
ведется в Технионе — Израильском
Технологическом институте в Хайфе, и
электродиализа — в Негевском инсти
туте по исследованию пустынной зоны
в Беершебе. Принимаются меры для
большего координирования исследова
тельской работы всех этих учрежде
ний.
 Estudio Sobre la
Agua en Israel
I. Vilentchuk
Israel
El consumo de agua en Israel está aproxi
mándose al 85% de los recursos totales
de agua en el pais, de tal modo que para
los primeros años de la década de 1970 se
experimentará una gran escasez de agua.
Una proporción considerable de estos re
cursos contienen minerales, lo que los hace
no aptos para la agricultura, a menos que
se mezclan con agua de buena calidad. Una
cantidad aproximada de 125 millones de
galones por día de agua de mar desalini-
zada será necesaria para los primeros años
de la década de 1970. Una planta de doble
fin, con capacidad de 200 megavatios de
energía y 1O0 millones de galones diarios
de agua de mar desalinizada, está en la
actualidad bajo la consideración de un
grupo de trabajo conjunto de Israel y
Estados Unidos sobre desalinización.
Una planta de doble fin de 6.00kw de
energía integrada con una unidad de con
versión de tipo instantáneo de 1 millón de
galones por día fue construida reciente
mente en la ciudad de Eilat en la región
más meridional de Israel que aumentará
el suministro existente de aguas salobres.
Esta planta se considera como una planta
de demostración en relación con el proyecto
extenso de conversión mencionado anterior
Desalinizacion del
mente. Se contempla una segunda unidad
de una capacidad casi igual para principios
de 1968.
También se ha construido en Eilat una
planta congeladora al vacío de 250.000 ga
lones diarios. Está en construcción en una
colonia en al sur una planta de electro-
diálisis de 125.000 galones diarios y, pen
diente de los resultados de su operación,
se está contemplando la construcción de
una planta de 1.250.000 galones diarios
para otra colonia agrícola ubicada en la
misma región árida.
Se están llevando a cabo trabajos de
investigación sobre los diferentes aspectos
de la desalinización en las instituciones de
enseñanza superior y en laboratorios espe
ciales de Israel. De especial importancia
son los trabajos de investigación sobre los
problemas de la transferencia del calor y
de la masa en los procesos de destilación
y congelación en el Instituto Tecnológico
Technion-Israel de Haifa, y sobre electro-
diálisis en el Instituto Negev de Investiga
ciones para Regiones Aridas en Beershcba.
Se están tomando medidas para una co
ordinación más estrecha de las actividades
de investigación entre todas estas institu
ciones.
101
 The "Siro therm" Demineralization

Process — An Ion-Exchange Process

With Thermal Regeneration

D. E. Weiss, B. A. Boko, R. McNeill, A. S. M acpherson,

R. Siudak, E. A. Swinton, and D. Willis

Australia

INTRODUCTION
Although the technology of water de-
mineralization is the subject of research
effort today, there is little evidence that
much thought has been given to the inte
gration of municipal demineralization
processes with other sources of water sup
ply to achieve minimum overall costs. We
have suggested elsewhere (ref. 1) that effi
cient integration of surface and under
ground water supplies, coupled with the
use of a demineralization plant to provide
a salt bleed from the supply system, pro
vides a realistic approach to preventing
the accumulation of salinity within water
supply systems considered on a regional,
rather than on a local basis.
The need for a salt bleed in arid regions
when complete utilization of water supplies
is in sight is well illustrated in a recent
report on the water supply situation in
Israel (ref. 2) . An almost completely closed
cycle of water use will occur in Israel by
1975 and means will then have to be found
for removing salt from the supply system
economically. As a result of accumulating
salinity, there will be available by 1970 a
daily flow of 200 million gallons of water
with an average salinity of 500 ppm (as
NaCl) , which will have to be reduced to
250 ppm to maintain the quality required
for growing high value export crops. An
investigation is now being made of the
feasibility of using sea water desalination
to provide distilled water for dilution of
the flow to the desired value by 1972.
Although political considerations and fu
ture long-term needs undoubtedly influence
the selection of the sea as an immediate
source of water, the fact that removal of
35.000 ppm of salinity by distillation can
be considered to compete with the removal
of 250 ppm of salts by alternative methods,
highlights the deficiencies of the latter, and
the lack of attention that the problem of
maintaining a salinity balance in water
supply schemes has hitherto received.
With processes such as ion-exchange and
electrodialysis, it is possible to remove
small amounts of salinity more cheaply
than large amounts, but the removal of
small amounts of salinity is currently re
ceiving comparatively little attention com
pared with sea water conversion. Priority
should be given to the development of
cheap methods for preventing excessive
pollution of existing water supplies by in
organic salts. Such methods are more likely
to achieve a treatment cost of about ten
cents per thousand gallons, and are more
urgently needed than the conversion of
heavily polluted resources such as sea
water. This paper presents a new approach
to the problem of salinity control and
demonstrates the feasibility, in the labora
tory, of using ion-exchange resins for de
mineralization by the "Sirotherm" process*,
in which regeneration of the spent resins
is performed with heat rather than chemi
cals. The work to date has been confined
mainly to equilibrium studies.
* Patent applications have been submitted in the
United States of America and in other countries.

103
 A SYSTEM OF WATER MANAGEMENT FOR CONTROLLING THE SALINITY
OF MUNICIPAL SUPPLIES ON A REGIONAL BASIS
Since incremental municipal water sup
plies become increasingly expensive and
quality deteriorates owing to extensive re
use, there arc four logical, successive stages
of water management for reducing costs:
1. Improvement of conservation methods;
2. Reclamation of effluents for reuse;
3. Demineralization of waters of mar
ginal quality which are too saline for
general use;
4. Once water is efficiently utilized, use
must be made of expensive supplies
from long-distance pipelines or from
desalination of the sea or highly
brackish waters.
Inorganic salts accumulate when river
water is reused extensively in an arid
climate. Consideration of the factors con
tributing to the salinity* of rivers shows
that the contributions from man's use of
the water, particularly for irrigation, is of
ten much greater than those from natural
THE "SIROTHERM" PROCESS
The purpose of the "Sirotherm" project
is to develop a demineralization process in
which regeneration of ion-exchange resins
is accomplished by the use of low grade
heat rather than by chemicals. The process
depends on the marked influence of temper
ature on the equilibrium between a solu
tion of sodium chloride and a mixed bed
of weak base (Rb) and weak acid (RaH)
ion-exchange resins:
R.H + Rb + NaCl ;± R.Na + R„HC1 (1)
Heating promotes hydrolysis of the resin
salts and thereby reduces the adsorption
of salt.
The equilibrium depends on many varia
bles besides temperature, such as the basicity
and acidity of the resins, pH value and
ionic strength of the solution, resin affin
ities for different ions, and the ratio of
equivalents of acid to base resin (resin
ratio) . The basicity and acidity of the
resins can be varied widely by changes in
polymer structure.
The first problem in the "Sirotherm"
project was the selection of the optimum
* In this paper, salinity refers to the total
amount of dissolved inorganic solids in a water.
104
phenomena (ref. 1) . Regional salinity con
trol requires the segregation of irrigation
drainage waters from the river, and a cheap
demineralization process for taking out the
salinity which accumulates with each mu
nicipal or industrial use cycle from supplies
derived from the river. If demineralization
were applied to nearby underground waters,
as shown in Figure 32, space would be
created which could be recharged with
surplus waters of good quality in wet
periods, and the demineralization load
would be thereby reduced (ref. 1) .
The use of demineralization for salinity
control warrants widespread attention, as
it would make possible complete utilization
of existing river supplies. Fundamental
considerations suggest that the cheapest
process for this purpose would use ion-
exchange resins regenerated with heat
rather than chemicals (ref. 1) . Our investi
gation of this approach is presented below.
resin pair and the optimum conditions of
pH and resin ratio, but this problem is
of unusual complexity, and is not suitable
for direct empirical experimentation owing
to the large number of resin pairs and
variables requiring study. A rapid scanning
procedure was therefore devised to select
the systems for detailed study.
It will be shown that the titration
curves of weak-acid and weak-base resins
provide a means of independent charac
terization which enables us to predict the
equilibrium behavior of a mixture of the
resins under many different conditions. As
a prelude to the scanning program, it was
necessary to synthesize a large number of
ion-exchange resins, as the structure of
commercial resins is not usually disclosed
by the manufacturers, and to study the
titration curves of the experimental and
commercial resins in detail. Detailed exam
ination of a pair of commercial resins,
selected on the basis of this information,
shows that the equilibrium changes on
heating are of a magnitude sufficient for
performing useful demineralization oper
ations.
tii

a.
t/J

Z
s
Q
W
H

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a:
O
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o
u,
Mi
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105
 PROPERTIES OF WEAK-BASE RESINS
Our experimental study of the properties
of weak-base resins, which will be presented
elsewhere (ref. 3) , shows that satisfactory
commercial resins* are available for use in
the "Sirotherm" project. Therefore this
paper will be concerned mainly with the
commercial resins.
(1) Homofunctional Resins: Titration
* The following registered trademarks are used
by ion-exchange resin manufacturers: "Amber-
lite", the Rohm and Haas Company, U.S.A.;
"Dowex", the Dow Chemical Company, U.S.A.:
"Duolite", the Western Division of Diamond
Alkali, U.S.A.; "Zeo-Karb" and "De-Acidite",
the Permutit Company, Ltd., London; "Lewatit",
the Farbenfabriken Bayer, A.G., West Germany.
curves of a number of resins are presented
in Figures 33 and 34 and show two types
of behavior. Two resins, "De-Acidite G"
and "Amberlite IRA-93", have titration
curves with a pronounced plateau region
of almost constant pH value, whereas the
curves for the other resins slope steeply,
but to different extents. The plateau be
havior occurs only with resins containing
functional groups having predominantly
the same basicity (ref. 3) . The latter resins
will be termed "homofunctional" whereas
resins with sites of different basicity will
be termed "heterofunctional".

pH

0 Acid Fraction 1

FIGURE 33. TITRATION CURVES OF AMINE RESINS IN

29,300 PPM SALINE AT ABOUT 20°C.
1. "De-Acidite J" S. "De-Acidite G"
2. "De-Acidite M" 4. "De-Acidite H"

106
 о I
Acid Fraction
FIGURE 34. TITRATION CURVES OF AMINE RESINS IN
29,300 PPM SALINE AT ABOUT 20°C.
1. Dowex 3" 5. "Ambcrlite IRA-9S"
2. "Dowex 4" 6. "Duolite A-30T"
3. "Amberlite IRA-45" 7. "Lewatit MP-60"
4. "Amberlite IRА 6И"

The commercial weak-base homofunc
tional resins contain mainly tertiary amino
groups but the presence of some quater
nary ammonium groups is unavoidable.
The titration curve of a special sample of
"De-Acidite C" containing 26 per cent of
its functional groups as quaternary am
monium centers given in Figure 35 shows
the resin to be heterofunctional. Heating
the resin with alkali dealkylates the quater
nary structures and yields a tertiary amine
resin with homofunctional properties (Fig.
35).
(2) Effect of Temperature: Titration
curves were prepared at 80°C for the resins
shown in Figures 33 and 34, the pH values
recorded being those of the supernatant
solutions, which were removed from the
resins while hot and cooled to about 20T.
before measurement. The data on hot titra
tion curves at acid fractions of 0.25, 0.50,
and 0.75 are shown in Table XX as the
difference- in pH value between the titra
tion curves at about 20°C and S0°C. The
data show that heating reduces the basicin
of the resins and that homofunctional resins
exhibit greater temperature effects over the
widest range of acid fraction. This is also
illustrated by the data in Figure 35.

107
 0 Acid Fraction 1
FIGURE 35. TITRATION CURVES OF AMINE RESINS IN
1,760 PPM SALINE AT ABOUT 20° AND 80°C.
1. "De-Acidite G," containing 26 per cent quaternary ammonium groups. The titration
curve was determined at about 20° C
2. Same at 80°C.
3. The above resin was treated with boiling 2N alkali for 48 hrs. to yield a resin
containing 5.5 per cent quaternary ammonium groups. The titration curve was
obtained at about 20°C.
4. Same at 80°C.
 TABLE XX. Difference in pH Valves for (3) Effect of Resin Structure and Ionic
the Titration Curves of Various Com Strength: A study of experimental homo-
mercial Resins in a 29,000 ppm Solution functional tertiary resins prepared from
of Sodium Chloride at about 20°C and crosslinked polystyrene beads showed that
Mr*C the pH value of the plateau may be varied
by three pH units by changing the alkyl
pH differe substituents on the amino nitrogen atoms.
Add fnotion The basicity and also the total exchange
Rata capacity of the resins increase with decreas
0.25 0.60 0.75 ing chain length of the alkyl substituents
so that the basic resins requiring further
Homofunctional resins: study may be limited to dimethyl, diethyl,
"De-Acidite G" 1.1 1.2 1.0 or monoethyl derivatives (ref. S) . The
"Amberlite IRA-98" 0.9 1.0 1.2 titration curve of an experimental dimethyl
Hcterofunctional resins: resin is very similar to that of "Amberlite
"De-Acidite M" O.S 0.5 0.7 IRA-93", and a diethyl tertiary amine resin
"De-Acidite J" 0.4 0.4 1.0 is available as "De-Acidite G".
"De-Acidite H" 0.7 0.7 0.6 Crosslinking does not have a great influ
"Amberlite IRA-46" 0.8 0.6 0.0 ence on the basicity of the resins (ref. 3) .
••Amberlite IRA-68" 0.1 -0.1 -0.2
"Dowel S" 0.5 0.8 0.2 Increasing the ionic strength of the solu
"Dowex 4" 0.8 1.0 0.8 tion in equilibrium with the resins has a
"Duolite A-SOT" 0.1 0.8 0.4 pronounced base-strengthening effect but
"Lewatit MP-60" 0.5 0.2 -0.4 does not greatly change the shape of the
titration curves (ref. S) .

PROPERTIES OF CARBOXYLIC RESINS

Available carboxylic resins with satis
factory thermal stabilities are limited to
polymers or copolymers of acrylic or meth-
acrylic acids. As shown in Figure 36, the
hot and cold titration curves of the poly
(methacrylic acid) resin, "Amberlite IRC-
50", differ by about one pH unit from
those of the poly (acrylic acid) resin, "Zeo-
Karb 226"*. A change in acidity of com
parable magnitude can also be made by
changing the crosslinking of the resin (refs.
4, 5) , but in practice resins with low cross-
linking must be used to obtain satisfactory
exchange rates. As shown in Figure 36, the
titration curves of the carboxylic resins do
not show a pronounced plateau, even
though the acidity of the resins is due
solely to carboxyl groups; while the acidity
• The titration curve of "Amberlite XE 282" ia
very similar to that of "Zeo-Karb 226".
decreases with temperature, the thermal
variation is not as marked as for the amine
resins. Calcium and magnesium ions exert
a much greater acid-strengthening effect on
the titration curve than do sodium ions,
probably because of chelation with the
carboxyl groups (ref. 4) .
We iave prepared copolymers containing
carboxyl groups which possess flatter titra
tion curves, but so far these resins are too
weakly acidic and have too small an ex
change capacity to be of practical interest
(ref. 4) . We have also enhanced the ther
mal effect by preparing snake cage polymers
from crosslinked poly (acrylic acid) cages
and linear polymeric snakes containing
ether and hydroxyl groups, but the lower
capacity and increased cost of these resins
do not warrant their use in place of exist
ing poly (acrylic acid) resins (ref. 4) .

SELECTION OF OPTIMUM RESIN PAIR

A detailed study of the procedure for de
termining the titration curves (ref. 6)
shows that for the hot and cold curves of
"Zeo-Karb 226", and the cold curve of
"De-Acidite G", the resin composition cal
culated from the amount of acid added
(acid fraction) agrees with that obtained
by direct analysis of the resin over the pH
range 4 to 9. There is a significant differ
ence of up to 8 per cent in the resin com
positions derived by the two methods for
the hot curve of "De-Acidite G". As a first
approximation, it is therefore permissible
to use the titration curve data for easily
determining resin compositions as a func
tion of pH. This information, approximate
as it is at 80°C, can be used in screening
tests to predict comparative equilibrium
data for various resin combinations under
different conditions of pH and ionic

109
 BASE FRACTION
FIGURE 36. TITRATION CURVES OF CARBOXLYIC ACID
RESINS IN 1,760 PPM SALINE.
1. "Amberlite IRC-50" at 80°C 3. "Zeo-Karb 226" at 80°C
2. "Amberlite IRO50" at about 20°C 4. "Zeo-Karb 226" at about 20°C

strength. From this data it is possible to
select a pair o[ resins for more detailed
study and to see the relative importance of
the different factors influencing the equilib-
riinn conditions of difference combinations
of resins.
Three alternative procedures may be used
to study the adsorption of salt by a pair of
acid and base resins in a salt solution: (1)
equimolar mixtures of the resins in the un-
dissociatcd form may be added to the salt
solution without any adjustment being
made to the final equilibrium pH value
of the solution; (2) equimolar mixtures of
the resin can be added to the solution to
gether with acid or alkali to adjust the
final equilibrium pH value to any desired
value; (3) resin ratios other than unity
may be used and the final equilibrium pH
value may be adjusted to any desired value
by the addition of acid or alkali.
(1) Resin Ratio of Unity Without pH
Adjustment: This situation can be con
sidered as in Figures 37 to 40 by super
imposing the titration curves of the acid
and base resins at the specified temperature
and equilibrium salt concentration, so that
the scales of the resin composition cor
respond. The equilibrium resin composition
and pH value of the solution are shown by
the point of intersection of the titration
curves, since this represents the individual
resin compositions which correspond to the
same pH value. Since at about pH 4 to 10

110
the hydrogen ion concentration in the solu
tion is negligible compared with that of
the ions of a 0.03 molar salt solution, there
will be one sodium ion adsorbed by the
acid resin for every chloride ion adsorbed
by the amine resin. Both resin composi
tions will change to the same extent after
adsorption, since the resin compositions
were the same before adsorption. The dif
ference between the projections onto the
resin composition axis of the points of
pH
3 h
IONIZATION
FIGURE 37. MATCHING OF TITRATION CURVES IN
1,760 PPM SALINE (RESIN RATIO UNITY).
1. "Amberlite IRC-50"
intersection of the hot and cold titration
curves shows the change in resin composi
tion which occurs on heating the resin
mixture in the salt solution.
The differences in the amount of salt
adsorbed by equimolar mixtures of undis-
sociated acid and base resins at about 20°C
and 80°C ("effective capacity") have been
measured by direct experiment for a large
number of resin combinations. They show
trends similar to those indicated by the
intercepts in Figures 37 to 40 (ref. 6) .
A comparison of Figures 37 and 38 shows
that the bigger effective capacity with a
poly (acrylic acid) resin, rather than a
poly (methacrylic acid) resin in combina
tion with "De-Acidite G", is due to greater
FRACTION 1
2. "De-Acidite G"
overlapping of the basic resin curves by
the titration curves of the more acidic poly
(acrylic acid) resin. A comparison of
Figures 37 and 40 reveals that the effective
capacity for a combination of "De-Acidite
G" with "Amberlite IRC-50" is consider-
Ill
 g

7 П

pH

5 h
io'c !

IONIZATION FRACTION
FIGURE 38. MATCHING OF TITRATION CURVES IN
1,760 PPM SALINE (RESIN RATIO UNITY).
1. 2.5 per cent cross-linked poly (acrylic acid) 2. "De-Addite G"

ably greater in a 29,300 than in a 1,760
ppm salt solution, since the effect of salt
concentration on the titration curves is such
as to favor better matching at the higher
concentration. Figures 39 and 40 show that
salt concentration has less influence on the
adsorptive behavior of heterofunctional
than of homofunctional amine resins,
since changes in the positions of the
hot and cold intercepts on the sloping
titration curves of heterofunctional resins
do not greatly change the distance between
the intercepts, in contrast to homofunc
tional resins.
These examples show that the effective
capacity increases as the overlapping of
the hot and cold acid and base titration
curves extends. The ideal resin combina
tion at a specified salt concentration is,
therefore, one in which both resins have
homofunctional titration curves which over
lap to the maximum extent. For maximum
performance it is also desirable that the
position of the titration curves of both
resins with respect to the pH axis should
shift as little as possible with changes in
ionic strength.
(2) Resin Ratio of Unity with pH Ad
justment: If the resin ratio is unity but
the pH value at equilibrium is altered by
the addition of acid or alkali, the situation
is described by superimposed titration
cunes as before, but shifted with respect
to each other along the resin composition
axis so that the point of intersection of the
cold curves is at the prescribed pH value.
Such an analysis shows that the pH value
has a large influence on the amount of salt

112
 IONIZATION FRACTION
FIGURE 39. MATCHING OF TITRATION CURVES IN
29,300 PPM SALINE (RESIN RATIO UNITY).
1. "Amberlite IRC-50" 2. "De-Addite M"

adsorbed by the mixed resins, particularly
when a homofunctional base resin is used
in which a large composition change can
occur with very little change in pH.
(3) Resin Ratios Other than Unity with
pH Adjustment: When the resin ratio is
no longer unity and the equilibrium pH
value after adsorption has been adjusted
to any desired value by the addition of
acid or alkali, the situation can be de
picted, as in Figure 41 for an acid to base
resin ratio of 3, by superimposing the titra
tion curve of the acid resin over that of
the base resin drawn on a composition
axis only one-third the length of that of
the acid resin. Since one sodium ion must
be adsorbed by the acid resin for every
chloride ion adsorbed by the anion resin to
maintain electrical neutrality, and there are
three equivalents of acid to base resin, the
change in composition of the acid resin on
the ionization fraction scale will be only
one-third that of the base resin. The rela
tive position of the curves can be moved,
as in the preceding examples, so that the
intercept of the titration curves occurs at
any desired pH value.
Figure 41 also shows the hot and cold
titration curves of the same resins drawn
on composition axes of the same length
and superimposed so that the point of
intersection corresponds with that of the
previous example. The diagram thus illus
trates the behavior of resin mixtures, with
resin ratios of 1 and 3 respectively, and equi
librated to the same pH value. It shows that
increasing the resin ratio increases the over
lapping of the two titration curves so that
the salt uptake is considerably greater than
for the equimolar mixture. The effect of
 9 h

7 h

PH

IONIZATION FRACTION
FIGURE 40. MATCHING OF TITRATION CURVES IN
29,300 PPM SALINE (RESIN RATIO UNITY).
1. "Amberlite IRC-50" 2. "De-Addite G"

increasing the resin ratio is therefore
equivalent to using an acid resin with a
flatter titration curve, and this approach
represents a practical method of improving
the matching characteristics of a pair of
resins, since homofunctional acid resins
are not available.
(4) Optimum Resin Ratio and pH: It
can be shown from an analysis of the titra
tion curve data that for each pH value
there is an optimum resin ratio for maxi
mum effective capacity (ref. 6) . Figure 41
shows that there will be greater overlap
ping of the titration curves as the resin
ratio increases. However, increasing the
resin ratio also increases the weight of the
resins per unit of base resin capacity, so
that the effective capacity passes through
a maximum when expressed on a unit of
weight basis, and there will be a different
optimum resin ratio at each pH level. Con
sequently, it is necessary to evaluate effec
tive capacities at various pH values and
resin ratios when selecting the optimum
resin pair from the many resins available.
Figures 42 and 43 show the effective
capacities at the optimum resin ratio for
a variety of amine resins in combination
with '"Zeo-Karb 226" plotted against pH:
the optimum resin ratios of the maximum
effective capacities are given in parentheses
is the figure legend. The curves show that
resins differ widely in their performance.
The effective capacity is critically depend
ent on pH when the amine resin is homo-
functional; the dependence is less critical
for the heterofunctional resin "De-Acidite
M". The pH values corresponding to maxi
mum effective capacities are shifted slightly
by a change in salt concentration.

114
 1,760
FOR
SALINE
UNITY
OF
RATIOS
RESIN
WITH
IN
BEDS
MIXED
AND
EPPM
3 QUILI
TG"
OF
"CURVES
AND
MFIGURE
226"
41.
DZIAET-ORAC-HKTIDAINROTBGE

3)
(resin
"IoZfor
F226
of
nratio
erioaz-catKiornb

00
06
05
2
3
01
00
074t
"Zefor
IoF-rnKaizcratb2io6n*
(Tft
0^2
<M
08

I)
of
(resin
ratio

AT
BRATED
20°C.
ABOUT
5.8
pH

1'—1i
11
 1-4,

i 1 i i 1
4-6 50 60 70
pH AT OPTIMUM RESIN RATIO
FIGURE 42. PREDICTED EFFECTIVE CAPACITY (20° TO 80°C)
VS pH AT OPTIMUM RESIN RATIO FOR MIXED BEDS OF
VARIOUS AMINE RESINS WITH "ZEO-KARB 226" IN 1,760 PPM
SALINE. THE OPTIMUM RESIN RATIO AT MAXIMUM EFFEC
TIVE CAPACITY IS SHOWN IN PARENTHESES.
1. 3 to 5 per cent cross-linked polyvinylbenzylethylamine (1.9)
2. "De-Aadite G" containing 2.6 per cent quaternary ammonium groups (2.5)
3. 7 to 9 per cent cross-linked polyvinylbemyldimethylamine (1.9)
4. "Amberlite IRA-9S" (2.5)
5. As in 2, but with "Amberlite IRC-50" as the acid resin (4.0)
6. 7 to 9 per cent cross-linked polyvinylbenzyldipropylamine (4.0)
7. "De-Acidite G" containing 26 per cent quaternary ammonium groups (1.5)
8. "De-Acidite M" (1.0)
116
 5 0 60
pH AT OPTIMUM RESIN RATIO
FIGURE 43. PREDICTED EFFECTIVE CAPACITY (20° TO 80°C)
VS pH AT OPTIMUM RESIN RATIO FOR MIXED BEDS OF
VARIOUS AMINE RESINS WITH "ZEO-KARB 226" IN 500 PPM
SALINE. THE OPTIMUM RESIN RATIO AT MAXIMUM EFFEC
TIVE CAPACITY IS SHOWN IN PARENTHESES.
1. "De-Atidite G" containing 2.6 per cent quaternary (S.3)
2. "Amberlite IRA-9S" (2.5)
3. "De-Acidite M" (1.0)

The results show clearly that "De-Acidite
C" and "Amberlite IRA-93" are the best
commercial amine resins for use with "Zeo-
Karb 226". Even higher effective capacities
are given by an experimental cross-linked
polyvinylbenzylethylamine resin in a 1,760
ppm salt solution. The data also confirm
the superiority of the poly (acrylic acid)
resin "Zeo-Karb 226" over the poly (mctha-
crylic acid) resin "Amberlite IRG-50". It
can be seen from Figure 42 that increasing
the quaternary ammonium content of "De-
Acidite G" from 2.6 per cent to 26 per cent
reduces its performance considerably.
A similar analysis is given in Figure 44
for the titration curves of "Zeo-Karb 226"
and "De-Acidite G" at about 20° and 80°C
in solutions containing 500 ppm or 1,760
ppm of sodium chloride or calcium sul
phate. The data in the latter case are for
a hypothetical calcium sulphate solution.
They were obtained from the titration
curves of "Zeo-Karb 226" versus calcium
hydroxide in calcium chloride solution, and
of "De-Acidite G" versus sulphuric acid in
sodium sulphate solution. The plots show
that divalent ions raise the pH values for
maximum effective capacities to slightly
higher values, and that, whereas at a con- of monovalent rather than in that of
centration of 1,760 ppm, the maximum divalent ions, the converse is true at a
effective capacity is greater in the presence concentration of 500 ppm.

FIGURE 44. PREDICTED EFFECTIVE CAPACITY (20° TO 80°C)

VS pH AT OPTIMUM RESIN RATIO FOR "ZEO-KARB 226"/"DE-
ACIDITE G" MIXED BED AND HYPOTHETICAL CaSO,
SOLUTION.
Nad CaSO.
 RESIN EQUILIBRIUM DATA
The performance of a distillation process ments show that this procedure is rigorous
can be predicted from an analysis of vapor- with accurately derived titration curve data
liquid equilibrium diagrams prepared at at about 20 °C, indicating that the resins
different pressures. The analogous data for behave independently in a mixed-bed (ref.
the "Sirotherm" process for a simple solu 6) . Accurate determination of the equilib
tion of sodium chloride are plots of amine rium diagrams at 80°C requires the direct
resin compositions versus acid resin com measurement of resin compositions.

FIGURE 45. CONSTRUCTION OF THE EQUILIBRIUM DIAGRAM

FOR A MIXED BED FROM THE SEPARATE RESIN TITRATION
CURVES IN 1,700 PPM SALINE AT ABOUT 20°C.
1. Titration curve of "De-Acidite G"
2. Titration curve of "Zeo-Karb 226"
3. Constructed equilibrium diagram for "Zeo-Karb 226"/ "De-Acidite G" mixed bed
X. Experimental points

positions at different temperatures and salt Equilibrium curves thus determined at

concentrations. As shown in Figure 45, such
plots can be derived from the relevant
titration curves, which express resin com
positions as a function of pH, by plotting
acid and base resin compositions that cor
respond to the same pH value. Experi-
about 20°C and 80°C for sodium chloride
solutions at concentrations of 500, 1,000,
1,760, 3,000 and 5,000 ppm are given in
Figures 46 and 47. From these curves it is
possible to calculate reliably the effective
capacity at optimum resin ratio and pH

119
 RC02Na RC02H

FIGURE 46. EQUILIBRIUM DIAGRAMS FOR "ZEO-KARB 226"/

"DE-ACIDITE G" MIXED BED AT ABOUT 20°C. CONSTRUCTED
FROM THE SEPARATE RESIN TITRATION CURVES DETER
MINED IN SOLUTIONS OF THE FOLLOWING SALT CONCEN
TRATION:
1. 5,000 ppm 3. 1,760 ppm 5. 500 ppm
2. 3,000 ppm 4. 1,000 ppm

120
FIGURE 47. EQUILIBRIUM DIAGRAMS FOR "ZEO-KARB" 226/
"DE-ACIDITE G" MIXED BED AT 80°C. DATA DETERMINED
DHtECTLY IN SOLUTIONS OF THE FOLLOWING SALT CON
CENTRATION:
1. 5,000 ppm S. 1,760 ppm 5. 500 ppm
2. 3,000 ppm 4. 1,000 ppm

121
 I I
2000 4000 6000
SALT CONCENTRATION, ppm
FIGURE 48. EFFECTIVE CAPACITY (20° TO 80°C) UNDER OP
TIMUM CONDITIONS FOR "ZEO-KARB 226'7"DE-ACIDITE G"
MIXED BED AT VARIOUS SALT CONCENTRATIONS.

as a function of salt concentration. These
data are given in Figure 48.
The maximum effective capacity, opti
mum resin ratio and pH, as determined
from the titration curves used in the screen
ing experiments, are compared in Table
XXI with similar data determined from the
experimentally derived equilibrium dia
grams. The results confirm the reliability of
the screening procedure for assessing major
differences in performance.

TABLE XXI. Data for "Zeo-Karb 226"/"De-Acidite G" Mixed Bed

Salt Source of 80°C Optimum* Optimum Optimum

concentration equilibrium effective capacity PH reain ratio
ppm data meq/g mixed bed value (acid/base)
500 A 0.78 5.5 S.S
500 B 0.97 6.4 4.0
1,760 A 1.12 6.0 2.6
1,760 B 1.45 5.9 2.2
A = Predicted from separate resin titration curves at 80°C.
B = Determined from the80°C equilibrium diagrams found by direct experiment.
* Capacities are expressed on a dry weight basis (ref. 3).

REVERSIBILITY
Mixtures of equivalent amounts of "De- in ampoules containing outgassed aqueous
Acidite G" and "Amberlite IRC-50", both solutions of sodium chloride. The mixtures
of particle size 2 to 50 microns, were sealed were subjected to 5,000 cycles of successive

122
heating (90°C, 8 min.) and cooling (about
20°C, 10 min.) without any loss in ex
change capacity (ref. 3) . These experiments
show the high thermal stability of the resins
in the absence of air, and the complete
reversibility of the adsorption-desorption
cycle in solutions of sodium chloride.
It has been shown that the "Sirotherm"
mixed bed is highly selective for divalent
ions, particularly magnesium and calcium
ions (ref. 6) . The high selectivity of the
carboxylic resin for calcium and magne
sium ions is probably due to chelation with
the carboxyl groups, but complete elution
MULTISTAGE OPERATIONS
Continuous countercurrent operation
would be the most efficient way of conduct
ing the "Sirotherm" process to obtain max
imum utilization of the resin. The data in
Figures 46 and 47 can be used to calculate
the equilibrium performance of an ideal
multistage system for various concentrations
of sodium chloride and for different num
bers of stages of adsorption and regenera
tion (ref. 12) . The ionic strength is differ
ent in each stage so that the problem of
selecting an optimum resin ratio and an
optimum pH at a specified adsorption stage
is complex. In practice, the problem with
actual waters is aggravated by the presence
of divalent as well as monovalent ions.
The simplest method of investigating the
complexities of multistage operation on a
laboratory scale is to use static columns
of resin in the usual cyclic fashion. Inter
pretation of the results requires the as
sumption that the peak concentrations at
tained could be realized as steady-state
conditions in a continuous countercurrent
process, or approximated in a cyclic batch
operation using split elution, although the
experiments do not indicate the number of
theoretical stages required.
A series of column experiments was per
formed with a mixture of "Zeo-Karb 226"
(SRC 44) and "De-Acidite G" (SRA 102)
with particle sizes less than 200 mesh (ref.
12) . Details are given in Figure 49 and
Table XXII. The data show that during the
adsorption cycle with a feed of 1 ,000 ppm
sodium chloride, a product is obtained with
a minimum concentration of about 230 to
250 ppm. Regeneration with the same feed
water at 80°C yields an effluent with a
peak concentration of 4,800 ppm (series 1) .
The equilibrium data show that resin per
formance should improve, under equilib
rium conditions, with the use of product
rather than feed water for regeneration.
is possible with acids since protons are
bound even more strongly. Elution in the
"Sirotherm" mixed bed is also affected by
protons since heating results in the transfer
of protons from the amine salt to the car
boxylic resin salt. It is to be expected, there
fore, that divalent as well as monovalent
ions will be adsorbed reversibly in the cold
and hot cycles of the "Sirotherm" process.
This expectation has been confirmed for
sodium chloride over 1,000 cycles for a
variety of solutions containing magnesium,
calcium, and sulphate ions (ref. 6) .
A comparison of the series I and 2 re
sults shows that slightly better peak con
centrations and column capacity are
obtained by regenerating with the 550
ppm solution. However, as the pH value
of the product water after regeneration
at 500 ppm was alxnit 0.5 of a pH
unit lower than in the first series of experi
ments, it seems likely from a consideration
of (he data in Figures 42 and 43 that a
better performance would have been ob
tained had the pH value of the column
been adjusted to a higher value. Hence,
comparison of the two sets of experiments
is not rigid. More experimental data, com
bined with an economic analysis of the
results, are required before it can be de
cided whether the regenerant should be
product or feed water. Another series of
experiments with a feed of 1,000 ppm
sodium chloride (series 3) was performed
with the resins adjusted to lower pH values
than used in the series 1 experiments.
The results in Figure 49 and Table XXII
show that the column capacity was consid
erably less than in the first series. A similar
experiment (series 5) was performed at
higher pH values and shows that the
column capacity was substantially reduced
by raising the pH to a value above that
used in the series I experiment. The re
sults thus confirm the importance of pH
in determining effective resin capacity. The
data in Figure 49 also show that the process
works satisfactorily with a feed concentra
tion of 3,000 ppm sodium chloride (series 4).
Another series of experiments (series 6)
was performed with a 1,000 ppm solution
of magnesium sulphate. The results show
that the process can treat a solution of
magnesium sulphate as well as one of
sodium chloride, but the operating pH was
probably too low for optimum performance
as suggested by the data in Figure 44.
123
 5 10 15 20 26 0 5 10 15 20 25
Bed Volumes
FIGURE 49. COLUMN EXPERIMENTS FOR CHROMATOGRAPHIC
GRADE "ZERO-KARB 226" SRC 44/"DE-ACIDITE G" SRA 102
MIXED BED, RESIN RATIO 2.5.
1. Feed 1,000 ppm NaCI, regenerant 1,000 ppm, pH 5.8-5.5
2. Feed 1,000 ppm NaCI, regenerant 500 ppm
S. Feed 1,000 ppm NaCI, regenerant 1,000 ppm, pH 5.1-4.6
4. Feed 3,000 ppm NaCI, regenerant 3,000 ppm
5. Feed 1,000 ppm NaCI, regenerant 1,000 ppm, pH 6.0-5.8
6. Feed 1,000 ppm MgSO„ regenerant 1,000 ppm

124
 TABU XXII. Column Result* with "Zeo-Karb 226" (SRC 44) and "De-Acidite G"
(SRA 102)

Effective capacity"
PH» Concentration, ppm (20°C to 80°C)
pH of
Series Resin before adsorption of column
no. ratio adsorp trough Adsorp Regen- Second Second
tion Feed Regen- tion erant adsorp regenera
erant mini maximum tion tion
mum meq/ml meq/ml
j 2.5 6.7 5.8-5.6 1,000 1.000 230 4,800 0.20 (4.4) 0.20 (4.4)
(Nad)
2.5 6.8 5.7-6.0 1,000 600 260 6,200 0.21 (4.6) 0.22 (4.8)
(NaCl)
g 2.6 6.2 5.1-4.6 1.000 1,000 190 4.100 0.12 (2.6) 0.12 (2.6)
(NaCl)
4 2.6 (.8 5.9-6.4 3.000 3,000 660 8,060 0.19 (4.2) 0.18 (4.0)
(NaCl)
6 2.6 6.4 6.0-6.8 1.000 1,000 275 6.000 0.10 (2.2) 0.10 (2.2)
(NaCl)
S.0 6.2 6.2-6.7 1.000 1.000 110 5.600 0.13 (2.8) 0.14 (8.1)
(MkSO.) (MbSO.)
* A suspension of the resins in feed water was adjusted to this pH value by addition of acid before
fillincr the column
•• Data with resin.
in parentheses are in units of kilograms of calcium carbonate per cubic foot.

These experiments serve only to demon After completion of a final regeneration

strate that the process works in the labora-
lory; many more experiments are required
(o ascertain the optimum pH values and
resin ratios for operation under different
conditions, and to permit rigorous com
parison of the results.
Better results could be obtained by using
a split elution technique in which only
the most concentrated effluent would be
rejected and the remaining less concentrated
fractions from the regeneration cycle would
be retained for use in the next cycle.
Regeneration would be completed with a
volume of hot product or feed water equal
to that rejected as the most concentrated
effluent. A similar technique could be ap
plied to the adsorption stage.
cycle in the series 6 experiments, the resins,
already loaded with magnesium ions, were
treated again at 80°C with a solution con
taining 800 ppm NaCl and 200 ppm MgSCv
After a further adsorption (about 20°C)
and regeneration (80°C) cycle with the
same feed solution, a second pair of adsorp
tion and regeneration cycles was com
pleted. The results of the latter cycles,
given in Figure 50, show that both sodium
and magnesium ions arc adsorbed at the
beginning of the adsorption cycle. As more
magnesium ions enter the feed solution,
the sodium ions that were initially adsorbed
are replaced by magnesium ions. Thus
softening may be combined with demin-
erali/ation (ref. 12) .

RATES OF ADSORPTION
Slow rate of reaction is the principal
practical barrier to the use of mixed beds
of weak-acid and weak-base resins, but
detailed kinetic studies are not available.
It is known, from investigations of the
kinetics of the sodium-hydrogen exchange
reaction in carboxylic acid resins in solu
tions of sodium ion concentration from
0.01 to 1.0N, that the rate of exchange is
independent of the concentration of sodium
ions and varies inversely with the square
of the diameter of the resin bead (ref. 7) .
It seems probable therefore that the rate
of reaction of the "Sirotherm" mixed bed
will be determined by the rate of transfer
of protons between the resins and that this
rate is low because the concentration of
hydrogen ions is very small in a solution at
about pH 6. It is known that the rate of
reaction of carboxylic acid resins increases
with their acidity (ref. 8) .
Rate studies for mixtures of "De-Acidite
G" and "Zeo-Karb 226" with different
particle diameters show that the rate of
reaction increases considerably with a de
crease in particle size. Microbeads with
diameters of 5 to 20 microns are currently
being studied, and it has been found that
the degTee of flocculation of the microbead
mixed bed has a considerable influence on
the rate of exchange. The degree of cross-
linkage of the resins is also important. The
results so far obtained suggest that satisfac
tory rales of exchange will most likely be

125
 obtained with microbeadv weak-acid snake, but the effective capacities
We have shown that fast rates of ex of these resins have so far been consider
change may be obtained with ion-retarda ably inferior to those of mixed individual
tion resins with a weak-base cage and a resins (ref. 9) .

126
 SOME PROCESS CONSIDERATIONS
Our experimental study of the "Siro-
therm" process has so far been confined al
most exclusively to a study of equilibrium
conditions with the objective of defining
resin specifications and optimum conditions
for operation. The probable necessity of us
ing microbeads to obtain satisfactory rates
of adsorption and of recovering heat from
the bed means that the process cannot be
operated with the procedures customary in
ion-exchange technology. Although we have
not yet worked on process aspects, we have
given the matter considerable thought. Our
tentative views on this subject will now be
presented.
Beds of resin several feet deep are not
practical if microbeads are used to obtain
satisfactory rates of adsorption, as the flow
rate is too low owing to the high pressure
drop over the bed. It is also difficult to
recover heat efficiently from a deep static
bed of resin without destroying the concen
tration gradient within the resin bed.
One simple method for operating the
process on a small scale might be to retain
the microresins as a layer about 0.25 to I
inch thick between the leaves of a plate
and frame filter press. The individual units
in such a filter are in parallel so that the
pressure drop over the bed will not be
excessively high. The resin bed would func
tion as only one reaction stage, but multi
stage countercurrent conditions could be
simulated by employing a split elution and
split feed technique. Since the rate of ex
change at 80°C is at least ten times that at
20°C. it would be possible to regenerate,
in the time required for performing a
single stage of adsorption, with a consider
able number of successive equilibrations in
volving fractions collected from the preced
ing regeneration cycle. As the quantity of
resin used is small, the cycle time will be
a matter of only a few minutes, so that the
volumes of the different fractions to be
stored for use in the next cycle will be
small and could be retained in radial com
partments within a single tank. It should
therefore be practical to operate the process
with several adsorption stages but with
many more regeneration stages. Since there
will not be a concentration gradient of any
magnitude within the resin bed as it oper
ates as a single stage, heat could be with
drawn or added by circulating a solution of
appropriate composition through the resin
bed and a heat exchanger.
• The water regain was 0.7.
•* This ream contains i% per cent divinyl ben-
lene. but lower crosslinking is preferred.
There are insufficient data for making
reliable estimates of the size of such a
plant, but the following hypothetical exam
ple shows the likely order of magnitude
involved for a plant producing 240,000 U.S.
gpd of water with a salinity of 500 ppm
from a feed solution of 1,000 ppm. Our
results suggest that if the regenerant ef
fluent concentration were 4,000 ppm, it
ought to be possible to obtain about 17
bed volumes of product per unit volume
of resin, since this would only assume an
effective capacity (0.15 meq/ml) well below
that attainable theoretically. Rate studies
tentatively suggest that a complete multi
stage adsorption and regeneration cycle
might be completed within 6 minutes, in
which case 8 cubic feet of resin would be
required. If the resin were retained in a
layer 0.5 inch thick, a filter area of only
190 square feet would suffice.
An alternative procedure may be desir
able for plants treating more than one
mgd of water. One possibility is a series of
mixer-filter units arranged countercurrently,
as shown in Figure 51. which warrants in
vestigation. A mixture of "De-Acidite G"
and "Zeo-Karb 226" with a particle size
range of approximately 10 to 20 microns is
highly flocculated. Fresh resin filters at the
rate of, 8 gals/sq ft/min under a vacuum of
20 inches of mercury and yields a cake one
quarter of an inch thick without cracking.
If this filtration rate could be maintained,
the largest disc filter available, with 12
discs 12 feet 6 inches in diameter, would
filter a flow of 10 mgd. In this flowsheet,
feed water is used for regeneration, but,
depending on economic circumstances, prod
uct water or a blend of both feed and
product water could be used. The upper
limit to the salinity of the water that
could be treated might be extended by
incorporating a wash cycle on the filters in
the regeneration cycle, so that void water is
displaced by the solution from the next
stage of the process receiving the resin.
Efficient heat recovery is possible if the
resins are transferred between the hot and
cold stages with similar flows of solution
so that the flows have the same heat ca
pacity on either side of the heat exchangers.
Success with the continuous process would
require resins with a high degree of me
chanical stability, but preliminary experi
ments are encouraging. A mixed bed of
microbeads of "De-Acidite G"4 and "Zeo-
Karb 226",#, with particle diameters of
about 10 to 20 microns, has been subjected
127
 to 6300 successive cold (32°C) and hot
(about 70°C) cycles with changes of solu
tion at each adsorption and desorption
cycle. A photomicrograph of the resins after
6,500 cycles given in Figure 52 shows that
there has been no major rupture of the
resin beads. It was observed that the only
beads which had cracked were the few
with particle diameters exceeding 20 mi
crons. A slurry of the separate resin beads
has also been subjected to violent agitation
for a month at room temperature by an
agitator designed for maximum shearing
stress. There was no visible cracking of any
of the minus 20 micron beads.

O in
tf) i- CL
Ul < > "J 22 I
O a. . tr to <r o o i- in
< WO UJ z < Q- o or h
I- Zo tr i- tu > < t- (To UJ O
<S) uJo UJ f *- o X if) OO
, CD oo o < < O u , w ex
o tu UJ UJ X Z
CD X x tr uj e58 O
M
h
U
z> 5
q »
O ©
rpS- CC
CL w
O
<
H
5/5

is
u
5/5 O
2*
O Cm
P.

2M
O
U
O
^—
6/5
06'
O

H
w
w
X
C/5

z
UJ Q
3 UJ
-I UJ
U. Ll 0
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128
FIGURE 52. PHOTOGRAPH OF MICROBEADS OF "ZEO-KARB
226" (STAINED DARK WITH FUSCHIN) AND "DE-ACIDITE G",
10 TO 20 MICRONS, AFTER 6,500 COLD ADSORPTION AND
HOT DESORPTION CYCLES.
It is well-known that colloids adsorbed
on the surface of ion-exchange resins can
reduce the rate of exchange substantially.
Colloids might enter the system in the feed
water, from which they could be removed
by pretreatment. They might also arise in
the continuous process from a gradual attri
tion of the resin, in which case it would
be necessary to remove them by backwash
ing, or by chemically treating a small side
stream of the resin flow.
The heat requirements of the process are
potentially low, since the energy required
for performing thermodynamic work is
negligible, compared with the sensible heat
required for heating the solution and resins,
and sensible heat can be recovered to an
extent dictated solely by economics. Heat
recovery will be easier in the continuous
than in the batch version of the process.
Cheap and efficient heat recovery is likely
to require the development of novel heat
transfer techniques, which use cheaply de
rived interfaces, and becomes increasingly
important as the desalination load increases.
If the process is to be used in an inte
grated municipal supply system, as described
in Figure 32. it will be treating under
ground waters which usually contain little
sediment, organic matter, or oxygen. Pre
treatment with a (macroporous) macro-
reticular organic trap resin and a polishing
filter might be all that is required. It is
advisable to prevent aeration of the water
until after treatment in order to avoid
precipitation of iron and manganese; the
low oxygen content will favor resin stabil
ity. Acidification of the feed water to about
pH 6 will be necessary and the optimum
operating pH value will need to be main
tained by insuring that the number of
protons entering the plant equals the
number leaving it.
In most waters, acidification will result
in the liberation of free carbon dioxide
which should be retained in the water in
the adsorption stage in order to dissolve
any calcium carbonate that might tend to
deposit during regeneration. Acidification
can be achieved by the addition of sulphuric
acid, carbon dioxide, or sulphurous acid.
Flue gas from the heater in the plant
might provide an inexpensive source of the
latter two acids, provided its use does not
contaminate the water with organic matter
which fouls the resins.
129
 CONCLUSIONS
Proper integration of surface and under
ground water supplies, coupled with the
use of a demineralization process to main
tain the salinity balance of the system, pro
vides a feasible long-term approach to
maintaining water quality in an arid region
at low cost. Low cost demineralization for
this purpose might best be achieved by the
development of an ion-exchange process
with thermal regeneration of the adsorbent.
It has been conclusively demonstrated in
principle that thermal regeneration of a
mixture of ion-exchange resins of the weak
electrolyte type is feasible and the condi
tions for maximum thermal effect have been
defined. Equilibrium studies make it pos
sible to write the following specifications
for the ideal "Sirotherm" resins:
(11 The acid and base resins should be
homofunctional, and the overlap of their
titration curves, determined at a given ionic
strength and two given temperatures, should
be as large as possible.
(2) Maximum thermal reduction of the
acidity and basicity of the respective resins
is desired.
(3) The position of the titration curves
of the acid and base resins with respect to
the pH axis should alter as little as possible
with changes in ionic strength.
(4) The resins must be stable at 80° to
90-C.
(5) The total exchange capacity should
be as high as possible.
Our experiments have demonstrated that
APPLICATION OF THE PROCESS
A useful feature of the "Sirotherm" proc
ess is its ability to soften and demineralize
simultaneously. In many waters, removal of
the hardness salts alone would suffice to
prevent the accumulation of salinity within
a regional supply system. Since the effluent
from the process (when operating on a
softening cycle) will consist mainly of
divalent ions, it may be of value in arid
regions for the displacement of sodium
from alkaline soils in soil reclamation
projects.
Until engineering feasibility is established,
and economic data become available from
a pilot plant operation, it will not be pos
sible to define the maximum salinity of the
feed water likely to be treated in economic
competition with other processes, although
our laboratory experiments show that it is
certainly technically feasible to treat waters
the process is reversible for monovalent and
divalent ions, and that the resins have
adequate thermal stability in the absence of
oxygen. It has also been shown that a multi
stage system with thermal regeneration can
produce water of good quality from pure
salt solutions, with an adequately concen
trated effluent to meet the requirements of
a practical process. The results suggest the
possibility of operating with microbeads to
obtain satisfactory rates of reaction. It has
yet to be shown that the process can be
operated with a resin life of at least 10,000
cycles. An experimental study of the factors
determining resin life will be required.
The main deficiency of existing homo-
functional amine resins is their low total
capacity. It would be valuable to have a
homofunctional resin of adequate stability
with the capacity of the heterofunctional
resin, "Duolite A-30T", whose capacity is
twice that of the present homofunctional
amine resins.
There is room for considerable improve
ment in the properties of carboxylic acid
resins, as their titration curves show that
they are heterofunctional and lack good
thermal effects, but such improvements will
be difficult to make at low cost. Existing
resins have excellent capacities and stabili
ties and are potentially cheap as they can
be made, in fewer stages and from cheaper
intermediates than polystyrene amine resins.
The simplest avenue for improvement may
therefore be to seek means for reducing
their cost.
with concentrations of at least 3,000 ppm.
There is no doubt that the process will
become increasingly attractive with reduc
tions in the salinities of the feed and prod
uct waters, and in this respect it differs from
electrodialysis and reverse osmosis.
The lowest practical salinity of the prod
uct water from electrodialysis is 350 to 500
ppm. as the electrical resistance of the cells
becomes excessively high at lower concen
trations. There may, therefore, be merit in
using electrodialysis to reduce the salinity
of sea water or highly brackish waters to
a level such that these waters could l>e fed
to a "Sirotherm" unit. Haven's process of
reverse osmosis, and possibly other similar
processes, operate in two stages (rcf. 10) .
In the first, the salinity of sea water is
reduced from 35,000 ppm to about 2.000
ppm. This product is an ideal feed for the
 "Sirotherm" process, as colloids have pre
sumably been completely removed. It would
be possible to utilize essentially all the fuel
energy of a heat engine for desalination by
combining the "Sirotherm" process with
electrodialysis or reverse osmosis, since most
of the energy of the fuel that is not con
verted to mechanical or electrical energy
for use in the latter processes would be
available as heat energy from the cooling
system at a suitable temperature for
use in a "Sirotherm" unit. Thus electricity
need not necessarily be a byproduct of
efficient sea water desalination
These possibilities present a major chal
lenge for the inventive use and develop
ACKNOWLEDGEMENTS
We are indebted to many people and
firms for assistance with the "Sirotherm"
project: to Union Carbide Australia for
sponsorship of the project and for the sup
ply of some monomer chemicals; to the
Permutit Company, Ltd., London, for
samples of their ion-exchange resins and for
preparing microbead resins to our specifica
tions: to the Dow Chemical Company, the
Rohm and Haas Company, and the Western
Division of Diamond Alkali, U.S.A., for
samples of their ion-exchange resins; to
REFERENCES
1. Weiss, D. E.; Bolto, B. A.: McNeill, R.;
Macpherson, A. S.: Siudak, R.; Swinton,
E. A.: Willis, D.: Part I submitted to
the Institution of Engineers, Australia,
for publication.
2. Report of the IJ.S.-Israel Desalting and
Power Team, (Oct. 1964) , U.S. Dept.
of the Interior.
3. Weiss. D. E.; Bolto, B. A.; McNeill, R.;
Macpherson, A. S.; Siudak. R.; Swinton.
E. A.; Willis, D.: Aust. J. Chem., Part
II submitted for publication.
4. Weiss. D. E.; Bolto, B. A.; McNeill. R.;
Macpherson, A. S.: Siudak, R.; Swinton,
E. A.; Willis, D.: Aust. J. Chem., Part
III submitted for publication.
5. Kunin, R.; Fisher. S.: /. Phys. Chem..
no. 66 (1962) p. 2275.
SUMMARY OF DISCUSSION
It was stated that water in California con
tains both boron and fluorides, and it was
asked how the process presented in this
paper would remove these ions. The reply
stated that there is an ion-exchange resin
ment of the principles outlined above, which
show for the first time that it is possible
to use heat to perform reversible work at
an adsorbent interface. As discussed else
where (ref. 1) , a process which can com
bine the utilization of the cheaply derived
interface of an adsorbent with that of low-
grade heat, the cheapest available energy
source, has excellent long-term prospects
for achieving low demineralization costs.
Furthermore, if the solar pond development
in Israel (ref. II) becomes operational, it
will offer the attractive long-term prospect
of performing a cheap demineralization op
eration in arid regions by the use of solar
energy.
Henry York, Pty., Ltd., Melbourne, for
samples of "Lutonal" polymers and "Lewa-
tit" resins; to Gardinol Chemical Co.
(A/asia) Pty., Ltd., for samples of acrylic
monomers; and to Dr. K. VV. Zimmermann
for performing microanalyses of the resins.
We are also grateful to Messrs. D. Lawrie
and N. Blesing of the Australian Mineral
Development Laboratories, Adelaide, who
assisted with some aspects of the project
under a C.S.I.R.O. development contract.
6. Weiss. D. E.; Bolto, B. A.; McNeill. R.:
Macpherson, A. S.; Siudak, R.: Swinton.
E. A.; Willis, D.: Aust. J. Chem., Part
IV submitted for publication.
7. Conway. D. E.; Green, J. H. S.; Reich
enberg, D.: Trans. Farad. Soc. no. 50
(1964) p. 511.
8. Kunin, R.; Vassiliou. B.: lnd. Eng.
Chem., "Process design and develop
ment" no. S (1964) p. 404.
9. Unpublished work.
10. Water and Water Eng. (1964) p. 414.
11. Tabor, H.: J. Solar Energy, no. 7
(1961) p. 189.
12. Weiss, D. E.: Bolto, B. A.; McNeill, R.:
Macpherson, A. S.; Siudak, R.; Swinton,
E. A.; Willis, D.: Aust. J. Chem., Part
V submitted for publication.
on the market which will remove these ions
but that their removal by the process de
scribed in this paper is inadequate.
A question was asked concerning the
energy requirement of the process pre-
sented. The author stated that this re
quirement must be evaluated on a larger
scale—possibly at the pilot plant level-
since it cannot be determined in the labora
Procède "Sirotherm"
lisation — Procède Par Echange
D'Ions Avec Regeneration
Thermique
D. E. Weiss, B. A. Bolto, R. McNeill, A. S. Macpherson,
R. Siudak, £. A. Swinton, et D. Willis
Australie
Du fait que les adductions d'eau muni
cipales deviennent de plus en plus coûteuses
et que la qualité se détériore en raison de
la ré-utilisation extensive, il existe quatre
étapes successives logiques pour l'aménage
ment des ressources hydrauliques, en vue de
réduire les frais:
1) Amélioration des méthodes de conser
vation;
2) Récupération des effluents pour leur
ré-utilisation;
3) Déminéralisation des eaux de qualité
marginale qui sont trop salines pour
l'usage général;
4) Une fois que l'eau est utilisée d'une
façon efficace, on doit utiliser des ad
ductions coûteuses provenant de pipe
lines de longue distance, ou de la
déminéralisation de l'eau de mer ou
des eaux fortement saumâtres.
Il se produit une accumulation de sels
minéraux lorsque l'eau des fleuves est ré
utilisée extensivement dans un climat aride.
Le contrôle régional de la salinité exige la
séparation des eaux de drainage d'irriga
tion et des eaux fluviales et un procédé de
déminéralisation bon marché pour retirer
la salinité que s'accumule avec chaque
cycle d'utilisation urbaine ou industrielle.
Celle-ci est généralement inférieure à 500
ppm. Si la déminéralisation était appliquée
aux eaux souterraines proches, un espace
serait ainsi créé qui pourrait être rechargé
avec des surplus d'eau de bonne qualité
pendant les périodes pluvieuses, et la
tory. A high energy recovery in the process
is expected; however, heat transfer rates
must first be determined.
de Déminéra
charge de déminéralisation se trouverait
ainsi réduite. L'application de la déminé
ralisation au contrôle de la salinité est
digne d'une attention étendue, car le retrait
de petites quantités de salinité pour 10
cents par mille gallons (moins de $0,02
par m') est plus vraisemblable, et est plus
urgent, que ne l'est le traitement d'approvi
sionnements fortement pollués comme l'eau
de mer. Ceci rendrait possible l'utilisation
complète des approvisionnements existants
d'eau fluviale. Des considérations fonda
mentales indiquent que le procédé le meil
leur marché dans ce but serait l'utilisation
de résines échangeuses d'ions régénérées par
la chaleur plutôt que des produits chi
miques.
Ce mémoire présente une étude de labo
ratoire montrant qu'un mélange de résines
d'acide carboxylique et d'amine faiblement
électrolytiques adsorbe le sel à la tempéra
ture ambiante et peut être régénéré avec
de l'eau d'alimentation ou de l'eau douce
à 80°C. Le chauffage désorbe le sel de la
couche mixte en réduisant la basicité de la
résine à base faible. Jusqu'à maintenant les
travaux ont porté principalement sur des
études d'équilibre.
Les résines amines possèdent des combes
de titrage avec soit un plateau, soit une
pente; la pente de la courbe et la basicité
de la résine peuvent varier considérable
ment en modifiant la structure de la résine,
mais- les résines d'acide carboxylique, dis
ponibles jusqu'ici, possèdent des courbes
 de titrage inclinées. La différence dans la
quantité de sel absorbé des solutions
froides et chaudes (capacité effective) est
la plus grande pour une paire de résines
dont les courbes de titrage, mesurées dans
les solutions chaudes et froides, se super
posent autant que possible. L'augmentation
de la proportion de la résine acide par
rapport à la résine basique augmente la
quantité de sel pouvant être désorbé par
chauffage, et pour chaque valeur de pH
pour l'adsorption il existe un rapport
optimum des résines. Un changement dans
la force ionique modifie la position rela
tive des courbes de titrage et influence
ainsi de façon marquée la capacité effective
et les conditions de performance optimum.
D'après les courbes de titrage, on peut
tracer des graphiques montrant, en tant
que fonction du pH, les capacités effectives
approximatives des différentes combinaisons
de résines estimées aux rapports optimums
des résines. Ces courbes sont utiles dans
des buts de sélection, car la sélection des
nombreuses combinaisons de résines dis
ponibles exige d'effectuer des comparaisons
à une force ionique donnée dans des condi
tions optimums de pH et de rapport des
résines. Les courbes de titrage fournissent
donc une méthode simple pour la caractéri-
sation des différentes résines.
Les expériences montrent que l'équilibre,
pour beaucoup de paires de résines, dépend
d'une façon critique du pH et que, de
celles examinées jusqu'à maintenant, la
meilleure paire disponible commerciale
ment se compose de "De-Acidite G" et
"Zeo-Karb 226". Des études détaillées ont
été faites de cette paire de résines à
environ 20 et 80°C, dans des solutions con
tenant 500, 1.000, 1.760, 3.000 et 5.000 ppm
de chlorure de calcium. La nature réversi
ble de l'équilibre a été démontrée dans des
échantillons scellés sur 5.000 cycles chauds
et froids pour les ions monovalents, et sur
1.000 cycles pour les ions calcium, mag
nésium et sulfate. Les résines sélectionnées
se sont avérées stables à 90"C dans des
solutions ne contenant pratiquement pas
d'oxygène. Il nous reste encore à démontrer
que le procédé peut être utilisé avec une
vie utile des résines d'au moins 10.000
cycles avec changement de la solution à
chaque cycle.
Les résultats suivants, avec des mélanges
de "Zeo-Karb 226", SRC 44, et de "De-
Acidite G", SRA 102 démontrent que l'effet
thermique entre 20 et 80°C est suffisant
pour l'accomplissement d'opérations utiles
de déminéralisation. Le traitement en co
lonnes d'une eau d'alimentation contenant
1.000 ppm de NaCI a donné un produit
avec une concentration minimum de 230
ppm, et un effluent avec une concentration
de pointe de 4.800 ppm, en utilisant l'ali
mentation à 80°C comme régénérateur. De
meilleurs résultats furent obtenus en se
servant d'un régénérateur contenant 500
ppm de NaCI. Une solution contenant
3.000 ppm de NaCI a été déminéralisée
avec succès. Une solution à 1.000 ppm de
MqSO, a donné un produit avec une con
centration minimum de 110 ppm et une
concentration d'effluent de 5.500 ppm. Il a
été démontré que l'adoucissement pouvait se
faire simultanément avec la déminéralisa
tion. Il est nécessaire d'effectuer d'autres
expériences en colonnes pour définir les
conditions optimums de fonctionnement, si
bien qu'une comparaison rigoureuse des ré
sultats n'est pas encore justifiée.
Des études utilisant des micro-perles avec
des diamètres d'environ 5 à 10 microns
suggèrent que leur taux de réaction sera
acceptable pour un procédé pratique, mais
les résultats concluants doivent attendre
l'issue des études en cours sur l'influence
de la floculation et de la réticulation. Les
études en colonnes classiques en discontinu
décrites ci-dessus sont la manière la plus
simple d'examiner en laboratoire le com
portement d'un procédé à étages multiples,
mais une telle méthode ne serait pas utili
sée en pratique. Sur une grande échelle,
il peut être possible d'exploiter le procédé
dans des ensembles de filtres-mélangeurs
disposés à contre-courant, car une couche
mixte floculée de micro-perles filtre rapide
ment, et il n'y a aucun fendillement dé
tectable des micro-perles de 5 à 10 microns
après agitation vigoureuse dans 6.500 cycles
chauds et froids successifs. Il serait néces
saire de prévoir des moyens pour éliminer
les colloïdes. Une autre méthode, pour une
utilisation sur une plus petite échelle, serait
d'utiliser les résines dans un seul étage de
réaction à couche fixe fonctionnant dans
un système cyclique intermittent et en
imitant les conditions de contre-courant
par des techniques d'alimentation dédou
blée et d'élution. Avant de disposer de
données d'installations pilotes, il n'est pas
possible d'estimer quelle sera la concentra
tion maximum de l'alimentation pouvant
être traitée d'une manière économique,
mais le coût augmentera avec l'accroisse
ment de la salinité de l'eau d'alimentation.
Si une centrale thermique fournissait l'éner
gie pour la déminéralisation partielle de
l'eau de mer, ou des eaux fortement sau-
mâtres, par électrodialyse ou osmose inversée,
la chaleur d'échappement serait disponible
133
 pour la régénération thermique d'un pro
cédé par échange d'ions pour achever la
déminéralisation. Comme toute l'énergie
d'entrée de combustible de la centrale
Опреснительный Процесс «Сайротерм» —
Ионообменный Процесс с Термической
Регенерацией
Д. Е. Вейсс, Б. А. Болто, Р. МакНейлл, А. С. Макферсон, Р. Сюдак,
Е. А. Суинтон и Д. Уиллис
Австралия
В то время как стоимость дополни
тельного снабжения городов водой не
прерывно возрастает, а ее качество
ухудшается при широко применяемом
повторном использовании, существуют
четыре логических, следующих одна за
другой стадии водяного хозяйства для
снижения расходов.
(1) Улучшение методов консервации;
(2) Регенерация сбросных вод для
повторного использования;
(3) Опреснение вод маргинального
качества, которые слишком со
лоны для общего употребления;
(4) По эффективном использовании
воды надо утилизировать отда
ленные ресурсы с помощью до
рогостоящих трубопроводов или
опреснять морские и сильно-со
лоноватые воды.
Когда в засушливых областях речная
вода усиленно и повторно использует
ся, то накапливаются неорганические
соли. Районные органы, наблюдающие
за солесодержанием, требуют отделе
ния от реки идущих на орошение сбро
сных вод с применением дешевого
опреснительного процесса для удаления
из них соли, которая накапливается с
каждым повторным муниципальным
или промышленным циклом. Солесодер-
жание обыкновенно не достигает 500
мг./л. Если бы опреснялись, находя
щиеся поблизости, подземные воды, то
создавалось бы пространство, которое
в дождливые периоды снова бы запол
нялось избыточными водами хорошего
качества, уменьшая этим опреснитель
134
thermique pourrait ainsi être utilisée, il
ne serait pas nécessaire de produire de
l'électricité en tant que sous-produit.
ную нагрузку. Применение местного
опреснения в целях регулирования со-
лесодержания заслуживает всеобщего
внимания, так как удаление небольших
количеств соли вероятно можно до
стичь за 10 центов/ 1.000 галлонов, и
оно более срочно требуется, чем обра
ботка сильно загрязненных источников,
как например морской воды. Это бы
позволило полностью использовать су
ществующие речные ресурсы. Основ
ные соображения наводят на мысль,
что наиболее дешевым процессом для
достижения этой цели является приме
нение ионообменных смол, регенери
руемых не химикалиями, а теплом.
В этом докладе приводится лабора
торное исследование, указывающее,
что смесь слабо-электролитных амино-
кислых и карбонокислых смол адсор
бирует соль при температуре окружа
ющей среды и может регенерировать
ся с помощью исходной или опреснен
ной воды при 80°С. Нагрев десорби-
рует соль из перемешиваемого слоя,
уменьшая основность смолы слабого
основания. Работа до настоящего вре
мени была преимущественно посвяще
на изучению равновесия.
Кривые титрования аминовых смол
либо плато-образны, либо наклонны.
Форму кривой и основность смолы мо
жно сильно изменить путем изменения
структуры смолы, но, у находящихся
сейчас в продаже смол карбоновой ки
слоты, кривые титрования наклонны.
Самое большое различие в количествах
адсорбированной соли из холодных и
 горячих растворов (эффективная спо
собность) бывает у двух таких смол,
кривые титрования которых, измерен
ные в горячих и холодных растворах,
как можно больше перекрываются.
Увеличение соотношения кислоты к
основной смоле увеличивает количе
ство соли, которое может десорбиро-
ваться посредством нагрева и при каж
дом отдельном значении pH для ад
сорбции существует оптимальное со
отношение смол. Изменение ионной
силы меняет относительное положение
кривых титрования и тем самым замет
но влияет на эффективную способность
и на условия оптимальной характери
стики. Из кривых титрования можно
получить диаграммы, где приблизитель
ные эффективные способности различ
ных комбинаций смол, при их опти
мальных соотношениях, могут быть
представлены, как функции pH. Такие
кривые ценны для производства отбо
ра, так как ввиду наличия многих ком
бинаций смол приходится делать срав
нения при заданной ионной силе и оп
тимальных условиях pH и соотношения
смол. Поэтому кривые титрования об
легчают возможность составления ха
рактеристик отдельных смол.
Опыты показывают, что равновесие
многих пар смол целиком зависит от
pH и, что среди изученных и находя
щихся в продаже, наилучшими сейчас
являются "De-Acidite G" и "Zeo-Karb
226". Эта пара смол была детально ис
следована при 20-80°С и в растворах,
содержавших 500, 1.000, 1.760, 3.000 и
5.000 мг./л. хлорида кальция. Обрати
мая сущность равновесия была нагляд
но показана на закрытых образцах при
более, чем 5.000 горячих и холодных
циклов с моновалентными ионами, и
при более, чем 1.000 циклов с ионами
кальция, магния и сульфатов. При
90°С выбранные смолы оказались ста
бильными в растворах, почти не содер
жавших кислорода. Но нам все же при
дется показать, что процесс сможет
функционировать при минимальном
сроке службы смолы в 10.000 циклов и
перемене раствора при каждом цикле.
Нижеследующие результаты, полу
ченные со смесями "Zeo-Karb 226",
SRC44 и "De-Acidite G", SRAI02, на
глядно показывают, что термический
эффект между 20°С и 80°С подходит
для производства важной опреснитель
ной работы. Обработка в колонке ис
ходной воды, содержавшей 1.000 мг./л.
хлористого натрия, давала продукт с
минимальной концентрацией 230 мг./л.
и сброс с максимальной концентрацией
4.800 мг./л. пользуясь в качестве реге
нератора исходной водой при 80JC.
Лучшие результаты были получены с
регенеративным раствором 500 мг./л.
хлористого натрия. Удачно опреснялся
рассол с содержанием 3.000 мг./л. хло
ристого натрия. Раствор 1.000 мг./л.
MgS04 давал продукт с минимальной
концентрацией ПО мг./л. и концентра
цией сбросного раствора 5.500 мг./л.
Было установлено, что одновременно
с опреснением можно достичь и смяг
чения воды. Для определения оптималь
ных рабочих условий потребуются
дальнейшие опыты с применением ко
лонок, а потому еще нельзя вынести
заключение в связи с полученными ре
зультатами.
Исследования с микро-шариками, ди
аметром около 5-10 микронов, дают
основание полагать, что скорость ре
акции будет приемлемой для практи
ческих целей, но с окончательными вы
водами придется обождать, пока не
окончено ведущееся сейчас изучение
влияния флоккуляции и поперечной
связи. Вышеописанные исследования,
производимые с помощью обычных
колонок периодического действия, яв
ляются самым простым лабораторным
методом для ознакомления с ходом
многоступенчатого процесса, но такие
приемы неприменимы на практике. На
работе большого масштаба может ока
заться возможным проводить процесс
в противоточно установленных ме-
шально-фильтрационных агрегатах, так
как флоккирующий перемешиваемый
слой микро-шариков быстро фильтрует
и не было замечено их растрескивания
после сильного перемешивания в те
чение 6.500, следовавших один за дру
гим, горячих и холодных циклов. При
дется принять меры для удаления кол
лоидов. Альтернативным методом ма
лого масштаба могло бы быть приме
нение смолы в одной стадии реакции
с неподвижным слоем, входящей в
циклическую систему периодического
действия, где условия противотока мо
гут симулироваться разделенным (на
двое) потоком исходной воды и элюи-
рованием. Пока не получены данные с
помощью пробной установки, невоз
можно подсчитать максимальную кон
центрацию исходной воды, поддающу
юся экономичной обработке, но ее сто
имость будет возрастать с увеличением
солесодержания. Если тепловая маши
на будет давать энергию для частич
ного опреснения морской или сильно-
135
 солоноватой воды методом электроди
ализа или обратного осмоса, то для за
вершения опреснения можно будет ис
пользовать сбросное тепло для терми
ческой регенерации ионообменного
процесса. В этом случае будет цели
El Proceso de
"Sirotherm" un
cambio Iónico con
Térmica
D. £. Weiss, В. A. Boite, R. McNeill, A. S. Macpherson, R. Siudak,
E. A. Swinton y D. Willis
Australia
A medida que incrementos de suministro
municipal de agua se encarecen progresiva
mente y la calidad sufre deterioro debido
a un reuso más generalizado, hay cuatro
etapas en la administración de aguas para
reducir costos:
1) Mejora de los métodos de conversación.
2) Recuperación de efluentes para reuso.
S) Desmineralización de aguas de calidad
marginal por su alta salinidad para
uso general.
4) Una vez logrado un uso eficiente del
caudal disponible, se deberán usar
fuentes de abastecimiento más caras,
por bombeo mediante tuberías muy
extensas o por desalinización de agua
de mar o aguas muy salobres.
Cuando agua de río es reusada extensiva
mente en climas áridos se produce una
acumulación de sales inorgánicas. Un con
trol regional de salinidad requiere la sepa
ración de aguas de drenaje de irrigación de
las del río y un proceso económico de des
mineralización para eliminar la salinidad
que se acumula en cada ciclo de uso muni
cipal o industrial. Salinidad ésta, que es
generalmente menor de 500 ppm. Si se des-
mineralizaran aguas subterráneas cercanas,
podrían establecerse depósitos que podrían
ser rellenados con excedentes de aguas de
buena calidad en tiempos de abundancia,
reduciéndose de este modo el volumen que
debe ser producido por desmineralización.
l.i utilización de la desmineralización en el
I 36
ком использовано горючее, израсходо
ванное тепловой машиной, и отпадает
надобность производить электрическую
энергию, являющуюся побочным про
дуктом.
Desmineralizacion
Proceso de Inter
Regeneración
control de salinidad justifica amplia aten
ción dado que la eliminación de pequeños
grados de salinidad de logra, probable
mente, por 10 centavos cada rail galones y
es más urgentemente necesaria que el trata
miento de aguas de fuentes altamente im
puras tales como el agua de mar. Ello
podría hacer posible una completa utiliza
ción de las fuentes existentes en los ríos.
Razones fundamentales sugieren que el pro
ceso más económico para esta finalidad
podría basarse en resinas permutadoras de
iones regeneradas por calor más que por
medios químicos.
Este trabajo presenta una investigación de
laboratorio mostrando que una mezcla de
amina débilmente electrolítica y resina de
ácido carboxílico absorbe sales a tempera
tura ambiente y puede ser regenerada con
aguas de alimentación o aguas resultado del
proceso a 80°C. El calor provoca desabsor
ción de sales de la mezcla por reducción
de la alcalinidad de la resina débilmente
básica. Hasta la fecha los trabajos se han
limitado mayormente a estudios de equi
librio.
Las resinas amínicas poseen curvas de
valoración de forma horizontal o inclinada;
la forma de la curva y la basicidad de la
resina pueden ser variadas considerable
mente por alteración de la estructura de la
resina, pero las resinas de ácido carboxílico,
disponibles hasta ahora, tienen curvas de
valoración inclinidas. La diferencia en la
 cantidad de sal absorbida de soluciones
Was y calientes (capacidad efectiva) es
mayor para un par de resinas cuyas curvas
de valoración, medidas en soluciones frías y
calientes, se sobre-montan tanto como es
posible. Incrementando la relación de resina
acida a la básica, incrementa la cantidad
de sal que puede ser desabsorbida por ca
lentamiento y para cada valor de pH de
absorción hay una proporción de resinas
óptima. Un cambio en la fuerza iónica
altera la posición relativa de las curvas de
valoración y de ese modo influye marcada
mente en la capacidad efectiva y en las
condiciones para un trabajo óptimo. De las
curvas de valoración pueden derivarse gráfi
cas que muestran las capacidades efectivas
aproximadas de diferentes combinaciones de
resinas como función del pH determinadas
a proporciones óptimas de resinas. Tales
curvas son valiosas como guias de selección
dado que la selección entre distintas com
binaciones de resinas disponibles requiere
comparaciones que deben ser hechas a una
fuerza iónica dada, bajo condiciones ópti
mas de pH y de proporción de resinas. Las
curvas de valoración, por lo tanto, sumini
stran un método simple para caracterizar
Tesinas individuales.
Los experimentos demuestran que el
equilibrio para muchos pares de resinas
depende del pH y que, de aquéllas exami
nadas hasta el presente, el mejor par co-
mercialmente producido consiste de "De-
Acidite G" y "Zeo-Karb 226". Se han hecho
estudios detallados de este par de resinas
a aproximadamente 20 y 80°C en soluciones
conteniendo 500, 1000. 1760 y 5000 ppm de
cloruro de calcio. La naturaleza reversible
del equilibrio ha sido demostrada en
muestras selladas sobre más de 5000 ciclos
en frío y caliente para iones monovalentes
y sobre 1000 ciclos para iones de calcio,
magnesio y sulfato. Las resinas seleccionadas
han demostrado ser estables a 90°C en solu
ciones casi exentas de oxigeno. Nosotros
tenemos aún que demostrar que el proceso
puede ser operado con una resina cuya vida
sea de por lo menos 10.000 ciclos con
cambio de solución en cada ciclo.
Los siguientes resultados con mezclas de
"Zeo-Karb 226", SRC 44 y "De-Acidite G",
SRA 102, demuestran que el efecto térmico
entre 20 y 80°C es adecuado para la efi
ciencia de operaciones de desmineralización.
Tratamiento de columna con agua de ali
mentación conteniendo 1000 ppm de NaCl
da lugar a un producto con una concentra
ción minima de 230 ppm y un efluente con
una concentración máxima de 4800 ppm,
usando el agua de alimentación a 80°C
como regenerante. Mejores resultados fueron
obtenidos mediante el uso de una solución
regeneradora conteniendo 500 ppm de NaCl.
Una solución conteniendo 5000 ppm de
NaCl ha sido desmineralizada con éxito.
Una solución de MgSO, con concentración
de 1000 ppm de un producto con una con
centración de 110 ppm y un efluente de
5500 ppm. Se ha demostrado que simultá
neamente con la desmineralización puede
lograrse ablandamiento. Se requieren más
experimentos en columna para determinar
las condiciones óptimas de operación, de
manera que no se justifican por el momen
to comparaciones rigurosas.
Estudios usando microperlas con diáme
tros de aproximadamente 5-10 micrones
sugieren que su velocidad de reacción será
aceptable para un proceso práctico, pero
para alcanzar resultados concluyentes, de
berá esperarse los resultados de los estudios
en proceso sobre la influencia de la flocula-
ción y enlaces cruzados. Los estudios con
columna convencional descriptor consti
tuyen el medio de laboratorio más simple
para examinar el comportamiento de un
proceso de múltiples etapas pero tales pro
cedimientos no se usarían en la práctica.
A escala mayor puede ser posible operar
el proceso mediante mezcladores-filtros dis
puestos en contracorriente dado que un
lecho floculado de microperlas filtra rápida
mente y no hay rompimiento observable de
las microperlas de 5 a 10 micrones después
de vigorosas agitaciones en 6.500 ciclos ca
lientes y fríos sucesivos. Sería necesario
contar con medios para remover los co
loides. Un procedimiento alternativo para
empleo en pequeña escala podría ser el
usar resina en una sola etapa de reacción
en un lecho fijo, funcionando en un sistema
de partidas cíclicas y simulando condiciones
de contracorriente mediante técnicas com
binadas de alimentación y elución. Hasta
contar condatos de planta piloto, no es
posible estimar la concentración máxima
del agua de alimentación que podría ser
tratada económicamente pero el costo
aumentará al aumentar la salinidad. Si un
motor térmico proporciona fuerza para la
desmineralización parcial de agua de mar o
aguas muy salobres, por electrodiálisis u
osmosis invertida, el calor de escape podría
ser usado para la etapa de regeneración
térmica de un proceso de intercambio iónico
para completar la desmineralización. Dado
que todo el insumo de combustible del
motor térmico podría entonces ser usado,
no sería necesario producir electricidad
como subproducto.
1S7
An Appraisal of
Methods at the
Evaporator Plant in San Diego,
California
Stewart Mulford, Julius Glater, J. W. McCutchan
United States of America
INTRODUCTION
The reliability of large-sized land-based
distillation equipment has been well estab
lished during the past decade. It would
appear that distillation, especially the multi
stage flash process, is presently the best
developed method for application to large-
scale demineralization of saline waters, es
pecially those of high salinity. Feasibility
studies are currently underway for nuclear
powered plants with capacities on the order
of 50 to 150 mgd.
The success of flash distillation arises from
inherent mechanical simplicity of design
and comparatively high resistance of equip
ment to scale formation. This is due, in
part, to the separation of evaporating and
heating functions in this type of plant. One
of the most important economic obstacles
to low cost distilled water is the accumula
tion of mineral scale. Scale deposits can
have two important effects in an evapora
tion apparatus. First, scale on heat transfer
surfaces offers a resistance to the flow of
heat which can be of the same order of
magnitude as the other major resistances in
the thermal circuit. The lower the original
"clean surface" resistance is, the less the
amount of scale required to produce a
noticeable effect. The effect of increasing
the resistance to heat transfer is usually to
increase the ratio of energy input to product
from the apparatus. Second, scale deposits
can accumulate in pipelines, orifices, and
other flow passages to the extent that the
flow of process fluids is seriously impeded.
Scale Control
O.S.W. Flash
This also results ultimately in an increase
in the ratio of energy input to product. In
either case there is a strong economic in
centive to prevent the deposits from becom
ing very thick, or better yet, to completely
prevent their forming. As an illustration of
these effects, deposits of scale and organic
sludge which occurred in the brine heater
and condenser
i tubes of the Office of Saline
Water Demonstration Plant in San Diego,
California, which were barely detectable by
observation of he surfaces, were neverthe
less sufficient to cause an increase in the
specific fuel consumption of the plant in
the order of 10 per cent.
Although flash distillation appears favor
able from a scale point of view, measures
must still be taken to restrict the accumula
tion of these troublesome mineral deposits.
In this paper, we shall report on a series of
experiments performed with a commercial
size 36-stage flash evaporator of one mgd
capacity. This water conversion plant, lo
cated in San Diego, California, was built
and operated under the auspices of the
Office of Saline Water Demonstration Plant
Program in cooperation with the California
Department of Water Resources, and was
"on stream" over a period of about twenty-
four months. In March of 1964, the plant
was dismantled and shipped to the U.S.
Naval Base at Guantanamo Bay, Cuba. This
experimental program had two basic objec
tives. First, we were interested in evaluating
current methods of alkaline scale control.
139
Second, we wished to study the performance
of this equipment at elevated temperatures
and salinities where calcium sulfate scale
usually presents a problem. The San Diego
plant showed excellent resistance to scale
accumulation because of certain unique de
sign features of the flash system. The effects
of these features on plant performance will
be discussed later.

SCALE FORMATION AND CONTROL

At this point we would like to review deposited on a metal surface, calcium sul
briefly the chemistry of scale formation, fate produces a hard tenacious coating
commenting on current practices in scale which is difficult to remove mechanically.
control. The vast literature on this subject Whereas alkaline scale is easily controlled
goes back over one hundred years and is by chemical additives and can be removed
often confused and controversial. Silver (ref. with acid, the only proven method for pre
1) emphasized the importance of scale con venting calcium sulfate scale is by control
trol in his statement, "The history of dis of evaporator operating conditions.
tillation is the history of control of scale All three varieties of calcium sulfate have
formation." Reviews of both old and cur been found in scales from saline water
rent literature have been presented by evaporation. Gypsum occurs only in low
Partridge (ref. 2) . Badger (ref. 3) . and temperature evaporators, since it become';
McCutchan and Glater (ref. 4) . a short-lived metastable phase above 99°F.
In an engineering sense, scale consists of The most often encountered scales consist
a mineral deposit of inorganic salts whose of hemihydrate, anhydrite, or a mixture of
solubilities decrease with increasing tem these forms. Langelier (ref. 5) was the first
perature. Scale deposited from sea water to define stability limits for hemihydrate
and most brackish waters is classified as and anhydrite in boiling sea water at 212T.
alkaline scale or calcium sulfate scale, de His work predicts hemihydrate formation
pending on the mechanism of formation. and offers a clear explanation for the pre
Alkaline scale results from thermal break cipitation of this compound in distillation
down of the bicarbonate ion found in all equipment operating at the atmospheric
natural waters. This process gives rise to boiling point. Although this solid hydrate
carbonate and hydroxide ions in the brine, is metastable above 99°F, it reaches equilib
producing insoluble precipitates with dis rium with dissolved ions more rapidly than
solved calcium and magnesium ions respec anhydrite. In supersaturated boiling brine
tively. The overall chemical mechanisms are solutions containing calcium and sulfate
summarized in Figure 53. The relative ions, hemihydrate l>egins to deposit almost
amounts of calcium carbonate and mag immediately and complete equilibrium with
nesium hydroxide deposited depend on the the solid phase is reached in about 2 hours.
temperature and rate of carbon dioxide evo Anhydrite is clearly the most stable phase
lution from evaporating brine. Alkaline above 99°F, but approximately 17 hours are
scale can. in fact, form in unconcentrated required before any transition of hemi
sea water as a result of heating alone: re hydrate to anhydrite occurs. Complete phase
lease of carbon dioxide is the onlv require transition is accomplished in about 40
ment. Calcium sulfate, on the other hand, hours. At 212°F, saturation with respect to
will not deposit until some critical concen hemihydrate occurs at a concentration fac
tration is reached at a given distillation tor of 3.1; for anhydrite the value is 1.5.
temperature. No chemical changes are in The latter figure is only hypothetical since
volved in this deposition process. You will in actual practice a residence time of 17
observe from Figure 54 that three different hours would be an unrealistic value in
crystalline modifications of calcium sulfate most distillation processes. Langelier's often
may exist in equilibrium with dissolved quoted threshold value of 3.1 has long been
calcium and sulfate ions. used as a guideline for the design of dis
Calcium sulfate encrustations pose a seri tillation equipment. It must be remembered,
ous problem in sea water distillation. Unlike however, that this value was derived from
alkaline scale, these deposits: (1) are in pure equilibrium considerations based on
soluble in most common laboratory rea bulk brine concentration. The effect of heat
gents: (2) cannot be controlled by simple transfer rate, local concentration effects, or
pH adjustment; and (3) present an es type of distillation process was not con
pecially serious problem at high tempera sidered in his studies. Although pure hemi
tures due to the steeply sloped inverted hydrate crystals are often found (as pre
solubility curves shown in Figure 55. Once dicted) in scale samples, Mcllhenny (ref. 6)
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 PFIGURE
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SCALE
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WATERS.
SALINE

Mineral
Name Hemihydrate
Aragonite Anhydrite
Calcite Brucite
Gypsum

CaSO^-i^O CaSO^I^O
Compound
Mg(0H)2 CaSO,.
CaC03
has consistently identified anhydrite scale in
high temperature effects at the Freeport and
Roswell Office of Saline Water demonstra
tion plants. The exact mechanism of an
hydrite deposition is not clearly understood
and could not be predicted fom Langelier's
stability diagrams (ref. 5) . Unfortunately,
Langelier's work was carried out at 140° and
212°F only. Since modern distillation equip
ment is designed to operate at 250° to
275°F, there is a pressing need to extend
these equilibrium and kinetic studies to
higher temperatures.
The equilibrium solubilities of anhydrite
 and hemihydrale in pure water have been
documented by several independent workers
(refs. 2, 7) at temperatures between 212°
and 400°F. Since calcium sulfate solubility
varies markedly with ionic strength, such
data cannot be applied directly to natural
brines. Very little work has been carried
out at temperatures above 212°F. Some
recent studies by Marshall (ref. 8) and
Power (ref. 9) , however, present high tem
perature solubility data for calcium sulfate
in pure sodium chloride solutions. MarshaH
hopes to use his data to make predictions of
calcium sulfate solubility in natural brine
solutions of varying ionic composition. At
present, there has been no experimental
verification of his predictions.
From an engineering viewpoint, the phase
diagram submitted by Standiford and Sinek
(ref. 10) is the only practical data which
has appeared to date. Although not rigor
ously developed, the diagram shown in Fig
ure 55 represents an attempt to predict
scaling limits in sea water up to 825°F.
Work at the San Diego plant involved,
among other things, a study of scale re
sistance in a large flash evaporator at tem
peratures up to 250°F. In these experiments,
our interest was focused on establishing the
validity of the Standiford and Sinek curves
for this plant.
Control of scale is the key to low cost
distilled water and presents a challenging
problem to both the chemist and the chemi
cal engineer. The most popular methods
of alkaline scale control are polyphosphate
based additives and acid injection. Both
methods arc effective and economical in
Hash evaporators. The first retards scale but
does not completely inhibit it. The use of
polyphosphate additives is also limited to
temperatures below 200°F. Hagcvap L.P.
(ref. 11), the leading proprietarv polyphos
phate formulation, was used successfully in
the San Diego program. The second method
may give rise to some corrosion and re
quires effective gas ejection equipment. De
tails of results with these methods will be
presented later.
Calcium sulfate scale control is best ac
complished by operating outside the "un
stable region" of potential scale formation.
The limit of this region undoubtcdlv varies
with the type of equipment used and dis
tilling conditions. F.lforts were directed to
ward finding a better definition of the
boundary of this critical region for a large
multistage flash evaporator. Other promis
ing methods for control of calcium sulfate
scale are seeding and ion-exchange de-
mineralization. Seeding techniques have
144
been extensively studied in the United
States and Japan (refs. 12, IS) and have
l>cen successfully applied in a number of
chemical processing industries. Basically,
these techniques involve the introduction
of small quantities of fine "seed" crystals
into the hot brine. Suspended crystals with
large surface areas may thus compete with
heat transfer surfaces in precipitation of
scale. The sludge thus formed remains sus
pended in the blowdown, leaving no residue
in the evaporator. A modification of this
method, called the sludge recycle system,
involves recirculating a small portion of
blowdown into the makeup water. In this
manner, seeds are generated in situ once
the distillation process is underway. Al
though the economics of seeding appear
attractive, no large-scale application has as
\et become operational. A unique, self-
generating, seeding technique recently de
scribed by Fisher and Cilbert (ref. 14) uses
a pilot plant multistage flash evaporator.
When acidified dearcated sea water is con
centrated rapidly to a C F. between 5 and
K. a milkv slum of calcium sulfate crystals
forms in the blowdown. Scale free operation
is realized at temperatures below 140°F.
Between CF. 3 to 5. scale formed readily:
above this concentration barrier, nucleation
look place preferentially in the evaporating
brine. The slurry was not analyzed but
probably consisted of gypsum crystals (since
the temperature approached the stable re
gion for gypsum shown in Figure 55) . This
phenomenon mav also indicate a positive
slope for the gvpsum solubility curve. Such
an orientation would favor more precipita
tion at lower temperatures. The explanation
for these results is unknown at this time,
but the development is interesting and
bears close scrutiny.
The reduction of calcium ion content in
saline waters by cation-exchange columns
has been studied extensivelv by the Dow
Chemical Company (ref. 15) . Good results
in the laboratory and pilot plant have led
to the installation of a large ion-exchange
system for the Office of Saline Water demon
stration plant at Roswell. Xew Nfexico. In
spite of favorable predictions, this system
has been plagued by numerous operational
problems and limitations. Anv method for
economically reducing the concentration of
calcium ion. sulfate ion, or both in evap
orator feed water would permit higher
temperature operation of distilling plants.
Until good low cost demineralization sys
tems can be developed, or seeding tech
nology is further advanced, we are faced
with the problem of better defining the
limits of temperature and concentration to this end that the experimental efforts at
factors permitting scale-free operation. It is the San Diego plant were directed.

EXPERIMENTS WITH ALKALINE SCALE CONTROL

The San Diego flash plant was the second chambers although this area is prone to
distillation unit built under the Office of corrosion and accumulation of silt or other
Saline Water demonstration plant program. suspended material. The San Diego plant
Active operation began in March 1962 and normally operated in a range of concentra
was terminated in March 1964, when the tion factors between 1-5 and 2.0, but in some
plant was dismantled and shipped to Guan- tests of short duration concentration factors
tanamo Bay during the Cuban water crisis. as high as 2.9 were achieved. Brine concen
Study and evaluation of two different meth tration was regulated by altering the por
ods of alkaline scale control were carried tion of blowdown recirculated through the
out during this period. Experiments were brine loop.
also performed to determine the effect of Initial runs at San Diego were carried out
temperature and brine concentration on at a maximum temperature of 200°F and a
deposition of calcium sulfate. The theory concentration factor of 1.5. Under these cir
and practice of multistage flash distillation cumstances, only alkaline scale formation is
have been discussed by Frankel (réf. 16) , anticipated. During the first 5,399 hours of
Silver (réf. 1) . Mulford (réf. 17) , and plant operation, scale was effectively con
Leitncr (réf. IR) . Specifications for the San trolled with Hagevap L.P. Hagcvap is a
Diego plant were prepared by the Fluor mixture of sodium polyphosphates, lignin
Corporation of Los Angeles and the final sulfonic acid derivatives, and various esters
design by Westinghouse Electric Company. of polyalkylene glycols. These ingredients
Design and operating data for this installa act synergist ically to prevent alkaline scale
tion have been described in several reports formation by a mechanism not clearly
(refs. 19, 20) . Ambient sea water passes understood since Hagevap is effective even
through the heat recovery section of the at very low concentrations (S to 5 ppm) .
evaporator where it picks up heat from The molar concentration of Hagevap in
condensing vapor. It then enters the steam gredients is only a small fraction of the
heated brine heater where the temperature molar concentration of scale-forming ions.
is raised to about 200°F under nonboiling Good results were obtained with Hagevap
conditions.^ Hot brine now enters the first but a slight decrease in output was noted.
of a series of 36 flashing chambers main This decrease, due to light scale deposits,
tained at progressively reduced pressures. In was reflected in a rise in pressure and tern
each chamber, a portion of steam is "flashed perature of steam supplied to the brine
off" and condensed, thereby reducing the heater and a fall in gain ratio." It is inter
pressure in the system and the temperature esting to note that thermal performance is
of the brine. This process is repeated 35 actually the most sensitive criterion of scale
more times until the discharge brine achieves formation. Deposits which drastically affect
a temperature of about 90°F and the pres heat transfer rates were often hardlv visible
sure in the final chamber reaches about 0.05 when the plant was shut down for cleaning
atm. The plant was designed to operate at purposes. During two long runs with Hage
a maximum temperature of 250°F and a vap (6 and 4 months) , a slow, steady de
brine discharge temperature of 90°F. Since terioration of performance was noted at a
scale-forming salts show inverted tempera rate of less than 5 per cent per month. After
ture solubility curves, the region of most shutdown, deposits were analyzed and found
severe potential scaling is at the exit of the to consist primarily of alkaline scale (i/j
brine heater which is the point of highest CaCO, and 2/¡ Mg (OH),) along with small
temperature in the brine loop. This was quantities of silica. The silica was believed
shown during plant shutdowns. In one test, to result from mechanical entrapment of
heavy scale was encountered in the last foot fine sand particles in the scale matrix.
of brine heater tubes and lighter scale At the close of the six-month Hagevap
throughout the rest of the heater length. run, the plant was shut down and com
Scale is rarely found in the flashing pletely descaled by an outside contractor.
Toward the end of the second run (4
* One of the distinguishing features of flash months} . an acid injection system was in
distillation is the fact that sufficient pressure is stalled. In addition to Hagevap, sulfuric
maintained throughout the brine heater to pre
vent boiling. acid was introduced for the last 168 hours
, ratio
••Gain . = lb distillate
тт-— of running time. This in situ descalinj;
lb steam
145
operation was apparently successful, as 56 summarizes thermal performance for the
shown by a return of thermal performance entire four-month run.
to the levels of clean tube operation. Figure
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 In September 1962, the Hagevap treat
ment was discontinued and sulfuric acid
injection was used as the sole method of
alkaline scale control. Acid injection was
continued for the duration of the plant's
stay in San Diego, a total of 8,649 hours of
running time. This change was introduced
in an attempt to operate at or near the
maximum design temperature of 250°F.
Such experiments could not be conducted
with Hagevap since it undergoes rapid
chemical decomposition above 200°F. As a
result of acid injection, excellent thermal
performance was maintained in the normal
range of temperatures and brine concentra
tions. It was also found that scale-control
costs, using either Hagevap or sulfuric acid,
were approximately equal. The cost of
either method is about three cents per 1,000
gallons distilled water. There is a very little
additional cost for a mi foam agent with acid
treatment.
Concentrated sulfuric acid (tech grade)
was introduced directly into the feed water
at a measured rate to give 120 ppm by
weight (stoichiometrically equal to bicar
bonate ion concentration) . The ambient
pH of about 8.3 dropped drastically at the
point of acid addition and rose rapidly due
to mixing and deaeration. After reaction
with bicarbonate ion, the residual alkalinity
was reduced from 140 ppm to about 12 ppm
EXPERIMENTS IN THE CALCIUM SULFATE SUPERSATURATED REGION
Although alkaline scale can be controlled
easily and at low cost, the calcium sulfate
problem is by no means near solution. Seed
ing or ion-exchange may provide an answer
but neither is operational at this writing,
and we must still rely on effective control of
distillation parameters. When the San Diego
plant was found to operate efficiently and
reliably with acid injection at approxi
mately 200°F and C.F. of 1.7, it was decided
to explore higher temperatures and concen
tration factors (known to be in the calcium
sulfate range) . These experiments were de
signed to collect badly needed data and also
to check the position of the Standiford and
Sinek curves (ref. 10) . The lines in Figure
55, passing through points A, B, C, and D,
represent the heating and concentrating of
the brine by recirculation. Details of this
cycle have been presented by Mulford (ref.
21). Segment DE shows the change in tem
perature and concentration factor during
the flashing process. Operational triangles
similar to CDE can be drawn through other
points representing higher temperatures and
concentration factors. In a given high tem
and the pH rose to 7.5, as measured at the
discharge side of the brine recycle pump.
The rapid reaction between acid and bicar-
Ixmate was enhanced by a very effective
deaeration system which caused the follow
ing reaction to proceed nearly completely
to the right.
HCO," + H* ;± H.O + CO, (g)
With acid injection, the volume of non-
condensable gases vented from the evap
orators was nearly doubled; about half this
volume was carbon dioxide. In order to
avoid excess corrosion, most plants using
acid injection are equipped with a system
for neutralizing excess unreacted acid. This
is done by introducing sodium hydroxide
at some point downstream from the acid
source. The San Diego plant was provided
with such an installation but neutralization
was unnecessary due to rapid recovery of
pH values. Acid injection worked excep
tionally well without abnormal corrosion
since excess acid (above stoichiometric
quantity) was never required. These good
results were probably due to uniform mix
ing of brine with acid and to rapid dissipa
tion of carbon dioxide from acidified brine.
It might be noted that acid injection was
regulated by flow control rather than level
control at this plant. A summary of alkaline
scale control runs is presented in Figure 57.
perature experiment, for example, water
might be distilled at 250°F with an initial
concentration factor of 15. This is repre
sented by operating line triangle CD,F.,.
Similar triangles could be drawn through
other points representing higher tempera
tures and concentration factors. Points D,
through D, correspond to actual cycle con
ditions for several different tests.
Short successful explorations into the high
temperature region were made by running
at points D, and D4. It is interesting to note
that maximum output was achieved during
these runs. In a single 24-hour period, dis
tilled water production totaled approxi
mately 1,400,000 gallons, limited only by
the capacity of the product pump Cdesigned
to handle only one mgd) . The plant was
then operated continuously in the range
represented by point Dt. This test was
carried out under scale-free conditions at a
point just under the hemihydrate curve for
a period of 884 hours. It was then decided
to check the apparent position of this curve
by exploring the supersaturated region as
represented by points D„ D„ D„ and D„.
The plant was run for 350 hours at point
D, and 357 hours at D, with no decline in
thermal performance due to scale. D, and
D, represent short runs of 57 and 24 hours,
respectively- When normal operation could
be maintained at C.F. 2.5 (Da) , the concen
tration factor was again increased to 2.9
(D,) . A few hours after this condition was
reached, a rapid fall in thermal performance
was observed. Scale was not appreciably
diminished by "throttling back" to 200°F
and C.F. of 1.35. The plant was ultimately
shut down and inspected. Heavy deposits
were noted in the downstream side of the
brine heater tubes with the most intense
scaling in the last foot. The deposit aver
aged i/£ inch thick, but some tubes were
completely plugged. Attempts to dissolve
this material indicated that it was probably
calcium sulfate: no crystallographic analyses
were made.
It would appear that an effective scaling
threshold had been reached at point D„ but
operating circumstances raise doubts that
this was the case. The uneven distribution
of scale deposits indicated the probability
that boiling had occurred in the brine
heater tubes just prior to this run. This
suspicion was borne out by certain recorded
operational difficulties in the boiler and
turbine-driven pumps. These malfunctions
resulted in a pressure drop in the brine
heater tubes below the saturation pressure
corresponding to 250°F. Under these con
ditions, the resultant higher wall tempera
tures could initiate premature scale forma
tion as compared with nonboiling operation.
Once nucleation was begun, scale would
CONCLUSIONS
The reliability of two different methods
of alkaline scale control has been clearly
demonstrated by this work at San Diego.
Both Hagevap and sulfuric acid injection
gave good results on long continuous runs.
Although periodic acid cleaning was neces
sary with Hagevap, it could be accomplished
while the equipment remained "on stream".
Acid injection was found preferable to
Hagevap, however, since no maintenance
was required under normal operating con
ditions. The acid system worked without
excessive corrosion, requiring no back neu
tralization with sodium hydroxide. Its chief
advantage was the extended range of pos
sible operating temperatures. High tem
perature experiments could thus be carried
out (in the calcium sulfate range) without
complications from alkaline scale. Scale-free
operation was consistently achieved in the
deposit rapidly in the unstable region even
if nonboiling operation was resumed. The
last series of experiments and explorations
could not be completed because the plant
was dismantled and shipped to Cuantanamo
Bay, Cuba.
The reader will note that points D3
through D5 are in the unstable region for
anhydrite and D is right on the line. Ex
perience at San Diego tends to support
Langelier's position since scale-free opera
tion was consistently achieved in this region.
Although the anhydrite precipitation thresh
old is exceeded, this scale would not be
anticipated because of the short residence
time of the supersaturated brine. The long
scale-free runs at points D, and D, appear
to be conclusive and would lend to chal
lenge the position of the hemihydrate curve
(Fig. 55) in this region. These results would
shift the Standiford and Sinek curve up
ward and to the right at 250° F for this
flash plant. Data indicated by points D» and
D, are inconclusive due to short duration
runs and boiler malfunctions accompanying
them. It would appear that the hemihydrate
line reaches point D7 or possibly higher.
What about points D, and D„? Is it possible
to carry out scale-free operation in this
region, or were these tests of such short
duration that equilibrium conditions could
not be achieved? Hopefully, these opera
tional areas will be re-explored at the flash
plant planned to replace this facility. Only
then can these experimental results be con
firmed. The work thus far at San Diego,
however, indicates a steeper slope for the
hemihydrate curve in the region investigated.
previously described unstable range for
anhydrite. Explorations in the hemihydrate
region gave scale-free performance at 250°F
and a concentration factor of 2.1. Operation
under more severe conditions may also be
possible, but results are inconclusive at this
time.
Several interesting questions are raised by
the high temperature data presented in this
paper:
1. Is the hemihydrate curve of Standiford
and Sinek (Fig. 55) incorrect for equilib
rium conditions? We might conclude that
this line was correctly drawn and that oper
atton of the San Diego plant was carried
out in a metastable supersaturated region
above the curve.
2. If, in fact, we were operating in a
supersaturated region, how long would it
be possible to continue without scale
 deposit?
3. Can flash plants operate at higher tem
peratures and concentration factors because
of the nonboiling conditions in the brine
heater? The effect of ebullition on scale
nucleation is probably an important factor
in defining threshold conditions.
Further experimentation is imperative.
Based on our findings to date, certain
recommendations can be made to plant
operators.
It has been shown that the precipitation
threshold measured under laboratory con
ditions of slow evaporation may not be the
same as that found in an evaporator operat
ing under industrial loading conditions. The
point made earlier for the anhydrite curve
may also be true for the hemihydrate curve,
i.e., it may be possible for an industrial
evaporator to operate far into the super
saturated region, with respect to hemi
REFERENCES
1. Silver, R. S.: "A review of distillation
processes for fresh water production
from the sea", Proceedings of the Euro
pean Federation of Chemical Engineers
(May 28-June 2, 1962) Athens, Greece,
Dechema Monographien, Nr. 718-834,
Band 47, pp. 1<M2.
2. Partridge, E. P.: "Formation and prop
erties of boiler scale", Univ. of Michi
gan, Dept. Engr., Research Engr. Re
search Bulletin no. 15 (June 1930) .
3. Badger, W. L., et al: "Critical review
of literature on formation and preven
tion of scale", Office of Saline Water
RtD Progress Report no. 25 (July
1959) .
4. McCutchan, J. W.; Glater, J.: "Scale
formation in saline water evaporators",
UCLA Department of Engineering Re
port no. 64-5 (Jan. 1964) .
5. Langelier, W. F.; Caldwell, D. H.;
Lawrence, W. B.: "Causes and preven
tion of scale and corrosion in thermo-
compression equipment when employed
for the distillation of sea water", Univ.
of Calif., Berkeley, IER Series no. 4,
Issue no. 12 (Aug. 1950).
6. Mcllhenny, W. F.: "Calcium sulfate
scale in sea water evaporators", Am.
Chem. Soc. Div. of Water and Waste
Chem. Preprints (Apr. 1965) pp. 42-47.
7. Kelley, K. K.; Southard, J. C; Ander
son, C. T.: "Thermodynamic properties
of gypsum and its dehydration prod
ucts", U.S. Bureau of Mines Tech.
Paper 625 (1941) .
8. Marshall, W. L.: Slusher, R.; Jones,
hydrate as well as with respect to anhydrite.
Thus, there is some danger in taking a
threshold curve developed on one type of
apparatus and under one set of conditions
and applying it indiscriminately to a com
pletely different apparatus and different
operating conditions. This makes it neces
sary to test each type of apparatus sepa
rately in order to determine its limitations,
at least until the phenomenon of scale for
mation is better understood than at present.
It should also be noted that operation of an
evaporator in the supersaturated region may
be tricky and certainly will require close
control of plant operating conditions. Gen
eral experience (possibly confirmed in these
tests) has been that once precipitation
starts, for whatever reason, it is necessary to
back down out of the supersaturated region
completely and probably to remove the
crystals which have deposited.
E. V.: "Aqueous system at high tem
peratures". /. Chem. and Engr. Data,
9:187-91 (Apr. 1964) .
9. Power, W. H.; Fabuss, B. M.; Satter-
field, C. N.: "Transient solubilities in
the calcium sulfate—water system", /.
Chem. and Engr. Data, 9:437-41 (July
1964).
10. Standiford, F. C; Sinek, J. R.: "Stop
scale* in sea water evaporators", Chem.
Engr. Prog., 57:58-63 (Jan. 1961) .
11. Liddell, R. W.: "Method of treating sea
water", Hagan Corp., Pittsburgh. Pa.,
U.S. Patent 2,782,162 (Feb. 19. 1957) .
12. Gainey, R. J.; Thorp, C. A.; Cadwalla-
der, E. A.: "Calcium sulfate seeding
prevents calcium sulfate scale", Ind. and
Engr. Chem. 55:39-^3 (March 1963) .
13. Sugi, J., et al: "On the scale prevention
by addition of crystal seeds", Bull. Soc.
Salt Science, vol. 9, no. 1, Japan (March
1955) p. 38.
14. Fisher, D. A.; Gilbert, F. W.: "Recent
developments in flash distillation". Am.
Chem. Soc. Div. of Water and Waste
Chem. Preprints (Apr. 1965) pp. 1-8.
15. Mcllhenny, W. F.: "Sea water softening
by ion-exchange as a saline water pre-
ireatment". Office of Saline Water R &
D Progress Report no. 62 (May 1962) .
16. Frankel, A.: "Flash evaporation for the
distillation of sea water", Proc. Inst.
Mech. Engrs., vol. 174, no. 7 (1960) .
17. Mulford, S. F.: "Low temperature flash
distillation of sea water", Proceedings
of Symposium on Saline Water Con
version, Office of Saline Water in co
 operation with NAS-NRC. NRC Publ.
568 (Nov. 4-6, 1957) pp. 91-102.
18. Leitner, G. F.: "Operating experience
with a multistage flash type sea water
evaporator and its effect on future de
sign", Proceedings of the European
Federation of Chemical Engineers (May
28-June 2, 1962) Athens, Greece,
Dechema Monographien, Nr. 781-834,
Band 47, pp. 99-112.
19. First Annual Report Saline Water Con
version Demonstration Plant No. 2, San
Diego, California, Office of Saline Water
R&D Report no. 102 (1964) .
20. Saline Water Conversion Report for
1962, U.S. Department of the Interior,
Office of Saline Water (1963) .
21. Mulford, S. F.: "Scale control in sea
water evaporators", M.S. Thesis, UCLA
Department of Engineering (Aug. 1964) .

SUMMARY OF DISCUSSION
There was no discussion.

Evaluation Des Méthodes de Lutte

Contre L'Entartrage Utilisées Dans

L'Installation a Vaporisation Par

Detente de L'Office of Saline Water,

a San Diego, Californie

Stewart Mulford, Julius Glater, J. W. McCutchan

Etats-Unis d'Amérique

D'excellents résultats dans les méthodes
de prévention de l'entartrage ont été ob
tenus à l'installation à multiples effets de
distillation et vaporisation par détente de
l'Office of Saline Water, à San Diego, Cali
fornie. D'une manière générale, les systèmes
à évaporation par détente font preuve
d'une bonne résistance aux incrustations.
Cet avantage résulte probablement de la
séparation des fonctions de chauffage et
d'évaporation, de sorte que l'ensemble du
circuit de chauffage n'est pas soumis aux
conditions d'ébullition. L'installation de
San Diego avait pour caractéristiques mar
quantes un système de mélange d'acide et
un désaérateur. Ces éléments parfaitement
mis au point permettaient d'assurer le
contrôle adéquat des incrustations alcalines
à faible concentration d'acide. Le fonc
tionnement à une température élevée de
250°F et des facteurs de concentration
supérieurs à deux ont permis d'obtenir un
rendement efficace sans formation d'incrus
tation de sulfate de calcium. Cette opéra
tion a dépassé les conditions de seuil dé
crites par d'autres chercheurs. Le pro
gramme expérimental se composait de trois
parties: 1. Lutte contre les incrustations
alcalines à l'aide de l'Hagevap L.P. 2. Lutte
contre les incrustations alcalines en appli
quant des traitements à l'acide sulfurique,
et 3. Expériences dans la zone d'instabilité
du sulfate de calcium.
Les premiers essais ont été effectués à une
température maximum de 200°F et à un
facteur de concentration de la saumure de
13- Dans ces conditions, on ne s'attendait
qu'à un entartrage alcalin. Au cours des
5.399 premières heures de fonctionnement
de l'installation, l'entartrage fut efficacement
contrôlé grâce à l'Hagevap. L'Hagevap est
un mélange de polyphosphates de sodium,
de dérivés d'acide sulfonique de lignine et
de divers esters de glycols polyalcylènes.
Ces trois ingrédients agissent de manière
synergique et empêchent la formation d'in-

151
 crustations, d'après un mécanisme dont on l'emploi d'un système d'injection caustique.
ne comprend pas très bien le fonctionne L'installation de San Diego fut dotée d'un
ment étant donné que l'Hagevap est efficace semblable système, mais la neutralisation se
même à des concentrations très basses (3 à révéla inutile étant donné le redressement
5 ppm) . L'Hagevap n'a pas réussi à empê rapide des valeurs du pH. La nécessité d'u
cher complètement l'entartrage mais en a tiliser un excédent d'acide (au dessus de la
radicalement ralenti la vitesse d'accumula quantité stoïchiométrique) ne s'est jamais
tion, ainsi qu'on l'a constaté par la baisse présentée dans la lutte contre l'entartrage.
du rendement de l'installation. Cette baisse, Ces résultats étaient probablement dûs au
due à de légères incrustations, était reflétée mélange uniforme de la saumure avec de
d'une part par un accroissement de la l'acide et à la dissipation rapide de bioxyde
pression et de la température de la vapeur de carbone.
du réchauffeur à saumure et, d'autre part, Lorsque l'on s'aperçut du bon fonctionne
par une chute du rapport rendement. Les ment de l'installation avec une injection
dépôts qui ont une influence néfaste sur les d'acide à environ 200°F et un facteur de
coefficients de transmission de la chaleur concentration de 1,7, on décida de pour
étaient souvent à peine visibles lors de la suivre l'expérience avec des températures et
fermeture provisoire de l'installation en vue des facteurs de concentration plus élevés.
d'assurer le nettoyage. Au cours de deux La zone de recherche avait été décrite
longues périodes de marche avec Hagevap comme étant une région instable pour les
(6 et 4 mois) une baisse du rendement incrustations de sulfate de calcium. Les
lente mais continue fut observée, dont le expériences effectuées à San Diego avaient
taux était inférieur a 5% par mois. Vers la pour but de réunir des données qui faisaient
fin de la seconde période (4 mois) on sérieusement défaut et de vérifier en outre
installa un système d'injection d'acide. la position des courbes du sulfate de cal
Outre l'Hagevap, de l'acide sulfurique fut cium proposées par Standiford et Sinek en
introduit dans le système pendant les 108 1961. On parvint à un fonctionnement libre
dernières heures de temps de marche. Cette de dépôts pendant de longs essais dans la
opération de détartrage "in situ" fut appa zone de l'anhydrite. Ces résultats correspon
remment couronnée de succès à en juger dent bien aux données recueillies par Lan-
par un retour du rendement thermique gelier et peuvent être expliqués par de
aux niveaux atteints lorsque les tubes longues périodes d'équilibre nécessaires au
étaient libres de toute incrustation. dépôt de l'anhydrite. A la suite de ces
A la suite de cet essai, le traitement à expériences, il fut décidé de vérifier la posi
l'Hagevap fut interrompu et l'injection tion apparente de la courbe de l'hémi-
d'acide sulfurique fut utilisée comme seul hydratc en procédant à des recherches dans
moyen de lutte contre les incrustations la région sursaturée où l'on espérait pouvoir
alcalines. On a eu recours à ce changement obtenir d'aussi bons résultats. L'installation
de méthode en vue de parvenir à un niveau fut mise en marche pendant 357 heures à
de marche égal ou proche à la température 250°F et à un facteur de concentration de
maximum projetée de 250°F. L'instabilité 2,1 sans que le rendement thermique
thermique de Hagevap avait interdit tout n'accuse de baisse par suite de l'entartrage.
fonctionnement dans de pareilles conditions. Lorsque l'on s'aperçut qu'un fonctionne
De l'acide sulfurique concentré fut intro ment normal pouvait être maintenu dans
duit directement dans l'eau d'alimentation ces conditions, le facteur de concentration
selon un dosage destiné à donner 120 ppm fut porté tout d'abord à 2.5 puis à 2,9.
par poids. Le pH ambiant qui était d'en Quelques heures plus tard, une chute
viron 8,3 accusa une baisse sensible au rapide du rendement thermique se pro
point d'injection d'acide puis s'éleva rapide duisit. L'entartrage ne diminua pas de façon
ment sous l'influence du mélange et de la notable après le "renversement" du procédé
desaération. A la suite de la réaction pro vers les températures et les facteurs de
duite à l'aide d'ions bicarbonates, l'alcali concentration plus faibles. Il fallut en fin
nité tomba de 140 ppm à environ 12 ppm de compte fermer l'installation pour pro
et le pH se stabilisa à 7,5, selon les indica céder à son inspection. On observa d'im
tions relevées au tuyau de décharge de la portants dépôts du côté aval des tubes du
pompe de recyclage de la saumure. La réchauffeur de saumure. Les incrustations
réaction rapide entre l'acide et le bicarbo atteignaient en moyenne une épaisseur de
nate fut accélérée par un système de desa î/J de pouce tandis que certains tubes
ération très efficace. Afin d'éviter une corro étaient complètement obstrués. Les tenta
sion excessive, la plupart des installations tives faites pour dissoudre ces matières
recourant à l'injection d'acide doivent neu laissèrent supposer qu'il s'agissait de sulfate
traliser l'excédent d'acide non réactif par de calcium, mais on ne procéda à aucune

152
analyse cristallographique.
Il semble qu'un seuil d'entartrage effectif
ait été atteint. Cependant les circonstances
de l'exploitation permettent de douter qu'il
en soit ainsi. La répartition inégale du
tartre indiquait que l'ébullition s'était
probablement produite dans le réchauffeur
à saumure juste avant la dernière période
de marche. Cette conclusion reposait sur le
mauvais fonctionnement de la chaudière
enregistré au cours des expériences. Dans
ces conditions, les températures plus éle
vées des parois engendrées par cet état de
choses pourraient amorcer un entartrage
prématuré, par contraste avec une exploita
tion où l'ébullition serait absente. Le début
de la cristallisation laisse supposer une
accumulation rapide du tartre même si l'on
revenait au fouctionnement sans ebullition.
La dernière série d'expériences n'a pu être
menée à bonne fin en raison du démontage
et du transfert de l'installation à Guanta-
namo Bay pendant la crise survenue à Cuba
au sujet de l'alimentation en eau de cette
base.
Les bons résultats d'exploitation obtenus
dans la zone de l'anhydrite ont été confirmés
à San Diego. Des périodes de fonctionne
ment prolongées sans formation d'incrusta
tions dans la zone de l'hemihydrate ten
draient a remettre en question la position de
la courbe de Standiford et Sinek à 250°F.
Des essais de fonctionnement dans des con
ditions plus rigoureuses se sont révélés peu
concluants en raison de pannes concomi
tantes de l'appareillage. Il est à espérer que
ces études pourront se poursuivre dans
l'installation de remplacement d'une capa
cité de 1 million de gallons par jour dont
on envisage l'implantation. D'autres inves
tigateurs sont en train d'étudier les condi
tions limites de l'hémihydrate dans des
appareils à évaporation par détente de
dimensions plus réduites. Il sera certes inté
ressant de comparer les résultats qu'ils
auront obtenus avec les nouvelles données
émanant d'une grosse installation.
Pour le moment, les travaux effectués à
l'installation de San Diego permettent de
tirer les conclusions suivantes:
1. La courbe de fonctionnement pratique
relative à l'hémihydrate a une pente plus
forte que la courbe calculée pour des condi
tions d'équilibre par Standiford et Sinek.
2. Il est possible que les installations à
évaporation instantanée soient en mesure
de fonctionner pendant de longues périodes
dans une zone sursaturée métastable, en ce
qui concerne à la fois l'anhydrite et
l'hémihydrate.
3. Des courbes d'exploitation différentes
peuvent s'avérer nécessaires pour décrire
les conditions limites du sulfate de calcium
dans divers types d'évaporateurs.
De toute façon, nous devons réaliser que
l'on ne saurait appliquer au hasard à tout
autre procédé de distillation la courbe de
seuil mise au point pour un appareil par
ticulier réagissant à une série de conditions
données.
153
 Оценка Методов Борьбы с Накипью
на Установке Мгновенного Испарения,
Принадлежащей У. С. В. (Управление
по Делам Соленых Вод) в Сан Диего,
Шт. Калифорния
Стюарт Молфорд, Юлий Глетер, Дж. У. МакКотчан
Соединенные Штаты Америки
На многоступенчатой установке мгно
венной дистилляции в Сан-Диего, шт.
Калифорния, которая принадлежит У.
С. В., были достигнуты прекрасные ре
зультаты в области предупреждения
накопления накипи. Системы мгновен
ного испарения вообще хорошо сопро
тивляются образованию накипи. Это
вероятно объясняется разделением
функций нагревания и испарения, вслед
ствие чего во всем тепловом цикле
отсутствует состояние кипения. Кислот
но-смесительная система и деаэратор
принадлежали к замечательным особен
ностям установки в Сан-Диего. Эти хо
рошо спроектированные детали позво
ляли удачно бороться со щелочной на
кипью при низкой кислотной концен
трации. Работа протекала в условиях
действенной производительности и без
отложения сульфата кальция, несмотря
на высокую температуру 250°F и ко
эффициенты концентрации более 2.
Она превосходила высоту порога, опи
сываемого другими исследователями.
Экспериментальная программа состоя
ла из трех частей:
1. Предотвращение образования ще
лочной накипи с помощью состава
"Hagevap L.P."
2. Предотвращение образования ще
лочной накипи с помощью серной
кислоты, и
3. Опыты в области неустойчивости
сульфата кальция.
Первоначально испытания велись при
максимальной температуре 200°F и ко
эффициенте концентрации рассола 1,5.
При этих условиях ожидалось только
образование щелочной накипи. В тече
154
ние первых 5399 часов работы уста
новки появление накипи эффективно
устранялось с помощью Hagevap'a.
Hagevap представляет собой смесь по
лифосфатов натрия, производных суль-
фокислоты и лигнина и различных
сложных эфиров полиалкиленовых гли-
колей. Эти три компонента действуют
синергетически, предотвращая образо
вание щелочной накипи посредством
механизма, действие которого невпол
не понятно, так как Hagevap эффекти
вен даже при очень низких концентра
циях (3-5 мг/л). Hagevap не останав
ливал вполне накипь, но радикально
замедлял скорость ее накопления, что
замечалось при замерах уменьшавшей
ся производительности установки.
Уменьшение, объяснявшееся неболь
шим отложением накипи, отражалось
на 1) повышении давления и темпера
туры пара, подогревавшего концент
рат, и 2) падение относительной про
дуктивности. При закрытии установки
с целью чистки, часто бывало трудно
обнаружить следы отложений, кото
рые весьма сильно влияют на скорость
передачи тепла. В течение двух дол
гих испытаний с Hagevap-ом (6 и 4
месяца), было замечено медленно-рав
номерное снижение производительно
сти, достигавшее менее 5% в месяц.
К концу второго испытания (4 месяца)
была построена система кислотной ин-
жекции. В течение последних 168 часов
кроме Hagevap-a вводилась тоже сер
ная кислота. Такой метод непосред
ственного удаления накипи на месте ее
появления видимо был удачен, судя по
тому, что тепловая производительность
 вернулась на тот же самый уровень,
где она была при чистых трубопрово
дах.
После этого опыта употребление
Hagevap-a было прекращено и инжек
тирование серной кислоты стало един
ственным средством борьбы со щелоч
ной накипью. Это изменение было вве
дено из за попытки начать работать
при максимальной или близкой к ней
температуре 250° F. Термическая неста-
бильиость Hagevap-a лишала возмож
ности добиться этих условий. Концен
трированная серная кислота непосред
ственно вводилась в исходную воду с
таким расчетом, чтобы получить по
весу 120 частей на миллион. Показа
тель концентрации водородных ионов
окружающей среды pH, стоявший пе
ред этим на высоте около 8,3, в момент
инжектирования кислоты сильно падал,
но затем, вследствие перемешивания и
деаэрации быстро поднимался. После
бикарбонатно-ионной реакции остаточ
ная щелочность уменьшалась со 140
частей на миллион до примерно 12 ча
стей на миллион, a pH останавливался
на уровне 7,5, замеренном на выходной
стороне насоса, рециркулировавшего
концентрат. Быстрая реакция между
кислотой и бикарбонатом ускорялась
с помощью весьма эффективной де-
аэрационной системы. Во избежание
чрезмерной коррозии на многих уста
новках нейтрализуют избыточную не
реактивную кислоту с помощью систе
мы, инжектирующей каустическую со
ду. Такая установка была также устро
ена в Сан-Диего, но нейтрализация
оказалась ненужной ввиду быстрой ре
генерации величин pH. Для борьбы с
накипью никогда не требовалось до
бавочной кислоты (превышавшей сте-
хиометрическое количество). Эти ре
зультаты вероятно зависели от одно
родного перемешивания рассола с ки
слотой и быстрого рассеяния двуокиси
углерода.
Когда выяснилось, что установка эф
фективно и надежно работает с кислот
ным инжектированием приблизительно
при 200° F и коэффициенте концентра
ции 1,7, было решено начать исследо
вать более высокие температуры и ко
эффициенты концентрации. Обследо
ванная зона была описана, как неу
стойчивая область накипи сульфата
кальция. Опыты в Сан-Диего предна
значались для собирания весьма необ
ходимых данных, а также для проверки
положения кривых сульфата кальция,
предложенных в 1961 г. Стандифордом
и Сайнекем. При долгих опытах в ан-
гидритной области работа регулярно
протекала в условиях отсутствия на
кипи. Эти результаты хорошо согласо
вались с данными, полученными Лан-
джелиэр-ом, и могут быть объяснены
долгим временем уравновешивания, от
которого зависит отложение ангидри
та. После этих опытов было решено
проверить кажущееся положение кри
вой гемигидратов, исследовав область
пересыщения, где надеялись получить
одинаково хорошие результаты. Уста
новку заставили работать 357 часов
при 250° F и коэффициенте концентра
ции 2,1, причем не было обнаружено
понижения производительности из за
накипи. Когда выяснилось, что нор
мальная работа может поддерживаться
при этих условиях, коэффициент кон
центрации был сначала увеличен до
2,5, а затем до 2,9. Через несколько
часов по достижению этого условия
наступило быстрое падение термиче
ской производительности. Образование
накипи ощутимо не изменилось, несмо
тря на «обратное дросселирование> к
более низким температурам и коэффи
циентам концентрации. В конце концов
установку пришлось остановить и про
извести инспекцию труб, подогреваю
щих концентрат. Были обнаружены
большие отложения на низовой по те
чению 'стороне. Отложение достигало
средней толщины 1/8", но некоторые
трубы были совершенно закупорены.
При попытках растворить этот мате
риал появлялась мысль, что он являет
ся сульфатом кальция, хотя кристалло
графические анализы не были произве
дены.
Может показаться, что тогда был до
стигнут эффективный порог образова
ния накипи, однако, условия работы вы
зывают сомнения, что это соответство
вало действительности. Неравномерное
распределение накипи указывало на ки
пение, которое видимо происходило в
подогревателе рассола как-раз перед
последним опытом. Это заключение
имело свое обоснование, ввиду неко
торых недочетов в работе котла, заме
ченных во время производства испы
таний. При этих условиях более высо
кие результирующие температуры по
сравнению с процессом без кипячения
могли вызвать преждевременное оса
ждение накипи. Полагают, что раз об
разование центров кристаллизации уже
началось, то накипь станет быстро от
кладываться, даже и при возобновле
нии работы без кипения. Последнюю
155
 серию опытов не удалось закончить,
потому что установка была разобрана
и отправлена в бухту Гуантанамо, вви
ду водяного кризиса на Кубе.
В Сан-Диего подтвердилась возмож
ность удачной работы в ангидритной
области. Продолжительные исследова
ния, проводившиеся в гемигидратной
области без образования накипи, выз
вали сомнение относительно положе
ния кривой Стандифорда и Сайнека при
температуре 250°F. Намеченные опыты
при более суровых условиях остались
неубедительными ввиду плохой рабо
ты оборудования, которая их сопро
вождала. Приходится надеяться, что
эти наблюдения будут продолжены на
новой установке, намеченной к по
стройке взамен прежней, которая будет
производить один миллион галлонов
пресной воды в день. Другие исследо
ватели, пользуясь меньшим оборудо
ванием, работающем на мгновенном
испарении, сейчас изучают погранич
ные условия гемигидратов, и было бы
интересно сверить их результаты с но
Una Evaluación
Control de Incrustaciones
Planta de Evaporación
de la Oficina de
San Diego,
Stewart Mulford, Julius Glater, N. W. McCutchan
Estados Unidos de Norteamérica
En la planta de destilación instantánea de
etapas multiples que la O.S.W.• opera en
San Diego, California, se han logrado re
sultados excelentes en la prevención de la
acumulación de incrustaciones. En general,
los sistemas de destilación instantánea
muestran una buena resistencia a las in
crustaciones. Esto probablemente se debe a
la separación de las etapas de calentamiento
y evaporación, lo cual conduce a condi-
* Office of Saline Water — Oficina de Agua
Salada.
156
выми данными, полученными на круп
ной установке.
В настоящее время, на основании
работы установки в Сан-Диего некото
рые выводы имеют свое обоснование.
1. Кривая для гемигидратов, полу
ченная в рабочих условиях, имеет бо
лее крутой уклон, чем кривая, постро
енная Стандифордом и Сайнеком для
равновесных условий.
2. Возможно, что установки с мгно
венным испарением смогут подолгу ра
ботать в метастабильной области пе
ресыщения, как в отношении к анги
дритам, так и гемигидратам.
3. Для различных типов испарителей
могут понадобиться различные рабочие
кривые, чтобы охарактеризовать погра
ничные условия сульфата кальция.
Во всяком случае мы должны пом
нить, что нельзя применять без разбора
пороговую кривую к любому дистил-
ляционному процессу, если она была
построена при заданных условиях для
оборудования определенного типа.
de Metodos de
en la
Instantánea
Agua Salada en
California
dones en las que no existe ebullición en
ninguna parte del circuito de calentamiento.
Las características más destacadas de la
planta de San Diego son el sistema de
mezclado del ácido y el desaireador. Estos
componentes, muy bien diseñados, permi
tieron un buen control de las incrustaciones
alcalinas a bajas concentraciones de ácido.
La operación a la elevada temperatura do
250°F y los factores de concentración mayo
res que dos, permitieron una eficiente labor
sin depósito de incrustaciones de sulfato de
 calcio. Esta operación excedió las condi
ciones iniciales descritas por otros investiga
dores. El programa experimental se dividió
en tres partes: 1) Control de incrustaciones
alcalinas con Hagevap L.P., 2) Control de
incrustaciones alcalinas con acido sulfúrico,
y 5) Experimentos en la región de la inesta
bilidad del sulfato de calcio.
Las operaciones iniciales fueron llevadas
a cabo a una temperatura máxima de
200°F y un factor de concentración de las
aguas madres de 13. Bajo estas condiciones,
sólo se anticiparon incrustaciones alcalinas.
Durante las primeras 5.399 horas de opera
ción de la planta, las incrustaciones se con
trolaron eficazmente con Hagevap. Hagevap
es una mezcla de polifosfatos de sodio con
derivados del ácido sulfónico de lignina y
distintos ésteres de glicoles polialquilcnos.
Los tres ingredientes actúan en forma si-
ncrgistica para prevenir la formación de
incrustaciones alcalinas, por medio de un
mecanismo no claramente entendido, dado
que Hagevap es efectivo aun a concentra
ciones muy bajas (3-5 ppm). El Hagevap
no previene completamente la formación
de incrustaciones, pero disminuye radical
mente la velocidad de acumulación, medida
a través de la disminución de eficiencia
de producción de la planta. El decrcmento,
debido a depósitos de incrustaciones livianas
se reflejó en: 1) Un aumento en la presión
y temperatura del calentador de aguas
madres, y 2) Una caída del porcentaje de
rendimiento. Depósitos que afectan consi
derablemente la velocidad de transferencia
de calor con frecuencia apenas fueron visi
bles cuando se peró la planta para su
limpieza. Durante dos períodos prolongados
de funcionamiento con Hagevap, (6 y 4
meses) se notó una lenta pero sostenida
disminución de la eficiencia de operación,
a razón de menos del 5% mensual. En
postrim.rías del segundo período de funcio
namiento (4 meses), se instaló un sistema
de inyección de ácido. Además de Hagevap,
durante las últimas 168 horas de operación,
se introdujo ácido sulfúrico. Esta operación
de desincrustación "in situs" aparentemente
fue exitosa dado que se observó un retorno
a la eficiencia térmica de los niveles de
operación con tubos limpios.
Luego de este período de funcionamiento,
se suspendió el tratamiento con Hagevap
y solamente se usó la inyección de ácido
sulfúrico como único medio para combatir
incrustaciones alcalinas. Este cambio se in
trodujo para tratar de operar a, o cerca de.
la máxima temperatura para la que
estaba diseñado el equipo, es decir 250°E.
La inestabilidad térmica del Hagevap impe
día la operación bajo estas condiciones. Se
introdujo directamente ácido sulfúrico con
centrado en el agua de alimentación a una
velocidad medida, con el objeto de dar 120
ppm por peso. El pH ambiente de 8,3
cayó radicalmente en el punto de inyección
del ácido y luego creció rápidamente de
bido al proceso de mezclado y de desairca-
ción. Luego de la reacción con el ion
bicarbonato, la alcalinidad residual se re
dujo de 140 ppm, a cerca de 12 ppm y el
pH se niveló a 7.5, medido en el punto
de descarga de la bomba de reciclaje de
las aguas madres. La rápida reacción entre
el ácido y el bicarbonato fue aumentada
mediante un sistema de desaireación muy
eficaz. A los efectos de evitar una corrosión
excesiva, muchas plantas que usan la inyec
ción de ácido deben neutralizar el exceso
de ácido no neutralizado durante la re
acción mediante un sistema de inyección de
sosa caústica. Tal instalación fue sumini
strada a la planta de San Diego pero se
encontró que la neutralización era innece
saria debido a la rápida recuperación de
los valores de pH. Para el control de las
incrustaciones nunca se requirieron excesos
de ácido (por encima de la cantidad este-
quiométrica). Estos resultados probable
mente fueron consecuencia de la mezcla
uniforme de las aguas madres con el ácido
y de la rápida degradación del anhídrido
carbónico.
Cuando se determinó que la planta ope
raba en forma eficiente y estable con in
yección de ácido a aproximadamente 200°F
y a un factor de concentración de 1.7. se
decidió explorar temperaturas más altas y
mayores factores de concentración. El área
investigada había sido descrita como una
región inestable para la incrustación de
sulfato de calcio. Los experimentos en San
Diego tuvieron la finalidad de recoger datos
sumamente necesarios y también la verifica
ción de la posición de las curvas de sulfato
de calcio propuestas en 1961 por Standi-
ford y Sinek. Una operación libre de in
crustaciones se logró consistentemente en
corridas largas en la región de la anhidrita.
Estos resultados están de acuerdo con los
resultados obtenidos por Langelicr y pue
den explicarse por el largo período de
estabilización requerido para el depósito
de anhidrita. Después de estos experimen
tos, se decidió verificar la posición aparente
de la curva del hemihidrato mediante ex
ploraciones en la región de sobresaturación
donde se confiaba podrían obtenerse resulla-
dos igualmente buenos. La planta operó
durante 357 horas a 250°F y a un factor
de concentración de 2,1, no registrándose
 ninguna disminución de la eficiencia tér
mica debida a incrustaciones. Cuando se
determinó que en estas condiciones podría
mantenerse una operación normal, se au
mentó el factor de concentración, primero
a 2,5 y luego a 2,9. Unas pocas horas
después de haber alcanzado estas condi
ciones, se produjo una sensible cafda de
la eficiencia térmica de operación. Las in
crustaciones no fueron disminuidas en
forma apreciable mediante el retorno a las
condiciones iniciales de temperatura y con
centración. Finalmente, la planta tuvo que
ser parada e inspeccionada. Se notó la
existencia de gruesos depósitos en los tubos
calentadores de la salmuera en la región
del flujo descendente. Los depósitos medían,
en promedio, i/s de pulgada de espesor,
pero algunos tubos se encontraban total
mente tapados. Los intentos que se reali
zaron para disolver este material indicaron
que se trataba de sulfato de calcio, pero
no se efectuaron análisis cristalográficos.
Parecía haberse alcanzado un punto de
partida para la eliminación efectiva de
incrustaciones. Sin embargo, los datos expe
rimentales crean dudas de que esto sea así.
Una distribución no uniforme de las incrus
taciones indicó que probablemente se había
producido ebullición en el calentador de
aguas madres inmediatamente antes de la
última corrida. Esta conclusión se basaba
en ciertas dificultades de funcionamiento
registradas mientras se realizaban los expe
rimentos. Bajo estas condiciones, un reca-
lentamiento de las paredes podría haber
causado la formación prematura de las
incrustaciones, en contraste con una opera
ción bajo condiciones de no-ebullición. Una
vez iniciada la formación de depósitos, que
actúan como núcleos de cristalización,
puede suponerse que habrá una formación
rápida de depósitos incluso si fuera reini-
ciada una operación bajo condiciones de
no-ebullición. La última serie de experi
mentos no pudo completarse debido a que
la planta fue desmantelada y enviada a la
158
Bahía de Guantánamo durante la crisis
cubana sobre el agua.
La posibilidad de una operación exitosa
en la región de la anhidrita fue confirmada
en San Diego. Operaciones largas sin in
crustaciones en la región del hemihidrato
tenderían a poner en tela de juicio la
posición de la curva de Standiford y Sinek
a 250° F. Pruebas experimentales mediante
operaciones intentadas a condiciones extre
mas no son concluyentes debido al funcio
namiento deficiente del equipo auxiliar.
Se confía que estos experimentos podrán
continuarse en la planta de reemplazo
propuesta, de una capacidad de un millón
de galones diarios. Otros investigadores se
encuentran estudiando actualmente las con
diciones de la frontera del hemihidrato en
equipos más pequeños de destilación ins
tantánea y podría ser de interés verificar
sus resultados con nuevos datos obtenidos
en una planta mayor.
En este momento, se justifica la presenta
ción de ciertas conclusiones, derivadas de
los trabajos de la planta de San Diego:
1. La curva práctica de operaciones de
terminada para el hemihidrato tiene
una pendiente mayor que la curva
derivada de las condiciones de equili
brio de Standiford y Sinek.
2. Podría ser posible para plantas de
destilación instantánea operar por
períodos largos en la zona metaestable
sobresaturada de anhidrita y del hemi
hidrato.
3. Pueden ser necesarias curvas diferen
tes de operación para describir las
condiciones límites del sulfato de cal
cio para diferentes tipos de evapo-
radores.
En todo caso, debemos tener presente
que no es posible aplicar indiscriminada
mente curvas desarrolladas inicialmcnte
para un determinado equipo, bajo un grupo
de condiciones dadas, a cualquier otro pro
ceso de destilación.
Improvement in Fabrication

Techniques for Reverse Osmosis

Desalination Membranes

S. Manjikian, S. Loeb, J. W. McCutchan

United States of America

INTRODUCTION
The term osmosis is used to describe in testing "Ultrafinc, Superdense" cellulose
spontaneous flow of water into a solution, acetate ultrafilters obtained from Schleicher
or from a dilute to a more concentrated and Schuell Company, Keenc. New Hamp
solution when the two are separated from shire, they undertook the fabrication of
each other by a semipermeable membrane. cellulose acetate membranes in the UCLA
In order to obtain fresh water from saline laboratory. Acetone was used as the solvent
water, the flow must be reversed from the and, based on work by Dobry (ref. 1) ,
solution into a fresh water stream, hence aqueous magnesium perchlorate was in
the term reverse osmosis. cluded in the casting solution as one of
Since 1952 when the first compendium the steps to control membrane porosity.
on "Existing and Potential Separation Loch and Sourirajan published the results
Processes," (ref. 11) was published, the of their development by which cellulose
search has gone on for a practical reverse acetate membranes with flow rates of from
osmosis desalination membrane. In this first 5 to 11 gal/ft=day could be made to produce
published list, two references were given, potable water from sea water at 1300 psig
Hassler (ref. 2) and an anonymous refer operating pressure.
ence. The next reported activity was from In essence, their technique is as follows:
Reid and Breton (ref. 12) , and Yustcr. 1. The casting solution is a quaternary
Sourirajan. and Bernstein (ref. 14) who. mixture of cellulose acetate-magnesium
although working along different paths, perchloratc-water-acetone in the proportions
arrived at the same conclusion, namely, 22.2-1.1-10.0-66.7 per cent by weight. Loeb
that cellulose acetate membranes have a and Manjikian (ref. 8) have reported im
high degree of semipcrmeability to saline provements with the addition of small
solutions. quantities of a fifth component such as
On the basis of the work of Reid and hydrochloric acid.
Breton, others (ref. 13) undertook improve 2. The membrane is cast on a glass plate
ments in membranes on the hypothesis having 0.025 centimeter side runners to
that the transport mechanism involved give this as-cast thickness to the membrane.
hydrogen-bonding. Membranes with large The casting solution and all casting com
numbers of known hydrogen-bonding sites ponents are at —5° to — 10°C.
were tried without success. It was also be 3. After an evaporation period of not
lieved that crosslinking of cellulose acetate- more than three minutes at this tempera
would improve the physical properties of ture, the membrane plate assembly is im
the membrane, but efforts in this direction mersed in ice water where it is kept for
seemed to be at the expense of permea about one hour.
bility. 4. The membrane is removed from the
Loeb and Sourirajan (ref. 9) took another plate and heated by immersion in water
approach. On the basis of experience gained for 5 minutes at 65° to 85°C.

159
 PRESENT STUDY
No fundamental improvement has been
reported in the casting solution or other
fabrication steps since 1960, although a
number of investigators have considered
the mechanisms involved in this fabrication
PROCEDURE
CASTING SOLUTION CONSTITUENTS
The various components of the casting
solution may be considered in the light of
their integration into the fabrication tech
niques described above. On this basis,
general requirements may be stated for the
various casting solution components.
1. Cellulose Acetate
The cellulose acetate should have an
acetyl content, molecular weight, and mo
lecular weight distribution in the same
general range as Eastman E-598-3 powder.
(In a later section the influence of these
parameters on membrane performance for
the new casting technique developed is
described.)
2. Solvent
An appropriate solvent for the casting
solution should meet the following mini
mum requirements:
(a) Miscibility with water, since the sol
vent is removed from the gel upon immer
sion in water.
(b) Lack of chemical reactivity with
other casting solution components.
Binary solutions of cellulose acetate in
acetone and similar solvents will produce
an impermeable membrane, but a solvent
such as glacial acetic acid can produce a
permeable membrane (ref. 6) . These sol
vents may be defined as "nonswelling" and
"swelling" solvents, respectively. When the
casting solution contains a "nonswelling"
solvent, one or more "swelling" components
or "additives" must also be included as
discussed below. In such a casting solution,
the solvent has two additional requirements:
(c) Miscibility with the additive.
(d) The capability of being leached out
of the water-immersed membrane prior to
the additive. If the additive were removed
first, the remaining casting solution would
be an undesirable binary, consisting solely
of cellulose acetate and "nonswelling"
solvent.
3. Additives
Additives should have requirements (a)
and (b) above, plus:
(C) Miscibility with the solvent.
(d') The capability of being leached
from the film subsequent to the solvent.
160
technique and reported on permissible mod
ifications thereto. It is the continuing
quest for a better and simpler system, both
in the casting solution composition and the
fabrication procedure, that has led to the
advances reported in this paper.
Additives may be characterized as flux-
inducing components of a casting solution
for the preparation of semipermeable cel
lulose acetate membranes. To date, investi
gations have been concerned mainly with
aqueous solutions of inorganic electrolytes
as additives. Since magnesium Perchlorate
was one of the first to be used in this capac
ity, it is not surprising to note that later
efforts were directed toward the investiga
tion of salts similar to magnesium Perchlo
rate in their physical and chemical
properties. In addition, the successful prepa
ration of the high flux membranes was re
lated to the structural properties of these
electrolytes.
Exhaustive experiments have increased
the number of inorganic electrolytes that
serve as successful additives. Loeb (ref. 7)
has stated that these electrolytes, by virtue
of their anions, have a common property in
their ability to "break" the structure of
water. Since this was the only common
quality, he concluded that the modification
of the structure of water was the primary
role of electrolytic additive. Resting and
Keilin (ref. 4) in their consideration of the
additive as a swelling agent for cellulose
acetate have assigned the active role to the
cation. Again the need for an electrolyte
was emphasized.
4. Water
Water is a desirable component of cast
ing solutions containing electrolyte (ref. 7) ;
however, it is not assumed in this study
that water is essential in every cellulose
acetate casting solution. Although water
constitutes a large fraction of a high per
formance cellulose acetate desalination
membrane, most of this water enters the
membrane upon immersion, i.e., is over
and above that contained in the casting
solution.
EXPERIMENTAL PROCEDURE
The casting solutions fabricated into
membranes contained cellulose acetate as
one component of a binary, ternary, or
quaternary mixture. The other compo
nents were always nonelectrolytes and usu
ally organic. The casting procedure was
"mity-mite" PRESSURE GAUGE
BACK
PRESSURE
REGULATOR OSMOTIC CELL, 600psig

MEMBRANE

DESALINIZED WATER-7
(LESS THAN 7cm3/min.)
RETURN BRINE
V
TEN MICRON
CUNO FILTER

AIR-OPERATED PUMP

FEED BRINE
0.5% NQCI
300 cm3/min

FIGURE 58. FLOW SYSTEM SCHEMATIC.

similar to that already described, with
modifications as indicated by the results
obtained. Membranes were tested in the
apparatus of Figures 58 and 59 at an ap
plied pressure of 600 psig and with a feed
brine of 0.5 per cent by weight (5.000 ppm)
sodium chloride.
Membrane performance was judged by
the flux and the salt content of the desal
inized water obtained. Membranes made
from the aqueous magnesium perchlorate
modificd casting solution give fluxes up to
25 gal/ft*day and salt contents as low as
300 ppm NaCl (ref. 8) . In this study efforts
were not always made to optimize perform
ance. Usually a membrane which delivered
a flux of 5 gal/ft'day at a salt content less
than 1,000 ppm was considered promising.

RESULTS
FORMAMIDE CASTING SOLUTIONS
Formamide was first tried in the fall of 1963
as a substitute for acetone in the quaternary
casting solution cellulose acetate-magnesium
perchlorate-water-acetone.# Formamide was
not useful for this purpose probably be-
* Dr. Gordon Atkinson of the University of
Maryland suggested this use of formamide at an
informal meeting during an ACS Symposium
there. It was his opinion that formamide, with its
high dielectric constant, might be more useful
than acetone with the aqueous electrolytes In the
casting solution.
cause it possesses inadequate solubility for
cellulose acetate. Manjikian (ref. 10) then
considered formamide as a substitute for
water in the basic magnesium perchlorate
formulation. Membranes fabricated from
this casting solution gave acceptable per
formance. This result led him to experi
ment with formamide as a replacement for
both water and magnesium perchlorate,
i.e., to try a casting solution consisting of
the ternary mixture cellulose acetate-form-
amide-acetone.

161
 1 . Casting Solution Composition
First, membranes were fabricated from
various combinations of the three compo
nents to ascertain the region of best per
formance. The region of permissible casting
solutions was limited to a large extent by
the physical properties of the casting solu
tion and the membrane obtained. Consider
ing casting solution viscosity, cellulose
acetate concentrations were kept in the
range 20 to 30 per cent. If formamidc
concentration exceeded 40 per cent, solu
tion solubility problems were encountered.
Thus, the range of casting solution studied
was:
Cellulose Acetate 20-30 wt %
Formamide 10-40 wt %
Acetone 35-65 wt %
Table XXIII summarizes the work done
with membranes prepared from casting solu
tions of various compositions. These mem
branes were cast both at — 10°C and at
ambient temperature (23°C) . Figure 60 is
a ternary diagram of the casting system.
The shaded area represents combinations of
the three components from which useful
membranes were prepared.

POROUS
STAINLESS STEEL
BACKUP PLATE
LOW
PRESSURE
0-RINGS
DESALINIZED 7
HIGH WATER OUTLET
PRESSURE OSMOTIC
0-RINGS MEMBRANE

RETURN BRINE FEED BRINE

OUTLET INLET
\\\\\\\\\\\\\\\\\\\\\\^

FIGURE 59. DESALINATION CELL-CROSS-SECTIONAL VIEW.

162

CELLULOSE ACETATE
FIGURE 60. CASTING SOLUTION REGION
CELLULOSE ACETATE-FORMAMIDE-ACETONE SYSTEM.
Several important conclusions can be
drawn from the results presented in Table
00. First, as can be seen from consideration
of solution 1, the function of aqueous mag
nesium perchlorate cannot be carried out
gram-for-gram by formamide. Second, the
formamide concentration had to be 20 per
cent or higher to get successful membranes.
Third, good performance could be obtained
from membranes cast at room temperature.
Next, the influence of formamide concen
tration on flux was further explored in
room temperature casting. The membranes
were tested without heating in order to
eliminate this variable. Tabic XXIV shows
results obtained with casting solutions hav
ing 25 per cent concentration of cellulose
acetate, the ratio of fonnamide:acetone
being varied. Also shown are results with
solutions for which the ratio cellulose
acctateracetone was held constant at 5:11
while the quantity of formamide in the
casting solution was varied. This latter
FORMAMIDE RANGE
10% -40%
ACETONE RANGE
35% -65%
FORMAMIDE
procedure was equivalent to adding varying
quantities of formamide to a 45.4 per cent
solution of cellulose acetate in acetone. The
results of Table XXIV are shown in graph
form in Figure 61. Three conclusions can
be drawn from this figure. First, it was
indicated that the percentage of formamide
should exceed 30 to 35 per cent for maxi
mum flux. Second, the flux was primarily
a function of formamide content. Third,
the flux attains a maximum and then drops
off with further increase in formamide.
This must be attributed to weakening of
the membrane due to an excess of forma
mide in the casting solution. Thus, upon ihe^j. ~
application of pressure, the membrane
compacted excessively, increasing the resist
ance of the porous understructure.
2. Evaporation Period
The results of varying evaporation pe
riods for membranes cast at room tempera
ture from composition 7 (standard) are
shown in Table XXV and Figure 62. All of
163
TABLE XXIII. Performance of Membranes Cast From Various Ternary Mixtures of
Cellulose Acetate-Formamide-Acetone
Cast at — 10°C
Casting solution composition Evaporation Heating Desalinated water
Solution (wt %)
no. penoa
Cellulose Formamide Acetone (min.) CO Flux Salt content
acetate <gal/ft"day) (ppm)
1 22.2 11.1 66.7 10 78.0 12 810
2 21.4 14.2 64.4 10 78.0 30 610
8 81.1 11.1 67.8 10 Unbeated 6.5 880
4 25 10 65 10 68.5 4.6 270
6 25 20 65 10 77.0 17 220
6 25 25 50 6 79.5 27 480
7 25 SO 45 6 81.5 22 190
8 26 35 40 8 85.8 14 150
Cast at 23°C
9 29.1 16.7 54.2 1 Unheated 2.7 810
10 80 14.8 55.7 1 Unhealed 8.1 410
7 25 SO 45 1 74.0 80 410
6 25 25 60 1 71.6 15 270
6 25 20 56 1 66.0 15 860
Cell operating pressure: 600 psig
Feed brine: 0.5% (5.000 ppm) NaCl

TABLE XXIV. Effect of Formamide Concentration in Casting Solution on Desalinated

Water Flux Through Unheated Membrane
__ . . . ratio
VVemht Cellulose
.. —,-j-acetate _ , .„
Formamide acetone Constant at 1/8
Casting solution composition (wt %) Desalinated water
Solution no. Cellulose Flux
acetate Formamide Acetone (gal/ft* day)
4 25 10 66 0.6
11 25 15 60 3.0
6 25 20 66 9.5
6 25 25 60 76
7 25 80 45 160
8 25 36 40 170
12 26 40 35 160
m ■ «... ratio
Weight ». Cellulose
.—: acetate Constant
_ at 6/11
Acetone
13 29.4 6.9 64.7 0.48
14 27.7 11.1 61.2 0.90
15 26.2 16.2 67.6 8.0
6 25 20 65 9.5
16 23.8 23.9 52.8 43
17 22.7 27.8 60 110
18 21.8 80.4 47.8 200
19 20.8 83.3 45.9 200
20 20 86 44 190
Casting temperature: 23°C Cell operating pressure: 600 psig
Evaporation period: one-half minute Feed brine: 0.5% (6,000 ppm) NaCl
 200 r- • CA: AC CONSTANT AT 5:11 PARTS BY WT TABLE XXV. Effect of Evaporation Period
O CA:(AC + F)CONSTANTAT 1:3 PARTS BY WT on Membrane Performance

Evaporation Desalinated water

period Flux Salt content
(mln.) (gal/ft" day) (ppm)
0.25 84 1,900
100 1 0.60 47 660
1.0 26 580
1.5 84 780
2.0 25 1,100
2.5 23 1.200
S.O 26 1,700
Casting solution composition No. 7:
26% cellulose acetate, 30% formamide,
46% acetone.
Casting temperature: 23'C
Heating temperature: 71.0° to 71.6°C
Cell operating pressure: 600 psig
Feed Brine: 0.6% (6,000 ppm) NaCl
z
<m modified membrane, except that a slightly
UJD higher heating temperature is required
with membranes made from the formamide
casting solution.
TABLE XXVL Effect of Heating Temper
ature on Membrane Performance

Heating Desalinated water

10 20 30
WEIGHT PERCENT FORMAMIDE
IN CASTING SOLUTION
FIGURE 61. EFFECT OF FOR
MAMIDE CONCENTRATION
IN CASTING SOLUTION ON
DESALINATED WATER FLUX
THROUGH UNHEATED MEM
BRANE.
See Table XXIV
Operating pressure: 600 psig
Feed brine: 0.5% (5000 ppm) Nad
the membranes were heated to 71.0° to
71.6°C. Evaporation periods longer than
one and one-half minutes were too long
since, for longer periods, salt content began
to rise for a given flux. With regard to
periods shorter than one-half minute, it
appears that higher heating temperatures
might bring performance into the desired
range. By contrast, when membranes made
from this composition were cast at — 10°C,
the optimum evaporation period was 10
minutes.
3. Membrane-Heating Temperature
The influence of heating temperature on
membrane performance is shown in Table
XXVI. The trend is similar to that obtained
with the aqueous magnesium perchlorate
temperature Flux Salt content
CO (gal/ft»day) (ppm)
Unheated 95 3,800
70.0 45 800
76.0 80 250
110
78.0 17
81.0 12 85
Casting solution composition No. 7:
25% cellulose acetate, 30% formamide,
45^fc acetone.
Casting temperature: 23°C
Evaporation period: one-half minute
Cell operating pressure: 600 psig
Feed brine: 0.6% (6,000 ppm) NaCl
4. Cellulose Acetate Specifications
The development of a reliable room
temperature-castable ternary mixture sim
plifies the examination of casting param
eters. One parameter which was so exam
ined was that of cellulose acetate type.
Cellulose acetate desalination membranes
have most frequently been fabricated from
Eastman 398-3. (The term_398 means that
the polymer_£QDXairis_aii average ot 39.8
weipfrr~pe7rfnt nf arrLyl ei('ilp<r~Arpr"Y;-
mately 81 per_cem_-Qf_the. hydroxy! jjroups
have ^r^'axelylated. The term -3 refers
to a viscosity rating, which ultimately
reflects polymer molecular weight.)
A study was undertaken with the stand
ard composition 7 to determine the influences
on membrane performance of three cellu-

165
 100

75 h-
£E o
UJ "O
< —
50
N_

<
tn 25H
UJ
Q

E °L
Q. 2000r
Q.

£ 1500 1-
o
o

1000 \

<
o 500
UJ
N

4
(A 1 1
UJ 0.0 1.0 2.0
o 3.0
EVAPORATION PERIOD, MINUTES
FIGURE 62. EFFECT OF EVAPORATION PERIOD OF FORMA-
MIDE-MODIFIED MEMBRANE PERFORMANCE.
See Table XXV.
Operating pressure: 600 psig
Feed brine: 0.5% (5000 ppm) NaCl

lose acetate variables, viz: molecular weight,
molecular weight distribution, and per cent
acctylation. Cellulose acetate samples were
provided through the courtesy of Mr.
William Gearhart, Eastman Chemical Prod
ucts, Kingsport, Tennessee.
The results with regard to influence of
molecular weight are shown in Table
XXVII. Molecular weight did not markedly
affect membrane performance. There was a
slight trend toward a required lower heat
ing temperature with higher molecular
weight, as shown by the results with E-594.
The influence of molecular weight dis
tribution is shown in Table XXVI II and
Figure 63. As shown in this figure, the "nar
row" distribution appeared to give a slightly
flatter flux-salt content curve than the
"medium" and "wide" distributions. These

166
 TABLE XXVII. Effect of Cellulose Acetate Molecular Weight on
Membrane Performance
Cellulose acetate Desalinated water
Molecular Heating
Acetyl Viscosity (wt«) temperature Flux Salt content
content indicator CO ( gal/ft' day) (ppm)
(per cent) ( Eastman )
39.4 - 30 50,000 79.0 34 660
- 45 51,000 79.0 32 510
(E-894) - 60 55,000 76.6 33 440
89.8 - 3 24,000 76.6 80 300
- 6 34.000 75.6 80 840
(E-S98) - 10 39,000 75.6 29 290
•From Mr. W. Gearhart, Eastman Chemical Products
Casting solution composition No. 7: 25% cellulose acetate, 80% formamlde, 46% acetone.
Casting temperature: 23°C
Evaporation period: one-half minute
Cell operating pressure: 600 psig
Feed brine: 0.5% (5,000 ppm) NaCl
curves were obtained by heating desalinated tion cellulose acetate may be slightly less
water to various temperatures. Therefore, it sensitive to heating temperature than those
appears probable that the performance of made from cellulose acetate having a wider
membranes made from a narrow distribu distribution.

TABLE XXVIII. Effect of Cellulose Acetate Molecular Weight Distribution on

Membrane Performance
Heating Desalinated water
Molecular wt Eastman temperature
distribution identification no. Flux Salt content
CO (Kal/ft-'/day) (ppm)
Narrow CAE-2196-1 72.0 82 370
Normal CAE-2 196-2 72.0 41 480
Wide CAE-2196-3 72.0 38 340
Narrow CAE-2196-1 74.6 27 240
Normal CAE-2 196-2 75.6 24 140
Wide CAE-2196-8 76.4 27 200
Narrow CAE-2196-1 77.8 24 120
Normal CAE-2196-2 77.8 22 100
Wide CAE-2196-8 77.8 22 100
Cellulose acetate similar in acetylation and molecular weight to E-398-3.
Casting solution composition No. 7: 26% cellulose acetate, 30% formamide, 45% acetone.
Casting temperature: 28°C
Evaporation period: one-half minute
Cell operating pressure: 600 psig
Feed brine: 0.5% (6,000 ppm) NaCl
The influence of acetylation on mem Of these materials only 602-C formed a
brane performance was examined by con homogeneous solution in the standard com
sidering two groups of polymers, one having position proportions. This composition gave
a higher degree of acetylation than the satisfactory performance. 25 gal/ft2/dav and
standard E-398-3. and the other a lower fiOO ppm when heated to 70°C.
degree of acetylation. The three samples of Results with polymers having a lower
higher acetylation, otherwise similar to degree of acetylation than E-398-3 are
shown in Table XXIX and Figure fit.
E-398-3, were designated as follows: These included:

Eastman Acetyl Degree of Eastman Acetyl Degree of

designation content acetylation designation content acetylation
per cent per cent per cent per cent
602-A 41.6 88 EMP-949-A 38.9 79
602-B 41.0 86 EMP-949-B 37.5 75
602-C 40.1 83 EMP-949-C 37.1 74

167
 ACETATE
MCON
OF
EFFECT
63.
DFIGURE
WEIGHT
OIESLTERICUBLUOTIASOREN

(CAE
I)
•
2196
MNDWOIAESLTRI-CGBULOHTIATWRN 450

O«».R.MAL (CAE
N(CAE
O
-2)
-2196 A
-3)
W..IDE.
-2196

brine:
Feed
NaCl
0.5%
(5000
ppm)
amide-mbodrifainede
Form
DEppm
CONTENT
SALT
WATER
SALINIZED
150
250
350

PMERFMOBRMANCE.

psig
600pres ure:

X VI I

50 Table
See Operating
501~
^
!40 30- 5
20 ?
10
cr _i
D TJ o x3 o UJ N <
 40 HEATING TEMP
О
тз

CT
(Л
Б 30

20

<
о
ш
У 10

<
СП

■69° С

Е
о.
800
ЕМР- EASTMAN
Z 949 -В
ш DESIGNATION EMP-
949 -А
о
и
600

со
к
ш
< 400 72е С

О
UJ
N

^ 200 •75вС

37 38 39
ACETYL CONTENT, PER CENT
FIGURE 64. EFFECT OF CELLULOSE ACETATE ACETYL ON
MEMBRANE PERFORMANCE.
See Table XXIX Feed brine: 0.5% (5000 ppm) NaCl
Operating pressure: 600 psig Formamide-modined membrane
169
 TABLE XXIX. Effect of Cellulose Acetate Acetyl Content on
Membrane Performance
Desalinated water
Acetyl content Eastman Heating-
(per cent) Identification no. temperature Flux Salt content
CO <gal/ft»/day) (ppm)
88.9 EMP-949-A 69.0 33 940
87.6 EMP-949-B 69.0 34 940
87.1 EMP-949-C 69.0 20 860
88.9 EMP-949-A 72.0 24 480
87.Б EMP-949-B 72.0 29 640
87.1 EMP-949-C 72.0 14 440
88.9 EMP-949-A 76.0 18 210
87.6 EMP-949-B 76.0 16 810
87.1 EMP-949-C 76.0 7.6 250

Cellulose acetate similar in molecular weight to E-S98-3.

Casting solution composition No. 7: 26% cellulose acetate, 30% formamide, 46% acetone.
Casting temperature: 23°C
Evaporation period: one-half minute
Cell operating pressure: 600 psig
Feed brine: 0.6% (6,000 ppm) NaCl
The chief conclusion to be drawn from
these curves is that the 37.1 per cent
content appears to be outside the lower
limit for obtaining good performance.
It may be concluded therefore that good
performance can be obtained between 37.5
and 40.1 per cent acetyl content. Within
this range no specific correlation can be
stated between either flux or desalination
and acetyl content.
5. Reproducibility
The composition 7 formamide solution,
cast at room temperature, has completely
replaced the cold-cast aqueous magnesium
Perchlorate solution as the standard casting
solution for UCLA desalination membrane
work, since membranes with reproducibly
high performance and good physical prop
erties can be obtained.
This membrane represents an advance
in efforts to develop a practical membrane
cast at room temperature. Resting (ref. 3)
succeeded in casting aqueous magnesium
Perchlorate membranes at room tempera
ture by using p-dioxane as the solvent
instead of acetone but had difficulty in
obtaining reproducible results.
CASTING SOLUTIONS CONTAINING
OTHER NONELECTROLYTES
Nonelectrolytic materials other than form
amide have been used in casting solutions
to produce cellulose acetate desalination
membranes showing promise. These solu
tions are listed in Table XXX in accordance
with whether they are quaternary, ternary,
or binary.

170
 Saltcontent
(ppm) o© o oo 88 St- Sti 8 3t- 2H
S5 5 S2 ion n lis!
!
1a
o
>.(0
! o u> T o M OO
Q Is AC4 _ td oo ci
r«» egO vhCO ts«B tm m o to us
m

£ Unheated Unheated Unheated

63.3 70.3 78.5 80.5 60.0 62.0 75.0 79.0 77.5 76.0 93.0 93.0 94.0
5|P
«|
Evaporation
period (min) ■oo
<0tO •Ht- OO
t-te-l COCO CO *HO C4 CN <0f-4 00 ©vH v-lvH

temperature
Casting OO O oo eoeo co04 COOJ CO<N O COCM
CO CJCN -Ho ofH fto flo
TT 7 77 1 1 1 1 1

sCoalsutiong CA14.S-
composit on

(%)
wt G4.6lyo-xal N13.0-M-2-P
Urea3.3- HaO18.2- 62.5Acet- Acet64.8- HiOj2.6- Acet65.0- DMF21.4- Acet64.8- DMSO87.6- Acet87.6- THFP20- Acet60- TEP25- Acet60- 68.4Acet— Acet65.0- DMF76- 80TEP-
CA21.0- CA- HiO9.2- CA22.0- HjO10.4-
21.5 25.0CA- 20CA- CA25- CA22.6- AA9.1- CA22.0- CA25- CA20- 80AA- 20CA-

ua
Tetrahydrofur- furylphosphate ■»*
Ad itive compound pyr olidone aDO AE
Hydrogen peroxide Dimethyl-formamide Dimeth-ylsulfoxide Triethyl-
phosphate acidAcetic N-methyl-2- Dimethyl- formamide acidAcetic Triethyl- phosphate
Glyoxal ■•o 9o
Urea Eo
1$ 8
Is
Quaternary component) 9 BU 3 8
Type of solution Ternary
(water fourth Binary " -J I *
being 13o u.* u< <w

171
 With regard to the quaternaries of Table
XXX, hydrogen peroxide is of special inter
est as an additive. Since water itself is use
less as an additive, it is quite surprising that
partial replacement of the water by such a
closely related compound makes so much
difference in membrane performance. Since
it has been shown that the utility of elec
trolytic additives is independent of their
oxidizing capabilities, it is unlikely that
the utility of hydrogen peroxide is due to
this effect.
As for the ternaries, tetrahydrofurfuryl
phosphate is an incomplete solvent for cel
lulose acetate, as is formamide. In contrast
to formamide, dimethylsulfoxide, N-methyl-
2-pyrrolidone. dimethylformamide, methyl
phosphate, and acetic acid are complete
solvents for cellulose acetate, and the latter
three are useful in binary mixtures.
A number of organic compounds gave
clear homogeneous solutions in ternary
mixtures with cellulose acetate and acetone,
but were not useful in producing good
membranes. This group included methyl
TABLE XXXI. Performance of Membranes Prepared from Ethyl Cellulose
Casting solution composition, wt (%) Evaporation
Ethyl Triethyl- period
cellulose phosphate P-dioxane (mln)
11 9 80 20
11 9 80 20
18 14 78 20
Casting temperature: 23°C
Cell operating pressure : 600 psig
Feed brine: 0.6% (5,000 ppm) NaCl
CONCLUSIONS
1. Reproducibly high performing cellu
lose acetate membranes can be cast at room
temperature from ternary solutions of cellu
lose acetatc-formamide-acetone. The per
formance and physical properties are equal
to or better than those of membranes
cold-cast from casting solutions containing
aqueous electrolytes.
2. The development of successful binary
and ternary mixtures demonstrates unequiv
ocally that neither water nor electrolytes
are necessary as components of casting
solutions. As a corollary to this statement.
ACKNOWLEDGEMENTS
This study was supported by funds pro-
vided by the California State Legislature.
They are administered through the Uni-
172
formate, acrylic acid, oleic acid, phenol,
propionic acid, diethanolamine, diethyl-
phthalate, tetrahydrofuran, diethylaraine,
acetonitrile, and pyrocatechol.
The inadequacy of some of these mate
rials must be attributed to their failure to
meet some of the previously stated neces
sary requirements of additives. However,
compounds which met all four require
ments and still were unsuccessful illustrate
the insufficiency of these requirements.
ETHYL CELLULOSE MEMBRANES
This paper is concerned primarily with
cellulose acetate membranes. However, it is
of interest to note that promising ethyl
cellulose desalination membranes can be
cast from suitable ternary mixtures, whereas
it has not been found possible to use ethyl
cellulose satisfactorily in the aqueous mag
nesium perchlorate casting solution (ref.
5) . On the other hand, a ternary mixture
of ethyl cellulose:triethylphosphate:dioxane
gave reasonably promising performance, as
shown in Table XXXI.
Heating Desalinated water
temperature Flux Salt content
<°C) (nal/ftVday) (ppm)
Unhealed 4.S 600
81.0 o.e 400
Unheated 4.8 700
it is clear that no ion-ion or ion-dipole
interaction is required between casting com
ponents at any stage of fabrication. This
latter statement also applies to casting
solutions containing water, as witnessed bv
the utility of urea, glyoxal, or hydrogen
peroxide in quaternary mixtures with cel
lulose acetate-water-acetone.
3. It is possible at the present time to
state definitive necessary but insufficient
conditions for components in cellulose ace
tate casting solutions.
versity of California Statewide Water Re-
sources Center located on the Los Angeles
campus of the University.
 REFERENCES
1. Dobry, A.: Bull, de la Société Chim. de
France, J« Serie, t. III, (19S6) pp. 312-
318.
2. Hassler, G. L.: "The use of molecular
oil films in a pressure method (or
obtaining irrigation water from the sea,"
Univ. of California, Dept. of Engr., Los
Angeles (Aug. 1950) .
3. Resting, R. E.: /. Appl. Polymer Sei.
vol. 9 no. 2 (Feb. 1965) pp. 663-668.
4. Resting, R. E.; Reilin, В.: "The mech
anism of desalination by reverse
osmosis," U.S. Department of the Inte
rior, Office of Saline Water R&D Progr.
Rept. 84 (Nov. 1963) .
5. Loeb, S.: "Sea water demineralization
by means of a semipermeable mem
brane," Univ. of California, Dept. of
Engr., Los Angeles, Progr. Rept. no.
61-42 (Aug. 1961) .
6. Loeb, S.: "Sea water demineralization
by means of a semipermeable mem
brane," Univ. of California, Dept. of
Engr., Los Angeles, Progr. Rept. no.
63-32 (July 1963) .
7. Loeb, S.: "Appropriate electrolytic ad
ditives in a casting solution used for
the production of high performance
cellulose acetate membranes used in
reverse osmosis desalination," Ph.D. Dis
sertation. Univ. of California, Dept. of
Engr., Los Angeles (May 1964) , Univer-
SUMMARY OF DISCUSSION
There was no discussion.
sity Microfilms, Inc., Ann Arbor,
Michigan (64-12525).
8. Loeb, S.; Manjikian, S.: "Brackish
water desalination by an osmotic mem
brane," Univ. of California, Dept. of
Engr., Los Angeles, Progr. Rept. no.
63-22 (May 1963) .
9. Loeb, S.; Sourirajan, S.: Advan. Chem.
Ser. no. 38 (1962) pp. 117-132.
10. Manjikian, S.: "Semipermeable desali
nation membranes from organic casting
solutions," Univ. of California, Dept. of
Engr., Los Angeles, Rept. no. 65-13
(May 1965) .
11. Office of Technical Services: "Deminer
alization of saline waters, a preliminary
discussion of a research program, with
an outline and description of potential
processes and a bibliography," U.S. De
partment of the Interior, PB 161373
(Oct. 1952) .
12. Reid, С. E.: Breton, E. J.: /. Appl.
Polymer Sei. no. 1 (1959) pp. 133-143.
13. "Saline water conversion report," U.S.
Department of the Interior, Office of
Saline Water (1960) .
14. Yuster, S. T.; Sourirajan. S.; Bernstein,
R.: "Sea water demineralization by the
'surface skimming' process," Univ. of
California, Dept. of Engr., Los Angeles.
Rept. no. 58-26 (Mar. 1958).
173
 Perfectionnement Des Techniques de
Fabrication Des Membranes Utilisées
Dans le Procède de Dessalement Par
Osmose Inversée
S. Manjikian, S. Loeb, J. W. McCutchan
Etats-Unis d'Amérique
Au cours de la dernière décennie, le
procédé de dessalement par osmose inversée
a fait des progrès tels, qu'il est sur le point
de devenir compétitif. Ces progrès sont,
pour une grande part, dus à la mise au
point d'une membrane ayant un rendement
amélioré, du point de vue des qualités de
la membrane en ce qui concerne le dessale
ment d'une part et d'autre part le débit
d'eau dessalée. Ce perfectionnement techno
logique de la membrane utilisée dans l'os
mose inversée résulte de deux événements
capitaux:
1. La découverte par Reid et Breton
que l'acétate de cellulose est fortement
semi-perméable aux sels marins. Sourirajan
parvint indépendamment à la même con
clusion et ajouta l'acétobutyrate de cellulose
à la liste.
2. La mise au point par Loeb et Souri
rajan d'une technique de fabrication en
vertu de laquelle les membranes d'acétate
de cellulose ont un débit suffisamment élevé
d'eau potable pour rendre le procédé inté
ressant sur le plan commercial.
Dans leur technique de fabrication, Loeb
et Sourirajan utilisèrent une solution de
coulée à l'acétone à laquelle, en se basant
sur les travaux antérieurs de Mlle Dobry.
furent ajoutés des électrolytes aqueux, tel
que le perchlorate de magnésium. La pré
sente communication traite de la mise au
point de solutions de coulée utiles ne con
tenant que des composants non électrolytes.
Les lignes directrices de l'étude ont été
obtenues sur la base de résultats antérieurs.
Tout d'abord, on a utilisé de l'acétate de
cellulose similaire à l'F.astman 398-3. Deu
xièmement, le solvant de l'acétate de cellu
lose devait être chimiquement inactif et
miscible avec l'eau, du fait que le solvant
est en grande partie retiré du gel par im
174
mersion dans l'eau. Troisièmement, si le
solvant se révélait incapable de produire à
lui seul une membrane semi-perméable à
haut débit, au moins un composant com
plémentaire devait être ajouté à cette fin.
Ces additifs devaient être miscibles avec le
solvant et avec l'eau, et être en outre
chimiquement inactifs. Quatrièmement, dès
son immersion dans l'eau, l'additif devait
pouvoir être soumis à la lixiviation et
extrait du gel par la solution dans l'eau
d'immersion, de préférence après le solvant.
Pour ce qui est du reste de la technique
de fabrication des membranes, la gamme
d'opérations qui avait antérieurement été
retenue par Loeb et Sourirajan a été suivie.
Les étapes de ces opérations comprenaient:
l'immersion de la membrane, ordinaire
ment dans de l'eau glacée, pendant une
durée déterminée à l'avance après l'étale
ment de la pellicule et, enfin, le chauffage
de la membrane à la température requise
pour produire de l'eau douce selon le maté
riel de dessalement utilisé. Les membranes
furent ensuite soumises à des essais dans
une petite cellule de dessalement capable
de faire passer rapidement de la saumure
sous pression sur la surface de la membrane
et d'évacuer l'eau dessalée avec un mini
mum de résistance à son écoulement.
La meilleure solution de coulée obtenue
jusqu'à présent est un mélange ternaire
d'acétate de cellulose-formamidc-acétone
dans la proportion de 25:30:45 pour cent
par poids. Les membranes obtenues à partir
de cette solution de coulée sont égales, voire
supérieures aux meilleures membranes ob
tenues à l'aide de la solution de coulée
modifiée par électrolytes qui était utilisée
auparavant. Les membranes modifiées à la
formamide donnent de bons résultats repro
ductibles et sont dotées de bonnes propriétés
 physiques. Fait des plus importants, la solu
tion à la formamide permet de procéder
rapidement à la coulée à la température
ambiante, ce qui constitue une notable
simplification par rapport à la technique
antérieure, où il fallait couler à une tempé
rature de — 5 à — 10°C pour obtenir les
meilleurs résultats.
La solution à la formamide et les modi
fications apportées à cette technique de
fabrication ont remplacé l'ancienne tech
nique employée pour les travaux de coulée
ordinaires poursuivis par l'Université de
Californie, à Los Angeles. En voici un
exemple caractéristique: une membrane
modifiée à la formamide est plongée dans
de l'eau glacée après une période d'évapo-
ration maximum d'une demi-minule à une
température ambiante. Par la suite, la
membrane est chauffée dans de l'eau
chaude pendant 4 à 5 minutes. Pour ob
tenir le dessalement de l'eau saumâlre
d'alimentation de, mettons, 5.000 ppm de
chlorure de sodium, la membrane est
chauffée à 75°C. On peut compter qu'une
telle membrane fournira 25 à 30 gallons/
pied carré-jour d'eau dessalée à 300 ppm
NaCl dans une cellule fonctionnant à 600
livres par pouce carré de pression mano-
métrique.
La mise au point d'un mélange ternaire
sûr, susceptible d'être coulé à une tempéra
ture ambiante, a simplifié l'étude des para
métres de coulée. L'étude d'un de ces
paramètres s'est portée sur la spécification
de l'acétate de cellulose. Le poids molé
culaire, la répartition du poids moléculaire
et la teneur en acétyle (degré d'acétylation)
ont été examinés. Il a été constaté que dans
les limites prises en considération, le der
nier facteur variable était le plus important,
les teneurs en acétyle entre 37,5 et 40,1%
(degré d'acétylation entre 75 et 85%) con
venant le mieux à la production de bonnes
membranes.
Il a également été observé que la tech
nique relative à la solution de coulée
ternaire était applicable à la préparation
de membranes éprouvées à partir d'éthylc-
cellulose. Dans ce cas particulier, la com
position de la solution de coulée était
la suivante: éthylecellulose-phosphate de
triéthyle-dioxane.
Des matériaux non électrolytes autres que
la formamide ont été utilisés dans les
solutions de coulée en vue de la production
de membranes de dessalement à l'acétate de
cellulose, offrant des perspectives intéres
santes. Ces solutions comprenaient des
mélanges quaternaires, ternaires et binaires.
Les mélanges quaternaires, qui avaient
donné de bons résultats, contenaient un
composé d'acétate de cellulose-eau-acétone
plus un quatrième composant (urée, gly-
oxal ou eau oxygénée) . Cette dernière
revêtait un intérêt particulier en raison de
son rapport chimique étroit avec l'eau,
laquelle n'est d'aucune utilité en tant qu'ad
ditif. Les solutions de coulée ternaires
retenues comme satisfaisantes contenaient
de l'acétate de cellulose-acétone plus un
troisième composant (phosphate de tétra-
hydrofurfuryle, oxysulfurc de diméthyle,
N-méthyle-2-pyrrolidone, formamide de di
méthyle, phosphate de triéthyle, ou acide
acétique cristallisable) .
Le phosphate de tétrahydrofurfuryle est,
au même titre que la formamide, un solvant
incomplet pour l'acétate de cellulose. Par
opposition à la formamide, l'oxysulfure de
diméthyle, le N-méthyle-2-pyrrolidone, la
formamide de diméthyle, le phosphate de
triéthyle, et l'acide acétique sont des sol
vants complets pour l'acétate de cellulose,
les trois derniers ayant leur utilité dans les
mélanges binaires.
Un certain nombre de composés orga
niques ont donné des solutions homogènes
claires dans les mélanges ternaires avec de
l'acétate de cellulose et de l'acétone, mais
ne se sont pas révélés utiles pour la produc
tion de bonnes membranes. Ce groupe
comprenait la formiatc de méthyle. l'acide
acrylique, l'acide oléique, le phénol, l'acide
propionique, le diéthanolamine, le phtalate
de diéthyle, le tétrahydrofuranne, la di-
éthylamine, l'acétonitrile, et la pyroca-
téchine.
L'imperfection de certains de ces maté
riaux peut être attribuée a leur défaut de
répondre aux exigences stipulées antérieure
ment. Toutefois, certains d'entre eux ont
satisfait à toutes les exigences mais n'ont
cependant pas réussi à s'imposer, illustrant
ainsi l'insuffisance de ces exigences.
La mise au point de mélanges binaires
et ternaires utiles démontre sans aucun
doute que ni l'eau ni les électrolytes ne
sont nécessaires à la composition des solu
tions de coulée destinées à la production
des membranes à l'acétate de cellulose
destinées à la déminéralisation. Cette dé
monstration fait également largement res
sortir qu'aucune interaction, ion-ion ou ion-
dipôle n'est nécessaire entre les composants
de la coulée à n'importe quel stade de la
fabrication. Cette dernière démonstration
s'applique également aux solutions de
roulée contenant de l'eau, comme l'illustrent
les solutions de coulée quaternaires dont les
essais ont été couronnés de succès.
175
 Усовершенствования в Методах
Промышленного Производства
Опреснительных Мембран, Работающих
Обратным Осмосом
С. Манджикиан, С. Леб, Дж. У. МакКотчан
Соединенные Штаты Америки
За последнее десятилетие обратный
осмос подошел к той черте, за которой
он может стать конкурентоспособным
опреснительным процессом. Значитель
ная часть этого прогресса зависела от
усовершенствования мембраны и ее
производительности, отразившейся на
опреснительных качествах мембраны и
интенсивности потока опресненной во
ды. Эти достижения в области техно
логии мембран с обратным осмосом
зиждились на двух основных усовер
шенствованиях.
1. Открытие Рейда и Бретона, что
ацетат целлюлозы весьма прони
цаем для солей морской воды. Су-
рираджан нашел это независимо и
дополнил список ацетатным бути-
ратом целлюлозы.
2. Усовершенствование Лебом и Су-
рираджаном производственной те
хники, благодаря чему мембраны
из ацетата целлюлозы теперь вы
пускают достаточно большой по
ток питьевой воды, чтобы сделать
процесс интересным с коммерче
ской точки зрения.
Частью производственной техники
Леба и Сурираджана стало использо
вание ацетонного раствора для отлив
ки, содержащего согласно предшество
вавшей работе мадемуазель Добри, та
кие водные электролиты, как перхло
рат магния. В настоящем докладе при
ведено описание развития пригодных
растворов для отливки, куда включены
только не-электролиты.
На основании предварительного опы
та были намечены вехи дальнейшей ис
следовательской работы. В первую
очередь был использован ацетат цел
люлозы, подобный Е -398-3. Во-вто
176
рых было установлено, что раствори
тель ацетата целлюлозы должен обла
дать химической неактивностью и сме
шиваться с водой, так как в значитель
ной степени растворитель удаляется из
гели посредством погружения в воду.
В-третьих выяснилось, что надо добав
лять один или два дополнительных
компонента, если из растворителя са
мого по себе невозможно выработать
полупроницаемую мембрану с сильным
потоком. Такие добавки должны сме
шиваться с растворителем и водой, и
быть химически неактивными. В-чет
вертых было обнаружено, что по по
гружению в воду следует иметь воз
можность выщелачивать из гели при
садку растворением в иммерсионной
воде, и предпочтительно после раство
рителя. Что касается остальных мето
дов производства, то в общей сложно
сти были использованы меры, ранее
рекомендованные Лебом и Сурираджа-
ном. К ним после распластания пленки
относилось погружение мембраны в во
ду, обыкновенно ледяную, на заранее
установленный промежуток времени, а
затем нагревание мембраны до темпе
ратуры, необходимой для производства
пресной воды в зависимости от опре
снительного оборудования. После этого
мембраны испытывались в небольшой
опреснительной ячейке, способной бы
стро пропускать сжатый концентрат в
пространство над поверхностью мем
браны и выпускать опресненную воду
с минимальным сопротивлением по от
ношению к ее протоку.
Наилучшим отливочным раствором,
который пока-что удалось получить,
оказалась тройная смесь ацетат целлю
лозы — формамид — ацетон с процент
яым соотношением 25 : 30 : 45 по весу.
Мембраны из этого раствора равноцен
ны или лучше самых лучших мембран,
которые делались из ранее употребляв
шегося электролитно-модифицирован-
ного отливочного раствора. Формами-
до-модифицированные мембраны, как
правило обладают высоким коэффици
ентом полезного действия и хорошими
физическими свойствами. Весьма важ
но, что отливка из раствора формами-
да всегда может происходить при ком
натной температуре, что является зна
чительным упрощением по сравнению
с предшествовавшими приемами, при
которых отливка лучше всего произ
водилась при 5°С - 10°С ниже нуля.
Раствор формамида и соответствен
ные изменения методов производства
заменили старую технологию стандарт
ной отливки, выработанной Универси
тетом Калифорнии в Лос-Анжелосе.
Обычно формамидо-модифицированная
мембрана после выпарки, берущей не
более 90 секунд и при температуре
окружающей среды, погружается в ле
дяную воду. После этого она нагрева
ется в течение 4-5 минут в горячей
воде. Для опреснения исходной воды,
скажем, с содержанием 5.000 мг/л хло
ристого натрия, мембрана нагревается
до 75°С. Такая мембрана может дать
25 - 30 галлонов/кв. фут х день обес
соленной воды с содержанием 300 мг/л
хлористого натрия, имея ячейку, рабо
тающую при манометрическом давле
нии 600 фунтов на кв. дюйм.
Развитие надежной тройной смеси,
отливаемой при комнатной температу
ре, упростило исследование параметров
отливки. Одним из них явилась специ
фикация ацетата целлюлозы. Были изу
чены молекулярный вес, распределение
молекулярного веса и содержание аце
тила (степень ацетиляции). Было уста
новлено, что в исследованных пределах
последняя переменная величина наибо
лее важна, причем для производства
хороших мембран желательно иметь
содержание ацетила 37,5% -40,1% (сте
пень ацетиляции 75% -83%).
Технология тройного отливочного ра
створа оказалась также применимой
для изготовления многообещающих
опреснительных мембран из этилцеллю-
лозы. В этом случае в отливочный ра
створ входили этилцеллюлоза — три-
этилфосфат — диоксан.
Для производства многообещающих
опреснительных мембран из ацетата
целлюлозы, кроме формамида были ис
пользованы в отливочных растворах и
другие не-электролитические материа
лы. К ним относились четверные, трой
ные и двойные растворы. Удачные чет
верные растворы содержали ацетат
целлюлозы — воду — ацетон плюс чет
вертый компонент: мочевину, глиоксал
или перекись водорода. Перекись во
дорода вызывала особый интерес, вви
ду ее близкого сродства с водой ко
торая безполезна в качестве добавки.
Удачные тройные отливочные раство
ры содержали ацетат целлюлозы —
ацетон плюс третий компонент: тетра-
гидрофурфурил фосфат, диметилсуль-
фоксид, Н-метил-2-пирролидон, диме-
тилформамид, трнэтилфосфат или ле
дяную уксусную кислоту.
Тетрагидрофурфурил фосфат явля
ется неполным растворителем ацетата
целлюлозы, так же как и формамил.
В противоположность формамиду ди-
метилсульфоксид, Н-метил-2-пирролн-
дон, диметилформамид, трнэтилфосфат
и уксусная кислота являются полными
растворителями ацетата целлюлозы,
причем последние три полезны в двой
ных смесях.
В тройных смесях ряда органических
составов с ацетатом целлюлозы и аце
тоном получались светлые гомогенные
растворы, но они не пригодились для
производства хороших мембран. В эту
группу входили метиловый эфир му
равьиной кислоты, акриловая кислота,
олеиновая кислота, фенол, пропионо-
вая кислота, диэтаноламин, диэтилфта-
лат, тетрагидрофуран, диэтиламин, аце-
тонитрил и пирокатехин.
Неприменимость некоторых матери
алов объяснялась их несоответствием
известным требованиям, которые были
раньше упомянуты. Однако, некоторые
из них соответствовали вполне, но все
же не были пригодными, что указывает
на недостаточность этих требований.
Эволюция удачных двойных и трой
ных смесей целиком подтверждает, что
ни вода, ни электролиты не являются
необходимыми компонентами отливоч
ных растворов для полезных опресни
тельных мембран из ацетата целлюло
зы. В виде заключения к этому поло
жению можно сказать, что ни в одной
из стадий производства не требуется
междуионного или ионо-дипольного
взаимодействия между компонентами
отливки. Последнее положение отно
сится также к отливочным растворам,
содержащим воду, как это было под
тверждено удачными четверными от
ливочными растворами.
177
 Mejoras en las
Fabricación de
Desalinizacion por Osmosis
S. Manjikian, S. Loeb, J. W. McCutchan
Estados Unidos de Norteamérica
En el curso de la década pasada, la
ósmosis inversa ha sido desarrollada al
punto de convertirse en un proceso de
desalinización competitivo. Una gran parte
de este progreso ha sido resultado del
desarrollo de una membrana de mayor efi
ciencia, a juigar por las cualidades de la
membrana de desalinización y el flujo de
agua desalinizada. Estos adelantos en la
tecnología de las membranas de ósmosis
inversa son consecuencia de dos desarrollos
básicos:
1. El descubrimiento de Reid y de
Breton de que el acetato de celulosa es muy
semipermeable a las sales del agua del mar.
Sourirajan independientemente llegó a estas
mismas conclusiones y amplió la lista, in
cluyendo el acetato butirato de celulosa.
2. El desarrollo de una técnica de fabri
cación por parte de Loeb y Sourirajan, por
medio de la cual las membranas de acetato
de celulosa permiten un flujo de agua
potable suficientemente elevado para dar al
proceso interés comercial.
Como parte de su técnica de fabricación,
Loeb y Sourirajan utilizaron una solución
acetónica de moldeo conteniendo, de acuer
do con los trabajos previos de la Srta.
Dobry, electrolitos acuosos tales como el
perclorato de magnesio. En este trabajo se
informa sobre los resultados obtenidos con
soluciones de moldeo que solamente contie
nen no-electrolitos.
Las pautas para el estudio se obtuvieron
con base en las experiencias anteriores.
Primero, se utilizó un acetato de celulosa
similar al E-398-3. Segundo, el solvente para
el acetato de celulosa debía ser química
mente inactivo y miscible con el agua dado
que el solvente es separado en gran parte
del gel cuando es sumergido en agua. Ter
cero, si el solvente era incapaz de producir,
por sí solo, una membrana semipermeable
de alto flujo, para lograr tal objeto debían
agregarse uno o más componentes adicio
Técnicas de
Membranas de
Inversa
nales. Tales agregados debían ser miscibles
con el solvente y con el agua y debían ser
químicamente inactivos. Cuarto, luego de
ser sumergido en agua, el aditivo debía
poder lixiviarse del gel por solución en el
agua de inmersión y preferiblemente des
pués del solvente. Con respecto al resto de
la técnica de fabricación de la membrana,
se utilizaron, en general, los pasos previa
mente determinados por Loeb y Sourirajan.
Estos pasos incluían la inmersión de la
membrana en agua, generalmente agua he
lada, dentro de un determinado período
después de la dispersión de la película y,
finalmente, calentamiento de la membrana
a la temperatura de trabajo del equipo de
desalinización a ser usado en la producción
de agua fresca. Las membranas luego fueron
comprobadas en una pequeña célula de
desalinización capaz de permitir el pasaje
rápido de aguas madres a presión sobre la
superficie de la membrana y de dar salida
al agua desalinizada, con una resistencia
mínima a su flujo.
La mejor solución de moldeo obtenida
hasta ahora ha sido una mezcla ternaria de
acetato de celulosa—formainida—acetona,
en la proporción de 25:30:45 por ciento por
peso. Las membranas obtenidas a partir de
esta solución de moldeo son iguales o me
jores que las mejores membranas obtenidas
de las soluciones de moldeo electrolíticas
modificadas utilizadas previamente. Las
membranas de formamida modificada traba
jan con una buena eficiencia reproducible
y tienen buenas propiedades físicas. Más
importante que ello, el moldeo puede ha
cerse rápidamente a temperatura ambiente
con la solución de formamida, lo cual cons
tituye una marcada simplificación respecto
de las técnicas previas, de acuerdo con las
cuales el moldeo se hacía mejor a una tem
peratura que oscilada entre —5 y — 10°C.
La solución de formamida y las modifica
ciones concomitantes en la técnica de fabri
ración han reemplazado a la vieja técnica
para el trabajo de moldeo empleada común
mente en la Universidad de California en
Los Angeles (UCLA) . Típicamente, una
membrana de formamida modificada se su
merge en agua helada después de un periodo
de evaporación máximo de medio minuto a
la temperatura ambiente. Posteriormente es
calentada en agua caliente durante 4 ó 5
minutos. Para desalinización de agua de
alimentación salobre, de 5.000 ppm de NaCI,
la membrana se calienta a 75°C. Es de
esperar que tal membrana produzca entre
25 y 30 galones, por pie cuadrado por día,
de agua desalinizada a 300 ppm NaCI en
una célula que opera a 600 libras por pul
gada cuadrada, presión manométrica.
El desarrollo de una mezcla ternaria se
gura, moldeable a temperatura ambiente,
simplifica el exámen de los parámetros de
moldeo. Uno de los parámetros así exami
nados fue el de la especificación del acetato
de celulosa. Se consideraron el peso mole
cular, la distribución del peso molecular y
el contenido acetílico (grado de acetilación).
Se encontró que dentro de la gama conside
rada, la última variable fue la más impor
tante, siendo conveniente un contenido
acetílico entre el 373 y el 40,1% (grado de
acetilación entre el 75 y el 89%) para
producir buenas membranas.
También se determinó que la técnica de
moldeo con solución ternaria resulta prác
tica para la preparación de membranas, de
interesantes perspectivas, partiendo de la
etilcelulosa. En este caso, la solución de
moldeo fue etilcelulosa-fosfato tri-etílico-
dioxano.
Otros productos no electrolíticos además
de la formamida han sido usados en solu
ciones de moldeo para producir promisoras
membranas de desalinización de acetato de
celulosa. Estas soluciones incluyen mezclas
cuaternarias, ternarias y binarias. Las mez
clas cuaternarias más apropiadas contienen
acetato de celulosa-agua-acetona, más un
cuarto componente, úrea, glioxal o peróxido
de hidrógeno. El peróxido de hidrógeno es
de especial interés por su relación química
cercana al agua que es inútil como aditivo.
Las mezclas ternarias que han sido más
exitosas contienen acetato de celulosa-
acetona, además de un tercer compuesto:
fosfato tetrahidrofurfurilo, dimetilsulfóxido,
N-metilo-2-pirrolidona, dimetilformamida,
fosfato trietílico o ácido acético glacial.
El fosfato tetrahidrofurfurilo es un sol
vente incompleto para el acetato de celulosa
al igual que la formamida. En contraste con
la formamida el dimetilsulfóxido, el
N-metilo-2-pirroIidona, el dimetil-formami-
da, el fosfato trietílico y el ácido acético
son solventes completos para el acetato de
celulosa y los tres últimos son útiles en
mezclas binarias.
Un cierto número de compuestos orgá
nicos dieron soluciones homogéneas claras
en mezclas ternarias con acetato de celulosa
y acetona pero no resultaron convenientes
para la producción de buenas membranas.
Este grupo incluye formiato de metilo,
ácido acrílico, ácido oléico, fenol, ácido
propíonico, dietanolamina, dietilftalato, te-
trahidrofurano, dietilamina. acetato de
nitrilo y pirrocatecol.
Lo inadecuado de algunos de estos mate
riales debe atribuirse a la circunstancia de
que no satisfacen algunos de los requisitos
previamente señalados. Sin embargo, algu
nos de ellos llenan todos los requisitos a
pesar de lo cual no dieron resultado, lo que
demuestra la insuficiencia de dichos requi
sitos.
La formulación de mezclas binarias y ter
narias demuestra inequívocamente que ni el
agua ni los electrolitos son necesarios como
componentes de soluciones de moldeo para
membranas de desalinización de acetato de
celulosa útiles. Como un corolario de esta
afirmación resulta claro que en ninguna
etapa del proceso de fabricación no se
requiere una interacción ion-ion o ion-
dípolo entre los componentes del líquido
de moldeo. Esta última afirmación es apli
cable también a soluciones que contienen
agua, según lo demuestra el éxito de solu
ciones cuaternarias de moldeo.
179
Vapor-Compression
With Direct Contact
K. L. Pinder
Canada
The following paper is a description of a
proposed desalination process which has not
yet been developed to the stage where esti
mated operating conditions could be mean
ingful. Besides this, the vapor-compression
system proposed here may be carried out
with widely different types of equipment.
The choice of equipment for any specific
plant will be governed by the results from
future pilot plant studies.
This process, like certain others, has been
designed to circumvent the evaporator prob
lems of scaling, size, and cost. Scaling has
been eliminated by the use of liquid-liquid
heat transfer in both the evaporator and
condenser. The high heat transfer coeffi
cients and large surface areas available in
the direct contact heat transfer make the
use of smaller equipment possible. Because
of these two considerations, it is expected
that appreciable cost reductions for desali
nation of water will be shown by this process
over the equivalent vapor-compression cycle
with conventional heat transfer surfaces.
Besides the possibility of cheaper water,
this process has two other immediately ob
vious advantages. It lends itself to economi
cal design over a wide range of plant sizes—
from household units to city units. Also,
outside the field of water recovery, it can be
used to evaporate to dryness many solutions
which are now dried only by batch multi-
step procedures.
BACKGROUND
Liquid-liquid heat transfer during evap
oration (refs. 1-12) and condensation (ref.
6) has in the last few years come under
closer research scrutiny. The impetus for
this activity has been three other desalina
tion processes.
Evaporation
Heat Transfer
1. In the direct refrigeration freeze de
salination process (refs. 13-16) , the heat is
removed from the water by the evaporation
of an insoluble liquid which boils below the
salt water freezing temperature. The roles of
the two liquids in the evaporative process
are reversed (the water evaporates and the
second liquid is cooled") but the experi
mental data and heat transfer correlations
are still applicable.
2. A similar desalination process uses a
gas hydrate instead of ice. In this case the
hydrate former is usually boiled to cool the
water to the hvdration temperature (refs.
17-19) .
3. The evaporation of water by heat
transferred directly from an immiscible heat
transfer medium is of a similar nature but
very little has been published on it. In the
flash evaporation processes (refs. 6, 20)
which use direct heat transfer heat, the sea
water is heated by the heat transfer medium
without evaporation.
PROCESS DESCRIPTION
Figure 65 is a schematic flow sheet of the
proposed desalination process for the case
in which the heat transfer medium is denser
than the salt solution. In the evaporator,
sea water, which has been preheated in
tube and shell heat exchangers by the prod
uct water and waste brine, is contacted in
an atomized form with hot heat transfer
medium. The water is evaporated from the
sea water droplets, producing superheated
steam which stirs the heat transfer medium
and holds the total mass of liquid in a
turbulent state. After demisting in the
upper section of the evaporator, the steam
passes to a compressor which raises the
steam pressure to that in the condenser.
181

COMPR
Steam
Heat Transfer Medium
FIGURE 65. DIRECT CONTACT VAPOR-COMPRESSION
EVAPORATION.
At the temperature corresponding to the
brine boiling point, the heat transfer me
dium-brine mixture from the evaporator is
drawn into a separator. From there the
waste brtne goes to the sea water prcheater
and the heat transfer medium is pumped
to the condenser. The compressed steam is
condensed by direct contact with the heat
transfer medium, which is heated to a tem
perature several degrees above the boiling
point of the waste brine in the low pressure
evaporator. From the top of the condenser,
the liquid mixture passes to a decanter
where the potable water is decanted from
the heat transfer medium which is recycled
to the evaporator.
For heat transfer mediums which are
lighter than water, the process operates in
a similar fashion but minor alterations in
the takeoff points for the various fluid
streams must be made.
DECANTER
Potable
Water
As can be seen, this is an exceedingly
simple system which should lend itself easily
to small low maintenance units. Only simple
controls will be needed to hold this in bal
ance since the mass flow of heat transfer
medium is so much greater than that of
water. Also, since the main transfer of heat
is across liquid-liquid interfaces, there is no
scaling problem, the temperature difference
between heat transfer fluids may be small,
corrosion is negligible, and there is only an
economic limit to the final brine concen
tration.
It is this last point which widens the field
of uses for this process immeasurably. Out
side the field of desalination there are many
solutions which are difficult to concentrate
because of scaling, stickiness, or corrosion.
By this process they could be evaporated to
dryness with very little loss of economy. The
high superheat produced in the steam by
this procedure is almost entirely recovered
in the condenser. Since the solids would
remain in the heat transfer medium, the
choice of heat transfer medium would be
specific in each case.
As mentioned earlier, the equipment de
sign and choice of heat transfer medium
will depend on their application and on
future pilot plant studies. Several alterna
tives may now be mentioned to show the
wide choice available.
HEAT TRANSFER MEDIUM
The criteria which have been considered
in screening heat transfer media are:
1. Vapor pressure: The heat transfer me
dium must have a low vapor pressure com
pared to that of water at the boiling point
of the brine.
2. Solubility: Water and the heat trans
fer medium should be mutually insoluble.
3. Stability: The heat transfer medium
must not react with water or brine, nor
must it decompose at the temperatures en
countered in the process.
4. Corrosion: For economy in construc
tion, the heat transfer medium must be
noncorrosive to ferrous metals.
5. Heat capacity: The heat capacity must
be as high as possible, since the heat is
transferred only as sensible heat. The circu
lation rate of the heat transfer medium is
inversely proportional to its specific heat.
6. Viscosity: The viscosity should be low
at the temperatures encountered in the
process.
7. Density: The density may be either
greater or less than that of water, but in
either case there should be a large differ
ence in density to enhance separation.
8. Emulsification: Since there is intimate
mixing in the evaporator and condenser,
the heat transfer medium must not have a
tendency to emulsify with water or brine.
9. Freezing temperature: The tempera
ture should be low enough so that solidifi
cation does not occur in cold spots in the
equipment. For equipment which is to have
intermittent use, the heat transfer medium
should not be solid at ambient temperatures.
10. Combustibility: Even though the
vapor pressure criterion requires a mini
mum of vapor from the heat transfer
medium, the best fluid should have low
combustibility so that special safety pre
cautions are not needed.
11. Toxicity: Since no two liquids are
absolutely insoluble, a small amount (a few
ppm) of the heat transfer fluid may appear
in the product water. Therefore, fluids
which are highly toxic or which exhibit
accumulative toxicity must be avoided.
12. Price: Because of the large inventory
of the heat transfer fluid in larger plants,
and because of the small losses which are
usually encountered in large-scale plants,
exotic high priced materials should be
avoided.
EVAPORATOR
In Figure 66 three of the possible evap
orator configurations are shown. F.ach con
figuration will have its particular field of
application. These are not design drawings
but are meant to show the flow pattern of
the three phases involved.
1. Water Spray: Rapid response to water
flow rate may be obtained in an evaporator
which acts as a spray column (Fig. 66A) .
Preheated water is sprayed into a large vol
ume of hot heat transfer medium and evap
orates in the turbulent atmosphere caused by
the almost explosive nature of the process.
Most of the heat transfer studies have
been made on such a system (refs. 10, 11,
16) , and for this reason it would be the
easiest to design. Although the large inven
tory of heat transfer medium is a disadvan
tage, this type of evaporator would be useful
for processes in which the solution is evap
orated to dryness.
2. Heat Transfer Medium Spray: More
reminiscent of a calandi ia-type evaporator
is the process shown in Figure 66B. Hot heat
transfer medium is sprayed into a pool of
salt water, thus imparting its heat to the
water which will boil at the liquid-liquid
surface. This configuration will allow phase
separation in the evaporator and will oper
ate more quietly than the water spray sys
tem because of the lower rate of heat
transfer. For a given rate of heat transfer,
a much smaller inventory of heat transfer
medium would be necessary in this evap
orator than in the first case.
3. Flow Contactor: Since heat transfer
rate and nucleation are enhanced by turbu
lence, the intimate mixing produced by
injecting the hot water into the throat of
a venturi would result in rapid evapora
tion. Disintegration of the steam from the
liquid mixture could be carried out by
centrifugal force (Fig. 66C) . The small size
of this type of equipment and the low in
ventory of heat transfer medium could make
up for the reduction in efficiency which
might result.
In place of a venturi, any flow mixer
could be used to mix the two fluids inti
mately. Because of the scrubbing effect of
the boiling mixture, erosion of spirals or
screens may be very rapid.
183
 ^ Steam
r

Brine < Cold H.T.M.

Hot H.T.M.

Steam
r
r
*******

Brine ♦ Cold H.T.M.

> Steam

I i
S*****S

Hot HT.M.

Sea Water

Brine «Cold H.T.M.

FIGURE 66. DIRECT CONTACT EVAPORATORS.
 CONDENSER
Figure 67 illustrates two of the possible
condenser flow patterns. Other designs, such
as the one used for direct steam heated in
dustrial hot water supply systems, could
also be used for this purpose. The final
design which is chosen in each case will
depend upon the results of pilot plant
studies and upon the purpose for which it
is to be used.
Steam
Noncondantibltt
, PotODlO
Wottr
.Hot H.T.M.
PotobH Wottr «
Hot H.T.M
Cold H.T.M.
FIGURE 67. DIRECT CONTACT
CONDENSERS.
1. Packed Condenser: Because of the
large density difference between steam and
the heat transfer medium, a packed column
would be necessary to give the needed resi
dence time. Noise, caused by the collapse of
the steam, bubbles, may be a nuisance in a
condenser ot this design and could easily be
reduced by mixing the two streams in an
ejector at the bottom of the column.
2. Spray Condenser: A standard spray
condenser could be converted for this serv
ice. The closed system shown in Figure 67B
would be very efficient in heat and fluid
inventory.
Since the steam will be superheated after
compression, it may be advantageous to
produce a higher temperature in the heat
transfer medium by using the outlet fluid
from the condenser to desuperheat the
steam. However, with liquid-liquid heat
transfer the increase in condenser size due
to superheat is not as great as in tube-type
heat exchangers.
BRINE REMOVAL
Several operational factors will influence
the design of the brine separator. If rapid
disengagement of the brine and heat trans
fer medium occurs by virtue of a large
density difference and rapid coalescence,
then a simple gravity settler may be used.
For cases in which dry salt is produced or
coalescence is slow, a continuous centrifuge
may be used. Again, the choice will be made
from well-defined systems and will require
no special equipment.
COMPRESSOR
The Office of Saline Water is presently
supporting a study of steam compressor de
sign. This newer data plus previous work
which has been done on the calandria-type
vapor -compression evaporators may be used
in the design of this portion of the equip
ment.
Steam ejector-type compressors may also
be used for this purpose in locations where
the steam cost proves to be less than electric
power cost for the compressor motor. These
considerations have already been thoroughly
studied and are not considered problems in
this process.
ECONOMICS
Because of the lack of reliable data on the
size and efficiency of the two main units of
equipment in this process, any economic
assessment could add very little to what can
be said about the vapor-compression evap
oration process in general. The differences
between this system and the standard system
are as follows.
1. Once the water droplet has begun to
boil, i.e., the boiling is nucleated, the differ
ence between its boiling temperature and
the heat transfer medium's temperature will
be quickly reduced by the high heat trans
fer coefficient and the large surface area
available for heat transfer. This is also true
in the condenser. Since there arc no solid
heat transfer surfaces, the high heat trans
fer rates are not reduced by scaling.
2. The temperature difference between
the boiling solution and the heat transfer
medium is not limited by high temperature
scale formation.
S. Evaporation per pass of the sea water
through the evaporator can be very high
185
without fear of surface fouling. This would
reduce the size of the waste brine heat ex
changers, the loss of heat in this stream, and
the power to pump the excess water. Where
waste brine disposal is a problem, it may be
more economical to evaporate the salt to
dryness and sell the salt.
4. Because of the high heat transfer rates
across a boiling or condensing interface,
plant size and capital cost can be much less
than that for calandria-type vapor com
pression equipment. This will be especially
advantageous in smaller and portable units.
5. Power consumption will be a function
of the percentage evaporation, since the
condenser pressure will increase as the final
boiling temperature of the solution in
creases. A multistage vapor compression
process of this type would provide the most
efficient power or steam consumption for
cases in which a large fraction of the water
is to be recovered. Only in very large units,
however, would the added equipment cost
be balanced by the reduction in power cost.
6. Since corrosion and scaling are neg
ligible, the maintenance cost of the evap
orator would be greatly reduced.
7. Since all the latent heat of evaporation
must be carried by the sensible heat of the
REFERENCES
1. Viskanta. R.; Lottes, P. A.: Proc. Heat
Transfer and Fluid Mechanics Inst.,
Seattle. Wash. (June 15-15. 1962) pp.
171-184.
2. Harriott, P.; Wiegandt, H.: Private
communication from Cornell University,
Ithaca, N. V. (Oct. 1963) .
3. Moore. G. R.: A.I.Ch.E. Journal, vol.
5 no. 4 (1959) pp. 458-466.
4. Moore, G. R.: Ph.D. Thesis. University
of Wise. (1956) .
5. Gordon, K. F.; Singh, T.; Weissman,
E. Y.: Int. J. Heat and Mass Transfer,
no. 3 (1961) pp. 90-93.
6. Wilke, C. R.; Cheng, C. T.; Ledesma,
V. L.; Porter, J. W.: Chem. Eng. Prog
ress, vol. 59 no. 12 (1963) pp. 69-75.
7. Sideman, S.: Shabtai, H.: Can. J. Chem.
Eng., vol. 42 no. 3 (1964) pp. 107-117.
8. Novakovic, M.; Stefanovic, M.: Int. J.
Heat and Mass Transfer, no. 7 (1964)
pp. 801-807.
9. Harriott, P.; Wiegandt, H.: A.I.Ch.E.
Journal, vol. 10 no. 5 (1964) pp. 755-
758.
10. Sideman, S.: Taitel, Y.: Int. J. Heat and
Mass Transfer, no. 7 (1964) pp. 1273-
heat transfer medium, the rate of circula
tion must be very high—between about 50
and 100 pounds per pound of water pro
duced. The heat transfer medium circula
tion rate is a function of the temperature
difference between the evaporator and con
denser and of its heat capacity. Because of
the relative cost of pumping a low viscosity-
fluid and compressing steam, it is expected
that when more data are available, a full
economic assessment will favor the highest
circulation rate for any given fluid. Paraf
fins tend to have higher heat capacities than
do other liquids which are insoluble in
water, hence a material like paraffin wax
may prove to be the best heat transfer
medium.
Although this process is still in the arm
chair engineering stage, there do not appear
to be too many problems left for the pilot
plant to solve. Work has been underway for
some time at the University of British Co
lumbia in Vancouver, British Columbia, on
the direct contact boiling and the direct
contact condensation of a liquid. Support
for this work has been given both by the
university and by the National Research
Council of Canada.
1289.
11. Sideman, S.; Barsky, Z.: A.I.Ch.E. Pre
print 33b, 55th National Meeting,
Houston, Texas, (Feb. 7-11, 1965).
12. Otterman. B.: Proc. Heat Transfer and
Fluid Mechanics Institute, Seattle, Wash.
(June 13-15, 1962) pp. 185-196.
13. Bosworth, C. M.; Carfagno, S. S.: Bar-
duhn, A. J.; Sandell. D. J.: Office of
Saline Water, R&D Rept. no. 32 (Julv
1959) .
14. Karnofsky. G.: Chem. Eng. Prog., vol.
57, no. / (1961) pp. 42-46.
15. Wiegandt, H. F.: Office of Saline Water
R&D Rept. no. 41 (Aug. 1960)
16. Kawasaki, S.; Umano. S.: Kagaku Koga-
ku, vol. l.no. 1 (1963) pp. 69-74.
17. Knox. W. G.: Hess, M.; Jones, G. E.;
Smith, H. B.: Chem. Eng. Prog., vol. 57
no. 2 (1961) pp. 66-71.
18. Anonymous: Chem. Eng. \'ews, no. 60-
61, (Dec. 12, I960) .
19. Barduhn, A. J.; Towlson, H. E.; Hu.
Y.: National A.I.Ch.E. Meeting. Lake
Placid, N. Y. (Sept. 24-27. 1961) .
20. Knuth. E. L.: /. & E.C. Proc. Design
and Bevel., vol. ) no. 1 (1964) pp. 55-60.
 SUMMARY OF DISCUSSION
It was asked how an emulsion was broken
in the event that one occurred. The author
stated that there was concern about emul
sion formation but that when it formed it
broke readily and gave no difficulty. It was
stated that demislers will be used to over
come entrainment problems.
In answer to a question concerning the
salinity of the product, it was stated that
the salinity of the product obtained by the
method presented in this paper is below 500
ppm. The author was asked for comments
concerning his experience with Arochlor and
the lighter hydrocarbons. The author stated
that his experience with Arochlor had been
satisfactory and that the hydrocarbons used
evaporated from the water. He stated further
that since this process is not run as a cyclic
process, appreciable time can be allowed for
separation. The thing they were looking for
in their experiments was good heat transfer
data.

Evaporation Par Compression de

Vapeur et Echange de Chaleur

Par Contact Direct

K. L. Pinder

La présente étude décrit un procédé de sations économiques dans une gamme de

dessalement projeté qui n'est pas encore tailles très étendue: depuis l'appareil mé
arrivé au stade où les prévisions d'exploita- nager jusqu'à l'usine municipale. Par
tation seraient significatives. En outre, le ailleurs, à part le dessalement, il peut servir
procédé par compression de vapeur envisagé à évaporer jusqu'à dessiccation complète
ici peut être appliqué dans une gamme bien des solutions qui ne peuvent être
d'appareils de types très différents. Le desséchées actuellement que par lots et
choix de l'équipement pour toute usine selon des procédés à stades multiples.
donnée dépendra des résultats obtenus par
la suite dans les essais en usines pilotes. DOCUMENTATION
Ainsi que d'autres, ce procédé a été L'échange de chaleur liquide-liquide pen
conçu pour éviter les difficultés d'entartrage, dant l'évaporation (refs. 1-12) et la conden
de dimension et de prix des évaporateurs. sation (réf. 6) a fait l'objet de recherches
L'entartrage a été éliminé par un échange plus poussées au cours des dernières années.
de chaleur par contact direct de liquide à Cet intérêt a été provoqué par trois autres
liquide, aussi bien dans l'évaporateur que procédés de dessalement.
dans le condenseur. Les coefficients élevés 1. Dans le procédé de dessalement par
d'échange de chaleur et les surfaces impor congélation directe (refs. 13-16) , la chaleur
tantes dont on dispose dans l'échange de est enlevée de l'eau par l'évaporation d'un
chaleur par contact direct permettent l'em liquide insoluble dont le point d'ébullition
ploi d'appareils de dimensions plus réduites. est inférieur à la température de congéla
En raison de ces deux facteurs, on s'attend tion de l'eau salée. Dans le processus d'éva-
à ce que ce procédé apporte une réduction poration, le rôle des deux liquides est
appréciable du prix de dessalement de l'eau inversé (l'eau s'évapore et le deuxième
par rapport au même cycle de distillation liquide est refroidi) , mais les données
par compression de vapeur, utilisant des expérimentales et les rapports d'échanges
surfaces d'échange de chaleur classiques. de chaleur restent applicables.
A part la possibilité de produire l'eau 2. Un procédé de dessalement analogue
à meilleur marché, ce procédé possède deux emploie l'hydrate d'un gaz à la place de la
avantages évidents. Il se prête à des réali glace. Dans ce cas, le producteur d'hydrate

187
 est mis en ebullition pour refroidir l'eau à
la température d'hydratation.
S. L'évaporation de l'eau par échange
direct de chaleur avec un véhicule d'échange
non miscible est un procédé similaire sur
lequel peu de chose a été publié. Dans les
procédés d'évaporation éclair (refs. 6, 20) ,
où la chaleur est appliquée par échange
direct, l'eau de mer est chauffée sans évapo-
ration par le véhicule d'échange de chaleur.
DESCRIPTION DU PROCÉDÉ
Considérons la progression du procédé de
dessalement envisagé, lorsque le véhicule
d'échange de chaleur a une densité plus
élevée que la solution saline. Dans l'évapo-
rateur, l'eau de mer, chauffée au préalable
dans un échangeur tubulaire par l'eau
produite et les saumures résiduaires, est
mise en contact sous une forme atomisée
avec le véhicule d'échange de chaleur porté
à une haute température. L'eau s'évapore
des gouttelettes d'eau de mer, produisant
de la vapeur surchauffée qui agit le véhicule
d'échange de chaleur et maintient la masse
liquide totale dans un état de turbulence.
Apres avoir dégorgé sa buée dans la section
supérieure de l'évaporateur. la vapeur passe
par un compresseur qui élève sa pression
au niveau de celle du condenseur.
Le mélange véhicule d'échange de
chaleur-saumure, provenant de l'évapora
teur, à une température correspondant au
point d'ébullition de la saumure, est dirigé
vers un séparateur. De là, les saumures
résiduaires sont envoyées au réchauffeur
d'eau de mer et le véhicule d'échange de
chaleur est pompé vers le condenseur. La
vapeur comprimée est condensée par con
tact direct avec la véhicule d'échange de
chaleur qui a été porté à une température
supérieure de plusieurs degrés au point
d'ébullition des saumures résiduelles dans
l'évaporateur à basse pression. Du sommet
du condenseur, le mélange liquide passe
dans un décanteur où l'eau potable est
séparée du véhicule d'échange de chaleur
qui va reprendre le cycle à l'évaporateur.
Avec des véhicules d'échange de chaleur
plus légers que l'eau, le procédé fonctionne
de façon analogue mais certaines petites
modifications doivent être apportées aux
points d'extraction des différents liquides.
Comme on peut le voir, il s'agit là d'un
procédé extrêmement simple qui devrait
bien se prêter à de petites installations
n'exigeant que peu d'entretien. Il suffit de
simples commandes pour maintenir l'équi
libre du système, par le fait que le débit du
véhicule d'échange de chaleur est tellement
plus élevé que celui de l'eau. En outre,
étant donné que l'échange de chaleur prin
188
cipal s'effectue par contact direct des
couches de liquide, il n'y a pas de problème
d'entartrage, les différences de température
entre les liquides d'échange de chaleur
peuvent être faibles, la corrosion est in
signifiante et la concentration finale des
saumures n'est bornée que par les considé
rations économiques.
C'est ce dernier point qui étend immensé
ment le champ d'application de ce pro
cédé. Le domaine du dessalement mis à
part, il existe de nombreuses solutions qu'il
est difficile de concentrer à cause de l'entar
trage, de l'adhésivité et de la corrosion.
Avec ce procédé, elles pourraient être éva
porées à dessiccation à peu de frais. L'in
tense surchauffe produite dans la vapeur
par cette manière de procéder est presque
entièrement récupérée dans le condenseur.
Etant donné que les solides resteraient dans
le véhicule d'échange, il importerait que
ce véhicule d'échange de chaleur soit choisi
spécifiquement dans chaque cas.
Comme on l'a mentionné plus haut, la
disposition des appareils et le choix du
véhicule d'échange de chaleur dépendront
de l'application visée et des résultats ob
tenus à l'avenir dans les usines pilotes.
Plusieurs options peuvent être citées ici
pour montre l'étendue des possibilités.
Le véhicule d'échange de chaleur doit
être choisi pour chaque application, en
considérant ses propriétés physiques: solu
bilité, tension de vapeur, stabilité, action
corrosive, chaleur spécifique, viscosité, toxi
cité, etc.
Il y a plusieurs types d'évaporateurs qui
peuvent être employés avec ce procédé. La
colonne à pulvérisation d'eau a fait l'objet
des recherches expérimentales les plus pous
sées mais, du point de vue économique, il
est plus que probable que le dispositif de
mélange des fluides par injection (flow
contactor) se révélera le meilleur dans les
grandes installations.
En résumé, les avantages de ce procédé
sur le cycle classique compression de vapeur-
évaporation sont les suivants:
1. L'absence de surfaces susceptibles de
s'entartrer permet des différences de
température élevées dans les échanges
de chaleur.
2. L'évaporation pour chaque passage
dans l'évaporateur peut être très forte
du fait qu'il n'y a pas à craindre
l'entartrage.
3. Les matériaux de construction sont
bon marché étant donné que la corro
sion est insignifiante.
4. La dimension des installations est
réduite du fait des taux élevés
d'échange de chaleur.
 5. Il peut être employé efficacement sur
une gamme de capacités étendue.
6. Au besoin, il peut évaporer des solu-
lions jusqu'à dessiccation.
Испарительная Установка со Сжатым
Паром и Теплопередачей Прямого
Контакта
К. Л. Пайндер
Канада
Этот доклад является описанием
предлагаемого процесса опреснения,
который еще не был развит до той
степени, когда намеченные рабочие
условия становятся выполнимыми. Кро
ме того, здесь предложенную систему
сжатия пара можно осуществить с по
мощью весьма различного оборудова
ния. Выбор оборудования для каждого
специфического объекта будет зависеть
от изучения результатов, которые по
лучатся на будущей опытной установ
ке.
Этот процесс был разработан с целью
обойти проблемы выпарки, состоящие
из образования накипи, больших раз
меров и высокой стоимости. Образова
ние накипи было устранено посред
ством переноса тепла жидкостью к
жидкости как в испарителе так и в
конденсаторе. При теплопередаче пря
мого контакта, благодаря высокому
коэффициенту теплопередачи и боль
шим поверхностям соприкосновения,
является возможным пользоваться обо
рудованием меньших размеров. Ожи
дается, что в связи с этими двумя при
чинами будет достигнуто значительное
удешевление процесса опреснения во
ды по сравнению с эквивалентным
циклом сжатия пара при пользовании
обычными поверхностями теплопере
дачи.
Кроме возможности удешевить воду,
этот процесс имеет еще два других,
сразу бросающихся в глаза, преиму
щества. Он экономически применим для
установок самого разнообразного мас
штаба, начиная односемейными жили
щами и кончая городскими водопрово
дами. Помимо регенерации воды он
L'inconvénient principal de ce procédé
est d'exiger un taux élevé de circulation du
véhicule d'échange de chaleur: de 50 à 100
litres par litre d'eau produite.
может быть также использован для
полной упарки до состояния сухости
многих растворов, которые в настоя
щее время выпариваются только мно
гоступенчатым способом периодическо
го действия.
Предшествовавшее Развитие
Перенос тепла жидкостью к жидко
сти во время выпарки (указаний 1 -12)
и конденсации (6) подвергся в течение
нескольких последних лет более вни
мательному изучению. Толчком к этому
послужили три других опреснительных
процесса.
1. В опреснительном процессе (ука
заний 13-16) по способу прямого ре-
фрижерационного замораживания теп
ло из воды отводится посредством ис
парения нерастворимой жидкости, ко
торая кипит при температуре ниже
точки замерзания соленой воды. В ис
парительном процессе роли обеих жид
костей перевернуты (вода испаряется,
а вторая жидкость охлаждается), но
экспериментальные данные и корреля
ции теплопередачи все-же попрежнему
применимы.
2. В подобном предыдущему опре
снительном процессе пользуются вме
сто льда гидроокисью газа. В этом слу
чае образователь гидроокиси обыкно
венно находится в кипящем состоянии
для охлаждения воды до температуры
гидратации (17, 18, 19).
3. Выпаривание воды посредством
прямого переноса тепла с помощью
несмешивающегося теплоносителя име
ет ту же самую сущность, но об этом
имеется очень мало печатных матери
алов. В процессах мгновенного испаре
 ния (6, 20), где используется тепло
прямой теплопередачи, морская вода
нагревается теплоносителем без выпа
ривания.
Описание Процесса
Морская вода, подогретая в трубча
тых теплообменниках опресненной во
дой и сбросом концентрата, приходит
в соприкосновение в распыленном виде
с горячим теплоносителем. Из капелек
морской воды испаряется чистая вода,
образуя перегретый пар, который соз
дает перемешивание теплоносителя и
поддерживает во всей массе жидкости
турбулентное состояние. После «расту-
манивания» (отложение воды) в верх
ней части испарителя, пар поступает в
компрессор, который повышает его
давление до уровня, поддерживаемого
в конденсаторе.
Теплоноситель, представляющий со
бой смесь концентрата из испарителя,
направляется в сепаратор при темпе
ратуре, соответствующей его точке ки
пения. Оттуда сбросный концентрат
идет в подогреватель морской воды, а
теплоноситель перекачивается в кон
денсатор. Сжатый пар конденсируется
посредством прямого соприкосновения
с теплоносителем, подогретым до тем
пературы, превосходящей на несколь
ко градусов точку кипения сбросного
концентрата в испарителе низкого дав
ления. Из верхней части конденсатора
жидкая смесь поступает в приемник,
где опресненная вода декантируется из
теплоносителя, который обратно ре-
циркулируется в испаритель.
При теплоносителях легче воды ра
бочий процесс протекает аналогично,
хотя придется немного изменить точки
ответвления различных потоков жид
кости.
Является очевидным, что эта крайне
простая система могла бы хорошо по
дойти к маленьким установкам, не тре
бующим большого ухода. Понадобятся
только простые регулирующие устрой
ства для удержания ее в равновесии,
потому что основной поток теплоно
сителя значительно больше потока во
ды. Кроме того, так как главный пере
нос тепла происходит на поверхностях
раздела двух жидкостей, отсутствует
проблема образования накипи, темпера
турные перепады между теплообмен-
нымн жидкостями могут быть малого
порядка, коррозия незначительна и для
конечной концентрации соленого раст
вора существует только экономический
предел.
190
Последний факт сулит неограничен
ные возможности для расширения обла
стей применения этого процесса. Кроме
опреснения воды имеется много дру
гих растворов, которые трудно концен
трировать ввиду образования накипи,
липкости и коррозии. С помощью вы
шеописанного процесса они могут быть
выпарены до состояния сухости с весь
ма малыми экономическими потерями.
Получаемый, благодаря этой процеду
ре, высокий перегрев пара почти це
ликом регенерируется в конденсаторе.
Так как в теплоносителе будут оста
ваться вещества твердой фазы, для
каждого отдельного применения при
дется выбирать специфический тепло
носитель.
Как сказано ранее, проект оборудо
вания и выбор теплоносителя будет
зависеть от области применения и от
будущего изучения работы опытной
установки. В настоящее время можно
упомянуть несколько альтернатив, что
бы показать широту имеющегося вы
бора.
Теплоноситель должен быть выбран
для каждого отдельного применения,
принимая во внимание его физические
свойства: растворимость, давление па
ра, устойчивость, коррозионную актив
ность, удельную теплоемкость, вяз
кость, ядовитость, и т.д.
Водораспылительная колонна лучше
всего изучена на опыте, но с экономи
ческой точки зрения поточный контак
тор, весьма вероятно, окажется наилуч
шим для больших установок.
Кратко говоря, преимущества опи
санной системы по сравнению со стан
дартным испарением со сжатым паром
состоят в следующем:
1. Так как отсутствуют поверхности,
подверженные образованию наки
пи, можно пользоваться высокими
перепадами температур теплопере
дачи.
2. Выпарка при проходе через испа
ритель может быть большой, по
тому что нет образования накипи.
3. Так как коррозия незначительна,
можно пользоваться дешевыми
строительными материалами.
4. Размер установок невелик, ввиду
больших скоростей теплопередачи.
5. Процесс может быть эффективно
применен при проектировании
установок, емкость которых ко
леблется в широких пределах.
6. Если желательно, можно выпари
вать растворы до состояния сухо
сти.
 Главным недостатком этой системы
является большой циркуляционный рас-
Evaporación por Compresión de
Vapor con Trasmisión Calórica
por Contacto Directo
K. L. Pinder
El trabajo que sigue es una descripción
de un proceso de desalinización propuesto
el cual no ha sido aún desarrollado al
punto que es puedan establecer condiciones
de funcionamiento estimadas que resulten
signiñcativas. Además, el sistema de com
presión de vapor propuesto aquí puede ser
puesto en practica mediante el empleo de
una gran variedad de equipo. La elección
del equipo para cada planta en particular
se regirá por los resultados de los futuros
estudios de planto piloto.
Este es otro proceso que está destinado a
solucionar los problemas que presenta el
evaporador en lo que se refiere a descascara
miento, tamaño y costo. El descascaramiento
ha sido eliminado mediante el empleo de
transmisión calórica líquido-liquido tanto
en el evaporador como en el condensador.
Los altos coeficientes de transmisión de
calor y las grandes áreas superficiales dispo
nibles en la transmisión de calor por con
tacto directo hacen posible el empleo de
aparatos de menor tamaño. Debido a las
dos consideraciones que se acaban de men
cionar, se espera que este proceso hará
posible una apreciable reducción en el costo
de la desalinización del agua con respecto
al ciclo de compresión de vapor equivalen
te que empica superficies de trasmisión
térmica convencionales.
Además de la posibilidad de agua más
barata, este proceso tiene dos ventajas más
que se evidencian inmediatamente. Se presta
para el diseño económico en una gran va
riedad de escalas desde unidades caseras
hasta unidades para ciudades. Además,
fuera del campo de la recuperación de
agua, el mismo puede ser empleado para
evaporar a sequedad muchas soluciones que
ход теплоносителя: 50 - 60 фунтов на
фунт пресной воды.
actualmente son evaporadas por procedi
mientos no continuos de varias etapas.
ANTECEDENTES
La transmisión calórica líquido-líquido
durante la evaporación (1,2,3.4,5,6.7,8,9,10.
11,12) y la condensación (6) han sido objeto
de mayor investigación durante los últimos
años. El impulso dado a esta actividad se
originó en otros tres procesos de desalini
zación.
1. En el proceso de desalinización me
diante la congelación por refrigeración
directa (13,14.15,16), el calor es extraído
del agua por la evaporación de un líquido
insoluble que hierve a una temperatura in
ferior a la de congelación del agua salada.
Los papeles de los dos líquidos en el pro
ceso de evaporación se invierten (el agua
se evapora y el segundo líquido se enfría)
pero los datos experimentales y las correla
ciones de transmisión calórica aún son
aplicables.
2. Un proceso similar de desalinización
utiliza un hidrato gaseoso en lugar de hielo.
En este caso, generalmente se hace hervir
al formador de hidrato para enfriar el agua
a la temperatura de hidratación (17,18,19).
3. La evaporación de agua por calor
trasmitido directamente en un medio termo-
trasmisor inmiscible es de naturaleza simi
lar, pero muy poco se ha publicado al
respecto. En los procesos de evaporación
instantánea (6.20) que emplean calefacción
por trasmisión calórica directa, el agua de
mar es calentada por el medio trasmisor de
calor sin producirse evaporación.
DESCRIPCIÓN DEL PROCESO
Veamos el proceso de desalinización pro
puesto, para el caso en que el medio
191
 trasmisor de calor es más denso que la
solución salina. El agua de mar, precalen-
tada en intercambiadores de calor de car
casa y tubos, por el agua y salmuera de
deshecho producida, es puesta en contacto en
el evaporador, en forma atomizada, con el
medio trasmisor de calor caliente. El agua
es evaporada de las gotitas de agua de mar
produciéndose vapor sobrecalentado el cual
agita al medio trasmisor de calor y man
tiene a la masa total de líquido en un
estado turbulento. Después de separarse de
la niebla en la sección superior del evapora
dor, el vapor pasa a un compresor el cual
eleva la presión del vapor a la existente en
el condensador.
La mezcla de medio trasmisor de calor y
salmuera, a la temperatura de ebullición
de la solución salina, es transferida del
evaporador a un separador. De allí la sal
muera de deshecho va al precalentador de
agua de mar y el medio trasmisor de calor
es transferido, mediante una bomba, al con
densador. El vapor comprimido se condensa
por el contacto directo con el medio tras
misor de calor que es calentado a una
temperatura varios grados por encima del
punto de ebullición de la salmuera de des
hecho en el evaporador de baja presión. De
la parte superior del condensador la mezcla
líquida pasa a un decantador donde el agua
potable es separada por decantación del
medio trasmisor de calor el cual es transfe
rido al evaporador para comenzar nueva
mente el ciclo.
En el caso de medios trasmisores de calor
que son mas livianos que el agua, el proceso
funciona en forma similar pero deben efec
tuarse pequeñas alteraciones en cuanto a la
ubicación de los puntos de derivación de
las distintas corrientes fluidas.
Como puede verse, éste es un sistema
sumamente sencillo que podría aplicarse
muy bien en unidades pequeñas que reque
rirían escaso mantenimiento. Dado que el
caudal de medio trasmisor de calor es tanto
mayor que el de agua, los controles necesa
rios para mantener el sistema en equilibrio
serán muy simples. Además, dado que la
transmisión de calor principal tiene lugar
a través de interfaces líquido-líquido no
hay problema de descascaramiento, la dife
rencia de temperatura entre Muidos trasmi
sores de calor puede ser pequeña, la
corrosión es despreciable y la concentración
final de la salmuera está sólo limitada por
consideraciones de orden económico.
Es este último punto que amplía inmen
samente el número de aplicaciones de este
192
proceso. Fuera del campo de la desalini-
zación hay muchas soluciones que son difí
ciles de concentrar debido a problemas de
descascaramiento, glutinosidad o corrosión.
Mediante este proceso dichas soluciones po
drían ser evaporadas a sequedad a un costo
adicional muy reducido. El alto sobrecalen
tamiento producido en el vapor por este
procedimiento se recupera casi totalmente
en el condensador. Dado que los sólidos
quedarían en el medio trasmisor de calor,
la elección de éste sería específica en cada
caso.
Como se mencionó anteriormente, el dise
ño del equipo y la elección del medio
trasmisor de calor dependenrán de la apli
cación y de los futuros estudios de planta
piloto. Pueden ahora mencionarse varias
alternativas para demostrar la amplia selec
ción disponible.
El medio trasmisor de calor debe elegirse
para cada aplicación teniendo en cuenta las
propiedades físicas: solubilidad, presión de
vapor, estabilidad, carácter corrosivo, calor
específico, viscosidad, toxicidad, etc.
Varios diseños de evaporadores pueden
empicarse en este proceso. La columna
atomizadora de agua ha sido objeto de
mayor experimentación, pero desde el punto
de vista económico es muy probable que el
contactor de corriente sea el mejor para
grandes instalaciones.
Resumiendo, las ventajas de tal sistema
sobre el ciclo convencional de compresión
de vapor y evaporación son:
1. Dado que no existen superficies que
se descascaren, pueden emplearse gran
des diferencias de temperatura en la
trasmisión calórica.
2. La evaporación por cada pasada a
través del evaporador puede ser gran
de debido a que no existe descascara
miento.
3. Los materiales de construcción son
económicos dado que la corrosión es
despreciable.
4. Es posible construir plantas de tamaño
reducido debido a las altas velocidades
de trasmisión calórica.
5. El proceso puede ser diseñado para su
eficiente empleo en un amplio orden
de capacidades de diseño.
6. Si así se desea, el proceso sirve para
evaporar soluciones a sequedad.
La principal desventaja de este sistema
es la alta velocidad de circulación del medio
trasmisor de calor, o sea, de 50 a 100 libras
por libra de agua producida.
Evaporation of Sea Water in Solar

Stills and Its Development for

Desalination

R. L. Datta, S. D. Gomkale, S. Y. Ahmed, and D. S. Datar

India

Although quite a few techniques (such TABLE XXXII. Solar Radiation Intensity
as multieffect evaporation, multistage flash in Some Regions of Saurashtra and
evaporation, electrodialysis, etc.) have Kutch, Btu per sq ft per day
reached a fairly high stage of technological
development, the cost of converted water Mahuva Bhavnagar Kandla
does not compare favorably with that of Month (lat. 21° N) (lat. 22° N) (lat 23* N>
conventional water; the former is 4 to 6 Jan. 1.330 1.290 1.248
times higher than the latter. Feb. 1,568 1.682 1.490
Mar. 1.8C0 1,840 1.815
In the water-scarce coastal regions of Apr. 2,100 2,180 2.090
India like Saurashtra and Kutch (latitude May 2.240 2,246 2,240
June 2,290 2.292 2,810
21°-24° N) where the gift of nature in the July 2,278 2,266 2.282
form of solar energy is plentiful, the solar Ann. 2.180 2.18S 2,180
Sept. 1.990 1,974 1.960
still technique for desalination of sea water Oct. 1.720 1,690 1.666
has special significance. Common construc Nov. 1.480 1,395 1.355
Dec. 1.268 1.230 1.190
tion materials required for solar stills and
cheap labor are available for the develop
ment of solar stills in these regions. In per day is available during five to six
the other evaporation techniques, out of months of the year (ref. 1) .
the total cost of production of converted The cost of transporting water, particu
water, cost for energy alone is as high as larly to some of the salt works in these
30 or 40 per cent. The high energy cost of regions, is very high. Therefore, there is
other techniques is definitely an impetus ample scope for the development of solar
to the development of solar stills in India stills though the cost of water from solar
where free solar energy can be trapped in stills is higher than that of conventional
the stills. From Table XXXII, it is seen that water. The statistics from the Saurashtra
solar energy of about 2,000 Btu per sq ft and Kutch regions, given in Table XXXIII,

TABLE XXXIII. Cost of Water in Some Salt Works of the

Saurashtra and Kutch Regions

Location Distance from Approximate

of aalt Requirement works to the fresh Mode of coat of water
works (gpd) water source transportation (in Rs. per
(in miles) thousand gals)
Kuda 1,000 4.6 Trucks 80
Mundra 6.000 7.5 Tank lorries 11
Port Albert 1,600 Trucks 25
Victor 1,400 -- Persons Not worked out
(will be still more)
Bherai 1,100 1 Bullock, carts, 18
and boats
Sikarpur 200 4 Bullock and carts 40

193
 reveal that the cost ot water at these places
is as high as Rs. 1 1 ($2.3) to Rs. 40 ($8.4)
per thousand gallons, whereas the calcu
lated cost of water even from the low
capacity 500 gpd solar still of this institute
is Rs. 8.45 ($1.77) per thousand gallons.
To obtain relevant design data, a study
was made of different angles of inclination
of the glass cover and the depth of the sea
brine. The covers are made of glass having
an Fe,Os content of less than 0.15 per cent.
The inside bottoms of the stills are painted
black. Sea brine of 2° Be is used for the
experiments until it attains nearly 10° Be.
Ambient temperature varies between 83°
and 85°F, the maximum temperature inside
the stills being 135° to 148°F. Typical data
on solar stills having surface areas between
3.4 sq ft and 34.5 sq ft were reported
earlier (ref. 2) . Calculations were also made
after Bloemer, Collins, and Eibling (ref.
3) for the percentage of incident solar
radiation utilized for evaporation in the
solar stills (Table XXXIV) . These calcula
tions show that less than one-third of the
incident solar energy is used for evapora
tion, the remainder being dissipated by re
flection, absorption by the cover and con
densate film, radiation from brine surface,
internal convection, conduction of heat to
the ground, and reevaporation of conden
sate. Increasing the angle of inclination of
the covers further reduces such utilization
for evaporation.
DESIGN OF 500 GPD CAPACITY
SOLAR STILLS
The average annual production rates of
fresh water from sea brine of 2° Be, as
obtained by laboratory solar stills, are 0.06
to 0.08 gallons per sq ft per day. For scal
ing up to 500 gpd, the lower value, namely,
0.06 gallons per sq ft per day, is taken.
Inclination of 10° of the cover of the stills
194
found suitable in the laboratory studies is
chosen, although for some unsymmetrical
stills, as well as for experimental purposes,
higher angles are also used. The 500 gpd
capacity experimental solar still unit con
sists of four blocks, covering an area of
8,415 sq ft (Fig. 68) .
In three of the blocks, there are 15 sym
metrical and unsymmetrical stills 55 ft by
8 ft and 55 ft by 5.5 ft, and angles of
inclination of covers as 10°-10°, 15°-15\
20°-20\ 10°-20°, 20°-40°. The fourth block
has 6 stills 55 ft by 8 ft, all symmetrical,
namely 10°-10°. The bottoms of the stills
of the first three blocks are of cement
concrete, painted with black anticorrosive
tank mastic piant; 2° Be sea brine in these
stills is at levels of 2 inches, 6 inches, and
12 inches. The fourth block has its still
bottoms lined with epoxy paint, asphalt
mat, tar, gravel mixture, and stabilized soil.
(Fig. 69 shows portions of blocks 2 and
4.) Provision exists for collection of rain
water. Glass sheets 4 ft by 3 ft by ys inch
are supported by precast, reinforced cement
concrete beams and channels: the latter,
together with aluminum channels, is used
to collect product water and rainwater as
shown in Figure 70. Glass joints are sealed
by putty (Shalibond-E) , and glass faces by
waterproof adhesive tape. The cost of the
solar still unit, construction of which is
Hearing completion, is estimated in Table
XXXV. Of the total cost of the unit, the
major share, namely 65 per cent, is for civil
engineering materials and work, which in
volves preparation of the soil bed and its
stabilization, blackening the stabilized soil
surface with asphalt material, and founda
tion work. Cost of materials such as glass,
asphalt, and sealing materials accounts for
25 per cent of the total cost; the remaining
10 per cent is for miscellaneous expenses,
including labor and maintenance.
 5SaltandC0at°e-nstrila CMRhaesrmeiacnrlcesh Pofsreaodcileantaiorgne
BInhsatvintaugtaer,

utilized
26.8 49.3 12.8 6.3 2.4 2.4

60°BtiU 0.023
81.5 101.4 86.4
90
ver)
isaCthet(glass
beequal
ofotosenmdpCOeunrmsaetuder
3CSaltandat0e°n-strial RCMheasrmeiacnrlcesh rofsPeaordcileantairogne
TABLE
CBXin
Energy
SaltcXuialIlntVico.ens
Solar BInhsatvintaugtea,r
Sir-stil 0.026
102.1 86.4
B1.5 91 utilised 29.6 43.6 15.2 6.9 2.4 3.3

hrpoffRateftwroapersqdpuetcnseertdhiros,n
andECBolibleimnesrg, solarrofPaedricaetnioange
(15°)
btaisln
ofsDeep

utilized
4)
(ref. 32 12 10 25 7 2 12
hrft
iBtuRnatdsqppereinasterioyn.
aAtvemopserhaetgruiec
(°F)

(tvemprFeatguer (°F)
°glass
A) bAtvermpirenatgeure

lTdataaybporiactoarly
filmcAandbyobnscdoernvpstaeiron
ofdMiseianpentrsigoyn riUen-acvlaopundrtaiendog

Rsfromaudriafticone
brine Cgofotonrduoctuino d
heat

Icnotvercntiaoln

Evaporation
Reflection
 EI
N
t
0)1
bi
o

2" deep stills 2 deep stills

J ah
□p 6 Nos 5 Nos

tn (block-4) (block-3)

Ml

l' deep stills 6"deep stills

5 Nos 5 Nos
(block- 1) (biock-2)

1 Settling tank A Area for expansion

2 Sea water tank B Space for instruments
3 Rain water tank P Pump
4 Product water tank Brine channel
5 Water supply tank Product
Sea waterwater
line line

scale I in = 32 ft
FIGURE 68. LAYOUT OF EXPERIMENTAL SOLAR STILLS
CENTRAL SALT AND MARINE CHEMICALS RESEARCH INSTI
TUTE, BHAVNAGAR, INDIA.
196
 A Sealing putty H Aluminum channel
B Glass shMt '/»" thick M Brick masonory
C Precast RCC. beam R Precast R.C.C channel
D Cement mortar S Sand
E Precast RCC. pillar W Rain water channel
F Cement concrete scale 1.5 in = I ft
FIGURE 70. DETAILS OF GLASS EDGE SUPPORTS EXPERIMENTAL
SOLAR STILLS CENTRAL SALT AND MARINE CHEMICALS RE
SEARCH INSTITUTE, BHAVNAGER, INDIA.

TABLE XXXV. Cost of Construction of 500 gpd Solar Still Unit at the Institute

Sr. no. Items Cost Per cent of total

(rupees) investment

1 Civil engineering work including cost of 44,180 78.6

materials and labor
2 Labor for Axing glass sheets, paints, etc. 2,200 3.4
3 Materials, such as glass, mastic paint, epoxy 18,620 23.0
paint, chlorinated rubber paint, sealing
tape, Shalibond-E, asphalt mat, stabilization
Total 60.000 100.0

Note: Re. 1/- = $0.21

198
 COST OF WATER
With an investment of Rs. 50,000 for the
500 gpd capacity unit, operational and
maintenance charges of 2 per cent of the
investment, life of 50 years, 300 working
days in a year, an average annual rainfall
of 20 inches, and the production rate of
water of 0.06 gallons per sq ft per day, the
following calculated data are obtained:
1. Area covered = 8,415 sq ft (including
channels, etc.)
2. Investment cost per sq ft =: Rs. 5.94
3. Amortization charges = Rs. 1,000
4. Annual operational and maintenance
charges = Rs. 1,000
5. Annual production of fresh water
— 150,000 gals
6. Quantity of rainwater in a year
= 87500 gals
7. Cost of converted water per thousand
gals = Rs. 8.45
In some regions of India (as shown in
Table XXXIII) , a cost of Rs. 8.45 per thou
sand gallons is not considered high; yet, com
pared to the cost of conventional water, it
is about 8 times higher. Such high cost of
solar still converted water is mainly due
to the high cost of investment per sq ft
(Rs. 5.94) . At present less than one-third
the incident solar energy is utilized in the
solar still; hence, better utilization of the
solar energy will reduce such cost. Use of
cheaper construction materials and of the
higher Be brine (10° Be) for salt farms is
likely to reduce the cost to some extent.
Hodges et al (ref. 4) claim that coupling
a solar still with a humidification-
dehumidification unit will also reduce the
cost.
Since the investment per sq ft is a major
cost for a solar still, a cost analysis for the
technique is made (ref. 2) with the help
REFERENCES
1. Seshadri, T. N.; Rao, K. R.; Sharma,
M. R.; Sarma, G. N.; Sharafat. Ali: "Cli-
matological and solar data for India."
Central Building Research Institute.
Roorkee, India.
2. Gomkale, S. D.; Ahmed, S. Y.; Datta.
R. L.; Datar, D. S.: "Fresh water from
sea by solar still," paper presented at
the annual meeting of the Indian In
stitute of Chemical Engineers, Banga
SUMMARY OF DISCUSSION
There was no discussion.
of a relationship (Eq. 1) which connects
such investment cost (Z) with the cost of
conventional water per thousand gallons
(C) , when the converted water cost is
equal to the conventional water cost.
Z = 0.75C (1)
The relationship is reached by taking an
average production rate of 0.06 gallons per
sq ft per day (which corresponds to an
incident solar radiation of 2,000 Btu per
sq ft per day and only 30 per cent of such
radiation being used) , an average life of
solar still as 50 years, and 20 per cent of
the investment cost as other charges. I(
indicates that with an investment cost of
Rs. 5.94 per sq ft of solar still (as at present
for the 500 gpd capacity solar still unit) ,
solar still technique may be applied in any
region where the cost of water is more than
Rs. 7.92 ($1.66) .
It is evident from the raltionship that
the necessary condition for the equality of
costs of converted and conventional water
is that the investment cost per sq ft of a
solar still should only be 75 per cent of the
cost of conventional water per thousand
gallons. If, instead of only 30 per cent of
the 2,000 Btu per sq ft per day solar
energy, 100 per cent can be utilized, then
the production rate will be 0.20 gallons per
sq ft per day; consequently, the cost of
converted water will be reduced to Rs. 3.73
per thousand gallons. This is certainly an
ideal state and is difficult to achieve.
Diathermanous properties of materials (in
cluding different plastic materials) , losses
due to reflection, absorption, internal con
vection, heat conduction to the ground,
and heat loss due to reevaporation must be
thoroughly studied in order to modify the
solar still for better utilization of the
incident solar energy.
lore, India (Dec. 1964) .
3. Bloemer, J. W.; Collins, R. A.; Eibling,
J. A.: "Field evaluation of solar sea
water stills," Advances in Chemistry
Series no. 27 (Saline Water Conversion)
p. 166.
4. Hodges, C. N.; Thompson, T. L.; Groh.
J. E.: "Separate component multiple-
effect solar distillation." Interim Report
2. Univ. of Arizona (Mar. 29, 1963) .
199
 Evaporation de L'Eau de Mer Dans

Des Alambics Solaires et Son

Développement Pour le Dessalement

R. L. Datta, S. D. Gomkale, S. Y. Ahmed, et D. S. Datar

Inde

Des études du prix de revient de l'eau laire de 2,3 m* par jour est conçu pour
normale et de l'eau douce provenant de produire de l'eau douce depuis l'eau de
l'eau de mer par différentes techniques de mer. Cet appareil couvre une surface de
dessalement indiquent que cette dernière 782 m' et possède 21 alambics dont les
est de six à sept fois plus coûteuse à l'heure dimensions sont de 16,7 m par 2,4 m et
actuelle et qu'une partie importante de ce 16,7 m par 1,7 m. la saumure de 10° Baumé
coût (environ 30 à 40%) est imputable à étant conduite à la zone de condensateur
l'énergie seulement. Dans un pays tropical approprié de la Station expérimentale d'ex
comme l'Inde, la technique par alambics traction de sel de l'Institut. Du coût total
solaires revêt une importance particulière de l'ensemble, la partie importante, à savoir
a cause (a) de la disponibilité en abon 65%, est pour des matériaux et des travaux
dance d'énergie solaire ne coûtant rien de génie civil, ce qui entraine la prépara
(environ 5.400 Kcal/m! par jour) pendant tion du sol et sa stabilisation, le noircisse
une longue période de l'année et (b) des ment de la surface des terrains stabilisés
matériaux plus simples et une main- avec des matériaux d'asphalte, et les travaux
d'oeuvre meilleur marché pour la con de fondations. Le coût des matériaux tels
struction. que le verre et l'asphalte, et des matériaux
Des expériences sur l'évaporation effec de scellement représente 25% du coût total;
tuées avec de l'eau de mer de 2" Baumé les 10% restants sont pour des dépenses
dans des alambics de laboratoire avec des diverses y compris la main-d'oeuvre et
surface variant entre 0,3 m' et 3.2 m* et des l'entretien.
angles d'inclinaison des couvertures en verre Les calculs avec l'alambic solaire de 23
varient entre 10° et 60°. des profondeurs m' montrent que l'eau douce obtenue coûte
de saumure entre 23 et 10 cm, et le revête 8,45 roupies ($1,77) par mille gallons im
ment noir des fonds des alambics, montre périaux, ce qui, en moyenne, est environ
que moins d'un tiers de l'énergie solaire huit fois le coût de l'eau normale dans
incidente est utilisée, le reste étant dissipé cette région ($0,39 par m") . Un coût aussi
en raison de la réflexion de l'absorption par élevé n'est pas considéré élevé pour cer
la matière de couverture (verre avec moins taines régions de l'Inde telles que Saurash-
de 0,15% FejOS) et la pellicule d'eau con tra et Kutch où le coût de l'eau normale
densée, la radiation de la surface de la elle-même peut atteindre de 11 à 40 roupies
saumure, la" convection interne, la conduc par mille gallons. Le prix de revient élevé
tion de la chaleur au sol et la ré-évapora- de l'eau convertie par la technique d'alam
tion. Les expériences ne sont pas conduites bics solaires est apparemment dû au coût
au-delà d'une saumure de 10° Baumé car, élevé de l'investissement par surface unitaire
alors, environ 72% de l'eau présente est de l'alambic solaire qui est à l'heure actu
évaporée, déposant des sels de calcium. elle d'environ 6 roupies ($1.26) et qui
D'après ces expériences, il a été prouvé que, pourrait être réduit par une meilleure
pour cette région, un alambic solaire à 10° utilisation de l'énergie solaire, une meilleure
convient et donne un taux de production compacité de l'alambic solaire, l'utilisation
maximum de 6 1 par m1 par jour, la de matériaux de construction meilleur
moyenne annuelle variant entre 3 et 4 1 marché, l'utilisation de la saumure à 10°
par m2 par jour. Baumé en tant que sous-produit pour l'ex
Basé sur ces données et autres conditions traction du sel, et l'accouplement de
ambiantes importantes, un distillateur so l'alambic solaire à un ensemble d'humidi-

200
fication et déshumidification. En supposant
une durée moyenne de l'alambic solaire de
50 années, son fonctionnement et son entre
tien coûtant 20% des frais d'investissement,
un rendement moyen annuel d'eau douce
d'environ 3 litres рат m' par jour et 300
jours de fonctionnement par an, le rapport
Выпаривание Морской Воды
вДистилляционных Установках,
Работающих с Помощью Солнечной
Энергии, и Усовершенствование
Его Применения для Опреснения
Р. Л. Датта, С. Д. Гомкел, С. Ю. Ахмед и Д. С. Датар
Индия
Исследование стоимости обыкновен
ной воды и пресной, полученной из
морской с помощью различных техни
ческих методов опреснения, показыва
ет, что в настоящее время опресненная
вода обходится в 5-6 раз дороже, и
что значительная часть ее стоимости
(около 30 - 40%) расходуется на одну
только энергию. Для тропической стра
ны, как Индия, техника дистилляцион-
ных установок, работающих с помо
щью солнечного излучения, имеет осо
бую важность вследствие: (а) изоби
лия бесплатной солнечной энергии
(около 2.000 Б.Т.Е. на кв. фут в день)
в течение значительной части года, и
(б) возможности использования на
постройке более простых материалов
и дешевого труда.
Посредством опытов по выпариванию
морской воды с солесодержанием 2°
Бомэ в лабораторных дистилляционных
установках площадью 3,4-34,5 кв. фу
тов, при углах наклона стеклянных
покрытий 10° -60°,' глубине рассола
1-4 дюйма и черной облицовке днищ
дистилляторов выяснилось, что исполь
зуется менее одной трети падающей
солнечной энергии, причем остальная
растрачивается вследствие отражения,
абсорбции материалом покрытия (стек
entre le coût de l'investissement par surface
unitaire d'un alambic solaire (Z) et le coût
de l'eau normale par mille gallons (C) ,
afin de rendre le prix de revient de l'eau
convertie égal à celui de l'eau normale,
doit être Z = 0,75 C.
ло с содержанием менее 0,15% Fe203)
и пленкой конденсата, излучения с по
верхности рассола, внутренней конвек
ции, потери тепла в грунт и переиспа
рения. Опыты не производились при
более, чем 10° Бомэ рассола, так как
уже тогда испаряется около 72% име
ющейся воды, образуя отложения солей
кальция. С помощью вышеуказанных
опытов было установлено, что для Ин
дии солнечная дистилляционная уста
новка при 10° Бомэ соответствует сво
ему назначению, давая максимальную
продуктивность в размере 0,12 галлона
опресненной воды на кв. фут в сутки
при колебании средней годовой про
дуктивности между 0,06-0,08 галлона
на кв. фут в день.
На основании этих данных и других,
относящихся к делу условий окружаю
щей среды, был спроектирован солнеч
ный дистилляционный агрегат для опре
снения 500 галлонов морской воды в
сутки. Он занимает пространство в
8.415 кв. футов, на котором находятся
21 дистиллятор размером по 55x8 фу
тов и 55 X 5,5 футов каждый, а рассол
при 10° Бомэ отводится для конденса
ции в соответствующую зону Опытной
соляной фермы Института. Главной
частью общей стоимости агрегата, а
201
именно 65%, является техническое обо
рудование и работа, куда входят
устройство основания для грунта, его
стабилизация, покрытие поверхности
асфальтовыми материалами черного
цвета и сооружение фундаментов. Сто
имость таких материалов, как стекло,
асфальт и изоляция, составляет 25%
общей суммы затрат; остальные 10%
относятся к различным расходам, вклю
чая рабочую силу и текущий ремонт.
Калькуляции, составленные для сол
нечной дистилляционной установки на
500 галлонов в сутки, указывают, что
стоимость опресненной воды достигает
8,45 индийских рупий (1,77 амер. дол
лар.) за 1.000 галлонов, что в среднем
превышает в 8 раз стоимость обыкно
венной воды в этом районе. Даже такая
сравнительно высокая стоимость не
считается чрезмерной для некоторых
областей Индии, как Саураштра и
Кутч, где обыкновенная вода обходит
ся 11-40 индийских рупий за 1.000
галлонов. Высокая стоимость опресне
ния на солнечных дистилляционных
установках видимо объясняется боль
шими капиталовложениями, приходя
щимися на единицу площади установ
La Evaporación de Agua del Mar en
Destiladoras por Energía
Perfeccionamiento para la
Desalinizacion
R. L. Datta, S. D. Gomkale, S. Y. Ahmed y D. S. Datar
El estudio de los costos del agua ordinaria
y del agua dulce obtenida del agua del mar,
por varios métodos de desalinización, indica
que esta última es ahora 5 a 6 veces más
costosa y que una proporción apreciable de
su costo (alrededor de 30 a 40%) está repre
sentada por la energía utilizada solamente.
En un pais tropical, como la India, la téc
nica del alambique solar tiene significa! ion
especial porque: (a) se dispone de gran
abundancia de energía solar gratis (alrede
dor de 2.000 BTU por pie cuad. por día)
202
ки. Они сейчас достигают примерно 6
рупий (1,26 долл.) на кв. фут, что мож
но уменьшить при лучшем использо
вании солнечной энергии, большей ком
пактности дистилляционной установки,
употреблении более дешевых строи
тельных материалов, применении, яв
ляющегося побочным продуктом, деся
тиградусного (по Бомэ) рассола на со
ляной ферме и присоединении солнеч
ной дистилляционной установки к
увлажняюще-осушающему агрегату. В
предположении, что средний срок
службы солнечного дистилляционного
агрегата достигает 50 лет, его эксплу
атация и ремонт составляют 20% ве
личины капиталовложения, а средняя
годовая выработка при 300 рабочих
днях в году соответствует 0,06 галлона
опресненной воды на кв. фут в сутки,
взаимоотношение между величиной ка
питаловложения на единицу площади
солнечной дистилляционной установки
(Z) и стоимостью 1.000 галлонов обык
новенной воды (С) должно быть
Z=0,75C, для того чтобы сделать сто
имости опресненной и обыкновенной
воды равноценными.
Solar y Su
durante una gran parte del año, y (b) se
cuenta con materiales y mano de obra bara
tos para la construcción.
Las pruebas de evaporación, efectuadas
con agua del mar de 2o Baumé (Bé) en
alambiques de laboratorio con superficies
entre 3,4 y 34,5 pies cuadrados, ángulos de
inclinación de las cubiertas de vidrio de
10° a 60°, profundidad de la salmuera de
1 a 4 pulgs. y forro negro en el fondo de las
destiladoras, indicaron que se aprovécha
menos de una tercera parte de la energía
solar incidente y que el resto se desperdicia
o disipa a causa de la reflexión, de su
absorción por el material de la cubierta (de
vidrio con menos de 0,15% de Fe,Ot) y por
la película de condensado, de la radiación
superficial de la salmuera, de la convección
interna, la transmisión de calor a tierra y
la reevaporación. Las pruebas no se conti
núan por encima de una densidad del agua
madre de 10° Bé, pues a esta altura ya se
ha evaporado el 72% del agua inicial depo
sitándose sales de calcio. Por medio de estos
experimentos se ha comprobado que en esta
región del pais la instalación destiladora
solar de 10° es adecuada, ya que tiene un
rendimiento máximo de 0,12 galón de agua
dulce por pie cuad. por día, variando el
pormedio anual entre 0,06 y 0,08 galones
por pie cuad. por día.
En base a estos datos y a otras condiciones
propias del medio ambiente, se diseñó un
grupo de destiladoras solares para convertir
agua de mar en agua dulce, a razón de 500
galones por dia. Este grupo ocupa una su
perficie de 8.415 pies cuads. y consta de 21
alambiques en tamaños de 55 por 8 pies y
de 55 por 53 pies. La salmuera de 10° Bé
es dirigida a la zona de condensación corres
pondiente del Centro Salino Experimental
del Instituto. La proporción mayor del costo
total del grupo de destiladoras, o sea el
65%, corresponde a los materiales y la obra
de construcción civil que entraña la prepa
ración y estabilización del subsuelo, el
revestimiento superficial del terreno con
materiales asfálticos y los trabajos de cimen
tación. El costo de los materiales, como el
vidrio, el asfalto y los compuestos aislantes
para obturación representan el 25% del
total; el 10% restante se destina a gastos
varios, incluso los de mano de obra y
conservación.
De acuerdo con los cálculos de la desti
ladora solar de 500 galones, el agua dulce
que se obtiene cuesta Rs. 8,45 ($1.77) los
mil galones que equivale, por término
medio, a 8 veces el costo del agua ordinaria
en esa región. Aun ese costo, relativamente
alto, no se considera excesivo para algunas
regiones de la India, como Saurashtra y
Kutch, donde el costo del agua común es
hasta de Rs. 11/ a Rs. 40/ el millar de
galones. El costo elevado del agua conver
tida por el método de destilación solar se
debe aparentemente a la alta inversión de
capital por unidad de superficie de la des
tiladora solar, que es actualmente de unos
Rs. 6/ ($1.26) y que probablemente se redu
cirá por medio del mejor aprovechamiento
de la energía solar, la reducción del tamaño
de la destiladora solar, el uso de materiales
de cosntrucción más baratos, la utilización
del subproducto de aguas madres de 10° Bé
en la estación salina y el acoplamiento de
la destiladora solar a un gmpo de humede-
cimiento y deshumedecimiento. Dando por
sentado que la duración media del grupo
de destiladoras solares sea de 50 años, que
su costo de explotación y mantenimiento
sea del 20% del capital invertido, que el
rendimiento medio anual de agua dulce
sea de 0,06 galones por pie cuadrado por
dia y que se trabaje a razón de 300 días al
año, la relación entre el costo de inversión
por superficie unitaria de una destiladora
solar (Z) y el costo del agua ordinaria por
mil galones (C) , para que el costo del agua
convertida sea igual al de agua ordinria,
es de Z = 0,75 C.
203
 Thin Film Distillation

T. C. Carnavos

United States of America

INTRODUCTION
The economical production of deminer-
alizcd water from sea water by distillation
depends upon a balance between energy
costs and fixed costs, both of which are
governed by the situation at the plant site.
High gain ratio plants with low energy
costs require that a very substantial fraction
of the heat of vaporization be continuously
recovered and reused in the cycle. However,
fixed costs for such plants increase with an
increase in gain ratio. The problem of
converting sea water is, therefore, one of
achieving high gain ratios without increas
ing the plant cost to a level at which fixed
charges become prohibitive. Many schemes,
loo numerous to detail here, have been
proposed for obtaining a high gain ratio,
low plant cost distillation system. The main
factor common to all schemes is that a
transfer of heal is required and the amount
is controlled by the magnitude of the over
all heat transfer coefficient, which, in turn,
strongly influences plant cost.
The resistance to the transfer of heat is
shown pictorial ly in Figure 71 where the
decrease in temperature level is brought

FOULING

LIQUID BEING
HEATED

LIQUID FILM

COLD

FIGURE 71. HEAT TRANSFER THROUGH A WALL.

205
 about by the relatively quiescent thick
films and solid obstructions. For economic
reasons, it is desirable to transfer the maxi
mum heat for the minimum surface and
temperature difference. The unit conduct
ances are unique values dependent upon
the mode of heat transfer, while the solid
resistances depend upon thickness and ther
mal conductivity. The choice of tube wall
material and thickness is virtually dictated
by the design life criterion. Hence, it be
hooves the designer to use the modes of
heat transfer which yield the highest over
all heat transfer coefficients, and his choice
is presently limited to condensing on one
THIN FILM HEAT TRANSFER
A novel heat transfer surface, called the
"Double Flute", has been developed which
produces and maintains thin films when
FIGURE 72. DOUBLE-FLUTED TUBE CONFIGURATION.
Tube orientation is vertical, with steam
condensing on the outside, and a falling
film of feed on the inside. Figure 73 is a
206
side and boiling or liquid heating on the
other. Much effort has been expended to
raise these coefficients above normal levels.
In the case of liquid heating, increasing
the tube-side water velocity, internal fins,
roughened surface, turbulence promoters,
and other techniques have increased the
coefficient. However, in many cases, the gain
is offset by larger pumping requirements
and greater tube corrosion-erosion damage.
This paper describes one solution to the
total problem through the use of a unique,
high heat transfer surface that can be used
in multiple-effect and vapor-compression
type cycles.
evaporating and condensing, and which has
no moving parts. The configuration of this
tube is shown in Figure 72.
pictorial representation of the tube and
liquid films.

THIN FILM REGION
HEAT FLOW
HGURE 73. THIN FILM, DOUBLE FLUTE HEAT TRANSFER.
The operating principle of the Double
Flute is such that the condensate film
which forms has surface tension forces
acting to drain it from the crests into the
grooves. This results in the major portion
of each crest having a very thin film of
condensate, which greatly reduces the resist
ance to heat flow through the crest area.
The condensate in the grooves is channeled
off by gravity with the heat flow through
this area somewhat less than at the crest.
The falling film of feed on the boiling side
also tends to drain into the grooves by
CONDENSING HEAT TRANSFER
Condensing steam heat transfer falls into
two classes: filmwise and dropwise. The
heat transfer coefficient for the filmwise
type on smooth tubes is limited by the
thickness of the condensate film and will
have mean values ranging from 1,000 to
4,000 Btu/hr ft* °F (refs. 1-3) depending
on heat flux, temperature level, vapor ve
locity, vertical or horizontal tube orienta
tion, tube length or diameter, turbulence
in the film, and noncondensables present.
Dropwise condensation occurs when, for
any reason, the condensate is unable to wet
the surface. Mean values ranging from
4,000 to 25,000 Btu/hr ft* "F (refs. 1^) have
been reported and are influenced by the
same variables as the filmwise type. Drop-
wise condensation can be accidentally in
duced by certain contaminants in the steam
or intentionally by the introduction of
promoters. However, the problem of main
taining dropwise condensation for long pe
riods in a simple, inexpensive manner has
EVAPORATION SIDE
CONDENSING SIDE
surface tension forces. Boiling takes place
in the thin film on each crest as well as
in the grooves. The crests are always kept
wet by the splash from the boiling action
in the grooves. Figure 74 shows this boil
ing action during an experiment which
was designed to observe this phenomenon.
The vapor which is generated travels con
currently with the feed. The flutes perform
a secondary but very important function in
organizing and controlling the falling film
to assure uniform distribution down the
length of the tube.
not yet been solved through the use of
promoters. Recently, work has been reported
(ref. 5) using surfaces thinly plated with
noble metals (gold, silver, etc.) , which are
hydrophobic in nature and appear to main
tain dropwise condensation for extended
periods of time. However, the economics of
using noble materials has yet to be proven.
Condensing steam on a fluted surface is
a filmwise process and the coefficients are
influenced by the variables mentioned
above. The data in Figure 75 are presented
on the basis of total outside surface, even
though the flutes do not function in the
same sense as an extended surface. The
condensing coefficient is 4.5 to 7 times
greater than that obtained for a comparable
smooth tube at a given heat flux. The
greatest gain is in the region of smaller
temperature differences, which are bene
ficial in the design of high gain ratio plants.
Data by others (ref. 3) for condensing on
fluted surfaces were reported as a band and
207
 FIGURE 74. DOUBLE FLUTE TUBE EVAPORATION.

compare favorably with this work. A com- strates the equivalence of these two modes
parison between fluted surface and drop- of heat transfer which is achieved, for
wise condensation coefficients is also shown fluted surfaces, in a simple, inexpensive,
in Figure 75. This figure clearly demon- and sure manner.

208
 BOILING HEAT TRANSFER
An increase in the condensing coefficient, increases in pool boiling over a comparable
while significant in itself, will lose practi smooth surface. The work was limited to
cally all its value if an improvement on the Hat strips and pure water. Additional data
evaporating side is not also made. Data (ref. 7) also indicate a sensitivity to spot
(réf. 1) for nucleate boiling using conven size and distribution. The low cost of sur
tional surfaces range from 200 to 7,000 Btu/ faoe preparation and durability of the
hr ft" °F, depending principally on heat flux treatment in actual service still remain to
and temperature level. The higher evapo be demonstrated.
rating coefficients are obtained at high film Boiling on a fluted surface is. as pre
temperature differences (25° to 30°F) , viously explained, a thin film process and
which are not conducive to high gain ratio the coefficients are influenced by tempera
plant design. ture level, heat flux, and the length-to-
Many attempts have been made to in diameter (L/D) ratio. The data of this
crease boiling coefficients. A recently pro work were obtained on actual tubes of
posed method (ref. 6) employs sharp parallel various L/D ratios using live sea water as
scratches on the surface with an improve feed and are presented in Figure 77 on the
ment on the order of 37 per cent of heat basis of total inside surface. It is readily
flux or 23 per cent of the temperature dif apparent from an examination of Figure
ference. HoweveT, the effectiveness of this 77 that higher boiling coefficients are ob
surface in sea water service over long tained with fluted surfaces than with
periods of time is still to be determined. smooth surfaces. Furthermore, an equiva
Still more recently, another method (ref. lence in boiling coefficient has been obtained
7) was proposed which treats a heat transfer for two different systems, but the fluted
surface with Teflon* to obtain a multiplic surface data are more realistic for the
ity of poorly wetted spots. The data (ref. intended service since sea water was used.
7) , reproduced in Figure 76, show significant

GENERAL DISCUSSION
The condensing and boiling coefficients
obtained with the Double-Flute tube are
among the highest ever reported with static
surfaces or treatments. Both inner and
outer surfaces are obtained in one manu
facturing operation. The modes of heat
transfer are conventional and represent no
radical departure. Increasing coefficients to
levels higher than presently obtainable
with Double Flute may not be warranted.
Maintaining higher coefficients during the
life of a plant would be a difficult operat
ing and maintenance problem. Undoubtedly
it could be done, but it must be justified
economically.
One method of increasing the overall
coefficient without incurring higher operat
ing and maintenance costs is reducing the
wall resistance, which accounts for some
30 to 40 per cent of the total resistance.
Unfortunately, a further increase in the
overall coefficient is presently limited by
the wall resistance of metals suitable for
this service. Metallurgists can contribute
handsomely to the field by providing a
low cost, high thermal conductivity and
high strength material that would be im
pervious to corrosion-erosion.
• E. I. du Pont de Nemours ft Co., registered trade
name for Tetrafluoroethylene Resin.
Thin film evaporators with Double-Flute
tubes have been operating in the field for
over two and one-half years. A pilot plant
installation was built at the Office of Saline
Water's Research and Development Test
Station at Wrightsville Beach, North Caro
lina. This is a two-effect plant rated at a
nominal 37,000 gpd and some of the early
results have been reported (ref. 8) . This
plant was operated over a range of temper
ature differences, tube length, and tempera
ture levels using deaeration-pH for scale
control with successful operation being
achieved up to 275°F boiling temperature.
In December 1962, an 8,000 gpd. two-
effect, thin film distiller for marine service
was installed aboard the "SS Tullahoma".
and the first year of operation has been
reported (ref. 9) . Scale control is achieved
by the addition of phosphates to the feed
water. The evaporator provides high purity
distillate for boiler makeup as well as for
all potable requirements even while oper
ating under pitch and roll conditions. This
installation, plus numerous others, has
added greatly to field operating data on
thin film evaporators.
In conclusion it may be said that the
Double Flute with high overall heat trans
fer coefficients will permit the design of
209
 much smaller evaporators, which will exert gain ratio plants of the multiple-effect or
a strong influence on plant cost. Further, vapor-compression type. The principle of
the high coefficients at small temperature thin film distillation has been demonstrated
differences will be most beneficial to high in the field.

210
104

0 5 10 15 20 25 30 35

At-°f

FIGURE 76. BOILING HEAT TRANSFER (REF. 7).

L'I2
 REFERENCES
1. McAdams, W. H.: "Heat transmission",
Third edition.
2. Eshaya, A. M.; Dodge, B. F.: "Applica-
tion of forced circulation and dropwise
condensation techniques to large-scale
distillation of sea water". Symposium
on Saline Water Conversion (1957) .
3. Lustenader, E. L.; Staub, F. W.: "Devel
opment contributions to compact con
denser design", Session II INCO Power
Conference (May 1964) .
4. Isachenko, V. P.: "Heat transfer in con
densation of water vapor in the form
of drops", Teploenergetika, vol. 12
(1962) pp. 54-56.
5. Erb, R. A.: Thelen. F..: "Dropwise con
densation on hydrophobic metal and
metal sulfide surfaces", ACS 149th Na
tional Meeting vol. 5 no. 1 (Apr. 1965) .
6. Bonilla, С. F.; Grady, J. J.; Avery, C.
W.: "Pool boiling heat transfer from
scored surfaces", Sixth National Heat
Transfer Conference AIChE-ASME
(Aug. 196S) .
7. Young, R. K.; Hummel, R. L.: "Higher
coefficients for heat transfer with nucle
ate boiling", Seventh National Heat
Transfer Conference AIChE-ASME
(Aug. 1964) .
8. Lou, C. W.: "Thin film distillation for
sea and brackish water", ACS H9th
National Meeting vol. 5 no. 1 (Apr.
1965) .
9. Carnavos, Т. C: "Thin film evapora
tors for marine service", paper Society of
Naval Architects and Marine Engineers,
Philadelphia, Pa. (Apr. 1964) .

SUMMARY OF DISCUSSION
The question was asked if higher heat replied that the operation was conducted
transfer coefficients are expected since rc- at 275°F sea water and steam at 285 °F,
rearch at the University of Toronto has that marine distillers are low temperature
obtained coefficients of 20,000 Btu/hr/sq ft°F and bleed steam at 190°F, and that for this
The reply stated that the quarrel is not reason phosphate can be used to control
whether higher heat transfer coefficients can scale.
be obtained, but rather that results with In answer to whether use of thin film
synthetic sea water are not comparable to distillation on a large scale is anticipated,
live sea water. the author replied yes. It was also asked
In answer to a question concerning the how water is distributed. The author replied
ratio of "U" of fluted tubes over conven that the manufacturing process leaves a
tional tubes, it was stated that it depends smooth surface and that water is distrib
on the materials of construction and that uted by spraying it inside the tube. It was
extra cost over smooth tube is the labor stated that weirs have also been used. It
cost to make flutes. In answer to a question was asked how critical the flow rate down
about the effect of "U" on the temperature the tubes is in the operation discussed in
drop, the author stated that the data here this paper. The author replied that the
is on short tubes (10 feet long by 3 inches plant has operated as low as 2.5 feet per
in diameter) . second, but that an operation at 3 or 3.5
The author was asked why scale was not and possibly 4 feet is preferred.
obtained in his experiments. The author

213
 Distillation a Pellicule Mince

T. C. Carnavos

Etats-Unis d'Amérique

La production économique d'eau déminé forces de tension superficielle agissant pour

ralisée, par distillation, en partant de l'eau entraîner cette pellicule des crêtes dans les
de mer, depend d'un équilibre entre les cannelures. Il en résulte qu la partie prin
frais d'énergie et les frais fixes, lesquels cipale de chaque crête possède une pellicule
sont tous les deux régis par la situation sur très mince de produit de condensation ce
les lieux d'exploitation. Des usines à rap qui réduit énormément la résistance de la
port de rendement élevé, ayant de faibles circulation de la chaleur à travers la surface
coûts d'énergie, doivent fonctionner avec la de la crête. Le produit de condensation
récupération et la ré-utilisation dans le dans les cannelures est entraîné par pesan
cycle d'une fraction très importante de la teur avec la circulation de chaleur quelque
chaleur de vaporisation. Cependant, les peu moindre dans cette région. L'écoule
frais fixes pour de telles installations aug ment laminaire de l'alimentation, sur le
mentent avec une augmentation du rapport côté ebullition, a également tendance à
de rendement. Le problème de la conver passer dans les cannelures par les forces de
sion de l'eau de mer consiste donc à arriver tension superficielle. I.'ebullition a lieu
à des rapports de rendement élevé sans dans la pellicule mince sur chaque crête
amener le coût de l'installation à un niveau ainsi que dans les cannelures. Les crêtes
où les frais fixes deviennent prohibitifs. sont maintenues constamment humides par
Pour des raisons d'économie, il est désirable les éclaboussures provenant de l'action
de transférer le maximum de chaleur pour (l'ebullition dans les cannelures. La vapeur
le minimum de surface et de différence de qui est engendrée se déplace concurremment
température. Le choix de la matière et de avec l'alimentation. Les cannelures remplis
l'épaisseur de la paroi des tubes est virtuel sent une fonction secondaire, mais très
lement dicté par le critère de la durée utile importante, en organisant et en contrôlant
de l'installation. Donc, il incombe à l'in l'écoulement laminaire pour assurer une
génieur d'utiliser les modes de transfert de distribution uniforme le long du tube.
chaleur qui conviennent le mieux pour La condensation de la vapeur sur une
donner les coefficients de transfert de surface cannelée est un procédé laminaire.
chaleur d'ensemble les plus élevés, et son Le coefficient de condensation est de 4i/2
choix est actuellement limité à la condensa à 7 fois supérieur à celui obtenu avec un
tion, d'un côte et à l'ebullition ou au tube lisse comparable pour un flux ther
chauffage du liquide, de l'autre. Ce mémoire mique donné. Le gain le plus important est
décrit une solution de la totalité du pro dans la zone des petites différences de
blème, grâce à l'utilisation d'une surface température, ce qui est utile dans la con
de transfert de chaleur élevée, de type ception des installations à rapport de rende
unique, que l'on peut utiliser dans des ment élevé. Des données par d'autres (3) ,
cycles du type à compression de vapeur et pour la condensation sur des surfaces
a effets multiples. cannelées, se présentent sous forme de bande
On a mis au point une surface originale et se comparent favorablement avec ces
de transfert de chaleur, appelée "Double travaux. Une comparaison des coefficients
Flute (c'est-à-dire à doubles cannelures) , de condensation sur surface cannelée et
qui produit et maintien des pellicules condensation en gouttelettes (refs. 1,2,3,4)
minces à l'évaporation et à la condensation, démontre clairement l'équivalence de ces
sans pièces mobiles. L'orientation du tube deux modes de transfert de chaleur; pour
est verticale, avec la vapeur se condensant à les surfaces cannelées, ce résultat est obtenu
l'extérieur et un écoulement laminaire de d'une manière simple, peu coûteuse et
l'alimentation à l'intérieur. certaine.
Le principe de fonctionnement de cette Une augmentation dans le coefficient de
surface est tel que la pellicule du produit condensation, bien qu'importante en elle-
de condensation qui se forme possède des même, perdra pratiquement toute sa valeur,

214
si on ne fait pas également une améliora
tion sur le côté évaporation. L'ébullition
sur une surface cannelée est, comme nous
l'avons expliqué, un processus à pellicule
mince. Les données de ces travaux furent
obtenues sur des tubes réels avec des rap
ports longueur/diamètre variés, en se ser
vant d'eau de mer naturelle comme alimen
tation. L'on obtient des coefficients d'ébulli-
tion plus élevés avec les surfaces cannelées
qu'avec les surfaces lisses. En outre, une
équivalence dans le coefficient d'ébullition
a été obtenue pour deux systèmes différents,
mais en reconnaissant que les données pour
les surfaces cannelées sont plus réalistes
pour le service que l'on doit en faire, car
on a utilisé l'eau de mer.
Les coefficients de condensation et d'ébul
lition obtenus avec le tube "Double Flute"
sont parmi les plus élevés que l'on ait notés
avec des surfaces ou des traitements sta
tiques. Les surfaces internes et externes
sont toutes les deux obtenues en une seule
opération de fabrication. Les modes de
transfert de chaleur sont traditionnels et
ne représentent rien de nouveau. Mal
heureusement, toute nouvelle augmentation
dans le coefficient d'ensemble est actuelle
ment limitée par la résistance de la paroi
des métaux pouvant convenir pour ce
service. Dans ce domaine, les métallurgistes
pourraient apporter une contribution im
portante en fournissant une matière bon
Тонкопленочная Дистилляция
T. К. Карнавос
Соединенные Штаты Америки
Экономически-выгодное опреснение
морской воды посредством дистилля
ции зависит от равновесия между сто
имостью энергии и капитальными за
тратами, которые диктуются условия
ми на месте установки. Установки с
высоким коэффициентом полезного
действия и низкими энергетическими
расходами должны непрерывно регене
рировать и повторно использовать в
своем цикле весьма значительную
часть теплоты парообразования. Одна
ко, капитальные затраты на такие уста
новки возрастают с увеличением коэф
фициента полезного действия. Поэтому
marché, résistante et à haute conductivity
thermique que serait inaccessible à la corro
sion et à l'érosion.
Des évaporateurs à pellicule mince avec
des tubes "Double Flute" ont été en utili
sation pratique depuis plus de deux ans et
demi. Une installation pilote a été installée
à la Station d'essais de développement et de
recherche de l'Office of Saline Water, à
Wrightsville Beach, North Carolina. On a
obtenu un fonctionnement avec succès jus
qu'à une température d'ébullition de
135°C. Un distillateur à pellicule mince,
à deux effets, de 50 m' par jour, pour
service maritime, a été installé à bord du
paquebot "Tullahoma". Ces installations et
de nombreuses autres ont permis d'ajouter
énormément de renseignements utiles aux
données de fonctionnement actif sur les
évaporateurs à pellicule mince.
Pour conclure, on peut dire que les tubes
"Double Flute" avec des coefficients d'en
semble de transfert de chaleur élevés per
mettront la construction d'évaporateurs de
dimensions beaucoup plus petites, ce qui
aura une forte influence sur le coût des
installations. En outre, les coefficients élevés
à de petites différences de température
seront très utiles pour les installations à
rapport de rendement élevé du type a
effets multiples ou à compression de vapeur.
Le principe de la distillation à pellicule
mince a été démontré en exploitation.
проблемой опреснения морской воды
является достижение высокого коэффи
циента полезного действия без повы
шения стоимости установки до того
уровня, когда капитальные (фиксиро
ванные) расходы становятся запрети
тельными. По экономическим сообра
жениям желательно передать макси
мальное количество тепла минималь
ной поверхности при минимальном тем
пературном перепаде. Выбор материа
ла труб и их толщины фактически за
висит от запроектированного срока
службы. Поэтому проектировщик дол
жен использовать способы теплоперс
 дачи, которые дают самые высокие об
щие коэффициенты теплопередачи, то
гда как в настоящее время его выбор
ограничен с одной стороны конденси
рованием, а с другой кипячением или
подогреванием жидкости. Этот доклад
описывает решение целой проблемы
посредством использования единствен
ной в своем роде поверхности с высо
кой теплопередачей, которая может
быть применена в многоступенчатых
циклах и циклах со сжатием пара.
Была разработана новая теплопере-
даточная поверхность, названная
«Двойной канавкой», которая при вы
парке и конденсации создает и регули
рует тонкие пленки без применения
каких-либо движущихся частей.
Принцип работы «Двойной канавки»
состоит в том, что образующаяся плен
ка конденсата обладает поверхностны
ми силами натяжения, стремящимися
дренировать ее по направлению от
гребней к бороздкам. Поэтому боль
шая часть каждого гребня остается по
крытой очень тонкой пленкой конден
сата, что сильно уменьшает сопротив
ление прохождению тепла через греб
невую поверхность. Конденсат, находя
щийся в бороздках, отводится силой
тяжести, причем тепловой поток в этой
зоне до некоторой степени менее ин
тенсивен. С помощью сил поверхност
ного натяжения стекающая пленка ис
ходной жидкости на стороне кипения
тоже имеет тенденцию дренироваться
в бороздки. Кипение происходит в тон
кой пленке на каждом гребне, а также
и в бороздках. Гребни все время оста
ются мокрыми вследствие разбрызги
вания конденсата, кипящего в борозд
ках. Генерируемый пар перемещается
в одном направлении с исходной жид
костью. Канавки выполняют вторич
ную, но очень важную функцию, соз
давая и регулируя количество стекаю
щей пленки, чтобы обеспечить одно
образное распределение (тепла) вдоль
по всей трубе.
Конденсирование пара на поверхно
сти, снабженной канавками, является
пленочнообразующим процессом. Ко
эффициент конденсации при «Двойной
канавке» в 4% - 7 раз выше, чем у
идентичной гладкой трубы при од
ном и том же тепловом потоке. На
ибольшие выгоды получаются в обла
сти малых температурных перепадов,
что весьма желательно при проек
тировании установок с высоким ко
эффициентом полезного действия.
Групповые, относящиеся к Конден
сированию на рифленых поверхно
стях, данные, были также представ
лены другими авторами и хорошо со
гласуются с этим докладом. Сравнение
коэффициентов конденсации, относя
щихся к «рифленой поверхности» и к
капельному процессу (1, 2, 3, 4) ясно
иллюстрирует равноценность этих двух
способов теплопередачи, которая в слу
чае поверхностей, снабженных канав
ками, достигается очень простым, де
шевым и надежным образом.
Повышение величины коэффициента
конденсации, хоть само по себе и зна
менательно, но может потерять всю
свою ценность, если одновременно не
будет усовершенствована сторона вы
парки. Как было ранее объяснено, ки
пячение на рифленой поверхности яв
ляется процессом тонкой пленки. Ка
сающиеся этого процесса данные были
получены на соответственных трубах,
имевших различные соотношения меж
ду длиной и диаметром, и при пита
нии естественной морской водой. Кро
ме того, хотя при двух различных си
стемах и были получены равноценные
коэффициенты кипения, но было отме
чено, что данне для рифленых поверх
ностей более реалистичны, принимая во
внимание намеченную работу и произ
веденные испытания с морской водой.
Коэффициенты конденсации и кипе
ния при трубах «Двойной Канавки»,
являются одними из самых высоких при
неподвижных поверхностях и различ
ных способах обработки. Выработка,
как внутренних, так и наружных по
верхностей «Двойной канавки» требует
только одну производственную опера
цию. Их способ теплопередачи обычен
и не вносит радикальной перемены. К
сожалению, дальнейшее повышение
общего коэффициента в настоящее
время ограничено сопротивлением
стенки, сделанной из металлов, при
годных для этой службы. Металлурги
могут здесь сильно помочь, изготовив
крепкий, дешевый материал с высокой
удельной теплопроводностью, который
бы мог противостоять ударной корро
зии.
Тонкопленочные испарители с тру
бами «Двойной канавки» работают в
полевых условиях уже в течение двух
с половиной лет. Пробная установка
была построена в Райтсвилл Бич, шт.
Северная Каролина, на Научно-исследо
вательской опытной станции Управле
ния по опреснению соленых вод. Удач
ная работа производилась при темпе
ратуре кипения до 275° F. Двухступен
чатый тонкопленочный перегонный ап
парат для морской службы, произво
дящий 8.000 галлонов пресной воды в
сутки, находится на пароходе «Тулла-
хома». С помощью этих и многих дру
гих установок было получено большое
количество сведений, относящихся к
полевой работе тонкопленочных испа
рителей.
В заключение можно сказать, что
трубы «Двойной канавки» с высокими
общими теплопередаточными коэффи
La Destilación por Medio de
Películas Delgadas
Т. С. Carnavoe
Estados Unidos de America
La producción económica de agua desmi
neralizada por destilación del agua de mar
depende del equilibrio entre el costo de la
energía y los costos fijos, estando ambas
partes regidas por la situación que reina en
la instalación. Las centrales de elevada
relación de ganancia, al tener costos de
energía reducidos, requieren que una parte
muy considerable del calor de vaporización
se recupere constantemente y vuelva a utili
zarse en el ciclo. Sin embargo, los costos
fijos correspondientes a dichas plantas se
elevan al aumentar la proporción de ga
nancia. Por consiguiente, el problema de
conversión del agua de mar consiste en
lograr elevadas proporciones de ganancia,
sin aumentar los costos de la central hasta
el punto en que los gastos fijos sean prohi
bitivos. Por razones económicas, conviene
transmitir el máximo de calor con respecto
al mínimo de superficie y diferencia de
temperatura. La elección del material y
espesor de la pared de los tubos depende,
virtualmente, del criterio relativo a la vida
prevista en el diseño. Así, pues, corresponde
al diseñador utilizar las formas de trans
misión térmica capaces de rendir los ma
yores coeficientes, totales de transmisión
de calor y su elección está limitada, en
la actualidad, a la condensación en uno
de los lados y la ebullición o calentamiento
de líquido en el otro. En el presente trabajo
se indica una solución a la totalidad del
problema, mediante el uso de una superfi
циентами, позволят уменьшить габа
риты проектируемых испарителей и тем
самым окажут сильное влияние на сто
имость установок. Кроме того, высо
кие коэффициенты при малых темпера
турных перепадах будут весьма полез
ны для многоступенчатых установок с
высоким коэффициентом полезного
действия и работающих со сжатым па
ром. Принцип тонкопленочной дистил
ляции был испытан в полевых усло
виях.
cie singular de elevada transmisión térmica
que puede utilizarse en los ciclos de efecto
múltiple y compresión de vapor.
Se ha creado una nueva superficie trans
misora de calor, llamada de "doble esetría",
la cual, sin pieza móvil alguna, produce y
mantiene películas delgadas en la evapora
ción y la condensación. La posición del
tubo es vertical, con el vapor condensándose
en el exterior y con una película descen
dente de agua de alimentación en el in
terior. El principio del funcionamiento de
la "doble estría" consiste en que la película
de condensado que se forma está sujeta a
fuerzas de tensión superficial que actúan en
el sentido de desaguarla de las crestas o
salientes haciéndola pasar a los canales o
depresiones. Esto hace que la mayor parte
de cada cresta tenga una película muy del
gada de condensado, lo cual reduce grande
mente la resistencia al flujo calórico a
través de la zona de la cresta. El conden
sado de los canales es desalojado por gra
vedad, con un flujo calórico algo menor
a través de esta zona. En el lado de la
ebullición, la película descendente de agua
de alimentación también tiende a desaguar
en los canales, debido a las fuerzas de ten
sión superficial. La ebullición ocurre en la
película delgada de cada cresta, así como
en los canales. Las crestas se mantienen
constantemente húmedas por las salpicadu
ras procedentes de la ebullición en los
canales. El vapor así formado se mueve
217
 junto con la corriente de agua de alimen
tación. Las estrías desempeñan una función
secundaria, pero muy importante: la de
organizar y regular la película descendente,
a fin de asegurar la distribución uniforme
a lo largo del tubo.
La condensación de vapor en una super
ficie estriada constituye un proceso pelicular.
El coeficiente de condensación es de 4i/2 a 7
veces mayor que el obtenido para un tubo
liso comparable, a un determinado flujo
térmico. La mayor ganancia se produce en
la región de menores diferencias de tempe
ratura, lo cual es favorable al diseño de
instalaciones de elevada relación de ganan
cia. Los datos de otros autores (3), acerca
de la condensación en superficies estriadas,
se representan como una banda y admiten
comparación favorable con el presente tra
bajo. Mediante una comparación entre los
coeficientes de condensación en superficie
estriada y de condensación a gota (1,2,3,4),
se puede demostrar la equivalencia de estas
dos formas de transmisión térmica que, en
las superficies estriadas, se consigue de modo
sencillo, económico y seguro.
Todo aumento del coeficiente de conden
sación, aunque significativo por si mismo,
perderá prácticamente todo su valor si no
se logra, además, un mejoramiento del lado
de la evaporación. La ebullición sobre una
superficie estriada constituye, como ya se
ha explicado, un proceso de película del
gada. Los datos correspondientes al trabajo
que nos ocupa se obtuvieron en tubos
reales, de diversas razones de longitud a
diámetro, sirviéndose de agua natural de
mar como alimentación. Con las superficies
estriadas se alcanzan coeficientes de ebulli
ción más altos que con las superficies lisas.
Además, se ha obtenido, por dos sistemas
distintos, una equivalencia del coeficiente
de ebullición, pero reconociendo que los
datos correspondientes a la superficie estria
da son más reales con respecto al servicio
que se pretende, puesto que se utilizó
agua de mar.
Los coeficientes de condensación y ebu
llición obtenidos mediante el tubo de doble
218
estría se encuentran entre los más altos
notificados hasta la fecha en relación con
superficies o tratamientos estáticos. Ambas
superficies, externa e interna, se consiguen
en la misma fase de fabricación. Los modos
de transmisión térmica son convencionales
y no representan cambio radical alguno.
Por desgracia, un mayor aumento del coefi
ciente total está limitado en la actualidad
por la resistencia de las paredes hechas con
los metales convenientes para este servicio.
Los metalúrgicos pueden contribuir gene
rosamente a este fin facilitando. un mate
rial de bajo costo, alta resistencia y alta
conductividad térmica que no resulte afec
tado por la corrosión y la erosión.
Los evaporadores de película delgada*
con tubos de doble estría funcionan en la
práctica desde hace más de dos años y
medio. Se instaló una planta piloto en la
Estación Experimental de Investigación y
Desarrollo sita en Wrightsville Beach, Caro
lina del Norte, y dependiente de la Oficina
de Agua Salada. Se ha conseguido un fun
cionamiento satisfactorio a temperaturas de
ebullición de hasta 275°F (135°C). Un
equipo destilador de película delgada de
doble efecto, para servicio marítimo, y con
una capacidad de producción de 8.000 ga
lones diarios, fue instalado en el buque a
vapor "Tullahoma". Estas instalaciones,
más muchas otras, han contribuido a
aumentar considerablemente los datos de
funcionamiento sobre el terreno, relativos
a los evaporadores de película delgada.
En conclusión, puede afirmarse que la
doble estría, con sus elevados coeficientes
totales de transmisión térmica, permitirá
el diseño de evaporadores de mucho menor
tamaño, lo cual ejercerá gran influencia en
el costo de las instalaciones. Además, los
altos coeficientes a pequeñas diferencias de
temperatura resultarán muy beneficiosos
para las centrales de alta relación de ganan
cia, pertenecientes a la clase de efecto
múltiple o de compresión de vapor. El
principio de la destilación por medio de
película delgada ha sido demostrado sobre
el terreno.
Some Phenomena
Concentration Polarization in
Electrodialysis
B. A. Cooke
United Kingdom
The concentration polarization which oc
curs at interfaces between electrolyte solu
tions and ion -exchange membranes is a
well-known factor in the design and opera
tion of an electrodialysis installation. When
the current passing through such an installa
tion operated under steady conditions of
liquid feed is increased, a situation is
reached in which either a further increment
in current can be obtained only at the cost
of a highly disproportionate rise in terminal
voltage or the pH values of the effluent
liquids differ markedly from those of the
feed streams. This situation is supposedly
associated with the initial attainment of
zero interfacial electrolyte concentration
over at least some regions of the membrane
surface employed, although so precise an
interpretation should be regarded with cau
tion in view of the arbitrariness with which
the changes in slope of current-voltage
curves must often be treated when dealing
with practical installations. Although ele
mentary considerations suggest that trans
ference of hydrogen or hydroxyl ions should
EXPECTED PATTERN OF BEHAVIOR OF
POLARIZED ION-EXCHANGE MEMBRANE SYSTEMS
In this section, an attempt is made to
forecast the overpotential resulting from
normal concentration polarization in elec
trodialysis systems over a current range em
bracing conditions below, at, and above
the limiting current. The simplifications
made include assumption of a single electro
Associated with
be the consecutive process supporting con
duction above the limiting current, the use
of pH displacement as a criterion of the
limiting condition is questionable because
the observed pH shift is generally opposite
to that anticipated (refs. 1, 2).
It is proposed to discuss in this paper a
number of phenomena found in practice
which are not readily fitted into a simplified
treatment of electrodialytic polarization such
as has often appeared in the literature. The
phenomena are of two sorts: those whose
occurrence is apparently independent of
the structure or method of manufacture of
the membrane used (the usual levels of ion
selectivity and electrolytic resistance being
assumed) , and those resulting from an ab
normality in the membrane. The main
emphasis in this. paper is on two instances
of the latter type, i.e., traceable to mem
brane abnormalities. Before proceeding, it
will be worthwhile to inquire into the ex
pected or "normal" behavior of an electro
dialysis system when direct current is passed.
lyte having univalent ions, unvarying elec
trolyte activity and diffusion coefficients, and
unvarying ion transference numbers and
mobilities in the aqueous solution and film.
The idealization, derived from the work of
Nernst. of supposing the diffusion layer to
be a sharply bounded region of linear con
219
 centration gradient is also used, and electro-
osmosis is ignored.
The simplest system is one in which mass
transfer conditions can be represented by
a value of the diffusion layer thickness, 4,
which does not vary from region to region
over the interface. If a current of uniform
density, i, is passed, it follows that the
resulting interfacial concentration, c', is
constant on each side of the membrane.
Considering the side on which c" <c„ (c„
being the bulk solution concentration) ,
i» (t-t)
FD
where t =s transference number of the coun-
terion in the membrane,
t transference number of the same
ion in the free solution,
F = Faraday constant,
D —diffusion coefficient of electrolyte.
The idealized system will reach its limiting
current abruptly at
FDc0
«(t-t)
In practice there are few systems in which
mass transfer conditions meet the require
ments for Equations (1) and (2) . One
which does may well be an arrangement
having carefully controlled stirring and
favorable geometry, e.g., that adopted by
Gregor and Peterson (ref. 3) . The writer
has preferred to experiment with vertical
membranes in unstirred solutions not only
because they display lower limiting currents
than systems with forced convection but
mainly because the laws of natural convec
tion are well established. This makes pos
sible a forecast of the variation in mass
transfer rate over the vertical interface and
an estimate in absolute terms of the rate
(and therefore the effective value of S) at
any point. These remarks certainly apply
if the membrane height is not great, say a
few cm. The applicability of the laws
of natural convection to such membrane
heights has been tested (ref. 4) . In this case
(S)
where a = a numerical constant, normally
0.51,
u = kinematic viscosity,
a = densification coefficient of the
electrolyte in water, p c
g = acceleration due to gravity,
y n ordinate of point considered
above bottom edge of membrane.
220
Here c* is the local interfacial concentration
produced at the point y by current of local
density i. At low current densities, uniform
current distribution is more likely in an
apparatus fitted with large plane electrodes
than the distribution of current necessary to
make C constant. The assumption of cur
rent uniformity has yielded good agreement
between theory and practice up to an in
cipient limiting current i'nm, given by
f-=(e) (£)"**«•« «,
where Y = total height of the membrane
(»> (rectangular section) .
At this current, the extreme upper edge of
the membrane is just carrying its limiting
current. Further current must be refracted
because of the rapidly increasing o"erpo-
tential encountered; that is to say, current
becomes redistributed so as ultimately to
cause C = o over the entire membrane face.
The average current density required to do
this might be called the final limiting cur
rent. By integration its value is found to be
(2)
— _ i< (5)
- s
In practice, uniform current distribution is
unlikely up to i'lim, but experimental re
sults (ref. 4) suggest that deviations are in
significant below about 0.8 i'Um and quite
small even up to i'nm.
Equation (3) can be used to forecast over-
potentials at currents up to i'um. In the
paper referred to (ref. 4) , this has been
carried out with various locations of the
sensing electrodes in respect of the non-
ohmic or "concentration" portion of the
overpotential .
A simple extension of the argument de
veloped for centrally located relatively re
mote electrodes leads to the following
expression for the apparent total overpoten-
tial while current is flowing, ij,, for the case
i < >'iim (' being the mean current density,
which for the present purpose is supposed
to be uniformly distributed) :
„=(e0 + b) j^T-l) (1-P) +
1 1 1 + 2i?+^J-6
1 1 I 5 .bp
5"+lp-+V (6)
.
where 2RT (t,- — t).. ,
e„ = ——
F
R =gas constant,
T = absolute temperature,
 FD tated by expanding the logarithmic term.)
b= The line OL in Figure 78 is a plot of
(t - t) A
A = equivalent conductivity of elec Equation (6) for an anion-exchange mem
trolyte, brane in 0.05 M NaCl at 25°C for which t
p = '/''"■• ''urn being obtained from = 0.99. The value of i',,m was calculated
Eq. (4). from Equation (4) taking a as 47.6 cm*
(N.B. Calculations using Eq. (6) are facili equiv _1.

FIGURE 78. FORECAST OVERPOTENTIAL CURVE (OLL'M') FOR

ANION-EXCHANGE MEMBRANE, IN UNSTIRRED 0.05 M NaCI
AT 25°C, MOUNTED IN CIRCULAR CELL OF 1.60 cm DIAMETER.
EXPERIMENTAL POINTS IN CIRCLES, JOINED BY LINE OLL'M.

It may be noted that although the total
overpotential at L is just over 80 mV, a
portion of the interface is about to carry its
limiting current and the consecutive process
is about to commence. This prediction has
been verified for an anion-exchange mem
brane in which OH" conduction is the
major consecutive process in concentration
polarization (ref. 4) . The region above L
is difficult to forecast but we may expect
the overpotential curve to have its maxi
mum slope at i = I,,m as forecast in Equa
tion (5) . At the latter current the entire
active membrane surface is carrying limit
ing current (no longer uniform) and the
overpotential must shift to that required to
drive the consecutive process. An estimate
of this overpotential can be made with the
aid of a simpler expression than Equation
(6) which describes, with comparable sim
plifications, the overpotential in a system
in which c" is constant and small compared
with c„ (ref. 4) .
„ = (e. + b) In £ _ b (7)
If transport of ions resulting from the dis

221
sociation of water is the consecutive process,
Equation (7) must be altered to take ac
count of the difference in ionic species
present at the interface in the depolarized
(c0) and polarized (cf) conditions respec
tively by introducing the appropriate equiv
alent conductivities:
„= (e. + b) ln-^-b (7a)
A.C
where A, = Xoh" + Xh*-
For the experimental case discussed, and
assuming Kw — 10"" (C = lO 'M) , this
gives r)t = about 600 mV at I = Inm, which
is shown as the point L' in Figure 78. If
this situation remains unchanged during
further increase of current, the overpoten-
tial curve would have a constant slope of
-£-(i>illm) = -— (In—-- 1)
«' in. A-c
(8)
which is shown as the line L'M'. Finally, L
and L' have been joined by an arbitrarily-
chosen smooth curve, the broken line in
Figure 78.
Discussion of the experimental points
shown in Figure 78 will be deferred until a
later section*. The case of unstirred solu
tion has been considered at some length
EVENTS OBSERVED WITH NORMAL MEMBRANES
A major problem in demineralizing under
ground waters by electrodialysis is the accu
mulation of alkaline scale on the sides of
the anion-exchange membranes which face
the anode. These scales are of variable com
position, comprising magnesium and cal
cium hydroxides, carbonates, and frequently
silicates. It may be presumed that they form
as a result of OH- transfer through the
membranes. Since operating conditions are
apparently selected to insure remoteness
from the limiting condition of polarization
(as judged by linearity of the current-
voltage relation or smallncss of pH shifts
in process streams) . this is difficult to under
stand without drawing from a more com
plex picture than the simple case of uniform
diffusion layer thickness. On the other hand,
* In obtaining the experimental points shown,
a eel] of circular section was used because of its
convenience. Analysis of this case as a series of
rectangles to each of which Equation (3) is
applicable indicates that a circular section of
diameter D is equivalent in limiting current be
havior to a rectangle of height Y = 0.826D. The
value of Y used in calculations based on Equa
tions (4), (6), and (8) was so obtained, the
experimental cell having D = 1.60 cm.
This refers to the short-range current dis
tribution, not the long-range current distribution
resulting from the demlneralization and concen
tration occurring in practical apparatus with long
flow paths for the process streams.
becaue it forms the basis of the experi
mental method by which membranes have
been tested for abnormality. The more
practical case of convection forced by now
through narrow compartments shows quali
tative similarities but, because S varies much
more widely over the membrane surface,
e.g., in laminar flow I is proportional to y*
rather than to y">, the incipient limiting
condition is attained at a lower fraction of
the final limiting current than in the case
of natural convection (ref. 5) . As a result,
the overpotential curves show less sharp
inflections, making final limiting currents
difficult to recognize. This is especially so in
arrangements incorporating a corrugated
perforated or similar material between the
membranes, in which case the pattern of
variation of 6 is presumably repeated for
every hydrodynamic "cell" present, corre
sponding to each hole in the material. Since
the disposition of the holes in relation to
the membrane surface is variable, the repe
titions are not likely to be exact. Experi
mental results (ref. 5) suggest that the
pattern of variation of S does not alter with
flow rate in an unfilled membrane cell, but
becomes more diverse as flow rate is in
creased when spacer is present.
it is readily explained with the aid of the
concept of variable 4, combined with essen
tially uniform current density" up to the
incipient limiting condition.
It follows from the work mentioned (ref.
5) that an apparatus incorporating a corru
gated spacer is likely to be more trouble
some than a spacer-free apparatus with
respect to scale formation under conditions
of apparent depolarization. This might be
reflected in a higher requirement of acid
dosing for the concentrated stream which
might offset the other advantages of the
construction with spacer. It would be inter
esting to know whether such a comparison
has been carried out.
Localized pH shifts at anion-exchange
membranes can be used to clear scale by
reversing polarity and thereby inducing
acid conditions at the affected interface (ref.
6) . Workers in Israel have extended this
approach bv employing short pulses of re
versed polarity rather than reversal for long
periods which necessitates interchange of
the flow connections. The method is said to
give rise to a loose precipitate which is re
movable by flushing.
An interesting case of scale formation and
descaling not owing its origin to pH shifts
 is lhat of barium and strontium sulphates
which can form a very tenacious scale on
cation-exchange membranes (ref. 6) . Re
versal of polarity was very effective although
manual scrubbing failed to dislodge the
deep-seated scale. In descaling affected mem
branes by electrodialysis with reversed po
larity, it was found that some of the alkaline
earth cation passed through the membrane
(as indicated by a faint precipitate on the
opposite face when sulphate was present on
that side; but this constituted only a minor
proportion of the total which remained as
innocuous loose scale removable by flushing.
Another material fact is that descaling oc
curred with sodium sulphate as an electro
lyte on the affected side but not with
barium chloride. Kvidently the divalent
cations form a strong bond between the
scale and the fixed anions of the membrane:
these cations are transported when concen
tration polarization gives rise to a low
interfacial concentration, the concentration
required presumably being governed by the
solubility product. In fact, descaling of these
membranes could not be induced by low
current densities nor with concentrated solu
tion on the scale side, so the descaling which
occurs in practice must be ascribed to the
existence of regions carrying current at or
near the limiting value. This was in a mem
brane assembly fitted with spacer and opcr
ated under conditions lying on the linear
region of the current voltage diagram and
without large pH shifts in process streams.
The evidence is, therefore, in line with the
effects of variable diffusion layer thickness
discussed above.
The pH shift is itself of great interest. In
electrodialvsing NaCl solutions, the cation-
exchange membrane reaches its limiting
current first so the stream being depleted
in salt (the dialysatc should become alka
line above this current. It has, in fact, been
commonly found that the dialysatc becomes
acid. Several reports indicate that the pH
shift is very small at individual cation-
exchange membranes frefs. 4, 7, R) or sets
in at higher current than expected (ref. 1) .
Careful tests have revealed that solute cat
ions continue to reach the membrane even
when overpotential indicates that iu„ is
exceeded (refs. 4, 7) , although Pears (ref.
8) , working with a heterogeneous mem
brane, reported lhat the consecutive process
was leakage of the co-ion chloride. A recent
paper by Gregor and Peterson (ref. 5) is
not in agreement with these findings. The\
report that the "expected" H* flux above
the limiting current occurs in the electro-
dialysis of KCl with a cation-exchange mem
brane (the writer found that neither KCl
nor NaCl did this (ref. 4)). A reconciliation
might be possible between Gregor and
Peterson and the other workers in that the
membrane of the former was of the unusual
"intcrpolymer" type, presumably comprised
of linear polystyrenesulphonic acid and a
film-forming polymer deposited together
from a mixed solution. Though the ion-
exchange component may not be leached
from the interior of such membranes by the
action of water, it is likely that the surface
is depleted of this component, leaving a thin
outer skin of an inert film-former. Such a
membrane would be cation-exchange analog
of the abnormal anion -exchange membranes
to be described. There is evidence for this
being the case with Gregor and Peterson's
membrane in their reported values of mem
brane resistance in KCl of 0.001 and 0.1 M
concentration. Such marked variation in re
sistancc over this concentration range is
abnormal for membranes of high fixed ion
concentration. A relation between such re
sistance variation and the presence of inert
regions in the membrane structure (which
may have the form of films) is developed in
the next section. It has been suggested (ref.
7) that the continuation of transfer of
solute cations above the limiting current
generally found in cation-exchange mem
branes is a result of electro-osmotic action
in the diffusion layer. This is likelv to lie
suppressed if the diffusion laver extends
into a relativelv impervious inert polymer
film, so that "abnormality" in a cation -
exchange membrane could he responsible
for "normal" behavior, i.e.. the expected H*
flux.

EFFECT OF MEMBRANE ABNORMALITIES

The experimental points in Figure 7Я siderable divergence. General experience
indicate that the overpotential behavior of with the system of anion-exchange mem
an anion-exchange membrane below the brane and unstirred 0.05 M NaCl has been
final limiting current is reasonably well that behavior above the limiting current
explained. This has consistently been found varies appreciably from one type of mem
to be the case with a variety of membranes, brane to another or even between samples
both anion- and cation-exchange, from of the same type, but that the total over-
various sources. Above \,,m, there is con potential at about twice T,iro seldom ex
 ceeds 1.5 v. If the discrepancy above i1(„
evident in Figure 78 is a consequence of
oversimplification in deducing Equations
(7a) and (8) , the error varies from mem
brane to membrane and it has not been
possible to associate it with any identifiable
property (except possibly that highly swol
len membranes generally display smaller
discrepancies than less swollen ones— the ex
perimental results are always higher than
forecast.) It may be remarked that a devi
ation from linearity in the concentration
gradient at the membrane end could give
rise to the discrepancies found. This could
be caused by any structural feature of the
membrane surface which makes for diffuse-
ness of the boundary between solution and
the main ion selective interior of the mem
brane. Abnormal membranes in which this
effect is evidently present to an exceptional
extent will be discussed later.
Deviations from expected behavior of a
much greater order of magnitude weTe
found when testing two commercial types
41—
i , mA cm"2
FIGURE 79. MEASURED OVERPOTENTIAL CURVES FOR ANION-
EXCHANGE MEMBRANES OF THREE TYPES IN UNSTIRRED
0.05 M NaCl SOLUTIONS AT 20°C.
In addition to the anomaly evident from
Figure 79, many 'A' and 'T' membranes
showed curious behavior when used in the
eleclrodialvsis of sodium sulphate solution.
This is summarized in Figure 80 which
224
of anion-exchange membranes, designated
for convenience the 'A' and 'T' types. These
membranes have been held responsible for
poor performance in pilot and full-scale
electrodialysis plants (ref. 9) . Both types
are understood to have been derived from
graft copolymers involving a polyethylene
substrate and are often loosely referred to
as "homogeneous". Features of the behavior
of these membranes are the reduced limiting
current and very high overpotentials at
higher currents. This is illustrated in Figure
79 which also shows, for comparison, the
performance of the l.C.I. , Ltd. type of
anion-exchange membrane. (Designated T.
this is the same membrane as that whose
overpotential curve is shown as OLL'M on
Figure 78.) The I.C.I, membrane, whose be
havior is discussed here, was also of the
graft copolymer type but was manufactured
by a process believed to differ materially
from that used in obtaining 'A' and "T* type
membranes.
shows a comparison of the behavior in
chloride and sulphate solutions of 'T' and
T type anion-exchange membranes. Whereas
the normal T type polarized more readily
in sodium chloride than in sodium sulphate
solution of equivalent concentration at the phate that the relation between its two
same temperature, the "T" type membrane curves was reversed,
behaved so much more abnormally in sul-

225
 The abnormal behavior of 'A' and T'
type membranes is attributed to the pres
ence of inert films, probably of unreacted
polyethylene, at their surfaces. This deduc
tion was confirmed directly by measuring
the overpotential curve of a sample oriented
in the test cell in a commonly accepted
fashion, then using wetted fine emery cloth
to scrape the surface of the membrane on
which dilution had taken place in the
polarization test, and finally redetermining
the overpotential curve with the same orien
tation. Figure 80 shows the results, the
sample chosen being one of the most ab
normal samples of 'T' type membrane
encountered. The results speak, for them
selves, the scraped side behaving virtually
normally. It was also observed that the
surface prior to scraping was distinctly hy
drophobic but the scraped surface was
hydrophilic.
An indirect confirmation of the associa
tion between inert polymer films and abnor
mal polarization was obtained by measuring
the electrolytic resistance of a sample over
a range of external solution concentrations
from 0.001 M to 0.1 M NaCl at 25°C, using
an a-c source at 1 kc/s and a conventional
cell with flowing solutions. The results are
shown in Figure 81 which also shows the
behavior of an T type membrane for
comparison (the "used" membrane will be
discussed later) . The basis of this test is
the fundamental property of a uniform
swollen ion-exchange structure: that its
electrolytic resistance is substantially inde
pendent of external electrolyte concentra
tion, provided that latter remains well
below the fixed ion concentration. (With
the normal highly dissociated crosslinked
structures, we may ignore secondary effects
such as variations in swelling.) That this
is normally so has been extensively con
firmed; therefore, it must be concluded that
a portion of the electrolytic path in the
abnormal membrane comprises material of
low or possibly zero fixed ion concentration.
An analysis of the results of Figure 81
could be made as follows. Suppose, as a
reasonable approximation, that the main
body of membrane is composed of material
whose areal* resistance is quite independent
of concentration and equal to r„. In addi
tion, assume that a film is present, situated
electrically in series, which can conduct only
by virtue of the external electrolyte per
vading it, so that its contribution to resist
* By areal resistance is meant resistance of unit
cross section when current flows normally to the
main plane of the membrane. This is the "
in ohms cm1, commonly used in raerabn
acterization.
226
ance is kp, where p is the resistivity of the
solution and k is the thickness of an
aqueous path whose resistance equals that
of the inert film. It is unlikely that a
combination of these two regions will suf
fice, so we add a third region of an inter
mediate character contributing a resistance
f (p) such that
lim f (p) =0
p-»0
(9)
lim f (p) _ q
p->oo p ~
which is the same as saying that f (p) in
creases from zero as p increases from zero, but
less rapidly than its first power. This term,
f (p) , would then describe any transitional
region joining the inert film with the main
active membrane interior. We then have for
the total areal resistance:
r = r„ + f (p) + kp (10)
It follows from Equations (9) and (10)
that
lim r = r„
p-»0 (II)
and lim r — r. = k
p-*QO p (12)
The result of the first extrapolation (Eq.
11) may be applied in Equation (12), a
more convenient form of which is
IJim0K(r-ro)=k
where K — specific conductivity — 1/p .
These extrapolations were carried out for
the results on the T membrane shown in
Figure 81. They gave r„ = 24.5 ohm cm*
and k = 0.012 cm. Over the concentration
range 0.1 M to 0.001 M, the value of f (p)
increased steadily from 15 to 14 ohm cm2.
The value of k might be used to furnish
a crude indication of the actual thickness
of polymer film. If we suppose that hetero
geneity is concentrated in two identical inert
films at each membrane face and that ionic
mobilities are depressed in the inert film to
the same degree as in the membrane phase
proper (a highly questionable step) , the
estimated inert film thickness 9 is
*~ 2A
where A'/A is the mobility depression factor.
For the T' membrane studied, this factor
was calculated from r„, the fixed ion con
centration, and the thickness of the mem
brane to be 0.004, giving f = 2.4 x 10"" cm.
This must be regarded as a high estimate
because ionic mobilities are likely to be
depressed to a greater degree in an inert
 !0"3M IO"2M
Ha CI CONCENTRATION
FIGURE 81. RESISTANCE OF THREE SAMPLES OF ANION-
EXCHANGE MEMBRANES AS A FUNCTION OF EXTERNAL
SODIUM CHLORIDE CONCENTRATION.
film than is indicated by properties of the
active interior. The indications are, there
fore, that the film is very thin compared
with the membrane (about 2.5 x 10~2 cm) .
Another possible use for the k value is in
predicting the depression of limiting current
caused by the presence of the film when
the membrane is polarized in a cell with
stirred external solution, making use of the
assumption that the residual aqueous film
in a stirred cell is of uniform thickness
so that Equation (2) is applicable. Under
given conditions of stirring, the residual
film thickness proved to be 0.0025 cm thick
(deduced from measurements using a nor
10" M IM
J»
mal T type membrane) , so the total effec
tive film thickness with the abnormal
membrane would be 0.0025 + k/2 = 0.0085
cm, for which Equation (2) indicates a
limiting current of 4.5 mA.cnr2 in 0.01 M
NaCl at 25°C. The observed value was
about 5 mA.cm-2, indicating reasonable
agreement.
The picture of an active membrane in
terior, represented by r„, joined at a sharp
boundary to an inert film, represented by
k. does not explain the very high overpoten-
tials found above Inm. Thus, the depression
of ionic mobility in the inert film affects the
diffusion coefficient and conductivity of the
 electrolyte to the same degree, leaving of the fact that the abnormal anion-exchange
Equation (8) for the slope of the over- membrane effect was long considered to be
potential curve above !,,„ unchanged except specific to sulphate-containing water; in
with respect to the reduced !,,„. This is fact, anomalies were present in chloride
much too small an effect to account for the solutions which passed unnoticed in electro-
observations. dialysis plant trials, but the sulphate anom
The explanation is thought to be as fol aly was more obtrusive (ref. 9) .
lows. It was found in applying Equation Abnormal behavior of the sort found in
(10) to the results on the "T membrane 'A' and 'T' type anion-exchange membranes
that the "transitional" contribution f (p) has never been found in cation-exchange
increased steadily with decreasing concen membranes from the same source, although
tration. Physically, this is thought to indi it is believed that the same grafted polymer
cate a region of varying fixed ion concentra sheet material is used to obtain both types.
tion lying between the inert exterior of the Although it is not proposed in this paper
film and the fully active interior. Associated to discuss membrane preparation, it may be
with this gradient of fixed ion concentra remarked that this is probably due to the
tion will be a gradient of ion selectivity: relative ease with which polyethylene reacts
when this composite system is polarized, the with strong sulphonating acids while being
fully inert film will sustain the concentra unaffected in, though swollen by, the chloro-
tion gradient and the transitional region methylation reagent used to obtain anion
will be totally depleted of external electro exchangers.
lyte. That is to say, very low electrolyte Another abnormality to which even mem
concentration will prevail over a finite dis branes free of inert films are subject can
tance rather than being of infinitesimal arise from exposure to polymeric or other
extent at the bottom of a concentration large counter-ions which are strongly bound
gradient. If the transitional region has a by the exchanger. The most important
high resistance when not pervaded by elec example is the organic matter present in
trolyte, the result will be the observed high surface or shallow well water which often
slope of the overpotential curve above In„. has the nature of polymeric polvhydric
We do not have information on f (p) at phenols. Figure 82 shows a section of an
external solution concentrations below 0.001 early "I" type anion-exchange membrane
M NaCI which was the least value at which after 1,000 hours use in desalting a synthetic
reproducible measurements could be ob brackish water made up from normal Ayr
tained in the experimental system, but f shire tap water. The sorbed. partlv pene
(p) certainly increased steadily and quite trating, dark material evidently results from
rapidly with decreasing concentration. The the "humic" acids normallv present in such
slope of the overpotential curve above TM„
on the sample of 'T membrane under dis
cussion was about 290 ohm cm1, of which
about SO ohm cm3 is explained by the con
centration gradient. The difference, about
200 ohm cm1, though much larger than 1.4 f
(p) at 0.001 M NaCI concentration, which
was 7 ohm cm1, could conceivably be the
value to which this quantity would rise
in pure water.
The sulphate effect mentioned probably
results from a greater depression of the
mobility of sulphate ions in the inert film
that is experienced by chloride. This is in
line with findings on normal anion-exchange
membranes in which sulphate conductivities
are lower than chloride conductivities, al
though the two ions are about equally con
ductive in free solution. It is interesting to
note that the resistance variation was very
pronounced in sulphate solutions (e.g., in FIGURE 82. SECTION (X200)
0.005 M Na,SO, the 'T' membrane had SHOWING SURFACE OF
a resistance of 90 ohm cm2 compared with ANION-EXCHANGE MEM
43 ohm cm' in 0.01 M NaCI) . and this fact, BRANE AFTER USE IN ELEC-
taken together with the overpotential evi TRODIALYSIS OF WATER
dence of Figure 80, provides an explanation CONTAINING "HUMIC ACID"
water. The overpotential curves of this by exposing anion exchange membranes to
membrane (Fig. 83) were highly abnormal such materials as tannic acid, sodium poly-
in both NaCl and NaOH solutions. The styrenesulphonate, sodium carboxymethyl-
effect could be simulated in the laboratory cellulose, and alkaline extracts of peat.

229
 Membranes poisoned with partly pene
trating polyelectrolyte behave in a similar
manner to those having inert polymer films,
so the effect may be visualized as a deacti
vation of the surface, giving rise to essen
tially the same situation. There are some
interesting differences. One is the effect
observed when hydroxyl ion is transported
instead of the more usual chloride. While
normal anion-exchange membranes, as well
as the abnormal types previously described,
show much higher limiting currents in
NaOH solution than in NaCl of the same
concentration (as a result of the high OH"
transference number and NaOH diffusion
coefficient) , Figure 83 shows that the situ
ation is reversed with a severely "humic"
acid poisoned membrane. This is ascribed
to the enhanced dissociation of the phenolic
substances in the presence of OH", enabling
the poison to deactivate the fixed cations of
the membrane to a greater depth.
Another difference between the two types
of abnormality is in the form of the depend
ence of resistance upon external concentra
tion (Fig. 81—the used membrane) . A simi
lar analysis to that previously attempted
indicates a small or even zero value for к
in Kquation (10) (the extrapolation was
rather uncertain) , so that all or nearly all
the anomaly is reflected in the value of
f (p) . (The original membrane which
yielded the results of Figure 83 was free of
the inert film defect.) It appears that the
IMPROVED GRAFT-COPOLYMER MEMBRANES
Although membrane preparation falls out
side the scope of this paper, it is appropri
ate to record that membrane development
work accompanied the studies reported here.
The object was to obtain membranes reli
ably free of inert films and as insensitive
to fouling by polymeric counter-ions as pos
sible without sacrificing other important
properties. It was indeed, repeatedly found
that anion-exchange membranes affected by-
inert films displayed poorer behavior when
exposed to organic poisoning than mem
branes not so affected; for example, the 'A'
and T" type materials were very sensitive.
The preparative work was chiefly aimed
at obtaining graft copolymer sheet material
which was suitable for chemical activation
and had a high degree of uniformity. Atten
tion was paid not only to variation from
region to region in a continuous sheet, but
also to variation in the plane normal to the
membrane surface. In the latter case, micro-
sections were examined to test the effect of
variations in formulation and procedure,
230
poisoned film can be regarded as continu
ously varying in ion-exchange activity and
the possibility cannot be excluded that the
outer face is actually cation selective, giving
rise to an interior region which on polariza
tion becomes completely devoid of electro
lyte, rather similar to the case of the
"bi-ionic" membranes.
A general feature of membranes affected
by inert or deactivated films is that they
nearly always display essentially normal
properties when tested by conventional pro
cedures entailing, among others, resistance
measurement to a-c in relatively concen
trated solution. This fact delayed identifica
tion of the reasons for the poor performance
of the 'A' and T type membranes until
some of the work reported in this paper
had been communicated to (he interested
parties. Mr. G. S. Solt is giving a fuller
account of this situation to the Symposium
(ref. 9) . Another common feature is that
even when the external solution in which
they are polarized is vigorously agitated,
these membranes show limiting currents
while normal membranes can always be
depolarized by sufficiently rapid stirring.
While an electrodialysis plant manufacturer
or operator can, in principle, arrange for
favorable mass transfer conditions in the
apparatus, his operating range is severely
curtailed if the membranes can not be prop
erly depolarized.
and it proved possible to modify microstruc-
turc considerably in the desired direction.
The sensitivity of various membranes to
organic fouling was compared by exposing
them to polystyrenesulphonate anion in a
system involving competitive electrodialysis
of sodium chloride and sodium (linear)
polystyrenesulphonate. After a fixed expos
ure time, the overpotential curve was meas
ured in pure 0.05 M NaCl solution. The
membrane development work was successful
to the extent of obtaining membranes dis
playing the same order of performance as
the best commercially available membranes
derived from random copolymers. The con
clusions reached have been borne out by
pilot plant trials on contaminated water
conducted outside I.C.I., Ltd.. laboratories.
The trials indicated a high degree of cor
relation between laboratory polarization
testing and pilot plant performance.
In addition to work on improving anion-
exchange membranes, an improved type of
cation-exchange membrane was developed
 which has a chemical and dimensional sta- mercially available,
bility superior to that of the types com-

NOTE ON EXPERIMENTAL METHOD

The basic electrodialysis train used for
total overpotential measurements on anion
exchange membranes was as follows:
a.-. T, T,
Here с is a selective cation-exchange mem
brane, a, and a., are equivalent anion -
exchange membranes, and a2isthe membrane
under test. The compartments joining the
membranes were of 1.6 cm internal diameter
flanged glass pipe, the end compartments
having elbows to accept the main current
electrodes and the center compartments 2,
3. and 1 having openings for filling and ad
mission of a stirrer when desired. Capillary
tubes T, and T, were sealed through the
walls of compartments 3 and 4 and bent so
as to reach within about I mm of the test
membrane face at its center. These tubes
were fitted with asbestos fiber tips of low
permeability sintered into their ends and
were connected externally to calomel elec
trodes, the electrolyte being either satu
rated or 0.1 M KCl under a few cm head.
The 0.1 M solution was preferred as a pre
caution against permeation from the tips,
but it necessitated potential difference meas
urements at about 0.5 MSI. A valve volt
meter of 1 1 MSI input resistance sufficed
for most measurements. In a typical meas
urement, the end compartments were filled
with buffer solutions (compartment 2 with
0.5 M NaCl, and S and 4 with 0.05 M
NaCl) .
The extension of the test method to cover
sensitivity to partly penetrating polyelec-
trolyte was carried out by filling compart
ment 3 with a mixed sodium chloride-
sodium polystyrenesulphonate solution, elec-
trolyzing at a fixed current for a fixed time
with compartment S stirred, then emptying
compartments 3 and 4 and replacing the
solution with 0.05 M NaCl test solution.
Typically, the mixed solution contained
approximately equivalent proportions of
chloride and polystyrenesulphonate, and
electrolysis was carried out at 5 mA.cm-1 for
30 minutes.
Total overpotentials (the sum of con
centration and ohmic overpotentials) were
estimated by substracting the pd correspond
ing to the depolarized condition from the
observed pd. as obtained from the initial
slope of the current-voltage curve. The over-
potential arising on the side of the test
membrane facing the anode was ignored.
The method used to isolate concentration
overpotential has been described in detail
(ref. 2) : this was the method employed to
test the importance of varying diffusion
layer thickness in electrodialysis systems.

ACKNOWLEDGEMENTS
The membrane development work men Development Director is thanked for agree
tioned here and the studies on membrane ing to publication. In addition. Mr. G. S.
abnormalities were carried out in the re Solt of William Boby, Ltd., Rickmans-
search laboratories of Imperial Chemical worth. Hertfordshire, England, is thanked
Industries. Ltd.. fNobcl Division) . Stevens- for valuable discussions and information
ton, Ayrshire, Scotland, whose Research and communicated in advance of publication.

REFERENCES
1. Rozcnberg: Tirrell: Induslr. Елдпд. 5. Cooke, B. A.; van der Walt: Electro-
Chem., no. 49 (1957) p. 780. chim. Ada no. 5 (1961) p. 216.
2. Cooke. B. A.: Eledrochim. Ada, no. 3 6. Cooke, B. A.: Chem. Ind. (1958) p. 555.
(1961) p. 307. 7. Frilette: ]. Phys. Chem. no. 61 (19571
3. Gregor: Peterson: /. Phys. Chem. no.
68 (1964) p. 2201. p. 168.
4. Cooke, B. A.: Elertrochim. Ada no. 4 8. Pears: Disc. Faraday Soc. no. 21 (1956)
(1961) p. 179. p. 124.

231
 9. Soit: "Influence of membrane phen
omena on electrodialysis operation",
SUMMARY OF DISCUSSION
When asked to comment further on the
reverse pH effect described in his paper,
the author replied that he knew of no satis
factory answer to this phenomena. The
author stated that one of the theories ad
vanced to explain this effect is based on
cation-water interaction but that even this
does not appear to be a completely accept
able answer.
Quelques Phénomènes Associes a La
Polarisation Par Concentration
Dans L'Electrodialyse
B. A. Cooke
Royaume-Uni
Cette communication traite d'un certain
nombre de conséquences de la polarisation
par concentration résultant de l'application
de l'élcctrodialyse au dessalement de l'eau.
Les phénomènes sont inattendus dans la
mesure où leur manifestation n'est pas
prévue par les théories simples qui expli
quent le transfert de masse à l'interface
membrane/solution par une pellicule de
diffusion d'épaisseur uniforme, limitée au
côté liquide de la surface de contact. Afin
de pouvoir établir une distinction entre la
polarisation normale et anormale, on a
recours à des prévisions de la surtension
portant sur une gamme de courant étendue,
en accordant une attention particulière au
système expérimental pratique dans lequel
le transfert de masse se produit par convec
tion naturelle. La principale simplification,
ici éliminée, est celle qui supposerait l'uni
formité de l'épaisseur de la couche de
diffusion, ce qui n'est certes pas habituel
dans la plupart des situations pratiques.
En tenant compte de la variation de
l'épaisseur de la couche de diffusion qui,
on le sait, survient dans la convection na
turelle, on démontre que ces systèmes
atteignent la condition limite initiale a
environ 75% du courant nécessaire pour
232
First International Symposium on Water
Desalination. Wash., D. C. (Oct. 1965) .
The question was raised as to the pos
sible advantage of using macrorecticular
resins (300 to 400 A) to make membranes
more resistant to the detrimental effects of
concentration polarization. The reply stated
that this approach was not believed to be
of much value primarily because of the poor
selectivity of the membranes that would be
developed by this method.
produire une concentration interfaciale
d'ordre essentiellement zéro sur la surface
toute entière de la membrane active. Toute
fois, à ce courant limite initial, la surtension
totale est très faible, de l'ordre de 80mV.
Le cas plus pratique de cellules d'électro-
dialyse alimentées par de l'eau courante est
traité qualitativement: des épaisseurs de
couches de diffusion de plus grande enver
gure sont mises au point, de sorte que la
condition de limite initiale se produit à
une fraction plus basse du courant limite
ultime, qui correspond à une surtension
totale plus faible. Ces faibles surtensions
pourraient fort bien passer inaperçues au
sein d'un appareil pratique qui, peut-on
le supposer, serait suffisamment dépolarisé.
Cet argument fournit une explication au
sujet du dépôt de tartre que accompagne
l'électrodialyse des eaux dures, même lors
que l'appareil fonctionne à un courant ap
paremment bien inférieur à la valeur limite.
L'efficacité du détartrage par inversion de
polarité est attribuée à la même cause.
On mentionne le problème des varia
tions du pH dans l'électrodialyse. Le poids
de l'évidence fait en effet ressortir que le
changement du pH prévu au voisinage des
membranes d'échange de cations ne se
produit pas dans de l'eau contenant du
chlorure de sodium comme principal élec-
trolyle. On pense qu'une observation d'un
phénomène contradictoire est due à l'ano
malie structurelle de la membrane utilisée.
Bien que la plupart des membranes mises
à l'épreuve se soient jusqu'à un certain
point écartées de la courbe de surtension
prévue à des courants dépassant la valeur
limite, leur comportement à des courants
plus faibles a été raisonnablement expliqué.
Il n'en a pas été de même de certaines
membranes anionites copolymère à greffe
de type commercial qui ont révélé des
courants limites anormalement faibles et
des surtensions extrêmement élevées, au-
delà de la condition limite. Ces membranes
ne pouvaient être entièrement dépolarisées
par une agitation de la solution externe.
Cet état de choses est attribué à la présence
d'une pellicule inerte à la surface des
membranes pouvant être enlevée par abra
sion. Les mêmes membranes ont, en outre,
accusé une variation de la résistance élec-
trolytique entièrement inusitée avec la con
centration d'une solution électrolytique
équilibrante. Les résultats sont traités quan
titativement en fonction de la pellicule
inerte ainsi que d'une région intermédi
aire de faible mais changeante concentra
tion d'ions fixes. Bien que la pellicule
inerte n'ait de toute évidence qu'une épais
seur d'une fraction d'un micron, elle est
pourtant suffisament épaisse pour expliquer
les courants limites anormalement bas qui
ont été observés. La région intermédiaire
est tenue pour la cause principale de la
surtension élevée constatée lorsque le cou
rant limite est dépassé.
Ces membranes à échange d'ions anormales
ont une autre propriété curieuse: leur
rendement exceptionnellement médiocre
dans de l'eau contenant du sulfate. Ce
phénomène peut également s'expliquer par
le fait qu'une pellicule inerte forme un
écran à l'intérieur de la membrane active.
On peut également induire une polarisa
tion par concentration anormale dans les
membranes en les exposant à l'absorption des
contre-ions polymères qui les pénètrent à
un degré restreint. Ce phénomène peut se
produire dans le traitement par électro
dialyse de l'eau contenant des impuretés
organiques. On peut interpréter cet effet
comme étant la désactivation de la surface
de la membrane; ce point de vue est étayé
sur l'accroissement frappant de l'anomalie
constatée lorsque des ions hydroxyles furent
transportés à travers une membrane à
échange d'anions chargée d'impuretés pro
venant d'un polyélectrolyte appartenant à
la catégorie du phénol polyhydrique ("acide
humique") . Les membranes ainsi affectées
accusent également une variation marquée
de la résistance avec une concentration
électrolytique externe, et les graves surten
sions qui risquent de survenir peuvent
constituer un obstacle à l'application de
l'électrodialyse au traitement des eaux sa
lines de surface ou de puits à faible
profondeur dans les régions tempérées.
Les travaux de mise au point des mem
branes effectués dans le laboratoire de
l'auteur ont eu, entre autres, pour objet
principal l'élimination de l'anomalie struc
turelle sus-mentionnée et la production
d'éléments peu sensitifs aux impuretés
organiques. La sensitivité aux impuretés
organiques des produits résultants a été
évaluée à l'aide des essais en laboratoire et
par l'électrodialyse d'eau souillée dans une
installation pilote indépendante. Ces deux
essais ont révélé que les objectifs que l'on
s'était fixés dans les travaux de mise au
point de membranes ont été atteints.
233
 Некоторые Явления, Связанные
с Концентрационной Поляризацией
при Электродиализе
Б. А. Кук
Соединенное Королевство
Этот доклад касается ряда послед
ствий концентрационной поляризации,
возникающих при применении электро
диализа к обессоливанию воды. Явле
ния являются неожиданными, посколь-
ко их появление не предусмотрено
простыми теориями, которые изобра
жают перенос вещества на поверхность
раздела мембрана-раствор в виде диф
фузионной пленки однообразной тол
щины, находящейся на стороне жидкой
фазы поверхности раздела. Для того,
чтобы помочь отличить абнормальную
поляризацию от нормальной, в докладе
делаются прогнозы перенапряжения
при силах тока большого диапозона,
причем обращается особое внимание
на удобную в экспериментальном от
ношении систему, где перенос веще
ства происходит путем естественной
конвекции. Не применяется главное
упрощение, будто-бы диффузионные
слои имеют одинаковую толщину, что
несомненно отсутствует в большинстве
практических случаев.
Принимая в расчет колебание толщи
ны диффузионных слоев, которое, как
известно, возникает при естественной
конвекции, указывается на то, что та
кие системы достигают начального
предельного состояния при приблизи
тельно трех четвертях силы тока, по
требной для создания по существу ну
левой концентрации на границе разде
ла фаз по всей активной поверхности
мембраны, причем полное перенапря
жение, обусловленное начальным пре
дельным током сравнительно невелико:
около 80 милливольт. Далее качествен
но обсуждается более практический
случай ячеек электродиализа, питае
мых текучей водой: образуется боль
шая протяженность толщин диффузион
ных слоев, вызывая появление началь
ного предельного состояния при малой
234
части конечной силы предельного то
ка и меньшем, соответствующем ему
полном перенапряжении. Такие неболь
шие перенапряжения могут легко прой
ти незамеченными при работе обычных
аппаратов, которые поэтому можно
считать хорошо деполяризированными.
Этот аргумент объясняет причину об
разования накипи при электродиализе
жестких вод даже тогда, когда аппарат
работает на токе значительно ниже
предельной величины. Эффективность
удаления накипи посредством переме
ны полярности приписывается той же
причине.
Затронута, существующая при элек
тродиализе, проблема смещения pH,
причем большинство наблюдений ука
зывает на то, что при главном электро
лите, состоящем из водного раствора
хлористого натрия, ожидаемое смеще
ние pH у катионитных мембран отсут
ствует. Предполагается, что одно по
лученное противоречивое показание,
объяснялось структурной абнормаль-
ностью мембраны, находившейся в упо
треблении.
Хотя большинство испытывавшихся
мембран при токах, превосходивших
предельную величину, до некоторой
степени отклонялось от прогноза кри
вых перенапряжения, тем не менее их
поведение при более низких токах до
вольно близко приближалось к нему.
Это не относилось к некоторым, нахо
дящимся в продаже, анионитным мем
бранам типа привитого сополимера, у
которых на уровне, превышавшем пре
дельное состояние, возникали абнор-
мально низкие предельные силы тока
и весьма высокие перенапряжения. Эти
мембраны не удавалось полностью де
поляризировать размешивением внеш
него раствора.
Это приходится приписать нахожде
нию на их поверхности инертной плен
ки, которая поддавалась удалению с
помощью шлифовки. Кроме того, у тех
же самых мебран с концентрацией рав
новесного электролитного раствора по
являлись довольно необычные колеба
ния электролитического сопротивления.
Результаты были количественно ана
лизированы в отношении инертной
пленки и промежуточной области низ
кой, но меняющейся концентрации
фиксированных ионов. Несмотря на то,
что толщина инертной пленки не пре
восходит частицы микрона, она, одна
ко, достаточна велика, чтобы объяс
нить абнормально низкий уровень пре
дельных токов, который был найден.
Предполагается, что за высокое пере
напряжение, возникающее при превы
шении величины предельного тока,
главным образом ответственна проме
жуточная область.
Другой любопытной особенностью
этих абнормальных ионитных мембран
является их исключительно плохая ра
бота в воде содержащей сульфаты; это
тоже можно объяснить присутствием
инертной пленки, которая экранирует
внутреннюю часть активной мембраны.
Аномальная концентрационная по
ляризация может быть также индуци
рована в мембраны, подвергая их аб
сорбции частично проникающих проти-
воионов. Это может происходить при
обработке диализом воды, которая со
держит органическое загрязнение. Эф
Algunos Fenómenos Relacionados
con la Polarización de
ción en la Electrodialisis
В. A. Cooke
Reino Unido
Este trabajo se refiere a diversas conse
cuencias de la polarización de concentración
que resultan de la aplicación de la electro-
diálisis a la desalinización de agua. Los
fenómenos ocurren en forma inesperada,
ya que el acaecimiento de los mismos no es
pronosticable mediante las teorías simples
que caracterizan a la transferencia de masa
фект поддается объяснению деактиви-
зацией поверхности мембраны, и это
мнение подкрепляется бросающимся в
глаза увеличением аномалии, которая
появляется при переносе гидрокснль-
ных ионов через анионитную мембра
ну, загрязненную полиэлектролитом,
принадлежащим к классу многоатомно
го фенола («гуминовая кислота>). По
добным образом пораженные мембраны
подвержены также заметным колеба
ниям сопротивления с внешней элек
тролитной концентрацией и сильным
перенапряжениям, которые могут огра
ничить применение электродиализа для
обработки соленых поверхностных и
неглубоких родниковых вод в зонах
умеренного климата.
Работа по усовершенствованию мем
бран, проводившаяся в лаборатории
автора, помимо всего прочего, имела
главной целью избежание вышеуказан
ной структурной абнормальности и из
готовление материала, обладающего
меньшей чувствительностью к органи
ческим загрязнителям. Окончательные
продукты подвергались анализу с по
мощью лабораторного испытания на
чувствительность к загрязнению, а так
же посредством электродиализа загряз
ненной воды, который производился
на самостоятельной опытной установке.
Оба испытания показали, что намечен
ные цели, связанные с усовершенство
ванием мембран были достигнуты.
Concentra
en la interfaz membrana/solución en tér
minos de una película de difusión de
espesor uniforme confinada al lado líquido
de la interfaz. Para facilitar la distinción
entre polarización anormal y normal, se
anticipa el sobrepotencial a distintas inten
sidades de corriente, prestando atención
especial al sistema experimentalmente con
235
 veniente, en el cual la transferencia de masa
ocurre por convección natural. La principal
simplificación de la cual se prescinde con
siste en suponer la uniformidad del espesor
de la capa de difusión, lo cual ciertamente
no ocurre en la mayoría de las situaciones
prácticas.
Teniendo en consideración la variación
en el espesor de la capa de difusión que se
sabe tiene lugar en la convección natural,
se demuestra que tales sistemas alcanzan
una condición limite incipiente cuando la
corriente llega a las tres cuartas partes del
valor requerido para producir esencialmente
concentración interfacial nula sobre la tota
lidad de la superficie de la membrana
activa; pero, a esta corriente incipiente limi
tante, el sobrepotencial total es muy peque
ño, alrededor de 80 mV. Se expone en forma
cualitativa el caso más práctico de células
de electrodiálisis alimentadas con agua co
rriente: se produce una variación mayor
en el espesor de la capa de difusión, la
cual hace que la condición incipiente limi
tante ocurra a una fracción menor de la
corriente límite final y a un sobrepotencial
total correspondiente más bajo. Estos sobre-
potenciales tan bajos, bien podrían pasar
inadvertidos en el funcionamiento de apara
tos prácticos los cuales, por consiguiente, se
considerarían suficientemente despolariza
dos. Esto explica la formación de costra
que acompaña a la electrodiálisis de aguas
duras, aun cuando el aparato funcione a
una corriente aparentemente bien inferior
al valor limite. La eficacia del descostra-
miento mediante la inversión de la polari
dad es atribuida a la misma causa.
Se comenta el problema de las variaciones
de pH en electrodiálisis, indicando el peso
de las pruebas que. en agua que contiene
cloruro de sodio como electrólito principal,
no se produce la variación esperada de pH
en las membranas de intercambio catiónico.
Se sugiere que un hallazgo contradictorio
registrado puede atribuirse a una anormali
dad estructural en la membrana empleada.
Aunque la mayoría de las membranas
probadas se desviaron en cierto grado de la
curva de sobrepotencial anticipada a co
rrientes superiores al valor límite, el com
portamiento de las mismas a corrientes
menores fue razonablemente bien explicado.
Tal no fue el caso de ciertas membranas
de intercambio aniónico comerciales del
tipo de copolímero injertado, las cuales
evidenciaron corrientes límites anormalmen
te bajas y sobrepotenciales excesivamente
altos por encima de la condición límite.
Estas membranas no pudieron ser completa
mente despolarizadas mediante la agitación
236
de la solución externa. Esto se atribuye a la
presencia de una película inerte sobre sus
superficies, la cual pudo ser removida me
diante la abrasión. Además, las mismas
membranas evidenciaron una variación
sumamente anormal en la resistencia elec
trolítica con respecto a la concentración de
la solución electrolítica equilibrante; los
resultados se explican cuantitativamente
considerando el efecto de la película inerte,
juntamente con una región intermedia de
concentraciones iónicas fijas bajas, pero
diversas. El espesor de la película inerte,
evidentemente, no es de más de una frac
ción de micrón; sin embargo, esto es sufi
ciente para justificar las corrientes límites
anormalmente bajas medidas. La región
intermedia es principalmente responsable
de los altos sobrepotenciales experimenta
dos cuando se excede la corriente límite.
Otra propiedad curiosa de estas membra
nas anormales de intercambio iónico es el
desempeño excepcionalmente deficiente de
las mismas en agua que contiene sulfatos;
esto también puede explicarse en virtud de
la existencia de una película inerte que
cubre el interior activo de la membrana.
También puede inducirse una polariza
ción de concentración anormal en las mem
branas, sometiendo a las mismas a la
absorción de contra-iones poliméricos que
penetran en un grado limitado. Esto puede
ocurrir en la electrodiálisis de agua conte
niendo impurezas orgánicas. Este efecto
puede interpretarse como una desactivación
de la superficie de la membrana y esta
hipótesis es apoyada por el sorprendente
aumento de la anomalía observado en el
caso de iones oxhidrilos transportados a
través de una membrana de intercambio
aniónico contaminada con poli-electrólito
del tipo del polioxi-fenol ("ácido húmico").
Las membranas afectadas de esta manera
también muestran una gran variación en
la resistencia con la concentración del elec
trólito externo, y los serios sobrepotenciales
que pueden producirse podrían constituir
un obstáculo para la aplicación de la
electrodiálisis al tratamiento de aguas salo
bres de superficie o de pozos poco profundos
en regiones de clima templado.
El trabajo de desarrollo de membranas
realizado en el laboratorio del autor tuvo
como principales objetos, entre otras cosas,
evitar la anormalidad estructural discutida
más arriba y producir material de escasa
sensibilidad a las impurezas orgánicas. Los
productos resultantes fueron evaluados por
medio de una prueba de laboratorio para
determinar la sensibilidad a la contamina
ción, así como también por electrodiálisis
de agua contaminada efectuada en planta fijados para el trabajo de desarrollo de
piloto independiente. Ambas pruebas indi- membranas,
carón que se hablan alcanzado los objetivos

237
Desalination by
Extraction
R. B. Beckmann and W. B. Ellis
United States of America
The object of this paper is to present a
brief discourse on the use of liquid-liquid
solvent extraction as a desalination process
for the production of potable water from
saline and/or brackish water supplies. It is
our intention to trace some of the signifi
cant historical developments, discuss the
current status, and perhaps hazard a guess
concerning the needs for continued develop
ment of solvent extractive desalination
processes.
Solvent extraction is one of the funda
mental mass transfer processes used for the
separation, purification, or other alteration
of a physical mixture of chemicals by
means of the preferential solubility of the
various components between two immiscible
or partially miscible solvents. As a means of
separation and/or purification it must com
pete with all other available processes, such
as distillation, evaporation, ion-exchange
adsorption, dialysis, or what have you, on
an economic basis of comparison. Extrac
tion processes are among the oldest known
to nature, but compared to many of the
mass transfer and separation processes,
liquid-liquid solvent extraction is, indus
trially, an infant. It is historically inter
esting to note that between 1910 and 1930
only six patents were issued in the United
States for solvent extraction equipment and
fifty were issued between 1930 and 1940
(ref. 10) indicating that solvent extraction,
as a commercial separation processing oper
ation, may be considered about 35 years
of age. Since 1940 it has become one of the
"standard" separation processes to be con
sidered in any chemical processing scheme
involving separation and/or purification of
chemical species.
The ideal solvent extraction desalination
process is simple to visualize even though
economic realization is quite difficult. Figure
Liquid-Liquid
84 shows a schematic representation of the
basic steps involved in desalination by
liquid-liquid extraction. Essentially, the
solvent and saline solution which are
mutually immiscible, or at most partially
miscible, are contacted in a conventional
extraction apparatus (Step I) . The two
liquid phases are separated by gravity or
centrifugal means and separately processed
(Steps II and III) for solvent recovery, for
solvent recycle to Step I, and for product
production: a brine, or solid salt compo
nent, and potable water. The solvent recov
ery operations (Steps II and III) may be
any of the conventional mass transfer
separation techniques such as distillation,
evaporation, adsorption, or even another
solvent extraction with a different solvent.
Figure 84 actually presents two distinctly
different extraction possibilities, depending
upon the physicochemical characteristics of
the solvent selected for the basic extraction
step. If the solvent has a preferential solu
bility characteristic for salt, compared to
water, the extract or solvent phase will be
the extracting solvent as the major com
ponent with the salt (or brine) as a solute.
The residual or raffinate phase will be the
water phase with the salt concentration
reduced to the "potable" level and contain
ing some solvent, present as a solute. In this
case. Step II in Figure 84 will involve the
removal of a small quantity of solvent from
the raffinate (water) phase to produce the
potable water, and the removal of a rela
tively large amount of solvent from the
residual brine or salt which is to be dis
carded. On the other hand, if the solvent
has a preferential solubility for water,
compared to the salt component, the extract
phase will be the bulk solvent stream con
taining dissolved water (nearly salt-free)
as the solute, and the raffinate phase will
239
 SALINE SOLUTION ©■ SOLVENT

LIQUID - LIQUID -9
EXTRACTION
r
SALT FREE WATER SOLVENT
+ +
SOLVENT SALT OR BRINE

1 SOLVENT 1
n m
SOLVENT SOLVENT
RECOVERY RECOVERY

t t
POTABLE SOLVENT SALT OR
WATER FOR BRINE
RECYCLE (DISCARD)
FIGURE 84. SCHEMATIC DIAGRAM FOR THE LIQUID-LIQUID
EXTRACTION OF SALINE WATER.

be a more cencentrated brine solution con brackish solution followed by recovery of

taining a small amount of solvent, present
as a solute. In this case, the production of
the potable water component requires sepa
ration from a relatively large amount of
solvent (extract phase) and the recovery of
a lesser amount of solvent from the brine
discard (raffinate phase) stream. In essence,
the two extraction schemes reverse the
function of the extract and rafnnate phases
insofar as the production of potable water
is concerned.
All of the fundamental research and
development work reported to date on
desalination by solvent extraction has util
ized the latter approach, namely, that of
extracting pure water from the saline or
the potable water from the extract phase.
Immiscible solvents that extract salts but
not water have not yet been developed for
use in desalination processes; at least, none
have been reported in the literature. Such
schemes would have the difficult problem-
of handling large volumes of solids or
sludge, problems of severe corrosion, and
the usually difficult and relatively expensive
solvent recovery problems from such resi
dues. Accordingly, the following section will
deal exclusively with the research, develop
ment, and current status of solvent extrac
tion desalination processes which extract
water from the saline feed solution to
produce the final potable water supply.

FUNDAMENTALS OF SOLVENT SELECTION

The pioneering work, directed toward
the delineation of the necessary character
istics of suitable solvents for the desalina
tion of saline water supplies, is that of
Dr. Donald W. Hood and coworkers of the
Texas A. & M. Research Foundation. In
fact, all of the currently proposed pilot
processes are based in whole or in part on
the pioneering solvent development work
of this group. In 1953, Hood and his co
workers began their development work
under contract to the Office of Saline Water
of the U.S. Department of the Interior,
and their works have been published in a

240
series of articles, and by reports of the
Office of Saline Water (refs. 5-8, 11) .
During the course of their work, Hood
and his coworkers evaluated the solvent
properties of about 400 organic compounds,
many of them synthesized for the project,
and were able to formulate certain molecu
lar structure rules to facilitate (he search
for effective solvents. Their studies have
indicated that the best solvents are com
pounds containing one or more highly
FIGURE 85. TYPICAL SOLUBILITY DIAGRAM FOR
DESALINATION SOLVENT.
As shown in Figure 85, if a typical sol
vent were contacted with a saline solution
at a lower temperature such that the solvent
phase would contain 25 to 50 per cent
water, and this extract solution were then
heated to an elevated temperature, the
mixture would separate into two phases: a
solvent phase depleted in water for recycle,
and a water-rich phase to be stripped of
the remaining solvent to produce potable
water.
The most suitable solvents indicated by
the Texas A. & M. Research Foundation
work are the secondary and tertiary amines
with five or six carbon atoms. The amino
nitrogen group in these compounds con
tributes to the center of high basicity and
a resultant rapid change in solubility with
electronegative atoms, such as oxygen or
nitrogen, which are capable of forming
hydrogen bonds with water at a lower
temperature and of breaking the bonds to
release water as a separate phase at an
elevated temperature. Thus compounds in
which water solubility decreases with increas
ing temperature show the most promise.
Figure 85 shows a typical solubility diagram
for an attractive solvent.
temperature; this property is enhanced by
multiple alkyl substitution on or near the
nitrogen atom. By using mixtures of the
secondary and/or tertiary alkyl amines, a
"solvent" can be formulated to meet the
varying needs of individual saline waters
and extraction temperatures. The solvent
properties of the amines or the mixed
amines are not without disadvantages: how
ever, magnesium removal is generally re
quired as a pretreatment step because of
the high pH of the amine water solutions,
and the amines tend to hydrolyze and in
some cases cause an ionic imbalance due to
the formation of amine hydrochlorides. The
major advantage of the amine systems is
the moderate extraction temperature (18°
to 55°C) , followed by a separation tempera
ture of only 15° to 20°C above the extrac
tion temperature.
In brief, the most attractive solvents
reported to date seem to be the secondary
and tertiary alkyl amines, either alone or
in mixture, ethereal oxygen compounds,
and perhaps some of the medium chain
length (4, 5, and 6 carbon atoms) alcohols;
although in the latter cases the advantages
are related more specifically to solvent
recovery methods than to extraction advan
tages per se. An excellent summary of the
solvent characteristics as well as the thermo
dynamics of solvent selection for desalina
tion extraction processes is given in the
Saline Water Research and Development
Progress Report No. 55 published by the
Office of Saline Water (No. PB 181036),
based on this work by Hood and his co
workers at Texas A. & M. Research Founda
tion (ref. 6) .

SOLVENT EXTRACTION PROCESSES

As indicated in Figure 84, any solvent ods, the cost of solvent recovery must be
extraction process for the desalination of reduced to the range of 5 cents per 1,000
saline waters is essentially composed of gallons of product water, or less.
three primary steps: (1) the basic extrac While there are probably several solvent
tion step in which the solvent selectively extraction desalination processes in various
extracts water with a minimum of salt stages of proprietary research and/or pilot-
transfer to the solvent phase, (2) separa scale development, there are only two
tion of the potable water component from processes that have been extensively reported
the solvent and the removal of the final in the literature. In 1963 the Brown and
traces of solvent from the product, and (3) Root Corporation constructed a 2,000 gpd
the removal of any dissolved solvent from potable water pilot plant for the aforemen
the more concentrated saline (raffinate) tioned Texas A. & M. Research Foundation,
phase before it is discharged. There will, under contract to the Office of Saline Water.
of course, be the usual heat interchange The pilot plant was designed on the basis
auxiliaries to maintain a high level of heat of the pioneering work of Hood and his
economy and lower the overall processing coworkers and the U.S. patent granted to
costs. The major difficulty with solvent D. W. Hood and R.R.Davison (ref. 2) .
extraction processes so far has been the Table XXXVI summarizes some of the
relatively high cost of solvent recovery. To pertinent design features of this pilot plant
compete with alternate desalination meth (refs. 12-14) :
TABLE XXXVI. Texas A. & M. Pilot Plant for Desalination by Extraction
Design capacity 2,000 gpd potable water
Feed water 6.000 ppm brackish water
Extraction solvent Mixture of triethylamine and dietbylmethyl amine, ratio variable
Extraction temperature Isothermal, between 18° and 60°C
Separation temperature 20°C above extraction temperature up to 70°C
Solvent recovery Air stripping of both product streams

The Texas A. & M. pilot plant utilizes a
variable solvent composition mixture to
adjust to any desired extraction tempera
ture within the range indicated, according
to the condition and type of saline feed
water being processed. Facilities are also
being provided for magnesium removal
from the feed water if this is required.
The separation temperature is dictated by
the solvent mixture and the extraction
temperature, and is at most about 20°C
higher than the extraction temperature.
This permits low level heat sources to be
used throughout the process. The plant
was originally designed to operate with hot
water from a gas fired heater, but a solar
heater capable of supplying the necessary
energy is reportedly being developed. A
unique feature of the pilot plant is the
recovery of the solvent from the potable
water product and the saline residue bv air
stripping. In the reported operating scheme,
the product water and the raffinate streams
at their separation temperatures are passed
through individual contacting columns,
countercurrent to an air stream. The air
streams laden with amines are in turn
contacted countercurrently to the feed water
which returns the amines to the extraction
system. The cost for this reported strip
ping operation is estimated to be less than
5 cents per 1.000 gallons of potable water
product.
The originally anticipated problem of the
possible toxicity to humans and animals
due to residual amine levels in the potable
water has not materialized. Toxicity studies
begun in 1960 have shown that albino rats
ingesting drinking water containing 500 ppm
amine (about 250 times that designed for
the plant effluent) have suffered no ad
verse effects. The one difficulty with the
Texas A. & M. process, as conceptually
designed, is the apparent inability to handle
high salt concentration saline waters (such
as sea water) at a low cost level. When
handling high salt concentration saline
feeds, a high solvent circulation rate is
required. This is necessary because the
equilibrium water content in the solvent
decreases with increasing salt content, at a
constant temperature. Fortunately, the
higher salt content also lowers the critical
solution temperature (Fig. 84), and a
lower operating temperature may offset
this factor to some extent. It appears that
the Texas A. & M. process is best suited
to the use of large quantities of low quality
energy.
A recent patent entitled "Desalination by
Solvent Extraction", issued to C. N. Kim-
berlin, Jr., et al, and assigned to the Esso
Research and Engineering Company (ref.
9) , is specifically pertinent to this point of
operation temperature. The Kimberlin pat
ent specifically relates to the multiple batch
or continuous countercurrent extraction of
saline waters using amine or amine-mixture
solvents with a temperature gradient im
posed upon the solvent extraction system.
The Kimberlin patent illustration shows a
conventional continuous countercurrent ex
traction column operating with the saline
feed entering the midsection of the column
at an intermediate temperature of about
1?°C. The bottom of the column, the sol
vent entry region, operates at a lower
temperature of 5°C, thus permitting dis
charge of a higher salt content brine. A
heater is located in the top section of the
column, providing the heat source and
raising the top section's internal tempera
ture to about 20°C, causing internal reflux
ing due to the lowered water solubility in
the solvent as the temperature is increased.
The alleged advantages of this mode of
operation are related to the increased salt
concentration tolerable at the raffinate exit
end of the extraction operation. This toler
ance permits the use of the amine solvents,
such as those used in the Texas A. &. M.
pilot plant, with high concentration saline
waters, such as sea water, plus the advan
tage gained above the feed point from the
refluxing caused by the internal heat input
at the extract exit end of the column. The
Kimberlin extraction scheme could, of
course, be used with any of the conventional
methods of solvent recovery from the raffi
nate saline residue and the potable water
product stream, including the air-stripping
method utilized by Texas A. & M. It is not
known whether the Kimberlin extraction
scheme has been incorporated into a com
plete pilot plant or whether cost estimates
have been made to evaluate its potential.
There will be an added cost, possibly offset
by the lower solvent circulation require
ments, in the extraction step due to the
low temperature requirements at the raf
finate exit end of the column. The solvent
recovery from the raffinate will be affected
by the lower temperature of the raffinate
leaving the extraction column.
B. B. Carr of the Callery Chemical Com
pany (ref. 1) has described a novel and
unique approach to desalination by solvent
extraction. The Carr-Callery process com
bines solvent extraction and hydrocarbon
flash vaporization to accomplish desalina
tion in a multistage countercurrent contact
ing processing operation. A schematic rep
resentation of the Carr-Callery process is
shown in Figure 86 which, for simplifica
tion, shows a three-stage unit. The saline
water feed, after contacting the enriched
solvent in a refluxing section, passes coun
tercurrent to the solvent in a multistage
contacting battery. The temperature within
each stage increases as the brine flows
through the system (from left to right in
Fig. 86) . The fresh solvent leaving the
final water solvent separation unit for
recycle flows from right to left through
the extraction battery, finally contacting
the saline feed in the refluxing section.
In each of the extraction batteries, hydro
carbon vapor is flashed, passing directly to
the upper section of the unit, the separation-
condensation section. Each increment of
hydrocarbon vapor removal increases the
water-carrying capacity of the solvent. The
final brine solution leaving the last extrac
tion unit is sent directly to solvent recov
ery facilities: at the same time, the potable
water stream leaving the separator is simi
larly freed of solvent traces through con
ventional solvent recovery schemes. The
enriched solvent leaves the reflux section and
passes successively through the separation-
condensation zones (from left to right in
Fig. 86) of each extraction unit, where it
contacts the vaporized hydrocarbon from
the extraction section immediately beneath
it. The hydrocarbon condenses, and part of
the water separates out because of the
salting effect of the hydrocarbon. If amine-
type solvents are used, some additional
243
 water will separate because of the increas-
ing temperature in each successive unit,
The solvent plus water is pumped as a
two-phase mixture through the successive
SAUNE FEED
S-C ZONES OF SEPARATION -CONDENSATION
EX : LIQUID -LIQUD EXTRACTION ZONES
H : HEATERS FOR TEMPERATURE ADJUSTMENT
FIGURE 86. SCHEMATIC DIAGRAM OF THE CARR-CALLERY
DESALINATION PROCESS.
Carr (réf. 1) illustrates the process capa
bilities for a diisopropyl amine-propane
system and an n-butanol-butane system
operating on sea water. The following is a
calculated process operating conditions for
a 13-stage evaporation-extraction system.
TABLE XXXVn.
Process Operating Conditions
Carr-Callery Desalination Process
System: Diisopropyl amlne-propane sea water
13 evaporation-extraction stag-ca
Salt content: Feed 35,000 ppm; Brine-120,000
ppm; Water-600 ppm
Temperatures: Feed 55°F: Brine-99°F;
Water-99°F
Solvent in brine and water,
final producta: 5.0 ppm
Feed water flow : 1.41 lbs/lb of final water
Capital cost of 10 mgd plant: $6,000.000
Operating coat of 10 mgd plant: $.60/1,000 gala
The process operating conditions used by
Carr in illustrating the potential of the
process, as shown in Table XXXVII, are not
necessarily the optimum. Conventional
steam stripping of the solvent was employed
to reduce the solvent content of the saline
residue and the potable water to the limits
shown. In all probability further cost reduc-
244
units until the final temperature adjust
ment is made and the final separation
accomplished in the separator,
tions could be made by utilizing alternate
solvent recovery methods, such as the air
stripping procedures used in the Texas A.
& M. pilot plant. The figures do, however,
illustrate the potential of the process. Can-
also points out that the same effect of the
hydrocarbon salting out procedure could be
achieved by evaporation of any part of the
solvent system in successive stages. This sys
tem would be preferred for those solvent
systems in which the water solubility in
creases with increasing temperature. This
latter modification is shown schematically
in Figure 87, and has been considered for
the system acetone-isobutanol, in which
acetone is the vaporizing solvent. In this
case, the isobutanol dissolves more water at
increasing temperatures and the water solu
bility is increased by the addition of
acetone.
The Carr-Callery approach to solvent
desalination presents a novel approach to
the use of solvent extraction methods for
desalination and offers considerable promise
for heat economies and process versatility.
Because of the combination evaporation-
extraction units employed, the capital costs
of this section of the plant will be greater
than those of a corresponding simple ex-
traction plant, but it should not be a sig
nificant increase on the final operating
costs. The Carr operating estimate of 60
cents per 1,000 gallons of final product
water certainly places this processing scheme
in a position to compete with alternate
extraction processes. Many alternate meth
ods have been proposed and are being
developed at the present time.
In presenting the above developments in
the use of liquid-liquid extraction processes
for desalinating brackish and sea waters,
only those processes which are fundamen
tally extraction processes have been consid-
245
 ered. Combination processes such as those
employing extraction combined with semi-
permeable membranes have not been con-
FUTURE DEVELOPMENTS
To hazard a guess on the direction of
future developments borders on the fool
hardy and should be done only with great
caution. The solvent chemistry to date has
been almost entirely directed toward the
selective extraction of the water; additional
work is needed to explore fully the possibil
ity of developing salt selective solvents, un
promising as this may seem at the moment.
The dual solvent route for the selective
extraction of the water shows the most
promise at the moment in that solvent
mixtures can be formulated for specific
saline water conditions and heat supplies
available.
At the present stage of development,
solvent extraction possibilities are most
vulnerable to cost considerations in the
areas of solvent recovery and required feed
pretreatment, particularly when these oper
ations are considered along with the temp
REFERENCES
1. Carr, В. В.: "Saline water conversion
via extraction", Chem. Engr. Progress,
vol. 59 no. 12 (Dec. 1963) pp. 59-62.
2. Davison, R. R.; Hood, D. W.: "Mixed
solvents for saline water extraction",
U.S. Patent no. 3,088,909 (May 7, 1963).
3. Davison, Richard R.; Hood, Donald W.:
"Desalination by liquid extraction",
National Academy of Sciences, N.R.C.,
publ. 568 (1958) pp. 408-416.
4. Davison, Richard R.; Smith, W. H., Jr.;
Hood, Donald W.: "Structure and amine
water solubility in desalination by sol
vent extraction", Journal of Chem.
Engr. Data, vol. 5 no. 4 (Oct. 1960) pp.
420-423.
5. "Development of the solvent demoral
ization of saline water". Office of Saline
Water, U.S. Department of the Interior,
Rept. no. PB 161769 (1960) .
6. Ibid., Rept. no. 181036 (1961) .
7. Hood, Donald W.; Davison, Richard R.:
"The place of solvent extraction in
SUMMARY OF DISCUSSION
It was commented that at Texas A. 8:
M„ studies indicated no adverse effects were
observed on rats after these rats had drunk
water containing as high as 1000 ppm of
246
sidered since the extraction role is a
secondary one.
erature level of energy interchange for
maximum efficiency. Single and dual solvent
systems which avoid the necessity for mag
nesium removal or any pretreatment step
prior to extractive processing should be
developed. Combination evaporation-
extraction methods for temperature and
solvent control seem attractive, particularly
if solvent recovery can be effected at a low
temperature level to maximize heat econ
omies. These schemes will, however, require
increased water-carrying capacity by the
solvent or solvent mixture.
In essence, solvent extraction desalination
processes are in their infancy insofar as
development is concerned. They look at
tractive but are particularly vulnerable to
solvent costs and solvent losses. Develop
ments in these areas will determine the
future potential.
saline water conversion", American
Chemical Society, Advances in Chem
istry Series, no. 27 (1960) pp. 40-49.
8. Isbell, A. F.; Hood, Donald W.: "Syn
thesis of solvents for water desalination,
amines and others", Journal of Chem.
Engr. Data, vol. 7 no. 4 (Oct. 1962) ,
pp. 575-580.
9. Kimberlin. Jr., C. N.. et al: "Desalina
tion by solvent extraction", U.S. Patent
no. 3.177,139 (April 6, 1965) .
10. Morello, V. S.; Poffenbcrger, N.: Ind.
& Engr. Chem., no. 42 (1950) p. 1021.
11. "Research on liquid-liquid extraction
for saline water conversion", Office of
Saline Water, U.S. Department of the
Interior, R&D Progress Rept. no. 22
(1958) .
12. Saline Water Conversion Report-1961 ,
Office of Saline Water, U.S. Department
of the Interior (Jan. 1962) .
13. Ibid., 1962 (Jan. 1963) .
14. Ibid., 1963 (1964) .
tertiary amines. However, when the rats
died and were aulopsied, indications were
that they had died from the alkalinity
caused by the amines. Further comment on
this process pointed out the feasibility of
using waste heat. Since the temperature
gradient required to operate solvent extrac
tion process is very low, solar energy has
been employed with some success. Removal
of solvent from product is best accom
Dessalement Par
Liquide/Liquide
R. B. Beckmann et W. В. Ellis
Etats-Unis d'Amérique
Les procédés d'extraction par solvant,
liquide/liquide, pour le dessalement des
eaux saumâtres et salines, afin de produire
de l'eau potable, ne sont pas arrivés au
développement important ou au succès éco
nomique des procédés concurrents, mais la
technologie de sélection des solvants et des
procédés améliorés de leur récupération
amènent les possibilités de dessalement par
solvant à une position qui est presque
compétitive. Les travaux de recherche aux
Etats-Unis, jusqu'à maintenant, se sont
portés sur l'extraction sélective de l'eau
pour obtenir le produit potable; on ne
mentionne, à l'heure actuelle, aucun travail
qui extraie le sel en tant que moyen pour
arriver au produit final d'eau potable.
Les solvants préférés sont les amines
secondaires et tertiaires, les composés éthé-
plished by steam stripping although air
stripping is fairly effective. The agitation
designed for the mixers in the pilot plant
were found to be superfluous and elimina
tion of agitators would result in considerable
cost savings.
Extraction
risés d'oxygène, et des alcools aliphatiques
sélectionnés. Des mélanges de solvants sem
blent particulièrement prometteurs. La plus
grande partie des travaux de développe
ment actuels se concentrent sur les méthodes
les plus économiques de récupération des
solvants et d'échange de chaleur pour
améliorer l'efficacité thermique. L'extrac
tion par solvant, avec un gradient imposé
de températures ou des compositions va
riables de solvants dans le cadre du pro
cédé d'extraction, augmentent les limites
de fonctionnement et les récupérations
possibles. Le prix de revient des installa
tions de dessalement à extraction par sol
vant, sur une grande échelle, est, à l'heure
actuelle, de l'ordre de 60 cents par 1.000
gallons de produit (environ $0,16 par m") .
247
 Опреснение Посредством Жидкостно-
Жидкостной Экстракции
Р. Б. Бекман и У. Б. Эллис
Соединенные Штаты Америки
Процессы экстракции, типа жидкость-
жидкостный растворитель, для опрес
нения солоноватых и соленых вод и
получения источников питьевой воды,
не достигли широкого развития и эко
номического успеха по сравнению с
конкурирующими методами; однако,
технология, связанная с выбором раст
ворителя и усовершенствованные про
цессы регенерации растворителей, при
ближают способ опреснения посредст
вом растворителей к конкурентоспо
собному положению. Исследователь
ская работа в Соединенных Штатах до
сих пор обращала главное внимание
на селективную экстракцию воды для
выработки питьевого продукта; до сих
пор не было никаких сведений о ка
кой-либо работе по селективному экс
трагированию соли, как пути к окон
чательному продукту питьевой воды.
Предпочитаемыми растворителями яв
La Desalinizacion por el Metodo
Extracción Liquida-Liquida
R. В. Beckman у W. В. Ellis
Estados Unidos de America
En materia de desalin ización de aguas
salobres o salinas para producir agua pota
ble, los sistemas de extracción líquida-
liquida por medio de disolventes no han
alcanzado el desarrollo extenso o el éxito
económico de los sistemas competidores,
pero la tecnología relativa a la selección de
disolventes y el mejoramiento de los mé
todos de recuperación de estos últimos están
transformando las posibilidades de desali-
248
ляются вторичные и третичные амины,
эфирно-кислородные соединения и не
которые алифатические спирты. Сме
шанные растворители кажутся наиболее
целесообразными. Большинство работ
по усовершенствованиям в этой обла
сти в настоящее время сосредоточено
вокруг более экономичных методов ре
генерации растворителей и теплообмена
для повышения термической произво
дительности. Экстракция растворителя
ми с наложенным температурным гра
диентом и/или переменными составами
растворителей расширяет круг рабо
чих возможностей и регенерации. Экс
плуатационные расходы крупной опре
снительной установки, пользующейся
методом экстракции растворителями, в
настоящее время колеблются в преде
лах 60 центов за 1.000 галлонов прес
ной воды.
de
nización por disolventes, llevándolas a un
punto cercano a la competencia. Hasta la
fecha, la labor efectuada en este campo en
los Estados Unidos ha hecho hincapié en la
extracción selectiva de agua para producir
la calidad potable de este elemento; hasta
hoy, no se ha dado cuenta de trabajo
alguno por medio del cual se haya extraído
selectivamente la sal como medio de con
seguir, en definitiva, agua potable.
 Los disolventes preferidos son las aminas
secundarias y terciarias, los compuestos eté
reos de oxígeno y diversos alcoholes alifá-
ticos seleccionados. Las mezclas de disolven
tes ofrecen particular interés. La mayor
parte de la labor de desarrollo gira actual
mente en torno del descubrimiento de mé
todos más económicos de recuperación de
disolvente y de intercambio calórico para
mejorar la eficacia térmica. La extracción
por medio de disolventes, con un grado
establecido de fluctuación de temperatura
y/o composiciones variables de disolventes
dentro del sistema de extracción, amplía el
campo de operaciones y aumenta el número
de recuperaciones posibles. Los costos de
funcionamiento de las instalaciones de desa-
linización en gran escala por el método de
la extracción por disolventes se aproximan
en la actualidad a 60 centavos por 1.000
galones de agua potable producidos.
249
 Ion-Exchange Pretreatment
W. F. Mcllhenny
United States of America
In the earlier days of saline water conver
sion, no pretreatment of the feed water was
necessary or considered practical. Scales, if
they formed, were accepted as a necessary
evil. Since these scales were almost always
alkaline and relatively nonadherent, they
could be removed by brute force or by
washing the surfaces with acids of various
kinds. Long-term continuous operation was
often not desired, and the cost of the water
produced was relatively unimportant.
Since that time, the growing sophistica
tion in saline water conversion equipment
design and in plant operation has increased
the need for better knowledge of the
reasons for the formation of scale, the
effects of scale on performance, and methods
to remove or prevent the formation of scale.
To reduce the cost of water produced,
higher and higher temperatures are being
considered and greater concentrations of
effluent brine are being attempted. Both of
these procedures require the development
of economical methods for the control of
scales.
Scales are the most troublesome of the
difficulties caused by the dissolved chemi
cals in the feed water. Scale precipitates
on the surfaces and is most damaging when
the scale layer acts as a growing barrier to
the transfer of heat. The scale also narrows
the fluid passages, causes pressure drop
which must be overcome, and, by increasing
turbulence in the liquid, increases entrain-
ment of highly saline droplets.
Other difficulties caused by the dissolved
chemicals are corrosion of the construction
materials and the generation of nonconden-
sable gases which interfere with condensation
of the water product.
The object of a pretreatment of the feed
water is to modify the water so that the
formation of scale is prevented or controlled
and the pretreated water is neither corro
sive nor productive of objectionable gases.
Increased sophistication in plant design
requires increased sophistication in pre
treatment processes, a fact which has all too
often been ignored by the designers and
evaluators of saline water conversion
processes.
Each pretreatment system, however, must
be both reliable and economical. The cost
of pretreatment cannot be more than the
benefit to be gained by decreasing water
cost or increasing process reliability.
The analysis of normal sea water is shown
in Table XXXVIII. Many brackish waters
waters are similar in composition and in
the salts expected to be deposited. Sea
waters vary widely in total concentration,
but only slightly in the proportions of ions
present.
TABLE XXXVin. Normal Sea Water
Concentration
Component ppm arm/liter eqs/llter
Sodium (Na) 10,768 11.036 0.4798
Magnesium (Me) 1,298 1.3S0 0.1094
Calcium (Ca) 408 0.418 0.0209
Potassium (K) 888 0.397 0.0102
Chloride (CI) 19,361 19.841 0.6696
Sulfate (SO.) 2,702 2.769 0.0576
Bicarbonate (HCOa) 148 0.146 0.002S
Total solids 36.175 36.047 0.621
Two major types of scale are found in
saline water conversion equipment. The
alkaline scales, calcium carbonate and mag
nesium hydroxide, form because of the shift
in the HCO, — COg — CO, — H.O equilib
rium at high temperatures. As the equilib
rium is shifted, hydroxyl ion is produced
which can react with the magnesium ion
present in sea water to form magnesium
hydroxide, and the calcium present can react
with the carbonate ion to precipitate as cal
cium carbonate.
251
 The other and more troublesome scale is
calcium sulfate in its various forms. It has
long been known that anhydrous calcium
sulfate (anhydrite) occurs as scale at high
temperatures, and that the dihydrate
(gypsum) occurs as scale at low tempera
tures with the metastable hemihydrate
often being found at intermediate temper
atures. All three forms have been found as
major constituents of scale samples taken
from operating saline water conversion
plants.
Pretreatment methods are available to
reduce the alkalinity of the sea water to
less than one ppm and the oxygen to less
than five parts per billion by adding acid
and degassing properly.
Chlorination will control biological foul
ing, so the chlorinated, decarbonated, de-
oxygenated sea water will be noncorrosive
and nonfouling and will not precipitate
alkaline scales. The principal remaining
pretreatment problem is the control of cal
cium sulfate.
As may be seen from Table XXXVIII, sea
water has more than twice as much sulfate
as calcium on an equivalent basis. The
solubility of any form of calcium sulfate
depends on the product of the concentra
tions of calcium and sulfate. If either con
centration can be lowered, the product is
lowered: the treated water can be heated to
a higher temperature and more water
removed to give a higher output brine
CALCIUM SULI TE SOLUBILITY
The design of evaporative processes for
the conversion of saline waters makes an
accurate knowledge of the solubilities of
the scale-forming compounds imperative.
In conjunction with a recently completed
evaluation by Dow of the multiple-effect,
vertical, falling film distillation process as
operated in the one mgd Office of Saline
Water demonstration plant at Freeport,
Texas, a study was undertaken to deter
mine, using available references, the best
solubility relationships for the various
forms of calcium sulfate in concentrated sea
waters at elevated temperatures.
The most complete information on the
solubilities of calcium sulfate in sodium
chloride solutions was found in a paper by
W. L. Marshall, Ruth Slusher, and Ernest
V. Jones of the Oak Ridge National Labo
ratory ('ref. 9) .
The solubility of CaSO, • 2HaO (gypsum)
was determined by Marshall and bis co
workers at 40° and 60°C and CaSO, (an
hydrite) at 125°, 150°, 175°, and 200°C in
252
concentration.
Cationic-cxchange can be used to lower
the calcium in the feed sea water (sea
water softening) . As in the block flow
diagram, calcium goes onto the resin in the
ion -exchange section releasing sodium which
replaces the calcium in the feed solution.
The calcium does not enter the evaporator
with the feed solution. Fresh water is
separated in the evaporator leaving a con
centrated brine. This brine then flows to
the ion-exchange section and regenerates the
resin by releasing the calcium from the
resin and replacing with sodium.
An ion-exchange system can be designed
to partially remove calcium from the feed
sea water, using the concentrated brine to
regenerate the ion-exchange resin.
The softening of sea water as a pretreat
ment for saline water conversion processes
has been patented (ref. IS) , the process
has been tested under contract to the Office
of Saline Water (ref. 12) , and refinements
in the design and process have been
engineered (ref. 5) .
It is neither necessary nor particularly
desirable to remove all of the calcium from
the feed solution. The removal of only that
part necessary to prevent scale formation
at the temperatures and concentrations to
be expected in the evaporators is all that
is required of the ion-exchange pretreat
ment section.
NaCl — H50 solutions varying from zero to
four molal NaCl. These data, combined
with additional literature values, agreed
with the Debye-Huckel theory at all temp
eratures and over the range of concentra
tions when a function of ionic strength was
used in the correlation. Marshall and his
associates concluded that from the solubil
ity results and the close agreement with the
Dcbye-Huckel theory, it should be possible
to estimate the solubilities of CaSO, and
its hydrates at temperatures between 25"
and 200°C in electrolytes other than NaCl
at ionic strengths up to 7.0.
The solubility of CaSO. • XH.O (follow
ing Marshall, Slusher, and Jones) is:
CaSO, • XH.O Ca" + SO.'-f XH.O
from which the thermodynamic solubility
product is obtained:
K" [=mCa"][mSOr][7Ca**]
[7SO.=] ["H.O] X
where:
_• — thermodynamic solubil-
"p ity product,
mCa**. mSO,- — molal concentrations,
7Ca",7SO," = activity coefficients,
■H,0 = activity of H,0 in the
solution,
X = number of moles of H,0
in the solid hydrate.
Using the Debye-Huckel theory, the solubil
ity quotient was shown to be:
- X log 'H,0
where:
K.,= the solubility quotient,
„• = the thermodynamic solubility
product,
S = the limiting Debye-Huckel
slope,
A = a constant (taken as 13) ,
I — the ionic strength.
The measured values were well correlated
for sodium chloride solutions when A = 1 .5
was chosen. The terms for 'H,0 drop out
when anhydrite is the solid of interest.
The measured and correlated data are
shown in Figures 88 and 89 from the paper
by Marshall, Slusher, and Jones (ref. 9) .
The extreme temperature dependence of
both hemihydrate and anhydrite and the
relative insensitivity of the dihydrate solu
bility to temperature can be seen.
Using values for the thermodynamic
solubility product, the ionic strength, the
limiting Debye-Huckel slope, and the proper
water activity, the solubility coefficient of a
desired form of calcium sulfate can be
calculated at a given temperature in a sea
water or concentrate of a given ionic
strength.
These calculations have been made and
the result is shown for anhydrite in Figure
90 and for gypsum in Figure 91. In both
figures the solubility product has been

NoCI ( molality )
0.01 0.1 C.5 1 2 4 6

1 1 l M 11

125-20Í)°C /

3L 25-10
«0p> о

D«byt •-Huck.lSlo ■■ 2.032

0 0.1 0.2 0.3 0.4 0.5 0.8

Ionic Strength Function, 1—
1 + 1.5 Iй

FIGURE 88. VARIATION OF ACTIVITY (7) WITH IONIC

STRENGTH (I) FOR CaSO, AND ITS HYDRATES IN NaCl — H20
(REF. 28).

253
 Temperature, °C
loo 200 17S 150
l—i r
CaS04-'2H20
lot
hM 2
a.
0.2
P.I
0.05
2.0 2.4
T(°K)
FIGURE 89. THERMODYNAMIC SOLUBILITY PRODUCT OF
CALCIUM SULFATE (REF. 28).
converted to (weight per cent) *, a more use
ful term to a design engineer than molality,
and plotted against the concentration factor.
It is interesting to note that both gypsum
and anhydrite pass through solubility max
ima at several times sea water concentra
tion. It is also quite apparent that the
effect of the other ions in solution (the
ionic strength) cannot be ignored and that
the solubilities of the various forms of
calcium sulfate in pure water solutions are
not reliable guides.
A line of constant ionic ratio can be
drawn in Figures 90 and 91 indicating the
concentration or dilution of normal sea
water without a change in composition.
The intersection of this line with the
solubility lines gives the temperatures at
which sea water of a given concentration
254
ion
—I
2.6 2.8 1.4
x 103
becomes saturated with anhydrite or
gypsum.
These values are replotted in Figure 92 in
which the concentration factor at saturation
of the concentrated (or diluted) sea water
is plotted against the temperature of the
brine. These are the temperatures and
concentrations to which sea water can be
carried without calcium sulfate precipi
tation.
These curves have been checked with the
best available data on the solubilities of
the various crystalline forms of calcium
sulfate in sea water and concentrated sea
water brines. These include the data of
Badger and Associates (ref. 17) , Tanaka,
Nakamura, and Hara (ref. 18) , Langelier
(ref. 8) , Mcllhenny (ref. 13) , Clampett and
Fowler (ref. 4) , and others (refs. 2, 3, 10. 1 1.
14, 15, 19) . Agreement with the curves is, in
general, quite good despite the obvious
difficulty in obtaining meaningful solubility
data at high temperatures in a temperature
dependent system.
If either calcium (as by an ion-exchange
softening (ref. 13)) or sulfate is removed from
the sea water, the solubility product is
changed and the concentration-temperature
FIGURE 90. SOLUBILITY OF CALCIUM SULFATE ANHYDRITE
IN CONCENTRATED SEA WATERS.
relationship is altered. Equal ratio lines
have been drawn in Figure 93 for sea
waters in which 50 per cent and 75 per cent
of the calcium have been removed.
It is known that in the temperature
range of 180° to 220° F, the metastable
hemihydrate (CaSOj • i/2 H,0) is the crys
talline scale form ordinarily encountered.
This form is more soluble at a given
sox CALCIUM
255
 temperature than either gypsum or anhydrite.
It should be noted that Figures 90, 91,
92, and 93 are for the solubilities of the
various forms of calcium sulfate at equilib
rium between the solutions and the solid
phases. They show the safe operating area
within which calcium sulfate scale forma
tion cannot be expected. Any operation
outside these areas depends upon a number
of factors including the kinetics of nuclea-
tion and crystal growth.
In Figure 94 is shown the operating
conditions for the Freeport Demonstration
plant on March 19, 1964, when no scale
was being formed at either end and other
conditions in which anhydrite was found
in the first effect and gypsum in the latter
effects.
During the more than three years of
operation of the Freeport long tube, vertical,
falling film distillation demonstration plant,
more than 30 analyses have been made of
various scales by The Dow Chemical Com
pany; these are shown in Table XXXIX. All
analyses were by X-ray diffraction with
checks by conventional wet methods when
the compounds were amorphous or the
identification in doubt. All five expected
types of scale were found: calcium carbon
ate, magnesium hydroxide, and three forms
of calcium sulfate (gypsum, hemihydrate,
and anhydrite. X-ray patterns were con
firmed by comparison with ASTM standard
patterns.
Aragonite (calcium carbonate) was found
only when a magnesium hydroxide slurry
was being recycled when acid was not being
added before degassing.
Alkaline scales were found in the higher
temperature effects through June 20, 1962,
and are probably indicative of inefficient
deaeration. No alkaline scales have been
found in any samples since this time, al
though the unusual compound Brugmatel-
lite (Mg„Fe (OH) laCOa • 4H,0) was found
in the Freeport first effect in August of
1964.
Anhydrous calcium sulfate has appeared
with monotonous regularity as the principal
constituent of scales from the higher temp-
8C I OO 1 20 1 40 1 60 1 60 20O 220 240 260 260 300
TEMPERATURE "P

257
258
OFALLING
SCALING
AND
94.
FCFIGURE
LTV
FD1M
PRENDREIAPTIORNTS,

DPLANT.
EMONSTRATION
 erature effects and has been found as far a 250°F first effect brine temperature was
down the system as the fourth effect when attempted. Anhydrite is the principal and.

TABLE XXXIX. Selected Scale Analysis (All by X-ray Diffraction)

Date Plant Place Minor Major

6/26/61 Freeport Deaerator CaCOa (Aragonite)
6/13/61 Freeport Effect III CaSO.. SiOa Mg(OH)>
6/13/61 Freeport Effect X SiOj (Quart*) CaSO. • 2HK)
6/18/61 Freeport Effect XI CaSO. • 2HsO
3/8/62 Freeport Effect I Fe»0. (Magnetite) CaSO. (Anhy.)
8/8/62 Freeport Effect XII CaSO. • ttisO
8/6/64 Freeport Effect I Mg«Fe ( 0H ) uCOs • 4HiO
( Brugmatellite)
8/6/64 Freeport Effect XII CaSO. • 2HjO
11/2/64 Freeport Effect I Cu, CujO, Fe CaSO. (Anhy.)
11/2/64 Freeport Effect XII CaSO. • 2H*0
1/7/66 Roswell Effect I Cu, SiOi. Fe Amorphous (Silicates)
1/7/66 Roswell Effect II CaSO. (Anhy.)
1/7/65 San Diego Brine heater CaSO. (Anhy.)
6/17/61 Small vapor Tube sheet SiOa. Fe CaSO. • Vi H.O
compression
4/27/61 Small vapor Tube sheet CaSO. (A) Mg(OH)i
compression

FIGURE 95. ANHYDRITE IN TWO-INCH I. D. STEEL TUBE.

260
in most cases, the only scale compuond
found in the first effect. Anhydrite scale is
shown in Figure 95.
Gypsum has appeared with equal regu
larity in the lower temperature effects and
has been found as far as the tenth effect
when a concentration factor of four in the
twelfth effect was attemped. In Figure 96
the large crystal size of a gypsum sample
taken from a two-inch evaporator tube is
evident.
Hemihydrate has been found only once
and is not considered a major scale under
the conditions of design of the Freeport
plant.
Quartz, the principal crystalline form of
sea water silt, was found in a majority of
the analyses as a minor or trace component.
FIGURE 96. GYPSUM FROM TWO-INCH I. D. TUBE.
Magnetite, the iron oxide formed when
oxygen is restricted, also occurred as a
minor constituent.
It can be concluded that in the Freeport
vertical falling film plant the loss of heat
transfer efficiency in the first effect is
caused by the formation of anhydrite and
the loss of efficiency in the lower tempera
ture effects caused by the formation of
gypsum.
In addition, analyses of scales from
several other operating conversion plants
have been undertaken and are shown in
Table XXXIX. Anhydrite has been found as
the major constituent on a sample of scale
from the brine heater of the Point Loma
flash plant and also from the second effect
of the Roswell vapor-comprcssion plant.
 100

1 1
0.01 0.1 1
Total Solution Normality

FIGURE 97. VARIATION IN SELECTIVITY COEFFICIENT WITH

TOTAL SOLUTION NORMALITY (REF. 36).

ION-EXCHANGE EQUILIBRIA
Careful design of an ion-exchange unit
requires knowledge of the ion-exchange
equilibria in the system to be designed.
The sea water-resin equilibria have been
reported previously (ref. 12) .
The system of interest is a ternary ionic
equilibrium with Ca**, Mg**, and Na* com
peting for sites on the resin. All three ions
must be considered in the design. Although
Mg** is no longer harmful as a scale former
when the alkalinity has been removed from
the sea water, it is still important to the
exchange equilibria.
The variation in selectivity coefficient
with total solution normality is shown in
Figure 97. Only the (wo monodivalent ion-
exchanges are dependent on the concentrat
ion. The Ca**-Mg** exchange is not
affected by the concentration of the solution.
The selectivity coefficients fit the equations:
Vï MgS + NaR ;± Vi MgR + NaS
Vi CaS + NaR ^ Vi CaR + NaS
Vi CaS + Vi MgR -pi Vi CaR + Vi MgS

262
and are: X, is the equivalent fraction of calcium
in the solution,
(equivalents Ca**)
solution normality
and:
Ca Mi He
X, + X, + X, =ïX,= l

c. + Xs + X. = 2 X. I
From these equations and the selectivity
coefficients from Figure 97, the resin com
where: position can be calculated if the solution
С» is the equivalent fraction of calcium composition and concentration are known,
on the resin, and vice versa.
From these calculated equilibria, a plot
(equivalents Ca**) of the equivalent fraction of calcium on
total capacity the resin can be made against the equiv

FIGURE 98. CALCIUM EQUILIBRIUM DIAGRAM SEA WATERS

—DOWEX-50.

263
alent fraction of calcium in the solution.
This has been done for various total solu
tion concentrations and calcium fractions in
solution and is shown in Figure 98.
It should be recognized that these plots
are for calcium in sea water and concen
trated sea waters only; similar sets exist
for Mg** and Na* and can be constructed
from the same data.
Figure 98 shows the equilibrium lines for
normal sea water and sea waters of various
ION-EXCHANGE UNIT DESIGN
Removal of 50 per cent of the calcium
from the feed sea water will allow heating
to 275°F without anhydrite precipitation.
This condition can be met in a single-stage
sea water resin softening, if the resin is
regenerated with brine at a four-times
concentration factor in a fixed bed. This
system has been thoroughly tested in a
pilot plant (ref. 12) .
The maximum temperature at which
saline water conversion plants can be oper
ated at the present level of knowledge of
construction materials for hot concentrated
brines and for which saturated steam of
the proper temperature is readily available
is about 325°F.
Operations at a first effect brine tem
perature of 325°F will require removal of
about 75 per cent of the calcium from
normal sea water and will allow a regen-
erant brine concentration factor of nearly
five in the last effect.
Temperature has relatively little effect on
the ion-exchange equilibria, but it does
have an effect on the kinetics of the ion-
exchange. The hotter the sea water being
treated, the more rapid the exchange. The
hotter the brine, the less the viscosity and
density, and the greater the exchange rate.
The ion-exchange equipment can be lo
cated anywhere in the sea water heating
circuit, either before or after the deaerator.
All ion-exchange designs are based on
normal sea water as a feed although it is
realized that in most seashore locations less
than normal sea water will be the feed.
Dowex 50 W, 50 to 100 mesh, eight per
cent cross-linked has been used as the
cation resin the equilibrium design and
capital cost estimates. The smaller mesh
resin is desirable because of its greater
physical strength and greater rate of mass
transfer.
Various methods of contacting sea water
and ion-exchange resins are available.
These include:
(1) Fixed bed softening; fixed bed regen
concentration factors. The difference be
tween the equivalent fractions of calcium
on the resin XJ' in equilibrium with sea
water and in equilibrium with a concen
trated sea water is the amount of calcium
that can be removed from a given volume
of solution by a given volume of resin. The
more concentrated the solution, the more
effective is the regeneration. The less con
centrated the sea water, the more effective
is the softening.
eration (upflow or downflow) ;
(2) Fluid softening single-stage, multiple-
stage, or countercurrent) ; fixed bed
regeneration;
(S) Fixed bed softening; fluidized bed
regeneration;
(4) Fluid softening; fluid regeneration.
Conventional fixed beds cannot be used
in ordinary sea water without prefiltration.
The silt and biological matter rapidly foul
the resin beds and cause an untenable
pressure drop.
Most desirable would be a continuous
countercurrent ion-exchange system. Such
systems have been tested (refs. 1, 6, 16),
but it was felt that no completely counter-
current system had yet been demonstrated
on a sufficiently large scale.
A continuous system could be made coun
tercurrent by conducting the ion-exchange
in equilibrium stages and forwarding the
resin counter to the liquid flow. The ad
vantage of this concept is that the maxi
mum benefit is obtained from the exchange
with a minimum of inventory of either
liquid or solid.
The design system chosen is shown in
flow sheet form in Figure 99. The resin and
sea water or brine are mixed in a contact
column in each stage and flow concurrentlv
to a hydraulic cyclone, where the resin is
separated and the clear liquid and resin
slurry forwarded as in the flow sheet.
The equilibrium diagram is shown in
Figure 100. The circled numbers correspond
to the circled numbers in the flow sheet.
The incoming raw feed sea water is
mixed with the underflow from the second
softening stage at ® and comes into equi
librium with the first stage softened water
at (§). The resin from the first stage is
forwarded to the second regeneration stage
at ©. The first stage softened water over
the cyclone is mixed with freshly regen
erated resin at (s) and comes into equilib
rium at ® to form the final softened sea
water and the second stage resin.
 The water is evaporated with no change
in the ratio of ions so the soft sea water
becomes the feed brine to the first re
generation stage at © where it is mixed
with the resin from the second regenera
tion stage. When equilibrium is reached
at ®, the regenerated resin is the under
flow from the cyclone and the overflow is
the feed to ©, where it is mixed with the
spent resin from (?). At point ®, the spent
regenerant is in equilibrium with the
second brine-stage resin. Because there has
been no precipitation or accumulation of
calcium, the equivalent fraction of calcium

0.15 —

0.05' 1 1 , 1
0.01 0.015 0.020 0.025 0.030
Equivalent Fraction Calcium in th« Solution (X )

FIGURE 99. ION-EXCHANGE EQUILIBRIUM DIAGRAM TO

PREVENT ANHYDRITE AT 325°F.
266
267
 in the spent brine must equal that of the the displacement of the liquid in the resin
raw sea water. interstices in order to prevent a dilution
The slope of the lines from points ® to of the concentrated brine in the regenera
®, (D to ©, etc. is set by the ratio of tion stages and an increase in concentra
solution to resin. There is some dilution tion of the soft sea water in the softening
of the second brine stage by the solution stages.
accompanying the spent softening resin and Cost estimates have been prepared for
some increase in concentration in the the capital costs and operating costs for the
second softening stage caused by the brine ion-exchange pretreatment (ref. 5) .
accompanying the regenerated resin. These The addition of the ion-exchange unit
dilutions and concentrations have been will allow the operation of sea water and
allowed for by the shift of the equilibrium other saline water evaporators at higher
lines. temperatures and at greater concentrations.
Klein, Villena-Blanco, and Vermeulen A comparison of the benefit to the falling
have discussed the ion-exchange equilib film, multiple-effect evaporator is shown
rium data in the design of a cyclic sea in Table XL (ref. 5) . Operation above
water softening process, and have char 250°F for extended periods in sea water
acterized the suitability of specific resins evaporators is unlikely without ion -exchange
for the removal of calcium or sulfate ions pretreatment.
from sea water (ref. 7) .
A flow sheet of a multiple-stage ion- TABLE XL. Cost Comparison of Multiple-
exchange process is shown in Figure 101. Effect, Long Tube Vertical Distillation
This process is designed to remove 75 per Process
cent of the calcium from raw sea water
to permit evaporator operation at more Operating Capital Operatin*
temperature Capacity cost coat
than 435°F and to be regenerated with CF) (srpd) (f) S/1000 gal
4.8 concentration factor blowdown brine. 280 1.000,000 1.604,406 1.20
In this case, two softening stages and three 27S 1.433.000 1.624.286 0.96
regeneration stages are necessary. Addi 800 1,812.000 1,678,627 0.83
tional cyclones have been added to permit 300 normalized 1.000,000 1,618.670 1.16

REFERENCES
1. Arehart; Bresee; Hancher; Jury: Chem.
Eng. Prog. no. 52 (1956) p. 353.
2. Axelrad, B. A.: U.S. 2,756.207 (July 24,
1956) .
3. Banchcro, J. T.; Gordon, K. F.: "Saline
water conversion". Advances in Chem.,
ser. 27, (1960) p. 105.
4. Clampett, J. B.; Fowler, R. T.: /. Appl.
Chem. no. i4 (1964) p. 81.
5. Dow Chemical: OSW R & D no. 139
(Feb. 1965).
6. Higgins, I. R.: Chem. Eng. Prog. no. 60
(1964) p. 6.
7. Klein, C; Villena-Blanco, M.; Ver
meulen, T.: J and EC Proc. Design no.
3 (1964) p. 280.
8. Langelier, W. F.; Caldwell, D. H.;
Lawrence, W. B.: / and EC vol. 42
no. i (1950) p. 128.
9. Marshall, W. L.; Slusher, Ruth; Jones,
E. V.: /. of Chem. and Eng. Data vol.
9 no. 2 (1964) p. 187.
10. Matuno, Y.; Koganemaru. T.; Hara. R.:
]. Soc. Chem. Ind. Japan no. 44 (1941)
p. 142.
11. McCutchan, J. W.; Glater, J.: Rept.
no. 64-5, Department of Engineering,
UCLA (1964) .
12. Mcllhenny, W. F.: OSW R & D no. 62,
PB 181298 (May 1962) .
13. Mcllhenny, W. F.; Baker. A. B.: VS.
Patent no. 3,056,651 (Oct. 2, 1962) .
14. Miyauchi, T.; Moriyama, T.: Chem.
Engr. Japan no. 25 (1961) p. 460.
15. Power, W. H.; Fabuss, B. M.: OSW
R & D no. 104, PB 181685.
16. Spinner, J. H.; Hunter, R. F.: Can. J.
Chem. Eng. vol. 42 no. i (1964) .
17. Standiford, F. C; Bjork, H. K.: "Saline
water conversion", Advances in Chem.,
ser. 27, (1960) p. 15.
18. Tanaka, T.; Nakamura, K.; Hara, R.:
J. Soc. Chem. Ind. Japan no. 34 (1931)
p. 779.
19. Toriumi, T.; Kuwahara, T.; Hara, R.:
/. Soc. Chem. Ind. Japan no. 36 (1933)
p. 1651.

SUMMARY OF DISCUSSION
There was no discussion.
 Prétraitement Par Echange D'Ions
W. F. Mcllhenny
Etats-Unis d'Amérique
Aux débuts de la conversion des eaux
salines, le prétraitement de l'eau d'alimen
tation n'était pas jugé nécessaire ou pra
tique. Les tartres qui pouvaient se former
étaient acceptés comme un mal inévitable.
Etant donné que ces tartres étaient presque
toujours alcalins et d'une adhésivité rela
tivement faible, les surfaces pouvaient être
détartrées de vive force ou en les lavant
avec divers acides. On envisageait rarement
une exploitation continue prolongée et le
prix de revient de l'eau produite n'avait
qu'une importance relativement faible.
Depuis cette époque, les raffinements
croissants apportes à la conception des
appareils de conversion des eaux salines et
à l'exploitation des usines ont accrue la
nécessité d'acquérir des connaissances plus
poussées sur les raisons de la formation du
tartre, les effets du tartre sur le rendement
et les moyens d'élimination du tartre ou
d'en prévenir la formation.
Pour réduire le prix de revient de l'eau
produite, on envisage des températures de
plus en plus élevées et on essaye des con
centrations plus élevées de saumure rési-
duaires. Ces deux mesures exigent la mise
au point de méthodes économiques pour la
lutte contre l'entartrage.
Le tartre est la difficulté la plus gênante
de celles qui sont causées par les substances
chimiques dissoutes dans l'eau d'alimenta
tion. Le tartre se dépose par précipitation
sur les surfaces et exerce son effet le plus
nuisible lorsque la couche de tartre oppose
un obstacle croissant aux échanges de
chaleur. Le tartre rétrécit en outre les
conduites de liquide, provoque des chutes
de pression qu'il faut surmonter et, en
augmentant la turbulence du liquide, accroît
l'entraînement de gouttelettes d'une forte
teneur saline.
L'objet du prétraitement de l'eau d'ali
mentation est de la modifier de façon à
empêcher ou à contrôler la formation du
tartre et de façon à ce que cette eau pré
traitée ne soit pas corrosive et ne produise
pas des gaz nuisibles.
La conception de plus en plus raffinée
des installations de l'usine exige un raffine
ment correspondant des procédés de pré
traitement; ce fait a été trop souvent ignoré
par ceux qui conçoivent ou qui évaluent
les méthodes de conversion des eaux salines.
Toutefois, tout procédé de prétraitement
doit être à la fois sûr et économique. Le
coût du prétraitement ne doit pas dépasser
le bénéfice que peut apporter la diminution
du prix de revient de l'eau ou l'améliora
tion de la régularité de marche du système.
On trouve deux types principaux de
tartre dans les appareils de conversion des
eaux salines. Les tartres alcalins, carbonate
de calcium et hydroxyde de magnésium, se
forment en raison du décalage aux hautes
températures de l'équilibre HCO, —
co; _ H.O.
L'autre type de tartre formé, plus sérieux,
est le sulfate de calcium sous ses différentes
formes. On sait depuis longtemps que le
sulfate de calcium anhydre (anhydrite) se
dépose sous forme de tartre aux hautes
températures, que le dihydrate (gypse) se
dépose sous forme de tartre aux basses
températures et que l'hémihydrate méta-
stable se forme souvent aux températures
moyennes. On a constaté que ces trois formes
de sulfate de calcium constituaient l'élément
principal des échantillons de tartre prélevés
dans des usines de conversion d'eaux salines
en exploitation.
On dispose de procédés de prétraitement
qui, par l'addition d'acide et par un dé
gazage adéquat, permettent de réduire
l'alcalinité de l'eau de mer à moins d'une
partie par million et l'oxygène à moins de
cinq parties par milliard.
La solubilité de toute forme de sulfate de
calcium dépend du produit de la concentra
tion de calcium et de la concentration de
sulfate. Si la concentration d'un des deux
peut être abaissée, leur produit est abaissé
et on peut porter l'eau traitée à une tempé
rature plus élevée, permettant d'obtenir
une plus grande quantité d'eau avec une
concentration plus élevée des saumures
résiduaires.
Il est possible de construire un système
d'échange d'ions pour extraire partielle
ment le calcium de l'eau de mer d'alimen
269
 talion, les saumures concentrées étant em
ployées pour régénérer la résine servant à
l'échange d'ions.
L'adoucissement de l'eau de mer comme
prétraitement dans les méthodes de conver
sion des eaux salines a été breveté; le pro
cédé a été mis à l'essai sous contrat pour le
compte de l'Office of Saline Water et
certains perfectionnements de construction
et de fonctionnement ont été mis au point.
Il n'est pas nécessaire ni particulièrement
désirable d'extraire tout le calcium de l'eau
d'alimentation. La section de prétraitement
est uniquement appelée à extraire la frac
tion qui suffit à prévenir la formation du
tartre aux températures et aux concentra
tions prévues dans les évaporateurs.
npe/jBapHTejiLHan HoHOOÔMeHHan
OôpaôoTKa
B. <P. MaxHjixeHHH
CoenHHeHHbie UItstu Aiwphkh
B paHHHe jihh onpecHeHHfl cojieHoft
BOAbi npeABapHTejibHM o6pa6oTKa hc-
XOAHOH BOAbi He ÔbIJia HVOKHa H He C<IH-
TaJiacb npaKTHMHoit. Ha o6pa30BaHHe
HaKHriH CMOTpe^H, KaK Ha HeH36e>KHoe
3Jio. TaK KaK 3Ta HaKHtib 6una noMTH
Bcema inejio<moR h cpaBHHiejibHO He-
cuenJinBiueHCfi, ee momcho ôujio yjianflTb
jih6o 4>H3mecKofl chjioh, jihôo oÔMUBa-
HHeM nOBepXHOCTefl pa3.1H1HbIMH KHCJIO-
TaMH. ripoao^>KHTe^bHafi HenpepbiBHan
pa6oTa 3awacTyio He ôbijia hcoÔxoahmoh,
a CTOHMOCTb OnpeCHeHHOtt BOAbi He Hrpa-
jia ôojibuioR pom.
C Tex nop, H3 3a HenpepuBHoro yco-
BepujeHCTBOBaHHH oÔopyaoBaHHH h îne-
TOflOB paôOTbt OnpeCHHTejIbHblX ycîaHO-
bok, B03pocjia noTpeÔHocTb jiymue no-
3HaTb npHIHHbl 06pa30BaHHH HaKHITH, a
TaK>Ke 03HaKOMHTbCH C ee B03JieHCTBHeM
Ha npoH3BOiiHTejibHOCTb h cnocoôaMH ee
yaajieHHH hjih npeaoTBpameHH».
Hjih yMeHbiueHHH ctohmocth onpecHeH-
Hott BOflbi npnôeraioT ko Bce ÔoJiee h 6o-
Jiee BbicoKHM TeMnepaTypain h kohuch-
TpauHRM BbneKaioiuero pacTBopa. 3th
o6a (paKTopa TpeôyioT pa3BHTHn skoho-
MHsecKHx MeToaoB 6opb6w c HaKWibio.
HaKHnb HBJIHeTCH CaMblM cepbe3HbiM
270
On a mis au point un échangeur d'ions
à effets multiples remarquable capable d'ex
traire 75% du calcium de l'eau de mer.
permettant ainsi de la chauffer à 325°F
(163°C) sans entartrage et de porter la
saumure à une concentration cinq fois plus
élevée que celle de l'eau de mer normale
également sans entartrage. La saumure
évacuée par l'évaporateur est l'unique agent
régénérateur. Aucun produit chimique sup
plémentaire n'est nécessaire.
La comparaison des prix de revient in
dique que le dispositif à échange d'ions
permet de réaliser des économies de 30%
et plus en rendant possible l'application de
températures de vapeur plus élevées et de
concentrations de saumure plus fortes.
3aipyflHeHHeM, BbiauBaeMUM pacTBopeH-
HblMH B HCXOAHOR BOAe XHMHKa.tHfIMH.
HaKHnb ocawAaeîca Ha noBepxHocTJtx h
Aejiae-rca Haiiôojiee BpeaoHocHott ajih
TenjionepeaaMH, Koraa cma CTaHOBHTcn
pacTyuiHM 6apbepHbiM cnoeM. HaKHnb
TaKwe cynoeT npoxoAM, rae npoTeKaei
>KHflKOCTb, Bbi3biBaeT naAeHHe aaBJieHHH,
hto HeoôxojiHMO npeoAOJieBaTb, h, yBejm-
MHBaa b whakocth TypÔyjieHTHOcrb, no-
BbiiuaeT yHoc KanejieK c bucokhm co-
jiecoAep>KaHHeM.
Uejibio npejBapitTenbHoft o6pa6oTKH
hcxoahoh BOAbi HB.naeTCH ee moahcdhuh-
poBaHHe, MToôbi npeaynpeflHTb bo3hhk-
HOBeHHe hjih peryjiHpoBaTb o6pa30BaHHe
HaKHnn, a npcaBapmeJibHO o6pa6oTaH-
Hyio Bojiy He TOJibKO cAuiaTb HeKoppo-
3HHHOH, HO H npeAOTBpaTHTb B Heft 06-
paaoBaHHe HOKejiaTejibHbix ra30B.
riOBblUieHHa» >TOH<teHHOCTb npoeKTH-
Pobkh ycîaHOBOK BJieieT 3a coôofi cnpoc
Ha noBbiuieHHo yTOHieHHbie npoueccbi
npeflBapHTewibHOH oÔpaôoTKH, hto cjihui-
kom lacro HrHopnpoBajiocb npoeKTitpoB-
uiHKaMH h oueHuiHKaMH npoueccoB onpe-
CHeHHH COJieHOH BOAbi.
OaHaKo, Kamnan cHCTesta npeaBapH-
TejIbHOH OÔpaÔOTKH AOJIWHa ÔHTb He
TOJIbKO HclAeMHOft, HO H 9KOHOMHMHOH.
CTOHMOCTb npeaBapHTejibHoil o6pa6oTKH
He aoJiwHa npeBbiLuaTb BbiroAy, noAyqa-
eMVK) OT CHH'/KeHHH CTOHMOCTH OnpeCHeH-
HOR BOAbI HAH yBejIHMeHHH Haae)KHOCTH
npouecca.
ripn nojibaoBaHHH, o6opyaoBaHHeM aa«
onpecHeHHH co.ieHoft boam BCTpeiaioTCfi
ABa rjiaBHbix THna HaxmiH. LU.eAoiHan
HaKHnb Kap6oHaia KajibUHH h thapookh-
ch uarHHH, o6pa3yeTcn 6jiaroAapH CMe-
meHHio paBHOBecHH b HCO,— COJ-H20
npH bwcokhx TeMnepaTypax.
CyjTbcfiaT Ka.ibu.HH b cbohx pa&nmHbix
ipopMax (nuineTCii ApyrHM h 6oAee cepb-
eSHblM pOAOM HaKHnH. BblAO AaBHO H3-
BeCTHO, MTO 6e3BOAHbltt cyjibipaT KaAb-
UHH (aHrHAPHT) nOHBJIHeTCH B BHAe Ha
KHnH npn bhcokhx TeMnepaTypax, a mto
AHrHApaT (rnnc) B03HHKaeT b BHAe Ha
KHnH npn TeMnepaTypax HH3KHX, b to
BpeMft KaK MeTacTa6H^bHbifl reMHrHApaT
qacTO BCTpeqaeTca npn cpeAHHX TeMne
paTypax. Bee tph (popMu OKasa.iHCb
r.iaBHbiMH cocTaBHHMii MacTBMH o6pa3-
uob HaKHnn, nOAyiembix Ha pa6oTaio-
UIHX BOAOOnpeCHHTeAbHHX yCTaHOBKaX.
CymecTByioT mctoam cHHweHHH me-
JIOWHOCTH MOPCKOA BOAbI AO ypOBHH HH-
we, ieM oAHa iacTb Ha mhaahoh, a khc-
jiopoAa HH>ne, MeM nsiTb iacTeA Ha mha-
jiHapA: 9to AOCTHraeTCH Ao6aBJieHHeM
khcaotm h npaBH.TbHbiM yAaJieHHeM ra-
SOB.
PaCTBOpHMOCTb AK>6oA (pOpMbl CyAb-
tpaTa KaAbUHO 3aBHCHT OT npoH3BeAeHHd
KOHUeHTpaUHH KaAbU.HH H KOHUeHTpaUHH
cy^bipaTa. Ecjih yAacTCH noHH3HTb koh-
ueHTpauHio Jiio6oro H3 hhx, to npoH3Be-
AeHHe CHHwaeTCH, a o6pa6oTaHHyio bo-
Ay mo/Kho HarpeBaTb ao 6oaee bmcokoA
TeMnepaTypw h yAaJidTb 6o.ibiue boan
jura no.iVMeHHH 6oAee BUCOKofl kohuch-
TpaiiHH BbixoAHiuero pacTBopa.
Mowho cnpoeKTHpoBaTb hohoo6mch-
Hyw CHCTeMy, KOTopan 6yAeT nacTHiHO
yAaAHTb KajIbUHfl H3 HCXOAHOH MOpCKOA
BOAbI, nOAb3ydCb KOHlieHTpHpOBaHHblM
pacTBopoM aah pereHepHpoBaHHH hoho-
06MeHH0H CMOJIbl.
CMHrMeHHe MOpCKOA BOAbI, HBJIHiOme-
ecd npeABapHTeAbHofl o6pa6oTKOH npn
npoueccax onpecHeHHH coachoA boam,
6uao 3anaTeHTHpoBaHo; corjiacno Aoro-
Bopy c YnpaBAeHHeM no onpeciieHHio co-
AeHNX boa npouecc noABeprcH iicnbira-
hhhm h 6wah npoBeAeHbi ycoBepuieH-
cTBOBaHim, KaK b caMOM npoeKTe, TaK h
npouecce.
YAaAeHHe Bcero KaAbUHS H3 pacTBopa
HCXOAHOH BOAbI He TOAbKO He RBJIIKTCJI
Heo6xoAHMbiM, ho h He oco6eHHO mtna-
TeAbHO. Ot hohoo6mchhor ceKUHH npeA-
BapHTeAbHoA o6pa6oTKH Tpe6yeTca TOAb-
ko yAaAeHHe toA wacTH, KOTopaH Hy>KHa
nnst npeAOTBpameHHd oopasoBamui Ha
KHnH npn TeMnepaTypax h KOHueHTpa-
UHdx, owHAaeMbix b HcnapHTeAHX.
Bwa cnpoeKTHpoBaH Heo6biKHOBeHHuA
MHorocTyneHMaTbiA HOHOo6MeHHbiA koh-
TaKTop, kotopoA 6yAeT yAaAUTb H3 Mop-
CKOA BOAbI 75% KaAbU.HH, n03BOAHT 6e3
o6pa30BaHHn HaKHnn HarpeBaTb MopcKyio
BOAy AO 325°F H AaCT B03MO>KHOCTb KOH-
ueHTpnpoBaTb pacTBop noqTH ao 5-KpaT-
hoA HopManbHoA KOHueHTpauHH mopckoA
BOAW 6e3 o6pa30BaHHn HaKHnH. PacTBop-
npoAyBKa H3 ncnapHTejiH hbahctcji eAHH-
CTBeHHbiM pereHepaTopoM. He Tpe6yeTCH
HHKaKHX Ao6aBoqHbix XHMHxajiHfl.
CpaBHeHHe ctohmocth noKaabiBaeT, ito
HOHO-o6MeHHbiA arperaT, 6AaroAapn npH-
MeHeHHio 6oAee bwcokhx TeMnepaTyp
napa h 6o;iee bwcokhx KOHU.eHTpau.Hfi
pacTBopa, chh3ht ueHy onpecHeHHoA bo
am na 30% hah 6oAee.
271
 Pretratamiento por Intercambio
Iónico
W. F. Mcllhenny
Estados Unidos de Norteamérica
En los primeros tiempos de la conversión
de agua salada no era necesario ni se con
sideraba práctico un tratamiento previo del
agua de alimentación. La formación de
incrustaciones, de producirse, se aceptaba
como un mal necesario. Dado que estas
incrustaciones eran casi siempre alcalinas y
relativamente no adherentes, podían ser
eliminadas mediante tratamiento mecánico
o lavando las superficies con ácidos de dis
tintas clases. Generalmente no se buscaba
la explotación continua y prolongada y el
costo del agua producido era relativamente
poco importante.
Luego de ese periodo, la creciente com
plejidad en el diseño de equipo para la
conversión de agua salada y en la explota
ción de las plantas, ha incrementado la
necesidad de un conocimiento más profun
do de las razones que motivan la formación
de incrustaciones, de la influencia de las
incrustaciones sobre el rendimiento y de
métodos para eliminar o prevenir la forma
ción de incrustaciones.
Para reducir el costo del agua producida,
se considera trabajar a temperaturas cada
vez más altas y se intenta emplear concen
traciones mayores de aguas madres de des
carte. En ambos casos se requiere el desarro
llo de métodos económicos para reducir la
formación de incrustaciones.
Las incrustaciones constituyen la dificul
tad más seria creada por las sustancias
químicas disueltas en el agua de alimenta
ción. Las sales precipitan sobre las super
ficies y son sumamente perjudiciales cuando
las incrustaciones asi formadas actúan como
una barrera de la trasmisión de calor. La
incrustación también provoca estrechamien
to de los tubos de circulación de los fluidos,
causa caídas de presión que deben ser
superadas y al incrementar la turbulencia
en el líquido, aumenta el arrastre de gotitas
de alto contenido salino.
El propósito de un pretratamiento de las
aguas de alimentación es modificar su con
tenido de manera tal de prevenir o reducir
272
la formación de incrustaciones. Las aguas
pretratadas no son corrosivas ni producen
gases indeseables.
Aumento de la complejidad en el diseño
de las plantas exige una mayor complejidad
en los procesos de pretratamiento. Este es
un hecho que ha sido a menudo ignorado
por los diseñadores y evaluadores de los
procesos de conversion de agua salobre.
Cada sistema de pretratamiento. sin
embargo, debe ser tanto seguro como eco
nómico. El costo del pretratamiento no
puede ser mayor que el beneficio que de su
uso se deriva al disminuir los costos de agua
o incrementar la seguridad del proceso.
Dos tipos principales de incrustaciones
se encuentran en los equipos de conversión
de agua salada. Las incrustaciones alcalinas,
carbonato de calcio e hidróxido de magne
sio, se forman debido al desplazamiento, a
alta temperatura, en el equilibrio entre
HCO~ — CO= — H.O. La otra incrustación
que crea más problemas, es la de sulfato
de calcio en sus distintas formas. Se conoce
desde tiempo atrás que el sulfato de calcio
anhidro (anhidrita) se dá como incrustación
a alta temperatura y que el di-hidrato
(yeso) se forma como incrustación a baja
temperatura, mientras que el semi-hidrato,
forma metaestable, se encuentra general
mente a temperaturas intermedias. Las tres
formas han sido encontradas como constitu
yentes mayores en muestras de incrusta
ciones tomadas de plantas de conversión de
agua salada.
Existen métodos de pretratamiento para
reducir la alcalinidad del agua de mar a
menos de una parte por millón y el oxígeno
a menos de cinco milésimas de parte por
millón mediante el agregado de ácido y una
desgasificación apropiada.
La solubilidad de cualquiera de las for
mas de sulfato de calcio depende del
producto de la concentración de calcio y
la concentración de sulfato. Si la concentra
ción de cualquiera de ellos puede ser dismi
nuida, el producto disminuye y el agua
 tratada puede calentarse a mayor tempera
tura y mayor cantidad de agua puede
extraerse dando una producción de aguas
madres de más alta concentración.
Se puede diseñar un sistema de intercam
bio iónico para extraer parcialmente el
calcio del agua de alimentación, usando las
aguas madres concentradas para regenerar
la resina de intercambio iónico.
El ablandamiento de agua de mar como
un pretratamiento para los procesos de
conversión de aguas salobres ha sido paten
tado. El proceso ha sido probado ba}o con
trato de la Oficina de Aguas Salobres
(Office of Saline Water) y se han efectuado
refinamientos de diseño y de proceso.
No es necesario, no particularmente de
seable, extraer todo el calcio de la solución
de alimentación. La eliminación de aquella
parte necesaria para prevenir la formación
de incrustaciones a las temperaturas y
concentraciones previstas en los evaporado-
res, es todo lo que se requiere de la sección
de pretratamiento por intercambio iónico.
Un equipo de intercambio iónico de eta
pas múltiples, realmente poco usual, ha
sido diseñado para eliminar el 75% del
calcio del agua de mar permitiendo calen
tamientos hasta de 325° y una concentración
de las aguas madres de aproximadamente
5 veces el agua de mar normal, sin for
marse incrustaciones. Las aguas madres
salientes del evaporador constituyen el
único regenerante. No se requiere el uso
de productos químicos adicionales.
Una comparación de costos indica que la
unidad de intercambio iónico permitirá re
ducciones en el costo del agua de 30% o
más dado que permite el uso de tempera
turas más altas y concentraciones de aguas
madres más elevadas.
273
Aspects of Two-Phase Flow and Heat
Transfer in Distillation Type
Conversion Processes
L. C. Elliott and A. E. Dukler
United States of America
INTRODUCTION
Vaporization and condensation steps in
distillation-type conversion processes are
characterized by the presence of two phases.
Under certain conditions, the flow behavior
of these phases and their interaction pro
foundly influence important design vari
ables such as rate of heat transfer, flow
capacity, equipment size, pressure drop, and
operating stability. Some examples can be
cited from the well-known multistage flash
(MSF) and the vertical tube (VT)
processes.
MAXIMUM NUMBER OF STAGES
IN AN MSF PUNT
Once the temperature in the first stage
and vacuum in the last stage have been set
by design considerations, the operating
economy (pounds of vapor produced per
pound of steam to the system) improves as
the number of stages is increased. With
terminal temperatures being fixed, increas
ing the number of stages results in less
temperature difference available between
adjacent stages. The corresponding pressure
difference is also lower. From a thermo
dynamic point of view, this can be extended
without limit until the pressure drop across
any one stage is differentially small. As a
practical matter, the number of stages can
be increased only so long as the pressure
drop is large enough to overcome friction
as the flashing liquid flows from one stage
to the next. Introduction of one additional
stage will cause unstable operation. Liquid
will then build up in the pressure drop
limiting stage until the hydrostatic head
added to available pressure difference is
sufficient to overcome friction and then the
liquid will "dump" to the next stage and
a new cycle will begin. In flash chambers
of the type now being used, the minimum
allowable pressure drop appears to be in
the order of 3 inches of water (ref. 1) . It is
thus clear that the maximum possible num
ber of stages depends on the friction loss
due to two-phase flow as the liquid flashes
during its passage through the submerged
orifice system. Before design parameters can
be developed, information on two-phase
friction in this configuration is required.
SIZING OF MSF CHAMBERS
Flashing of vapor as liquid flows into a
stage is, of course, not an instantaneous
process. In order to achieve near equi
librium release of vapor, the liquid must
have a finite residence time. This is achieved
by making the chamber of a finite length.
Just how long, however, depends on the
rate of mass transfer between liquid and
vapor. Studies (ref. 2) have shown that the
required length is very sensitive to flow rate.
This is to be expected. Mass transfer rates
in two-phase flow depend on the interfacial
geometry of the two phases as well as on
the degree of turbulence which exists. If,
for example, the liquid releases into the
chamber as a flat liquid jet. then the inter
facial shear will play an important role in
the mass transfer from the surface and on
the place along the chamber at which the
jet finally breaks up. The interaction be
tween gas and liquid thus play a primary
role in determining the shape of the liquid
stream, its surface area, the rate of mass
275
 transfer from the surface, and the rate of
breakup of the jet. These are the quantities
which determine the residence time re
quired and thus the size of the chamber.
Only limited study of the problem has
been reported (refs. 3,4) .
HEAT TRANSFER RATES IN THE
VERTICAL TUBE IVT) FALLING MM SYSTEM
The Freeport plant is a multieffect sys
tem, each effect operating with falling films
on vertical tubes. The local rate of heat
transfer at any position in the tube depends
on the overall heat transfer coefficient and
the temperature driving force at that point.
This local overall coefficient in turn depends
on the magnitude of the individual coeffi
cients. The amount of heat transferred by
one entire tube is
fh
q, = / Ux (t, — t») x TD dx
J O (1)
Ux hcx h,x
The design question of how many tubes
are necessary in the effect is answered by
dividing the heat duty of the effect by the
q, as calculated above. The design problem
is thus reduced to finding q,. The three
principal factors in the integral, he, h. and
(t, — tT) all depend directly on the magni
tude of the two-phase pressure drop. Pres
sure drop manifests itself as shear at the
gas-liquid interface. This shear causes the
liquid film to thin, and the liquid veloci
ties to increase, resulting in substantially
higher heat transfer coefficients (refs. 5,6) .
This is a positive effect tending to increase
U and q, and decrease the number of tubes
required. However, the pressure in the sep
arator below the tubes is fixed by the heat
balance between effects. Any frictional pres
sure drop means that the pressure rises up
the tube and thus is accompanied by a rise
in the saturation temperature, tT. With a
constant steam temperature, t„ the tem
perature driving force, (t, — tT) , thus de
creases up the tube, tending to decrease qt.
These two effects of pressure drop act in
opposite directions, tending to increase h
and U and to decrease AT. Once the pres
sure drop of this two-phase stream can be
reliably predicted, it will be possible to
select tube sizes and flow rates so that the
product, UaT, is a maximum.
PREVENTION OF HIGH LOCAL
CONCENTRATION WITH ACCOMPANYING
SCALING IN THE VT SYSTEM
The interface of the falling film in a ver
276
tical tube is covered with waves. Measure
ments (refs. 7,8) have shown that the wave
heights may be S to 5 times as large as the
mean film thickness itself. Under conditions
of no gas flow (and thus zero interracial
shear) , these waves travel down the surface
maintaining their identity (ref. 9) . How
ever, when a vapor phase is present and
interracial shear exists, the tops of these
waves are sheared and the liquid, thus
removed, moves along with the vapor in the
form of entrained drops (refs. 10,11). Unless
the space below the tubes is designed to
separate the entrained vapor, contamination
of product water can result. A more serious
result of entrainment is that the heat trans
ferred through the wall is absorbed by the
liquid flowing on the wall with the vapor
being generated from this wall liquid. The
entrained drops contribute little, if any.
vapor and move down the tube essentially-
unchanged. The wall liquid concentration
is thus higher than it would be if there
were no entrainment, since all of the vapor
comes from the wall liquid alone. In the
low temperature effects, the liquid oper
ates near the solubility limit of the scale
components. Thus the disproportionate re
moval of vapor from the wall liquid can
result in high local concentrations and
scaling. It should be noted that this would
not be apparent by sampling the liquid
stream leaving an effect. In the exit stream,
the high concentration material from the
wall has already mixed with the low con
centration entrained liquid which has sep
arated from the gas. The combined liquid
concentration may appear to be well below
the solubility limit while the wall liquid
stream may have been scaling. In order to
design a method to prevent this condition,
it is necessary to develop data and theory
to predict rates of entrainment as functions
of the liquid and gas rates involved. It
should be quite clear that a series of basic
design decisions depends directly on an
understanding of the character of the two-
phase flow. Much work has been devoted to
problems in two-phase flow, and a number
of reviews have recently appeared (refs.
12,13) . However, the current state-of-the-
art does not permit a direct resolution of
these problems of design. It is, therefore,
necessary to develop theoretical and empiri
cal attacks for the particular problems as
they arise. One such study which reports
the preliminary results of an investigation
of pressure drop, heat transfer, and en
trainment is described in this paper.
SOME ASPECTS OF HEAT TRANSFER IN A VERTICAL TUBE EVAPORATOR
THE MODEL observed this type of evaporation. Lisbin,
The mechanism by which vapor is gener et al (ref. 19) , also report this mechanism.
ated from a vertical falling him is not yet In view of the small temperature differences
fully understood. At least two extremes are which exist in vertical tube units, the sur
possible: face evaporation model seems realistic. This
(1) Vapor is generated by nucleation model is represented in Figure 102. Heat
at the wall (liquid-solid interface) . flows through the wall, then through the
(2) Vapor is generated by evaporation ai film to a sink at the interface where vapor
the film surface (gas-liquid interface) . is released. This vapor joins the rest of the
Both of these mechanisms could be opera vapor and moves in a direction parallel to
tive at one time. Any mathematical model the liquid flow.
constructed for heat transfer depends, of
course, on the mechanism selected. Sinek THEORY FOR LOCAL HEAT TRANSFER
(ref. 14) has proposed a model based on COEFFICIENT
wall nucleation combined with Dukler's The transfer theory based on a continu
transport theory for continuous liquid film. ous film model has been presented for the
Sinek develops relationships for the heat case of a condensing film (ref. 5) and has
transfer coefficient by assuming that the been shown to be in good agreement with
Dukler theory applies equally well when existing data. The identical relationships
the liquid is not continuous. The existing apply for a film with surface evaporation
evidence, however, seems to point to sur as long as the film is continuous. The
face evaporation. Jakob (ref. 15) discusses original publication can be examined for
this type of behavior and reports data show details of the development. Results appli
ing apparent superheating of this liquid cable to the study will be summarized here.
to 24"F with surface evaporation taking Figures 103 through 105 present local co
place before the film breaks up by nuclea efficients for film Prandtl numbers 1, 2,
tion. Lacy. Hewitt, and their coworkers and 5. It can be seen that the local co
(refs. 16,17) have done extensive studies of efficient of heat transfer depends on four
film heat transfer which appear to demon
strate that film surface boiling is the pre factors:
vailing mechanism. Unterberg (ref. 18) , (1) The liquid film Reynolds' number
operating with glass equipment, has also
ReL, = •4WL (3)
\ CONTINUOUS (2) The dimensionless interfacial shear
\ LIQUID
FILM VAPOR PHASE 1/3
\ _ (dP/dL) Tr Dg«
s 4Pl* ml** (4)
k
(3) The physical property grouping for
\
the liquid
\ LIQUID VAPOR 1/3
\ FLOW FLOW (5)
\ '-(PL2g?kL»)
s (4) The liquid Prandtl number
\
(f* SURFACE
\ EVAPORATION Pi (6)
-en
\ HEAT
It should be noted that this theory predicts
\ FLOW the heat transfer coefficient over the full
\ range of flow rates extending from laminar
to turbulent flow. At the low Reynolds'
numbers, the theory predicts coefficients in
FIGURE 102. THE HEAT agreement with the classical Nusselt (ref.
TRANSFER MODEL. 20) theory for laminar flow.

277
280
 TEST OF THE THEORY was applied, that the agreement is very
A definitive test of this theory must come good indeed.
from direct measurement of local evaporat
ing coefficients and local interfacial shear TABLE XLI. Comparison Between Theory
stress. While plans for such measurements and Wrightsville Beach Data (Two-Inch
are underway, no data exist at this time. Tubes)
The Office of Saline Water has issued the
results of a study (ref. 20) , in which the Temperature No. Deviation (%)
level
•F runs Mean Maximum
heat transfer which took place in an entire absolute absolute
tube was measured. These data do not 240-250 t G.4 10.8
permit direct comparison with the theory 200-220 6 1.0 7.5
because the local Reynolds' number and 141-150 10 2.8 1.4
interfacial shear changed along the length 120-127 t 5.8 18.5
of the tube and local values were not 102-103 < 1.8 2.8
measured. However, these data included the
flow rate of liquid entering the tube, the THE PRESSURE DROP QUESTION
exit concentration, and the temperature Central to the calculation of the thermal
difference and the absolute pressure at the performance of the tube is the method
bottom of the tube. From this information used to calculate two-phase pressure drop.
and an estimated pressure drop, it was pos This factor affects both the heat transfer
sible to numerically integrate Equation (1) coefficient via f} (Eq. (4) ) and the tempera
up the tube and compare the calculated ture driving force. In the results discussed
heat transfer in the tube with that meas above, executed before experimental data
ured experimentally. This was done by became available, the following empirical
using (1) the results of the heat transfer relationship was used:
theory to calculate the individual coeffi
cients and U at each increment up the tube /AIVN / AfVV-
and (2) a method for estimating of two- V APo ) ~ \ AP0 / (8)
phase pressure drop to arrive at the static where
pressure at each increment, thus obtaining K, a — constants,
the saturation temperature, and the tem APtp = pressure drop in two-phase flow,
perature driving force. Because of the na APo = frictional pressure drop with gas
ture of the method, the calculations were flow alone,
programmed for the electronic computer APl = frictional pressure drop with liq
with the program accounting for sensible uid flow alone.
heating effects, boiling point rise, etc. A This type of correlation was based on the
summary of the results appears in Table idea originally presented by Martinelli (ref.
XLI. The mean deviation is defined as 21) with the constants evaluated from the
data of Dukler (ref. 22) and modified in
n this study to account for the higher pres
Mean = i. Y lq"" = 100 sure drops expected at low vapor densities
n ^ q,„ as noted by Martinelli and Nelson (ref. 23) .
1 (7)
where q,„ is the total measured heat trans It is quite apparent that a correlation
constructed and modified in this way with
ferred to the tube and qlc is the calculated out actual experimental data leaves consid
value. Deviations were calculated without erable uncertainty. For this reason, a sys
regard to sign. The largest single deviation tematic study of pressure drop and en-
in the set of n points is listed as the maxi trainment was undertaken which included
mum deviation. It seems clear, using the both accurate experimental determination
pressure drop estimating procedure which and correlation analysis.

EXPERIMENTAL EQUIPMENT FOR MEASUREMENT

OF PRESSURE DROP AND ENTRAINMENT
A schematic diagram of the experimental flow through a special entrance section and
equipment appears in Figure 106. This is down the insulated tube. At the bottom,
an isothermal test unit. Water at a satu an adjustable cone removes most of the
rated, subcooled or superheated condition vapor through an entrainmcnt knockout.
flows to an inlet tank where it is joined Entrained liquid is measured directly. The
by desuperheated steam. The two phases annular liquid passes by the cone as a sheet

281
 into a separator where it is pumped to
waste. Steam flows to a two-stage noncon-
densing vacuum jet system. The equipment
has been designed so that different types
of entrance configuration can be explored,
tube diameter and length can be varied,
and the fraction of the vapor stream which
is sampled can be changed. Pressure drops
are measured using absolute manometers,
with lead lines from each pressure measur
ing station being carried to a manometer
board located at a level about 29 feet
from the ground. The entire system is
282
thoroughly insulated. The tests reported
below were conducted with a two-inch,
16-gauge aluminum-brass tube which was
21 feet long.
Since no vaporization takes place, the
interfacial shear stress over the entire test
section length is equivalent to that which
exists in a differential length of a tube in
which vaporization takes place. Because of
its finite length, it is possible to make rea
sonably accurate measurements of pressure
drop in the test section.
 PRESSURE DROP STUDIES
BASIC DATA
Basic data were obtained in the clean
2 inch X 21 ft test section with a smooth,
annular type liquid overflow entrance, with
liquid and vapor entering at saturated con
ditions, and with the mean of the tube
inlet and outlet pressure being kept at a
constant value of 25 inch mercury vacuum.
Liquid rate was varied from 0 to 800 lb/hr
with a range of steam flow from 20 to 140
lb/hr. These flow rates extend well below
and above the conditions in the demonstra
tion plant's vertical tubes at the equivalent
pressure level. Results are shown in Figure
107. It is seen that at the lowest flow rates,
the pressure of the liquid has little effect
on the pressure drop of the steam; at
higher liquid and gas rates, the pressure
drop represents a substantial fraction of the
absolute pressure level.

T T T T T

SYMBOLS WATER RATE -LB/HR

X 800
A 600
О 360
□ 120

hi"

SINGLE PHASE FLOW

lal

CONDITIONS
CLEAN TUBE
VACUUM: 25" Hg
tube i.d.: 1.870 in.
tube length! 2i ft
steam: saturated

STEAM 1 RATE LB/HR

I

20 4P 60 80 ICO '20 140

FIGURE 107. PRESSURE DROP BASIC DATA.

283
 It was possible to predict these data in
a very satisfactory manner using the cor Reo =-^- (9)
relation suggested by Bergelin, et al (réf.
24) . This correlation is shown in Figure f= <dP/dL)" (10)
108 as redrawn from the original source.
The terms are defined as follows:

284
30 0

800 LB/HR
10.01
BERGELIN THEORY
EXPERIMENT
50

//
30
// 120 LB/HR H20

a:3

a.

05

0 3

STEAM RATE LB/HR

0I
0 20 40 60 80 100 120 140
FIGURE 109. COMPARISON OF EXPERIMENTAL aP WITH
VALUES PREDICTED BY BERGELIN.

A comparison of pressure drop, as calcu
lated from the Bergelin correlation, with
experimental values appears in Figures 109
and 110. It seems quite clear that the agree
ment is satisfactory.
INFLUENCE OF DIRT OR SCALE
Clean tube operation is, of course, a con
dition characteristic of the laboratory only.
Commercial systems will operate with some
degree of dirt or scale on the tube. During
the operation of this experimental equip
ment, some slight scale buildup was ob
served after a period of several months, and
a series of measurements was undertaken
to determine its effect on pressure drop.
In order to obtain some measure of the
degree of added roughness, tests were run
with steam in a dry tube and the results
were compared with previous similar tests
made when the tube was clean. Results are
shown in Figure 111. For dry tubes, there
is a small but definite increase in friction
of the order of 10 per cent as a result of
the scale. A relative roughness of 0.001
would account for the increase.

285
 *00 LB/HR Нг0

BERGELIN THEORY
EXPERIMENT

ОorQ.
с

STEAM RATE LB/HR

20 40 60 80 00 120 140
FIGURE 110. COMPARISON OF EXPERIMENTAL дР WITH
VALUES PREDICTED BY BERGELIN.

286
 The effect of this scale on the two-phase
pressure drop is much greater. Figures 112
and 113 show pressure drops measured in
the scaled tube for two flow rates compared
with the pressure loss in the clean lube.
In this case, the pressure drop is 25 to 50
per cent higher than for the smooth tube.
While the scale has only a small effect when
exposed directly to steam flow, its presence
apparently disrupts the flow of the liquid
film causing increased interfacial disturb
ance and higher exposed roughness to the
gas. The mechanism for this action is not
yet clear and work is continuing.

30r

10

5.0

3.0 h

OQ. SLIGHTLY

UJa.
CLEAN TUBE
</>
1-0

0.9 SLIGHTLY SCALED

TUBE
CONDITIONS
03 H VACUUM : 25" Hg
TUBE I.D. I 1.870 IN.
TUBE LENGTH! 21 FT
STEAM! SATURATED

STEAM
I RATE, LB/HR
I
0.1
20 40 60 BO 100 120 140

FIGURE 111. PRESSURE DROP IN CLEAN AND SLIGHTLY

SCALED TUBE. Liquid Rate = 0 lb hr

287
 SLIOHTLY
lOOf— SCALED
X = OATA TUBE

Q
I
• Q.
o
CLEAN TUBE
=>
LU
tr
CONDITIONS
VACUUM'. 28" Hg
/ TUBE 1.0. : 1.870 I N.
TUBE LENGTH! 21 FT
/ STEAM: SATURATED

STEAM RATE, LB/HR

_J I
20 40 60 100 120 140

FIGURE 112. PRESSURE DROP IN CLEAN AND SLIGHTLY

SCALED TUBE. Liquid Rate = 800 lb hr

288
 INFLUENCE OF INLET FLASHING
A series of tesls was executed with varying
degrees of superheat and flash as the liquid
flowed into the test section. These tests were
made to determine the manner in which
entrance flow configurations due to flashing
could influence friction. Liquid superheated
up to 18°F gave identical pressure drops
as with saturated feed, provided that com
parisons were made at corresponding steam
and water rates in the tube after the flash.

FIGURE 113. PRESSURE DROP IN CLEAN AND SLIGHTLY

SCALED TUBE. Liquid Rate = 360 lb hr

289
 ENTRAINMENT STUDIES
Entrainment carried by the vapor leaving
the test section was measured at 25 in. Hg
vacuum for the range of liquid and gas
rates described above. Typical data taken
at 25 in. Hg vacuum with a smooth,
annular entrance configuration appear in
Figure 114. It should be noted that at the
low liquid rates, entrainment is negligible.
However, in the range of liquid loadings
which is commercially feasible, entrainment
can be as much as 10 to 20 per cent of the
feed stream. As is expected, the amount
entrained drops off rapidly with steam rate.
A generalized model for entrainment re
quires information on the interfacial struc
ture and the stability of the waves under
shear. While research is now underway in
a number of laboratories to obtain this
information, our knowledge is as yet in
complete (ref. IS) . In order to build a
correlation, some recourse to intuition is
needed.

300.0

100.Or-

40 60 SO
STEAM RATE, LB/HR

FIGURE 114. ENTRAINMENT DATA.

 As a first approach, it is suggested that damped wave action. So
in the vertical film, the fraction of the
liquid which is torn from the sheet should - , M,TA, (11)
depend on the total interfacial shear force Wb
acting. However, this shear would be ex- or
pected to entrain more liquid from a E/W,
'hick film than from a thin one which has ~\Г^ ~ * (т * A»> (12)

291
 where E/WL is the fraction of input liq
uid entrained, M is the film thickness, T
is the shear stress, and A, is the lateral
surface area of the film exposed to shear.
Note that the shear stress can be calculated
from the pressure drop by the equation
AP D
AL 4 (13)
Values of film thickness, M, needed to
test this correlation were obtained from the
correlation proposed by Dukler (ref. 5)
This correlation is shown in Figure 115. The
Reynolds' number is defined by Equation
(3) , and the interfacial shear parameter.
/3, is defined by Equation (4) .
This correlation was used to calculate film
thickness, and the ratio of the fraction en
trained to the film thickness group was
plotted against interfacial shear force as
shown in Figure 116. This method of co
ordination of the data appears to be quite
satisfactory. It remains to be seen if this
simplified model will accommodate other
tube sizes and fluid properties. At this time,
the correlation must be considered pre
liminary.

30

— 10

50
o.
s 3.0
«^
I g I
It CONDITIONS
SLIGHTLY SCALED TUBE
VACUUM: 23" Hg.
1.0 h- tube i d. . 1.870 in
2 tube length: 21 ft
steam: saturated
03

0.3

SYMBOL WATER RATE.LB/HR

X — 600
0.1 r- A — 600
O — 360
z □ — 120
<
.09

03 A X
o<1-

v INTERFACIAL SHEAR » SURFACE AREA* TA. , LB — FORCE

* < i ' I C i
0.4 0.8 20 2.4 2.8

FIGURE 116. PRELIMINARY CORRELATION FOR

EN TRAIN M EN T.

292
 ADDITIONAL STUDIES
This work is now being extended to de
velop data and test the correlations for:
(1) Circulation of saline water brines,
(2) Higher and lower test section pres
sures,
(3) Other tube sizes,
NOMENCLATURE
: Lateral surface area of film ex
posed to shear.
: Specific heat of liquid.
(dP/dL) : Frictional pressure gradient,
(dP/dL) TP for two-phase flow.
E ; Entrainment rate.
E/WL : Fraction of input liquid en
trained.
: Friction factor defined by Equa
tion (10) .
: Newton's conversion factor.
: Acceleration of gravity, local.
: Individual film coefficient lo
cated at an arbitrary position
along the axis of the tube. h„
for condensing steam, hr, for
evaporating water.
: Thermal conductivity, kt of
liquid.
L : Tube length.
M : Liquid film thickness.
n : Number of data points.
D : Tube diameter.
Pr : Liquid Prandtl number, Pr —
: Rate of heat transfer, q, for
entire length of one tube, q,„
for total measured rate, qlc for
total calculated rate.
R : Thermal resistance. R„ for tube
wall. R, for scale.
Re0 : Reynolds' number for gas only
defined in Equation (9) .
: Liquid film Reynolds' number
defined by Equation (3) , Re^i
REFERENCES
1. Fisher, D. A.; Gilbert, F. W.: Paper
presented to American Chemical So
ciety Meeting, Washington, D. C. (Apr.
1965) .
2. Richardson Westgarth & Co., Ltd.:
"Chamber geometry in multistage flash
chambers". Saline Water R&D Rept. no.
108 (July 1964).
3. Hagerty. T. J.: Shea, J. F.: ]. App.
Mech. no. 22 (1955) p. 509.
(4) Other entrance configurations.
A test program will be initiated shortly
for direct measurement of individual film
coefficients. These heat transfer data, along
with the pressure drop and entrainment in
formation, will permit definitive design of
equipment of this type.
for arbitrary position along tube
axis.
S./S = Ratio of surface tension of
water at normal boiling point
to surface tension of flowing
liquid at actual temperature.
t = Bulk fluid temperature, t. for
steam, tT for saturation tem
perature.
U - Overall heat transfer coefficient,
U, for U located at an arbi
trary position along the axis
of the tube.
V8 — Average velocity of gas.
WL — Liquid mass flow rate.
X — Distance in direction of flow.
Greek
p = Dimensionless interfacial shear
defined by Equaiton (4) .
T = Mass rate of liquid flow per
unit perimeter lb/ (hr) (ft) .
AP = Frictional pressure drop, APTP
for two-phase flow, .}P„ for gas
flow only, aPl for liquid flow
only.
in = Liquid viscosity.
p - Density, pn for gas. pL for liq
uid, dimensions are Ib/cu ft for
Bergelin correlation.
t = Shear stress at interface, lb
force/sq ft.
<)> = Physical property grouping for
the liquid defined by Equation
(5).
4. York, T. L.; Stubbs. H. F.; Tek. M. R.:
TR. ASME no. 75 (1953) p. 1279.
5. Dukler, A. E.: Chem. Eng. Progress
Symposium series 56 no. 30 (1960) .
6. Houston Research Institute: "Heat
transfer in the LTV evaporator", Saline
Water R&D Rept. no. 74 (June 1963).
7. Charvonia, D. A.: Rept. 50-1, Jet Pro
pulsion Center, Purdue University
(1959) .
293
 8. McManus, H. N.: OOR Project 2117,
Cornell University, Sibley School of
Mechanical Engineering, Cornell Univ.
Interim Rept. no. 1 (Oct. 1959) .
9. Kapitza, P. L.: Zh. Eksperim. i Tear.
Fiz. no. 18 (1948) p. 3.
10. Hanrathy, T. J.; Hershman, A.: AIchE
J. no. 7 (1961) p. 488.
11. Wicks, M.; Dukler, A. E.: AIChE J.
no. 6 (1960) p. 463.
12. Silvestri, M.: Advances in Heat Trans
fer vol. 1, Academic Press (1964) .
13. Dukler, A. E.; Wicks, M.: Chapter 7,
Modern Chemical Engineering, vol. I,
Ed. A. Acriuos, Reinhold (1964) .
14. Sinek, J. R.: Ph.D. Thesis. University
of Michigan (1961).
15. Jakob, M.: "Heat transfer", vol. I,
Wiley (1953).
16. Collier, J. G.; Hewitt, G. F.: British
TR. Inst. Chem. Engrs. no. }9 (1961)
p. 127.
17. Hewitt, G. F.; King, I.; Love. P. C:
British Chemical Engineering no. 8
(1963) p. 311.
18. Unterberg, W.: Personal Communica
tion (Feb. 1965).
19. Lisbin, H. S.; Vanderwater, R.; Fauske,
H.; Singh, S.: TR. ASME J. Heat Trans,
no. 83 (1961) p. 149.
20. W. L. Badger, et al: "Operation of the
LTV evaporator at Wrightsville Beach.
North Carolina", Saline Water R&D
Rept. no. 26 (Dec. 1959) .
21. Lockhart, R. W.; Martineiii, R. C:
Chem. Eng. Progress no. 45 (1949)
p. 39.
22. Dukler, A. E.: Ph.D. Thesis. University
of Delaware (1951) .
23. Martineiii, R. C; Nelson, D. В.: TR.
ASME no. 70 (1948) p. 695.
24. Bergelin, et al: "Proc. Heat Transfer
and Fluid Mech. Inst.". A.S.M.E. (1949)
p. 19.

SUMMARY OF DISCUSSION
A question was asked about the methods fluted tubes. The author replied that he
on which the author based his figures and does not believe the method of analysis is
if his method of analysis would apply to applicable.

Aspects du Courant en Deux Phases

et du Transfert de Chaleur Dans Les

Procedes de Conversion Par

Distillation

L. C. Elliott et A. E. Dukler

Etats-Unis d'Amérique

INTRODUCTION
Les étapes de vaporisation et de conden de chaleur, le débit, les dimensions de
sation dans les procédés de conversion par l'équipement, la chute de pression et la
distillation sont caractérisés par la présence stabilité de fonctionnement. On peut citer
de deux phases. Dans certaines conditions, quelques exemples de cette influence dans
les caractéristiques d'écoulement de ces les procédés bien connus à tubes verticaux
phases et leur action réciproque influencent et à vaporisation spontanée en étages multi
profondément d'importantes variables de ples. Les facteurs de conception que l'on
conception telles que le taux de transfert montre comme dépendant des caractéris

294
tiques du courant des deux phases com sions des chambres à vaporisation éclair,
prennent: (a) le nombre maximum d'étages (c) le transfert de chaleur, et (d) les taux
qui peuvent être incorporés dans une instal d'entraînement dans un évaporateur à
lation à étages multiples, (b) les dimen écoulement laminaire descendant.

QUELQUES ASPECTS DU TRANSFERT DE CHALEUR DANS UN EVAPORATEUR

A TUBES VERTICAUX
Le transfert de chaleur dans un évapo En utilisant une méthode par estimations
rateur à écoulement laminaire, à tubes pour calculer la chute de pression des deux
verticaux, est analysé en détail. On propose phases, on a comparé les hypothèses avec
un modèle de transfert de chaleur, basé sur les données obtenues dans l'installation
la vaporisation de l'interface gaz-liquide où pilote à tube vertical de l'OSW (Office de
la chaleur est transférée de la paroi, à l'eau saline) , à Wrightsville Beach. Ces
travers un substrat laminaire continu, à données pilotes représentent le transfert de
l'interface ondulée où la vaporisation a chaleur, tel qu'il est mesuré dans l'en
lieu. On présente les résultats d'une analyse semble d'un tube, tandis que la théorie
théorique pour un coefficient de transfert donne les coefficients locaux. Il a donc été
de chaleur basé sur ce modèle, et on montre nécessaire de calculer la performance sup
que le coefficient local dépend du nombre posée pour le tube dans son ensemble, en
local de Reynolds, du nombre de Prandtl, faisant des intégrations numériques le long
d'un groupe de propriétés physiques et du tube, en commençant aux conditions
d'une forme sans dimensions de la rupture d'entrée observées expérimentalement. A
interfaciale. On montre que cette rupture cause de la nature répétitive des calculs et
interfaciale peut se calculer d'après la chute des nombreuses opérations de tâtonnement,
de pression par frottement dans ce système ce travail a été effectué par calculatrice. Les
à deux phases. On montre également qui conditions de fonctionnement ont couvert
la chute de pression par friction détermine les températures de 37 ä 120°C. Les écarts
la force motrice des températures à diffé moyens absolus, entre l'expérience et l'hypo
rentes positions dans le tube. thèse, sont allés de 1,8 à 5,8%.

EQUIPEMENT EXPERIMENTAL POUR LA MESURE DE LA CHUTE

DE PRESSION ET DE L'ENTRAINEMENT
On décrit un dispositif d'essais isother quantités. On peut explorer l'effet du débit,
miques, conçu pour mesurer directement la du niveau de pression, de la géométrie du
friction et l'entraînement des deux phases tube, de la configuration de l'entrée et des
et les variables influençant ces importantes conditions du courant d'entrée.

ETUDES DE CHUTE DE PRESSION

On présente des données de chute de exceptionnelle avec la méthode proposée
pression pour un courant d'eau saturée et par Bergclin, et d'autres.
de vapeur dans un tube vertical propre de Des essais dans un tube légèrement en
5 cm X 6 m 10, sous vide de 835 mb. On tartré ont révélé que cet entartrage peut
a varié les débits de l'eau et de la vapeur, avoir un effect considérable sur la chute de
de zéro à des vitesses bien supérieures à pression des deux phases dans l'écoulement
celles utilisées a l'heure actuelle dans l'in laminaire. Des mesures avec le courant de
stallation de démonstration à tube vertical. vapeur dans un tube sec ont révélé une
Comme prévu, la chute de pression augmente augmentation de friction de l'ordre de 10%
avec les vitesses de liquide et de vapeur. sur celle du tube propre. Cependant, la
L'influence du liquide sur la paroi est très chute de pression des deux phases a
significative aux vitesses de gaz plus élevées présenté une augmentation de 25 à 50%.
où le frottement se révèle être de 100 á On suggère que la présence de légèrej
300% supérieur avec le courant liquide que rugosités superficielles peut provoquer des
celui attendu lorsque la vapeur circule perturbations de la phase liquide qui sont
seule dans un tube sec. La perte de friction traduites par une ondulation intcrfaciale
dans le tube lisse s'avère être en corrélation accrue et donc un frottement plus élevé.

295
 ETUDES DE L'ENTRAINEMENT
On indique les mesures de l'entraînement ment. On montre que les épaisseurs lami
pour l'ensemble des conditions pour les naires sont en rapport avec la rupture
quelles on a obtenu des données de chute interfaciale et le débit du liquide. En se
de pression. Les données montrent que l'en- basant sur ces idées, on montre que le
trainement peut représenter de 10 à 20% rapport entre la fraction du courant liquide
du taux d'entrée de l'alimentation dans les entraîné et l'épaisseur laminaire est une
conditions de vide et la gamme de charges fonction unique de l'effort de rupture inter-
de liquide et de gaz qui sont commerciale faciale et de l'aire laminaire exposée. Le
ment possibles. premier terme se calcule d'après la chute
On suggère que la fraction du coûtant de pression et le second d'après le diamètre
qui est entraînée dépend de la force totale et la longueur du tube. On montre que les
de rupture agissant sur l'écoulement lami données sont bien en accord avec cette
naire, ainsi que de l'épaisseur de cet écoule corrélation préliminaire.

ETUDES SUPPLEMENTAIRES
On décrit des études supplémentaires, y et dimensions de tubes, et la mesure directe
compris des extensions des mesures et des des coefficients locaux de transfert de
corrélations à des pressions plus élevées et chaleur.
plus faibles, d'autres configurations d'entrée

Черты Двухфазного Потока

и Теплообмена в Процессах

Опреснения Перегонного Типа

Л. К. Эллиот, А. Е. Даклер

Соединенные Штаты Америки

ВВЕДЕНИЕ примеров относительно многоступен

Испарение и конденсация в перера
батывающих процессах перегонного
типа характеризуются присутствием
двух фаз. При некоторых условиях, по
ведение потока этих двух фаз и их
взаимодействие глубоко влияют на та
кие проектные переменные, как ско
рость теплообмена, мощность потока,
размеры оборудования, перепад давле
ния и оперативная устойчивость. Мож
но упомянуть несколько известных
чатых испарительных установок с мгно
венным вскипанием и с вертикальными
длиннотрубными испарителями. Факто
ры проектирования, которые зависят
от характеристик двухфазного потока
включают в себе (а) максимальное ко
личество ступеней, которые могут
быть включены в многоступенчатую
установку, (б) размеры камер мгновен
ного вскипания, (в) теплообмен, (г)
скорость уноса в испарителе стекаю
щей пленки.

Некоторые черты теплообмена в вертикально-трубном испарителе

Теплообмен в вертикально-трубном
испарителе стекающей пленки рассма
тривается в подробностях. Предлага
ется модель теплообменника, основан
ная на испарении с поверхности раз
дела газ-жидкость, причем теплота пе-
реносится от стенки сквозь субстрат
непрерывной пленки к волнистой по
верхности раздела, где происходит ис
парение. Представлены результаты те
оретического анализа коэффициента
теплообмена этой модели и показано,
что местный коэффициент зависит от
местного числа Рейнольдса, числа
Прандля, группировки физических
свойств и безразмерной формы сдвига
по поверхности раздела. Этот сдвиг по
разделу может быть рассчитан по пе
репаду давления трения в этой двух
фазной системе. Падение давления тре
ния определяет движущую силу тем
пературы в различных точках вверх по
трубе.
Применяя предположительно выра
ботанный метод расчета двухфазного
перепада давления, прогнозы теории
были проверены на основании данных,
полученных на вертикально-трубной
опытной установке Райствиль Бич,
управления по опреснению соленых
вод. Эти испытательные данные каса
ются теплообмена по всей трубе, тогда
как теория указывает местные коэффи
циенты. Таким образом стало необхо
димым рассчитать ожидаемое действие
для всей трубы, делая многочисленные
интеграции вдоль трубы, начиная с
экспериментально установленных усло
вий у ее входа. Вследствие повторного
характера этих расчетов со многими
пробными и ошибочными операциями,
эта работа была сделана вычислитель
ной машиной. Рабочие условия меня
лись в порядках температур от 100 до
250°Ф. Средние абсолютные отклоне
ния опыта от теоретических прогнозов
колебались между 1,8 и 5,8%.

Опытное оборудование для измерения перепада давления и коэффициент

увлечения
Описывается опытное изотермическое
устройство, которое сконструировано
для того, чтобы непосредственно из
мерять трение двух фаз и увлечение, а
также переменные, влияющие на эти
важные величины. Могут быть исследо
ваны: эффект скорости потока, уровня
давления, очертания трубы, формы вхо
да и условий входящего потока.

Изучение перепада давления

Представлены данные о перепаде
давления в насыщенном потоке воды
и пара в чистой 2-х дюймовой трубе в
20 футов высоты при вакууме в 25
дюймов ртутного столба. Скорость по
токов, как жидкости, так и пара в от
дельности изменялись от нуля до ско
ростей значительно выше тех, которые
в настоящее время применяются в вер
тикальных трубах показного завода.
Перепад давления повышается вместе
со скоростями жидкости и пара, как
это и ожидалось. Влияние жидкости у
стенки очень значительно при высоких
газовых скоростях, когда трение ока
зывается на 100 - 300% выше при жид
ком потоке, чем ожидается при исклю
чительном потоке пара в сухой трубе.
Потери на трение в гладкой трубе опре
деляются особенно хорошо методом,
предложенным Бергелином и др.
Опыты с трубой слегка покрытой на
кипью показали, что накипь может
оказывать значительное влияние на пе
репад давления двухфазного пленочно
го течения. Измерения потока пара в
сухой трубе показали увеличенное тре
ние порядка 10% выше трения в чи
стой трубе. Однако, было показано,
что перепад давления в двухфазном
потоке увеличивается на 25 - 50%. Ука
зывается, что наличность небольшой
шероховатости поверхности может при
вести к значительным нарушениям жид
кого потока, что выражается в усилен
ной волнистости поверхности разделе
ния и в большем трении.

Изучение коэффициента увлечения

Представлены измерения увлечения потока, которая увлечена, зависит от
для всего диапазона условий, для ко общей силы сдвига, действующей на
торых получены данные относительно пленку, а также от толщины пленки, в
перепада давления. Эти данные указы которой он течет. Показано, что тол
вают, что увлечение может достигать щины пленок связаны со сдвигом на
10 - 20% скорости питания на входе при поверхности разделения и со скоро
этом уровне вакуума и в пределах стью жидкого потока. На основании
нагрузок жидкости и газа, которые этого показано, что отношение фрак
коммерчески выполнимы. ции увлеченного жидкого потока к
Указывается, что та часть текущего толщине пленки является уникальной

297
функцией напряжения сдвига поверх второе на основании диаметра и длины
ности разделения и подверженной дей трубы. Все эти данные находятся в хо
ствию поверхности пленки. Первое рас рошем соответствии с этим предвари
считывается из перепада давления, а тельным соотношением.

Дополнительные
Описываются дополнительные иссле-
дования, включая распространение из-
мерений и корреляций на более высо-
кие и низкие давления, другие формы
исследования
у входа и размеры труб, а также пря-
мые измерения местных коэффициен-
тов теплообмена,

Aspectos del Flujo Bifásico y de la

Trasmisión de Calor en Los Proce

sos de Conversion Del Tipo

Distilacion

L. C. Elliot y A. E. Dukler

Estados Unidos de Norteamérica

INTRODUCCION
Las etapas de vaporización y condensación
en los procesos de conversión del tipo
destilación se caracterizan por la presencia
de dos fases. En ciertas condiciones, el com
portamiento del flujo de estas fases y sus
interacciones ejercen una profunda influ
encia sobre importantes variables de diseño
tales como régimen de trasmisión de calor,
capacidad de flujo, tamaño del equipo,
caída de presión y estabilidad de la opera
ción. Pueden citarse algunos ejemplos de
estas influencias en los conocidos procesos
de destilación por expansión instantánea en
etapas múltiples y en evaporadores de tubos
verticales. Los factores de diseño cuya de
pendencia en las características del flujo
bifásico se demuestra, comprenden (a) el
número máximo de etapas que pueden in
corporarse en una planta de etapas múlti
ples, (b) la fijación de las medidas de las
cámaras de expansión instantánea, le) la tras
misión de calor, y (d) régimen de arrastre
en un evaporador de lámina descendiente.

ALGUNOS ASPECTOS RELATIVOS A LA TRASMISION DE CALOR

EN UN EVAPORADOR DE TUBOS VERTICALES
Se analiza en detalle la trasmisión de de trasmisión de calor basado en este mo
calor en un evaporador de tubos verticales delo y se demuestra que el coeficiente local
y lámina descendiente. Se propone un mo depende del número de Reynolds local, del
delo de trasmisión de calor basado en la número de Prandtl, de un grupo de pro
vaporización desde la interfase gas-líquido, piedades físicas y de una forma adimen-
de acuerdo con el cual el calor es trasmi sional del corte interfacial. Se demuestra
tido desde la pared a través de un substrato que, en este sistema bifásico, el corte inter
pelicular continuo hasta la interfase ondu facial puede calcularse de la caída de pre
lada donde se produce la vaporización. Se sión por la fricción. También se demuestra
discuten los resultados de un procedimiento que la caída de presión por la fricción de
analítico teórico para llegar al coeficiente termina la fuerza de impulsión de la tem
peratura a distintos niveles en el tubo.
Utilizando un procedimiento de estima
ción para calcular la caída de presión en
los sistemas de dos fases, se comparó la
predicción de la teoría con los datos obteni
dos en planta piloto de evaporadores de
tubos verticales que la Oñcina de Agua
Salada posee en Wrightsville Beach. Estos
datos de planta piloto representan la tras
misión de calor medida a lo largo de todo
el tubo, mientras que la teoría proporciona
coeficientes locales. Es así que fue necesario
predecir mediante cálculo la trasmisión de
calor para todo el tubo haciendo integra
EQUIPO EXPERIMENTAL PARA LA MEDICION DE LA CAIDA
DE PRESION Y EL ARRASTRE
Se describe una unidad de prueba iso
térmica, diseñada para medir directamente
la fricción y el arrastre en los sistemas bi
fásicos y las variables que afectan estas im
portantes cantidades. Se pueden estudiar los
ESTUDIOS SOBRE LA CAIDA DE PRESION
Se presentan los datos relativos a la caída
de presión para un flujo de agua y vapor
en estado de saturación en un tubo vertical
limpio de 2 pulgadas por 20 pies a un
vado de 25 pugadas de Hg. Los caudales del
flujo del líquido y el vapor fueron variados
cada uno desde cero hasta valores bien por
encima de los empleados actualmente en la
planta de demostración de evaporadores de
tubos verticales. La caída de presión aumenta
con los caudales del líquido y del vapor en
la forma esperada. La influencia del líquido
sobre la pared se manifiesta más a flujos
gaseosos elevados y se demuestra que, en
estas condiciones, la fricción con flujo líquido
es de 100 a 300% más alta que la esperada
cuando el vapor circula sólo por un tubo
seco. Se demuestra que la caída de presión
por fricción en un tubo de superficie lisa
puede calcularse excepcionalmente bien me
ESTUDIOS SOBRE EL ARRASTRE
Se dan a conocer mediciones del arrastre
para toda la gama de condiciones dentro de
la cual se obtuvieron datos sobre la caída
de presión. Los datos muestran que el arras
tre puede representar entre un 10 y un
20% del caudal de alimentación de entrada
en estas condiciones de vacío y dentro de
los caudales líquidos y gaseosos comercial-
mente factibles.
Se sugiere que la fracción de la corriente
arrastrada depende del esfuerzo total de
ciones numéricas a lo largo del mismo a
partir de condiciones observadas experi-
mentalmente a la entrada del tubo. Debido
a la naturaleza repetitiva de los cálculos
y a los numerosos pasos que debían efec
tuarse por método de tanteo, este trabajo
fue realizado mediante una computadora
electrónica. Las condiciones de funciona
miento abarcaron una gama de tempera
turas de ÍOCF (37,66°C) a 250°F
(121,11°C). Las desviaciones absolutas me
dias entre los datos experimentales y las
predicciones teóricas oscilaron entre el 1,8
y el 5,8 por ciento.
efectos del caudal de flujo, el nivel de la
presión, la geometría del tubo, la configura
ción de la entrada y las condiciones del flujo
de entrada.
diante la correlación propuesta por Bergelin
y otros.
Las pruebas realizadas con un tubo con
leves incrustaciones revelaron que las mis
mas pueden ejercer gran influencia sobre
la caída de presión en el flujo de la lámina
en los sistemas bifásicos. Las mediciones
realizadas sobre flujos de vapor en un tubo
seco revelaron un aumento en la fricción
del orden del 10% con respecto a la experi
mentada en un tubo limpio. Sin embargo,
se demostró que la caída de presión en un
sistema de dos fases aumenta de un 25 a
un 50%. Se indicó la posibilidad de que
la rugosidad de la superficie levemente
descascarada cause perturbaciones en la fase
líquida que se reflejan como un aumento
en la ondulación interfacial, incrementando
de este modo la fricción.
corte aplicado sobre la lámina así como
también del espesor de la lámina en la
cual fluye. Se demuestra que los espesores
de la lámina guardan relación con el corte
interfacial y con el caudal del flujo líquido.
Con base en estas ideas, se demuestra que
la relación entre la fracción del flujo
líquido arrastrado y el espesor de la lámina
es una función singular del esfuerzo de corte
interfacial y la superficie expuesta de la
lámina. La primera magnitud puede calcu-
299
 larse de la caída de presión y la segunda Se demuestra que los datos están bien co-
a partir del diámetro y la longitud del tubo. ordinados por esta correlación preliminar.

ESTUDIOS ADICIONALES
Se describen estudios adicionales, inclu- otras configuraciones de la entrada y di-
sive la extensión de las mediciones y de las mensiones del tubo y las mediciones directas
correlaciones a presiones mayores y menores, de coeficientes locales de trasmisión de calor.

300
General Review of
Sea Water Conversion
at the University of California
Everett D. Howe
United States of America
INTRODUCTION
Experimental research on the desalination
of water has been in progress since 1952
at the University of California. Investiga
tions in this field are being carried on at
the Berkeley, Los Angeles, and San Diego
campuses. A report on the accomplishments
up to 1961 was presented in June of that
year at the Woods Hole Desalination Re
search Conference and is reported in the
Proceedings (ref. 55) . This report will,
therefore, deal with more recent programs
of research and the results obtained.
Before discussing specific investigations, it
is advisable to consider certain facts about
the University of California research pro
gram. The purpose of the research is to
determine whether any methods can be
found or evolved by which large quantities
of fresh water—50 mgd or more—could be
obtained from the sea or other saline
sources at a cost competitive with the maxi
mum costs of normal water supplies. The
maximum cost of municipal water is about
30 cents per thousand gallons (kgal) and
that of irrigation water is about 12 cents
per kgal. The major financial support for
the research has been annual appropriations
the Work of the
Laboratory
by the California State Legislature. Recently
there have been several grants from the
Office of Saline Water for specific investiga
tions.
It will be noted that a large variety of
investigations is being made on the several
campuses of the University. This variety is
due to the differences in interests of the
faculty members who participate in the
work. By tradition a faculty member may
choose the subject on which he wishes to
do research; and in this program, the faculty
member proposes the objectives and meth
ods to be followed. The proposal is reviewed
by a committee, and funds are appropri
ated after it it determined that the investi
gation falls" within the scope of the research
effort. Investigations are carried out by the
faculty member assisted by graduate stu
dents and, in some cases, by full-time gradu
ate engineers and scientists.
Results of the various investigations arc
summarized in occasional project reports,
issued whenever the experimental results
may be complete in some particular phase.
A list of these reports will be found in
the references at the end of this paper.
301
 Summary of Research and Development Studies
The experimental investigations may be arrangement is only for convenience:
grouped in various ways. The following
Basic studies Distillation Electrodialysis
Thermoeconomic studies Multiple-effect rotating; evaporator
Corrosion Vacuum flash distillation Freeze separation
Properties of sea water Thin film heat transfer studies
Effect of air on condensation Ion-exchange
Biological studies Immiscible heat transfer liquids Nuclear heat sources
Temperature for maximum economy
Humidification processes
Scale formation and control
In the following paragraphs an attempt reverse osmosis, since it is the subject of
will be made to give the principal findings a full-length discussion in another paper
in the several fields, except that only very being presented at this Symposium.
general remarks will be made concerning

BASIC STUDIES
THERMOECONOMIC STUDIES leadership of Professor K. Nobe. The re
ports of these investigations (refs. 11, 16. 17.
tarlv in the research program an investi 18. 39. 40, 41, 48) cover a wide range of
gation was begun of the general relation topics. The effects of stress, illumination
ships between thermodynamic and economic intensity, arid oxygen concentration have
factors. The final report by Tribus and been studied, as well as the characteristics
Evans (refs. 19, 49) which appeared in of certain corrosion inhibitors. These basic
1962 presented an "optimum energy tech studies are preliminary to the study of cor
nique" for determining the energy require rosion problems in distillers or other de
ment corresponding to the minimum unit salting equipment.
cost of water produced by any plant. Л
consideration of the general problem of PROPERTIES OF SEA WATER
separating fresh water from sea water shows Calculations relating to the desalination
that the energy required by an ideal process of sea water require the use of numerical
would be only a small fraction of that re data on the various physical and thermo
quired by existing processes. Since the cost dynamic properties of sea water and its
of energy' is a major component of the total concentrâtes. A search of the literature fur
cost of desalinated water, there is much to nished data for atmospheric conditions but
be gained by increasing the efficiency of gave only a few discordant data at elevated
separation processes. However, as the au temperatures. Gastaldo (réf. 21) used the
thors repeatedly point out. if increases in available data to evaluate the constants in
efficiency are accompanied by increases in a series of interpolation equations. He
capital costs, the amortization of such in studied vapor pressure, density, partial
creased costs may outweigh the gains ac molal volume of the water component, os
complished in decreasing the cost of energy. motic pressure, and boiling-point elevation.
The general methods in the report are Values for some of these properties were
applied to a series of typical plants and the computed and tabulated in the report.
conditions for minimum cost of water de A parallel study was made by I'nterberg
termined. For example, a multiple-stage (ref. 51) on sodium chloride solutions. In
flash distillation plant is considered and addition to those noted above, other prop
shown to yield distillate at the rale of 50 erties, including viscosity, thermal conduc
mgd and at a cost of .13 cents per kgal. tivity, and diffusivity were studied. This was
Using design parameters with currently ac possible because of the greater number of
cepted magnitudes, the heat transfer area experimental data available for sodium
would need to be of the order of 8,000.000 chloride solutions as compared to those for
sq ft. It would be interesting to apply this sea water. Results of this study are given in
method to some of the new conceptual de a scries of graphs for temperatures up to
signs for plants of 50 mgd capacity. 212°F.
CORROSION In addition to the above studies, it should
be noted that an Office of Saline Water
A major study of corrosion was under grant is being used by Professor L. A. Brom
taken at the Los Angeles campus under the ley to study the heat capacity and boiling
point elevation of sea water at high tem
peratures. This work is being done at the
San Diego campus.
BIOLOGICAL METHODS
Experiments on the treatment of waste
waters issuing from waste treatment plants
had indicated that algae were capable of
absorbing certain ions, such as phosphates
and carbonates, in the process of growth. It
was thought that some strain of algae might
be found which would absorb other ions,
such as sodium, magnesium, sulphate, and
chloride. Careful experiments by Oswald
(ref. 56) at the Berkeley campus led him
to conclude that the strains of algae which
he was able to use would not absorb the
ions normally found in sea water. However,
he suggested that some strains of algae
could be found which would propagate very
rapidly in solar stills at the elevated tem
peratures therein. If the algae were then
harvested and utilized for fuel, the heat
generated by the combustion of the fuel
could be used to produce water by distilla
tion: the carbon dioxide in the exit gases
from the combustion device could be used
for the nurture of more algae in the solar
still basins. In spite of the apparently at
tractive features, no experiments have been
done along this line.
Experiments with blends of sea water and
DISTILLATION
Numerous investigations in this held
undertaken by the University of California
researchers have ranged from the study of
scaling or salt deposition on heating sur
faces to the testing of pilot plants which
exemplify untried arrangements of equip
ment.
MULTIPLE-EFFECT ROTATING EVAPORATOR
Probably the best known of the Univer
sity of California pilot plant studies has
been the multiple-effect rotating evapo
rator (ref. 15) conceived and built by
Professor L. A. Bromlev. This equipment
consists of a steel drum, rotating about a
vertical shaft and containing a stack of
thin concentric circular copper plates four
feet in diameter and spaced about one-half
inch apart. .Sea water is admitted at the
center on the top of each plate and is
thrown toward the periphery by centrifugal
force. The flow rates and geometry are de
signed to produce a rather uniform thin
layer of water moving outward over the sur
face of the plates. The priphery of the plates
is sealed by gasket rings about five inches
waste water at the Los Angeles campus led
Bush (refs. 6-10) to conclude that algae were
capable of adsorbing certain unwanted ions
from sea water. He turned his attention to
the exploitation of this phenomenon but was
unable to obtain results in a large tank
comparable with those he obtained in a
small tank. As an offshoot of this work,
considerable work was done with the growth
of algae in circulating ponds at the Hy
perion waste treatment plant. The effluent
from the activated sludge section was run
through a shallow U-shaped pond into
which CO, gas had been introduced as a
nutrient. The growth rates of algae were
observed, as well as several of the physical
and chemical characteristics of the water
entering and leaving. While high values of
algal growth rate were observed for short
periods of time, the sustained high yield
expected on the basis of the small-scale ex
periments on the Los Angeles campus was
not realized. Thus, the use of algae for the
desalination of sea water or other water con
taining objectionable cations and anions
other than carbonates and phosphates does
not seem promising. However, the use of
algae for tertiary treatment of waste treat
ment plant effluents would seem desirable
and could make possible extended reuse
of waste water.
wide which, together with the copper
plates, form a heat exchanger for counter-
currently heating the incoming sea water
with the outgoing brine and distillate.
Steam is used to heat the bottom side of
the plate next above it. thereby reusing the
heat energy. This device was first tested at
the Richmond Field Station where water
from San Francisco Bay was used as the feed
supply and. finally, at the University of
California Sea Water Test Facility, on the
San Diego campus, where full-strength ocean
water was avaiable. The final tests of this
device were conducted using twenty-four
plates in the stack. This assembly produced
nearly 8000 gpd with a gained output ratio
of lfi.5 pounds of product per pound of
steam. The rotation of the assembly at 700
rpm required about nine kilowatts of elec
trical power. Based on these tests, a cost
estimate for a 10 mgd plant was made,
assuming the use of 1,000 units was 10,000
gpd capacity each, and showed a water pro
duction cost of 60 per cents per thousand
gallons. Since this estimated cost was un
attractive as compared with the estimated
303
 costs of water now being claimed for large
plants of other types, it was decided to dis
continue the work on this unit even though
certain problems had not been completely
solved.
The present experimental program at
San Diego is concerned with another type
of distillation, the multieffect flash (MEF)
system. As conceived by Professor Bromley,
this consists of a vertical tower containing
a number of effects. Within each effect,
there occurs a flashing process so that vapor
is produced both by flashing and by surface
evaporation. Preliminary design estimates
indicate attractive economies in both con
struction and operational costs. Experi
mental work on a small-scale tower has
begun.
VACUUM FLASH DISTILLATION
Another pilot plant investigation has been
carried on for the study of vacuum flash
distillation using low temperature differ
ences (refs. 4, 5) . This scheme uses two
sources of saline water at different tempera
tures, the warmer being used to furnish heat
for evaporation and the colder being used
to absorb heat and cause condensation.
Early tests of a pilot plant using a dome-
shaped vacuum chamber twelve feet in
diameter revealed that the useful output
was limited to about 2.000 gpd due to the
carryover of saline fog droplets which had
been formed during the flashing process.
Studies of various devices for decreasing
the amount of fog formed during flashing
were completed in 1964 and led to an in
crease in the capacity of the pilot plant up
to about 6,000 gpd. The pressure-reducing
device used for the flash evaporation process
is an annular orifice which discharges
supersaturated water downward over the
surface of a vertical tube some five inches
in diameter. The design information from
this pilot plant is nearlv complete and will
be used to predict the performance of a
large plant.
THIN FILM HEAT TRANSFER STU0IES
Several studies have been made of the
high heat transfer rates possible when
water, from which evaporation is to take
place, is arranged in thin films. Thin films
may be produced on solid surfaces in a
variety of ways. The multiple-effect rotating
evaporator already discussed utilizes cen
trifugal forces to produce thin films. The
use of gravity to produce thin films on
vertical surfaces is exemplified by the Free-
port distillation plant, using vertical tubes
two inches in diameter and 26 feet in
304
length. Since values of the heat transfer
coefficients reported for the Freeport plant
were thought to be low, experiments were
undertaken by Broker and McCutchan (ref.
57) and by Unterberg et al (refs. 50-53) at
the Los Angeles campus. Broker and Mc
Cutchan used falling films on the insides of
long tubes with a maximum size of 0.90
inches in diameter, whereas Unterberg et al
tested falling films on the outer surface of
a tube three inches in diameter but only 23
inches in length. These experiments indi
cated that it was possible to achieve heat
transfer coefficients of the order of 1500
hr x f«* X ^* for evaporation and, further,
that there was a maximum tube length foi
given conditions of flow rate and tempera
ture beyond which the total rate of evapora
tion for the whole tube would decrease. This
latter effect would be of prime importance
to designers of plants of the Freeport type
and is being investigated.
Another scheme for producing thin films
during evaporation is the use of wiper
blades to spread the water over the surface,
as reported by Lustenader et al (ref. 58) .
An experimental unit designed for evapora
tion from a film on the outside of a three-
inch tube was tested at Los Angeles by
Unterberg et al (refs. 10. 53) . The use of
wipers on the outside rather than on the
inside of the tube made it possible to ob
serve and photograph the effects of wiper
motion. It has been established that overall
heat transfer coefficients as high as 1500
to 2,000 -r 5^ can be achieved
hr x ft* X F
by this means. Experimental work is con
tinuing.
EFFECT OF AIR ON CONDENSATION
Another heat transfer problem is the
effect of air or other noncondensable gases
on the condensation process. While it is
clear that total elimination of such gases
would be preferred, it is equallv clear that
such elimination may be expensive in some
cases and impossible in others, such as the
humidification processes. Under the direc
tion of Professor P. B. Stewart (refs. 45, 46} .
an investigation was made of the effect of
varying amounts of air on the condensation
of steam in a single-tube condenser. The
per cent of steam by volume in the mixtures
tested varied from nearly 100 per cent to
a minimum of about 10 per cent. Results
showed that heat and mass transfer coeffi
cients decrease exponentially with increas
ing air concentrations. Comparison of the
 test results and their empirical formulations
with those of other investigators was satis
factory. In most cases, data from the litera
ture covered only a small range of air-steam
concentrations for any given investigation,
so that the wide range covered by the U.C.
tests serves to relate the data from several of
the older investigations.
USE OF IMMISCIBLE HEAT TRANSFER LIQUIDS
Another study related to heat transfer is
the use of an immiscible liquid for the
transport of heat. Conceived by Professor
C. R. Wilke, the general proposal (refs.
2, 54) is to use a liquid heat transfer mate
rial which is mutually insoluble with water
and has a very high boiling point, for
example, Aroclor. This material is heated
and then mixed with sea water, thus
heating the water by direct contact. The
purpose of this is to greatly reduce the
amount of corrosion-resistant tubing ordi
narily used in condenser evaporators and
thereby reduce the capital cost of the plant.
Measurements have been made of the im
portant parameters in the evaporating and
condensing processes. Using these data, cost
estimates were made for a 14 mgd plant.
The design arrived at by an optimization
procedure would require 26 stages and
showed a capital cost of 77 cents per gpd
capacity and an operating cost of 75 cents
per kgal. Experiments are continuing on
the parametric studies.
TEMPERATURE FOR MAXIMUM ECONOMY
Efforts to reduce the cost of distillation
have centered around the possible increase
in thermal economy. One way to accomplish
this would be to increase the maximum
brine temperature so that additional effects
or stages might be added. MacLeod et al
(réf. 34) made a study of this subject on
the assumption that means could be found
for controlling scale deposition at all tem
peratures. Thermodynamic considerations
indicated that the critical quantities were
the values of latent heat, which become
zero at the critical temperature, and those
of the specific heat measured along the
saturated liquid line, which become infinite
at the critical temperature. A multiple-
stage flash distillation process was assumed,
and calculations were carried out for l>oth
a finite and an infinite numl>er of stages.
It was shown that the minimum value for
the sum of the costs of heat energy, pump
ing energy, and amortization of the heat
exchanger tubes would occur with a maxi
mum brine between 350" and 400°F.
SCALE FORMATION ANO CONTROL
When sea water is being distilled, the
evaporation of water causes local super-
saturation of the brine and precipitation of
one or more of the scaling components,
calcium carbonate, magnesium hydroxide,
and calcium sulphate. McCutchan and
dater (ref. 37) summarized the available
information on this subject and recom
mended further study of several facets. The
program at the Berkeley campus includes
a study of the equilibrium concentrations
of the scale ingredients (refs. 4. 5) at tem
peratures from 212° to 400°F. So far, data
on calcium sulphate have been completed,
and the study of calcium carbonate has been
started.
At the Los Angeles campus, experiments
(ref. 8) were started on the addition of
carbon dioxide gas to sea water. The general
hypothesis was that the addition of CO,
would retard the decomposition of the bi
carbonate ion and thereby reduce the scal
ing tendency. A submerged combustion
burner was assembled, and the gases of
combustion containing about 12 per cent
CO, were discharged into the sea water.
Final results of this test are not vet avail
able.
Under the auspices of UCLA. S. Mulford
observed scale formation in the one-mgd
distillation plant at Point Loma (réf. 10)
and prepared an M. S. thesis on the subject.
Two methods for scale control used at this
plant were (1) the addition of Hagevap
and (2) the addition of sulfuric acid. With
the latter treatment, maximum brine tem
peratures of 250°F were used, and a range
of concentrations was explored. While these
tests gave significant information on scal
ing tendencies, the time and expense re
quired were great. An attempt was made
to set up a small-scale laboratory experi
ment (ref. 10) which would behave simi
larly to the Point Loma plant. This work
is currently under way.
HUMIDIFICATION PROCESSES
Solar distillation has been dealt with in
a number of reports (refs. 1-5, 32. 53^ . The
work at the Richmond Field Station has
been directed toward the development of
low cost, but efficient, simple distillers,
suitable for producing small quantities of
potable water. The most efficient units con
structed thus far are of the tilted-trav tvpe:
one version of this has a copper-foil water
tray and a glass cover. Other units reentlv
developed are constructed with sheet plastic
materials for basin liner and transparent
cover. The cost of materials alone for this
305
 latter design is about $5 per gpd capacity.
Extensive testing of various designs has
demonstrated that wood, even though care
fully painted, is not suitable for use in
contact with saline water. For maximum
efficiency, the two most important factors
seem to be (1) the heat capacity of the
water and its container, which should be
as small as possible, and (2) the average
distance between the water surface and the
glass or plastic condensing surface, which
should also be a minimum.
The use of solar distillers can be made
economical in special cases if these devices
are also arranged to collect rainfall on
their upper surface, or if warm cooling
water from Diesel engines can be circulated
through the water trays. For example, a
rainfall average of 25 inches annual pre
cipitation would increase the useful output
of the still by nearly 20 per cent if about
half of the rainfall were collected. The use
of waste heat for increasing solar still out
put is extremely effective and, in certain
cases, may triple the output. Papers dealing
with these two methods of increasing the
output have been presented by Tleimat
and Howe (ref. 59) and Howe (ref. 60) .
The use of very narrow air gaps between
two water surfaces at different temperatures
was proposed by Hassler (ref. 8) some
years ago as a means of achieving high mass
transfer rates. It was estimated that the
spacing between water surfaces could be
of the order of .001 to .005 inches for good
economy, and various means were tried for
achieving such small spacings. Thin copper
sheets were folded along a series of parallel
lines to provide water passages of roughly
triangular cross section between two parallel
surfaces. Alternate water passages opened
onto each side of the folded sheet, so that
one set of alternate passages could be mani
folded together to carry the brine, and the
other set to carry the condensate. Capillar)
forces were depended on to draw water from
the subsurface passages and spread it over
the entire exposed surface. Small grains of
graphite glued to the surface assisted in
maintaining these forces. It was supposed
that a stack of these plates with a tempera
ture gradient imposed across it would con
stitute a diffusion still. After considerable
testing, it was concluded by Thorsen (refs.
10, 47) that the gap spacings required for
economical operation were less than could
be practically and economically achieved.
Solar stills seem particularly applicable to
small installations because the unit cost
varies little with size. The University of
California (Berkeley) has been cooperating
with the .South Pacific Commission in the
possible use of solar distillation on the coral
islands and atolls of the south Pacific
Ocean. These islands, lying at latitudes
within 15° to 20° of the Equator, have
relatively high temperatures—conditions fa
vorable for solar distillation—and have peri
ods of low rainfall running from S to 5
months. Installations of about 25 gpd capa
city are in operation at Lautoka, Fiji, and
at Tiputa, Rangiroa Atoll, French Polynesia.

ELECTRODIALYSIS
The possible use of electrodialysis for the from a systems viewpoint rather than from
desalination of water having salinities of the viewpoint of membrane and stack design
10,000 to 35,000 ppm prompted the research alone.
on electrodialysis. A small pilot plant using Assisted by an Office of Saline Water
an Ionics Mark II stack was used. By re grant, research on the properties of poly-
arranging the stack to have three internal stvrenesulfonic membranes (ref. 5) has been
stages in series, it was demonstrated that underway at the Berkeley campus. Mem
high salinity water could be pumped branes of various degrees of sulfonation
through the stack without excessive short- have been produced, and instrumentation
circuiting of the electric current. Based on has been set up to measure the electrical
these tests (ref. 43) , it was estimated that properties of small samples.
an appropriate arrangement of stacks would A design study of the use of electrodialy
be capable of desalting sea water with an sis for improving the quality of drainage
energy requirement of about 45 kwhrs per water (ref. 12) was made. The example
kgal (ref. 44) . chosen related to the south San Joaquin
A small AQUAFRESH eleclrodialyver was Valley, where some 200 mgd of water with
used for studying the phenomena of polari salinity of about 8000 ppm was proposed
zation (refs. 5, 42) and ion selectivity for disposal. A plant layout was made
of various membranes. These tests showed for recovering 171 mgd of this water. The
conclusively that the characteristics of mem cost of the water produced was estimated
branes from three companies were very at 36 cents per kgal. half of which was
different. It was concluded that water desal the amortization of the plant cost.
ination by electrodialysis should be viewed
306
 FREEZE SEPARATION
Several years ago it was suggested that
the freezing point of sea water could be
lowered by the solution of COs gas and
that this lowering could serve as a regener
ative of the cooling effect. Since the solu
bility of C02 in sea water was not accurately
known or predictable, arrangements were
made (refs. 2-5) to measure it. A suitable
ION-EXCHANGE
The use of ion-exchange for desalting sea
water has proven unattractive in the past
due to the high cost of regeneration of the
exchanger materials. Another application of
this process is the softening of sea water
as a means of preventing scale deposition
in distillation plants. Under the leadership
of Professor T. Vermeulen, and with the
assistance of an Office of Saline Water grant,
both experimental and analytical work are
going forward (refs. 2-5. 22) . After testing
a number of resins, macroreticular polysty
NUCLEAR HEAT SOURCES
Recent interest in the use of nuclear
explosives has resulted in a proposal that
nuclear bombs be exploded deep in the
earth to produce a "chimney" of broken
rock. Sea water pumped into the bottom
of the fractured zone would percolate
through the broken rock and absorb from
it the residual heat due to the geothermal
gradient originally present. By using avail
REVERSE OSMOSIS
As noted at the beginning of this paper,
reverse osmosis is the subject of a full-
length paper at this Symposium. A major
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Water Resources Center Contribution
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Univ. of Calif.. Los Angeles (Mav
1964) .
53. Webb, R., et al: "Evaporation experi
ments with wiped and falling saline
SUMMARY OF DISCUSSION
It was stated that municipal water in
California costs 30 cents per thousand gal
lons, and the question of whether or not
this included all operating and mainte
nance costs through treatment plus all capi
tal costs was raised. It was also asked how
this figure was obtained. The speaker stated
that the figure was arrived at as a result
of a survey made by the University of
California staff and that it is the maximum
value; however, since the figure was arrived
at by juggling the numbers in the text of
310
water films", Water Resources Center
Contribution no. 91, Dept. of Engr.
Rept. no. 64-23, Univ. of Calif., Los
Angeles (Aug. 1964) .
54. Wilke, C. A., et al: "Sea water evapora
tion by direct contact heat transfer",
Water Resources Center Contribution
no. 79, Sea Water Conversion Lab.
Rept. no. 63-6, Univ. of Calif. Berkeley
(Aug. 1963) .
OTHER REFERENCES
55. National Academy of Sciences—National
Research Council: Desalination Re
search Conference Proceedings, Publ.
942 (1963) 451 pp.
56. Oswald, W. J., et al: "An engineering
evaluation of some currently proposed
methods for biological conversion of
saline waters", Sanitary Engineering Re
search Lab., Univ. of Calif., Berkeley
(Feb. 1960).
57. Broker. В.; McCutchan, J. W.: "Heat
transfer in a single vertical tube
falling film evaporator with dropwise
condensation", Dept. of Engr. Rept. no.
60-58, Univ. of Calif., Los Angeles
(July 1960) .
58. I.ustenader, E. L.. et al: "The use of
thin films for increasing evaporation
and condensation rates in process equip
ment", J. of Heat Transfer Trans, of
the ASME, paper no. 59-SA-30 (1959) .
59. Tleimat, B. W.; Howe. E. D.: "Noctur
nal production of solar distillers",
paper presented at the Solar Energy-
Society symposium (Mar. 1965) .
60. Howe, E. D.: "Solar distillation in the
developing countries". ASME paper no.
64-WA/SOL-7 (Dec. 1964).
61. Delort, F.: "Use of underground nu
clear explosions for sea water conver
sion", unpublished internal report, Sea
Water Conversion Lab., Univ. of Calif.,
Berkeley (May 1965) .
this paper and others, what in includes is
debatable. It was stated that the cost to a
city for bringing water in large volumes
100 miles from the mountains is about
15 cents per 1,000 gallons to which must
be added the distribution costs.
In answer to questions concerning the
number of people employed and the yearly
budget of the University of California, the
author replied that the number of gradu
ate and undergraduate students employed
(many on a part-time basis^ total about
30 at Berkeley, 25 at Los Angeles, and 8 to grants from the Office of Saline Water
12 at San Diego. The author said the totalling about $100,000.
annual budget is $450,000 plus several

Revue Generale Des Travaux

Effectues Par Le Laboratoire de

Conversion de L'Eau de Mer a

L'Université de Californie

Everett D. Howe

Etats-Unis d'Amérique

Les travaux de recherche sur le dessale dynamiques et économiques, tant dans des
ment de l'eau de mer se poursuivent à installations de dessalement théorique que
l'Université de Californie depuis 1952. Un dans des installations en fonctionnement, a
rapport antérieur, présenté à la Conférence abouti à l'élaboration d'un rapport, paru
de Woods Hole sur les recherches en ma en 1962 dans lequel a été exposée une
tière de dessalement, a résumé les progrès "technique d'énergie minimum". Cette
réalisés jusqu'en 1961 dans le domaine de technique est destinée à être utilisée pour
la recherche; le présent rapport porte sur établir un rapport optimal entre l'économie
les résultats obtenus depuis 1961. Il con de l'utilisation énergétique et les frais d'im
vient de noter que les travaux de recherche mobilisation de l'installation en vue d'assurer
sont effectués sous la direction d'un certain un prix de revient minimal pour l'eau
nombre de professeurs des sections de produite.
Berkeley, Los Angeles et San Diego. Les Une deuxième étude fondamentale, effec
intérêts variés des différents professeurs se tuée par un certain nombre d'étudiants
retrouvent dans la diversité des solutions diplômés de la section de Los Angeles,
préconisées en ce qui concerne les pro porte sur la corrosion. Une grande variété
blèmes de dessalement. de questions ont été traitées, y compris les
Les travaux de recherche de l'Université effets de l'intensité de l'éclairage et de la
de Californie sont financés, en majeure charge à une des extrémités du spectre, et
partie, au moyen de crédits extraordinaires l'emploi d'inhibiteurs à l'autre extrémité.
votés par l'Assemblée législative de l'Etat La troisième étude fondamentale traite
de Californie et sont gérés par le Centre des propriétés thermiques et physiques de
de ressources hydrauliques de Californie, l'eau, dont la plupart ne sont connues que
créé par l'Université. Quelques travaux de pour une gamme très limitée de tempéra
recherche ont bénéficié récemment d'une tures et dont la précision laisse à désirer.
assistance financière de l'Office of Saline Etant donné que l'eau de mer est une
Water (Office de l'eau saline) . Les résul solution complexe et n'est pas susceptible
tats des travaux paraissent dans des rap d'être traitée au moyen de formules phy
ports annuels succincts et dans les rapports siques et chimiques employées pour les
sur des projets particuliers; ces derniers solutions diluées simples, on a procédé à
rapports sont publiés lorsque les résultats une série d'études en vue d'établir des
des travaux sont suffisamment au point valeurs précises pour les propriétés, valeurs
pour en justifier la publication. qui sont nécessaires aux projets d'installa
Parmi les études fondamentales effectuées, tions de dessalement. Il existe quelques
il convient de mentionner les problèmes rapports ayant trait à un certain nombre de
thermo-économiques, les propriétés de l'eau ces travaux.
de mer et les problèmes de corrosion. Une On vient de terminer des études bio
étude à long terme des corrélations thermo logiques sur l'utilisation des algues dans

311
 les opérations de dessalement. Bien que l'on
ne dispose pas encore du rapport définitif
sur les travaux réalisés, on peut affirmer
que 1 'adsorption d'ions de l'eau de mer,
qui a été observée dans de petits étangs
d'algues, ne permet pas d'envisager la pos
sibilité de l'utilisation de cette méthode
pour le dessalement. L'utilisation des algues
en vue de retirer certains éléments nutritifs
des effluents des installations de traitement
de déchets de type secondaire semble- pré
senter des avantages intéressants et pourrait
être importante dans la ré-utilisation des
eaux résiduaires.
Les études relatives à la distillation ont
constitué la plus grande partie des recherches
effectuées à l'Université de Californie. Elles
ont porté sur un vaste domaine, depuis des
essais d'installations-pilotes jusqu'à l'étude
des caractéristiques d'entartrage. Les re
cherches ont porté notamment sur l'utilisa
tion de membranes minces, propres à
faciliter l'échange de chaleur pendant l'éva-
poration, en utilisant les forces centrifuges,
de gravitation et de glissement. Aucun de
ces procédés n'a donné lieu à l'élaboration
de projets rentables présentant un intérêt.
L'utilisation de liquides immiscibles pour
l'échange de chaleur par contact direct
est actuellement à l'étude en tant que
moyen propre à diminuer le nombre de
tubes d'échange de chaleur résistant à la
corrosion, abaissant ainsi le prix de revient
de l'installation. Une étude théorique a
indiqué que les distillateurs à évaporation
Общий Обзор Работы Лаборатории
по Опреснению Морской Воды
при Университете Калифорнии
Эверетт Д. Хау
Соединенные Штаты Америки
Исследовательская работа Универси
тета Калифорнии по опреснению воды
началась в 1952 г. Предыдущий доклад,
представленный на Конференции об
исследовательской работе по опресне
нию воды, имевшей место в Вудс Хол,
подвел итог тому, что было достигнуто
до 1961 г., поэтому настоящий доклад
касается результатов, полученных по-
812
instantanée a plusieurs étages auraient une
efficacité thermique maximum si les tempé
ratures des saumures étaient de l'ordre de
177 à 204°C au début de l'opération. Les
tendances des saumures d'eau de mer à l'en
tartrage à ces températures sont à l'étude,
ainsi que l'utilisation des résines échangeuses
d'ions en vue d'éliminer de l'eau de mer,
avant la distillation, les ions produisant des
dépôts de tartre. On étudie également des
méthodes d'humidification dans la distilla
tion solaire en utilisant des alambics simples.
Une étude a porté sur les surfaces capil
laires en tant qu'éléments d'un alambic à
pression atmosphérique.
L'électrodialyse a fait l'objet d'études en
laboratoire des propriétés des membranes,
de la polarisation et de la disposition des
blocs. Une évaluation du prix de revient
du dessalement de l'eau ayant une salinité
initiale de 8.000 parties par million a permis
certains espoirs pour l'emploi de cette
méthode avec de l'eau ayant un taux de
salinité encore plus élevé.
Une étude sur l'emploi des explosifs
nucléaires en vue d'utiliser la chaleur géo
thermique souterraine a fait ressortir que
le prix de revient d'une telle entreprise ne
semble guère présenter d'intérêt à l'heure
actuelle.
L'osmose inversée a été un élément im
portant du programme de recherche à Los
Angeles et fait l'objet, à ce Symposium,
d'une communication distincte.
еле этого времени. Надо отметить, что
научно-исследовательская работа ве
дется в университетских кампусах Бер-
келей, Лос-Анжелос и Сан-Диего под
руководством членов академического
состава. Их различные академические
интересы отражаются на разнообразии
подходов к проблемам опреснения.
Научно-исследовательская работа
Университета Калифорнии главным об
разом поддерживается за счет специ
альных ассигнований со стороны Зако
нодательного собрания штата Калифор
ния, которые распределяются через
Всештатный центр водяных ресурсов
Университета Калифорнии. На несколь
ко исследований расходуются допол
нительные дотации со стороны Управ
ления по опреснению соленых вод. Ре
зультаты исследований печатаются в
кратких годовых отчетах и докладах,
касающихся специальных заданий, ко
торые выпускаются, когда результаты
научной работы становятся достаточно
законченными чтобы оправдать их
опубликование.
В основных трудах были изучены
термоэкономические проблемы, свой
ства морской воды и проблемы корро
зии. Доклад, выпущенный в 1962 г., в
котором излагается «техника минималь
ной энергии», был апогеем анализа
долгосрочной термодинамической и
экономической зависимости, существу
ющей в опреснительных установках,
как теоретического, так и практическо
го назначения. Эти технические прие
мы предназначены для выбора наилуч
шего решения, диктуемого бережли
вым использованием энергии и капи
тальными затратами по постройке
установки, с целью снижения до мини
мума стоимости опресненной воды.
Вторым объектом основных исследо
ваний была коррозия, чем занимался
ряд студентов-аспирантов в Лос-Анже-
лосе. Было рассмотрено много вопро
сов, включая эффект интенсивности
освещения и приложения нагрузки на
одном конце спектра и применения ин
гибиторов на другом конце.
Третий объект основных исследова
ний относился к термическим и физи
ческим свойствам воды, большинство
которых изучено лишь при очень узком
диапозоне температур и недостаточно
точно. Так как морская вода представ
ляет собой сложный раствор, не под
дающийся обработке с помощью физи-
ческо-химического подхода, как к про
стым разбавленным растворам, был
проведен ряд исследований для уста
новления надежных критериев, необхо
димых при проектировании опресни
тельных установок. Доклады, касающи
еся части этой работы, опубликованы.
Недавно были закончены биологиче
ские исследования, касающиеся мор
ских водорослей, с целью их приме
нения для опреснения воды. Хотя окон
чательный доклад об этой работе еще
не готов, можно, однако, с уверенно
стью сказать, что адсорбция ионов из
морской воды, наблюдавшаяся в ма
леньких бассейнах с морскими водо
рослями, не привела к положительным
результатам в области опреснения
большого масштаба. Применение мор
ских водорослей для удаления некото
рых питательных веществ из вытекаю
щей воды второклассных сбросоочи-
стительных установок, видимо имеет
значительные преимущества и может
оказаться весьма полезным при пов
торном использовании сбросных вод.
Большинство работ Университета Ка
лифорнии относилось к исследованию
дистилляции. Они простирались от
испытания пробных установок до ана
лиза характеристик накипи. Для улуч
шения теплопередачи во время процес
са выпаривания было изучено примене
ние тонкой пленки, подверженной дей
ствию центробежной и гравитационной
силы, а также трения. Но это не дало
особенно положительных результатов
в области разработки экономичных
конструкций.
С целью уменьшения количества
теплопередаточных труб, сопротивляю
щихся коррозии, и тем самым удешев
ления установки, изучается применение
несмешивающихся жидкостей при не
посредственном теплообмене. Теорети
ческое исследование показало, что мно
гоступенчатые испарители с мгновен
ным вскипанием достигают максималь
ной термической производительности,
когда в начале процесса мгновенного
вскипания температура соленого раст
вора достигает 350°F-400°F. Изуча
ется склонность конденсатов морской
воды к отложению накипи при этих
температурах, а также применение ио
нообменных смол для удаления, до на
чала дистилляции, ионов из морской
воды, которые способствуют образова
нию накипи. Исследуются процессы
увлажнения, применимые при выпари
вании солнечной теплотой с помощью
простых перегонных аппаратов. Были
изучены капиллярные поверхности, яв
лявшиеся составной частью выпарного
аппарата, работавшего при атмосфер
ном давлении.
Что касается электродиализа, то
свойства мембран, поляризация и уст
ройство мембранных групп явились
предметом лабораторных исследований.
Были составлены сметы стоимости оп
реснения воды с исходным солесодер-
жанием 8.000 мг/л, которые дают на
дежду, что этот процесс применим к
313
 воде, обладающей даже еще большим
солесодержанием.
Изучение ядерных взрывчатых ве
ществ для получения подземног гео
термического тепла показало, что в
настоящее время такое предприятие
Exposición General
Realizados por el
Conversion del Agua
Universidad de California
Everett D. Howe
Unidos de America
Investigaciones sobre la desalinización del
agua de mar se han llevado a cabo en la
Universidad de California desde 1952. Un
informe anterior que se presentó ante la
Conferencia de Investigaciones sobre la De
salinización reunida en Woods Hole, dió un
resumen de los adelantos obtenidos hasta
1961, de tal manera que el presente informe
trata sobre los adelantos realizados desde
1961. Se hace notar que estas investiga
ciones se realizan bajo la dirección de dife
rentes miembros de las facultades de Berke
ley, Los Angeles y San Diego. La diversidad
de intereses de los miembros de las dife
rentes facultades se refleja en la variedad
de los enfoques de los problemas de de
salinización.
Los trabajos de investigación efectuados
por la Universidad de California son fi
nanciados principalmente a base de partidas
especiales asignadas por la legislatura del
estado de California, las cuales a su vez
son administrados por el Centro Estatal de
Recursos de Agua de la Universidad de
California. Fondos adicionales provistos por
la Oficina de Agua Salada también se utili
zan en algunos de estos estudios. Los re
sultados de las investigaciones se publican
en los informes anuales resumidos y en
los informes de proyectos especiales. Estos
últimos se expiden cuando los resultados de
las investigaciones son suficientemente com
pletos como para justificar su publicación.
Entre los estudios básicos que se consi
314
невыгодно.
Обратный осмос был важной частью
научно-исследовательской программы в
Лос-Анжелосе и на этом Симпозиуме
о нем представлен отдельный доклад.
de los Trabajos
Laboratorio de
de Mar de la
deraron estaban comprendidos los proble
mas termocconómicos, las propiedades del
agua de mar y los problemas de la corro
sión. Un estudio a largo plazo de las inter-
relaciones termo-dinámicas y económicas de
plantas de desalinización, tanto ideales com
prácticas, dió como resultado la publica
ción de un informe en 1962, en el cual se
describió una "técnica de energía óptima".
Esta técnica tiene por objeto obtener la
relación óptima entre la economía en la
utilización de energía y el costo de capital
de la planta, para que el costo de la pro
ducción de agua resulte el mínimo.
Un segundo estudio básico, que trata
sobre la corrosión, se llevó a cabo en Los
Angeles por un grupo de estudiantes uni
versitarios posgraduados. Se consideró un
número amplio de factores, incluso los efec
tos de la intensidad de iluminación, y de
la concentración en un extremo del espectro
y el empleo de inhibidores en el otro.
El tercer estudio básico se relaciona con
las propiedades térmicas y físicas del agua,
la mayoría de las cuales se conocen sola
mente dentro de una gama de temperaturas
muy limitada y con exactitud moderada.
En vista de que el agua de mar es una
solución compleja y no es susceptible de
ser tratada con las fórmulas físicas y quími
cas para las soluciones diluidas simples, se
ha llevado a cabo una serie de estudios
con el objeto de establecer valores con
fiables de las propiedades necesarias para
 el diseño de las plantas desalinadoras. resultados de un estudio teorético indican
Pueden obtenerse los informes sobre estos que plantas destiladores de varias etapas
trabajos. y de vaporización rápida, serían térmica
Recientemente se han completado estu mente eficientes si la temperatura de la
dios biológicos relacionados con el uso de salmuera fuera de 350°F o 400°F al co
algas en la desalinización del agua. A pesar mienzo del proceso de vaporización rápida.
de que el informe final de las investiga Se están estudiando las tendencias de la
ciones todavía no está disponible, se puede salmuera a formar incrustaciones a estas
decir con seguridad que la adsorción de temperaturas, como también el uso de resi
iones del agua de mar que se ha observado nas para remover del agua de mar, antes
en pequeños estanques de algas, no ha de la destilación, los iones que forman estas
demostrado que este método tenga alguna incrustaciones. También se están estudiando
posibilidad para la desalinización del agua procesos de humidificación para destilación
en gran escala. El uso de algas para elimi solar en destiladoras simples. Otro estudio
nar ciertos materiales nutritivos del agua que se ha llevado a cabo se relaciona con su
efluente en instalaciones para el tratamiento perficies capilares como partes componentes
de residuos de tipo secundario parece tener de una destiladora a presión atmosférica.
considerable mérito y podría ser impor La electrodiálisis ha sido objeto de estu
tante en la reutilización de aguas residuales. dios de laboratorio sobre las propiedades
La mayoría de las investigaciones sobre de las membranas, de la polarización y de
destilación se han llevado a cabo en la los efectos del arreglo en superposición. Se
Universidad de California. Estas investiga ha estimado el costo de la desalinización
ciones han variado desde pruebas de plantas del agua con uno contenido salino inicial
piloto hasta el estudio de las propiedades de 8000 partes por millón, y el resultado
de las incrustaciones salinas. Se ha estu ha dado lugar a cierto optimismo respecto
diado el uso de películas delgadas para del uso de este método con aguas de salini
facilitar la termotransferencia durante la dad aun más elevada.
evaporación, mediante el empleo de las Un estudio del uso de explosivos nu
fuerzas centrífuga, de la gravedad y la cleares para producir calor geotérmico sub
frotación. Ninguna de estas fuerzas ha re terráneo dió como conclusión que el costo
sultado en un diseño económico de con de tal proceso es demasiado elevado en el
sideración. Se estudia el uso de líquidos momento actual.
inmiscibles para la termotransferencia por La ósmosis en reverso ha sido un renglón
contacto directo, como un medio para importante del programa de investigaciones
reducir la cantidad de tubos termotransmi- en Los Angeles, por lo cual es objeto de
sores resistentes a la corrosión, lo cual a un informe separado en este Simposium.
su vez reduciría el costo de la planta. Los

315
 Methods for Scale Control in
Flash Systems
R. A. Tidball and R. E. Woodbury
United States of America
INTRODUCTION
The thermal efficiency of a multistage
flash distillation sea water conversion plant
is, to a large extent, dependent on the tem
perature range over which flashing occurs.
This is demonstrated in Figure 117. The
sea water or brine enters the condenser tubes
at the last stage at a temperature, t„ and
is heated regeneratively by the condensing
product in the condenser tubes of all the
stages to a temperature, t„ at the outlet
of the first stage condenser. It is then fur
ther heated to a temperature, ts, by an
external source of energy and introduced
into the first stage flashing chamber. The
brine is then sequentially flashed through
all stages to a temperature, I,, at the outlet
of the flash chambers of the last stage.
If boiling point elevation, nonequilibrium,
and heat losses from the plant are ignored,
the total product can be predicted by the
equation:
w„cp (t.,-t.)
Q= (I)
The energy required in the heat input
section (heating the brine from t2 to t,) is
determined by the equation:
H (t.-g
where
Q — Product water—lbs/hr
w. = Flow rate of brine—lbs/hr
c. = Specific heat of brine—Btu/
lb°F
h. = Latent heat of vaporization
—Btu/lbs
q = Heat input—Btu/lb prod
uct
ti, t,, t„ t. — Brine temperature from
Figure 117
Since the temperature rise in the brine
heater is limited to a minimum figure of
8° to 10°F by such factors as the boiling
point elevation of the brine, nonequilib
rium, pressure loss in the vapor between
the flashing brine and the condenser and
the economic requirement of a reasonable
quantity of heat transfer surface in the
stage condensers, the only method of reduc
ing the external energy requirements is to
increase the flashing range, t,-t4.
Increasing the flashing range of the brine
also reduces the quantity of brine circu
lated for any given output. This decrease
in brine flow rate can result in an
appreciable reduction in the number of
parallel tubes in the stage condensers, de
creasing the capital cost of the plant.
In general, the more stages included in
any flash distillation plant, the less surface
will be required to achieve a given economy.
The number of stages is limited by the
flashing range of the brine in each stage.
Increasing the flashing range permits the
inclusion of more stages, decreasing both
the capital cost of the plant and the energy
requirements.
SOURCE OF SCALE
Scale, as it occurs in flash distillation
plants, can be defined as "a deposit formed
by precipitation from solution of a sub
stance which has solubility that decreases
with an increase in temperature (inverse
solubility) " (ref. 1) . In today's state-of-the-
art (temperature below 300°F) , scale is
formed by calcium carbonate, magnesium
hydroxide, or calcium sulphate. Minor foul
ing constituents such as ferric hydroxide
and silica have been observed but are of
317
 HEAT INPUT
FIGURE 117. THERMAL DIAGRAM-MULTISTAGE RECYCLE
PLASH PLANT.
lesser importance.
Calcium carbonate is formed by the
thermal decomposition of calcium bicar
bonate in sea water
Ca (HCO.) , -» CaCO, + CO, f +H.O
(3)
When normal sea water has been heated
to approximately 170°F. a sufficient amount
of calcium bicarbonate has been decom
posed and (at normal pressures) enough
of the carbon dioxide formed has been lost
from the solution to reach a condition of
calcium carbonate content and pH of the
solution where supersaturation exits and
calcium carbonate is precipitated in the
hottest part of the system.
As the brine is heated further, additional
carbon dioxide is released and the brine
.818
becomes more basic and permits the forma
tion of magnesium hydroxide scale. At tem
peratures above 200 °F and with a pH of 8.S
or greater in the hot brine, magnesium
hydroxide scale is rapidly formed. This con
dition is easily reached in a submerged tube
plant but is seldom reached in a multistage
flash plant at temperatures below 250°F.
Therefore, most of the scale found in multi
stage flash plant operating at 250T or lower
is calcium carbonate.
The stability diagram (ref. 2, p. 31) indi
cates that magnesium hydroxide scale will
never be formed when brine is below 212°F.
the pH less than 7.8, and the concentration
factor less than 3.5 (where the concentra
tion factor is based on normal sea water—
55.000 ppm).
If the formation of calcium carbonate
and magnesium hydroxide is prevented and
the brine is heated to higher temperatures,
calcium sulphate becomes the predominant
scale.
Work on calcium sulphate solubility has
been published by many investigators. These
data, along with data collected on the LTV
pilot plant, were correlated and published
by Standiford and Sinek (ref. 3) .
The effect of temperature on the solu
bility of the three scaling compounds in
sodium chloride solutions is shown in Fig
ure 118 (ref. 2, p. 24).

TEMPERATURE, °F
246 264 320 356 392 428

0 20 40 60 60 100 120 140 160 160 200 220

TEMPERATURE, °C

FIGURE 118. SOLUBILITY CURVES OF SCALING COMPOUNDS.

319
320
 It is seen that the anhydrous form of
f a SO, should limit the operating tempera
ture of the plants. However, the kinetics of
the precipitation of calcium sulphate an
hydrite are slow enough that scale does not
normally occur. The gypsum is insoluble
at all temperatures when the concentration
factor exceeds 4; but, since the higher con
centration factors are not attractive in flash
distilling processes, the formation of gypsum
is not a problem.
The hemihydrate scale (CaSO, • i/$H,0)
is of great concern and can occur in flash
distillation plants at any temperature to the
right of the hemihydrate line in Figure 118.
The Office of Saline Water has sponsored
an intensive program to determine the cal
cium sulphate scaling conditions in flash
evaporators. A portion of this work was
carried out by the Baldwin-Lima-Hamilton
Corporation under contract no. 14-01-0001-
304. A 6-stage. 10,000 gpd flash plant has
been operated at various conditions of brine
concentrations, temperature, and pH. The
brine heater used in this program was de
liberately oversized so that the approach
temperature between the brine and the heat
transfer surface was of the order of 1°F.
Therefore, the measured bulk temperature
of the brine at the heater outlet was essen
tially the scaling (interface between the
tube wall and brine) temperature.
The scaling characteristics of calcium sul
phate sea water brine solutions in flash
evaporators are shown in Figure 119. This
shows the hemihydrate (CaSO, • i/gH.O)
scaling temperature as a function of brine
concentration. These scaling points are
somewhat lower than those reported by
Standiford and Sinek (ref. 2) for the solu
bility of calcium sulphate hemihydrate in
MECHANISM OF SCALE FORMATION
The mechanism of scale formation in
flash distillation plants differs from that in
submerged tube distilling plants in that the
concentration of scaling salts is uniform
throughout the heated stream in the flash
plants while it is more concentrated at the
heat transfer surface in the submerged tube
system than in the bulk of the brine. Since,
in a submerged tube plant, the evaporation
takes place on the heating surface, the brine
in contact with the surface is both the
hottest brine in the system and the most
concentrated. It is shown in Figure 120 that,
as the temperature of the tube wall is in
creased, the temperature at the wall be
brine solutions. This difference is probably
due to the influence of salts other than
sodium chloride in concentarted sea water,
or the formation of some anhydrite during
the recycle period.
Tests were made on both normal sea
water (35,000 ppm) and on diluted sea
water (approximately 33300 ppm) , which
had been concentrated to 35,000 ppm by
recycling in the flash plant. The results
indicate that when the diluted water is
concentrated in flash evaporators to a con
centration factor of 1.0, scaling can be ex
pected at approximately 282°F. It is also
shown that when full strength sea water
is heated in a flash plant, scaling is not
observed below 300°F. The exact cause of
this phenomenon is not known at this time
but additional studies have been proposed
to determine the mechanisms. It is postu
lated that the scale formed in the high
temperature recycle tests is calcium sulphate
anhydrite and the scale formed in the
"once-through" tests is the hemihydrate. It
follows that the scaling points on the
straight line portion of the curve of Figure
119 is a hemihydrate scale and the scale
formed on the curved portion of the graph
is the anhydrite form.
Other fouling substances—not scale in
accordance with the definition presented
earlier—must be controlled since, if they are
allowed to deposit on the heat transfer sur
face, the heat transfer rates are reduced,
decreasing the thermal efficiencies of the
system. Some of the more common fouling
materials are ferric oxide, silica, silts, kelp,
and marine life. These deposits can be con
trolled by common means (filtration, sedi
mentation, chlorination, etc.) and will not
be discussed in detail in this paper.
comes hotter than the bulk temperature of
the brine. Then, when vapor is formed, the
dissolved salts that were present in the
liquid are left behind in the surrounding
liquid, locally increasing the concentration.
As the concentration of scaling salts reaches
the saturation point at the bulk tempera
ture of the brine, the higher temperature,
more concentrated brine at the tube wall
will become saturated and scale will form.
If the concentration of scaling salts in the
bulk of the brine is just below saturation
and high heat fluxes are used, the concen
tration of scaling salts at the wall can be
supersaturated and scaling will occur.
321

tn
о
<
BULK TEMP OF
HEATING STEAM
TEMPERATURE
FIGURE 120. MECHANISM OF SCALE FORMATION IN
SUBMERGED TUBE PLANTS.
The mechanism of scale formation in a
flash plant is demonstrated in Figure 121, a
temperature-radius plot showing the tem
perature profile from the centerline of the
brine passage to the bulk temperature of
the heating steam. Since no vaporization
takes place at the tube wall, the concentra
tion of scaling salts is uniform throughout
the cross section of the tube. However, if
the concentration of scaling salts in the
brine is just below saturation at the bulk
temperature of the brine, the saturation
level may be exceeded near the tube wall
and cause scaling. It is obvious that, for any
scaling condition, the temperature of the
brine at the interface between the liquid
and the solid (not the bulk temperature of
the brine) is the limiting factor.
The temperature difference between the
bulk of the brine and the tube wall varies
with heat flux and velocity. High heat
fluxes are desirable to lower the capital
cost of the brine heater and low velocities
are desirable to reduce pumping costs. How
ever, the scaling potential is increased with
both factors, and an optimization study
322
BRINE
SUPER SATURATED
REGION
TUBE WALL
TUBE WALL
must be made for each specific application.
The variations in temperature differences
between the tube surface and the bulk tem
perature of the brine with changes in ap
proach temperature (temperature difference
between the heating medium and the
brine) are shown in Figure 122 for three
conditions. In all three cases the bulk tem
perature of the brine was fixed at 250°F.
and the brine velocity was fixed at 6 ft/sec
through a one-inch 20 BWG 90-10 CuNi
tube. The saturated temperature of the con
densing stream in the shell of the heater
was taken at 265°, 275°, and 285°F.
It is shown that, while the bulk tempera
ture of the brine remains constant for the
three cases, the temperature causing scaling
varies from 258.1° to 267.5°F. If a plant
were designed to operate at a bulk tem
perature of 250°F with a concentration
factor of 1.9, the scaling temperature at the
wall would be exceeded by approximately
4°F at the 265°F condition. If the concen
tration factor were dropped to 1.85, the
scaling condition would be exceeded by ap
proximately 20F, and at a concentration
CO
2[
o
<
V///////A—TUBE WALL
TEMPERATURE
FIGURE 121. MECHANISM OF SCALE FORMATION IN FLASH
PLANTS.
factor of 1.8, no scaling would occur. How
ever, if the concentration factor were main
tained at 1.8 and the steam conditions
raised to 275^, the wall temperature would
be approximately 5°F above the scaling
temperature; if the steam condition were
raised to 285"F, the wall temperature would
be approximately 9°F above the scaling
temperature. An economic balance must be
developed between the capital cost of the
brine heater and the energy costs of opera
tion in each specific case since the surface
in the heater varies inversely with the heat
flux or approach temperature.
The variation in temperature difference
between the tube surface and the bulk tem
perature of the brine at different brine
velocities is shown in Figure 123. The bulk
BULK TEMPERATURE
OF HEATING MEDIA
brine temperature was maintained at 250°F,
and the saturated temperature of the heat
ing steam was maintained at 265°F. The
brine velocity was taken as 3, 6, and 9
ft/sec through one-inch BWG 90-10 CuNi
tube. It is shown that, as the velocity is
increased, the temperature difference be
tween the bulk temperature and the inter
face temperature is decreased. The effect
of velocity is not as great as the effect of
heat flux. Increasing the velocity from 6 to
9 ft/sec lowers the interface temperature
2°F and decreasing velocity from 6 to 3
ft/sec increases the interface temperature
1.6°F. In designing flash distilling plants,
the optimum velocity must be chosen, con
sidering scaling factors, pumping require
ments and tube erosion.
s
h

w
h
z
w
2

3
h

0
sc
0
p

>
gj
 -TUBE
WALL
IBRINE
123.
FIGURE
VTOF
WITH
NEAMTLRPEOIRCAFITAUCYOR.NE

SATURATED
TOF
EMPERATURE

Z Z Z Z Z Z Z Z Z Z Z2

STEAM
HEATING

290

280

SEC
3FT 270
F9T 6FT
SEC SEC
 METHODS OF PREVENTING SCALE
Several methods have been successfully used to the brine stream. This method has been
to retard or prevent the formation of scale in quite successful in some plants and quite
sea water evaporators. One of the earlier unsatisfactory in others. This inconsistent
methods of retarding calcium carbonate scale performance is probably due more to vari
was the addition of sodium polyphosphates ations in sea water chemistry than to the

326
design of the flash plant. One I8-stage flash
plant supplied by the author's company has
been in service five years at 205° F maximum
using polyphosphate as scale control. A fall-
off in performance of about 4 per cent is
observed approximately every SO days. The
scale is then removed with hydrochloric
acid, and the plant returns to its normal
operating characteristics.
In developing the LTV plant now oper
ated for the Office of Saline Water at Free-
port, Texas, a technique was developed to
prevent scale formation on the heat transfer
surface by promoting the precipitation of
the scaling salts on seed crystals (ref. 4) .
This process was modified, and techniques
were developed to use the seeding technique
to retard scale formation in multistage Bash
plants by the Baldwin-Lima-Hamilton Cor
poration under Office of Saline Water con
tract no. 14-01-001-207. A 6-stage, 10,000 gpd
pilot plant was operated at temperatures
as high as 275°F without excessive scaling.
Several runs were made at 250°F using cal
cium carbonate seed to retard scale. A
typical performance is shown in Figure 124.
It is shown that, without the seed treat
ment, the heat transfer coefficient of the
stage condenser dropped from 700 to 460 in
140 hours while, with the seeding treatment,
the heat transfer coefficient dropped from
700 to 650 in 230 hours. Runs of 2,000 hours
were made to verify the results of this
technique (ref. 5) .
It has been known for some time that
the calcium carbonate and magnesium
hydroxide scale can be prevented by main
taining the pH of the brine below 7. It is
also recognized that the nonscaling tem
perature of unconcentrated sea water can
be increased to 300°F if all the bicarbonate
can be neutralized and the pH controlled
within some limits. It was decided by the
Office of Saline Water and BLH to investi
gate this method of scale control in the
6-stage pilot plant at Wrightsville Beach.
A sulphuric acid injection system was in
stalled and a program initiated to investi
gate scale control to 300°F.
The Office of Saline Water one mgd flash
distillation demonstration plant at Point
Loma was converted from polyphosphate
scale control to a pH system to investigate
this technique. It has been reported (ref. 6)
that the operating temperature was ex
tended from 200° to 250°F and the capacity
increased to 1.4 mgd.
The development work in the BLH 10,000
gpd plant at the Office of Saline Water's
Wrightsville Beach Laboratory has resulted
in the successful operation of flash plants
at 300°F. The method is shown diagram -
matically in Figure 125. Sea water is supplied
to the condenser tubes of the heat rejection
stages and the majority of this cooling
water is returned to the sea. However, a
fixed proportion is removed from the waste
line as makeup to the plant. A controlled
amount of sulphuric acid is added to the
makeup to neutralize the calcium bicar
bonate. The carbon dioxide formed by this
reaction reduces the pH of the makeup
stream to approximately 4. The makeup
stream is then put through an atmospheric
pressure decarbonator where most of the
carbon dioxide is removed.
The decarbonator din be a spray pond,
a cooling tower, or a packed column. It is
usually economical to use air to sweep the
escaping gases from the stream since the
water is already saturated with oxygen. The
effluent from the decarbonator is then fed
to a vacuum deaerator where the remaining
carbon dioxide and dissolved air are re
duced to a level low enough to eliminate cor
rosion. The decarbonated-deaerated makeup
is mixed with the brine recycle stream
where the mixed stream has a pH of 6.8
to 72.
Since it is evident (Fig. 119) that higher
temperature operations are more likely with
nonconcentrated brines than with recycled
brines, a system was designed to pass the
makeup stream through all the stages in a
separate system of condenser tubes and then
to install a "topping effect" to heat the
unconcentrated sea water an additional 20°
to 25°F to take advantage of the increased
thermal efficiency made possible. This sys
tem, illustrated in Figure 126, is a multi-
effect, multistage plant with the first effect
limited to the makeup stream. The system
also allows the use of two levels of energy
in the heat input sections. This is some
times attractive since the more expensive
high level energy is used only for the
makeup stream while most of the energv
required to heat the brine in the second
effect has a lower value. The brine dis
charge stream from the last stage of the
first or "once- through" effect is mixed with
the brine discharge stream from the second
effect brine heater in the first stage flash
chamber of the second effect. The mixed
brine then flows through the remainder of
the plant.
This system can be used equally well in
either a multieffect, multistage flash plant
or a simple recycle flash plant.
One other innovation, shown in Figure
125, is a relatively high temperature de
carbonator and deaerator to reduce the
327
energy costs in the degassing processes.
Instead of acidifying, decarbonating, and
deaerating the makeup after the first heat
rejection section (approximately 95°F) , the
acidifying, decarbonating, and deaerating
are performed at approximately 145°F. This
higher temperature operation greatly de
creases the air and steam required for
stripping and reduces the power required
to maintain the necessary vacuum. In a 50
mgd plant the steam consumption is re
duced from 64,000 lb/hr to 48,000 lb/hr
and the pumping energy from 1035 hp to
355 hp.

t
< »"
O O<

o. UJ o
3
UJ t- o
5
2 < u
w 3>
2 or

K
UJ
o "J
UJ o
rr <x
CO
<
 PRODUCT BLOWDOWN PLANT
"IMEMS
A
126.
FIGURE
HIGH
AND
EFFECT
ONCOER-PTOHRAOTUIGNHG"
WATER
SEA

CO LING
WATER

TMAKEUP
OF
WATER.
ERMEPATRAMTEUNRTE

TREATMENT SECTION
MAKEUP

SECOND EFFECT

FIRST EFFECT
 FUTURE DEVELOPMENTS
Methods have been proposed by several
oragnizations to further increase the non-
scaling temperature ranges in flash evap
orators. This is not necessarily desirable in
dual-purpose plants since using high level
steam reduces electrical production. How
ever, if methods can be economically de
veloped to prevent scale formation at
temperatures of 400" to 450°F, "water-only"
plants may be more attractive than dual-
purpose plants.
Some of the methods under study are:
(1) Combination of pH control and seed
crystals to remove the calcium sul
phate formed at the high tempera
tures to produce a recycle brine
CONCLUSIONS
It has been demonstrated that scale for
mation can be reduced in flash evaporators
at temperatures below 250°F by seeding
techniques. It has also been demonstrated
that scale can be eliminated at tempera
tures to 280°F in brine recycle streams and
to 300°F in "once-through" systems by pH
REFERENCES
1. Badger, W. L.: Chemical Engineering
Handbook, Third edition, McGraw-Hill
Publishing Co., New York (1950) p.
518.
2. McCulehan, J.; dater, J.: "Scale for
mation in saline water evaporators".
Dept. of Eng. Rept. no. 64-5, Univ. of
Calif. Los Angeles.
S. Standiford, F. C; Sinek, Jr., R.: Chem
ical Engineering Progress no. 56 (1961)
p. 59.
4. VV. L. Badger and Associates, Inc.:
"Operation of pilot plant LTV evap
orator at Wrightsville Beach, North
SUMMARY OF DISCUSSION
There was no discussion.
330
stream with a total calcium sulphate
content below the solubility at the
maximum temperature condition;
(2) Cation-exchange to remove the cal
cium ion from the brine and replace
it with an ion which has a positive
solubility curve;
(3) Anion-exchange to replace the bicar
bonate and sulphate ions with chlor
ide or some other anion which forms
soluble compounds with calcium;
(4) Chemical or mechanical scale remov
ing techniques to encourage the scal
ing salts to deposit in a manner
which would allow high temperature
removal from the brine stream.
control followed by adequate carbon di
oxide removal. These techniques have been
used successfully in the operation of large
distilling plants to produce water at prices
competitive with natural waters in many
parts of the world.
Carolina", PB-161290 R&D Progr. Rept.
no. 26 (1962) .
5. Woodbury, R. E.; Cadwallader, E. A.:
"Alkaline scale control by internal con
tact stabilization", presented at the
Division of Water, Air, and Waste
Chemistry, American Chemical Society,
Detroit. Michigan (April 5-9. 1965) .
6. Burns and Roe, Inc.: Second Annual
Report, PB-166247 R&D Progr. Rept.
no. 114, Saline Water Demonstration
Plant Point Lorria 1, San Diego, Cali
fornia (July 1964) .
Méthodes Pour
L'Entartrage Dans
Vaporisation Par Detente
R. A. Tidball et R. E. Woodbury
Etats-Unis d'Amérique
L'efficacité thermique du procédé de dis
tillation à vaporisation par détente en
étages (stades) multiples dépend en grande
mesure de la gamme de températures sur
laquelle se produit la vaporisation par
détente. Comme la température dans les
étages (stades) les plus froids, ou étages
d'élimination thermique, est limitée par la
température de l'eau de mer, la méthode
la plus économique d'augmenter la gamme
de vaporisation instantanée est d'augmenter
la température la plus élevée des étages
d'entrée de chaleur. Le nombre des étages
est limité par des facteurs économiques,
tels que les frais d'équipement, le niveau
de température de la source thermique et
la température d'entartrage de la saumure.
Des recherches continuelles et des pro
grammes de développement de la part de
l'OSW (Office of Saline Waters) , des uni
versités et des entreprises privées ont abouti
à des techniques qui ont permis de faire
passer la température maximale d'environ
75°C à 150°C au cours des 10 dernières
années.
Les installations à vaporisation par
détente peuvent fonctionner sans additif
anti-tartre à des températures inférieures à
75"C dans la plupart des eaux. A environ
75°C, assez de bicarbonate de calcium se
trouve transformé en carbonate de calcium
pour dépasser la solubilité du carbonate de
calcium a cette température. En continuant
le chauffage, la saumure devient sursaturée
et il se produit une précipitation sur les
parois des tubes provoquant l'entartrage.
L'entartrage au carbonate de calcium
peut être retardé, mais pas empêché aux
températures inférieures a 90°C par l'addi
tion à la saumure de quelques parties par
million de polyphosphates de sodium. Bien
que ce système de prévention de l'entartrage
ait très bien fonctionné dans certaines
installations, des sédiments de polyphos
la Prevention de
Les Systèmes a
phates se sont déposées dans les tubes
d'autres installations provoquant de sérieuses
pertes de rendement.
Au fur et à mesure que l'on continue à
augmenter la température de la saumure,
plus de bicarbonate de calcium se trouve
décomposé et si les conditions de tempé
rature et de pression permettent le dégage
ment de l'anhydride carbonique élevant le
pH de la saumure, il se forme des dépôts
d'hydrate de magnésium.
Deux méthodes ont été mises au point
pour étendre la température de fonctionne
ment au-delà de 95°C.
La première méthode utilise des germes
cristallins suspendus dans les courant de
saumure pour retarder la formation du
tartre sur les parois des tubes. Les tech
niques ayant le plus de succès utilisent des
germes de carbonate de calcium précipités
de l'eau de mer pour aider le dipart de
la réaction. Comme des cristaux supplé
mentaires de carbonate de calcium se for
ment, l'achat de produits chimiques n'est
pas nécessaire pour la bonne continuation
de l'opération. En fait, le retrait de l'excès
de carbonate de calcium engendré dans le
courant de saumure pourrait constituer un
problème important. Des procédés ont été
mis au point pour l'utilisation de cette
technique d'ensemencement à des tempé
ratures allant jusqu'à 120°C. Cette tech
nique retarde, mais n'empêche pas, la
formation du tartre. Les installations fonc
tionnant à 120°C doivent être détartrées
chimiquement de 4 à 6 fois par an.
La seconde méthode mise au point con
siste en un système de contrôle du pH,
dans lequel l'ion bicarbonate dans le
courant d'appoint est neutralisé à l'acide
sulfurique, l'anhydrique carbonique formé
est évacué et l'appoint est ajouté au courant
de recirculation de la saumure. La solubi
lité du sulfate de calcium dépend du
331
 facteur de concentration et de la tempéra
ture de la saumure. Des méthodes ont été
mises au point pour le fonctionnement
d'installations à recirculation à 120°C,
d'installations à effets multiples, en étages
multiples (MEMS) à 1S2°C, et d'installa
tions à "un seul passage" à 14S°C. Comme
ces températures sont à des conditions de
masse, on rencontrera une température
plus élevée de parois ou d'interface. Les
températures ci-dessus permettent 4°C pour
la chute de température à travers la couche
de saumure et 1,7°C pour les fluctuations
de contrôle.
Il semble qu'une combinaison de l'instal
lation MEMS et de celle à "un seul passage"
offre la conception la plus économique
pour les installations produisant le dessale
ment de l'eau seulement. Ce concept est
basé sur le fait que l'eau de mer non
concentrée peut être chauffée jusqu'à 150°C
sans entartrage, tandis qu'une saumure de
concentration plus faible (33.000 ppm)
concentrée à la même salinité que l'eau de
mer normale (35.000 ppm) s'entartre à
I39°C. Ce phénomène n'est pas complète
ment compris, mais on suppose que dans
l'installation "à un seul passage" le tartre
est de l'héraihydrate et que dans l'installa
tion à recirculation l'anhydride se forme
au-dessus de 132°C.
L'installation combinée comprend un effet
"à un seul passage" ou "d'appoint" et trois
effets de recirculation. L'eau de refroidisse
ment circule à travers les étages d'élimina
tion de la chaleur du quatrième effet et
une fraction en est retirée comme appoint.
Cet appoint passe par un jeu parallèle de
tubes condenseurs (non mélangé avec le
courant de recirculation) par les tubes de
récupération de la chaleur du quatrième
effet à une température de 63°C. Il est
alors acidifié à un pH de 4 et pulvérisé
dans un décarbonateur atmosphérique. La
saumure décarbonisée est envoyée dans un
désaérateur sous vide puis pompée par l'in
332
termédiaire d'un jeu parallèle de tubes
condenseurs dans les troisième et deuxième
effets (à nouveau non mélangée aux courants
de la saumure de recirculation) .
Elle passe alors par les tubes du premier
effet et le réchauffeur de saumure où l'ap
point est chauffé à 143°C. Puis elle passe
par les chambres de vaporisation par dé
tente du premier effet, produisant de l'eau
dessalée.
Le courant de recirculation de la
saumure du deuxième effet est chauffé dans
un réchauffeur de saumure séparé à une
température égale à la saumure d'appoint
dans le dernier étage du premier effet et
mélangé avec le courant de chasse du
premier effet dans la chambre à vaporisa
tion par détente du premier étage du
deuxième effet. Le reste de l'installation
fonctionne comme une installation MEMS.
L'injection d'acide, la décarbonation et la
désaération se font à des températures plus
élevées qu'à la normale afin de réduire le
débit d'énergie pour le maintien du vide
dans le désaérateur, réduire la quantité
nécessaire de vapeur de séparation et dimi
nuer les gaz résiduels dissous.
CONCLUSIONS
Il a été démontré que la formation du
tartre peut être réduite dans les évapora-
teurs instantanés par détente à des tempé
ratures inférieures à 120°C, grâce aux
techniques d'ensemencement. Il a été égale
ment démontré que le tartre pouvait être
éliminé à des températures allant jusqu'à
132°C dans des courants de recirculation
de la saumure et jusqu'à 143° C dans des
systèmes à "un seul passage", par le con
trôle du pH suivi d'une élimination suffi
sante de l'anhydride carbonique. Ces tech
niques peuvent être utilisées avec succès
dans l'exploitation de grandes installations
de distillation pour produire de l'eau a des
prix pouvant soutenir la concurrence des
eaux naturelles dans de nombreuses parties
du monde.
 Методы Борьбы с Накипью в Системах,
Применяющих Мгновенное Испарение
Р. А. Тидболл и Р. Е. Вудбори
Соединенные Штаты Америки
Тепловая производительность дистил-
ляционного со многими стадиями про
цесса «со вскипанием» для опреснения
морской воды в значительной степени
зависит от температурных грниц, в ко
торых вскипание происходит. Так как
температура в самой холодной или те-
плосбросной стадиях зависит от тем
пературы морской воды, наиболее эко
номичным методом для расширения
пределов мгновенного испарения явля
ется повышение максимальной темпе
ратуры в периодах затраты тепла. Ко
личество стадий зависит от таких эко
номических факторов, как капитальные
расходы на оборудование, температур
ный уровень источника тепла и темпе
ратура раствора, при которой образу
ется накипь.
За последние 10 лет, благодаря не
прерывным научно-исследовательским
программам Управления по опреснению
соленых вод, университетов и частной
промышленности, были разработаны
технические методы, позволившие по
высить максимальную температуру со
170°F до 300°F.
Установки со вскипанием при тем
пературах ниже 170° F могут работать,
не прибегая к примесям для борьбы с
накипью, почти во всяких водах. При
170°F достаточное количество бикар
боната кальция успевает обратиться в
карбонат кальция, чтобы превзойти
пределы растворимости карбоната каль
ция при этой температуре. При даль
нейшем нагреве рассол становится пе
ресыщенным и на стенках труб начи
нается осаждение, вызывающее накипь.
С помощью добавки к раствору не
скольких частиц на миллион полифос
фатов натрия при температурах ниже
195°F образование накипи карбоната
кальция может быть замедлено, но не
предотвращено. Хотя на некоторых
установках эта система борьбы с на
кипью прекрасно функционировала, но
на других она вызывала в трубах от
ложение полифосфатного отстоя, спо
собствовавшего серьезному падению
производительности.
При дальнейшем увеличении темпе
ратуры рассола происходит добавочное
разложение бикарбоната кальция, и
если существующее давление допуска
ет выделение двуокиси углерода, повы
шающее pH рассола, то образуется на
кипь гидроокиси магния.
Было разработано два метода для
расширения области рабочих темпера
тур над уровнем 200°F.
При первом способе, для замедления
образования накипи на стенках труб
пользовались затравкой кристаллов,
взвешенных в потоке раствора. Для
того, чтобы начать процесс, самым
успешным техническим приемом явля
лось применение затравочных кристал
лов каобоната кальция, осажденных из
морской воды. Для продолжения удач
ной работы не требовалось покупных
химикалий, так как новые кристаллы
карбоната кальция образовывались са
ми собой. Даже наоборот, удаление
излишнего карбоната кальция, генери
ровавшегося в потоке раствора, могло
бы обратиться в важную проблему.
Были выработаны методы применения
такой затравки при температурах до
250°F. Этот метод задерживает, но не
предотвращает образование накипи.
На установках, работающих при 250°F
требуется химически удалять накипь
4-6 раз в год.
Второй разработанный способ был
основан на системе регулирования pH,
где бикарбонатный ион в подпиточном
потоке нейтрализуется серной кисло
той, образующаяся двуокись углерода
удаляется, а подпитка добавляется к
потоку рециркуляционного рассола.
Растворимость сульфата кальция зави
сит от коэффициента концентрации и
температуры рассола. Были усовершен
ствованы методы работы рециркуляци
онных установок при 250°F, многосту
333
 пенчатых со многими стадиями (MEMS) лельную группу конденсаторных труб
при 270°F и «прямоточных» при 290°F. в третью и вторую ступень (опять без
Эти температуры зависят от условий смешивания с потоками рециркуляци
образования накипи. 3 настоящего до онного раствора).
клада. Так как они относятся к объем Затем подпитка пропускается через
ным условиям, появляется более высо- трубы первой ступени и подогреватель
кая температура стенки или поверхно раствора, где ее температура повыша
сти раздела. В вышеуказанные темпе ется до 290°F. Потом она проходит че
ратуры включены поправки в 7°F на рез камеры вскипания первой ступени,
падение температуры из за пленки рас производящей пресную воду.
сола и 3°F на колебания регулирова Рециркуляционный поток рассола
ния. второй ступени подогревается в отдель
Комбинация многоступенчатой со ном нагревателе рассола до одинако
многими стадиями установки и «прямо вой температуры с подпиткой в послед
точной» видимо является наиболее вы ней стадии первой ступени и смеши
годным решением для агрегатов, про вается с потоком продувки, выходящим
изводящих только воду. Такой проект из первой ступени, в камере вскипания
основан на факте, что не концентриро первой стадии второй ступени. Осталь
ванная морская вода может быть на ная часть агрегата работает, как мно
грета до 300°F без образования наки гоступенчатая установка со многими
пи, в то время как рассол более низ стадиями (MEMS).
кой концентрации (33.000 частей на Кислотное инжектирование, декар-
миллион), сконцентрированный до оди бонация и деаэрация производятся при
накового солесодержания (35.000 ча температуре выше нормальной для сни
стей на миллион) с обыкновенной мор жения потребных количеств энергии и
ской водой, образует накипь при 283°F. дистилляционного пара, поддержания
Это явление невполне понятно, но пред вакуума в деаэраторе и уменьшения
полагается, что в «прямоточной» уста количества растворенных остаточных
новке накипь состоит из гемигидрата, газов.
а в рециркуляционной ангидрид обра
зуется при температуре, превышаю Заключение
щей 270°F. Было указано, что в испарителях со
В комбинированую установку вклю вскипанием при температурах ниже
чены одна «прямоточная» или <до- 250°F, образование накипи может быть
ливная» и три рециркуляционных сту уменьшено с помощью метода затравки
пени. Вода охлаждения протекает кристаллов. Было также указано, что в
через теплосбросные стадии четвер рециркуляционных потоках рассола
той ступени, а часть ее отбирается при температурах до 270°F и в «пря
в качестве подпитки. Эта подпитка до моточных» системах при температурах
стигает температуры 145°F после про до 290°F можно избежать образование
пуска через параллельную группу кон накипи посредством регулирования pH
денсаторных труб (не смешиваясь с ре с последующим удалением двуокиси
циркуляционным потоком) и тепло-ре- углерода. Эта техника может быть
генериующие трубы четвертой ступе успешно применена на работе крупных
ни. После этого она подкисляется до дистилляционных установок во многих
рН=4 и разбрызгивается в воздушном частях мира для производства опрес
декарбонаторе. Обезуглероженный рас ненной воды по таким ценам, которые
сол впускается в вакуумный деаэратор, смогут конкурировать со стоимостью
а затем перекачивается через парал пресной естественного происхождения.

334
Método Para Reducir la Formación
de Costra en los Equipos de Desti
lación por Expansion Instantánea
R. A. Tidball y R. E. Woodbury
Estados Unidos de Norteamérica
La eficiencia térmica del proceso de desti
lación por expansión instantánea en etapas
múltiples, aplicado a la conversión de agua
de mar, depende en un alto grado del
intervalo de temperaturas sobre el cual
tiene lugar la evaporación. Dado que la
temperatura en las etapas más frias o de
salida del calor, es limitada por la tempera
tura del agua de mar, el método más
económico de aumentar el intervalo de
evaporación es elevando la temperatura más
alta de las etapas de entrada de calor. El
número de etapas es limitado por factores
económicos tales como costo del equipo, el
nivel de temperatura de la fuente calórica
y la temperatura a la cual la salmuera
forma costra.
Los continuos programas de investigación
y desarrollo llevados a cabo por la Oficina
de Agua Salada ("Office of Saline Water") ,
las universidades y la industria privada, en
los últimos 10 años han tenido como re
sultado técnicas que han posibilitado la
elevación de la temperatura máxima de
170-F (77°C) a 300°F (149°C) .
Las plantas de destilación por expansión
instantánea pueden operar sin aditivos para
la prevención de costra con la mayor parte
de las aguas a temperaturas inferiores a
170°F (77°C) . A 170°F el bicarbonato de
calcio se ha convertido en carbonato de
calcio en grado suficiente como para exceder
la solubilidad de este último a esa tempera
tura. Continuando el calentamiento, la sal
muera se sobresatura y se produce precipi
tación sobre las paredes del tubo, formán
dose costra.
A temperaturas inferiores a los 195°F
(90,6° C) , la formación de costra de carbo
nato cálcico puede retardarse, pero no im
pedirse, mediante la adición a la salmuera
de algunas ppm de polifosfatos de sodio.
Aunque este sistema de prevención de la
costra ha tenido muy buenos resultados en
algunas plantas, en otras se han depositado
sedimentos de polifosfatos en los tubos oca
sionando una seria disminución en el rendi
miento.
Al elevar aún más la temperatura de la
salmuera, se produce una mayor descompo
sición de bicarbonato cálcico y si las condi
ciones de temperatura y presión permiten
el desprendimiento de dióxido de carbono,
aumentando el pH de la salmuera, se forma
costra de hidróxido de magnesio.
Se han desarrollado dos métodos para
extender la temperatura de trabajo por en
cima de los 200°F (93°C) .
El primer método utiliza cristales de
"semilla" suspendidos en la corriente de
salmuera para retardar la formación de
costra sobre las paredes del tubo. Las técni
cas más exitosas emplean cristales de "se
milla" de carbonato cálcico precipitado de
agua de mar para iniciar la operación.
Dado que se forman cristales de carbonato
cálcico adicionales, no se necesita comprar
productos químicos para continuar exitosa
mente la operación. En rigor de la verdad,
la eliminación del exceso de carbonato cál
cico generado en la corriente de salmuera
podria llegar a ser un problema serio. Se
desarrollaron técnicas para utilizar este
método de cristalización por "semilla" hasta
una temperatura de 250°F (121 °C). Esta
técnica retarda pero no previene la forma
ción de costra. Las plantas que trabajan a
250°F requieren la remoción de la costra,
por métodos químicos, de cuatro a seis
veces al año.
El próximo método desarrollado fue un
sistema de regulación del pH de acuerdo
con el cual se neutraliza con ácido sulfúrico
el ion de bicarbonato en la corriente de
alimentación, se extrae el dióxido de car
bono y se agrega el líquido de alimenta
ción a la corriente de recirculación de sal
muera. La solubilidad del sulfato de calcio
335
 depende del factor de concentración y de
la temperatura de la salmuera. Se han de
sarrollado métodos para hacer trabajar
plantas de recirculación a 250°F (121°C) ,
plantas de acción múltiple en etapa múlti
ple a 270°F (132°C) y plantas "en un sólo
paso" a 290" F (143°C) . Dado que estas
temperaturas se registran en la masa de
fluido, en lugares próximos a la pared o
en la interface se registrarán temperaturas
superiores. Las temperaturas mencionadas
más arriba dejan un margen de 7°F (3,9°C)
para compensar la calda de temperatura a
través de la película de salmuera y de 3°F
(1.7°C) para compensar las fluctuaciones de
registro.
La planificación más económica para
plantas de destilación de agua exclusiva
mente, parece consistir en una combinación
de una planta de acción múltiple en etapa
múltiple con una planta "de un solo paso".
Este diseño se basa en el hecho de que el
agua de mar no concentrada puede calen
tarse a 300°F (149°C) sin formar costra,
mientras que una salmuera de inferior con
centración (33.000 ppm) concentrada a la
misma salinidad que el agua de mar normal
(35.000 ppm) forma costra a 283°F (HOT) .
No hay una comprensión absoluta de este
fenómeno, pero se supone que en una
planta "de un solo paso" la costra consiste
en hemihidrato y que en una planta de
recirculación por encima de los 270°F
(I32°C) se produce la forma anhidra.
La planta combinada comprende una
acción "de un solo paso" o inicial ("top
ping") y tres acciones de recirculación. El
agua de enfriamiento circula a través de
las etapas de salida del calor de la cuarta
acción y se extrae una parte para contribuir
a la corriente de alimentación. Esta co
rriente de alimentación se pasa a través de
un sistema paralelo de tubos condensadores
(sin mezclarse con la corriente de recircula
ción) a través de los tubos de recuperación
de calor de la cuarta acción elevándose su
temperatura a 145°F (63°C) . Luego se aci
difica a un pH de 4 y se introduce por
atomización en un descarbonatador atmos
férico. La salmuera descarbonatada se intro
336
duce en un desaireador por vado y luego
se bombea a través de un sistema paralelo
de tubos condensadores en la tercera y
segunda acción (nuevamente, sin mezclarse
con las corrientes de salmuera de recircula
ción) .
Luego se pasa a través de los tubos de
la primera acción y del calentador de sal
muera donde la alimentación se calienta a
290°F (143°C) . A continuación se envfa a
través de las cámaras de evaporación in
stantánea de la primera acción, formándose
agua de producción.
La corriente de recirculación de salmuera
de la segunda acción se calienta en un ca
lentador de salmuera separado, a una tem
peratura igual a la de la salmuera de
alimentación en la última etapa de la pri
mera acción y se mezcla con la corriente
de purga de la primera acción en la cámara
de evaporación instantánea de la primera
etapa de la segunda acción. El resto de la
planta trabaja como una planta de acción
múltiple en etapa múltiple.
La inyección de ácido, la descarbonata-
ción y la desaireación se efectúan a tem
peraturas superiores a la normal para re
ducir los requerimentos de energía a los
efectos de mantener el vacio en el desairea
dor, para reducir la cantidad de vapor de
agotamiento requerido y para disminuir la
cantidad de gases residuales disueltos.
CONCLUSIONES
Se ha demostrado que puede reducirse la
formación de costra en evaporadores por
expansión instantánea a temperaturas in
feriores a 250°F (121 °C) mediante técnicas
de cristalización por "semilla". También se
ha demostrado que la formación de costra
puede eliminarse a temperaturas hasta de
270°F (132°C) en corrientes de recircula
ción de salmuera y hasta de 290°F (I43°C)
en sistemas "de un solo paso" mediante la
regulación de pH seguida por una adecuada
remoción del dióxido de carbono. Estas
técnicas pueden emplearse exitosamente en
muchas partes del mundo para la operación
de grandes plantas destiladoras para pro
ducir agua a precios competitivos de aguas
naturales.
 An Engineering Evaluation of the
Vertical Tube, Falling Film,
Distillation Process
D. L. Preddy
United States of America
The first saline water conversion demon
stration plant constructed by the Office of
Saline Water was a long tube, vertical,
falling film, multiple-effect distillation plant
at Freeport, Texas.
The long tube vertical evaporator design
was first suggested by W. L. Badger and
Associates. In 1957, a 2000 gpd pilot plant
was erected. As a result of the pilot plant
test work, a 12-eSect evaporator saline
water conversion plant was designed by
W. L. Badger and Associates and con
structed by Chicago Bridge and Iron. Since
June 6, 1961, the Freeport plant has been
operated by the Stearns-Roger Corporation
of Denver, Colorado.
After three years of successful operation,
the Office of Saline Water requested an
engineering evaluation in order to use the
operational knowledge to advance the
SUMMARY AND CONCLUSIONS
SUMMARY
An engineering evaluation of the Office
of Saline Water Demonstration Plant No. 1
has been completed. Heat and material
balances for three sets of operating condi
tions were calculated. The intake complex
was evaluated. The preheaters and cross
exchangers were evaluated for the present
operation and designed for two other
operations.
An extensive study of the deaerator and
its operation was carried out, including
sampling and chemical analysis. The evapo
rator design was evaluated for varying tube
sires and brine recirculation rales under
three sets of conditions. The entrainment-
science and technology of saline water con
version. It was felt this evaluation would
contribute materially to low cost desalina
tion by increasing operational reliability
and production of the long tube, vertical,
falling film process.
Under contract to the Office of Saline
Water, The Dow Chemical Company
made an engineering evaluation of the
vertical tube, falling film distillation proc
ess in the summer of 1964. The objective
of this evaluation was to examine the
process and the design of major items of
equipment with particular emphasis upon
improving production and operational re
liability to reduce product cost. Each part
of the evaluation was considered both on
the basis of what could be done in the
existing demonstration plant at Freeport
and what should be done in future plants.
separator design was evaluated for the pres
ent operation, and a study was made on
the use of wire mist eliminators.
The construction materials and corrosion
problems of the plant were studied, samples
examined, and radio logs taken. The pumps
and other mechanical equipment were
studied with emphasis on the more severe
operating conditions proposed. The planl
instrumentation was reviewed and evalu
ated.
A review of location and procedures for
chemical sampling and analysis was made.
The acid and caustic treatment of the sea
water feed was reviewed and evaluated.
Through a literature survey, correct solu
 bility limits for calcium sulfate scales were
calculated and the scaling limits for the
LTV plant determined. Ion-exchange soft
ening for feed pretreatment was studied,
and softening units were designed for plant
operation at 275°F and 4:1 brine concentra
tion and at SOOT and 5:1 brine concentra
tion. Application of the calcium-sulfate
slurry process for feed water treatment to
the LTV plant was extensively studied.
Treatment of the product water was
studied, and the effect of the product water
on the materials of construction was evalu
ated. Test spools and plant piping were
examined and the corrosion evaluated. The
effect of mixing product water with Free-
port city water was studied. A normalized
plant to produce one mgd was designed
and the economics determined.
CONCLUSIONS
The major conclusions from the evalu
ation were:
(1) Economic evaluation of the present
plant operation and two revised plant oper
ations with ion-exchange pretreatment indi
cates that the most economical process is
the operation of the plant at a first effect
temperature of 300°F with ion-exchange
softening of the sea water feed.
(2) Using all of the process improve
ments determined in the engineering evalu
ation, a normalized, one mgd plant was
designed at a capital cost of $1,518,570,
which would operate for $1.16 per thou
sand gallons.
(3) A systematic study of the solubilities
of calcium sulfate and a review of the scal
ing in the LTV plant have led to the
conclusion that the first effect temperature
should not exceed 240°F to prevent CaSO,
(anhydrite) formation and that the last
effect concentration factor should not ex
ceed three times normal sea water to pre
vent CaS04.2H20 (gypsum) formation.
(4) Removal of 50 per cent of the calcium
by ion-exchange softening in a Buidized bed
HEAT AND MATERIAL BALANCE
A summary of the major points of the
heat and material balances is shown in
TABLE XLII. Summary of Heat and Material Balances
Effect I
Plant brine temp. °F concentration factor
Existing: Freeport plant 232
Revised 275° plant 275
Revised 800° plant 800
Normalized plant 300
* Normalized plant capacity and economy ratio expressed as net lbs water/lb steam.
338
and regeneration with concentrated brine
will allow operation at 275 °F in the first
effect and a concentration factor of four
times normal sea water in the last effect.
(5) Removal of 75 per cent of the cal
cium by ion-exchange softening will allow
operation at 300°F in the first effect and
a concentration factor of nearly five times
normal sea water in the last effect.
(6) Adaptation of the Badger anhydrite
seeding process at the present plant to
permit 300°F operation is economically at
tractive provided that hydraulic cyclone
seed recovery of 98 per cent can be
achieved prior to the first effect and that
the feed sea water can be heated to 300°F
without scaling.
(7) The existing vacuum deaerator in
the Freeport plant is adequate in size and
design to maintain the total CO, concen
tration of its effluent brine in the range
of two to three ppm COj and the O, con
centration at an approximate 100 parts per
billion level, if operated under the condi
tions suggested in the evaluation report.
(8) The present location of the deaera
tor in the Freeport demonstration plant is
considered proper for overall plant economy
and operating efficiency.
(9) The product water being pumped to
Freeport is considerably more corrosive to
ward plain steel than Freeport well water.
( (10) The corrosiveness of the product
water is due to its lack of scaling properties
which correlates with its occasionally rather
high C02 content. This condition can be
economically corrected by chemical treat
ment.
Specific conclusions and recommendations
concerning special problems studied in the
evaluation will be found throughout this
paper. For more detailed discussion of the
information developed by the evaluation,
refer to the Office of Saline Water Research
and Development Report no. 139. The data
and graphs presented in this paper are
extracted from this report.
Table XLII.
Blowdoum Gross capacity Gross economy ratio
gpd lb» water/lb eteam
2.87 1,000.000 10.95
4.0 1,433,000 11.1
6.0 1,812,000 11.1
5.0 1.000.000* ».$•
 FREEPORT DEMONSTRATION PUNT
Three heat and material balances were
calculated for the Freeport demonstration
plant.
A detailed heat and material balance of
the existing plant was prepared from plant
operating data. The calculated balance ob
tained was well within the accuracy of plant
measurements and was representative of
plant operations. This balance was used as
the basis for design calculations for the
process equipment.
Then two revised heat and material bal
ances were prepared. These balances were
based on the assumption of installing ion-
exchange pretreatment facilities in the
Freeport plant and the heat transfer capac
ity of the first effect evaporator as calcu
lated from existing plant operations. Two
ion-exchange systems were assumed; one
was for removal of 50 per cent of the
GENERAL PLANT DESIGN
INTAKE DESIGN
The intake structure in the Freeport
plant is a reinforced concrete pit which
contains a traveling screen, two pumps, and
a recycle chamber. It is approximately 50
ft long, by 15 ft wide, and 12 ft deep. Inlet
capacity is provided by two underground
30-inch steel lines pile-supported in the
Ethyl-Dow sea level intake canal.
Basically, the intake structure is well-
designed and is adequate for the intended
service. The only change recommended in
the existing intake was to replace the two-
mesh screen on the traveling screen with
a six-mesh screen.
A few physical features were noted which
should not be repeated in future installa
tions. Among these were:
(1) Untreated timber piles were used to
support the intake lines. These piles are
exposed and vulnerable to attack by marine
borers.
(2) Steel pipe was used for the intake
lines. Concrete culvert pipe can be installed
more economically and will give satisfac
tory service.
(3) The intake has an elaborate bottom
configuration supposedly for silt separa
tion. This adds to the cost and does not
contribute to the performance.
Consideration was given to pretreating
the sea water with magnesium hydroxide
in a settling pond for desilting. The in
creased operating and maintenance cost
caused by silt is not well-defined; but it is
not considered to be sufficient to justify
calcium from the sea water feed to allow
a brine temperature of 275 °F in the first
effect without scale formation; the second
was for removal of 70 per cent of the cal
cium from the sea water feed to allow a
brine temperature of 300°F in the first
effect without scale formation. For com
parison, the maximum allowable brine tem
perature in the first effect without scale
formation with normal sea water feed is
about 240°F.
NORMALIZED PLANT
A detailed heat and material balance was
prepared for a normalized plant. Based on
the conclusions of the evaluation, this plant
would use an ion-exchange pretreatment
system for a 500°F first effect operation to
achieve a net production of one mgd. In
this plant, condensate from the first effect
would be returned to the steam boiler.
the $50,000 expenditure that would be re
quired for the Freeport plant.
PREHEATER AND CROSS EXCHANGER DESIGN
Although subject to some inaccuracy be
cause of the difficulty of temperature meas
urements and small differential tempera
tures involved, comparison of observed and
calculated overall heat transfer coefficients
did reveal some trends worthy of note.
Overall heat transfer coefficients in the
preheaters and cross exchangers increase
with increasing sea water temperature. This
is due to silt deposits on the heat transfer
surfaces being greater in the first exchanger
in the series than in subsequent exchangers
and to the decreasing tendency of marine
organisms to grow at higher temperatures
in sea water.
Overall heat transfer coefficients in the
preheaters and cross exchangers increase
substantially after deaeration. In the cross
exchangers where product water is ex
changed with sea water, this must be due
to the difference in corrosion of the heat
transfer surface by the aerated and de-
aerated sea water. In the preheaters where
product vapor is condensed with sea water,
this corrosion effect must still be the pri
mary cause. Since this change is observed
between the product condensers on effects
eleven and twelve, only a very small differ
ence in the level of noncondensables would
be expected due to air leaking into the
vacuum system.
In the Freeport demonstration plant.
339
equipment for two different methods of
heat recovery from the product water was
installed (Fig. 127) . One method was to
pump the product water streams coming
from each evaporator steam chest through
a series of cross exchangers to transfer the
heat back to the feed sea water. The other
method was to let the product water
streams flow by gravity through a series
of flash tank* with the flash steam going
8 7
pH OF SEA WATER © 50°C BEFORE CONTACT WITH AIR
FIGURE 128. DISTRIBUTION OF GROSS COa IN SEA WATER
AT 50°C CHLORINITY = 15<>/00 PC02 IN EQUILIBRIUM WITH (C02).
into the vapor lines from each evaporator.
Heat balance calculations around the plant
showed no significant difference in produc
tion or steam economy between the two
methods. Therefore, the choice is one of
strictly capital cost. The use of the flash
tanks with an incremental increase in the
product condenser size would require a
much lower initial investment and have
lower maintenance cost.
DEAERATION DESIGN
For the Freeport demonstration plant, an
effluent from the deaerator with a dissolved
O, concentration of 100 parts per billion
and a dissolved CO, concentration of one
to two ppm is considered satisfactory. The
present deaerator is adequate in size, and,
in general, its design is proper to reduce
both the O, and CO, content of the in
coming brine to satisfactory levels.
Basic data were obtained from literature
surveys to permit calculation of the equi
librium relationships in the CO, sea water
and O, sea water systems. No applicable
data could be found in the literature for
the stripping of either O, or CO, from fresh
water or sea water by using steam. Ade-
6 5 4
quate design data does exist for desorbing
both CO, and O, from fresh water by strip
ping with air. Since the liquid film provides
the controlling resistance to mass transfer
in the desorption of O, and CO, from fresh
water and since the viscosity of sea water
approximates that of fresh water, these data
were assumed valid for steam.
The critical factor in decarbonating sea
water is to maintain the pH low enough
to release the CO, which is chemically
bound (Fig. 128) . Complete removal of the
gross CO, content of the sea water can not
be obtained above 4 pH. In the Freeport
demonstration plant, the pH of the deaera
tor feed was adjusted by adding concen
trated sulfuric arid with a manually
controlled piston pump and was subject to
341
 operating variations. Because of the critical
nature of the pH, the pump should be
provided with an automatic control in
strument.
In addition to the pH problem, the
major difficulty in the design of a deaerator
for a saline water conversion plant is the
high ratio of liquid to vapor mass velocity
encountered. The conditions prevailing in
side the stripping column in such a case
fail to achieve countercurrent action since
the relatively feeble upward flow of gas is
induced to reverse its direction in places
bv the much greater momentum of down
ward flowing liquid. From the test results
on the Freeport plant, it is doubtful that
the deaerator will operate with more than
one transfer unit regardless of packed
height. This is inherent in the operating
conditions imposed on it. The use of a
packing having as great as possible a void
volume per cubic foot will minimize the
troubles just described but definitely will
not eliminate them entirely.
In June 1964. a test run was made on
the deaerator with all of the packing re
moved. With only the eight-inch Sprayco
nozzle in the top of the tower and no
packing, the deaerator is able to reduce
the O, content of brine to 10 parts per
billion. Incomplete data on COa removal
were obtained. Therefore, the theoretically
calculated amount of packing was recom
mended. Based on mass transfer calculation,
an eight-foot depth of 3.75-inch size poly
styrene "Maspac FN-90" is recommended
for improvement in deaerator performance
with respect to decarbonation.
The data taken on the deaerator indi
cates that the conditions for desorbing Oa
and COj from brine with steam are appar
ently more favorable than those predicted
from air stripping data. This points out the
need for experimentally obtaining basic de
sign data for deaerating and decarbonating
sea water by steam.
Relocation of the deaerator in the flow
scheme was considered. The conclusion that
the present location (between the heat ex
changers from the eleventh and twelfth
effects) is the proper one is based on the
following points:
(1) Moving the deaerator further down
stream would expose more upstream piping
and heat exchangers to attack by dissolved
Oj and to possible carbonate scaling.
(2) Relocating to operate at a higher
temperature means using higher pressure
steam for stripping and is contrary to the
interest of heat economy. Relocating to
operate at lower temperature, say to am
bient, will result in a greater packing
342
requirement.
As part of the evaluation, a study was
made of the available commercial or stand
ard deaerator types. A vacuum deaerator of
the same general type as the deaerator in
the Freeport plant is the only commercially
available deaerator found in the study
which is compatible with the flows and
corrosive conditions involved.
EVAPORATOR DESIGN
Under the direction of The Dow Chemi
cal Company, extensive computer calcula
tions of the overall heat transfer coefficients
for evaporator design were done by Hous
ton Research Institute, Incorporated. To
check out the theoretically predicted de
signs, a complete calculation was performed
on the first, eight, and eleventh effects
using the existing plant heat and material
balance and mechanical design parameters.
The predicted total area of heat transfer
was in very good agreement with actual
design. To match the actual design and
to evaluate the effect of fouling on the
evaporators, the following fouling factors
were used:
Effect Fouling
number factor
I .00097
VIII .00015
XII .00125
These fouling factors agree with plant
experience where fouling by anhydrous cal
cium sulfate scale has been experienced in
the first effects and fouling by calcium
sulfate dihydrate (gypsum) has been ex
perienced in the last effects. In all later
calculations of alternate evaporator designs,
these fouling factors were applied.
Three studies of evaporator design were
made to determine the effects of tube diam
eter and length, recirculation, and maldis
tribution.
The results of the study of tube diameter
and length are presented in Figures 129, ISO.
131, 132, and 133. These data indicate that
from the point of view of heat transfer,
the two-inch, 24-foot tube is best for the
first eleven effects and that a larger tube
would be favored in the twelfth effect.
However, economic evaluation of the effects
with various tubes indicates that there is
no advantage in changing to a larger tube
size. For the existing Freeport plant opera
tion, the cost of operating the twelfth
effect with two-inch or four-inch, 24-foot
tubes was estimated at $35,000; whereas
with three-inch, 20-foot tubes, the cost
would be $36,900. These cost figures are for
343
 TUBE DIAMETER, I D., INCHES

FIGURE ISO. TOTAL AREA VS TUBE DIAMETER EIGHTH EFFECT.

vessels constructed and delivered to the site, plant. In each case, the tube
but not installed. were fixed at 2 inches in diameter and 24
At this time, it should be pointed out feet in length. Calculations of the heat
that the optimum plant design, using ion- transfer areas required were based on three
exchange pretreatment of the sea water different recycle flows and expressed as
feed with a first effect temperature of percentages of the normal feed. The results
S00°F, undoubtedly will be one with more of recirculation in these two effects are
than twelve evaporator effects. In this case, summarized below.
the problem of the most economical tube
configuration should be re-evaluated accord Recirculation Area required (eq ft)
ingly. Unfortunately, time was not avail (per cent) Effect I Effect XII
able to examine this possibility as part of
the evaluation. 0 6896 6811
Recirculation studies were made on the 100 6268 7263
6196 7811
first and twelfth effects of the Freeport 6168 7361
344
 1.5 2.0 2.5 3.0 35 4.0
TUBE DIAMETER, I. D., INCHES
FIGURE 131. TOTAL AREA VS TUBE DIAMETER
TWELFTH EFFECT.

Note the inverted effect of recirculation
between the first and twelfth effects. In the
first effect, recirculation decreases the area
required; in the twelfth effect, the result is
an increased area. This is perfectly reason
able. Recirculation tends to decrease the
sensible heat required to heat the feed and
thus to utilize more of the energy trans
ferred in latent heat. It does this at the
expense of increased flow and pressure drop
in the tube. In the first effect, the increased
pressure drop actually increases the coeffi
cient with a negligible temperature drop.
In the twelf'h effect, the increased coefficient
is more than offset by a decreased tempera
ture driving force.
Because of the increased pumping cost
involved, there is no justification for recir
culation from economic or heat transfer
considerations. Any justification for recircu
lation must be on the basis of scale
prevention, but it is believed that other
means of insuring distribution will be more
economical.
Extensive computer runs were made for
the first and twelfth effects to determine
the effect of maldistribution on heat trans
fer and local concentrations.
 EFFECT
VTUBE
FOR
SIZES.
VS
FLUX
HEAT
133.
FIGURE
ARIOUS

NumlMi
Effect
 Calculations were made with the evapo various percentages of normal flow. The
rator divided into three zones. The liquid results appear in Figures 134 and 1S5. Be
flow was increased in one zone, kept at cause of the operating conditions, the
normal in the second, and decreased in the twelfth effect is much more subject to this
third to meet total flow requirements. behavior. An average evaporator effluent of
These calculations showed that maldistribu 95 per cent saturation reaches saturation in
tion has a negligible effect on the overall a tube with 60 per cent of normal flow in
heat transfer coefficient of the evaporator. the first effect while the same effluent
Despite the fact that maldistribution has reaches saturation in a tube with 75 per
essentially no effect on overall heat transfer, cent of normal flow in the twelfth effect.
it is undesirable because of the higher local
concentration which results. Calculations
show that the heat flux of a tube is rela
tively insensitive to maldistribution. There
fore, a tube with low flow will transfer
about the same amount of heat and vapor
ize the same amount as the tube with
normal flow. Thus, the liquid leaving a low
flow tube is of a higher concentration than
normal. The degree of maldistribution
within an evaporator is a function of how
close to saturation that evaporator can be
operated without scale formation. In order
to determine how critical this problem is,
calculations were performed assuming aver
age effluent concentrations from the first
and twelfth effects and solving for the
outlet concentration from a tube with

FIGURE 1S5. EFFECT OF MAL

DISTRIBUTION ON LOCAL
CONCENTRATION TWELFTH
EFFECT.

Distribution in the Freeport plant was

achieved by a perforated plate located
above the tube sheet with the holes above
the blank spaces between the tubes. The
ends of the tubes were flush with the tube-
sheet. Observations made in the plant show
that this perforated plate gives very good
distribution when clean, but areas of it are
plugged by rust flakes end then silt during
operation. The addition of "V"-notched
weir inserts has been tested in the plant
PERCENT OF NORMAL FLOW and gives added assurance of good distribu
tion even when areas of the plate are
plugged. This appeared to be an adequate
FIGURE 154. EFFECT OF MAL solution to the problem although addi
DISTRIBUTION ON LOCAL tional work should be undertaken to deter
CONCENTRATION FIRST mine the optimum height and configuration
EFFECT. for the weirs.
348
 ENTRAPMENT SEPARATOR DESIGN
The velocity reduction separator used in
the Freeport plant appears to be the proper
type of separator for this service. Data
from the Freeport plant, while running at
design capacity, show the product water to
contain less than half of the planned 50
ppm dissolved solids.
The only other type of separator design
capable of meeting the low pressure drop
requirements of the Freeport plant is a
wire-mesh separator. Estimates of wire-mesh
separators for the Freeport plant show that
an initial savings in investment could be
made only in the last three low pressure
effects. Because of the high brine concentra
tions involved, fouling is very likely to
occur. Wire mesh was used successfully in
the San Diego multistage flash demonstra
tion plant; but the entrained brine was
onlv about 1.7 times normal sea water con
centration. Difficulty has been experienced
at the Roswell, New Mexico, vapor compres
sion demonstration plant with mesh protect
ing the compressor from second-stage
entrainment where the brine is also about
1.7 times normal sea water; but the basic
composition is different.
The high brine concentration encountered
in the Freeport plant is three times normal
sea water; and in the proposed normalized
plant with ion-exchange pretreatment, it
would be five times normal sea water.
Therefore, it is recommended that only the
simpler and more trouble-free velocity re
duction separators be used in LTV evapo
ration plants until further research is done.
MATERIALS OF CONSTRUCTION
AND CORROSION
A Probolog, an eddy-current device which
senses pits, holes, cracks, and changes in
the tube-wall thickness, was employed to
evaluate the tubing. With one exception
the tubing is in good shape. This is heat
exchanger 215 which receives raw sea water
at ambient temperature. The tubes are
aluminum-brass, severely pitted on the first
pass near the inlet nozzle, and will probably
have to be replaced within 6 to 24 months.
There is pitting in both passes, and it is
estimated that complete retubing will be
required in three to four years. The pitting
is caused by marine biofouling. Downstream
from this unit, water temperatures are high
enough to kill the fouling organisms.
There are three methods by which this
fouling can be controlled: (1) continuous
chlorination to a chlorine residual of one-
half ppm as determined by methyl-orange
titration; (2) periodic heating to 150°F or
more obtained by temporary shutdown or
crossover piping with a hotter downstream
heat exchanger; and (3) retubing with
copper.
There are serious objections to chlorina
tion. Water velocity in this unit is reported
to be about 1.5 feet per second. Copper
will maintain a protective film in ambient
sea water up to two feet per second. If
copper is considered, a few experimental
tubes should be installed to make certain
that copper will withstand the operating
conditions.
Other heat exchangers Probologed were
301, 304 . 311, 201, 211, and 214. These in
cluded Admiralty, aluminum-brass, and
90:10 cupro-nickel. They were all in very
good condition.
Dow experience with aluminum -brass and
90:10 cupro-nickel indicates a life of 11 to
15 years. There is no general thinning or
attack. The greatest single cause of failure
is the lodging of shell fragments or other
foreign bodies in the tubes. This creates
local turbulence which destroys the protec
tive film and causes perforation. Some shell
fragments, small crabs, etc. were noted on
the top tube sheets. There were also large
thick flakes of rust from the piping and
water boxes. Plant experience indicates
that these interfere with operations and
could cause trouble when lodged in a tube.
The water box shells in the Freeport
plant are corroding rapidly and dividing
plates have to be renewed from time to
time. This corrosion and that of the tube
sheets can be completely and permanently
arrested with impressed current. In general,
the water temperature is too high to make
magnesium anodes practical. Impressed-
turrent anodes of platinized titanium or
titanium tipped with carbon or Durichlor
Alloy are inexpensive and practical. Those
used by Dow cost S6.00 each for materials
and are easily assembled by any mechanic.
In addition to permanently protecting the
water boxes and tube sheets, this will elimi
nate part of the rust flake problem.
Tubes in the first four effects were
Probologed. The aluminum-brass tubes in
the first effect were in "like-new" condition.
Some experimental Type 304 stainless tubes
in this effect showed moderate to severe
pitting, which would be expected. The
Admiralty tubes in the second effect showed
some very slight pitting and some super
ficial layer-type dezincification. Aluminum-
brass in the third effect was in excellent
condition. Probolog tapes on the 90:10
cupro-nickel indicated some pitting. Pitting
in this effect was most unexpected. Removal
of two tubes for metallurgical examination
349
 showed that the "pits" were actually dents
and bruises of mechanical origin.
An investigation of coatings suitable for
this service produced three recommenda
tions (based on manufacturers' suggestions):
(1) Napko S 1670 S.T.P. Bakelite Phenolic,
(2) Carboline Phenoline S68, and (3)
Amercoat D-4 overcoated with 1741. Applied
cost is estimated at $1.50 to 52.00 per
square foot. Laboratory tests conducted by
Dow indicate a life for these coatings of
3 to 12 months, depending on temperature.
It would obviously be cheaper to replace
this portion of the evaporators every three
years than to employ these coating systems.
The replacement could probably be made
for $2.00 per square foot. Coal-tar epoxies
were considered, but they impart taste and
color to the water.
In the Freeport plant, severe pitting is
occurring under the holes in the distributor
plate. When measured in May 1964. the
loss in thickness amount to about one-
fourth inch. This corrosion will accelerate
because of the recent installation of copper
weir inserts into the top of the tubes. It
will be further accelerated as corrosion lays
bare the rolled-in portion of the tubes.
These copper inserts preclude the applica
tion of impressed current below the dis
tributor plate. An anode will protect only
"what it can see".
A protective coating or "puttying up"
the deep pits with some kind of mastic is
not deemed advisable. In order to be suc
cessful, this method would have to be 100
per cent perfect; even near-perfection would
be disastrous. All of the galvanic corrosion
would be concentrated on any unprotected
spots.
In the piping, the first perforation occurs
in 18 to 36 months depending on tempera
ture, turbulence in elbows, etc. In addition
to shutdowns, operational trouble is caused
by rust flakes, and as explained earlier,
lodging of these flakes in heat exchanger
tubes can cause some pressure drop.
Some test spools of reinforced plastic arc
in operation. There is serious objection to
reinforced plastic due to its sensitivity to
water hammer. This, together with its cost
(three to five times that of steel) , does not
make it an attractive solution.
The condition of the 90:10 cupro-nickel
tubes in the evaporators and heat ex
changers clearly demonstrates that 90: 10
cupro-nickel would be a suitable piping
material. However, when the cost of ten-
gauge cupro-nickel is compared with that
of steel, it is found to be about four times
as expensive. The sea water and brine lines
350
could be installed for $60,000 using steel
pipe, whereas the cost of installed 90:10
cupro-nickel pipe would be $242,000.
The nonferrous alloys, including cupro-
nickel, are subject to deposit attack, a form
of Oj concentration cell corrosion. In han
dling normally aerated sea water, it is
necessary to maintain a velocity of five feet
per second to avoid deposit attack. It is
not known whether such attack would
occur, or to what extent, downstream of the
deaerator.
Cavitation attack is a combination of
mechanical and corrosion effects. The col
lapsing force of the bubbles has been esti
mated to be in the order of 50,000 to 60,000
pounds per square inch. This is sufficient to
destroy the protective film on most metals.
Without a film corrosion can be very rapid.
The instantaneous corrosion rate of bare
iron in sea water has been estimated at
one inch per year. Cavitation attack can be
stopped or greatly reduced by cathodic
protection, but it is not very practical for
application to pump impellers.
In cavitation tests in sea water. Cr-Ni
stainless steel has proved superior to all
other materials commonly available for
pump impellers. Dow has standardized on
19-9 extra-low-carbon stainless steel and
now has ten years' successful experience
with it (ASTM A 296 Grade CF8 extra-low
carbon) . This cxtra-low-carbon stainless
steel is greatly superior to Ni-Resist cast
iron. The 19-9 is recommended for ambient
sea water and for temperatures up to
I20°F. Above this temperature it is believed
that stress-corrosion cracking will be a
problem.
ASTM Specification A 296 Grade CN-7M
(commonly known as "20 Alloy") is more
resistant to stress-corrosion cracking than
the other stainless steels, but it is not im
mune. It might be useful up to 200°F and
would have better cavitation resistance than
Monel Alloy 505 (formerly known as S
Monel) or Ni-Resist cast iron. Both stain
less alloys can be repaired by welding.
Monel Alloy 505 should be used above
200°F. It is immune to stress-corrosion
cracking. It is more resistant to cavitation
attack than Ni-Resist but somewhat less
resistant than the stainless steels. However,
it cannot be welded.
Failures of the Monel shafts have not
been a serious problem, but some trouble
can be expected from corrosion fatigue.
This is brought about by an imbalance of
the impellers or a hydraulic imbalance
resulting from local corrosion of the casing.
It has been Dow's experience that pump-
shaft materials must combine a high yield
strength with corrosion-resistance. The ideal
material is Monel Alloy K 500, which was
standard with Dow for many years. Extended
and uncertain deliveries led to the trial
and ultimate adoption of Armco 17-4 PH
Temper H 1075 stainless steel, which has
proved quite satisfactory. This material is
recommended for temperatures up to 200°F.
Above this temperature, Monel Alloy K 500
is recommended for use with Monel Alloy
505 impellers.
MECHANICAL EQUIPMENT DESIGN
Considerable difficulties have been con
tinually experienced with the pumps in the
Freeport plant. The particular problem of
cavitation caused by insufficient net positive
suction head accounts for the majority of
the problems encountered with pump im
pellers. The recommendations set forth
under "Materials of Construction and
Corrosion" should be followed. The Model
Goulds pumps installed in the Freeport
plant have several shortcomings which
should not be repeated. These pumps can
not be equipped with shaft sleeves which
are very desirable for a brine pump in
continuous operation. In place of shaft
packing, it is recommended under all plant
PROCESS CHEMICAL CONSIDERATIONS
CHEMICAL ANALYSES PROCEDURES
AND SAMPLE POINTS
The data sample points and chemical
analyses procedures for the plant were
extensively examined as part of the overall
evaluation. For a detailed discussion of
these points, please refer to the Office of
Saline Water Research and Development
Report no. 139.
SOLUBILITY OF CALCIUM SULFATE
AND ITS HYDRATES
Calcium sulfate, in its various hydrated
forms, is the most troublesome scale en
countered in the distillation of sea water.
It is known that anhydrous calcium sulfate
occurs as scale at high temperatures and
that the dihydrate (gypsum) occurs as
scale at low temperatures. Both forms, as
well as the metastable hemihydrate, have
been found as major constituents of scale
samples taken from tubes in the Freeport
conversion plant.
A study was undertaken to determine,
using available references, the best solubil
ity relationships for these forms of calcium
sulfate in concentrated sea water at elevated
temperatures. The results of the literature
search and calculations are presented in
operating conditions that the appropriate
size and type mechanical seal be utilized.
In all cases, where pumps operate with
suction condition of subatmospheric pres
sure, the pumps should have a discharge
pressure above atmospheric pressure applied
to the shaft seal. All shaft seals on all brine
pumps should be flushed with product
water.
INSTRUMENTATION
The condensate pumps in the Freeport
plant are presently running with unthrot-
tled discharge. Since they are capable of
delivering more than the required flow at
the required head, this allows the pump to
run- dry and cavitate. In such cases, level
controls should be used to maintain suffi
cient net positive suction head.
As discussed previously, automatic pH
controllers should be added to control
sulfuric acid and caustic addition before
and after the deaerator. This would allow
narrowing the pH control range and would
make neutralization easier. Because of the
susceptibility of glass pH electrodes to
poisoning by sodium ions, an antimony
electrode is recommended to control the
caustic addition for neutralization.
Figure 136. Operating data for a typical
period are shown, and periods of known
scale formation are indicated. It can be
concluded that if scaling is to be prevented,
operation of the F'reeport conversion plant
is limited to brine temperatures of less than
240°F in the first effect and brine concentra
tions with a concentration factor of less
than three in the twelfth effect.
If either calcium or sulfate is removed
from the sea water, the solubility product is
changed and the concentration-temperature
relationship is altered. Figure 137 shows
the concentrations and temperatures to
which softened sea water, with 50 per cent
and 75 per cent of the calcium removed,
can be carried before the solubilities of
either anhydrite or gypsum are exceeded.
PLANT SCALE EXPERIENCE
Anhydrous calcium sulfate has appeared
with monotonous regularity as the principal
constituent of scales from the higher tem
perature effects and has been found as far
down the system as the fourth effect when
a 250°F first effect brine temperature was
attempted.
Gypsum has appeared with equal regu
larity in the lower temperature effects and
351
SCALING
OCLTV
AND
136.
FFIGURE
FALLING
PFILM
RENDREIATPIORNTS

DPLANT.
EMONSTRATION
SCOF
137.
CALCIUM
FIGURE
IN
WATER
SEA
OUNLCLEBFNITALRITEYD

T(REFS.
VARIOUS
AT
4).
35,
28,
EMPERATURES
has been found in the tenth effect when a
concentration factor of four in the twelfth
effect was attempted. All operations at
brine concentration factors exceeding three
in the twelfth effect have been accompanied
by the formation of gypsum.
Experience in the Freeport demonstration
plant has shown that operation of a long
tube, vertical, falling film distillation plant
in supersaturated regions for any extended
period is highly unlikely.
ION-EXCHANGE SOFTENING DESIGN
Designs for ion-exchange softening units
were prepared for the two revised operating
conditions for the Freeport plant and for
the normalized plant. In each of the de
signs, regeneration is accomplished using
only the concentrated blowdown brine from
the plant. For a detailed discussion of these
processes, refer to the paper "Ion-Exchange
Pretreatment in Process Development" by
\V. F. Mcllhenny of The Dow Chemical
Company.
REVIEW OF BADGER 300°F
SEEDING PROCESS
A detailed study of the Badger seeding
process was made as part of the evaluation.
Adaptation of the Badger anhydrate-seeding
process to the vertical tube, falling film
distillation process to permit 300°F opera
tion is economically attractive provided
hydraulic cyclone seed recovery of 98 per
cent can be achieved prior to the first effect
and provided the feed sea water can be
heated to 300°F without scaling. Because
of the highly experimental nature of the
process, it can not be recommended at this
time. It should be pointed out that this
process might only substitute one problem
ECONOMICS OF DESALINATION PLANTS
Economic evaluation of the present and
revised operations of the Freeport conver
sion plant and a normalized long tube,
vertical, falling film distillation plant is
based on criteria set forth by the Bechtel
Corporation. Refer to "A Study of Large
Size Saline Water Conversion Plants", Re
search and Development Report no. 72
(PB 181470), pp. 30-48, Office of Saline
Water (1963) . All cases are evaluated for
330 operating days per year.
PRESENT PLANT ECONOMICS
The principal items of equipment are
estimated at 1964 prices, and the equipment
costs shown in Table XLIII arc installed
costs. All equipment used in the present
for another by eliminating scaling in the
first effect evaporator and permitting scaling
in the preheated feed sea water instead.
For a detailed discussion of this process,
refer to the Office of Saline Water Research
and Development Report no. 139.
PRODUCT WATER
A typical analysis of the product water
to the city of Freeport is as follows:
Total dissolved solids - 20 ppm
Total hardness - 3.0 ppm CaCOi
Total alkalinity - 4.0 ppm CaCOt
pH - 6.8
This water has a Langelier Index of
— 3.85 and is considerably more corrosive
than either raw Freeport well water or
chlorinated Freeport well water. Corrosion
rates of plain carbon-steel measured by
weight loss ranged from 5.5 to 13.0 mils
per year as compared with 1.23 to 5.05 mils
per year for Freeport well water.
Its normally corrosive nature is due to
its lack of scale-forming ability and is en
hanced by the presence of free CO, in
varying amounts, depending upon the oper
ation of the deaerator in the conversion
plant.
During the evaluation, tests were made
on treatment of the product water with
CaCl, and Na,CO, with varying degrees of
success. Treatment of product water at the
Freeport conversion plant with ten ppm
CaClj plus ten ppm Na,COs has been bene
ficial. This has decreased the corrosion rate
of plain steel in the water to about one-half
of that which would exist without the treat
ment. Much work still remains to be done
on this problem, and a final recommenda
tion can not be made at this time.
operation is included for the determination
of the capital cost. Erection and assembly
cost is calculated as 20 per cent of the cost
for the principal items of equipment and
includes site development, concrete work,
overhead crane, painting, and insulation.
Engineering and startup costs used were
given for the demonstration plant by
Bechtel. The capital cost is $1.60 per gpd
capacity.
The per diem chemical consumption at
a production of one mgd is 40 pounds of
CaCl,, 40 pounds of Na,CO„ 1200 pounds
of HsSO,, and 320 pounds of NaOH.
The operating costs are computed from
plant data for steam, chemicals, and electric
power consumption. Prices for these items
 TABLE XLD.I. Capital Cost for the
Present Plant
Principal items of equipment
1. Evaporator effects
2. 300 Series exchangers
3. 200-Series exchangers
4. 812 condenser
5. Deaerator
6. Flash tanks
7. Pumps
8. Vacuum and air compressors
9. Acid and caustic systems
10. Sea water intake
11. Deauperheater
12. Electrical and piping
13. Product storage tank
Total principal items of equipment
14. Erection and assembly
15. Instruments
t exchangers with flash tanks, and by the
16. Operations buildings
17. Land
18. Engineering
19. Startup
Total capital cost
Capital cost per gpd capacity
were obtained from plant records. The
labor cost was obtained from Steams-Roger
Manufacturing Company (Second Annual
Report, Saline Water Conversion Demon-
stration Plant, Freeport, Texas, Office of
Saline Water) and was based on present
operating procedures. The cost of water,
computed from annual operating costs and
$ 608,896 annual production, was found to be $1.29
103,288 per thousand gallons of product water
91,124 (Table XLIV) .
24,215
19,822 REVISED PLANT ECONOMICS
12,652 As part of the overall engineering evalua
78,368
14,898 tion, the cost of the changes required and
6,680 recommended for the Freeport plant was
49,317 estimated for the two revised operating
2.080 conditions. These changes are incorporated
140,400 in the capital cost estimates.
8,500 The equipment required for the two
revised plant operations is the same, with
81,158,635 only small differences in size. Equipment
168,842 varies from that in the present plant by
52,629 replacement of the product water cross
42,800
8,000 addition of an ion-exchange unit for sea
167,000 water feed pretreatment.
22,000 (1) Revised 725" plant: The capital cost
81,604,406 of the revised plant was changed by the
$1.60 removal of the heat exchangers at $30,820
and by the addition of an ion-exchange
unit at $53,415. The recommendations of
the engineering evaluation were incorpo
rated in the estimation of capital cost
shown in Table XLV.

TABLE XLIV. Cost of Water for the Present Plant Operation

Plant data
Plant capacity, mgd 1
Annual production, millions of gallons 330
Economy ratio, gross lb water/lb steam 10.95
Capital cost, dollars 1,604,406
Direct operating eott t/year t/1000 gal
Steam, 454/1000 lb 111.875 83.75
Electricity. 8 mils/kwh 26.648 8.08
Chemicals 8,608 2.68
Stores and maintenance mat'ls 8.022 2.48
Maintenance labor 19,780 6.00
Operating labor 40.659 12.82
Total 214,987 66.16
Indirect operating coat
Payroll extras 9.670 2.98
General and administrative overhead 17,627 5.31
Taxes and insurance 31,648 9.59
Amortization 118,727 86.98
Interest on working capital 2,858 0.87
Total cost 895,417 119.84
or
61.20

355
 TABLE XLV. Capital Cost for
Revised 275° F Plant
Principal items of equipment
1. Evaporator effects
2. 300-Series exchangers
s. 200-Series exchangers
4. 812 condenser
5. Deaerator
6. Flash tanks
7. Pumps
8. Vacuum and air compressors
». Acid and caustic systems
10. Sea water intake
11. Desuperheater
12. Electrical and piping
IS. Product storage tank
14. Ion-exchange unit
Total principal items of equipment
It. Erection and assembly
16. Instruments
17. Operations buildings
18. Land
1». Engineering
20. Startup
Total capital cost
Capital cost per gpd capacity
Erection, assembly, engineering, and start
up for the revised plant are the same as for
the present plant. The total capital cost is
$1.13 per gpd capacity.
$ 608,396 The per diem chemical consumption is
104.877 1488 pounds of H,SO„ 596 pounds of NaOH,
51.068 and 105 pounds of Ca (OH) ,. The ion-
24.216 exchange resin makeup would be 22 cubic
19,822 feet per year.
12,662 Operating costs were estimated from the
87.587 revised heat and material balance. Steam,
14.878 chemicals, and resin consumption were
6.630 calculated from the balance. Electric power
49.317
consumption was taken from the recom
2.080 mended pump changes for the revised plant.
137,014 Labor costs are the same as those used for
8,600
68.415 the present plant. The cost of water (Table
XLVI) of $0.95 per thousand gallons was
$1,178,941 calculated from annual operating cost and
163.342 the production estimated from the revised
275°F heat and material balance.
52,202 (2) Revised 300°F plant: The capital
42.800 cost (Table XLVII) includes the required
3.000
167,000 changes to the heat exchangers and the
22.000 addition of an $86,548 ion-exchange unit.
Engineering, erection, assembly, and startup
$1,624,286 are the same as for the present plant. The
$1.18 capital cost is $0.93 per gpd capacity.

TABLE XLVI. Estimated Cost of Water for Revised 275°F Plant Operation
Plant data 1
Plant capacity, mgd 1.48$
Annual production, millions of gallons 472.870
Economy ratio, gross lb water/lb steam 11.1
Capital cost, dollars 1.624.286
Direct operating cott t/year t/1000 gal
Steam, 46«/1000 lb 159.910 33.82
Electricity, 8 mils/kwh 25.041 5.30
Chemicals 9,726 2.06
Resin 617 0.14
Stores and maintenance mat'ls 8.122 1.72
Maintenance labor 20,029 4.24
Operating labor 40.659 8.60
Total 264.004 55.88
Indirect operating cost
Payroll extras 12,833 2.71
General and administrative overhe«id 18.380 8.89
Taxes and insurance 82,046 6.78
Amortisation 120.199 26.42
Interest on working capital 3.254 0.69
Total cost 460.716 95.87
or
$0.96
 TABLE XLVII. Capital Co« for
Revised 300° F Plant
Principal item* of equipment
1. Evaporator effects
2. 300 Serie» exchangers
a. 200 Series exchangers
«. 812 condenser
6. Deaerator
6. Flash tanks
T. Pumps
8. Vacuum and air compressors
9. Acid and caustic systems
10. Sea water intake
11. Desuperheater
12. Electrical and piping
18. Product storage tank
U. Ion-exchange unit
Total principal items of equipment
1С. Erection and assembly
16. Instruments
17. Operations buildings
18. Land
19. Engineering
20. Startup
Total capital coat
Capital cost per gpd capacity
The per diem chemical consumption ii
1753 pounds of H.SO., 466 pounds of NaOH,
and 131 pounds of Ca (OH),. The resin
makeup would be 73 cubic feet per year.
The cost of water (Table XLVIII) of $0.83
f 619,567 per thousand gallons was calculated for the
117,020 300°F revised plant operation. Steam, chem
49,712 icals, and resin consumption were calculated
29.267 from the revised 300°F heat and material
19.822
balance. Power consumption was calculated
12.662 from the recommended pump changes.
80.886 Labor costs were the same as the costs used
14,898
for the present plant. Water cost was calcu
6,680
49.817 lated from annual operating cost and revised
2,460 annual production for 300°F operation.
187,014
8.500 NORMALIZED PLANT
86,548 The capital cost (Table XLIX) was esti
81,228,288 mated from the criteria established in the
Bechtel Corporation Research and Develop
163,842 ment Report no. 72 (PB 181470). The
52,202 major equipment changes were the addition
42,800 of an ion-exchange unit at $67,400 and
8.000 redesign of the heat exchangers for the
167,000
22,000 one mgd capacity. The costs of insulation
and painting were combined because of the
81,678,627 use of insulation which does not require
$0.93 paint. The capital cost is §1.52 per gpd
capacity which is $0.08 per gpd capacity
less than the present Freeport plant capital.

TABLE XLVni. Estimated Cost of Water for Revised 300°F Plant Operation
Plant data
Plant capacity, mgd 1.812
Annual production, millions of gallons 598.085
Economy ratio, gross lb water/lb steam 11.1
Capital cost, dollars 1,678.627
Direct operating coat t/year (/1000 gal
Steam, 45«/ 1000 lb 200,821 88.58
Electricity,8 mils/kwh 25,518 4.27
Chemicals 11.482 1.92
Resin 1.716 0.28
Stores and maintenance mat'Is 8,393 1.40
Maintenance labor 20,707 3.46
Operating labor 40.659 6.90
Total 809,290 51.81
Indirect operating coet
Payroll extras 9,819 1.64
General and administrative overhead 17,796 2.98
Taxes and insurance 88,072 5.63
Amortication 124,216 20.77
Interest on working capital 3,594 0.60
Total cost 497,787 83.33
or
$0.83

357
 TABLE XLIX. Capital Cost for Electrical costs were based on a load
Normalized One MGD Plant requirement of 556 horsepower and the
procedure presented by Bechtel. Chemicals
Principal items of equipment used included 1,062 pounds per day of
1. Evaporator effects 8 499.000 sulfuric acid and 282 pounds per day of
2. Deaerator equipment 16,500
3. Heat exchangers 123,900 sodium hydroxide. The resin makeup would
4. Pumps and drivers 86,100 be 45 cubic feet per year.
5. Desuperheater 4,650
6. Flash tanks 16,600 Labor costs were based on one operator
7. Air compressor and vacuum equipment 1 1,460
8. Acid and caustic equipment 5.860 per shift, one extra day operator, and a
9. Sea water screen 26,000
10. Ion-exchange unit 67,400 supervisor charging half time to the plant.
11. Sea water intake piping 14,000
12. Electrical 80,000 Operating cost estimation followed the
13. Boiler 150,000 Bechtel procedure. Fuel requirements were
|Total principal items of equipment 81,100,470 based on steam requirements for the nor
Erection and assembly of plant malized balance. The cost of water (Table
14. Site development 88,270| L) is $1.16 per thousand gallons. This is a
16. Concrete 17,600
16. Overhead crane 9.780 reduction of $0.04 from water costs of the
17. Insulation} 57 800 present plant. The water cost of $1.16 per
18. Painting I
19. Spare parte 21,200 thousand gallons for the normalized plant
20. Miscellaneous 84,600
Total erection and assembly of plant I 178.600 compares very favorably with costs pre
Other viously presented in the Bechtel Corpora
21. Instruments 85,000 tion Research and Development Report no.
22. Operating building 44,600 72 (PB 181470) Bechtel reports the water
23. Land 20.000
24. Enstineering 110,000 cost for the normalized long tube, vertical
25. Startup 80.000 distillation plant at $1.46 per thousand
Total other $ 239,500 gallons and the normalized multistage flash
Total capital cost 81.618,570 plant at $1.30 per thousand gallons.
Capital cost per gpd capacity $1.62

TABLE L. Estimated Cost of Water Normalized Plant

Plant data
Plant capacity, mgd 1
Annual production, millions of gallons 830
Economy ratio, net lb water/lb steam 9.8
Capital cost, dollars 1,618.670
Direct operating cost t/vear 4/1000 gal
Fuel 122,820 87.22
Electricity 22,656 6.78
Chemicals 6,711 2.03
Resin 1,068 0.32
Stores and maintenance mat'ls 7,443 2.26
Maintenance labor 18.607 6.64
Operating labor 37,624 11.40
Total 216,919 66.66
Indirect operating cost
Payroll extras 8.997 2.73
General and administrative overhead 16,307 4.94
Taxes and insurance 29,771 9.02
Amortization 112,874 34.05
Interest on working capital 2,796 0.86
Total cost 387.168 117.24
or
$1.17

358
 SUMMARY OF DISCUSSION
Asked about costs for a 50 mgd plant,
the speaker stated that plant cost would be
$38.1 million with a water cost of 47 cents
per thousand gallons and that the perform-
Evaluation Technique
de Distillation Par
Tubes Verticaux,
Laminaire Descendant
D. L. Preddy
Etats-Unis d'Amérique
Aux termes d'un contrat passé avec
l'Office of Saline Water, la Dow Chemical
Company a procédé au cours de l'été 1964
à une évaluation technique du procédé de
distillation a tubes verticaux, à écoulement
laminaire descendant. Le but de cette éva
luation était d'étudier le procédé utilisé
ainsi que la conception des principaux
éléments entrant dans la composition de
l'équipement, en mettant notamment l'ac
cent sur l'amélioration de la production et
de la sécurité de marche en vue d'abaisser
le prix de revient du produit.
Des bilans thermiques et de matériaux
ont été calculés pour trois jeux différents
de conditions d'exploitation. Les installations
de prise d'eau ont fait l'objet d'une évalua
tion. Les préchauffeurs et les échangeurs à
courants croises ont été évalués en fonction de
l'exploitation actuelle et leur structure a été
adaptée à deux autres types d'opération.
Le dégazeur a été soigneusement examiné
et son fonctionnement a été soumis à une
étude poussée comportant notamment un
échantillonnage et une analyse chimique.
La structure de l'évaporateur a été évaluée
en fonction de tubes de dimensions diverses
et de divers taux de recyclage de la saumure,
selon trois différents ensembles de conditions.
La structure du séparateur d'entraînement
a été évaluée pour l'exploitation actuelle et
on a étudié l'utilisation des éliminateurs de
buée à fils métalliques.
Les matériaux de construction de l'usine
et les problèmes posés par la corrosion ont
ance ratio would be 17 to 1. The speaker
also stated he prefers LTV evaporators over
MSF evaporators because of cost of con-
struction and maintenance.
du Procede
Evaporateur a
a Ecoulement
été étudiés, des échantillons ont été soumis
à un examen et on a effectué des radiosco
pies. Les pompes et le reste de l'équipement
mécanique ont fait l'objet d'une étude
mettant en relief les conditions d'exploita
tion plus rigoureuses envisagées. L'instru
mentation a été examinée et évaluée.
L'emplacement et les méthodes d'échan
tillonnage et d'analyse chimique ont été
passés en revue. Le traitement acide et
caustique de l'eau de mer d'alimentation a
été évalué après examen.
L'étude de la documentation spécialisée a
permis de calculer les limites exactes de la
solubilité des incrustations de sulfate de
calcium et de déterminer les limites d'entar
trage des installations à longs tubes verticaux.
Il a été procédé a l'étude de l'adoucissement
préliminaire de l'eau d'alimentation par
échange d'ions. A cet effet, des groupes
d'adoucisseurs ont été mis au point en vue
du fonctionnement de l'installation à une
température de 275°F (135°C) avec un
coefficient de concentration de saumure de
4:1, et à 300oF (149°C) avec un coeffi
cient de concentration de saumure de 5:1.
L'application à l'usine a longs tubes verti
caux du procédé consistant à utiliser de la
boue de sulfate de calcium pour le traite
ment de l'eau d'alimentation a fait l'objet
d'une étude approfondie.
Le traitement de l'eau produite a été
étudié et l'effet de l'eau produite sur les
matériaux de construction a été évalué. Les
bobines d'essai et la tuyauterie de l'installa
359
 tion ont été examinées et la corrosion a
été évaluée. L'effet résultant du mélange de
l'eau produite et de l'eau de ville de Free-
port a été étudié. Une installation norma
lisée d'une capacité de production de 1
million de gallons d'eau déminéralisée par
jour (4.000 m'/j) a été conçue et sa renta
bilité a été déterminée.
Les principales conclusions tirées de l'éva
luation sont énumérées ci-dessous:
1. Il ressort de l'évaluation économique
du processus actuel d'exploitation et de
deux processus d'exploitation révisés com
portant un prétraitement à échange d'ions
que le fonctionnement en usine à une
température de 300°T (149°C) corres
pondant au premier effet avec adoucisse
ment de l'eau de mer d'alimentation par
échange d'ions constitue le procédé le plus
économique. Les dépenses d'investissement
de l'installation actuelle s'élèvent à $1.60
par gallon ($0,42 par litre) de capacité
journalière et le prix de revient de l'eau
s'établit à S 1.20 par millier de gallons
($0,32 par m') . Pour une installation
révisée fonctionnant à une température de
275°F (135°C). l'investissement serait de
$1,13 par gallon ($0.30 par litre) de capa
cité journalière et le prix de revient s'élè
verait à $0,95 par millier de gallons ($0.25
par m") . Pour une installation révisée
fonctionnant à 300°F (149°C) . les inves
tissements tomberaient à $0,93 par gallon
($0,29 par litre) de capacité journalière et
le prix de revient se situerait à $0.83 par
millier de gallons ($0,21 par m*) .
2. En mettant en oeuvre toutes les amé
liorations de procédés déterminées lors de
l'évaluation technique, une installation
normalisée d'une capacité de 1 million de
gallons par jour (1.000 m"/j) a été conçue
pour un investissement de $1.52 par gallon
($0,40 par litre) de capacité journalière et
un prix de revient de $1,16 par millier de
gallons ($0,31 par m') .
3. Une étude systématique des solubilités
du sulfate de calcium et un examen de
l'entartrage de l'installation à longs tubes
verticaux ont conduit à la conclusion que
la température correspondant au premier
effet ne devrait pas dépasser 240°F (115°C)
afin d'éviter la formation de CaSO, (an
hydrite) , et que le coefficient de concentra
tion du dernier effet ne devrait pas être
de plus de trois fois supérieur à la concen
tration de l'eau de mer normale afin d'éviter
la formation de CaSO» ^HjO (gypse) .
4. L'élimination de 50 pour cent du
calcium par adoucissement au moyen
d'échange d'ions dans une couche fluidisée
et par régénération avec de la saumure
360
concentrée, permettra le fonctionnement de
l'installation à une température de 275°F
(135°C) dans le premier effet et donnera
un coefficient de concentration de quatre
fois supérieur à la concentration de l'eau
de mer normale dans le dernier effet.
5. L'élimination de 75 pour cent du
calcium au moyen de l'adoucissement par
échange d'ions permettra à l'installation de
fonctionner à 300°F (149°C) dans le pre
mier effet et donnera un coefficient de con
centration de près de cinq fois supérieur
à la concentration de l'eau de mer normale
dans le dernier effet.
6. L'adaptation du procédé d'ensemence
ment d anhydrite mis au point par Badger
A l'installation actuelle afin de permettre
son fonctionnement à 300°F (149°C) pré
sente un intérêt économique, à condition
que l'on puisse récupérer 98% de la
semence au moyen d'un cyclone hydraulique
préalablement à la mise en oeuvre du
premier effet. Il importe également que
l'eau de mer d'alimentation puisse être
soumise à une température de 300°F n49°C)
sans risque d'entartrage.
7. Les dimensions et la structure du dés-
aérateur à vide installé à l'usine de Free-
port sont satisfaisantes pour maintenir la
concentration totale de CO, dans son effluent
de saumure à un niveau de deux à trois
parties de CO, par million et la concentra
tion de O, à environ 100 parties par
milliard, si toutefois le désaérateur fonc
tionne selon les conditions énoncées dans le
rapport d'évaluation. Le facteur d'exploita
tion le plus critique consiste à maintenir
l'alimentation destinée au désaérateur en
dessous de 4 pH.
8. L'emplacement actuel du désaérateur
dans l'installation de démonstration de
Freeport est jugé apte à assurer l'économie
d'ensemble de l'installation et son efficacité
de fonctionnement.
9. L'utilisation de réservoirs à vaporisa
tion spontanée pour récupérer la chaleur
de l'eau produite se traduit par des dépenses
d'investissement sensiblement moindre que
ne l'exige l'emploi d'échangeurs à courants
croisés.
10. Dans une installation à douze effets
d'une capacité de 1 million de gallons par
jour (4.000 m'/j) comme l'usine de Free
port, les dimensions les plus économiques
pour les tubes d'évaporateur sont, pour
tous les effets, un diamètre de 5 cm sur une
longueur de 7,3 m. La conception optimale
d'installation, avec prétraitement de l'eau
de mer d'alimentation par le procédé à
échange d'ions et une température de
300°F (149°C) dans le premier effet, aura
sans aucun doute plus de douze effets et
l'emploi de tubes d'un diamètre de 7,6 cm
pour les derniers effets se révélera avan
tageux du point de vue économique.
11. En raison du coût accru du pompage,
le recyclage des évaporateurs ne se justifie
pas, tant sur le plan économique que sur
celui de l'échange de chaleur. Toute justifi
cation du recyclage doit reposer sur la pré
vention de l'entartrage, mais on estime
toutefois qu'il sera préférable d'assurer la
distribution du liquide par des moyens plus
économiques.
12. La mauvaise distribution du liquide
aux tubes de l'évaporateur n'a aucune in
fluence sur l'échange de chaleur de l'en
semble. La mauvaise distribution permet
toutefois de limiter la formation d'incrusta
tions de sulfate de calcium à un niveau
inférieur au point de saturation.
13. Outre la plaque de distributeur per
forée utilisée dans l'installation de Freeport,
les tubes de l'évaporateur doivent être
munis de dispositif de trop-plein pour
assurer la distribution du liquide lorsque
la plaque perforée est partiellement obturée.
Техническая Оценка Дистилляционного
Процесса, в Котором Применяются
Вертикальные Трубы с Стекающей
Пленкой
Д. Л. Предди
Соединенные Штаты Америки
Летом 1964 г., на основании договора
с Управлением по опреснению соленых
вод, Дау Кемикал Компани составила
техническую оценку дистилляционного
процесса, в котором применяются вер
тикальные трубы с стекающей пленкой.
Целью этой оценки было исследование
процесса и проектирование главных
элементов оборудования, обращая осо
бое внимание на повышение произво
дительности и функциональной надеж
ности, чтобы понизить стоимость опре
сненной воды.
Были подсчитаны тепловые и мате
риальные балансы для трех групп ра
бочих нагрузок. Был произведен расчет
14. L'eau produite, qui est fournie à
Freeport par pompage, est nettement plus
corrosive à égard de l'acier ordinaire que
l'eau de puits de Freeport.
15. Le caractère corrosif de l'eau produite
est dû à son manque de propriétés d'en
tartrage lié à sa teneur parfois assez forte
en COa. Il peut être remédié économique
ment à cet état de choses par un traitement
chimique. C'est ainsi que le traitement de
l'eau produite à l'installation de Freeport
à l'aide de dix parties par million de CaCls
auxquelles on a ajouté dix parties par
million de Na,COa, a réduit la corrosion
de l'acier ordinaire dans une proportion
notable.
On trouvera tout au long de la communi
cation des conclusions et recommandations
spécifiques ayant trait aux problèmes par
ticuliers étudiés au cours de l'évaluation.
Pour un compte rendu plus détaillé des
résultats et constatations de l'évaluation, il
y a lieu de consulter le Research and
Development Report No. 139, public par
l'Office of Saline Water des Etats-Unis.
комплекса водозаборных устройств.
Подогреватели и теплообменники были
проверены в условиях текущей работы
и спроектированы для двух других про
цессов.
Был подробно изучен сам деаэратор
и его работа с отбором проб и произ
водством химических анализов. Был
составлен проект испарителя с различ
ными размерами труб и скоростями ре
циркуляционного раствора для трех
групп различных нагрузок. Была про
изведена оценка проекта ловушки для
работы в настоящее время и обследо
вано применение проволочных осади-
телей жидкости («тумана»).
361
 Были изучены строительные матери
алы и проблемы коррозии, связанные
с установкой, взяты пробы и сделаны
рентгенные снимки. Были исследованы
насосы и прочее механическое обору
дование, причем было обращено осо
бое внимание на рекомендованные бо
лее тяжелые рабочие нагрузки. Была
просмотрена и оценена оснастка уста
новки приборами.
Был составлен список местоположе
ний и процедур, касающихся отбора хи
мических проб и производства анали
зов. Была проверена и проанализиро
вана обработка исходной морской во
ды кислотами и каустической содой.
С помощью обзора литературы бы
ли рассчитаны правильные пределы
растворимости накипи сульфата каль
ция и определено для длиннотрубной
вертикальной установки предельное об
разование накипи. Была изучена пред
варительная обработка исходной воды
посредством ионообменного смягчения
и были спроектированы смягчающие
агрегаты для установки, работающей
при 275°F и концентрации рассола 4 : 1,
а также при 300°F и концентрации рас
сола 5:1. Была подробно исследована
в рамках длиннотрубной вертикальной
установки обработка исходной воды с
помощью шламма сульфата кальция.
Была изучена обработка опресненной
воды и произведена расценка воздей
ствия опресненной воды на строитель
ные материалы. Были осмотрены проб
ные шпули и трубопроводы установки,
и подсчитана коррозия. Был изучен ре
зультат смешивания опресненной воды
с городской водой Фрипорта. Была
спроектирована стандартизированная
установка на производство одного мил
лиона галлонов опресненной воды в
сутки и приготовлены соответственные
экономические расчеты.
С помощью оценки были сделаны
следующие главные заключения:
1. Экономический подсчет стоимости
эксплуатации существующей установки
и двух улучшенных вариантов с пред
варительной ионообменной обработкой
указывает, что экономически оптималь
ным решением является работа установ
ки при температуре 300°F первой сту
пени и ионообменном смягчении исход
ной морской воды. Существующая
установка стоит 1,60 долл. на каждый
галлон дневной производительности и
вырабатывает тысячу галлонов за 1,20
долл. Для варианта, работающего при
275°F, стоимость установки составляет
1,13 долл. на каждый галлон дневной
362
производительности, а стоимость выра
ботки 0,95 долл. за тысячу галлонов.
Для варианта, работающего при 300°F,
стоимость установки составляет 0,93
долл. на каждый галлон дневной про
изводительности, а стоимость выработ
ки 0,83 долл. за тысячу галлонов.
2. При использовании всех улучше
ний процесса, намеченных технической
оценкой, была спроектирована стандар
тизированная установка на один мил
лион галлонов в сутки, сметная стои
мость которой составляла 1,52 долл. на
каждый галлон дневной производитель
ности, а проектная стоимость выработ
ки 1,16 долл. за тысячу галлонов.
3. Систематическое изучение раство
римости сульфата кальция и наблюде
ние на установке LTV за образованием
накипи привели к заключению, что для
предотвращения образования CaS04
(ангидрита) температура первой ступе
ни не должна превосходить 240°F, а
что коэффициент концентрации послед
ней ступени, чтобы предупредить об
разование CaS04 • 2Н20 (гипса), не
должен быть больше, чем в 3 раза, со
ответственного коэффициента обыкно
венной морской воды.
4. Удаление из воды 50% кальция
посредством ионообменного смягчения
в движущемся слое и регенерации с
помощью концентрированного рассола,
позволят работать в первой ступени
при 275°F и пользоваться в последней
ступени коэффициентом концентрации,
превосходящим в 4 раза соответствен
ный коэффициент обыкновенной мор
ской воды.
5. Удаление 75% кальция посред
ством ионообменного смягчения позво
лит работать в первой ступени при
300° F и пользоваться в последней сту
пени коэффициентом концентрации,
превосходящим почти в 5 раз соответ
ственный коэффициент обыкновенной
морской воды.
6. Применение на существующей
установке процесса Баджера с затрав
кой ангидрита, для того, чтобы иметь
возможность работать при 300°F, вы
глядит экономически привлекательным
при условии, что перед первой сту
пенью с помощью гидравлического
циклона удастся регенерировать 98%
затравочного кристалла, и что можно
будет нагревать до 300°F исходную
морскую воду без образования накипи.
7. Существующий на установке во
Фрипорте вакуумный деаэратор по
своим размерам и конструкции доста
точен, чтобы удерживать полную кон
центрацию С02 в его вытекающем рас
соле на уровне 2-3 частей на миллион,
а концентрацию 02 приблизительно на
уровне 100 частей на миллиард, если
он будет работать в согласии с усло
виями, рекомендуемыми технической
оценкой. Наибнлее критическим рабо
чим фактором является удержание по
ступающего в деаэратор рассола на
уровне pH < 4.
8. Настоящее местоположение деаэ
ратора на опытной установке во Фри-
порте признано правильным с точки
зрения общей экономичности и рабо
чей эффективности.
9. Применение разервуаров вскипа
ния для регенерации тепла из опреснен
ной воды требует значительно меньше
капитальных затрат, чем теплообмен
ники.
10. На теперешней двенадцатиступен-
чатой Фрипортской установке с произ
водительностью 1 миллион галлонов
опресненной воды в сутки, двухдюй
мовая труба общего назначения дли
ной 24 фута является самой экономич
ной для испарителей всех ступеней. У
оптимально-спроектированной установ
ки с предварительной ионообменной
обработкой исходной морской воды и
температурой 300°F на первой ступени,
будет несомненно более двенадцати
ступеней, а потому на последних сту
пенях окажется выгодным применять
большие трехдюймовые трубы.
11. С экономической или теплопере-
даточной точки зрения нет оправдания
для рециркуляции испарителей, так как
это увеличивает стоимость перекачки.
Подобное оправдание может только
базироваться на предупреждении наки
пи, но есть основание полагать, что
другие способы улучшения распределе
ния (тепла) будут более экономичны
ми.
12. Плохое распределение жидкости
по трубам испарителя не влияет на об
щую теплопередачу. Однако, плохое
распределение затрудняет подход к ли
нии насыщения накипи сульфата каль
ция.
13. В дополнение к перфорированной
распределительной тарелке, применяе
мой на Фрипортской установке, трубы
испарителей должны быть оборудованы
водосливными вставками, чтобы обес
печить распределение, если перфориро
ванная тарелка будет частично закупо
рена.
14. Опресненная вода, перекачивае
мая во Фрипорт, гораздо более корро-
зионна по отношению к обыкновенной
стали, чем Фрипортская родниковая
вода.
15. Коррозионная активность опрес
ненной воды объясняется ее неспособ
ностью образовывать накипь, что на
ходится в связи с ее время от времени
довольно высоким содержанием С02.
Это состояние может быть экономиче
ски исправлено с помощью химической
обработки. Обработка опресненной во
ды Фрипортской установки десятью
частями на миллион СаС12 плюс де
сятью частями на миллион Na2C08
значительно уменьшало коррозию
обыкновенной стали.
Особые заключения и рекомендации,
касающиеся специальных изученных
проблем, разбросаны по всему докладу.
Для более детального рассмотрения ин
формации, разработанной технической
оценкой, можно найти нужные справки
в Научно-исследовательском Докладе
№ 139 Управления по опреснению со
леных вод.
363
 Evaluación Técnica
Destilación en
Tubos Verticales con Película
Descendente
D. L. Preddy
Estados Unidos de Norteamérica
Bajo contrato con la Oficina de Agua
Salada, la Dow Chemical Company llevó a
cabo, en el verano de 1964, una evaluación
técnica del proceso de destilación en eva
poradores de tubos verticales con película
descendente. £1 objetivo de dicha evalua
ción fue examinar el proceso mismo y el
diseño de las piezas principales del equipo
usado, poniendo especial énfasis en el me
joramiento de la producción y la seguridad
de funcionamiento para reducir el costo del
producto.
Se hicieron cálculos del balance calórico
y del material para tres grupos de condi
ciones operativas. Se evaluó el sistema de
admisión. También fueron evaluados los
precalentadores y los intercambiadores atra
vesados para la instalación actual, y se
diseñaron otros para dos condiciones opera
tivas adicionales.
Se hizo un estudio extensivo del desairea-
dor y de su funcionamiento, incluyendo la
extracción de muestras y el análisis químico.
El diseño del evaporador fue evaluado para
tubos de varios tamaños y con regímenes
variables de recirculación de salmuera para
tres grupos de condiciones operativas dife
rentes. Se evaluó el diseño del separador de
material de arrastre para la instalación
actual y se hizo un estudio del uso de
mallas de alambres para eliminar neblina.
Se hicieron estudios de los materiales de
construcción y de los problemas de corro
sión; se examinaron muestras y se con
dujeron pruebas de radiometalografla. Se
estudiaron las bombas y otros equipos
mecánicos, dando mayor énfasis a las con
diciones más severas de funcionamiento
propuestas. Se revisó y evaluó el sistema
de instrumentos de la planta.
Se hizo una revisión de la ubicación y
procedimiento para la toma de muestras y
364
del Proceso de
Evaporadores de
los análisis químicos. También se revisó y
evaluó el tratamiento ácido y cáustico del
agua de alimentación.
A través de un estudio de la literatura
técnica se calcularon los límites correctos
de solubilidad de la costra de sulfato de
calcio y se determinaron los límites de
formación de costra para la planta con
evaporador de tubos verticales (ETVL) . Se
estudió el ablandamiento por intercambio
iónico para el tratamiento previo del agua
de alimentación, y se diseñaron ablanda
dores para el caso de la planta que funciona
a 275°F (135"C) con una concentración de
salmuera de 4 a 1 y para el funcionamiento
a 300°F (149°C) con una concentración de
salmuera de 5 a 1. Se estudió extensamente
el proceso de lechado del sulfato de calcio
para el tratamiento del agua de alimenta
ción para la planta ETVL.
Se hizo un estudio del tratamiento del
agua producida y se evaluó el efecto de
dicha agua sobre los materiales de construc
ción. Se hizo una inspección de las válvulas
de prueba y del sistema de cañerías de la
planta y se evaluó la corrosión. Se estudió
el efecto de la mezcla entre el agua pro
ducida y el agua de la ciudad de Freeport.
Se diseño una planta normalizada para
producir un millón de galones al día y se
determinaron los factores económicos de la
misma.
Las conclusiones mayores de esta evalua
ción fueron las siguientes:
I. La evaluación económica del funciona
miento de la planta actual y de dos alterna
tivas de funcionamiento revisadas para
incluir un tratamiento inicial por medio
de intercambio iónico, indican que el pro
ceso más económico es el de hacer funcionar
la planta a una temperatura de 300°F en
la primera etapa, con ablandamiento del
 agua de alimentación por medio de inter
cambio iónico. La planta actual cuesta,
capital de inversión, $1,60 por galón diario
de capacidad y produce agua a un costo de
$1,20 los mil galones. Con una temperatura
de 275°F, el costo del capital de inversión
de la planta así modificada seria de $1,13
por galón diario de capacidad y el costo
de producción de $0,95 los mil galones. Con
una temperatura de 300°F, el costo del
capital de inversión sería de $0,93 por
galón diario de capacidad y el costo de
producción de $0,83 los mil galones.
2. Usando todos los métodos de mejora
miento determinados en la evaluación téc
nica, se diseñó una planta normalizada para
producir un millón de galones de agua por
día, cuyo costo en capital de inversión sería
de $132 por galón diario de capacidad y
con un costo de producción de $1,16 los
mil galones.
3. Un estudio sistemático de la solubili
dad del sulfato de calcio y la revisión de
la formación de costra en la planta ETVL,
han dado como conclusión que la tempera
tura de la primera etapa no debería exceder
240°F (116°C), para evitar la formación
de CaSO, (anhidrita) y que, el factor de
concentración de la última etapa no debería
ser más del triple del agua de mar, a fin de
prevenir la formación de CaSO, • 2H,0
(yeso).
4. La extracción del 50 por ciento del
calcio con ablandamiento por intercambio
iónico en un lecho fluidificado y regenera
ción con salmuera concentrada, permitirá
trabajar a 275°F (135°C) en la primera
etapa y un factor de concentración de
cuatro veces el de agua de mar normal en
la última etapa.
5. La extracción del 75 por ciento del
calcio con ablandamiento por intercambio
iónico permitirá trabajar a 300°F (149°C)
en la primera etapa y un factor de con
centración de casi cinco veces el de agua
de mar normal en la última etapa.
6. La adaptación del proceso Badger a
la planta actual para la siembra de anhi
drita es una posibilidad económicamente
atractiva, siempre que, con el uso de un
proceso centrífugo hidráulico en la primera
etapa, se recupere el 98 por ciento de tal
siembra y que el agua de mar pueda ser
calentada a S00°F sin formar costra.
7. El desaireador al vado actualmente
en uso en la planta de Freeport, es ade
cuado en tamaño y en diseño para mante
ner la concentración total de CO, de la
salmuera de descarga, en la vecindad de
dos a tres partes por millón y la concen
tración de 0, a un nivel de aproximada
mente 0.1 parte por millón, si es que se lo
hace funcionar bajo las condiciones suge
ridas en el informe de la evaluación técnica.
El factor operativo más crítico es mantener
el pH de la alimentación al desaireador por
debajo de 4.0.
8. La ubicación actual del desaireador en
la planta de demostración de Freeport se
consider adecuada para obtener la econo
mía máxima y la eficiencia operativa total.
9. El uso de tanques de evaporación
instantánea para recobrar calor del agua
producida, resulta en una inversión sub-
stancialmente menor que la que es necesa
ria para usar intercambiadores atravesados.
10. En una planta de doce etapas di
señada para producir un millón de galones
por día, las dimensiones más económicas
de los tubos del evaporador son de dos
pulgados de diámetro por 24 pies de largo
para todas las etapas. El diseño óptimo de
una planta que incluya tratamiento inicial
del agua de alimentación por medio del
intercambio iónico, con una temperatura
de 300°F (149°C) en la primera etapa,
indudablemente tendrá más de doce etapas,
y sería económicamente más conveniente
usar tubos más grandes, de 3 pulgadas de
diámetro, en las últimas etapas.
1 1 . Debido al mayor costo de bombeo
en que se incurriría, no hay justificación
económica o de termotransferencia que
permita recirculación en los evaporadores.
Cualquier razonamiento que justifique la
recirculación debe basarse en la prevención
de la formación de costra; sin embargo, se
cree que hay otros métodos más económi
cos para obtener una distribución adecuada.
12. La mala distribución del liquido en
los tubos del evaporador no afecta la tras
misión de calor total. Sin embargo, una
mala distribución si limita la aproximación
a la línea de saturación de la costra de
sulfato de calcio.
13. Además de la placa perforada dis
tribuidora que se usa en la planta de Free
port, los tubos del evaporador deben estar
equipados con inserciones vertederas, para
obtener una buena distribución en caso que
la placa perforada se obture parcialmente.
14. El agua producida que se bombea a
Freeport es mucho más corrosiva con re
specto al acero común que el agua de pozo
de la misma ciudad.
15. La corrosividad del agua producida,
se debe a la falta de propiedades para
formar costra que esta sufre, lo cual se
relaciona con su contenido de CO, oca
sionalmente bastante alto. Esta condición
puede corregirse económicamente por medio
de un tratamiento químico. El tratamiento
365
 del agua producida en la planta de Free
port con diez partes de CaCl2 por millón,
más diez partes de Na,CO, por millón, ha
reducido substancialmente la corrosión del
acero común.
Este informe contiene conclusiones y re
comendaciones específicas que se relacionan
con problemas especiales estudiados en la
366
evaluación técnica. Si los lectores tienen
interés en una discusión más detallada de
la información expuesta en la evaluación
técnica, sería conveniente que se refieren al
informe No. 139 de la Sección de Investiga
ción y Desarrollo de la Oficina de Agua
Salada.
Design Criteria for Reverse Osmosis
Desalination Plants
B. Keilin and C. G. DeHaven
United Sutes of America
INTRODUCTION
The major advantage of reverse osmosis
as a saline water conversion process is the
low energy requirement as compared to
other processes. The large area of mem
brane which must be employed and the
requirements of a desalination cell to (1)
provide a support for this membrane, (2)
provide a means of removing the fresh
water produced, (3) separate the 1500 psi
brine stream from the low pressure fresh
water after desalination has been accom
plished, and (4) maintain a minimum con
centration at the membrane surface, imply
system complexity. To take full advantage
of the low cost potential of the reverse
osmosis process, capital costs must be main
tained at a low level commensurate with
the cost savings which the low energy re
quirement offers. A cell design study has
been conducted to determine the materials
MATERIALS OF CONSTRUCTION
MEMBRANE SUPPORT
An examination of the basic cost of
materials for potential use in any configura
tion was made to narrow the field of useful
materials as much as possible before looking
into specific configurations.
Laboratory evaluation of membranes were
carried out using porous stainless steel
Supporting the membrane. First considera
tion in design of a 1,000 gpd pilot plant
was given to the use of an impermeable
stainless steel membrane support, equipped
with holes perpendicular to the plate and
also radially within the plate to carry the
product water. It was recognized, however,
that chejBtrjcate^arul^ extensive jmachining
and designs that offer optimum methods
for utilizing the membrane. A survey has
been made to find suitable, low cost materi
als which satisfy the requirements of mem
brane support and product removal. Various
designs have been evaluated for utilization
of suitable materials. Reported in this paper
are:
(1) A comparison of gross configurational
aspects of the desalination cell with empha
sis upon the relative merits of the tube vs
flat-plate concepts.
(2) An evaluation of various methods of
using both the tube and the flat-plate
configuration.
(S) An evaluation of construction materi
als for major cell component parts and
refinement of concepts to simplify construc
tion and reduce costs.
required for such a- design rendered it eco-
aojnicallj. useless_and_ the concept was^aban"-
doned, even for pilot purposes.
In actual construction, porous-sintered
bronze was used as the plate material.
Though suitable for pilot plant operation,
the porous bronze was recognized to be
unsuited for economical, large-scale opera
tion; and a search for more economical
materials continued. Recently, another mod
ification was introduced—support plates
.fabricated from porouijaminated fiberglas
resin. This represented a major cost im
provement; however, for this process, total
capital cost is so dependent upon the cost
of membrane-support material that the re
367
 search for still less expensive materials
continued. The concept of using a struc
turally impermeable membrane support
with some novel method of removing prod
uct seemed intuitively less costly than a
crush resistant (at 1500 psi pressure) porous
material, and the investigation for materials
was subdivided into the two categories,
porous and nonporous.
(1) Porous materials: A major criterion
for porous material was that it withstand
the (1500 psi) compressive force exerted by
the high pressure brine. Other factors evalu
ated were cost, permeability, corrosion re
sistance, and flexural strength.
Porous carbon, rubber and polymer foams,
and honeycomb products were all rejected
due to inadequate compressive strength.
Porous ceramics must be excessively thick
to resist bending stresses imposed in han
dling or resulting from any pressure differ
ential from one side to another if used in
plate form. Ultrasmall tubes could he.
formed from rrrsmir materials but these
would be highly fragile and have been
i ejected for this reason. In either form,
plate or tube, the cost of ceramic materials
is higher than for other more suitable
materials. Stainless steel honeycomb ma
terial is too expensive by a factor of more
than ten over the least costly suitable
material and can be rejected. Three types
of laminate materials (items 1, 2, and 3
above) appear to possess the necessary
physical properties and are in the same
general cost range of approximately S1.50/ft*
membrane area. The fiberglas cloth lam
inate is the material presentlv in use in the
pilot plant, but the cost is estimated on a
thinner laminate (fewer layers of cloth) . In
view of the similarity of cost among these
three materials and the success which has
Material Cotf Comprenivt
1. Fiberglas laminate: 1.80
multilayer prepreg cloth
(H-in.)
t. Screen laminated 1.50
between perforated
■beets
a. Solid sheet with poroua 1.50
cloth on each side
4. Ceramic. 2.00-10.00
5. Porous carbon (1-ln.) 12.00
6. Rubber and synthetic
foams
T. Honeycomb products 2.00-25.00
*l/ft' of membrane
368
been achieved with the fiberglas cloth lam
inated material, the latter appears to be the
most satisfactory of the porous materials
considered.
(2) Nonporous materials: During the in
vestigation of possible porous membrane
support materials, a sample of phenolic
sheet I/6-in. thick with very shallow
grooves in the surface was obtained. It had
been demonstrated that a membrane sup
ported by filter paper would bridge a
1/32-in. hole at 1,500 psi without any harm
to the membrane. A promising design for
membrane support material would be a
checkered surface pattern, which would pro
vide an adequate flow channel for removal
of water from under the membrane and
still not require a porous material. The
sample sheet was used in a test cell for
several days, and performance was as good
as that of the sintered stainless steel for the
relatively short test period. Materials which
could be made in this form were evaluatert.
The molded phenolic resin, 0.10-in. thick,
yielded the lowest cost per square foot of
the technically acceptable materials con
sidered. This thickness is adequate if em
ployed in plate form with membranes on
either side. The applicability of products
such as asbestos board, masonite, and ply
wood is difficult to assess: but due to the
rather poor water resistance of the latter
two, and the brittle nature of asliestos
board, these were not considered suitable
for future development. The molded phen-
olic was found to be the rnost satisfactory'
of the nonporous materials" CTjtlfaie<r
Comparative prices of fiberglas porous
plates and of solid phenolic plates give an
indication of the economics of using solid
plates rather than porous fiberglas. Porous
fiberglas plates for a 36-in. cell will cost
Strength, psi
TenriU Remarks
2200 >20,000 Material currently In use
in pilot plant. Adequate
porosity demonstrated.
>1600 >20,000 Suitable, no cost
advantage over fiberglas
laminate, requires
development.
>1500 >20,000 Suitable, no cost
advantage over fiberglas
laminate, requires
development.
2500 100 Brittle in thin form,
expensive in adequate
thickness. Rejected.
1000 «00 Inadequate compressive
strength: high cost.
>1500 Inadeouate compressive
strength.
1400 Inadequate compressive
strength: high cost.
 Strength, psi
Material Cost* Compressive Tensile Remarks
1. Copper tubing H-in. Ml 1500 60.000 Least expensive tubular
standard wall thickness metal support material with
corrosion resistance.
2. Polyester, fiberglas 1.50 1500 20,000 Possibly difficult to fabricate
laminate in required shape.
». Asbestos, masonite 0.15 Unable to retain intricate
plywood board shape for extended period of
time in water.
4. Fiberglas cloth 1.50 1600 20,000 Suitable.
6. Phenolic resin, 0.77 1600 10,000 Preliminary tests satis
0.10-in. thick factory, lowest cost of
suitable nonporous materials.
•$/ft2 of membrane

approximately $70 each or S5.95/sq ft of made, assuming the use of this material.
membrane. Solid slotted plates will cost
approximately $15 each or $1.28/sq ft of VESSELS AND PIPING
membrane. These figures include amortiza Since there are several metals and metal
tion of the die cost over the quantity of combinations (clad steels) which can be used
plates required for a one mgd plant. Some for the construction of all pressure contain
what lower cost figures have been shown in ing components, the problem is the selec
a previous chart; these were based on pro tion of the best combination of corrosion-
jected costs for very large quantities, in resistance, material cost, fabrication cost,
which the prorated die or tooling cost was and material strength. The most prom
a minor item. Die costs in the present esti ising of the metals considered are clad
mate do contribute a significant amount to carbon-steels with alloys of copper and
the total plate cost and result in a somewhat nickel or stainless steels as the cladding
higher estimated plate cost. material. Initial cost of a system using these
The cost of tubular support materials was materials is quite high. Organic coatings
considered next. as a protective surfacing material for a com
pletely carbon-steel system promises many
advantages. Filament-wound reinforced -
Copper plastic vessels cannot be considered as long
O.D. Wall I.D. ft/ft1 tin t/ff as the system must be opened for membrane
0.250" 0.035" 0.180" 21.2 0.084 1.67 replacement. Development of a membrane
0.500" 0.035" 0.430" 8.« 0.160 1.42 cast-in-place technique would make it
1.000" 0.065" 0.870" 4.4 0.486 2.14 worthwhile to consider this material.
1.500" 0.109" 1.282" 3.0 1.22 3.66
Stainless steel As an example of basic relative cost, the
svstem would require a vessel of 1.750-in.
O.D. Wall I.D. ft/ft' t/jt tllf thick wall. The base cost of 70-30 CuNi
0.250" 0.020" 0.210" 18.2 0.188 3.42 clad carbon-steel would be SI2.10/sq ft.
0.500" 0.025" 0.450" 8.5 0.224 1.90
1.000" 0.049" 0.902" 4.2 0.584 2.45 Base cost of 1.750-in. thick carbon-steel with
1.500" 0.065" 1.37" 2.8 1.26 3.60 0.050-in. organic coating applied would be
Filament-wound fiberglas Sh.-lü/sq ft, The disparity in price is not
O.P. Wall I.D. ft/ft' $/ff t/ff quite as great in the "as fabricated" cost of
0.250" 0.063" 0.376" 15.3 0.066 1.00 the two systems. The completely fabricated
0.500" 0.094" 0.688" 7.8 0.198 1.60 vessel. 36 in. I.D. x 36 ft long, in clad
1.000" 0.125" 1.260" З.Я 0.478 1.81 steel and in organic-coated steel would cost
1.500" 0.180" 1.860" 2.5 1.03 2.68
SI 12/st] ft and S51/sq ft, respectively. Even
• Based on »1.25/lb fabricating cost and 0.07216
lb/in.' density. at these prices, the organic system could be
recoated approximately twenty-five times
for the cost of the clad steel vessel.
The costs of copper and stainless steel Data on the behavior of organic coatings
tubes are practical for large scale pioduc- in sea water at high pressures are scarce.
tion. The estimated costs of filament-wound From limited applications of epoxies in oili
fiberglas-epoxy tubing arc considered ex wells at a pressure of 16.000 psi. it appcars|
tremely optimistic; since they are lower that the epoxy mav expand and becomel
than the costs of metal tubes, a detailed spongy upon sudden release of the pressure.
study of the tubular configuration was This is apparently caused by the expansion
 1 ' I I 1 1 L
12 16 20 24 28 32 36
PRESSURE VESSEL DIAMETER - INCHES
FIGURE 138. VESSEL VS COST
1,000,000-GPD PLANT.

of water and/or gases which have pene epoxies arid phenolic.

trated the epoxy film under the high pres
sure, and breaks down the effectiveness of
the surface protection by the coating. Sev
eral classes of organic coatings have been
considered and many have been eliminated
because of poor protection, complexity of
application, poor bonding, etc. Those which
are still under study fall into two categories.
Samples of seven coatings were exposed
to sea water at 1500 psi in the pilot plant,
pressure cycled for a period of six weeks.
These samples were inspected, first, to de
termine whether or not "sponging" had
occurred at the system pressure, and second,
to determine short-term corrosion-resistance
Samples tested were:

370
 Coating tyttem Type
1. Macor S47-M Epoxy- Furane
Macor 559-M Epoxy-Furane
s. Phenoline 300 Coal tar epoxy
Phenoline 302
4. Carbo Zinc. no. 11 Coal tar epoxy
Carbomastie no. 12
6. Carbomastic no. 3 Coal tar epoxy
Carbomaatic no. 12
6. Specote Modified epoxy
7. Flakeglaa Epoxy-glass flake
Of these, the Magna Corporation products
(items 1 and 2) and one of the Carboline
systems (item 3) failed in test. The Magna
coating had poor adhesion and allowed
water permeation. Corrosion occurred under
the coatings even though the coatings ap
peared intact. The Carboline system failed
at one corner but failure may have been
initiated by a break caused by mishandling.
The other coatings showed excellent pro
tective characteristics. Similar coatings were
examined recently at a Los Angeles Depart
ment of Water and Power test site (sea
water) and were in excellent condition
after two to three years of immersion and
alternate immersion -exposed conditions. Sev
eral successful operations with coatings in
salt water service at elevated pressures have
been reported. A Red Phenolic coating.
(Pittsburgh Plate Glass No. H-13817A) has
CELL DESIGN
CONFIGURATION
The function of a desalination cell for
the reverse osmosis process is to bring a
saline solution at high pressure in contact
with the properly supported semipermeable
membrane. Several methods accomplish this
technical requirement satisfactorily. These
can be classified primarily by the configura
tion of the membrane in use. The two
different configurations that have been con
sidered are tubular and flat sheets (plates) .
The 1,000 gpd pilot plant currently in
operation was designed on the basis of
plates since the state-of-the-art in mem
brane technology did not, at the time, in
clude a method for manufacturing tubular
membranes. A more detailed analysis of
comparative economics was necessary prior
to any scale-up of pilot operations to insure
development of equipment with the lowest
long-range cost potential. To compensate
for the possibility that the experience with
flat plates would prejudice the study in that
direction, a deliberate attempt was made to
give advantage to the tube concept by
making unusually favorable assumptions
Manufacturer Thicknets
Magna Corp. 16 mill
Magna Corp. IB mil*
Carboline 26 to 28 mils
Carboline 10 to 12 mila
Carboline 28 to 30 mila
Specialties en*. 26 to 30 mila
Fiberglaa eng. 30 mila
been in service for four years a,r in 000 psi
operating pressure, with no apparent coating
deicrioratiojrTn "another case, Capon's epoxy
Chem Cure No. 850-JW9-329 has been suc
cessfully used for six years at 10,000 psi
operating pressure.
Although not every user of organic coat
ings reported success, the results of the
investigation and tests are sufficiently re
assuring to allow organic coatings to be
specified with confidence for salt water ex
posure under elevated pressures. A life of
two or three years between coatings can be
considered certain, with six to ten years
expected. This will tip the economic bal
ance in favor of the organic coatings
applied over carbon-steel for pressure vessels
and piping, as opposed to the more expen
sive clad or solid corrosion-resistant metals.
with respect to tube-fabrication costs.
(1) Porous tubular supports: The various
concepts for tubular membrane supports
can be divided into four general configura
tions:
(a) Multiple small-diameter tubes ter
minating in tube sheets, with the salt water
feed inside the tubes. Membranes are
mounted inside the tubes. VesseLhcads con-
tain the high pressure feed stream and
channel it to the tubes.
(b) Same as above, except that the mem
branes are outside the tubes, and the high
pressure salt water feed is in the shell.
(c) Single porous tubes connected to
form long, continuous tubes. Membranes
are mounted inside the tubes, and the salt
water feed is also inside the tubes. Tubes
are connected as required.
(d) Single porous tubes mounted within
outer solid tubes, with the salt water feed
stream channeled between them. The mem
brane is mounted on the outside of the
porous tube.
These four general configurations include
all of the schemes for tubular membrane
371
 supports which have been considered in
this evaluation. For the purpose of this
evaluation, the following assumptions were
made:
Case 1—That techniques are available to
mount membranes inside porous tubes up
to 16 ft long and from \/t in. to 2 in. inside
diameter.
Case 2—That techniques are available to
mount membranes outside of porous tubes
16 ft long and \/t in. to 2 in. outside
diameter.
Case S—That uniformly porous tubes are
available to withstand internal or external
pressures of 1500 psi in 16 ft lengths and
diameters from \/A in. to 2 in.
Case 4—That tubes can be sealed into
tube sheets by O-ring installed in female
O-ring grooves milled into the tube sheets;
these must be removable to install mem
branes. A triangular array of tube spacing
is assumed so that there is an \/t in. liga
ment of tube sheet between O-ring grooves.
It was the purpose of this analysis to
ascertain if any of the four general tube
configurations could be competitive with
flat-plate construction. To simplify the
study, Cases 2 and 4 were eliminated. Case
2 will be nearly identical to Case 1 insofar
as cost is concerned. Tubes can be packed
together at the same density in each, and
the major vessel components will be similar,
if it is assumed that pressure tube sheets
arc equivalent in cost to high pressure
shells. Therefore, the evaluation for Case 1
will also serve for Case 2. Case 4 can be
eliminated because it is apparent that it
has all the cost factors of Case 3 plus the
additional cost of the outer tube and its
connections.
Case 1—Heat Exchanger Configuration
The Case 1 general configuration bears a
rough resemblance to a heat exchanger. As
such, it has most of the component parts of
the pressure vessel contemplated for the
flat-plate design, plus some extra parts
peculiar to its own design. Starting from
one end, it will have a vessel head, a slip-on
flange, a tube sheet, a second slip-on flange,
No. lUm
2 Heads
4 Flanges
2 Tube sheets
1 80 ft, 86-in. shell
2300 80-ft, tt-in. tuba
Total cost
372
and a cylindrical vessel shell. At the oppo
site end, this sequence is duplicated, i.e..
two flanges, a tube sheet, and a head. Total
parts include 4 slip on flanges, 2 heads, 2
tube sheets, and one cylindrical shell, plus
the tubes themselves.
Flat sheets exposed to an unbalanced pres
sure of 1500 psi will need the strength of a
blind flange. The structure will be weak
ened by the holes necessary for the insertion
of the tubes and further weakened by the
O-ring grooves which must be milled in
each hole. These weakening effects will re
quire additional thickness and the tubes,
being sealed in only by O-rings, can offer
no bracing. Thus, a cylindrical vessel ca
pable of withstanding longitudinal tension
is needed. For purposes of this cost estimate,
the cost of tube sheets was estimated at
double the price of a plain blind flange, to
account for the required extra thickness
and the extra machining.
For a required membrane area, the vol
ume of vessel (s) required is an inverse
function of the membrane packing density:
that is, sq ft of membrane per cu ft of
vessel volume. The packing density that
can be obtained for various diameters of
tubular membrane supports ranges from
10.5 ft'/ff for 2-in. tubes to 100 ft'/ft* for
i/£-in. tubes. It was assumed that ■/£ in. is
the smallest practical diameter tube that
can be considered without requiring an im-
practically large number of tubes. This pro
vides a membrane density of 40 ft'/ft* of
vessel volume. For the calculation it was
assumed that a 56-in. diameter vessel. 30
ft long is used. Estimated prices are avail
able for all major component parts of this
vessel:
Case 1:
Tube length - 30 ft Tube material - fiberglas
Area per tube - 4 ft' Tube cost per ft1 inside
area - 31.60
Tubes/unit - 2300 Shell diameter - 36 in.
Area/unit - 9200 ft* Tube pattern - triangular:
pitch zllji tube
diameter
Tube I.D. - ft In.
Cott/ff
Unit cost Total eott membrane
$ 866 ea. $ 780 30.079
1.270 ea. 6.080 0.662
8,000 ea. 6.000 0.652
90/ft 2.700 0.294
1 18,800 1.500
828.810 88.077
 Case S—Single Tube Configuration
The configuration of Case 3 has often
been viewed as "ideal", since the single
porous tube serves the triple function of
supporting the membrane, conveying the
product water which passes through the
membrane, and containing and conveying
the high pressure salt water feed stream.
No pressure vessel is required, only suffi
cient manifolding to connect the feed steam
to the multiple pipes. The pipes could be
stacked in banks on oversize pipe racks,
the product water percolating through the
pipe wall and collecting in a trough under
each bank of pipes.
Membrane density as such would have
little effect on cost, since no enclosing vessel
is required. Assuming membranes could be
satisfactorily placed in any size tubing, the
size chosen would depend on the cost per
sq ft of internal surface, considering the
cost of tubing and the connectors. In a one
mgd plant, either 800,000 ft of 1,4-in. tubing
or 200,000 ft of 2-in. tubing would be
needed. Smaller sizes would require more
tubing length and more connectors; larger
sizes would require less length, but thicker
walls and more expensive connectors. In any
event, one of the major items of expense
for the Case 3 configuration will be the
connectors and other fittings, for no low
cost fittings are available for service at
these pressures. Assuming that 30 ft of
tubing of i/£-in. diameter represents maxi
mum size and minimum diameter in which
membrane can be cast, estimated costs are:

Case 3a - Same Tube Parameters as in Case 1

Cost/if
No. Item Unit coet Total cost membrane
2300 80-ft. 4,-in. tubes (6.00 (18,800 $1.50
4600 Connectors 6.60 29,900 8.2Б
Total coat $43.700 »4:76

To realize the full potential of Case 3, plate configuration was made. A plate thick
one must assume capacity to use extremely ness of 0.100 in. and a gap height of 0.100
long tubes. Case 3b treats the cost of the in. was assumed. This is a conservative
tube configuration by assuming that mem assumption and produces a membrane
branes could be cast in place in S50-ft density of 97 sq ft per cu ft. Assuming
tubes. again a 36-in. vessel, the volume is 7.25
cu ft per linear foot of vessel length and 700
Case 3b: sq ft* of membrane per linear foot. For a
Tube length - 350 ft
Tube diameter - V4 in. 30-ft length, each vessel has 20.300 sq ft
Area per tube - 48.7 sq ft of membrane and five vessels would be
Coet/ff
No. Item Cost membrane required for 100,000 sq ft of membrane.
1 850-ft, %-in. tube $66.60 $1.50 At sixty plates per foot, each vessel con
2 Connectors 13.00 0.80 tains 1,740 plates, each weighing 5.9 pounds.
Total cost $78.60 $1.80 Cost estimates were made based on the lami
For such an extremely favorable situation, nated fiberglas-epoxy plates now in use and
assuming a favorable tube fabrication cost on the phenolic plate projected for use.
($0.198 pr ft for i/2-in. fiberglas tubing) , Cell diameter - 86 in.
the total cost is $1.80/fta of membrane. Cell length - 30 ft
Pressure rating of cell - 1600 psi
(2) Generalized flat-plate configuration: Membrane area per plate - 11.7 ft1
A generalized consideration of the flat- No. plates per call - 1,740
Membrane area per cell - 20,300 ft2

Laminated fiberglae-epoxy (present technology)

Cost/ft'
No. Item Unit coot Total coet membrane
2 Heads $ 365 $ 730 $0.036
2 Flanges 1,270 2,640 0.126
1 Shell (80 ft. 36-in.) 2,700 2,700 0.188
1,740 Support plates 17.60 80,450 1.60
Total cost $86.420 $1.794
Phenolic plate
Coet/ft'
No. Item Unit cost Total coet membrane
2 Heads $ 365 $ 730 $0.036
2 Flanges 1.270 2.540 0.126
1 Shell (30 ft, 36-in.) 2.700 2,700 0.188
1,740 Support plates ( 16,660 0.770
Total cost $21,630 $1.064
 Note that, with present technology, the
projected cost of $1.79/ft' of membrane
is almost identical to that projected for the
most favorable tube configuration. With
developments now underway, the cost will
be reduced to $1.06/ft*.
It should be emphasized that these cost
figures are based on the minimum desali
nation cell cost attainable by large quantity
manufacture and include only the major
cost items in each unit configuration. As
such, the cost figures are comparable with
each other but should not be considered as
total plant cost.
From these cost figures, it is seen that
none of the tubular arrangements can be
considered as economically competitive with
flat-plate construction even if the technical
problems associated with tubular construc
tion are considered as solved (e.g., the
problems of producing uniformly permeable
tubes of adequate strength and of mounting
and sealing membranes either inside or
outside of small diameter tubes 30-ft to 350-
ft long) . Note that membranes must also
be removable for replacement.
In the light of the comparative costs
compiled, design efforts have been directed
toward optimization of the fiat-plate con
figuration.
CHI SIZE AND ARRANGEMENT
The optimum cell size, shape, and con
figuration are influenced by many factors,
some of which can be analyzed objec
tively and some of which can be evaluated
only by using engineering judgment.
Several assumptions were made for con
venience in making the calculations. These
include:
Product/feed ratio =0.50
Product rate = 1,000,000 gpd fresh
water
Feed rate = 2,000,000 gpd salt
water
Average flux rate = 10 gfd per sq ft of
membrane
With the foregoing assumptions, the fol
lowing conclusions were drawn:
(1) With the total product rate and flux
rate assumed, the total area of membrane
required is fixed at 100,000 sq ft, regard
less of its arrangement.
(2) With the flux rate and product/
feed ratio assumed, the required contact
time of the feed stream against the mem
brane is fixed for any given membrane
spacing.
374
(3) For a required contact time as
found in item 2, there will be a required
length of Sow channel for each assumed
feed velocity. For example, with a mem
brane spacing of 0.1 -in. and an initial
feed stream velocity of 2 fps, the feed
stream must flow for 200 ft between mem
branes to allow 50 per cent of the initial
feed stream to pass through the mem
branes. This may be achieved by a com
bination of vessel lengths, baffling, or
vessels in series, or by recirculation or
mixing. Reducing either the flow channel
height or the feed stream velocity reduces
the path length proportionately.
(4) Since the total required membrane
area is fixed, for a given membrane
density, the total required vessel volume
is also fixed. Also, since full diameter
flanges are expensive, the longer the vessels
can be made, the less the unit volume cost
will be. Finally, the larger in diameter
the vessels can be made, the less the unit
volume cost will be. The curve is steepest
at the left end, but is monotonically de
scending: that is, it exhibits no minimum
unit cost. Thus, a single large vessel would
be slightly less costly than two or three
smaller ones, but no great cost penalty
would be incurred by going to five or ten
vessels if other factors so indicated.
There are several considerations which
tend to make smaller vessels more desirable.
In a plant with multiple units, production
is not so severely crippled when one unit
is down for maintenance. Vessel parts be
come extremely heavy in the larger sizes,
and operations become clumsy and slow.
With too few vessels, it becomes more
difficult to achieve the required flow path
length for the feed stream.
As mentioned before, for a given diam
eter, the longer the vessel, the less costly
it is per unit volume. But, the vessel
must be entirely accessible so that mem
branes can be removed and replaced, which
tends to limit the length. A satisfactory
approach would be to assemble groups of
plates and membranes (say 100 to 500
plates) in standard cartridges already
clamped together and tested for leaks.
These cartridges would be placed in the
vessel and slid into position. The product
stream from each cartridge would be
brought out in a high pressure tube which
would be connected to a suitable fitting
on the side wall of the vessel adjacent to
the cartridge and thence brought to the
outside of the vessel for collection. With
this arrangement, a relatively long vessel
could be utilized, providing that its diam
eter is large enough to allow a man to
enter to make the necessary connections.
DESIGN CRITERIA
An evaluation of tie-bolt, tension vessel,
and pressure vessel construction of desali
nation cells for flat-plate configuration
was carried out. The 1,000 gpd pilot plant
desalination cell is constructed of top and
bottom heads and flanges held together by
tie-bolts. The stack of desalination plates
serves as the pressure vessel, with O-ring
seals between each pair of plates at their
periphery. Salt water feed is channeled from
plate to plate through a number of holes
drilled through each plate and sealed from
the porous interior of the plate.
For scaling-up to larger vessels, alterna
tive methods of construction were investi
gated. Three posible methods for using
flat-plate membrane supports were evalu
ated:
(1) Pilot plant construction, with top
and bottom heads welded to flanges, and a
stack of flat plates interposed between. Top
and bottom heads are held together with
tie-bolts.
(2) A solid vessel wall substituted for
the tie-bolts to hold the top and bottom
heads together. The cylindrical vessel wall
is not exposed to pressure, but serves only
as a tension member to replace the tie-bolts.
Short bolts only are required to fasten the
flanges together. The membrane support
plates serve to confine the feed stream as
shown in column (a) below.
(3) A complete pressure vessel to contain
the feed water and channel it through be
tween plates. The plates would merely
support the membrane and convey the prod
uct water, whereas the pressure vessel would
contain the pressure.

(c) Complete
(a) Tie-bolt (b) Cylindrical sheU pressure
construction in tension only vessel
1. Top head Required Required Required
2. Bottom head Required Required Required
3. Top S.O. flange Required: heavier than Required Required
for others
4. Bottom S.O. flange Required; heavier than Required Required
for others
6. Flange bolts None required Required Required
«. Tie-bolts Required None required None required
7. Seals on plates Full diameter seals Full diameter Small seals only
required seals required required
8. Vessel seals Required top and bottom Required top and None required
bottom of vessel
9. Cylindrical vessel None required Required; thickness Required: full thick
shell about 60 per cent of ness for pressure
that required for vessel
pressure vessel
10. Plate materials Must be strong to resist Must be strong to May be cheap
tensile stresses resist tensile stresses materials, no tensile
loading
11. Plate machining Complex; large seal, two Complex; same as Simple; little or no
separated fluid paths tie-bolt construction machining required
required in each plate
12. Plate thickness Must be thick to accom Must be thick, May be thin;
modate O-ring groove as tie-bolt con no O-ring grooves
and still have sufficient struction
tensile strength

Additional comments on specific items are:
Heads — same on all.
Flanges — same number required on all,
but flanges for tie-bolts con-
struction must be heavier be-
cause of the overhung load.
Bolts — method (a) requires long tie-
bolts, the full length of the
vessel. .Method (b) and (c)
require only short bolts to join
the two adjacent flanges.
Cylindrical vessel shell — method (a) does
not need any: method (c) re-
quires full thickness cylindri
cal shell; method (b) requires
a cylindrical shell about 60
per cent as thick as method
(c) .
The principal trade-off which can be
evaluated economically lies between the in-
cremental cost of the long tie-bolts in
method (a) and the cost of the half-thick
shell in method (b) and the cost of the
full-thick shell in method (c) . The follow-
ing costs were calculated:

375
 For an 18-in. vessel, 18 ft long, 20 bolts Seals in vessel—methods (a) and (b) re
n-8 -in. dia. quire seals at the top and bottom of the
Cost of long tie-bolts = $2,860 slack of plates at the junction between
Minus cost of short the plate stack and the vessel heads. One
bolts - 180 of these must be a movable piston, to
accommodate bolt and vessel stretch. This
Incremental bolts cost — 2,680 expense and potential source of trouble is
Cost of 18 ft of 18-in. not presented in method (c) .
Sched. 80 pipe = 610 Plate materials and machining—methods
Plus extra welding (a) and (b) require strong plate materials
cost — 70 to withstand the tensile forces of the water
Total incremental feed stream, and relatively complicated
shell cost = 680 machining to provide for separate channels
Excess cost of tie-bolt in each plate for salt feed water at 1,500
construction _■ 2,680 — 680 psi and fresh water at atmospheric pres
over pressure vessel sure. Method (c) requires virtually no ma
construction — 2,000 for 18-in. chining, no holes, no O-ring grooves, and
vessel no filling in with epoxies.
For a 24-in. vessel. 24 ft long, 24 bolts Plate thickness—a serious disadvantage of
\7/g -in.—dia. methods (a) or (b) is that the plate must
Cost of long tie-bolts - $3,730 be made thick enough to accommodate the
Minus cost of short O-ring groove without excessive weakening
bolts — 335 of the plate. Thick plates have a serious
effect on membrane density. Combined with
Incremental bolt cost — 3,395 an 0.062-in. flow channel, an 0.062-in. plate
Cost of 24 ft of 24 in. thickness will result in a membrane density
pipe = 1 ,800 of 155 sq ft/cu ft. If the plate thickness
Plus extra welding = 175 must be increased to 0.200 in., density is
Total incremental reduced to 74 sq ft/cu ft, one-half the
shell cost — 1,975 original value. This would require doubling
Excess cost of tie-bolt the number of pressure vessels as well
construction = 3,395— 1,975 as the cost of plate materials and would be
over pressure vessel a most serious penalty.
construction = 1,420 for 24-in. PLATE ARRANGEMENT AND BAFFLING
vessel
For a S5-in. vessel. 30 ft long. 28 bolts Assuming a cylindrical pressure vessel
2 1/£ -in.—dia. containing flat-plate membrane supports,
Cost of long tie-bolts = S9.660 there are two principal plate arrangements
Minus cost of short possible. Plates may be arranged with their
bolts = 700 planes perpendicular to the vessel axis, mak
ing plate diameters roughly equal to vessel
Incremental bolt cost = 8,960 diameter. Plates may also be arranged with
Cost of 30 ft of 36-in. their planes parallel to the vessel axis, with
pipe = 3,000 plate width roughly equal to vessel diam
Plus extra welding = 300 eter and plate length as long as desired.
Total incremental Either approach is feasible. The first ar
shell cost — 3,300 rangement would be somewhat easier to
Excess cost of tie-bolt baffle, but plates and membranes would be
construction = 8,960 — 3,300 limited in size to approximately the vessel
over pressure vessel diameter. There would be less efficient use
construction = 5,660 for 36-in. of membrane material (circles cut from
vessel strip) , but more efficient use of vessel space. «
The second arrangement allows plates and
Thus, there is a cost penalty of $1,400 to membranes to be as long as desired, and
$5,600 per vessel on bolts alone if the tie- makes more efficient use of membrane mate
bolt construction is used. There are also rial, but makes less efficient use of vessel
other serious penalties: volume (unless plate and membranes
Seals on plates—in methods (a) and (b) . widths are tailored to match the local vessel
high pressure seals are required on each in height) . The final choice depends on
plate at the outer edge. In method (c) , the selection of vessel size, required feed stream
seals will be less expensive and should be path length, and perhaps fluid dynamics
less liable to leakage. considerations.
 The feed stream in the 1,000 gpd pilot
plant has been subjected to improved con
trol, so that it is channeled through an
extended path length in a more efficient
fashion. Each membrane support plate in
a large plant would be provided with an
outer rim on both sides of the plate, con
tinuous except for a S-in. gap. When the
plates are clamped together in a module,
these rims meet and prevent the feed
stream from entering the space between the
plates except at the gaps. After passing
through the gap, the feed stream would be
guided in a multilimb spiral baffle clamped
S77
 between adjacent plates. This baffle would weigh about 900 lbs and would be sup
extend the feed stream path to as much ported by a hydrostatic slipper bearing rest
as thirty times the plate radius. The braces ing on the bottom of the cell. When
between adjacent limbs of the baffle serve installing or removing a module, the slipper
the dual function of stiffening the baffles bearing would be temporarily connected by
and producing additional turbulence in the hose to the domestic water system. The
feed stream. pressurized water, introduced between the
With the possibility of achieving the bearing and the vessel wall, would support
desired degree of product recovery in a and lubricate the bearing while the module
single pass of the feed stream across the was being moved.
plates, construction of the cell may be fur These concepts greatly simplify the overall
ther simplified. All desalination plates cell design and insure a more economical
would be in parallel flow relationship to and trouble-free desalination cell.
the feed stream, so that there would be no
need to provide baffles or seals between FLOW CHANNEL WIDTH
modules to guide the feed stream through Flow channel width (i.e., the spacing be
more than one module in a series. This tween plates) has been established as 0.100
simplifies the interior hardware required in in. This figure is a compromise between
the cell. The feed stream would surround conflicting factors. For a given feed stream
all of the modules, enter the spaces between velocity, the effect of increasing the flow
the plates through the rim gaps, and spiral channel width is to:
into the center of the modules. After com Increase the required volume of flow,
pleting its pass across the plates, the re Increase the feed stream Reynolds num
mainder of the feed (now the waste stream) ber,
would move axially through the central Decrease the membrane area per unit
holes of the plates to one end of the volume of desalination cell,
module. Decrease the pressure drop per ft of
The end plates on each module would flow channel, and
carry no membranes and would be thick Increase the feed stream path length
and sturdy: they would have two holes required to effect a given recovery
to accommodate the product tubes, but no ratio of product to feed.
central hole. Instead, a tube would l>c The last effect is most important, and its
connected through the center of one of influence makes a narrow flow channel
these end plates, and the waste stream (i.e., close plate spacing) desirable. There
would be conveyed away through it. Anv is a practical lower limit, however, on the
pressure drop occurring in the feed stream plate spacing that can be achieved and
as it flows around the spiral to the center maintained between thin plastic disks, 3 ft
of the module would be reflected as an in diameter. A gap of 0.100 in. was chosen
integrated force on the end plates, tending as a reasonable figure which can be accom
to force their centers inward. A relatively plished with suitable care.
small pressure drop would cause a large Allowing 0.125 in. for plate thickness,
force on the plate, since it would be oper 0.100 in. for flow channel space, and 0.015
ating over such a large area. Forces on each in. for two membranes and two filter
individual desalination plate would be bal papers, each plate and adjacent space will
anced, since pressure drops from rim to occupy 0.240 in., and the plates will stack
center would be the same on each side of at approximately 50 per ft, or two feet per
the plate. Similarly the net force on each module of 100 plates, or 10 feet for 5 mod
module would be zero, but the end plates ules. A pressure vessel 12 ft long tangent-to-
must withstand a substantial force. tangent, for example, will accommodate five
The modules of plates would be pre modules with two feet allowance for mod
assembled outside the cell and slipped into ule end plates and tube connections. The
position, and the product and waste stream pressure vessel size is established at 40 in.
hose connections made. Each module would O. D., to accommodate the 36 in. plates.

OPERATING VARIABLES FOR A ONE MGD PLANT

FEED STREAM COMPOSITION
The one mgd plant should, for best effi
ciency, be designed for the particular saline
feed source to be used. Salinity may vary
from 3.5 per cent total dissolved solids
(tds) for sea water to less than 0.5 per
cent for some brackish sources. Membrane
flux, feed stream cross section, required
feed stream path length, required flow vol
ume, and required membrane area will all
 be affected by the solids concentration in
the feed stream. Of these variables, mem
brane flux rate has the most powerful effect
on plant capital costs, for it determines
the required membrane area and desalina
tion cell size.
Several interrelated factors control the
flux. First, pressure affects the flux rate in
a direct manner. Strictly speaking, it is the
effective pressure (the excess of applied
feed pressure over the opposing osmotic
pressure) which is pertinent. Osmotic pres
sure, in turn, increases with increasing brine
concentration, reaching 350 psi for sea
water feed. Thus, a given feed stream pres
sure will produce a greater effective flux
producing pressure with brackish water
than with sea water feed. The second fac
tor controlling flux is the permeability of
the membrane. The permeability, or salt-
rejection efficiency, of the membrane must
be tailored during membrane fabrication
such that the quality of the product is
satisfactory. The target for saline water con
version processes producing potable water
is less than 500 ppm tds. Thus, if the feed
stream contains 0.5 per cent (5000 ppm)
tds, the membrane must exhibit a salt per
meation of less than 10 per cent. On the
other hand, if sea water (8.5 per cent tds)
is the feed stream, membrane salt perme
ability must be less than 1.4 per cent to
maintain product quality at less than 500
ppm tds.
Another factor influencing membrane
selection is the preferential rejection of
certain ions, particularly those responsible
for hardness, calcium, and magnesium.
These ions also constitute proportionately
larger fractions of the solids content of
many brackish waters. The higher rejection
of such ions enables the use of membranes
with higher flow rates while maintaining
the required product purity.
BRACKISH WATER OPERATION
(1) Recovery of water: The energy re
quirement for reverse osmosis is propor
tional to the feed rate to the system. For
a fixed capacity plant, the feed rate is
determined by the percentage of the water
that is recovered from the feed stream.
Minimum energy would be required at the
point of 100 per cent recovery: product is
equal to feed. The maximum recovery is
limited by the final concentration of the
waste stream and, to a lesser extent, by the
ratio of feed to waste stream volumes. A
design value of 80 per cent has been chosen
for brackish water. The limiting factor is
the feed-to-waste ratio, that is, the 5:1
change in volumetric flow rates. Provisions
must be made to reduce the cross-sectional
area of the flow channel for the brine in
order to maintain adequate velocity in the
exit end of the cell without starting with
exceptionally high velocity flows. The com
plexity in design to accommodate a greater
recovery than 80 per cent appears to be
more than the saving involved.
(2) Power recovery: The waste stream
from a reverse osmosis desalination plant
is at the operating pressure and contains
useful energy. Cost estimates for sea water
operations often take a credit for 70 to
80 per cent of this energy in a one mgd
brackish water conversion plant at 80 per
cent water recovery. The waste stream of
175 gpm is marginal from the standpoint
of realistically recovering as much as 70 per
cent of the energy because of the lack of
suitable equipment in the standard equip
ment market. One scheme considered for
power recovery involves a multistage cen
trifugal pump operated in reverse. Pumps
with this head capability are available for
a minimum capacity of 300 gpm. Due to
the high recovery of water being achieved
in the operation, the energy available in
the waste stream is small. In view of these
facts, the recovery of power in a one mgd
brackish water plant is questionable.
SEA WATER OPERATION
In spite of specific differences between sea
and brackish water operations, the processes
are basically similar. In this section the dif
ferences between the two will be discussed.
(1) Water recovery: The factor expected
to limit the percentage of water recovered
from sea water is the final concentration
of the waste stream. A major power saving
has been accomplished if \/s of the water
can be recovered. At this point, the con
centration of the waste stream will be
5.25 per cent and the membrane efficiency
must be in excess of 99 per cent. It is
reasonable to establish this target for sea
water operation as a basis for design.
(2) Power recovery: The waste stream
of a one mgd sea water plant, operating
at 33 per cent recovery of water from the
feed, will have a flow rate of 1,390 gpm.
The recovery of power from this stream at
70 per cent efficiency and 0.7 cents per kwh
amounts to $32,000 per year or 10 cents per
million gals and makes a substantial con
tribution toward reducing the unit cost
of fresh water.
COST ESTIMATES
Utilizing the concepts outlined in this
paper, the costs of ten mgd plants have
379
 I>een calculated. For sea water operations, gallons; whereas, a brackish water plant is
the cost would be $5300,000, and the total estimated to cost $2,700,000, and total water
operating cost would be $0.44/thousand cost would be $0.21/thousand gallons.

SUMMARY OF DISCUSSION
There was no discussion.

Critères a Appliquer Dans Les

Projets D'Usines de Dessalement Par

Osmose Inversée

B. Keilin et C. G. De Haven

Etats-Unis d'Amérique

INTRODUCTION
Parmi les procédés de conversion des été effectué, et 4) maintenir une concentra
eaux salines, l'avantage principal de l'osmose tion minimum à la surface de la membrane.
inversée est la faible quantité d'énergie Pour porter au maximum les possibilités
qu'elle exige par rapport aux autres pro économiques du procédé par osmose in
cédés. L'installation est nécessairement versée, il importe de maintenir les immo
complexe, en raison de la surface étendue bilisations de capital à un faible niveau
de la membrane employée et par le fait proportionné aux économies que la basse
que la cellule de dessalement doit: 1) consommation d'énergie promet. La con
assurer le support structural de cette mem struction de la cellule a fait l'objet d'une
brane, 2) permettre l'extraction de l'eau étude visant à déterminer les matériaux et
douce produite, 3) séparer le courant de les dispositifs permettant d'utiliser la
saumure à haute pression du produit à brane à son mieux.
basse pression après que le dessalement a

MATERIAUX DE CONSTRUCTION
SUPPORT DE LA MEMBRANE de caoutchouc et de polymères, les céra
miques et les produits alvéolés ont été
De faible structure, la membrane exige rejetés en raison de leur résistance insuffi
un support mécanique pour résister à la sante à la compression, de leur fragilité et
chute de pression de 1500 psi* (105 kg/cm") de leur coût. On a constaté que la matière
a laquelle elle est soumise. Les auteurs ont poreuse qui convenait le mieux était un
étudié le prix de base des matériaux suscep stratifié de fibre de verre à époxy raréfiée,
tibles de servir de support dans une variété composé de plusieurs couches de tissu im
de configurations. Les matières poreuses, à prégné au préalable de résine d'époxy. Son
travers lesquelles le produit peut facilement coût serait d'environ 1,50 dollar par pied
s'écouler, ont été examinées du point de carré de surface de membrane (environ $15
vue de leur résistance à la compression, à par m*) , pour une matière d'une résistance
la tension et à la flexion, de leur perméabi de 2.200 psi (155 kg/cm1) à la compression
lité, de leur résistance à la corrosion et de
leur coût. Le charbon poreux, les mousses et de plus de 20.000 (1.400 kg/cm») psi à
la traction.
• psi = pounds per square inch = liv Les matières non poreuses ayant les
pouce carré. qualités nécessaires pour la fabrication
d'une plaque d'appui ont été également
sélectionnées. On a constaté que la matière
la plus satisfaisante était une résine phéno-
lique de 1/10 de pouce (2,5 mm) d'épais
seur, ayant une résistance à la compression
de plus de 1.500 psi (100 kg/cm2) et une
résistance à la traction de plus de 10.000
psi (700 kg/cm1) et coûtant 0,77 dollar par
pied carré ($7,75 par m2) de membrane.
Les matériaux non poreux tels que les
panneaux d'amiante, de masonitc et de
contre-plaqué sont beaucoup moins coûteux,
mais manquent de stabilité dans l'eau.
Parmi les différents matériaux tubulaires
de support, on a constaté que la fibre de
verre, sous forme de filament bobiné, était
le matériau le moins cher, coûtant 1,00
dollar par pied carré (S 10 par m2) de
membrane en tubes de 14 de pouce (6 mm)
de diamètre intérieur et 1,50 dollar par
pied carré ($15 par m2) de membrane en
tubes de \/2 pouce (12.5 mm) de diamètre
intérieur.
CUVES ET TUYAUTERIES
Pour les cuves et les tuyauteries sous
pression, trois types de combinaisons de
métaux capables de résister à l'action corro
sive de l'eau de mer ont été considérés:
aciers inoxydables et monels; aciers au
carbone revêtus d'alliages de cuivre, de
nickel ou d'acier inoxydable; et aciers au
carbone enduits de matières organiques.
Parmi ceux-ci, ces derniers se sont révélés
les moins coûteux, l'enduit organique pou
vant être remplacé vingt-cinq fois pour le
prix de la cuve en acier recouvert.
On a constaté que plusieurs variétés d'en
duits d'époxy sur acier au carbone sup
portaient en service les essais de corrosion
à court terme. Les époxys comme les phéno-
liques ont fait preuve d'une bonne résis
tance à la corrosion aux hautes pressions
dans l'eau de mer.

CONSTRUCTION DES CELLULES

DISPOSITION le coût total de l'appareillage principal
serait de 4,75 dollars par pied carré ($50,80
Pour amener la solution saline a haute par m2) de membrane; dans le cas d'un
pression en contact avec une membrane tube de 350 pieds (106 m) de longueur et
semi -perméable convenablement supportée, de 1/2 pouce (125 mm) de diamètre inté
on a considéré des dispositifs tubulaires et rieur, le coût total serait de 1,80 dollar
un dispositif à panneaux plats. Quatre dis par pied carré ($19.25 par m*) de
positifs tubulaires ont été étudiés: 1) Tubes membrane.
multiples de petit diamètre aboutissant à Pour le dispositif à panneaux plats, utili
des panneaux de tubes, l'eau salée étant sant des plaques d'appui de stratifié poreux
envoyée à haute pression dans les tubes en fibre de verre-époxy, le coût de l'ap
depuis les collecteurs de la cuve; 2) Même pareillage principal s'est établi à 1,80 dollar
dispositif que pour 1) , sauf que les mem par pied carré ($19,25 par m2) de mem
branes sont à l'extérieur des tubes et que brane. Pour le dispositif à plaque d'appui
l'alimentation d'eau salée sous pression se non poreuse en résine phénolique, ce coût
fait dans l'enveloppe; 3) Tubes poreux s'est établi à 1.06 dollar par pied carré
distincts joints pour former de longs tubes ($11,35 par m2) de membrane.
ininterrompus, les membranes étant montées Donc, parmi les formules considérées, le
à l'intérieur; 4) Tubes poreux séparés dispositif à panneaux plats utilisant des
montés à l'intérieur de tubes non poreux, plaques d'appui non poreuses en résine
l'alimentation se faisant à l'intérieur des phénolique s'est montré le plus économique.
tubes.
Pour la formule 1) , avec le dispositif
d'échange de chaleur considéré valable pour DIMENSIONS ET ARRANGEMENT
les deux formules 1) et 2) , le coût des DES CELLULES
principales pièces d'appareillage s'élève à On a constaté qu'un élément unique de
3,08 dollars par pied carré ($32.95 par m2) grandes dimensions serait moins coûteux
de membrane. Pour la formule 3) , le dis que plusieurs éléments plus petits; cepen
positif à tubes séparés considéré valable dant, si d'autres facteurs militent en faveur
pour les deux formules 3) et 4) , les de l'adoption de plusieurs éléments, la
raccords et les armatures influent au plus différence de coût ne serait pas prohibi
haut point sur le coût et le chiffre total de tive. En fait, plusieurs éléments de petites
ce coût est donc fonction de la longueur de dimensions sont préférables, car le fonction
chaque tube. Par exemple, dans le cas d'un nement de l'usine ne souffre pas beaucoup
tube de 30 pieds (9 m) de longueur et de en cas d'arrêt d'un élément pour entretien
Yi pouce (125 mm) de diamètre intérieur. ou autre raison.

381
 CARACTERISTIQUES DE CONSTRUCTION
On a étudié divers dispositifs dans les
quels: 1) les plateaux de pression supérieure
et inférieure étaient chacun soudé à une
bride, une série de panneaux empilés entre
eux et le tout maintenu par des tirants;
2) une paroi pleine remplaçait les tirants,
agissant uniquement comme pièce de ten
sion sans supporter la pression; 3) une cuve
complète sous pression contenait l'eau d'ali
mentation, les panneaux agissant unique
ment comme support des membranes. On a
constaté que cette dernière disposition est
la moins coûteuse.
La largeur du canal d'écoulement a été
établie à 0,100 pouce (2,54 mm) . Avec une
épaisseur de 0.125 pouce (3,175 mm) pour
la membrane et le papier de renforcement,
les panneaux s'empilent à raison de 50 par
pied (164 par m) .

FACTEURS D'EXPLOITATION VARIABLES POUR UNE USINE

DE 1.000.000 DE GALLONS PAR JOUR
Dans une usine pour eau saumâtre, une n'offrant pas les machines qui conviendraient.
récupération de 80% d'eau produite est Dans une usine pour eau de mer. on
raisonnable. Il se produit un changement estime satisfaisante une récupération de
de 5:1 dans le taux volumétrique de 33% d'eau produite, avec une concentration
l'écoulement à travers la cellule et il im de saumure résiduaire de 5,25%. La récupé
porte de réduire la section du canal ration d'énergie à partir des eaux rési
d'écoulement de la saumure afin de main duaires peut réduire le prix de revient de
tenir une vitesse suffisante à la sortie. La l'eau produite de 0,10 dollar par millier
récupération d'énergie à partir des eaux de gallons ($0,026 par m') et est consi
résiduaires est marginale, le marché normal dérée indispensable.

CALCUL DU PRIX DE REVIENT

Employant la méthode normalisée d'éva ont été établis pour des usines de 10.000.000
luation du prix de revient de l'Office of de gallons par jour (40.000 m"/j) :
Saline Water, les chiffres estimatifs suivants

Eaux saumâtres: Eaux de mer:

Immobilisations de Immobilisations de
capital: S2.70O.OO0 capital: $5.500.000
Total des frais d'ex Total de frais d'ex
ploitation par ploitation par
millier de gallons: $0,21 millier de gallons: $0,44
($0,055 par m1) ($0,1 16 par m*)

382
 Критерии для Проектирования

Опреснительных Установок,

Применяющих Процесс Обратного

Осмоса

Б. Кейлин и К. Г. ДеХэвен

Соединенные Штаты Америки

ВСТУПЛЕНИЕ
Главным преимуществом обратного 4) поддерживала на поверхности
осмоса при его применении к опресне мембраны минимальную концен
нию соленой воды является малая за трацию, а также большая площадь
трата энергии по сравнению с другими самих мембран осложняет систе
процессами. му.
Требования, чтобы опреснительная Чтобы использовать до предела по
ячейка: тенциальную дешевизну процесса об
1) служила опорой для мембраны, ратного осмоса, необходимо удержать
2) предоставляла возможность уда капитальные затраты на низком уровне
лять опресненную воду, в соответствии со сбережениями, по
3) после окончания опреснения от лучаемыми от малого потребления
деляла поток концентрата, нахо энергии. Были изучены проекты ячеек
дящегося под высоким давлением,с целью использования для мембран
от полученного продукта, находянаиболее подходящих материалов и
щегося под низким давлением, и конструкций.

СТРОИТЕЛЬНЫЕ МАТЕРИАЛЫ
Опора мембраны
Структурно слабые мембраны нуж
даются в механической опоре, чтобы
выдерживать перепад давления 1.500
фунтов /кв. дюйм. Была выяснена
основная стоимость материалов, при
годных для разных форм опор. Было
произведено исследование пористых
материалов, через которые может сво
бодно просачиваться опресненная вода,
на сжатие, растяжение, сопротивление
на изгиб, проницаемость, коррозион
ную стойкость, и была изучена стои
мость. Были забракованы пористый
уголь, резина, полимеровые пенопла-
сты, керамические и ячеистые матери
алы из за недостаточного сопротивле
ния на сжатие, хрупкости и высокой
стоимости. Было обнаружено, что наи
более подходящим пористым матери
алом является, обработанное эпоксид
ной смолой, слоистое стеклянное во
локно, т.е. многослойная ткань, пред
варительно пропитанная эпоксидной
смолой. Предел прочности этого мате
риала на сжатие достигает 2.200 фун-
тов/кв. дюйм, а на растяжение превы
шает 20.000 фунтов/кв. дюйм. Он обхо
дится около 1,50 долл. на квадратный
фут поверхности мембраны.
Был произведен отбор непористых
материалов, пригодных для подкладок.
Наиболее подходящей была признана
фенольная смола толщиной 0,10 дюйма.
Ее предел прочности на сжатие прево
сходит 1.500 фунтов/кв. дюйм, а на
растяжение 10.000 фунтов/кв. дюйм.
Она стоит 0,77 долл. на кв. фут мемб
раны. Такие непористые материалы,
как асбестовый материал, масонит и
фанера, хоть и обходятся много дешев
ле, но недостаточно стойки в воде.
Среди различных трубчатых матери
алов, применимых для опор, оказалось
наиболее дешевым стеклянное волокно
с витыми нитями. При соответственных
383
 трубах со внутренним диаметром Ы"
оно стоит 1,00 долл. на кв. фут поверх
ности мембраны, а при трубах со вну
тренним диаметром Уг" оно обходится
1.50 долл. на кв. фут поверхности мем
браны.
Сосуды* и трубопроводы
Для сосудов, находящихся под дав
лением, и трубопроводов, которые дол
жны противостоять коррозийности мор
ской воды, были приняты во внимание
системы трех типов: нержавеющая
сталь и сплавы монель; углеродистая
сталь с одеждой из меди, никкеля или
КОНСТРУКЦИИ ЯЧЕЕК
Форма
Были рассмотрены трубчатые и пло
ско-тарелочные формы, пригодные для
приведеняи в соприкосновение хорошо
опертой полунепроницаемой мембраны
с находящимся под высоким давлением
соленым раствором. Были обследованы
четыре трубчатых системы:
(1) ряд труб малого диаметра, за
канчивающихся трубными досками, с
находящейся в трубах под высоким
давлением исходной соленой водой,
поступающей туда с днища сосудов;
(2) то же, что и (1) с тем исключе
нием, что мембраны расположены сна
ружи труб, а находящаяся под высоким
давлением исходная вода проходит че
рез кожух;
(3) одиночные пористые трубы, сое
диненные между собой так, что они
образуют сплошные трубы с мембра
нами, смонтированными внутри;
(4) одиночные пористые трубы,
смонтированные внутри непроницаемых
наружных, причем исходная вода про
ходит внутри труб.
В случае (1) форма теплообменников
типична для обоих случаев (1) и (2),
а стоимость главного оборудования
составляет 3,08 долл. на кв. фут по
верхности мембраны. В случае (3)
форма одиночной трубы типична для
обоих случаев (3) и (4), а стоимость
сильно зависит от соединительных и
фасонных частей, так что общая сто
имость является функцией длин от
дельных труб. Например, при трубах
со внутренним диаметром Уг" и дли
ной 30 футов общая стоимость главно
го оборудования достигает 4,75 долл.
* Примечание переводчика: Сосуды,
вмещающие группы мембран.
384
нержавеющей стали; и углеродистая
сталь, покрытая органическими мате
риалами. Из них последняя система
оказалась наиболее дешевой; органи
ческий покров сам по себе обходился
в 25 раз дешевле стали.
Несколько сортов покрытий углеро
дистой стали эпоксидными смолами
выдерживало кратковременные рабочие
испытания на сопротивление коррозии.
Как эпоксидные, так и фенольные смо
лы хорошо сопротивлялись коррозии,
находясь в морской воде под высоким
давлением.
на кв. фут мембраны; при трубах со
внутренним диаметром V4" и длиной
350 футов общая стоимость главного
оборудования достигает 1,80 долл. на
кв. фут мембраны.
Для плоско-тарелочной формы с по
ристыми слоистыми подкладочными та
релками из эпоксидной смолы и стек
лянного волокна, расчетная стоимость
главного оборудования составляла 1,80
долл. на кв. фут мембраны. При непо
ристых фенольных тарелках стоимость
главного оборудования достигала 1,06
долл. на кв. фут мембраны.
Таким образом, плоско-тарелочная
форма и применение опорных мембран
ных тарелок, сделанных из непористой
фенольной смолы, являлась, среди рас
смотренных, самой экономичной кон
струкцией.
Размер ячеек и устройство
Было высчитано, что один большой
сосуд стоит меньше, чем несколько ма
лых, но это не имеет большого финан
сового значения, если другие факторы
говорят против этого. Малые сосуды
фактически более желательны, так как,
если такой сосуд выбывает из строя
для текущего ремонта или по другим
причинам, это почти не влияет на ра
боту установки.
Критерии для проектирования
Были изучены формы, при которых:
(1) верхнее и нижнее днища сосуда,
находящегося под давлением, были при
варены к фланцам, между ними была
помещена группа тарелок и система
соединена болтами;
(2) вместо соединительных болтов,
которые были оставлены только для
работы на растяжение, а не на сжатие,
в сосуде была установлена сплошная
стенка; и
(3) полный сосуд высокого давления
вмещал исходную воду, а тарелки
только поддерживали мембраны.
Оказалось, что последнее решение
РАБОЧИЕ ПЕРЕМЕННЫЕ ВЕЛИЧИНЫ ДЛЯ УСТАНОВКИ, ПРОИЗВОДЯЩЕЙ
ОДИН МИЛЛИОН ГАЛЛОНОВ ВОДЫ В СУТКИ
Для установки, работающей на соло
новатой воде, 80% — регенерация
опресненной воды вполне возможна.
При прохождении через ячейку полу
чается изменение объемной скорости
потока в отношении 5 : 1, вследствие
чего приходится уменьшить площадь
поперечного сечения русла потока ра
створа, чтобы сохранить соотвествен-
ную скорость на выходном конце.
Сбросный поток является маргиналь
ным для регенерации энергии, ввиду
ПОДСЧЕТ СТОИМОСТИ
С помощью «Стандартизированной
процедуры для составления смет»
Управления по опреснению соленых
вод, были составлены следующие сме
Солоноватая вода:
2.700.000 долларов — Капитальные
затраты
0,21 долл./ 1.000 галлонов — Полная
стоимость производства
было наиболее дешевым.
Для русла потока была установлена
ширина 0,100". При толщине тарелки
0,125" и мембраны с бумажной подклад
кой 0,015" — на погонный фут сосуда
приходилась группа из 50 тарелок.
отсутствия подходящего оборудования
на обычном рынке.
Для установки, работающей на мор
ской воде, 33% — регенерация опре
сненной воды и 5,25% — концентрация
сбросного рассола признается прием
лемой. Регенерация энергии из сброс
ного потока может уменьшить стои
мость опресненной воды на 0,10 долл.
за 1.000 галлонов, что считается нуж
ным делать.
ты для установок, производительно'
стью 10 миллионов галлонов опреснен
ной воды в сутки.
Морская вода:
5.500.000 долларов — Капитальные
затраты »
0,44 долл./ 1.000 галлонов — Полная
стоимость производства.
385
 Criterios para el Diseno de Plantas

de Desalinizacion por el Sistema

de Osmosis Inversa

B. Keilin y C. G. DeHaven

Estados Unidos de America

INTRODUCCION
La ventaja principal de la osmosis in
versa como proceso de conversión de agua
salada es la baja proporción de energía que
se requiere en comparación con otros pro
cedimientos. La complejidad del sistema es
debida a la gran extensión de la membrana
que se ha de usar y a la necesidad de que
la célula de desalinización cumpla las fun
ciones de: (1) proporcionar apoyo mecá
nico a la membrana; (2) proporcionar el
medio de retirar el agua potable produ
cida; (3) separar la corriente de salmuera
a alta presión del producto a baja presión
después de efectuarse la desalinización y
(4) mantener una concentración mínima en
la superficie de la membrana. A fin de
aprovechar al máximo las ventajas que ofre
cen las posibilidades de costo bajo del
procedimiento de ósmosis inversa, la in
versión de capital debe ser baja, ajustada
al ahorro de costo que proporciona la poca
energía necesaria. Se ha hecho también un
estudio de la construcción de la célula para
determinar el diseño y los materiales que
ofrezcan los medios más eficaces de utilizar
la membrana.

MATERIALES DE CONSTRUCCION
APOYO DE LA MEMBRANA
Las membranas estructuralmente débiles
necesitan un apoyo mecánico para poder
resistir la calda de presión de 1.500 libras
por pulgada cuadrada (lpc) a través de
ellas. Se investigó el costo básico de mate
riales de apoyo para su empleo en una
gran variedad de configuraciones. Se toma
ron en consideración materiales porosos por
los cuales pudiera pasar fácilmente el pro
ducto, teniendo en cuenta la resistencia a
la compresión, a la tracción y a la flexión,
su permeabilidad, su resistencia a la corro
sión y su costo. Se rechazaron los productos
de carbón poroso, de espumas de goma y
de polímero, de cerámica y alveolados por
ser su resistencia a la compresión, su fragi
lidad o su costo inadecuados. Se comprobó
que el material poroso más adecuado era
una lámina de vidrio fibroso pobre en
epoxia, una tela de varias capas preimpreg-
nada con epoxia. El costo aproximado sería
(1) Marca registrada de un ytipo de madera
sintética fabricada con aserrín resinas (N. del drado de membrana por tubos con diámetro
T.)
386
de 51,50 el pie cuadrado de superficie de
membrana por un material con resistencia
a la compresión de 2.200 lpc y resistencia
a la tracción de > 20.000 lpc.
Se seleccionaron, por medio de pruebas,
materiales no porosos que pudieran elabo
rarse para satisfacer las exigencias de un
material de apoyo. Se logró comprobar que
el más adecuado de ellos era una resina
fenólica de 0,10 pulg. de espesor, con re
sistencia a la compresión de > 1.500 lpc
y resistencia a la tracción de > 10.000 lpc,
cuyo costo era de $0,77 por pie cuadrado
de membrana. Los materiales no porosos,
tales como el cartón de asbestos, el "maso-
nite"'" y la madera terciada son mucho
menos costosos, pero se considera que care
cen de estabilidad en el agua.
Se verificó que entre los materiales de
apoyo tubulares la fibra de vidrio arrollado
con filamentos era el menos costoso, siendo
su precio de $1,00 el pie cuadrado de mem
brana por tubos adecuados con diámetro
interior de yi pulg. y de $1¿0 el pie cua
interior de i/2 pulg.
 RECIPIENTES Y TUBOS
Para los recipientes y tubos a presión,
adecuados para resistir la acción corrosiva
del agua de mar, se tomaron en considera
ción tres tipos de sistemas, a saber: los
aceros inoxidables y el metal monel; el
acero al carbono revestido con aleaciones
de cobre, níquel o acero inoxidable; y el
acero al carbono con revestimiento de ma
teriales orgánicos. Entre todos estos, el
último resultó ser el menos costoso; el
revestimiento orgánico puede reemplazarse
veinticinco veces por el costo del recipiente
de acero revestido.
Pudo comprobarse que varias variedades
de revestimiento de epoxia sobre acero al
carbono resistían con éxito las pruebas de
corrosión de corta duración en servicio.
Tanto las resinas epóxicas como las fenó-
licas demostraron tener gran resistencia a la
corrosión a alta presión en agua de mar.

DISEÑO DE LA CELULA
CONFIGURACION laminadas de fibra de vidrio y resinas
epóxicas, el costo del equipo principal se
Para poner una solución salina a alta calculó en $1,80 por pie cuadrado de mem
presión en contacto con una membrana brana. Se calculó también que el costo del
semipermeable adecuadamente apoyada, se equipo principal para la configuración de
consideraron configuraciones tubulares y de placas fenólicas no porosas era de $1,06
chapas planas. Se tomaron en cuenta cuatro por pie cuadrado de membrana.
configuraciones tubulares, a saber: (1) De este modo, se considera que la confi
tubos múltiples de diámetro pequeño ter guración de placa plana en que se utilizan
minando en placas tubulares, con la alimen placas de apoyo de membrana, fenólicas y
tación de agua salada a alta presión dentro no porosas, es la más económica entre los
de los tubos, encauzada ésta hacia ellos diseños que se han tomado en cuenta.
desde la parte superior de los recipientes;
(2) lo mismo que (1) , con la diferencia TAMAÑO Y DISPOSICION DE LA CELULA
de que las membranas se encuentran fuera Se ha podido comprobar que un solo
de los tubos y la alimentación de agua recipiente grande resultarla menos costoso
salada a alta presión se halla en el casco; que varios más pequeños, aunque la dife
(3) tubos porosos individuales conectados rencia de precio no sería muy desventajosa
entre sí para formar tubos continuos de si otros factores señalaran la conveniencia
gran longitud, con membranas montadas en de usar estos' últimos. En realidad, los reci
su interior; (4) tubos porosos individuales pientes pequeños convienen más porque no
montados dentro de los tubos sólidos exte se entorpece mayormente el funcionamiento
riores, con la alimentación encauzada dentro del sistema cuando se retira un recipiente
de los tubos. para su reparación o por otro motivo.
Para el caso (1) , considerándose la con
figuración del intercambiador de calor CRITERIOS PARA EL DISEÑO
representativa de tanto el caso (1) como el Se estudiaron las configuraciones en las
(2) , el costo de los elementos principales cuales (1) los cabezales de presión, superior
es de $3,08 por pie cuadrado de superficie e inferior, estaban soldados a las bridas,
de membrana. Para el caso (3) , la configu con una pila de placas interpuesta entre
ración de tubo individual, considerada ellas y el sistema armado por medio de los
representativa de los dos casos (3) y (4) , pernos; (2) se substitutyeron los pernos
el costo depende principalmente de los tirantes por una pared de recipiente sólida,
empalmes y las guarniciones, siendo el actuando solamente como órgano tensor,
costo total, por lo tanto, una función de sin soportar la presión; y (3) una vasija
las longitudes de los tubos individuales. de presión, completa, contenía el agua de
Por ejemplo, para los tubos de 30 pies de alimentación y las placas sólo tenían que
largo con diámetro interior de i/2 pulg., el servir de apoyo a la membrana. Se logró
costo total del equipo principal seria de establecer que esta última configuración
$4,75 por pie cuadrado de membrana; para entraña un costo mínimo.
tubos de 350 pies con diámetro interior de Se estableció que el ancho del canal de
Vi Pu'f?-> e' costo total del equipo principal escurrimiento es de 0,100 pulg. Como la
seria de $1,80 por pie cuadrado de placa tiene un espesor de 0,125 pulgs. y la
membrana. membrana con respaldo de papel un espe
Para una configuración de placa plana, sor de 0,015 pulgs., pueden aplicarse las
en que se utilizan placas de apoyo porosas, placas a razón de 50 por pie.

387
 VARIABLES DE TRABAJO EN UNA INSTALACION DE 1.000.000
DE GALONES/DIA
En una instalación de agua salobre, la de un equipo adecuado en el mercado
recuperación de un 80% de agua potable corriente.
es razonable. Sobreviene entonces un cam En una instalación para desalinizar agua
bio de 5:1 en el caudal de flujo volumé de mar, se juzga razonable recuperar un
trico a través de la célula y por eso es 33% de agua potable, con un agua madre
necesario reducir la superficie de la sección de deshecho con una concentración salina
transversal del canal de escurrimiento del de 525%. La recuperación de potencia de
agua madre, a fin de mantener una veloci la corriente rechazada puede reducir el
dad adecuada en el extremo de salida. La costo del agua en $0,10 por cada mil galo
corriente residual es despreciable para la nes, y por eso se considera indispensable.
recuperación de energía, a causa de la falta

CALCULOS DE COSTOS
Utilizando el Procedimiento Uniformado cálculos para instalaciones con capacidades
de Estimaciones de Costos de la Oficina de de 10.000.000 de galones/dia:
Agua Salada, se han hecho los siguientes

Agua Salobre: Agua de Mar:

$2.700.000—inversión de $5500.000—inversión de
capital capital
$0,21 /mil galones—costo $0,44/mil galones—costo
total de explotación total de explotación

.488
A Survey of Electrodialysis Develop
ments in the United States
Howard J. Cohan and Roger W. Kennedy
United States of America
INTRODUCTION
The electrodialysis process has proven
useful in the chemical, paper manufactur
ing, and food processing; industries, as well
as in the desalting of saline waters. A
complete survey of the present status of the
electrodialysis process in the United States
would include descriptions of each of these
applications. In keeping with the objectives
of the Symposium, this paper will discuss
HISTORY
Although the literature contains many
earlier references to electrodialysis and asso
ciated phenomena, it can be said that elec
trodialysis engineering was first initiated by
the multicompartment concept of Meyer
(ref. 1) in 1940 and by the development of
ion selective membranes made from stable
polymeric ion-exchange resins by Juda (refs.
2. 3), and Kressman (ref. 4) in 1949. In
the United States the first practical work
ing electrodialysis device was placed on
public display by Ionics, Incorporated, in
1952. The development of the process for
use in water desalting was in part stimu
lated by research contracts from the Office
of Saline Water of the U.S. Department of
the Interior. The results of this work were
reported in publications of that office (refs.
5. 6) . and led to the construction of the
eiectrolydialysis demonstration plant at
Webster. South Dakota, which is also de
scribed in Office of Saline Water publica
tions (refs. 7, 8) . The operation of this
plant was initiated in 1962. Shortly after
wards, a larger desalting plant was built In
the town of Buckeye, Arizona. Another large
municipal plant is now under construction
only the application of this process to de
salting water and other applications which
can either directly or indirectly contribute
to an increased useful water supply. The
discussion will be limited to applications
which have either been reduced to engineer
ing practice and are now under study in
the pilot plant stage or for which full-
scale plants are commercially available.
at Port Mansfield. Texas, and is scheduled
for completion during the summer of 1965.
Since 1950, three U.S. industrial firms
have manufactured both electrodialysis de
vices and membranes for water desalting:
another firm has manufactured devices to
utilize the membranes made by others: and
two other firms have manufactured mem
branes to be used in devices made by others.
Some of the results of this work are de
scribed by Farrell (ref. 9) and by Cohan
(ref. 10) . For various reasons many of
these firms are not presently actively en
gaged in this field. There is currently only
one firm manufacturing both equipment
and membranes; one other firm is manu
facturing equipment only: and two firms
are manufacturing membranes only.
Although laboratory research in electro
dialysis will not be discussed in this paper,
it should be stated that a large number of
laboratory studies are being carried out in
university and industrial laboratories. A
substantial portion of this research work is
proprietary in nature, and thus information
about it is difficult to obtain.
389
 EQUIPMENT PRESENTLY AVAILABLE
The use of electrodialysis for desalting of the so-called "tortuous-path" type in
ocean water as discussed by Langelier (ref. which the liquid flows at relatively high
11) has not proved economically feasible. velocities along a tortuous path formed by
The reasons for this are well-known and the configuration of the separator. Katz
are presented by Spieglcr (ref. 12) . With (ref. 18) reported that there are now more
further development in the process and than 120 electrodialysis water desalting
with low cost electrical energy, ocean water plants manufactured by Ionics, Incorporated
desalting by this process may still become in daily use throughout the world with
a reality and, in fact, one foreign firm is an aggregate capacity in excess of 3 mgd.
now marketing a small device for use in Figure 141 shows a typical separator
oceangoing vessels. The equipment pres manufactured by this firm. Table LI lists
ently available from commercial sources the major characteristics of the more im
in the United States is intended to be most portant individual plant components manu
suitable for operation on inland brackish factured in two basic sizes for use in wateT
water containing considerably fewer dis treatment plants by this firm. Figure 142
solved solids than ocean water. The dis shows a typical membrane pack assembled
tribution of these brackish waters, as sur from basic components of the largest size.
face and groundwater, is shown in Figure The water desalting plant shown in Figure
140. Studies (refs. 14, 15) have shown that 142 is at Buckeye, Arizona, and is now
these waters vary widely in both the quan entering its third year of continuous opera
tity and the composition of dissolved salts. tion. Certain characteristics of this plant are
The equipment made to desalt these shown on Table LII.
waters must be able to cope with this wide Another large plant built by this firm is
variety of feed waters. Because of this re located at Port Mansfield, Texas. Some of
quirement for flexibility, the present manu its characteristics are also shown in Table
facturers of electrodialysis equipment can I.II; however, these data should be consid
not easily produce a so-called "package" ered only as preliminary design informa
device. Instead they have concentrated on tion. The plant was scheduled for accept
standardized production line components ance tests in July 1965, and actual operating
that can be built up into desalting plants data had not been released at the time of
engineered to meet the demands of a speci this writing.
fic customer. THE EQUIPMENT OF
The components produced in this way AQUA-CHEM, INCORPORATED
include almost all of the parts that go into F.quipment is produced by Aqua-Chem,
the membrane packs such as frames, end Incorporated under license from the TNO.4
plates, electrodes, gaskets, separators, and This equipment is of the "sheet-flow" type
membranes. Using these basic components, in which the liquid flows at relatively mod
the engineer designing the membrane packs erate velocities along a flow path established
has only the problem of deciding how by perimeter gaskets. In addition to the
many packs, how many flow compartments perimeter gaskets, a separator of expanded
in each pack, and what set of operating rigid polyvinylchloride (PVC) is used to
conditions can best be used for each specific support the membranes and create turbu
installation. Because of this situation, the lence in the stream. Figure 143 shows a
following discussion on electrodialysis equip typical separator manufactured by this firm.
ment presently available in the United Table LIII lists the major characteristics of
States will include the characteristics of the individual cells manufactured in two
certain of these individual components as basic commercial production sizes by this
well as a description of typical large desalt firm. Figure 144 shows a water desalting
ing plants that have been built from these unit with the membrane pack, including
components. Thorough discussions of the auxiliary equipment, assembled from basic
principles of plant desien are prrsentfd by components of the larger size.
Mintz (ref. 16) and Mason and Kirkham Membrane pack assemblies as shown in
(ref. 17). Figure 144 are available for saline water
THE EQUIPMENT OF IONICS, INCORPORATED demineralization installations. Much devel
The equipment produced by this firm is opment work oriented toward the needs of
• Central Technical Institute. TNO, The Hague, chemical process industry has been done bv
Netherlands, referred to as TNO. this firm.

.590
FIGURE 141. SEPARATOR (LEFT) AND MEMBRANE (RIGHT)
MANUFACTURED BY IONICS, INC.. FOR USE IN THE MARK
III ELECTRODIALYSIS MEMBRANE STACK. THE OUTER DI
MENSIONS OF THESE COMPONENTS ARE 18 BY 40 INCHES
(IONICS, INC., PHOTOGRAPH).
BUCKEYE,
AT
PLANT
ELECSTRAOLDITALIYNSIG STACKS
INC.,
IONICS,
THE
142.
DFIGURE OF
SIX
MMARK
INC.,
(IONICS,
UETIMLBIRZAINEG
ARIZONA,
THE
III

PHOTOGRAPH).
 (2,760) Mi)
Cre/s.
Tmh SnglUh
laid.
«0, (260.0 0)
(175) \iir 40)
(18x (66) (85)

III
Mar* 8• 88 Moo 82007000$40 ,0 0
650 70 48 57 PlanU
miDe
EnIonics,
leInc.
and
of
SrTABLE
Two
LII.
Data
apclteirczoadtfioacnlytriojn

MawPert
Metric 946 478 662 881 2.8 0.84 255 4.6 Metric
tA 946 29
46x102

19)
18,
(refs.
Stacks
MIOieDesign
IX
aoTABLE
mrnbctrieacinsteics Bngluh (6 .0 0) (0.80) EngUth (6 0,0 0)
(45) (60) (18x20)(760) (80)
ABarcifscoengae,
It)
(re/.

IIMara 6 2 25 2,10060088
800 66 48
ntion.
sol
NaCl70'Fwapurete,r
Metric Metric 2.460 27
166 170 1.11 If 46x61 70

ns)».
percent valueinesent
1961.

merit
D(gpm)
c1/min
flowfullRiorate,almpu—taerdt c(Dosemntipassperrdaeinltdniagorend ibut60InRpsi,
I960tomepprb.
asa.ro vted FeedcSotwneadmipntedreaontrsud.e
(wmRpoarxktiesmegnudr)me-,
kg/cm*
gpd)
(U.S.
m/day
ctWarpcuae tcmietnry, (*F) °Cr(for
tFeedawetmapietnreag,tsru)e cload,
aEewcscost,
ntaistmu/aketglrad
taforrofPervcentaonitlsrafbelare feedofcentmBrate,laperoxwidmouwnm apsPawrppm,loaxidtnmuiaectryl,/kgal full
load,
cEcost,
wsetaintmaetsrd ftotal
ofeEmcostlsnetrialmiat eond sEwcost,
dplant autciptmlaeitlredy
ft)all
(sq
mTotalemsqmbaraenas, aspFeedawrlppm,oaixtnmiaetryl,
gpd)
(U.S.
m/day
flowRrate,aented
gpd)
(U.S.
1/min
flowRrate,ated (pal)
kdrop,
SUckgp/recsmur"e (mofNteyumpbircbanelr)*.(Site
ofmienmemcbrhaens),
sof
MarkIIINtuamcbkesr bond
of
iAsma.ouen.t

Nofsutmabgers
flowRated lowflowRated full
full flowRated low
flowRated flowRated lowflowRated
full flowRated lowflowRated
full
 QENPUFARC-ATCUROHERDEM,AND
AMWHICH
PER
SIN
BY
INC.
THE
FIGURE
143. SGASKETS
MGASKET,
EARE
FABRI
IMETER
PVC
AXPNAIRNFADOTELODR,

INTO
SCATED
RPIECE
OF
BUREAU
A
P(U.S.
EHINGLE
COLTAOMGARTIPOHN).
396
 TABLE LUI. Design Characteristics Aqua-Chem Inc., Membrane Stacks (reí. 22)
WDi-i WD 10-4
Metric English Metrie English
Liquid velocity, em/sec (inchee/eec) 10 (4) 10 (4)
Maximum hydraulic flow rate
Cu m/day (U.S. «rpd) 77 (20.300) 1Б1 (39.900)
l./min (U.S. g-pm) 58 (14.1) 106 (27.7)
l./min (U.S. gpm)—Dilute compartment 1.1 (0.29) 2.1 (0.66)
Number of membranes (typical) 100 100
Site of membranes, cm (inches) 60x20 (24 X 8) 100 X 40 (40 X 16)
Total membrane area, sq m (sq ft) 12 (120) 40 (480)
Per cent reduction of solids each pass 1Б 40

MEMBRANES PRESENTLY AVAILABLE

Development of ion selective membranes United States in commercial quantities.
for use in the process for electrodialysis de-
mineralization of saline water has been THE MEMBRANES OF
undertaken by numerous research institutes IONICS, INCORPORATED
and commercial organizations throughout
the world since the initial inception of the These membranes are relatively rigid with
art in the 1940s. However, a recent inquiry high burst strength due to use of Dynel
by the Bureau of Reclamation, sent to 20 or glass backing reinforcement. They are
selected commercial and research organiza manufactured in three weights, 4-, 8-, and
tions which had all been active in this 15-ounce, the 15-ounce weight being de
field, produced only 8 replies indicating signed for use adjacent to the anode and
availability of membranes in commercial cathode. Membranes in small quantities
quantities: 4 in Japan, 3 in the United are generally offered for experimental use.
States, and 1 in South Africa. Possible Larger quantities are available as replace
sources in Europe and England were not ment parts for equipment manufactured by
completely surveyed at that time. The fol Ionics. Incorporated, or to purchasers hold
lowing discussion will be limited to mem ing a license from Ionics for use of such
branes suitable for electrodialysis deminer material. Table I.IV lists the characteristics
alization currently being produced in the of membranes manufactured by this firm.
TABLE LIV. Ionics Nepton Membranes (ref. 23)
Nominal •properties Anion Cation
(Formerly called AR-111A) (Formerly called CR-«l)
Thickness, mm 0.6 0.5 0.9 0.6 0.5 0.9
(mils) 24 20 86 24 20 86
Reinforcement Dynel Dynel Dynel Dynel Dynel Dynel
Resistance, ohm-cm3 6 — — 6
(0.5N NaCl)
Current efficiency, per cent 90-96 90-95 90-96 90-96 90-96 90-95
(0.6N NaCl)
Ion-exchange capacity, dry 2.0 2.0 2.0 2.8 2.8 2.4
(meq/g)
Gel water, weight, per cent 40-45 40-45 40-45 45-50 46-50 46-60
Mullen burst strength, kg/cm1 7.7 14.1 16.9 7.7 14.1 16.9
(psig) (110) (200) (240) (110) (200) (240)

THE MEMBRANES OF AMERICAN MACHINE sheet flow demineralizers. The membranes

AND FOUNDRY COMPANY
This company is listed by TNO as their
licensee for membrane manufacture in the
U.S. The membranes produced under the
"Amfion" trade name are flexible and par
ticularly adapted to use in low pressure.
are available in three series, 60, 100, and
300. The Series 300, cation permeable only,
are recommended for fuel cell use. Table
LV lists the nominal chemical and physical
properties of Series 60, 100, and 300 Amfion
membranes.

397
 TABLE LV. Amfion Ion Selective Membranes (ref. 24)
American Machine and Foundry Company
Nominal propertiem Anton Cation
Series 10 Series 100 Sertee $0 Series 100 C-tlO c-tis
Thickness, wet, mm 0.8 0.16 0.8 0.2 0.28+0.01 0.15+0.01
(mils) (12) («) (12) (8) (11.0+0.4) (6.8+0.4)
Resistance, effective 6±2 9+8 6+2 7+2 4.5+2.0 4.6+2.0
(0.6NKCI), ohm-cm1
Permselectivity (0.5N/ 84±4 92+8 80+6 98+2 86+6 85+6
1.0NKC1) , per cent
Ion-exchange capacity, 1.6+0.8 1.8+0.8 1.5+0.8 1.8+0.8 0.6+0.2 0.8+0J
dry, meq/j;
Gel water (dry-oasis). 28+5 20+5 85+7 22+7 17+4 17+4
per cent
Mullen burst strength, 8.2+0.88 8.6+0.88 8.2+0.86 4.2+0.85 T.7+0.86 8.8+1.4
wet. kg/cm' (psisj) (45+5) (60±6) (46+6) (60+6) (110+6) (65+20)
THE MEMBRANES OF acteristics, either wet or dry. They are avail
IONAC CHEMICAL COMPANY able in three series, J100, 3200, and 5400,
Ionac membranes are strongly ionized, the latter two series having chemical sta
heterogeneous, and reinforced with special bility characteristics required for use in the
fabrics. These membranes are unique in chemical process industry. Table LVI lists
their dimensional stability, wet to dry, and the chemical and physical properties of
are flexible with excellent handling char Ionac ion-exchange membranes.

TABLE LVI. Ionac Permselective Membranes (ref. 25)

Nominal propertiea Anion Carton
MASHI MA-stse MA-SWxL MC-SHt MC-StSS MC~3i70xL
Membrane thickness, mm 0.18 0.80 0.80 0.15 1 0.80 0.80
(mils) (7) (12) (12) (6) (12) (12)
Electrical resistance, ohm-cm", 10.1 85 18 9.1 18 9.6
AC Heas., 0.1N NaCl 96
Permselectivity, per cent 90 98 94 94 95
0.5N NaCI/l.ON NaCl
Exchange capacity, meq/g 0.96 0.766 0.748 1.06 1.26 1.05
Mullen burst strength, kg/cm" 18.4 18.0 14.4 18.0 18.0 18.4
(Pit*) (190) (186) (206) (186) (185)
Approximate density* K/m1 196 858 368 196 868 ar
(net as shipped) (os/yd*) (6) (11) (11) (6) (11) (ID

OTHER USES THAT CAN CONSERVE WATER

Secondary conservation of our water re ELECTRODIALYSIS IN THE MANUFACTURE
sources can be achieved through reclaim OF PAPER
ing and purifying water polluted by sewage Stream pollution from disposal of waste
or industrial wastes, or by preventing such products is a continuing major problem in
pollution. The electrodialysis process can the manufacture of paper. The Sulphite
provide: Pulp Manufacturers' Research League (ref.
(a) Reduction of impurities to a level 26) has developed an electrodialysis method
tolerable for discharge into the water for processing spent sulfite liquors which
shed system, preferably with recovery achieves a three-fold objective in one process
of values for reuse or sale. system, as follows:
(b) Modification of a waste product to (1) Recovery of cations from the spent
provide products of economic value sulfite liquor;
and facilitate disposal problems. (2) Makeup of sulfite liquor for reuse
Reclamation of sewage for consumptive in the pulping process;
reuse is technically feasible today. However, (3) Electrically induced filtration and
complete biological purification of sewage separation of the organic constituents
still results in buildup of inorganic impuri of the spent sulfite liquor into large
ties ftds) and here electrodialysis deminer- and small molecule components.
alization can make a definite contribution.
Any chemical process use of electrodialysis This process, developed over the past 6
in modification of waste products or recov years, is based on the so-called "BALC"
ery of values that in turn reduces the waste design, a modified Aqua-Chem, Inc. mem
discharged to our rivers is a contribution brane pack, in which four process streams
to the conservation of water and. in effect, are fed to a multicompartment electrodi
increases the water supply. alysis stack, as basically outlined in Figure
398
145. Each repeating cell configuration con
sists of an anolyte, a liquor and a catholyte
stream, separated by a barrier stream from
the adjacent repeating cell configuration.
The function of each stream in Figure 145
is. briefly, as follows:
(1) The barrier streams (stream 5 in
Figure 145, bounded by anion and
cation permeable membranes, serve as
makeup for introducing the sulfite
ion to the process system. The anode
and cathode frame rinses (streams 1
and 9) serve the functions of one
barrier stream.
(2) The catholyte (streams 4 and 8) ,
bounded by reverse sequence anion
and cation permeable membranes,
make up sulfite liquor for use in the
pulping process, recovering cations
from the spent sulfite liquor (streams
S and 7) and receiving fresh sulfite
ion from the barrier stream.
(3) The spent sulfite liquor stream,
bounded by a cation permeable mem
brane and a nonselective membrane,
is modified in passage through the
system, the base cation values being
transferred for use to the catholyte
stream with an equivalent amount of
small molecule lignosulfonic acid
(LSOa) filtered through the nonselec
tive membrane to the anolyte (streams
2 and 6) , which is the vehicle for
recovery of the small molecule frac
tion of the modified spent sulfite
liquor.
The BALC system operates at high cur
rent efficiencies and extremely high current
densities due to the conductive nature of
FUTURE POTENTIAL
As previously mentioned, the electrodialy-
sis process shows great potential for ex
panded use in the chemical, paper manu
facturing, and food processing industries.
Improvements in the process which may be
developed to serve the needs of these indus
tries can certainly result in improved plants
for desalting water. In addition to this,
development work specifically for the im
provement of water desalting plants is also
being carried on by many organizations, and
it is difficult to predict what cost benefits
may result from this effort.
When a new or enlarged water supply is
needed for a municipality, industry, or agri
cultural district, the comparative costs of all
feasible alternatives are studied, and costs
may be estimated on the basis of future
the streams processed. Anion permeable
membranes are isolated from the organic
constituents of the spent sulfite liquor so
that organic fouling is not a problem.
Spent sulfite liquor, after processing, has
economic potential for uses such as adhes-
ives, oil well muds, flotation agents,
chelating and sequestering agents, dishwash
ing compounds, and concrete additives
which reduce water requirements and in
crease early strength. Otherwise the spent
sulfite liquor may be concentrated by
evaporation and burned or discharged into
rivers.
This process has been discussed here in
some detail because not only can it con
tribute indirectly to increased water supply,
but also the techniques for handling the
process streams that contain organic mate
rials may be useful in water desalting plants
where the brackish water sources contain
fouling organic materials.
ElECTRODIALYSIS IN SEWAGE RECLAMATION
The increase of water supplies by the
reclamation of sewage can utilize electrodi-
alysis as one of the process steps. Municipal
water use results in a sewage stream con
taining organic and biological contaminants.
Municipal use also causes a salinity increase
above that of the original water supply.
Conventional sewage treament systems can
remove the biological and organic con
taminants but do not reduce the salinity.
The necessary reduction of salinity can be
accomplished by electrodialysis as shown in
Figure 146. The U.S. Public Health Service
is sponsoring studies on such systems and a
pilot electrodialysis unit with a capacity of
70,000 gpd is now being tested.
needs and predicted technological develop
ments. When such studies include the elec
trodialysis process as one of the alternatives,
the effect of future lower cost electrical
energy is one very important factor which
must be taken into consideration.
THE EFFECTS OF LOWER COST
ELECTRICAL ENERGY
Hammond (ref. 27) and Spiewak (ref.
28) have indicated that in the future very
low cost electrical energy may become avail
able from large, nuclear reactor fired gener
ating stations. These stations may be either
single-purpose in nature (electrical genera
tion only) or dual-purpose (electrical gener
ation combined with sea water distillation) .
This electricity can then be marketed
399
 NEC SPC"BALC"
FIGURE
ETHE
145.
HLOREC-MOTARCADIECLASLYEIYDS SULFITE
SPENT
OF
TRUSED
THE
IN
CAN
PROCESS
THIS
BE
EPERASTEMNETNDT.
cathooeI PER
ONE
FRAME STACK

CATHOLYTE

LIQUOR í^/LaroÉN
7

NS
ANOLYTE
6

ANOL-CATH
BETWE N (REF.
26).
LIQUORS
PULPING
PAPER
SULFITE
FROM
BAR IER EACH
5

Id
ICATHOLYTE
4
CATION
SCs
ELECTIVE A5
SELECTIVE
ANION
NS
-SELECTIVE
NON
LARGER
LIQUOR
3
MEMBRANES
NS
lANOLYTE
2

ONE
PER STACK
ANODE FRAME

+ POS.
 SLUDOI TEUSEWAGE
SYSTEM
A
LRTYECITPALROTIDMCZAEILANYSLTIG
mgd
0.1 mgd
1 mgd
l
1 1
1

SEWAGE PLANT CARBON FILTER

FOAM SAND FILTER
AIR
INC..
(IONICS,
DAS
OF
ONE
PRAOWCIENSG).
THE
STEPS
9 00ppm^^
mgd

70 010.0ppm gd
69.9/7
m~qd100 70 p m »9 70ppm0 70 p m
■•no
mgd
^LOSS RINImgd
■ -pVi.é mgd
*3

POP.
TOWN ADDS
so p m
450,000
ELECTRODIALYSIS

9 07ppm
mgd
ii,

SO p m
mgd
01

DISINFECTION 9i.3mgd S
03ppm *\.*nyjd 350ppm
MUNICIPAL
WATER SUPPLY
I

"JO p m
imqd14^.

146.
FIGURE
SU•P LY lOUtCI
FROM
 through the large interconnected power
transmission systems, which will soon be
a reality; and electrodialysis desalting plants
sitnated at great distances from the power
generating stations will have access to this
low cost power. The effect of this advancing
technology upon the cost of water desalted
by the electrodialysis process can be pro
found.
Figure 147 is based on data reported by
Hamner (ref. 29) and shows the effect of
lower cost electrical energy on the cost of
water produced by the electrodialysis plant
at Buckeye, Arizona. If power could be
made available to this plant at a cost of
say 0.2 cents per kwh, the cost of water
would be reduced from the present 33 cents
60
0 0.2 0.4 0.6
COST OF ELECTRICITY
FIGURE 147. THE CAST OF DESALTED PRODUCT WATER VS
THE CAST OF ELECTRICITY FOR THE ELECTRODIALYSIS
DESALTING PLANT AT BUCKEYE, ARIZONA, BASED ON DATA
FROM HAMNER (REF. 29).
•102
per thousand gallons to about 213 cents
per thousand gallons for a reduction of 35
per cent. The data used assumes the unreal
istic condition of full load. Under the more
realistic conditions of 48 per cent load, the
savings would amount to about 23 per cent.
The preceding discussion is based on
data from an operating plant and takes into
account the cost savings that could be real
ized by changing one single factor, the cost
of electricity. Further savings may be real
ized if lower cost electrical energy affects
the optimization of plant design. The Office
of Saline Water has shown (ref. 30) that
the optimum economic current density for
plant operation is far above the operating
current density in existing plants. The
0.8 1.0 1.2 1.4
(CENTS/KWH)
optimum economic current density cannot
be approached in existing plants because of
the very real limitations on operating condi
tions set by the effects of polarization. The
basic mechanism of this phenomenon is
under study and, hopefully, future plants
will be able to operate at current densities
that may approach the optimum. When this
occurs, it will affect the design and capacity
of equipment in such a way that the cost
of electrical energy may become an even
greater part of the total cost of water pro
duced by future plants. This means that
lower cost electrical energy will not only
reflect upon the design and optimization of
these plants, but also can in turn greatly
affect the cost of water produced by these
plants.
The cost savings which could l)c achieved
by building larger plants have also received
much attention. Cost estimates for electro-
dialysis desalting plants ranging in size from
250,000 gpd to 2 mgd are reported by the
Office of Saline Water (ref. 31) ; plant sizes
up to 10 mgd were later reported by the
Office of Saline Water (ref. SO) ; and plants
ranging in size from 2 mgd to 200 mgd are
reported by Ionics (ref. 32) . Figure 148 is
taken from the latter report. It is based
upon electricity costs ranging from 0.4 to
0.8 cents kwh. We estimate that if 0.2 cents
kwh power was used as a basis, savings of
more than 15 per cent would be realized
in the water costs shown.

50

INSTALLED PLANT CAPACITY - 1,000,000 gpd

FIGURE 148. THE COST OF DESALTED PRODUCT WATER VS
INSTALLED PLANT CAPACITY BASED ON 0.4-0.8 CENTS/KWHR
ELECTRICITY, 7 PER CENT PER YEAR AMORTIZATION, 90
PER CENT LOAD FACTOR, AND 20 PER CENT PER YEAR
MEMBRANE REPLACEMENT (REF. 32).

REFERENCES
1. Meyer. К. H.; Strauss. W.: Helv, Chim.
Acta no. 23 (1940) p. 795.
2. Juda, W.; McRae. W. A.: U.S. Patent
2636851 (July 9, 1949) .
3. Juda, W.; McRae, W. A.: J. Am. Chew.
Soc. no. 72 (1950) p. 1044.
4. Kressman, T. R. E.: Brit. Patent 693166
(Nov. 2, 1949) .
5. "Results of selected laboratory tests of
an Ionics demincralizer", (Ionics) , U.S.
Department of the Interior, PB 161376
(1954) .
6. "Design, construction, field testing, and
cost analysis of an experimental elec-
trodialysis demineralizer for brackish
waters", (Ionics) , U.S. Department of
the Interior, PB 161386 (1956) .
7. "First annual report, saline water

403
 conversion demonstration plant at
Webster, South Dakota", VS. Depart
ment of the Interior, PB 181680 (1964) .
8. "Second annual report, saline water
conversion demonstration plant, Web
ster, South Dakota", Office of Saline
Water R&D Prog. Rept. no. 132 (1964) .
9. Farrell, J. B.; Smith, R. N.: Ind. and
Eng. Chem. vol. 54 no. 6 (1962) p. 29.
10. Cohan, H. J.: Chem. Eng. Prog. vol. 57
no. 2 (1961) p. 72.
11. Langelier, W. F.: /. AWWA vol. 44 no.
9 (1952) p. 845.
12. Spiegler, K. S.: "Salt water purifica
tion", John Wiley and Sons (1962) .
IS. Ackennan, E. A.; Lof, G. O. G.: "Tech
nology in American water develop
ment", The Johns Hopkins Press for
Resources for the Future, Inc. (1959) .
14. "Inventory of published and unpub
lished data on the characteristics of
saline surface and ground waters of
South Dakota", South Dakota School of
Mines PB 161381 (1954) .
15. Kreiger, R. A., et al: "Preliminary sur
vey of the saline water resources of the
United States", Geological Survey Water
Supply Paper 1374 (1957) .
16. Mintz, M. S.: Ind. and Eng. Chem. vol.
55 no. 6 (1963) p. 19.
17. Mason, E. A.; Kirkham, T. A.: Chem.
Eng. Prog. Symposium Series vol. 55 no.
24 (1959) p. 173.
18. Katz, W. E.: Advanc. Chem. Ser. no. 27
(1960) p. 232.
SUMMARY OF DISCUSSION
A question was raised concerning the cost
of converted water using electrodialysis in
sewage reclamation as described in this
paper. The reply stated that published fig
ures give an estimated cost of 7 to 10 cents
19. Katz, W. E.: Advanc. Chem. Ser. no. 58
(1963) p. 158.
20. The Municipal South (Feb. 1965) .
21. Memorandum from the Housing and
Home Finance Agency, Community Fa
cilities Administration.
22. Manufacturer's data sheet AD 189-4M,
Aqua-Chem, Inc.
23. Saline Water Conversion Technical Data
Book, Office of Saline Water (May
1964) p. 200.0.
24. Manufacturer's data sheet, American
Machine and Foundry Company.
25. Manufacturer's data sheet, Ionac Chem
ical Company.
26. Dubey, G. A., et al: /. of TAPPI no. 48
(1965) p. 95.
27. Hammond, R. P.: Nucleonics vol. 20
no. 12 (1962) p. 45.
28. Spiewak, I.: Nucleonics vol. 21 no. 7
(1963) p. 64.
29. Hamner, W. G.: The American City
(Mar. 1963) .
30. An Engineering Evaluation of the Elec-
trodialysis Process Adapted for Com
puter Methods for Water Desalination
Plants, U.S. Department of the Interior,
Office of Saline Water, no. 134 (1965) .
31. "A study of large-size saline water con
verson plants", (Bechtel Corporation) ,
U.S. Department of the Interior, PB
181470 (1963).
32. "Large-scale electrodialysis", Ionics, Inc.,
presented at the Southern California
Seminar (1965) .
per 1,000 gallons in plants with capacities
of 10 mgd or higher and that these figures
only apply to the cost of using single-stage
electrodialysis for tertiary treatment of
sewage waters.
 Revue Des Développements de
L'Electrodialyse Aux
Howard J. Cohan et Roger W. Kennedy
Etatt-Unii d'Amérique
On donne un bref historique du dévelop
pement de l'électrodialyse aux Etats-Unis,
suivi d'une discussion de l'équipement et
des membranes disponibles, à l'heure
actuelle, chez les fabricants commerciaux
dans ce pays. Des discussions supplémen
taires couvrent d'autres utilisations de
l'électrodialyse, et les possibilités futures de
ce procédé, qui peut aider à conserver les
resources aqueuses. Il existe actuellement en
Amérique deux fabricants d'équipement de
déminéralisation par électrodialyse et trois
de membranes. On résume les caractéris
tiques de conception pour l'équipement des
blocs de membranes et les propriétés chi
miques et physiques des membranes ionosé-
lectives; on présente également les données
Исследование Развития Электродиализа
в Соединенных Штатах
Говард Дж. Коган и Роджер В. Кеннеди
Соединенные Штаты Америки
Приводится короткая история разви
тия электродиализа в Соединенных
Штатах, а затем подвергаются обсуж
дению оборудование и мембраны, ко
торые теперь продаются американски
ми торговопромышленными фирмами.
Дополнительно комментируется приме
нение электродиализа с целью сохране
ния водяных ресурсов и будущие по
тенциальные возможности опресни
тельного процесса. В настоящее время
две американские фирмы производят
оборудование для обессоливания, а
три деляют мембраны. Резюмируют
ся расчетные характеристики обору
дования мембранных групп и химиче
ские и физические свойства ионо-се-
Etats-Unis
de construction pour deux grandes instal
lations municipales qui ont été terminées
au cours de ces dernières années. Dans le
cadre des autres applications qui peuvent
économiser l'eau, on discute le traitement
par électrodialyse des liqueurs déchargés de
sulfite pour la récupération des valeurs et
la modification des résidus provenant de la
fabrication du papier, et l'utilisation de
l'électrodialyse comme moyen de corriger
l'accumulation de salinité dans les installa
tions d'épuration des eaux d'égout. La
discussion des possibilités d'avenir du pro
cédé par électrodialyse comprend les efte's
de l'énergie électrique bon marché prove
nant des centrales nucléaires.
лективных мембран; приводятся про
ектные данные, относящиеся к двум
крупным муниципальным установкам,
которые были закончены в течение по
следних лет. Обсуждаются другие ме
ры для сохранения воды, как например
обработка электродиализом сбросной
сульфитной жидкости при регенерации
и модификации отходов бумажного
производства, а также применение
электродиализа для удаления солеоб-
разования при очистке сточных вод.
Во время обсуждения будущих потен
циальных возможностей электродиали
за рассматривается также влияние уде
шевления электроэнергии, вырабатыва
емой с помощью ядерной силы.
405
 Análisis del Desarrollo de la Electro-
diálisis en los Estados
Howard J. Cohan and Roger W. Kennedy
Estado* Unidoi de America
Los autores presentan una historia breve
del desarrollo de la electrodiálisis en los
Estados Unidos, seguida por una discusión
del equipo y de las membranas que hoy
en dia existen en este pais en escala comer
cial. También se discuten otros usos de la
electrodiálisis que pueden servir para con
servar el agua, asi como las posibilidades
futuras de este proceso. En el pais hay
actualmente dos fabricantes de equipos de
desmineralización por electrodiálisis, y tres
de membranas. Se hace un sumario de las
características de diseño del equipo con
membranas en superposición, asi como de
las propiedades físicas y químicas de las
membranas selectoras de iones. Además, se
406
Unidos
presenta datos del diseño de dos instala
ciones municipales grandes que han sido
terminadas en años recientes. Se discute el
tratamiento por electrodiálisis de líquidos
sulñtados usados en la manufactura de
papel, para recobrar residuos de valor y
modificar los productos de desperdicio.
También se discute el uso de la electro-
diálisis para reducir la concentración de
sales en el tratamiento de aguas cloacales,
así como en otras aplicaciones que pueden
servir para conservar agua. La discusión
de las posibilidades futuras del proceso
de la electrodiálisis incluye los efectos del
uso de energía eléctrica más barata gene
rada en plantas nucleares.
 Some British Achievements in
Desalination
Andrew C. Smith
United Kingdom
INTRODUCTION
I should like to begin by expressing
thanks on behalf of my company and my
self for the invitation to give this paper.
It would be ludicrous to attempt to pre
tend that we have no commercial interest,
and I shall not do so. Indeed, I should like
later on to say something specifically re
lated to commercial aspects of desalination.
But, nevertheless, my colleagues do sincerely
regard the growth of interest in desalination
in recent years as something of great benefit
to human affairs and, indeed, essential for
the future of civilization. We are proud to
have been closely associated with such de
velopments, and we intend to continue that
work most actively.
This statement means that we are as
much concerned as anyone else with design
studies, economic surveys, optimization cri
teria, fundamental research, distillation,
freezing, osmosis—and anything else your
scientists, or ours, think up. But in this
paper, I am deliberately going to ignore all
that—including what we are doing our
selves, as well as what is being done by
the Office of Saline Water, by the U.K.A.E.A.,
and others—in order to concentrate on an
account of what has already been success
fully done on a commercial basis. The rea
sons for this choice are important, and
should be stated. Of course, for many pur
poses desalinated water must be produced
more cheaply in the future, and hence, of
course, there must be active research, de
velopment, and economic study in many
places and by many people. But such
studies can be needlessly expensive, need
lessly timewasting, and definitely mislead
ing, if they fail to take proper account of
what is already possible in practical de
salination. At this point I might suitably
interject a remark on the commercial
situation.
It seems to me that there is a real risk
that the considerable publicity naturally
given to research and development in de
salination may in practice be slowing down
development. Nothing stimulates real de
velopment so much as an active market,
and a market that is waiting for prices to
fall is not active. I feel that the general
literature on desalination has erroneously
conveyed an impression that desalinated
water is currently very expensive and may
shortly become very cheap. Both parts of
that impression are false. It is already com
petitive with conventional water in many
parts of the world, has been installed com
mercially because it is so, and could be
provided more cheaply right now without
any further advances in technology if pur
chasing were more active. Delay in placing
orders caused by the hope of some drastic
reduction in price as a result of new de
velopments can, therefore, actually slow
development and keep costs up. We have
spent much time and money on research
and development. I have already indicated
that we intend to continue to spend more.
But the possibility of doing so depends
naturally upon adequate return from what
has already been achieved. This is not
merely a statement of truth for one par
ticular commercial firm. It is true of all
firms as well as of the national economy.
Research and development which is not
adequately exploited at every intermediate
stage cannot earn the means for its own
continuance and for the ultimate attain
ment of some final objective. I should like
407
 to hope that this situation will be noted by
those concerned with the overall economic
studies of desalination now being made by
many organizations.
SUBMERGED TUBE EVAPORATORS
Weir Westgarth Limited is owned jointly
by G. and J. Weir, Ltd., and Richardsons,
Westgarth, Ltd., having been formed in
1962 for reasons which will be discussed
later. Both parent companies have long
been associated with marine and steam
power plant engineering, and experience in
these fields was both a stimulus and an
asset in the development of sea water dis
tillation. It appears that the first commer
cially successful marine desalination plant
was supplied and patented by G. and J.
Weir, Ltd., in 1884. The plant was a boiling
distillation unit, in which steam direct from
the boiler passed through coils submerged
under a pool of brine. The pool was con
tinuously fed with sea water to maintain
the level while evaporation occurred. The
vapor was condensed over tubes through
which cold sea water was passed. The prac
tical success was largely due to the design
of the steam coils which allowed consider
able flexibility so that scale could be broken
off by thermal shock at intervals.
This method of pool boiling of brine by
submerged coils or tubes remained dom
inant throughout the whole development
of marine and land desalination from 1884
up to 1956, a total period of 72 years. It
began with a production capacity of about
250 U.S. gpd and reached its zenith in the
Aruba and Curacao installations of 1.7
million U.S. gpd, which were in fact in
stalled by G. and J. Weir in the 1956-1958
period. During the whole of that period
the Weir contribution was distinguished,
and by about 1956 this single British com
pany had in fact installed more than three-
quarters of all desalination plants in the
world.
One of the most difficult technical prob
lems which affects distillation techniques
is the formation of scale which occurs be
cause of calcium carbonates and sulphates
present in the sea water. In the early days
of the marine distillation plant, it could in
fact be said that this was the only impor
tant problem, simply because nothing very-
difficult thermodynamically was attempted.
The single effect submerged coil pool boil
ing plant was working with a substantial
temperature difference, perhaps as much as
90°F, and using about 1,170 Btu to produce
one lb of fresh water. Fouling of the heat-
408
From these introductory remarks, let me
now pass to a review of distillation experi
ences in my company.
ing surface was practically, the only thing
which could go wrong apart from carryover,
occasionally causing impurity. Hence for
many years considerable research was done
on the chemistry of scale formation in
evaporators, and substantial development
work was undertaken to give longer periods
between the necessary cleanings. This work
became more important as plant sizes in
creased. When sea water distillation began
to be used for land-based installations,
greater reliability was needed. Meanwhile
to improve the energy consumption, double-
effect and then triple-effect systems were
installed and the available temperature dif
ference in any one effect was cut to about
35°F. The heating surface increased far
more than the proportionate output of the
plant; access to it and cleaning became
more difficult. Some method for definite
prevention of scale was needed. The de
velopment of the ferric chloride treatment
method by the Weir Company achieved
this objective. The economic realization of
this method of acid treatment was the key
to the installation of the Aruba and Curacao
plants. The research on scale formation and
the development of the treatment method
was largely due to F. B. Ling of the Weir
Chemical Laboratory staff under the direc
tion of the late Harold Hillier. With the
extension of industrial development and
greater general use of desalination, it is
now usually possible to use acid treatment
economically by more convenient means,
notably sulphuric acid.
The Aruba and Curacao plants were
sextuplejeffect, and the specific energy con
sumption was approximately 216 Btu per
lb. The intereffect operating temperature
difference was down to about I9°F. The
scale problem had been solved, and the
plants were very successful and satisfactory.
But it was realized that they represented
about the end of that road, thermody
namically. One reason was the sheer diffi
culty of getting all the heating tubes for a
large plant properly submerged under the
pool of brine. To achieve this, the pool had
to be quite deep, and the hydrostatic head
above the lower tubes required an appre
ciably higher boiling point. Hence, in fact,
the temperature difference on such tubes
was reduced, and so more tubes were
 needed. Larger plants or more economic
plants could not be easily obtained via
this basic method.
Moreover, in order to satisfactorily achieve
the energy consumption in multiple-effect
plants, it is essential to introduce feed
preheaters. These feed preheaters are es
sentially brine-in-tube exchangers condens
ing some of the vapor outside the tubes.
Again the feed flowing from effect to effect
necessarily flashes. Thus in the -most eco
nomic arrangement of submerged tube pool-
boiling evaporators, some of the vapor is
formed by flash, and some of the vapor is
condensed around tube banks to heat liquid.
An account of the need for this arrange
ment is given by Silver (réf. 1) . The en
gineering of such a plant was, therefore, a
MULTISTAGE FLASH DISTILLATION
In discussing this subject it is impossible
to ignore the competitive position. It has
to be faced frankly, and so I should like to
set down what I understand to be the
sequence of events. The use of preheaters
in multiple-effect plants has already been
mentioned. It was quite natural to seek
arrangements by which the proportion of
vapor formed by flash would be increased
to 100 per cent. Single-stage and two-stage
flash evaporators were used for many years
by French and American manufacturers for
marine evaporators, and Westinghouse in
troduced flash evaporators to land practice
in a 4-stage unit at Kuwait in 1956. But the
essential features of multistage flash and the
thermodynamic effects of using a large
number of stages compared with the per
formance ratio were first etablished by G.
and J. Weir, Ltd., and by Richardsons,
Westgarth, Ltd., independently. The Weir
plant of two units each of 1.2 mgd at
Kuwait (19 stages, performance ratio 6)
and the Weir plant of 600.000 gpd (40
stages, performance ratio 10.6) at Guernsey
were both commissioned in 1960. These
were commercial units, supplied in the
ordinary way of business, to serve, by de
PRESENT PLANT CHARACTERISTICS
When discussing a possible future in
which units of 50 to 500 mgd are regarded
as desirable, it should be useful to have
some figures representative of present day
possibilities. The following table gives some
relevant data on actual installations either
completed or in the course of construction.
The figures in Table LVII show several
complex arrangement of vessels with sub
merged tubes linked through preheaters,
i.e., it required a mixture of "liquid out
side" and "liquid inside" heat exchangers
which was expensive.
Nevertheless, the successful design and
operation of such plants established a basis
for desalination activity throughout the
world. The experience which we gained in
linking desalination with process steam and
power production is of considerable value.
Confronted with the difficulties of further
economy and complexity of engineering,
we had to find an alternate method and, of
course, the research and development as
well as the experience led directly to our
initiation of the multistage flash process.
salination, needs which could not be eco
nomically satisfied otherwise. They were
successfully operated on the mgd. scale of
multistage flash distillation, and they were
in commercial operation before the first
Point Loma demonstration plant of the
same process-. I make this point with some
sense of apology to the Office of Saline
Water, localise that office and those directly
concerned with it have always stated clearly
that the Point Loma plant was not designed
to demonstrate the process which had al
ready been proved commercially by us, but
to investigate and test other features such
as construction and tube materials and tem
perature range. This situation has not.
however, always been evident to others.
The general technical and economic situ
ation of the multistage flash process as it is
now has been adequately dealt with in a
Nominated Lecture to the Institution of
Mechanical Engineers by Professor Silver,
who first designed the multistage flash sys
tem for G. and J. Weir, Ltd., and is now
Consultant to Weir Westgarth, Ltd., I shall
not discuss this furthers but believe that a
more particular and detailed statement re
garding present possibilities will be useful.
principal points of interest. First of all.
these are all commercial installations, pro
viding needed water at a satisfactory
cost to the areas concerned. Secondly, the
maximum unit size is below 2 mgd. Hence
it is apparent that in many areas of the
world it is quite unnecessary to wait for
very large units before distillation water
409
 supply can become economic, i.e., competi
tive with other possible sources. Further
more, in comparison with the previous best
figures for pool boiling multiple-effect evap
oration which are also included in the table,
it is apparent that multistage flash did
provide a breakthrough to new possibilities
of unit size and cheaper capital cost for
higher performance ratio.

TABLE LVII. Relevant Data on Actual Installations

Output - Volume Capital

mgd Perform
No. of ance rate of No. of cost in
Date Site (U.S. ratio recircula
units lb/1000 Btu tion flow staffes dollars
sals) ftVaec (approx.)
March 1969 Kuwait 0.36 1 4.25 7.5 22 870,000
August 1959 Qatar* 0.18 2 4.5 4.88 80 680.000
Dec. 1969 Ecuador* 0.06 1 4.6 1.45 It 186,000
June/August Kuwait 2.4 2 6.7 26.2 19 1.64 m
1960 717.000
Sept. 1960 Kharg Island* 0.8 2 6.25 3.78 38
Dec. 1960 Guernsey* 0.6 1 10.6 10.47 40 608,000
October 1961 LfideriU 0.14 1 7.7 8.12 24 267,000
June 1962 Marine 0.18 1 6 2.91 20 219,000
June 1962 Kuwait 0.72 1 6 16.86 21 492.000
Dec. 1962 to) Qatar 1.8 2 6 17.4 28 1.65 m
Feb. 1968 f 244,000
Jan. 1968 Netherlands 0.184 1 12 2.65 28
Antilles*
Jan. 1963 Curacao 8.44 2 7.6 88.6 80 2m
July 1968 Holland 0.76 1 12 9.1 28 460,000
July 1968 Curacao 1.69 1 7 19 18 875,000
July 1968 Italy 0.16 1 4 8.8 14 121,000
Nov. 1963 Chile* 0.26 1 6 6.44 24 460.000
Feb. 1964 Sinai 0.6 1 9.8 12.48 84 819.000
June 1964 Gibraltar 0.084 1 4.5 1.61 18 123,000
1966 Kuwait 6.0 6 7.8 26.8 80 6.8 m
1966 Khars Island* 0.8 1 6 6.86 29 712,000
1966 Kuwait 0.72 1 6 - 21 700,000
Largest submerged tube plant
1966/67 Aruba 2.66 | 6.6 i
* Prices include boilers and ancillary equipment.
Another important feature which I should engineering conditions which must be ob
like to stress is the relationship to power served and again knowledge of or experience
production. The surveys by the United with these requirements is essential at the
Nations F.A.O., and the studies by other design and planning stage. Given that. I
authorities have all drawn attention to the think there is no need to stress the diffi
desirability of linking water production culties unduly.
with power production, and there has natu I would not want to give the impression
rally been some heart searching and query that my company is not interested in ad
ing as to how practical such combinations vancement to larger unit sizes. We certainly
are. The certain answer from our experience are, and have active studies for these on the
is that they are entirely practical. Most of drawing board now. The larger unit size
the plants shown in Table LVII are operated possibility/is of particular interest when the
in conjunction with electric power produc heat source is nuclear energy. It is correct
tion, drawing some or all of their heating to say that one of the things which slows
steam from the power turbines. Some were up the advance to larger units is that we
specifically designed along with the power do not know all that we would like to
installation as combined installations; others know about the behavior of flashing brine
were simply added to an existing power and hence find it difficult to make reliable
site and steam connections taken accord predictions of behavior in units too far re
ingly. It is possible to spend much time moved in size from our present experience.
and energy thinking about the difficulties of In brief, it is correct to say that lack of
dual-purpose operation and load factor knowledge is one deterrent to advance in
problems and economies. I do not suggest size, but it is equally correct to say that
that such anxieties are entirely wasted and another thing which slows up the advance,
that these points do not require considera at least in our case, is that we do know a
tion. But experience shows that good power substantial amount about the behavior and
station personnel can take the joint opera the design requirements. In brief, our
tion of a sea water distillation plant in their knowledge makes us proceed cautiously.
stride. There are of course certain system Moreover, as Professor Silver has pointed
410
 out (loc. cit.) , the reduction in cost by unit
size increase is perhaps not as great as some
have hoped. He has expressed it mathe
matically; let me give it from a simpler
point of view. In a flash plant the flashing
brine necessarily flows as a river. For high
performance ratio on the order of one mgd
product, that river is about 15 to 20 ft
wide, having a combined liquid/foam depth
of approximately 2 ft. It should not be
made a deeper river, otherwise flashing
could be restricted—nor can it be made to
go much faster. Hence 50 mgd means a
width of order 300 yards, and a 500 mgd
unit about one to one and three-
fourths miles. Some ingenuity may be exer
cised to reduce these widths, but the order
of magnitude seems unavoidable. The pros
pect of single pumps to handle such quan
tities at the conditions needed is quite out
of sight, and multiple pumps are essential.
The tube surface parameters are fixed by
thermodynamic conditions, and, while their
arrangement may be varied, they are almost
exactly proportional to product quantity.
Hence, the building of a single unit means
crudely that you put a number of units
side by side and take out the adjacent walls,
and supply something else to give equiva
lent structural stability. The possible cost
saving is limited by these considerations. It
should he quite clear that if a large plant
is ordered to be made up of a number of
units, there will be immediate cost saving
for obvious commercial reasons of bulk
ordering and repetition of production, and
these may well be as much as could be
offered for a single large unit with its
attendant commercial risks.
This brings me to my closing point. Some
of those now interested in desalination
favor the large plant concept because of an
imagined difficulty in operating several units
in parallel. Table LVII shows that in prac
tice the commercial installations throughout
the world are usually multiunit. Most of
REFERENCES
1. SilveT, R. S.: Nominated Lecture "Fresh
water from the sea", I. Mech. E. (Nov.
1964).
SUMMARY OF DISCUSSION
There was no discussion.
them have grown naturally by the addition
of new units and the largest now comprise
mixed plant, i.e., older pool boiling
multiple-effect, and multistage flash, side by
side. Again the operational situation can be
handled with experience. Of course some
advantage accrues because one unit out of
service for any reason is not 100 per cent
shutdown.
I believe we shall see the unit size rapidly
extended in the immediate future to 5 mgd
and perhaps somewhat more slowly to 15
mgd. Unit size advance beyond that will
depend on two things: (1) incentives in
water cost both to the purchaser and, com
mercially, to the supplier, and (2) new
technical developments. Quite frankly, (1)
is at present doubtful on both counts. I
have already dealt with the water cost
aspect, and in regard to the suppliers' in
centive I would refer to my opening re
marks on the state of the market and the
need to benefit fully from all the research
and development already done in order to
support further advance. In regard to (2) ,
I welcome the current situation in the
United Kingdom which has been reported
by Dr. Kronberger in his paper. The recog
nition of the importance of desalination by
the British Government has now given the
U.K.A.E.A. a major responsibility for ad
vance in all economic methods of desalina
tion. The resources of that organization in
brains, equipment, and finance, and their
ability to sponsor research in our univer
sities will now bring to bear on desalination
an effort which will be much beyond that
which my company could make alone. That
effort will be made in close cooperation
with our experience and with our own con
tinuing research and development, and I
am confident that in the future we shall
make an even greater contribution than we
have already made to the provision of a
basic need of developing humanity.
411
 Quelques Realisations
Dans le Domaine du Dessalement
Andrew C. Smith
Ce mémoire est un exposé des réalisations
commerciales dans la distillation de l'eau
de mer, basées sur les travaux de G. Se J.
Weir, Limited. Richardson Westgarth, Lim
ited, et la société filiale, dont ils sont
maintenant conjointement propriétaires,
Weir-Westgarth, Ltd. Leur expérience ini
tiale était orientée sur la distillation à
l'usage de la marine et a évolué graduelle
ment pour produire des usines terrestres à
effets multiples avec des bassins à tubes
submergés. La dimension des installations
de ce genre a augmenté jusqu'à une capa
cité d'environ 500.000 imperial gallons
(2.250 m*) par jour, par appareil, avec un
rapport de rendement juste inférieur à 5.
Des installations à groupes multiples ont
été montées dans de nombreux endroits.
Des études importantes sur l'élimination de
l'entartrage furent nécessaires pour ces
développements.
Au cours de la période 1956/60, le pro
cédé de distillation à vaporisation instan
Некоторые Британские Достижения
в Области Опреснения
Эндрю К. Смит
Соединенное Королевство
Доклад описывает достижения в об
ласти коммерческого опреснения мор
ской воды, базирующиеся на работе
Г. энд Дж. Вейр, Лимитед, Ричардсон
Вестгарт, Лимитед и теперь находя
щегося в их совладении, филиала
Вейр-Вестгарт, Лимитед. Первоначаль
ный опыт относился к дистилляционным
аппаратам на судах, из которых посте-
412
Britanniques
tanée en étages multiples fut introduit et
des installations commerciales d'une capacité
unitaire de 1,2 millions de imperial gallons
(environ 5.500 m*) par jour, et avec un
rapport de rendement supérieur à 10, furent
commandées et mises en service avant l'in
stallation de démonstration de Point Loma
du programme de l'Office of Saline Water.
Le procédé est maintenant bien établi et
de nombreuses usines ont été installées sur
une base commerciale dans le monde entier.
La plus grande capacité unitaire construite
jusqu'à maintenant est de 1,7 millions de
gallons (environ 7.750 m") par jour. De
nombreuses usines à appareils multiples
sont en exploitation.
On discute des réductions possibles des
coûts ultérieurs de développement. On at
tire également l'attention sur l'expérience
acquise dans là construction de projets
combinant la production d'énergie élec
trique et d'eau et dans l'exploitation d'in
stallation à groupes multiples.
пенно возникли наземные, многосту
пенчатые установки с скипятильными
бассейнами». Производительность от
дельных установок этого типа возросла
до 500.000 галлонов опресненной воды
в сутки с рабочей характеристикой
близкой к 5 (в фунтах/1.000 Б.Т.Е.).
В ряде мест были построены много-
агрегатные установки. При этом разви
 тии понадобилась большая исследова
тельская работа для борьбы с накипью.
В 1956 - 1960 г.г. был применен про
цесс многоступенчатой дистилляции со
вскипанием и пущены в эксплуатацию
установки коммерческого типа с произ
водительностью по 1.200.000 галлонов
в сутки и рабочей характеристикой вы
ше 10, что опередило опытную уста
новку Пойнт Лома, построенную со
гласно программы (американского)
Управления по опреснению соленых
вод. Процесс теперь широко привился
Algunos Progresos en Desalinizacion
Realizados en Gran Bretaña
Andrew С. Smith
Gran Bretaña
El trabajo dá un informe sobre los ade
lantos comerciales en destilación de agua
de mar basados en el trabajo de G. 8e J.
Weir, Limited, Richardson Westgarth,
Limited y de su subsidiaria, de la que
actualmente ambas firmas son propietarias,
Weir-Westgarth, Limited. La experiencia
inicial fue sobre destilación a bordo de
buques y ésta gradualmente se desarrolló
hasta llegar a instalaciones terrestres de
plantas de múltiple efecto de ebullición y
condensación en estanque. El tamaño de
las plantas de este tipo creció hasta alcan
zar una capacidad de 03 millones de
galones por día por unidad, con una rela
ción de eficiencia de algo menor a 5. Se
instalaron plantas de unidades múltiples
en muchos lugares. Fue necesaria amplia
investigación sobre prevención de incrusta
ciones durante este proceso de desarrollo.
En el período 1956/60 fue introducido
el proceso de destilación instantánea de
и по всему миру сооружено много
установок коммерческого типа. Самая
большая из них достигает производи
тельности 1.700.000 галлонов в сутки.
В действии находится значительное ко
личество много-агрегатных установок.
В докладе обсуждается возможность
снижения стоимости в будущем. Обра
щается внимание на приобретенный
опыт в областях постройки комбини
рованных систем для выработки элек
троэнергии и воды, и эксплуатации
много-агрегатных установок.
múltiples etapas. Plantas comerciales de
capacidad unitaria de 1,2 millones de galo
nes por día y de relación de eficiencia
mayor que 10 fueron encargadas y entre
gadas en producción antes que la planta
de demostración de Punta Loma del pro
grama de Oficina de Agua Salada. El proce
so está actualmente bien establecido y se
han instalado muchas plantas sobre base
comercial en todo el mundo. La unidad de
mayor capacidad construida es de 1,7 mi
llones de galones por día. Muchas plantas
de unidades múltiples están en funciona
miento.
Se discute las posibles reducciones de
costo debido a mejoras futuras. También
se hace notar la experiencia ganada en la
construcción de plantas combinadas de
energía eléctrica y desalinización de agua y
en el funcionamiento de plantas de unida
des múltiples.
413
 A Simple Calculation Method for
the Vapor Reheat Process
Arthur Brehm
Germany
Among the different processes for saline
water conversion, the most advanced one
today is the multistage flash evaporation
process. Many plants have been built, even
on a large scale, and successfully operated.
An improvement of this process is the so-
called vapor reheat process in which the
normally used tube bundle condensers are
replaced by injection condensers which are
operated with fresh water. The heat ex
change between the produced hot fresh
water and cold sea water will then be done
by liquid-liquid heat extractors.
However, the calculation of the vapor
reheat process and its optimization with
regard to the specific energy consumption
is extremely complicated. D. F. Othmer,
R. F. Benenati, and G. C. Goulandris (refs.
1-4) have programmed the complete calcu
lation process for an electronic computer,
of the type IBM 650, and reported the re
sults in detail. The complexity of the calcu
lation process may be seen from the fact
that only plants up to 25 stages have been
calculated; otherwise even the computer
time becomes too long. An essential result
of these calculations is that optimum energy-
consumption will be reached if the tem
perature drop from stage to stage is con
stant. By fixing equal temperature drops in
all stages, it is possible to produce a simple
calculation scheme which gives the tempera
tures, concentrations, and mass flows in each
stage as well as in the whole process.
Figure 149 shows a schematic flow sheet of
the process. Here the leaving streams have
the index n. The amount of vapor pro
duced in the n"1 stage is DW„. The incom
ing brine comes from the preceding stage,
therefore B„_i. The incoming fresh water
comes from the following stage, therefore
Wntl. For the convenience of the reader.
the same notation has been used as by
D. F. Othmer, et al.
VARIABLES
Total number of stages N; temperature
of hot brine into top stage TBu,; tempera
ture of cold fresh water into last stage
TW1S; reflux RFX.
KNOWN DATA
Temperature of cold sea water TSEA;
terminal temperature difference of HETTD
of the heat extractors HEB and HEW;
temperature difference DFT of the streams
leaving the same stage (driving force tem
perature) ; boiling point elevation BPE:
heat of vaporization of water r.
ASSUMPTIONS
Equal temperature drop AT in all stages;
equal terminal temperature difference
HETTD of the heat extractors HEB and
HEW; specific heat of fresh water c,W =
const. = 1.0; specific heat of sea water or
brine c,,B — const. — 0.965; heat content of
vapor less heat content of brine at the same
temperature is equal to heat of vaporiza
tion; r„ — iWD. — iB« (this assumption
gives an error in the heat of vaporization
in order of 0.4 per cent) .
WANTED DATA
Amount of distillate D per unit amount
sea water feed D/B,N; heat load QH in
prime heater H per unit amount distillate
QH/D; heat load QHEB and QHEW of the
heat extractors HEB and HEW; amount of
fresh water W,K per unit amount of sea
water feed W„,/BIN; amount of distillate
DW, of any stage; temperatures TB„ and
TW, of any stage.
415
 The brine leaving the last stage is colder
TSEA by N AT degrees than the brine entering
W$EA the top stage of the evaporator:
RFX TBS = TB1S - N AT (2)
The fresh water leaving the last stage is
HEW warmer by AT degrees than the fresh water
HEB
entering this stage:
TW„ = TW„ + AT (3)
QH Substituting Equations (2) and (S) into
Equation (1) gives:
TB,* - TWIM _ DFT (°C)
OW, AT = N+1
With this, all temperatures may be cal
DW„ culated:
TB. = TBI1( - n AT (°C)
a. (5)
DW,
TW. = TBIS - n AT - DFT CQ
(6)
(2) The Amount of Distillate D
The heat content of the vapor produced
Bn-2j_ k., in any stage must be equal to the differ
ence of the amounts of heat entering and
DWn-1 leaving this stage with the brine:
Wn QWD^QB.^-QB. (7)
Bn-li
or:
DW„ (iDW.) (DWJ = <iB„_0 (B_t)
- (iBJ (B.) (8)
wn.i
B. = B„., - DW„ (9)
DWnl
Wn.2 iB.,, - iB„ (kg/h)
DW„ = B„_, iDW. _iB„
(10)
Because the heat content of the sea water
BN- » WN iB is equal to the product of specific heat
c,B and temperature TB and the specific
heat does not change with the existing
small temperature drops within one stage.
B„ TB Equation (10) may be written:
RFX
AT (kg/h)
DW.= (CpB) (B..,)
r.
SLOWDOWN (")
where r„ is the heat of vaporization of
FIGURE 149. SCHEMATIC FLOW water at the temperature TB„ and stands
SHEET OF VAPOR REHEAT for (iDW„ — iB„) according to the assump
PROCESS. tions made.
Therefore, for the first stage:
(I) The Temperature Difference AT DW, = (c„B) (BIN) (12)
The brine leaving the last stage is warmer
by DFT degrees than the fresh water leav and for the second stage:
ing this stage:
DW, = (cpB) (BO ^
TB„ - TW„ + DFT (1) ri

416
with B, = BIN - DW,: W..1 = W. + DW„. (20)
DW,= (epB) (Bn.) (1 -c,B ^) ^ giving:
W. = DW,„iD:-- Z~ (21)
(IS) iW.., - iW.
and analog for the third stage: respectively
DW, = (q3) (BIN)
DW„ = W„ iW. _ iW„
iDW. _ iW. (kg/h) (22)
The sum of all the amounts of distillate Writing again instead of iW. — iW«« =
U: (c,W) (AT) and instead of iDW. — iW„
n=N = r». Equation (21), respectively Equation
(22), reads as follows:
^DW=D= (c,B) (B„)
r»-,
W„=DWM (c,W) (AT) (kg/h) (23)

[ r, and
AT
-+...+ (l-cpB^,
r» r,
AT DW, = (c,W) (W.(1) (kg/h) (24)
(1 'a
rH-l
(15) Making Equation (11) equal to Equation
(24) leads to:
Introducing a mean heat of vaporization
r„ for the heats of vaporization r„ r„ r„ (kg/h) (25)
. . . , rH brings Equation (15) to Equation
(16):
This means the streams entering any stage
are equal, if we do not look to the factor
^-(1-cBfV c,B/c,W.
Dm >m ($)<«>
The amount of water entering the first
Equation (16) shows the amount of distil stage W„ therefore is:
late per unit amount of sea water feed.
(3) The Amount of Brine BK W, = B,!,^W
The amount of brine obviously is: W, + DW, = W,
BH — Biic — D
Wl = B'*^v7 + DWl
Substitution of Equation (16) gives:
or introducing Equation (12) for DW,:
«is r„ W, = BINi£(,+£pwi£) (kg/h) (26)
This expression simultaneously shows the
range of conversion. For the amount of water entering the last
(4) The Amount of Fresh Water FW stage W„:
WIM = W, _ D
The amount of fresh water brought into
the evaporator shall condense all the pro introducing Equation (26) for W, and
duced vapor; this means the amount of heat Equation (16) for D leads to:
leaving one stage with the fresh water must
be equal to the amount of heat entering
this stage with the fresh water and the heat
content of the vapor:
QW„.1=QWn + QDW.., (18)
Equation (27) shows the relation between
(iW.,0 (W_0 = (iW.) (W.) + the amounts of fresh water and brine enter
(iDW..O (DW..0 (19) ing at both ends of the evaporator.

417
 (!) The Heat Extractor HEB
In the heat extractor HEB no more heat
can be picked up than will be delivered
from fresh water in the heat extractor
HEW. Therefore:
QHEB = QHEW (kcai/h) (28)
(6) The Heat Extractor HEW
In the heat extractor HEW, the amount
of fresh water W, shall be cooled down from
the temperature TW, to not more than the
temperature TW,„. The heat load of the
heat extractor HEW, therefore, is:
QHEW = (c,W) (W,) (TW, _ TWIN)
Introducing Equation (26) for W, and
Equation (6) for TW, gives
QHEW
Bin (c„B) (N) (AT) (1 + c,W ^)
(kcal/kg) (29)
(7) The Heater H
In the heat extractor HEB, the amount
of heat QHEB as denned by Equation (28)
will be added to the amount of sea water
BIS at the temperature TB:
(B„) (c,B) <TB) + QHEB =
(BIK) (c,B) (T'„)
introducing Equation (28) for QHEB gives
T', = T. + (N) (AT) (1 + c.W-^1)
(°C) (SO)
In the heater H, the brine BIN shall
further be heated from the temperature T'„
to the temperature TBi„. The necessary
heat, therefore, is:
QH= (c,B) (BIN) (TB„,_T'B)
or after introduction of Equation (50) for
T',
"IN
[ TB,* _ T„ - (N) (AT) (1 +c„W AI) J
(kcal/kg) (31)
The heat added in the heater H per unit
amount distillate QH/D will be found by
dividing Equation (31) by Equation (16)
QH _
D ~ AT
c„B TB,„ - T» - (N) (AT) (1 + cpW £_)
'1
rm
(kcal/h) (32)
Consideration of Equations (31) and
(32) shows that the necessary heat de
creases as T„ and AT increase. However,
both terms are variable. For example, T„
418
can be increased by reflux of brine. How
ever, T„ has an upper limit as follows:
T, <S TW„ + 2HETTD
TW,B =
TB,,, - DFT - (N + 1) AT
(*)
TB g TB,, -
DFT + 2HETTD — (N + 1) AT
(S3)
Furthermore the temperature T'B has an
upper limit by the following equation:
T'„ g TW, - 2HETTD
Introducing Equation (SO) for T'B and
Equation (6) for TW, gives
T„ g TB,N _ DFT _ 2HETTD — AT
- (N) (AT) (1 + c,W ^) (S4)
Of the two limiting equations. Equations
(33) and (34) , the latter is the more
serious, because the term 1 4. (c,W)
(AT/r,) ) is always larger than 1 . There
fore, from this equation the maximum and
optimum values for T„, respectively RFX.
and AT, respectively TW,,,, can be cal
culated.
Refluxing a part of the produced brine
gives the mixing temperature TB:
T„ - TSEA + RFX
Bin
(TB — (N) (AT) _ TSEA)
(35)
If AT, respectively TW,N, is fixed, then
T„ can become not more than equal to the
right hand side of Equation (34) . The
maximum reflux ratio then can be calcu
lated by combining Equations (34) and
(35):
TB,„ — TSEA — DFT - 2HETTD
-AT - (N) (AT) (l+c,W^)
RFX
TBIK _ TSEA - (N) (AT)
(fcg/h)
kg/h (S6)
If someone wants to operate without re
flux of brine, T„ becomes TSEA and from
Equation (34) AT is calculated as follows:
AT = + iJi (N)*c,W (TB,K - DFT -
2HETTD _ TSEA) + / V
' + / (N + 1) r, \
(N + 1) r, I (2) (N) c.W J
(2) (N) c,W \ /
(°C) (37^
respectively TW,„ becomes:
TWIK = TBIK - DFT _ (N + 1)
(TB„ — DFT -2HETTD .
(N) CpW
TSEA) + (N + 1} r' + <N + ')'r-
; + (2) (N) cpW ^ (2) (N) CpW
CO (38)
The same result will be received naturally
if RFX equals zero in Equation (36) . Intro
ducing Equation (31) for T„ Equations
(35) and (36) leads to the simple expres
sion for the necessary heat input QH/BIN-
into the heater H, if operating with opti
mum reflux ratio:
c„B (AT + DFT + 2HETTD)
Bin
(kcal/kg) (39)
For QH/D follows
QH _ c..B (AT + DFT + 2HETTD)
D 1- (1-CpB^I)"
(kcal/kg) (40)
The same relations are found if intro
ducing into Equation (31) or Equation
(32) instead of maximum TR, maximum
AT as defined by Equation (37) . It should
be kept in mind, however, that AT is
defined by Equation (4) if operating with
reflux and by Equation (37) in the other
Operating with maximum AT is a little
bit more favorable with regard to the
specific energy consumption QH/D than
operating with reflux. This is explained by
the fact that the amount of distillate D in
creases more rapidly with increasing AT
than the heat input QH.
(8) The Amount of Heat Lost with the
Distillate QD
The amount of heat lost with the distil
late is
QD = (c,W) (D) (TW,„)
Introducing Equation (16) for D gives:
QD
~=z (CpW) (TWIN)
AT
I (1 c,B—)» (kcal/kg) (41)
(9) The Amount of Heat Lost with the
Brine QBS
The amount of heat lost with the blow-
down brine is
QB* = (CpB) (TB„) (B„ - RFX) (42)
Introducing Equation (17) for BN and
Equation (5) for TB„ gives:
QBl,-=CpB (TB,N- (N) (AT))
B,:
(1 _c,b4^)»-RFX (kcal/kg) (43)
1m
(10) The Concentration of Brine CB„
The brine concentration of any stage is
equal to the concentration of the brine feed
divided by the range of conversion reached
in this stage:
CB„ = CB l±T— (weight %) (44)
(l-c,B-^)»
Here r„* means the mean heat of vaporiza
tion of water between the first and the n"
stage.
(11) Comparison of Different Methods of
Operation
According to the different variables, there
are several ways of operating the vapor
reheat process. Keeping constant the tem
perature drop AT within the stages, this
temperature drop can be varied either by
varying the temperature of the cold fresh
water inlet or by maximizing AT. The per
formance ratio can be increased by recycling
part of the brine produced. The difference
between these three methods of operation
may be shown by examples A, B, and C.
Initial data:
Amount of sea water BIX = 1.0 kg/h;
specific heat of sea water CpB = 0.965 kcal/
kg, °C; temperature of cold sea water TSEA
= 15.5°C; temperature of hot brine into
top stage TBIN — 120°C; thermodynamic
driving force DFT = 0.5°C; number of
stages N = 10; terminal temperature differ
ence in each heat extractor HETTD = 1°C.
Measured values for the thermodynamic
driving force in the vapor reheat process
(ref. 1) are in order of 0.01 °F and, there
fore, are negligible. The value of 0.5°C used
here approximates the boiling point eleva
tion of sea water.
(A) TWjg will be chosen
TWIN will be chosen at random at
20.5 °C
AT then becomes, by Equation (4) ,
120.0 — 20.5 - 0.5
AT = I0+T = 90°C
(B) Maximum AT, no reflux
When operating with maximum AT
without reflux, AT becomes, by Equa
tion (42) :
532 04 1
AT •*4 10
419
 (120 - 0.5 - 2 - 15.5) + RFX = 120 - 153 — 0.5 —
120-
532.041 (10 + 1) I
( ?5wTm
(2) (10) )'— 9
2 - 9 - (10) (9) (1 + 531.95)
532.041 (10 + 1) 155 - (10) (9)
(2) (10) AT = 9.13 °C
= 0.101.882.7595 kg/h
(C) Operating with reflux
When operating as in example A, The differences of the operation methods
but refluxing part of the brine, re as described under examples A, B, and C
flux is calculated by Equation (41) : are summarized in Table LVIII.

TABLE LVIIL Comparison of Different

Example A B C
TWin CC) 20.6 19.07 20.5
AT CO 9.0 9.18 9.0
■q. (4) (17) (4)
RFX <kg/h). Eq. <B«) 0 0 0.101.88
r. <kcal/k») 666.85 667.26 656.85
n <kcal/kg) 531.95 632.041 S3 1.95
Wm <kg/h). Eq. (27) 0.8368 0.8841 0.8858
QHEW (kcal/h). Eq. (29) 88.8194 89.6164 88.3194
D (kg/kg). Eq. (16) 0.1466 11.1474 0.1466
QH (kcal/h). Eq. (39) 12.523 11.226 11.0976
QH/D (kcal/kg), Eq. (40) 86.0 76.14 76.2
QH/D (% of 78.14) 112.95 100.00 100.08

As can be seen from Table LVIII, nearly matically.

13 per cent of the heat input per unit weight
of distillate produced can be saved by maxi
mizing AT or refluxing part of the brine.
Though the difference between the tempera
tures of the fresh water, entering the last
stage, or AT is very small, a considerable
amount of heat may be saved. This indi
cates that the plant must be operated very
carefully and should be regulated auto
(12) Results of Basic Equations
Using the previous developed basic equa
tions, heat requirements per unit weight of
distillate have been calculated for different
numbers of stages, temperatures of hot
brine into top stage, and sea water tempera
tures. Some of the data are shown in Table
LIX.

TABLE LIX. Heat Requirements per Unit Weight of Distillate in kcal/kg as Function
of Number of Stages, Brine Inlet Temperature, and Temperature of Sea Water
DFT = 0.5 °C 2 HETTD = 2.0 °C
(Multiply kcal/kg with 1.8 to obtain Btu/lb)
Tempera Tempera
ture of ture of Number of stages N
brine Inlet sea water
TBm CO TSEA CC) 2 6 10 20 30 60
10 339.08 166.22 94.28 68.04 62.68 44.19
60 20 348.77 164.51 102.30 70.98 60.60 62.11
30 367.07 179.69 116.64 84.96 74.37 65.89
10 323.87 145.28 84.37 58.68 43.19 34.88
80 20 327.03 148.34 87.60 56.90 46.61 88.36
30 332.42 153.19 92.46 61.83 61.67 43.35
10 314.86 139.36 79.08 48.44 38.13 29.86
100 20 I1E.M 140.05 80.58 50.16 39.94 31.78
80 317.36 142.42 82.72 62.49 42.36 34.20
10 308.63 136.62 76.81 46.28 35.00 26.73
120 20 308.26 136.92 76.60 46.23 36.04 27.85
30 308.37 136.56 77.60 47.48 87.88 29.27
10 301.37 131.99 72.76 42.34 32.06 23.77
160 20 300.28 131.64 72.86 42.72 82.55 24.36
30 299.34 181.43 73.OR 43.23 88.16
420
 As can be seen from Table LIX, the heat
requirements increase with increasing sea
water temperature when operating with
only a few stages and low temperatures of
hot brine into top stage. Increasing this
temperature reduces the influence of the
sea water temperature and finally reverses
its effect. This means, operating with high
temperatures of hot brine into top stage,
-£-<kg/kg)
0.02f
FIGURE 150. AMOUNT OF DISTILLATE PER UNIT AMOUNT
OF FEED AS FUNCTION OF BRINE INLET TEMPERATURE,
NUMBER OF STAGES AND SEA WATER TEMPERATURE.
that heat requirements decrease with in
creasing sea water temperature. The larger
the number of stages, the higher the tem
perature of the hot brine has to be to show
the reversion of this effect. This can easily
be explained by Figures 150 and 151.
Figure 150 shows the amount of distillate
produced per unit amount of feed as a func
tion of brine inlet temperature, number of
lO'OOO^F)
strewn
WttWF)
300 (*F)
TBIN.CC)
421
 QH/B|N(Kcol/kg)(Btu/lb)

FIGURE 151. HEAT INPUT PER UNIT WEIGHT OF FEED AS

FUNCTION OF BRINE INLET TEMPERATURE AND SEA
WATER TEMPERATURE.
QH/D(Kcol/Kg)(Btu/lb) PERFORMANCE RATIO

80 110 140 170 200 230 260 270 300 («F)

20 ' 30 6^0 80 l55 ' ilO-1 140 160 TB,N CcT
FIGURE 152. HEAT REQUIREMENTS PER UNIT WEIGHT OF
DISTILLATE AS FUNCTION OF BRINE INLET TEMPERATURE,
NUMBER OF STAGES AND SEA WATER TEMPERATURE.
DJT — 0.5°C
2 HETTD = 2.0°C

423
 stages, and sea water temperature. As can
be seen, the amount of distillate increases
with the brine inlet temperature and the
number of stages. The lines form a bundle
of rays with slopes, decreasing with the
number of stages. Variation of sea water
temperatures gives only a parallel displace
ment and does not alter the slope of the
lines.
From Figure 151, which shows the heat
input per unit weight of feed as function
of the brine inlet temperature and sea
water temperature, it can be seen that the
heat input increases with increasing brine
inlet temperature and decreasing sea water
temperature. Here again the lines form a
bundle of rays. The dashed line has been
transferred from Figure 150 and shows the
amount of distillate produced. It can be
seen that the slopes of the lines become
more and more equal to the dashed line.
REFERENCES
1. Othmer, D. F.; Benenati, R. F.; Gou-
landris, G. C.: "Vapor reheat flash evap
oration system for production of fresh
water from saline water", Final reports
for the Office of Saline Water, Contract
nos. 14-01-001-162 and 183.
2. Othmer, D. F.; Benenati, R. F.; Gou-
landris, G. C.: Dechema—Monographien
no. 47 (1962) pp. 73-98.
3. Othmer, D. F.; Benenati. R. F.; Gou-
NOMENCLATURE
BIN Brine flow at top of the cascade,
kg/h or lb/hr
Bi, Ba BB
Amount of brine leaving the 1",
2"* n'6 stage of the evap
orator, kg/h or lb/hr
BPE Boiling point elevation, "C or
°F
CB], CBI( . . . , CB„
Concentration of brine leaving
the I", 2nd n" stage of the
evaporator, weight %
cpB Specific heat of sea water, kcal/
kg, °C or Btu/lb, °F
CpW Specific heat of fresh water, kcal/
kg, °C or Btu/lb, °F
D Total amount of distillate pro
duced, kg/h or lb/hr
DFT Driving force temperature, de
gree of approach to equilibrium
in each stage, °C or °F
424
This means that the heat input increases
more rapidly with the sea water tempera
ture than the amount of distillate with the
number of stages.
In Figure 152 the heat requirements per
unit weight of distillate are presented for
various temperatures of hot brine into top
stage, number of stages, -and sea water tem
perature. On the right hand side, a scale
has been drawn to read the corresponding
performance ratio. The performance ratio
represents the amount of distillate which
can be produced from a unit amount of
steam, either in kg/kg or lb/lb. Steam is
considered to be saturated at 1 atm and
100°C (14,696 psia and 212°F) . For the
convenience of the reader, all scales are in
British and metric units. From Figure 152 it
can be seen that performance ratios of 20
or more are feasible with the vapor reheat
process.
landris, G. C: "Sea water desalination
by vapor reheat flash evaporation". Ab
stract of Ph.D. thesis of G. C. Goulan-
dris, Brooklyn Polytechnic Institute.
June 1963, Chem. Engr. Progr. vol. 59
no. 12 (1963) pp. 63-68.
4. Othmer. D. F.; Benenati, R. F.; Gou-
landris, G. C.: Chem. Engr. Progr. vol.
57 (Jan. 1961) pp. 47-51.
DW„ DW DW,
Amount of distillate produced
in the 1", 2** n" stage of
the evaporator, kg/h or lb/hr
H Heater
HEB Heat extractor for brine
HF.TTD Heat extractor terminal tem
perature difference, °C or "F
HEW Heat extractor for fresh water
iB Heat content of brine, kcal/kg
or Btu/lb
iDW Heat content of the vaporous
distillate, kcal/kg or Btu/lb
iW Heat content of fresh water,
kcal/kg or Btu/lb
n Any stage of the evaporator
N Last stage of the evaporator,
total number of stages
QB,. QB,. , QB„
Amount of heat carried with
 brine leaving the 1", 2,d, .... n" stage of the evaporator,
ntb stage, kcal/h or Btu/hr kcal/kg or Btu/lb
QBK Amount of heat lost with brine, RFX Reflux of brine, kg/h or lb/hr
kcal/h or Btu/hr
AT Temperature drop within a stage
QD Amount of heat withdrawn with of the evaporator, °C or °F
distillate, kcal/h or Btu/hr
T» Temperature of sea water enter
QDW„ QDW, QDW. ing heat extractor HEB, °C or
Amount of heat carried with the •F
vaporous distillate of the 1", 2",
.... n" stage, kcal/h or Btu/hr TBi„ Temperature of hot brine into
top stage, "C or °F
QH Heat input into the heater, kcal/
h or Btu/hr TB„ TB , TB„
Temperature of brine leaving
QHEB Amount of heat transferred in the 1", 2" n'" stage of the
heat extractor HEB, kcal/h or evaporator, °C or °F
Btu/hr T'B Temperature of brine leaving
QHEW Amount of heat transferred in heat extractor HEB, °C or °F
heat extractor HEW, kcal/h or
Btu/hr T'w Temperature of fresh water leav
ing extractor HEW, °C or "F
QW, QW, . . . . QW.
Amount of heat carried with TW„ TW TW,
fresh water leaving the 1", 2"*. Temperature of fresh water leav
.... n" stage, kcal/h or Btu/hr ing the 1", 2"" n" stage of
the evaporator, °C or °F
*u r* • • •. r.
Latent heat of vaporization of TW,„ Temperature of fresh water into
water at the boiling temperature last stage, °C or "F
in the 1", 2**,... n" stage, TSEA Temperature of cold sea water,
kcal/kg or Btu/lb °C or °F
Mean latent heat of vaporization W„ W, W,
of water between the first and Amount of fresh water leaving
the last stage of the evaporator, the 1", 2" n" stage of the
kcal/kg or Btu/lb evaporator, kg/h or lb/hr
Mean heat of vaporization of WSEA Flow of sea water in, kg/h or
water between the first and the lb/hr

SUMMARY OF DISCUSSION
There was no discussion.

425
 Methode de Calcul Simple Pour le

Procede Par Rechauffage de la

Arthur Brehm

On donne une méthode de calcul simple
pour le procédé par réchauffage de la
vapeur, qui fait partie des procédés d'éva-
poration en étages (stades) multiples. Les
équations fondamentales sont développées
et les résultats sont présentés dans des tab-
leaux et des graphiques. On discute les dif-
férentes méthodes de fonctionnement, ainsi
que les résultats,

Простой Расчетный Метод

для Пароподогревательного Процесса

Артур Брем

Германия

Дается простой расчетный метод для новные уравнения, а результаты пред-

пароподогревательного процесса, кото- ставляются в форме таблиц и графиков,
рый принадлежит к процессам много- Обсуждаются различные оперативные
ступенчатого испарения. Выводятся ос- методы, а также их результаты.

426
Metodo de Calculo Simple Para el

Proceso de Recalentamiento

de Vapor

Arthur Brehm

Alemania

El autor presenta un método simple desarrollo de las ecuaciones básicas, y los

para calcular el proceso de recalentamiento resultados se presentan en tablas y gráficos.
del vapor en la evaporación etapas múl Además, se discuten diferentes métodos de
tiples. Se incluye en esta presentación el funcionamiento y sus resultados.

427
Solar Powered Humidification Cycle
Desalination
(A Report on the Puerto Penasco
Pilot Desalting Plant)
Carl N. Hodges, John £. Groh, and T. Lewis Thompson
United States of America
INTRODUCTION
The Puerto Peflasco Pilot Desalination
Plant, shown in Figure 153, is a joint re
search project of the Solar Energy Labora
tory of the University of Arizona, Tucson,
Arizona, and the Center for Scientific and
Applied Research of the University of
Sonora, Hermosillo, Sonora, Mexico. It was
constructed under the sponsorship of the
Office of Saline Water, United States De
partment of the Interior, to investigate and
develop a multiple-effect desalination sys
tem which utilizes large-scale solar collectors
PLANT DESCRIPTION
A Sow diagram for the pilot plant is
presented in Figure 154. Feed water for the
plant is taken from a salt water well lo
cated 50 yards from high tide. The well
intake avoids the long lines necessary to
take water directly from the sea and also
provides feed water which is free from
marine life.
Water from the well, which has a nearly
constant temperature of 78°F throughout
the year, is pumped at a flow rate of 60
gpm to the bottom of the condenser and is
shown in detail in Figure 155. The salt water
flows upward through the condenser on the
inside of high-tinned Admiralty lined alumi
num tubes (ref. 1) . These tubes are ar
ranged in five bundles housed inside the
coated metal tower. As the salt water flows
upward through the tubes, it serves as the
to provide thermal energy.
Puerto Peflasco, Sonora, Mexico, is a fish
ing village on the Gulf of California, 220
miles southwest of Tucson, Arizona. The
area has ideal meteorological conditions for
solar experimentation, while the village is
particularly suited for desalination investi
gation. The entire water supply for the
5,000 inhabitants is trucked from inland
wells at the high cost of $6.00 per 1,000
gallons.
system coolant. Water vapor from a stream
of hot moist air passing over the outside of
the fins condenses on the fins. The heat of
condensation is transferred through the
tubes and heats the sea water inside to an
exit temperature of 142°F.
The temperatures vary somewhat during
actual operation, but those used here for
illustration indicate actual plant capabilities.
From the condenser, the salt water flows
to the 86,000-gallon collector inlet reservoir.
This is an underground reservoir con
structed with vertical cement block walls,
as shown in Figure 156. The reservoir has a
sand bottom and is made watertight with a
12 mil polyvinylchloride liner. The reser
voir cover is made of plywood and is insu
lated with two inches of styrofoam.
During the eight hours of maximum solar
429
430
radiation, the 142°F salt water is pumped
at 180 gpm (three times the flow rate
through the rest of the plant) from the
collector inlet reservoir through the solar
collectors. The collectors consist basically
of three plastic films: (1) a black film
which rests directly on leveled desert sand
and is covered with two inches of sea water;
(2) a clear film which floats on the surface
of the sea water; and (3) a second clear
film which is air supported above the first
FIGURE 154. PILOT PLANT FLOW DIAGRAM.
clear film. The black film serves to absorb
solar radiation and to contain the salt
water. The first clear film prevents evap
oration, while the second clear film pro
vides an insulating layer of air above the
first film. There are five separate collectors
with a total area of 10,400 sq ft, although
for experimental runs all five collectors are
not always utilized. As the water flows
through the solar collectors, it is heated
from 142° to 150°F.
Collector Flow Diagram
Normal Collector Operation
Collector Flow Diagram
Evening Ruth
431
 From the collectors the salt water is The 150oF salt water is pumped from the
pumped at 180 gpm to the collector outlet collector outlet reservoir at 60 gpm, 24
reservoir, the design of which is identical hours per day, to the top of the packed
to that of the collector inlet reservoir. tower evaporator shown in Figure 157.

433
 1

9 Eunpty »ooils

pepod suapes

PȒC 0| i
талой ¿si aaxDVd H3MOI •>ioxvho«iva:i
 The evaporator consists of a plastic-coated
steel cylindrical shell which houses five
packed beds filled with two-inch poly
ethylene Pall rings (ref. 2) .
The 150°F salt water is pumped into a
liquid distributor in the top of the evap
orator and falls downward through the
Pall rings, spreading over their surface. A
stream of air is blown by an axivane blower
upward through the evaporator counter-
current to the falling salt water. A small
percentage (varying from three to eight
per cent) of the hot salt water evaporates
into the air stream as hot fresh water vapor.
The water vapor and air are carried
through cross-ducts to the condenser where
they pass downward over the finned tubes.
The vapor condenses on the fins as the
fresh water product.
The salt water in the evaporator is cooled
to 86°F by giving up the heat of vaporiza
tion. The excess brine is collected at the
bottom of the evaporator and pumped back
to the sea as waste. The dehumidified air
EVAPORATOR—CONDENSER PERFORMANCE
The example temperatures given in the
previous section are for the pilot plant
operating at approximately eight effects.
The number of effects, as used here, is
defined as the ratio of the amount of energy
used in the evaporator or condenser for
water production to the amount of energy
provided by the solar collectors. The
number of effects may be determined ap
proximately, neglecting the sensible heat
corrections for the air stream bv:
N', At, 142 - 78 : 8 effects
Atcoii 8
(»)
Where N'0 — approximate number of effects,
Ate — temperature gain in the condenser
and Ate„ii = the temperature gain in the
collectors. The pilot plant is designed to
operate at various number of effects as the
performance of the evaporator and con
denser are varied during experimental runs.
In the analysis of the evaporator-condenser
performance, the overall enthalpy transfer
unit method by Merkel (ref. 3) is used.
The transfer unit is defined as:
(2)
where iw is the enthalpy of air saturated
at the temperature of the main water
stream, and i. is the enthalpy of the air
stream. N, may also be shown to be equal
leaving the bottom of the condenser is re
circulated through the blower to the evap
orator. The fresh water product which falls
to the bottom of the condenser is pumped
to storage.
It can be noted from Figure 153 that, in
stead of a single cross-duct at the top of
the evaporator for carrying the hot water
vapor in the air stream to the condenser,
there are five cross-ducts spaced at various
heights between the towers. Since the water
vapor carrying capacity of air changes
rapidly with temperature, it is necessary to
circulate more air through the lower levels
(and lower temperature regions) of the
evaporator and condenser. To accomplish
this, air is bled off from the evaporator to
the condenser at appropriate levels through
the cross-ducts.
Due to the reduced air flows through the
top section of the evaporator and condenser,
the cross-sectional area of the towers is re
duced as the height increases.
to KA/Wb where К is the overall mass
transfer coefficient, A is the appropriate
area, and W„ is the brine flow rate.
Figure 158 presents a simplified flow dia
gram. Referring to that and to Figure 159
Solar
Collector
Air Cycle
l2.*,2
a.8
I ^ I
Feed Blowdown
FIGURE 158. SIMPLIFIED FLOW
DIAGRAM.
435
 which presents a sample enthalpy-tempera
ture plot for the simplified flow diagram,
an equation relating the overall number of
effects to the transfer units in each com
ponent may be derived.
Assuming steady-state condition and Wb
>> D,, where D, is the production rate,
then
At. = tM — U, = tM - tbl = At, (3)
where At. is the temperature drop in the
evaporator, At, is the temperature rise in

FIGURE 159. ENTHALPY-TEMPERATURE DIAGRAM FOR

SIMPLIFIED FLOW DIAGRAM.
■436
 the condenser, and t„ is a brine temperature
at points indicated in Figure 158. N«.= t., - t. (5)
When the slope of the operating line is
parallel to the saturation curve and the Since the line slopes are equal
saturation curve is approximated by a '•г — t.i - tb, — tbl = At. (4
straight line, then the number of transfer or
units in the evaporator may be approxi N, At,
mated by: 1ы — '»1 О
and
N«„ = - (4) N.. = At. (8)
'.i - tbl
where t, is an air temperature as indicated therefore
in Figure 158. The number of transfer units 1 'm — t«i + t.i — tbl
in the condenser may be approximated by: N.. + N.. - (»)
At.

J
)
)
)
)

Е> ponenticil Appr<Jximotio п

— CS/
ч и» 1.65 ЕХР(-С).0246l г)

0.30

0.20
о
е"
Theoreîic ol Curve

Ок.
и
оо
I

с 0.05
соф
0.04

0.03

0.02

Temperature, "F

FIGURE 160. PLOT OF SENSIBLE HEAT CORRECTION

FACTOR VS TEMPERATURE.

437
 and since
— t»i = tks — Ui = Atco,, (10)
1 Ateou
At.
Then, neglecting the energy used to warm
the air, the approximate overall number of
effects is given by:
1 The slope of the operating- lines is equal
N'.= 1 (12)
N,.
Adding the correction for air heating makes
the equation exact and is given by:
n„ = -—y-/- (13)
N, N.
where (c,/m) is the mean ratio of the
humid heat to slope of the enthalpy tem
perature saturation curve which can be
evaluated from Figure 160.
For the approximation in this deriva
tion to be valid, it is necessary that the
operating lines of the evaporator and con-
SOLAR COLLECTOR DESIGN AND CONSTRUCTION
The design of the Puerto Peftasco solar
collectors is shown in Figure 162, and the
actual construction of a collector in Tucson
is shown in Figure 163. The construction is
explained by referring to the sequence of
photographs in Figure 163.
(1) Redwood curbs are pinned to the
ground in a rectangular shape of the col
lector dimensions.
(2, 3) A black film is placed on the
ground between and over the redwood
curbs.
(4, 5) A distribution pipe is placed at the
inlet end of the collector and two inches of
salt water are pumped onto the bottom
film.
(6) An outlet pipe is installed in the
opposite end of the collector. The outlet
design was later altered in Puerto Peiiasco
collectors, as indicated by Figure 161.
(7, 8) A clear plastic film is floated on
the water surface.
(9) The bottom film, water surface film,
and shadow boards are attached to the red
wood curbs. The shadow boards protect the
edges of the black film which are not under
the water from the direct sunlight.
(10,11) The clear film is flattened on
the water surface and trimmed.
(12, 13) A second clear film is rolled over
138
always be approximately parallel to
the saturation curve of an air water mix
ture. As mentioned, this is accomplished by
increasing the ratio of the water to air flow
in the equipment as the temperature in
creases. This can be seen in Figure 161,
which presents the theoretical operating
lines for operation at N'„ = 8, neglecting
the energy input of the blower.
to Wb/W, where W, is the air flow rate.
The number of transfer units in the evap
orator can be predicted from data provided
by U. S. Stoneware (ref. 2) . The number
of transfer units in the condenser can be
calculated (ref. 4) from modified correla
tions by Ward and Young (ref. 5) for the
air side heat transfer for the finned tubes
used. The derivation can then be applied
to each section.
The evaporator-condenser height is over-
designed by a factor of almost two to allow
variation in the performance by changing
the amount of packing in the evaporator.
Also, the width of the condenser shell is
designed to allow enlarging the condenser
tube bundles.
the collector and attached to the redwood
curb.
(14) A small blower is used to inflate
the second clear film.
(15) The collector is complete.
The pilot plant has five solar collectors
utilizing different films. Black butyl rubber
(ref. 6) and black polyethylene (ref. 7)
are used for bottom films. Polyvinylchloridc
(ref. 8) and polyvinylfluoride (ref. 9) are
used for the clear films.
The solar collectors have four possible
modes of operation. Three of these are
shown in Figure 154.
In the morning the collectors are full of
cool water from nocturnal cooling, so before
the normal collector operation is begun,
the cool water is forced out of the collectors
by water from the collector inlet reservoir
and pumped to waste. This is the morning
flush cycle of Figure 154.
The collectors are operated normally for
an average period of eight hours. This
period, of course, is a seasonal function of
the length of the solar day.
At the end of normal operation, the
warm water remaining in the collectors is
forced into the collector outlet reservoir bv
diverting the plant blowdown into the col
lectors. This is the evening flush cycle of
Figure 154.
301 I I I I I
70 90 110 130 150 170
Temperature, eF

FIGURE 161. OPERATING CURVES FOR EIGHT-EFFECT

PERFORMANCE.

439
440
FIGURE 163. SOLAR COLLECTOR CONSTRUCTION SEQUENCE.

441
 A fourth mode of collector operation is
possible during cold nights. To reduce the
nocturnal cooling of the soil below the col
lector, warm plant blowdown is pumped
SOLAR COLLECTOR ANALYSIS
To correctly predict the performance of
solar collectors of the type described here,
it is necessary to determine the amount of
solar radiation absorbed by the bottom and
the amount of energy which will be lost
through the collector cover and the bottom
during the operating period.
In calculating the solar radiation ab
sorbed by the collector bottom, the total
horizontal radiation must be separated into
direct and diffuse components, and the
angle at which the direct radiation strikes
the various glazings must be determined.
The diffuse radiation may be treated as a
beam of direct radiation at an angle of
incidence of 58" (ref. 10) . The transmit -
tance of solar radiation through different
numbers of glazings may be determined
from the literature (ref. 11). With this
collector design the angle at which the
beam of direct radiation strikes the black
bottom is less than the angle of incoming
radiation, due to the difference between the
indices of refraction of air plastic and water.
This angle may be determined by Snell's
law, and the reflection from the bottom
adjusted accordingly.
Figure 164 shows the calculated absorp
tivity of the collector for various angles and
number of glazings. Figure 165 shows a
comparison between the reflection meas
ured from an operating collector in Tucson
and which is calculated in the same manner
as those in Figure 164. The difference in the
two curves is due to dust on the top
glazing and deposition on the bottom: meas
urements on clean, flat collectors showed a
closer agreement with the calculated values.
In dealing with heat losses from the col
lectors after the radiation absorbed by the
bottom has been determined, it is necessary
to compute the conduction into the ground,
the rate of convective transfer between glaz
ings, the radiative transfer between the
brine, glazings, and surroundings, and the
convective heat transfer between the top
glazing and ambient air.
The morning flush cycle of the collectors
presents a heat transfer problem which is
analogous to the classical heat conduction
through the collector to waste when the
collector temperature drops below the blow-
down temperature.
problem of heat transfer into a semiinfinite
solid suddenly exposed to a surface tem
perature change (ref. 12) . The expression
for the total heat flow into the solid or, in
the case of the collector, the ground, is
given by:
Q, = At^4k^ ^8 (H)
where At is the increase in temperature
and e is the time from the beginning of
the change in temperature.
This expression neglects heat storage from
day to day. A more realistic picture may be
gained by solving for the case in which the
temperature at the surface of a semiinfinite
solid initially at t„ is suddenly raised by an
amount At and held at this level for 0
hours, then dropped back to t„ for (24-tf)
hours, then increased by the amount At, etc.
The solution for the total heat flow into
the solid during the period 9. after cyclic
equilibrium has been attained, is shown in
Figure 166. The ordinate f(fl) from this fig
ure replaces V9 in Equation (14). For
short time periods V # «*> f (0) . however, as 0
increases, V 9 becomes greater than f (0)
due to the heat storage in the cyclic case.
Neither case is strictly correct, due to the
heat input from the sun as the brine flows
through the collector. In the classical case,
the rate of heat transfer into the soil will
drop from infinity at 9 — 0 uniformly to
a relatively constant value as the day pro
gresses. This corresponds to conditions at
the collector inlet. By the time the brine
reaches the outlet of the collector, the
heat loss curve assumes the more compli
cated shape shown in Figure 167. However,
where average temperatures are used. Fig
ure 166 usually agrees with the measured
heat loss to within ten per cent.
As Figure 162 and Equation (14) indicate,
the group kpc, or V 4kpC,/ir will largely
determine the ground conduction loss. Table
LX (ref. 13) gives typical values for this
group for various materials with different
moisture contents, as well as that of the
soil measured at Puerto Pefiasco. As the
moisture content is decreased in a given
soil, this value is rapidly reduced. The
444
445
FIGURE 167. HEAT FLOW INTO THE GROUND
NEAR COLLECTOR OUTLET.
 drying out of the soil under the solar col for air at room temperature. The geometric
lector decreases the thermal conductivity of term used in the Reynold's number in Equa
the soil and has a favorable influence on tion (18) is the collector width, which
collector performance. gives a maximum value for the coefficient.
Figure 168 compares Equation (19) with
TABLE LX. Thermal Properties experimental coefficients measured in Puerto
Determining Bottom Peñasco. The low points are caused by
changes in the direction of the wind, which
tend to increase the geometric term in the
Material V4kcpp/T к P ep Reynold's number and cause a correspond
Soil at Puerto ing decrease in the heat transfer coefficient.
Pefiaaco 1.4 0.094 100 0.17 This plot is also affected by the degree of
Sawdust (Typical) 0.Б4 0.034 12 0.ББ
Styrofoam 0.12 0.018 2 0.80 gustiness of the wind, since the coefficient
Gravel does not vary linearly with wind velocity.
0% Moisture 2.0 0.15 112 0.19
2.9% Moisture 8.8 0.36 112 0.21 Convective heat transfer coefficients be
Coarse Sand tween the black bottom and the brine in the
0% Moisture 1.8 0.12 106 0.19
Б.1% Moisture 8.9 0.Б1 112 0.21 collector are sufficiently large so that any
Medium Sand resistance between the brine plastic inter
0% Moisture 1.7 0.12 100 0.19 faces may be neglected (ref. 17) . Also, due
7.4% Moisture 3.8 0.48 106 0.22
Sandy Loam to the thinness of the plastic films, the re
0% Moisture 1.5 o.io 94 0.19 sistance to heat transfer by conduction
14.6% Moisture 4.0 0.46 100 0.27
Silt Loam through them may be neglected.
0% Moisture 1.2 0.078 87 0.18 There are a number of uncertainties in
17.8% Moisture 4.8 0.БЗ 100 0.27
Clay volved in treating the infrared radiation
0% Moisture 1.8 0.078 81 0.22 exchanges in these collectors. Most of the
28.1% Moisture 4.7 0.48 100 0.36 plastic films now available for use in solar
collectors are at least partially transparent
Convective heat transfer between the glaz to long wavelength radiation. Radiation
ings of the collector may be determined which is passed through a plastic film or
from equations presented in the literature. radiation emitted from a plastic film is not
For convective heat transfer between two gray. The term gray radiation refers to
surfaces across an enclosed horizontal air radiation for which, at each wavelength,
space. McAdams (ref. 14) gives the ex the intensity of radiation is smaller by a
pressions: fixed ratio than that for blackbody radi
NXo = 0.21 (N„rNPr) 101<NOr<3.2xl0' ation.
(15) To calculate the total infrared radiation
exchange occurring in a solar collector with
N*„ = 0.075 (N„rN„) 3-2xl0»<NOr<10' a plastic cover, monochromatic properties
(16) must be integrated over the entire wave
The latter expression normally applies to length range.
the collectors at Puerto Peñasco; the rela Monochromatic emissivity (ref. 18) is
tively large air space in the collectors nor defined as:
mally gives Grashof numbers in excess of «x = Ex/Ebx (20)
3.2 X 10*. For air at 100°F, Equation (16)
becomes where E„ is the emissive power of the sur
h^O.lZAt.1" (17) face, and Ebx is emissive power of a black-
body, both at wavelength \. Ebx may be
The convective heat transfer coefficient at evaluated for a given temperature by the
the outside of the top glazing is more diffi Planck equation or from the tables in the
cult to calculate accurately. Due to the literature (ref. 18) . For exchange between
relatively large size of the collector cover a blackbody and a plastic film, the overall
and its close proximity to the ground sur value of the emissivity of the plastic is:
face, the values (ref. 15) normally used for
smaller flat plate solar collectors do not (21)
apply. Colburn's relationship (ref. 16) for
convective transfer from flat plates is given
bv: For interchange between two plastic films,
N», NP, - 0.036 NE. -»•• (18) neglecting multiple reflections:
which simplifies to the expression:
(22)
h^O^V.0' ("»
447
448
Similarly for the transmission of blackbody
radiation through the plastic:
fori1 fib
for film (23)
for n films (24,
while for the transmission of radiation from
the plastic surface through another film of
plastic:
(86)
The evaluation here will be limited to a
particular polyvinylfluoride film, Tediar,
whose integrated radiative properties do not
change appreciably over the temperature
range of interest.
For a double glazing solar collector of
the design used in Puerto Peñasco, the rate
of heat loss through the cover is given by:
q. = {«„И + [tí]} <г( Ть'_ T. ) + ~
(T¿-T.) + h..(t„-t..) (26)
while for a three glazing collector the rate
will be:
q< = {И Ь + [г» «]} <г( Ть*_ т; ) + [г.] с
(т,4, _ Т.)+ "(т^ - Т.)+ hc
(t*,-t.m) (27)
These expressions assume that atmospheric
radiation may be approximated by black-
body radiation at T„ the apparent sky
temperature. Since atmospheric radiation
may also be nongray, this may lead to error
in some cases. Table LXI gives integrated
values for Tediar for use in Equations (26)
and (27) , based on values for Eb> from a
source at I50°F.
TABLE LXI. Properties of Tediar for
Evaluating Infrared Radiation Exchange
€ = 0.6» T"t = 0.08 f» = 0.« tV = 0.02
г» = 0.18 r»» = 0.02 Tt' = 0.07 T«e» = 0.01
The transmission of blackbody radiation
through n glazings of Tediar may be cal
culated from the expression (ref. 19) :
т*=0.3*/{1—0.45}-1 (28)
Expressions similar to Equations (26) and
(27) may be derived for any number of
glazings. In order to use this type of equa
tion to determine heat loss from the collec
tor cover for a given brine temperature
and set of ambient conditions, it is neces
sary to write a heat balance around each
glazing and solve the resulting system of
equations for the film temperatures. For
example, a balance around the second glaz
ing of a two glazing collector is given by:
(M + W «ь>(ть - T.',) + Ь-и(1* - '••)
(29)
Balances around the second and third
glazings of the three glazing collectors are
given by:
{[<]+ [««ь}*(ть4-т,4,)+ь«»
( t„ - 1„, ) = и, ( T4, _ T;, )+ Ы*
(Te4,-T4.)+h-(t.,-t.,)
(50)
M » ( т.', - т4, ) + + * M> »
( т» - тс4 ) + h«« ( '«•-'•• ) =
« ( т.! - т.* ) + h«. ( - )
(81)
For a given set of ambient conditions,
the heat balance expressions may be solved
for values of the film temperatures cor
responding to various brine temperatures
and the results applied to the overall heat
loss equations. Figure 169 shows a typical
set of heat loss curves for collectors having
one to four glazings. The ambient condi
tions chosen correspond to the yearly
average values for Tucson in 1961, between
the hours 0800 and 1600 solar time. The
apparent sky temperature was calculated
from the wet and dry bulb surface tem
peratures based on correlations in the liter
ature (ref. 20) . The equilibrium brine
temperature is less than the air temperature
for the various collectors, as the difference
between sky and ambient air temperatures
is in excess of 20eF.
An overall heat transfer coefficient may
be determined from the curves in Figure
169 based on the air temperature by ap
proximating the curves with straight lines
passing through 74.1 °F at qe - 0 and
through a point on the curve in a tern-
449
 BRINE TEMPERATURE, 9F
FIGURE 169. HEAT LOSS THROUGH COLLECTOR COVERS.
perature range of interest. For example, if
the temperature of interest is 160°F, the
coefficients will be Ue,.„ = 1.39 for two
glazings. Uc,.m = 0.89 for three glazings,
and Uc..m = 0.63 for four glazings.
Utilizing these curves, one may choose a
typical day of solar radiation data, and with
the ground loss relationships previously
given, determine the collector efficiencies for
various collector designs as a function of
average brine temperature in the collector.
Figure 170 was determined in such a man
ner, using mean hourly solar radiation data
from March of 1961, with sum angle cal
culations based on March 15. It was as
sumed that collector operation was started
at when q. = q» and ended at «, (in
450
the afternoon) when q, was also equal to
q„. That is, the collector operated over the
period 8t — Si. when q„ (the useful, or
unreflected incoming radiation) exceeded
qc (the heat loss from the cover) . Taking
the operating period at $, — with a base
temperature equal to the ambient air tem
perature, the total daily ground loss could
be determined by Figure 166. The energy
collected during the day was taken as:
Qco,,= /f», q.d»- 1f«,qcd#_Qf (32)
J #i J «i
while the efficiency was expressed by:
1=Qcii/Q. (S3)
±N30 tí3d 'A0N3OUJ3

451
 SOLAR COLLECTOR PERFORMANCE
The relationships presented in the pre from the collector inlet reservoir was
ceding section may now be used to deter 122.7°F, while the average temperature into
mine the magnitude of the various heat the collector outlet reservoir was 1J6.1°F.
losses from operating data. Based on the brine flows into and out of
Figure 171 shows the inlet and outlet brine the reservoirs, the collector efficiency was 4S
temperatures from the collectors on 24 May per cent. This is defined as the effective
1964. Blowdown from the evaporator was collector efficiency. If the curves on Figure
circulated through the collector during the 171 are multiplied by their respective load
night. Brine from the collector inlet reser ings and the difference between the curve*
voir was pumped into the collectors at integrated, an apparent efficiency of 46 per
1700 hours and the brine from the exit cent is obtained. This is defined as the
end was discharged as waste until 0750 overall collector efficiency. In comparing
hours when it was diverted into the col this data with the efficiency curves of Fig
lector outlet reservoir. Normal operation ure 170, it should be pointed out that the
was continued until 16S5 hours when the ambient wet and dry bulb temperatures
inlet stream was cut off, and blowdown was in Puerto Pefiasco on this day were ap
diverted into the collectors to flush the proximately 10°F above the temperatures
hot water remaining in the collectors into used in calculating Figure 165.
the collector outlet reservoir. The evening Table LXII gives an energy balance for
flush was ended at 1900 hours when the 24 May 1964. The balance extends over
collector exit temperature had dropped to the time period covered by Figure 171.
112°F. The average temperature of brine

TABLE LXII. Typical Solar Collector Energy 24 May 1964

Btu/.o ft per cent
(1) Total incoming solar radiation 2,513 100.00
(2) Collector efficiency (energy removed by brine) —1,162 — 48.8
(8) Reflected solar radiation — 415 — 16.5
(4) Conduction loss to ground — 1B5 - 6.2
(6) Convection from top glazing to ambient air — 268 — 10.7
(S) Radiation from top glazing to sky — 230 — 9.2
(7) Radiation from glazing on brine surface to sky — 128 - 4.9
(8) Radiation from brine to sky - 147 - 6.8
(») Storage in collector - 91 - 8.6
(10) Imbalance + 68 + 2-7

The incoming total horizontal solar radi
ation was measured with a pyrheliometer.
The reflected solar radiation was calculated
by using the curves of Figure 164. There was
no allowance for increased reflection due
to dust on the glazings, as the glazings were
cleaned just prior to this run. The conduc
tion loss into the soil was taken as the
average of the inlet and outlet losses. The
total long wave radiation from the collector
is nearly 20 per cent of the total solar
radiation, which points out the disadvan
tage of using a plastic film which is par
tially transparent to infrared radiation.
The calculation of the amount of energv
stored in the collector is based on a
weighted average temperature which de
pends on the duration of the evening
flush and the temperatures involved. The
imbalance of approximately three per cent
could indicate that one of the loss terms
was overestimated, but could also be due
to experimental error.
Figure 172 presents collector operational
data for 17 July 1964, a day close to the
example conditions in the first section.

CONCLUSIONS
The Puerto Pefiasco pilot plant operates this system is more complicated than a
at over eight effects and produces more single-effect scheme, and reliable cost com
than 5,000 gpd of distilled water from the parisons between this system and the green
energy supplied by 10,000 sq ft of solar house solar still, as well as conventional
collector area. This is approximately five distillation systems, will not be firmly
times as much water as would be produced established until the completion of the pilot
from the same collector area for a single- plant program.
effect greenhouse-type solar still. However, Preliminary cost estimates based on the

452
 T 1 1 1 1 1 1 I T r
S
tin — ~ If)

II?
111

140 h
Outlet Brine Temperature
t- 136.1
130 r-

120 h
t - 122.7

K 100 h

Ambient Temperature

Puerto Penasco 24 May 1964 /'Collector Loading

|_ Solar Radiation -2513 Btu/(sq ftXday) lb/(sq ft)(hr)
Overall Collector Efficiency = 460 %
Effective Collector Efficiency =43.0%

J L J I 1 L J L _1_ _l l_
6 7 8 9 K> II 12 13 14 15 16 17 18 19 20
LOCAL TIME, HOURS
FIGURE 171. SOLAR COLLECTOR PERFORMANCE 24 MAY 1964.

standardized estimating procedure of the range of $1.00 per 1,000 gallons.

Office of Saline Water, utilizing necessarily With the completion of the pilot plant
premature estimates of the serviceability of operation in the fall of 1965, it should be
the solar collectors, indicate the product possible to make detailed cost projections.
cost from a one mgd plant would be in the

453
 (20 h

ПО h

3 loor-
Aabient Temperature

90 h

L Puerto Peflaeco 17 July 1964 /'Collector Loading

Solar Radiation ■ 2497 Btu/(sq ft )(day) lb/(»q ftKhr)
Overall Collector Efficiency * 32 .9%
Effective Collector Efficiency «25.6 %

10 II 12 13 14 15 16 17 18 19 20
LOCAL TIME, HOURS

FIGURE 172. SOLAR COLLECTOR PERFORMANCE 17 JULY 1964.

 GLOSSARY OF TERMS
A — Appropriate area for mass trans
fer, sq ft.
c, — Specific heat of soil, Btu/lb°F.
c„ — Specific heat of air, Btu/lb°F.
c. — Humid heat of air, Btu/lb°F.
EX — Monochromatic emissive power,
Btu/(sq ft) (hr) (micron) ; E„k
for a blackbody.
g — Acceleration due to gravity, ft/hr*.
gpm — Gallons per minute.
h, — Convection heat transfer coeffi
cient, Btu/(sq ft) (hr) (°F) ; h„
at the outside of the top collec
tor cover; hci2 between covers or
glazings I and 2; and hc„ be
tween covers 2 and 3.
i — Enthalpy, Btu/lb.
K — Overall mass transfer coefficient.
Btu/(sqft) (hr) (unit Ai) .
k — Thermal conductivity of soil, Btu/
ft hr0F.
k. — Thermal conductivity of air, Btu/
ft hr°F.
L — Characteristic length term in Rey
nolds number, ft.
N„ — Overall number of effects.
— Approximate overall number of
effects.
N, — Overall enthalpy transfer unit.N,,
in evaporator, N,e in condenser.
N0r — Grashof number: x'p*g/3At//i*
a Wb — Brine flow rate, lb/hr.
Nu« — Nusselt number: hcx/k,
NPr — Prandtl number: Cp^i/k.
GREEK LETTERS
0 — Coefficient of volumetric expan-
sion, 1/°R.
< — Emissivity of Tedlar; ek ait wave-
length x.
o, — Emissivity of brine.
^ — Collector efficiency.
X — Wavelength, microns.
EQUIPMENT
1. Admiralty lined, high-finned aluminum
tubes, Catalog no. 62-0910035-26, Type
L/C, Y„ in. o.d., 0.035 in. wall, manu
factured by: Wolverine Tube. Division
of Calumet and Helca, Inc., Allen Park,
Michigan.
2. Carbon filled polyethylene two-inch
Pall rings, manufactured by: The
United States Stoneware Co.. Akron,
Ohio.
3. Butyl rubber sheet, manufactured by:
NR. — Reynolds number: LVp.//i
N„, — Stanton number: hc./c„Vp,
Q — Total heat flow, Btu/sq ft; Q,
into ground; Qcoii total gain
from collector; Q. total horizon
tal solar radiation,
q — Heat flow rate, Btu/ (sq ft) (hr) ;
qe from collector cover; q„ radi
ation absorbed by collector
bottom.
T - Absolute temperature, °R T„ of
brine; T, apparent sky tempera
ture; Tei, TC2, TCJ temperatures
of covers No. 1, 2, and 3, num
bered from brine up.
t — Temperature "F; t. air tempera
ture; tb brine temperature; t.„
ambient dry bulb air tempera
ture; Ma temperature differ
ence between glazings; Ate„n
temperature rise in collector;
At. temperature drop in evapo
rator; Atc temperature rise in
condenser; other subscripts are
the same as for T.
U. ,«| — Apparent overall cover loss heat
transfer coefficient, based on
ambient temperature, Btu/ (sq
ft) (hr) (°F) .
V — Velocity, ft/hr: Vw wind velocity,
mph.
W. — Air flow rate, lb/hr.
x — Distance between glazings, ft.
n — Viscosity of air, lb/ (fr) (hr) .
P ~ Density of soil, lb/ (cu ft) .
p. — Density of air, lb/(cu ft) .
a — Stefan—Boltzmann constant, Btu/
(sqft) (hr) CR)«.
Transmissivity of Tedlar; T> at
wavelength X.
Goodyear Tire and Rubber Co., Akron,
Ohio.
4. Polyethylene film, manufactured by:
Gering Plastics Co.. Kenilworth, New
Jersey.
5. Goodyear vinylfilm AV-1972. manufac
tured by: Goodyear Tire and Rubber
Co., Akron, Ohio.
6. Tedlar, PVF film, manufactured by:
E. I. duPont de Nemours and Co., Inc..
Wilmington, Delaware.
455
 REFERENCES
1. Perry, J. H.: "Chemical engineer's hand
book", Third Ed., New York, McGraw-
Hill (1950) p. 763.
2. Hodges, C. N.; Thompson, T. L.;
Groh, J. E.: "Separate component mul
tiple-effect solar distillation. Interim
report number 2", Solar Energy Re
search Laboratory, University of Arizona
(1963) p. 27.
3. Ward, D. j Young, E. H: "Heat
transfer and pressure drop of air in
forced convection across triangular pitch
banks of finned tubes", 2nd National
Heat Transfer Conference, A.I.CH.E.—
A.S.M.E. Reprint no. 26, Chicago, 111.
(1958) p. 15.
4. Zarem, A. M.; Erway, D. D.: "Introduc
tion to the utilization of solar energy",
McGraw-Hill (1963) p. 94.
5. Edlin, F. E.; Willauer, D. F..: "Plastic
films for solar energy applications",
United Nations Conference on New
Sources of Energy (1961) Paper no.
E./Conf. 35/S/S3.
6. Jacob, M.: "Heat transfer", vol. I, John
Wiley and Sons (1949) pp. 41 and 256.
7. Sellers, Dr. W. D.: Lecture notes, In
SUMMARY OF DISCUSSION
It was asked how many skilled and un
skilled employees are required to operate
(he plant discussed in this paper and if any
corrosion in the towers had been observed.
The reply stated that the plant can be
operated entirely by the local Mexican citi
zens who are largely unskilled, that it is
a turn-on-turn-off system, and that corro
sion to a limited extent had been observed
on impellers of pumps but that no corro
sion had been observed in the condenser.
It was asked if an energy balance of the
system could be given and if it were pos
sible to operate under cloudy conditions.
The reply stated that on cloudy days the
plant is operated on water storage and that
456
stitute of Atmospheric Physics, The
University of Arizona.
8. McAdams, W. H.: "Heat transmission",
McGraw-Hill Third Ed. (1954) p. 182.
9. Hottle, H. D.; Woertz, B. B.: "Perform
ance of flat plate solar heat collectors",
Trans. A.SM£. no. 64 (1942) pp. 91-
104.
10. Colbum, A. P.: "A method of correlat
ing forced convection heat transfer data
and a comparison with fluid friction",
Trans. Am. Inst. Chem. Engr. no. 29
(1933) pp. 174-210.
11. Jacobs, M.; Gupta, P. C: "Heat trans
fer by free convection through liquids
between two horizontal surfaces".
A.I.CH.E. Heat Transfer Research Stud
ies for 1954, pp. 15-20.
12. Eckert, E. R. G; Drake, R. M.: "Heat
and mass transfer", McGraw-Hill (1959)
pp. 364 and 373.
13. Whillier, A.: "Plastic covers for solar
collectors", vol. VII no. 3 (1963) pp.
148-151.
14. Bliss, R. W.: "Atmospheric radiation
near the surface of the ground—A sum
mary for engineers", Solar Energy vol.
V, no. 3 (1966) pp. 103-120.
an energy balance has been computed.
Operating at 140°F, the pump input is 10
per cent of solar energy. The lower the
operation temperature, the more efficient
the system. Heat losses are thereby mini
mized, but yield product is also reduced.
The system must be optimized for a given
set of conditions.
It was asked if aluminum finned tubes
would be cheaper and if any scaling had
been observed. The author stated that the
aluminum finned tubes would be cheaper
and that no scaling problems had been
encountered at Puerto Penasco. He added,
however, that the carbonate in feed water
at Tucson had been a problem.
 Le Dessalement a Cycle

D'Humidification Utilisant

L'Energie Solaire

(Rapport sur l'installation pilote de

dessalement de Puerto Penasco)

Carl N. Hodges, John £. Groh et T. Lewis Thompson

Etats-Unis d'Amérique

Sous contrat avec l'Office of Saline Water, sous forme de déchet â 30°C. L'eau dis
l'Université d'Arizona met au point un tillée tombe à la partie inférieure du
système de dessalement à effets multiples condenseur et est recueillie, formant ainsi
utilisant l'énergie solaire. Dans le cadre du le produit.
programme de développement, en coopéra Comme l'évaporateur-condenseur utilise
tion avec l'Université de Sonora, une instal l'air comme porteur pour la vapeur d'eau,
lation pilote de dessalement a été construite cette partie du système a été désignée sous
à Puerto Penasco, Sonora (Mexique) . le nom de "cycle d'humidification".
Bien que l'installation pilote utilise Par une conception correcte de l'équipe
l'énergie électrique ordinaire pour les ment et de l'échange d'air entre l'évapora-
pompes et les souffleries, le soleil constitue teur et le condenseur, il est possible de
la source d'énergie primaire du système de faire fonctionner ce cycle à la manière d'un
distillation. système à effets multiples.
L'eau de mer est chauffée à 66°C dans L'installation pilote de Puerto Penasco
des collecteurs solaires en matière plastique. utilise cinq points d'échange d'air entre
L'eau de mer chauffée est alors pompée l'évaporateur et le condenseur et fonctionne
dans un évaporateur à colonne à garnitures, à plus de huit effets tout en produisant
où environ cinq pour cent se trouve évaporé de l'eau distillée à un taux supérieur à
sous forme de vapeur chaude d'eau fraîche 15 litres par m' de surface du collecteur
dans un courant d'air en déplacement. Le solaire et par jour.
courant d'air transporte la vapeur chaude L'économie d'un procédé à humidifica
sur un condenseur à surface allongée. Le tion, à énergie solaire, ne sera pas établie
condenseur est refroidi par l'eau de mer avant l'automne de 1965 lorsque le fonc
d'arrivée 25,6°C. Au fur et à mesure de tionnement de l'installation pilote de
sa condensation, la vapeur chaude réchauffe Puerto Penasco sera terminé. Il semble
l'eau de mer de refroidissement pour cependant que le système présente des pro
l'amener à 61 °C. L'eau de mer à 61 "C messes d'être économiquement rentable dans
est alors pompée dans le collecteur solaire des régions où on à faire face au problème
pour être chauffée 66°C et le cycle se des coûts élvés de l'eau et des combulstibles
répète. L'eau de mer non évaporée dans la fossiles, mais où il y a abondance de radia
colonne à garnitures est retournée à la mer tion solaire.

457
 Опреснение с Циклом Увлажнения,
Приводимое в Действие Солнечной
Энергией
Карл Н. Ходже, Джон Е. Гро и Т. Льюис Тоисон
Соединенные Штаты Америки
Согласно договору с Управлением
по опреснению соленых вод. Универ
ситет шт. Аризона разрабатывает си
стему многоступенчатого опреснения,
приводимого в действие солнечной
энергией. За счет этой программы, про
водившейся при участии Университета
шт. Сонора, была построена опытная
опреснительная установка, которая на
ходится в Пуэрто Пеньяско, шт. Соно
ра в Мексике.
Хотя насосы и нагнетательные вен
тиляторы опытного агрегата питаются
обыкновенной электросилой, для ди-
стилляционной системы солнце являет
ся основным источником энергии.
В коллекторах солнечного тепла,
сделанных из пластмассы, морская во
да нагревается до температуры 150°F.
Затем нагретая морская вода перекачи
вается в испаритель типа «башни с на
садкой», откуда, ввиде горячего прес
новодного пара, около ее пяти процен
тов попадет в движущийся воздушный
поток. Воздушный поток переносит го
рячий пар в конденсатор большой пло
щади. Вступающей морской водой кон
денсатор охлаждается до 78°F. Во вре
мя своей конденсации горячий пар на
гревает охладительную морскую воду
до- 142" F. Затем эта вода перекачи
вается в коллектор солнечного тепла
для нагрева до 150°F и цикл повторя
458
ется. Вода, не испарившаяся в башне
с насадкой, сбрасывается при 86* F об
ратно в море. Дистиллированная вода
падает на дно конденсатора и там со
бирается в качестве опресненного про
дукта.
Так как в испарителе-конденсаторе
воздух служит носителем пара, эта
часть системы была названа «циклом
увлажнения».
При правильно спроектированном
оборудовании и воздухообмене между
испарителем и конденсатором, такой
цикл может работать, как многоступен
чатая система.
Опытная установка Пуэрто Пеньяско
имеет между испарителем и конденса
тором пять точек воздухообмена и ра
ботает более, чем с восемью ступенями,
производя свыше 0,5 галлона опреснен
ной воды в сутки на кв. фут площади
коллектора солнечного тепла.
Экономическая сторона процесса ув
лажнения, приводимого в действие сол
нечной энергией, не будет точно выяс
нена до осени 1965 г., когда закончит
ся опытная эксплуатация установки
Пуэрто Пеньяско. Однако, создается
впечатление, что система может стать
экономически привлекательной для
районов, где имеется сильное солнечное
излучение, а пресная вода, уголь и
нефть очень дороги.
Desalinizacion
Humidificacion con
(Un informe sobre la Planta Piloto de Desalinización de Puerto Peñasco)
Cari N. Hodges, Jonh E. Groh y T. Lewis Thompson
Estados Unido* de Norteamérica
La Universidad de Arizona, bajo con
trato con la Oficina de Agua Salada, está
desarrollando un sistema de desalinización
de múltiple efecto utilizando la energía
solar. Como parte del desarrollo del pro
grama, en cooperación con la Universidad
de Sonora, se ha construido una planta
piloto de desalinización en Puerto Peñasco,
Sonora, México.
Aunque la planta piloto utiliza fuerza
electromotriz convencional para bombeo )'
ventilación, el sol es la fuente primaria de
energía para el sistema de destilación.
El agua de mar es calentada en colecto
res solares de plástico a 150°F (66°C). De
aquí es bombeada a un evaporador de torre
empacada donde aproximadamente el 5% es
evaporado como vapor de agua en corriente
de aire. La corriente de aire lleva el vapor
caliente a una superficie extendida que
actúa como condensador. El condensador es
enfriado mediante agua de mar de entrada
a 780F (25"6C) . El vapor de agua, al con
densarse, calienta el agua de mar que sirve
de refrigerante hasta una temperatura de
142°F. El agua de mar a 142°F (61 °C) es
bombeada al colector de rayos solares donde
es calentada hasta 150°F (66°C) y el ciclo
se repite. El agua de mar no evaporada
en la torre empacada se vierte al mar como
por el Ciclo de
Energía Solar
deshecho a 86°F (30"C) . El agua destilada
cae a la base del condensador y es recogida
como producto.
Dado que el evaporador-condensador uti
liza aire como medio de transporte para el
vapor esa parte del sistema ha sido desig
nada "ciclo de humidificación".
Mediante el diseño correcto del equipo
y del intercambio de aire entre el evapora
dor y el condensador, es posible operar
dicho ciclo como un sistema de múltiple
efecto.
La planta de Puerto Peñasco utiliza cinco
puntos de intercambio de aire entre el
evaporador y el condensador y funciona con
más de ocho efectos produciendo agua
destilada a razón de más de 0,5 galones
por pie cuadrado de superficie de colector
solar por día.
La economía de un proceso de humidifi
cación con energía solar no será claramente
establecida hasta el otoño de 1965 fecha en
que se completará la explotación de la
planta piloto de Puerto Peñasco. Parece,
sin embargo, que el sistema promete ser
económicamente interesante en zonas en las
que existen problemas derivados de alto
costo de agua y de combustibles fósiles y
que cuentan con abundancia de energía
solar.
459
The Limitations
Water Desalting with
Membranes and
for Electrodialytic Equipment
W. G. B. Mandersloot
South Africa
SUMMARY
The application of electrodialytic desalt
ing is limited by the high electric resistance
at low electrolyte concentrations, resistance
to mass transfer (concentration polariza
tion) on the membrane surfaces, osmotic
and electro-osmotic water transport, back
diffusion of salt, co-ion transport, and the
presence of precipitate-forming substances
and poisons.
Electrodialytic equipment should satisfy
certain, often contradictory, mechanical, hy-
drodynamic, and electrical requirements.
INTRODUCTION
The principle of multicompartment elec
trodialytic desalting using permselective
membranes (Fig. 173 was conceived (ref. 1)
about ten years before the first efficient
membranes were developed. This, in turn,
led to the development of electrodialytic
equipment, further improvement of the
membranes, investigation of their proper
ties, and a better understanding of electro-
dialysis as an operation. Both electrodialytic
desalting and permselective membrane prep
aration may now be considered as well-
developed fields, and further developments
will probably be limited to refinements.
At the Woods Hole conference in 1961.
the following items were suggested (ref. 2)
for further investigation, besides the con
tinuation of equipment development:
(1) -Phenomena taking place at high mass
of Electrodialytic
Permselective
the Requirements
The SACSIR Mark III design meets these
requirements to a great extent. It uses
multislot compartment feeding with narrow
bend slots connected tangentially to the
channels through the membrane packs, thin
intermediate plates, and external manifolds.
The compartments are built up from only
two components (gasket and spacer) and
membranes. Membrane area utilization is
high (80 per cent) . The design gives good
liquid distribution over and in the com
partments.
transfer rates in and near the perm
selective membranes, including the re
lationship between mass transfer and
hydrodynamics in the spacer-filled com
partments;
(2) The production and maintenance of
poorly soluble materials in supersatu
rated conditions;
(3) The irreversible absorption of "poisons"
by the ion-exchange resin membranes.
It has become apparent that electrodia
lytic water desalting has only limited appli
cation. The points mentioned are related
to the limitations of the process. The prog
ress in recent years on reducing these
limitations and on constructional details of
the equipment are the main subjects of
this paper.
 Cathode — -Ha* -Na+ Na+ Anode
Side Side

cr — CI- —

Dlaiysate Brine Oialytate Brine

+
NoVh 0)

Counter-ion transport with

electro -osmosis co-ion
ciVh2o)- —j-NaVH20)

NaCI back -diffusion No CI

H2°-h

Brine Dlaiysate Brine

Compartment Compartment Compartment

FIGURE 173. THE PRINCIPLE OF MULTICOMPARTMENT ELEC-

TRODIALYTIC DESALTING (TOP) AND THE SIMULTANEOUS
PROCESSES IN A DIALYSATE-BRINE COMPARTMENT PAIR
(BOTTOM), + AND — INDICATE ANION-EXCHANGE AND
CATION-EXCHANGE RESIN MEMBRANES RESPECTIVELY.
L4-157S/1

THE ELECTRODIALYSIS PROCESS

The fact that the useful part of the
process—the transfer of ions from the de
salting stream (dialysate) to a more concen
trated waste stream (brine) —occurs without
a change of (water) phase was originally
considered a great advantage, because it
seemed that by reducing frictional en
ergy losses to a minimum, the energy con
sumption could approach the minimum
value determined by thermodynamics. The
lack of a phase change, the sorption of
electrolyte by membranes which have a
limited concentration of fixed ions, and
the presence of concentration gradients in
the membranes give rise, however, to the
detrimental processes of co-ion transport,
back diffusion of salt, and osmosis. These
processes set limitations in addition to those
set by unavoidable frictional losses (electric
resistance) , by concentration polarization,
and by the presence of "poisoning" or
precipitate-forming substances.

462
 ELECTRICAL RESISTANCE
In desalting brackish water, the major
electric resistance is in the dialysate com
partments, the resistance being inversely
proportional to the electrolyte concentra
tion in the dialysate. Consequently, the
electric resistance increases sharply below
about 500 ppm electrolyte in the dialysate.
To overcome this problem, the dialysate
compartments may be filled partly with ion-
conductive material (mixed ion-exchange
resin particles (ref. 3) ) and this process
comes into consideration for the treatment
of nuclear wastes. If heat is available, the
electric resistance can be decreased by oper
ating at an elevated temperature, but a
limit is set by the dimensional and chemi
cal stability of the membranes employed.
CONCENTRATION POLARIZATION
According to Faraday, virtually one gram
equivalent of ions of one charge is trans
ported through each membrane, while only
about 0.5 gram equivalent (geq) is trans
ported in the adjacent solutions toward and
away from the membrane surface. This
causes the formation of layers on the mem
brane surfaces with lower and higher elec
trolyte concentration than in bulk of the
adjacent solutions (refs. 4, 5) . The concen
tration profile for a moderate current
density is then illustrated by Figure 174. Part
of the electrolyte transport between the
bulk of the solutions and the solution mem
brane interfaces is the result of diffusion
caused by the concentration gradient. The
thickness of the layers is determined by the
hydrodynamic conditions in the compart
ments.
+ - + Ca** HCO," and Mg** are present in the
FIGURE 174. CONCENTRA
TION PROFILES IN A COM
PARTMENT PAIR.
At high current density, the electrolyte
concentration on the dialysate side of the
membranes approaches zero and conse
quently the electric resistance of the layer
becomes very high, as both the electric
potential drop across this layer and the
electric potential jump across the mem
branes (this jump being proportional to the
log of the electrolyte concentration ratio on
either side) .
High current density at low electrolyte
concentration requires a high velocity of
the hydrated ions in the polarization layer
depleted of salt. This itself leads to a dis
turbance of the layer and consequently to
a lower effective thickness. This effect can
be expected to be more pronounced when
the ions passing toward the adjacent mem
brane are more hydrated than the ions of
opposite charge (e.g., cations moving to
wards a cation-exchange resin membrane
compared to anions moving toward an
anion-exchange membrane) . Through the
disturbance of the layer by the highly
hydrated ions passing at high velocity, the
electrolyte concentration at the membrane
interface may be kept away from zero to
such an extent that the hydrogen ions from
the water do not get a chance to carry a
considerable part of the total current, and
water splitting is then negligible. This view
is in accordance with the observation that
relatively less hydrogen transport occurs
through the cation-exchange membranes
than hydroxyl ion transport through the
anion-exchange membranes when desalting
an initially neutral NaCl solution under
polarizing conditions. This results in an
acid dialysate and alkalinity in the brine
and it may lead to the precipitation of, for
example, CaCO, and Mg (OH), (when
water) on the brine side of the anion-
exchange membranes through which OH-
ions move from the polarization layer on
the dialysate side. Cooke (ref. 6) has
pointed to the strong cation-water inter
action and the relatively weak anion-water
interaction. It is not clear how interfacial
microstreaming (ref. 7) could explain the
high ration of hydroxyl ions over hydrogen
ions transported even under slightly polariz
ing conditions.
The work on the influence of the hydro-
dynamic conditions in the compartments on
the degree of polarization was reviewed
recently (ref. 8) . It was concluded that the
limiting current density, bulk electrolyte
concentration, and flow velocity could be
correlated in analogy to the usual correla
tion for polarization on electrodes for
463
 transitional type of flow. The established
relationship between the variables involved
can be used to prove that, when desalting
sea water or highly brackish water electro
dialytically, a tapered flow path (or other
measures to increase the liquid velocity with
progressive desalting) is useful (ref. 9) .
The importance of polarization lies in
the fact that the present cost of membranes
requires operation at high current densities
to approach the economic optimum oper
ating conditions. The many limitations of
the application of electrodialysis prevent
large-scale developments and related cost
reductions. Large-scale application of ion-
exchange resin membranes in electrochemi
cal inorganic and organic processes may
improve matters in the future.
OSMOTIC AND ELECTRO-OSMOTIC
WATER TRANSPORT
The ions transported through the mem
branes are hydrated ions, therefore, a mini
mum water transport of about 10 gmol
H,0 per gram equivalent NaCl is found
(Fig. 175) . At brackish water concentrations,
the specific water transfer is often higher
because osmotic water transport occurs, in
addition to electro-osmotic transfer, when
a concentration difference exists between
brine and dialysate. Below drinking water
concentrations in the dialysate and with a
80r
OIALYSATE CONCENTRATION geq/l
FIGURE 175. THE WATER TRANSFER FROM DIALYSATE TO
BRINE PER GEQ OF SALT TRANSPORTED. MEMBRANES:
A.M.F. 3129-B; 0.75 V PER COMPARTMENT PAIR.
L4-1573/6
464
concentrated brine, the specific total water
transported may amount to several hun
dreds of gmol H,0 per gram equivalent
NaCl at the low current densities used at
these low concentrations.
It has been shown (ref. 10) that electro-
osmotic water transfer is the major reason
that the electrodialysis process cannot be
efficient when large desalting ranges are
involved (e.g., from sea water to drinking
water) . At very low electrolyte concentra
tions in the dialysate, osmotic water transfer
may become excessive unless the brine is
also of low concentration (ref. 3) , but that
would introduce extra electric resistance. In
the slightly brackish water concentration
range, the volume changes due to water
transfer are of minor importance. The
presence of ions other than Na* and Cl~
may cause a slightly higher water transfer.
BACK DIFFUSION OF SALT AND
CO-ION TRANSPORT
The electrolyte concentration difference
l>etween brine and dialysate gives rise to
the diffusion of salt from one stream to the
other: this process is exactly the opposite
of the desired desalting. When the electro
lyte concentration in the dialysate is close
to drinking water composition, the back
diffusion of salt can easily reach a consider
able percentage of the total salt transfer
because current density is limited by the
high resistance of the dialysate and polar
ization. Consequently, the coulomb efficiency
of the desalting process decreases pro
gressively with a decrease in electrolyte
concentration in the dialysate.
The rate of salt diffusion through the
membranes is determined mainly by the
concentration difference of the adjacent
solutions, the concentration of fixed ions
in the membranes, the membrane thickness
(ref. 11), and the interaction between
diffusion and osmosis (refs. 12, 13, 14) . The
transport of co-ions (ions with the same
charge as the fixed ions in the membranes)
is determined by much the same factors as
is back diffusion, but the deciding electro
lyte concentration (except in anomalous
cases (ref. IS)) is the concentration in the
brine rather than the concentration differ
ence across the membranes.
The effect of back diffusion on efficiency:
In recent years the mathematical descrip
tion of electrodialytic desalting has been
given considerable attention because rele
vant equations are required for process
optimization with respect to cost and for
cost estimates for intended applications. It
is customary to relate the compartment pair
resistance to the other major variable, the
local or log mean electrolyte concentration
in the dialysate (refs. 10, 15, 16) , because
there is a physical relationship between
these variables. Only Tye (ref. 17) uses an
empirical relationship between the resist
ance and the dialysate outlet concentration
for which no physical ground exists. In all
this work, a constant (average) value is
assigned to the "coulomb efficiency", or to
the "overall efficiency" of the process, and
only in the "overall efficiency" (ref. 10) is
water transfer taken into account. The
theory for the prediction of production
rate and power consumption is then valid
only if no serious deterioration of efficiency
occurs due to the back diffusion of salt from
brine to dialysate.
It was shown previously (ref. 10) that
the rate of desalting can be expressed by
dC AE
— ~H— - K— * *
' FVT(a + _) (1)
when using an overall eaciency factor
and by
dC AE (1 - 2HC)
dt FVT (a + 1) (1 _ HCt) (2)
when using the coulomb efficiency <p.
If, however, the coulomb efficiency is re
placed by the efficiency due to the transport
numbers of the counter-ions in the two
membranes and, additionally, a term ex
pressing the back diffusion rate (making
the approximation that the back diffusion
is proportional to the concentration differ
ence across the membranes) , then the de
salting rate can be expressed by
dC _ AE (1 - 2HC) -
dt FVT (a + -1) (1 - 2HC,)
AD (B _ C) (1 - 2HC) (S)
VT (1 _ HCx)
in which the last term is the back diffusion
term, which was incorporated in <p' in
Equation (2) .
The relation between the overall efficiency
<p and t can now be expressed by
1 - 2HC
9 ~ 1 - 2HCX
t — FD (Bv _ C)' (a
K +^ -£-)
C ' (4)
E J
or in words: the overall efficiency is the
product of a water transport correction
factor and the difference between the effi
ciency due to the transport numbers of the
counter-ions in the membranes and relative
contribution of back diffusion. In this
respect, it should be remembered that the
.term a -)-, —
b is. the
. compartment pair resist-
ance and, therefore, E — is the current
b
a+c
density at dialysate concentration C. A
numerical example of the part in Equation
(4) between square brackets is shown in
Figure 176.
PRESENCE OF PRECIPITATE-FORMING
IONS AND POISONS
Three types of troublesome components
may be present in the feed water:
(1) Inorganic ions which form precipitates,
either because of pH changes in the
polarization layers or because of satura
tion (e.g.. CaSO, in the brine (ref.
18) ). Preferential ion transport (ref.
19) can make a considerable contribu
tion to the accumulation of certain ions
in the brine.
(2) Ions which are very strongly or irre
versibly absorbed by the ion-exchange
resin membranes and which conse
quently cause an increase of membrane
resistance and often a decrease of mem
465
 brane selectivity (e.g., many multi
valent cations and organic anions such
as humic acids) .
(3) Colloidal matter and organic ions stable
in a specific pH range only (e.g., clay,
silica, and proteinaceous matter) .
Electrodialytic desalting has been con
sidered or used for borehole water, mine
water, river and sea water, glycerol (ref.
20) , glucose, milk whey, irrigation drainage
water (ref. 21) , and treated sewage works
effluent (ref. 22a) . Very few waters were
found without at least one of the trouble
some components. Removal by pretreatment
before desalting may be technically possible
in many cases, but the cost involved is often
considerable when compared with desalting
ELECTRODIALYTIC EQUIPMENT
The electrodialytic desalting plant which
was in operation at the Free State Ceduld
mine (ref. 27) revealed certain shortcom
ings (refs. 28, 29) , such as leakage between
the dialysate and brine systems within the
membrane packs. Subsequently, the design
was reviewed and the desirable features of
electrodialytic equipment were considered,
taking into account mechanical, hydrody-
namic. and electrical aspects.
costs (ref. 23) .
Special operation techniques such as the
use of short pulses of reversed current
(refs. 5, 24) may be used to prevent the
building up of scale on the membranes,
but it is doubtful (ref. 22b) that the pre
cipitation of colloidal matter and organic
fouling of the membranes can be combated
by this technique. Daily reversals of current
direction, with a simultaneous switchover
of brine and dialysate compartments, were
found to be ineffective against organic foul
ing (ref. 25) without the use of pretreat
ment. Even membranes specially prepared
for the purpose are not completely free
from organic fouling (ref. 26) .
MECHANICAL ASPECTS
The mechanical aspects incorporate de
sign as well as the selection of suitable
materials. The requirements are:
(1) The membrane surface area utilization
should be at least around 80 per cent,
because membrane cost is one of the
important contributions to total cost.
(2) There should be few components per
 compartment pair to facilitate easy
assembly of membrane packs.
(3) The gasket material should be readily
available and exhibit negligible cold
flow.
(4) The membranes should be supported in
the active area by a spacer material
which causes effective depolarization
under practical hydrodynamic con
ditions.
(5) The intersystem leakage in the liquid
distribution area of the gaskets should
be negligible.
(6) The membranes should remain flat in
one plane so that brittle membranes
can be used.
(7) The sealing of the membrane packs
should be achieved with a low sealing
pressure so that the support structure
can be light.
(8) There should be few electrodes in a
membrane stack and the stack should
be subdivided into membrane packs
which can be handled separately.
(9) The compartment size should be such
that various makes of membranes can
be accommodated.
HYDRODYNAMIC ASPECTS
The general problem of getting liquid
into and out of adjacent compartments
about 1 mm thick can be specified further
as:
(1) The liquid introduction into (and
withdrawal from) the compartments
should be divided over the edge of each
compartment to prevent the develop
ment of active membrane areas with
lower liquid velocities in which polar
ization may occur and scaling may
start.
(2) The liquid should be distributed evenly
to all compartments of each system;
this requires a low flow resistance in
the liquid channels formed by the cor
responding holes in gaskets and mem
branes.
(3) The liquid should be distributed evenly
to all channels of each system; this re
quires a low flow resistance in the
manifold.
(4) The pressure drop should be low, par
ticularly in the connections between
channels and compartments: the pres
sure drop in the compartments them
selves can have a useful depolarization
effect.
ELECTRICAL ASPECTS
The prevention of electrical leakage (refs.
30, 31, 32) requires that:
(1) The liquid channels through the mem
brane packs, particularly those of the
brine system, should have a small
cross-sectional area; this requirement
contradicts the requirement of low flow
resistance ( (2) in the above section) .
(2) The connection between channels and
compartments should have a high elec
trical resistance; this requirement con
tradicts the requirement of low flow
resistance ( (4) in above section) .
(3) The number of brine compartments
connected to one set of channels should
he low.
THE SACSIR MARK III DESIGN (REF. 331
In this design it was attempted to in
corporate as many of the useful features
mentioned in the previous sections as pos
sible. One membrane pack of 72 compart
ment pairs was built and submitted to
various tests extended over a period of
about two years, so that some of the tests
were carried out after a considerable life
time had been attained.
Compartment shape and size: To accom
modate various makes of membranes avail
able on the market, it was decided to use a
membrane width of 50 cm and length of
110 cm. The dimensions of the gaskets con
fining the compartments (Fig. 177) are
slightly larger; this provided very good
sealing so that no external leakage occurred
from the edges of the membrane pack. The
gasket material used is "Klingerit" steam-
jointing one-thirty second of an inch thick.
The center (active) area in the gaskets is
filled with a corrugated, perforated spacer
material, as used previously in the Free
State Geduld plant. The corrugations form
an angle of 15° with the long vertical axis
of the compartments, taking opposite angles
in the adjacent brine and dialysate com
partments. The membrane area utilization
amounts to 80 per cent, which is considered
very high for the compartment size used.
Liquid distribution: The liquid distribu
tion in the compartments was judged to be
good because no scale formation occurred
except in a few compartments which were
confined by uneven membranes. The good
liquid distribution is attributed to jet
effects and convection caused by the very
high liquid velocities at the points where
the narrow slots meet the compartment
edge, and to the fact that the slots are not
perpendicular to this edge. The velocity
in the slots is about thirty times as high as
the velocity in the compartment.
The liquid distribution over the compart-
467

FIGURE 177. GASKET FOR
SACSIR MARK III COMPART
MENTS.
merits was judged to be good from retention
time distribution data obtained by means
of an acid injection. A precise interpreta
tion of the results is impossible because a
large part of the observed retention time
spread is caused by retention in the mani
fold and in the channels through the mem
brane pack.
All channels were fed from both sides of
the membrane pack so that the maximum
velocity at both ends of each channel was
about 1 ft/sec for a velocity of 10 cm/sec
in the compartments (for a pack containing
75 compartment pairs) . The channels were
formed by double rows of holes in the
gaskets and membranes, each pair of chan
nels having one external connection on the
intermediate plate. The interconnection of
the channels of each system was made in
external manifolds of generous dimensions
so that the intermediate plates confining a
membrane pack could be only 1 inch thick,
and the channel and slot area of the mem
branes was reduced to a minimum. The
double rows of channels allowed two slot
468
connections per compartment for each single
connection on the intermediate plate.
Pressure drop: When designing the slot
feeding system, it was impossible to estimate
the pressure drop in the selected narrow
slot feeding system, but previous results on
a laboratory pack were promising. To im
prove matters as much as possible, the slots
were connected tangentially to the channels.
With a pack of 72 compartment pairs, a
total pressure drop of about 4 lb/sq in. was
measured for a liquid velocity of 8 cm/sec
in all compartments. This was a great im
provement over the previous design.
Intercompartmental leakage; The meas
ures taken against intercompartmental leak
age were: (1) the use of very narrow slots
of 1 mm width which were bent to prevent
the sagging of the membranes into the slots,
and (2) the formation of a liquid leakage
path on the "wrong" side of the mem
branes. In leakage tests, flimsy plastic sheets
were used instead of ion-exchange resin
membranes, so that salt diffusion through
the membranes was eliminated and the
leakage could be determined by measuring
salt concentration changes in the dialysate
when circulating a more concentrated brine.
When using equal flow rates and equal
inlet and outlet pressures for brine and
dialysate, no intercompartmental leakage
could be measured. But even with grossly
different flow rates in the two systems and
consequently different pressures, the leakage
was small compared with the diffusional
salt transfer through ion-exchange resin
membranes.
Desalting tests: In desalting runs with
CSIR-PS and TA membranes the following
results were obtained:
c„ CT B F. <
0.057 0.0034 0.1 1 1.00 0.84
0.079 0.0062 0.70 0.75 0.65
0.027 0.0055 0.13 1.04 0.86
0.043 0.0025 0.14 1.04 0.84
0.170 0.0081 0.60 1.04 0.78
0.152 0.0080 0.37 1.04 0.78
0.155 0.0105 0.20 1.04 0.84
Electrical leakage (ref. 32) : Using very-
narrow slots, the electric resistance between
brine compartments and brine channels is
a factor of about 107 as high as the com
partment pair resistance and, for the finite
number of compartment pairs (72) used
per membrane pack, this should be ade
quate to achieve a very low leakage per
centage.
 CONCLUSIONS
ElectTodialytic desalting can find only The SACSIR Mark III design meets the
limited commercial application because of requirements of electrodialytic equipment
the electric, physico-chemical, and hydro- with respect to mechanical, hydrodynamic,
dynamic factors involved. and electrical aspects.

NOMENCLATURE
A Total active compart cm" C Electrolyte concen- geq-1"1
ment pair area tration in dialysate
E Voltage drop per com Volt dC/dt Electrolyte concen- geq.l-'.s-1
partment pair tration change rate
,fi Overall efficiency H Specific water transfer 1 .geq-1
q[ Coulomb efficiency C, Product electrolyte g^-1"1
concentration
T Efficiency due to Salt diffusion rate per Lcra"^"1
transport numbers unit area of compart
counter-ions ment pair and per unit
F Faraday 96500 Coul.s-> concentration difference
VT Volume of dialysate at 1 Electrolyte concen - geq . 1 -1
product concentration tration in brine
a Constant O.cm1 Initial electrolyte con- g^l-l-1
b Constant Ocm'.geq.l-1 centration in dialysate

REFERENCES
1. Meyer, K. H.; Strauss, W.: Helv. Chim.
Acta no. 23 (1940) p. 795.
2. McRae, W. A.: Nat. Acad. Sci.-Nat.
Res. Council Publ. no. 942 Washing
ton, D. C. (1963) .
3. Gittens, G. J.; Glueckhauf, E.: Proc.
Am. Inst. Chem. Eng.—Inst. Chem.
Eng. Joint Meeting, Section 9 London
(1965) p. 67.
4. Partridge, S. M.; Peers, A. M.: ]. Appl.
Chem. no. 8 (1958) p. 49.
5. Spiegler, K. S.: Adv. Chem. Series no.
38 (1963) p. 179.
6. Cooke, B. A.; van der Walt, S. J.:
Electrochim. Acta no. 5 (1961) p. 216.
7. Frilette, V. J.: /. Phys. Chem. no. 61
(1957) p. 168.
8. Mandersloot, W. G. B.; Hicks, R. E.:
/. and E.C. Proc. Des. Dev., in press.
9. Mandersloot, W. G. B.; Koen, J.:
/. and E.C. Proc. Des. Dev., in press.
10. Mandersloot, W. G. B.: /. Electrochem.
Soc. no. Ill (1964) p. 838.
11. Wills, G. B.; Lightfoot, E. N.: Am.
Inst. Chem. Eng. J. no. 7 (1961) p.
273.
12. Eder, G.: Z. Phys. Chem. N.F. no. 39
(1963) p. 218.
13. Mandersloot, W. G. B.: Electrochim.
Acta no. 9 (1964) p. 395.
14. Dorst. W.; Staverman, A. J.; Cara-
mazza. R.: Recueil no. 83 (1964) p.
1329.
15. Ments, M. V.: Ind. Eng. Chem. no. 32
(1960) p. 149.
16. Solt, G. S.: Trans. Inst. Chem. Eng.
no. 41 (1963) p. 365.
17. Tye, F. L.: Trans. Inst. Chem. Eng.
no. 41 (1963) p. 72.
18. Lurie, R. M.; Berg, M. E.; Giuffrida,
A.: Office of Saline Water R. & D.
Rept. no. 48, PB171261, Washington,
D. C. (1961) .
19. Mandersloot, W. G. B.: Bull. Chem.
Soc. Japan no. 37 (1964) p. 1442.
20. Sanders, B. H.; Parsi, E. J.: Proc.
Symp. on Less Common Means of Sep
aration, Inst. Chem. Eng. (1962) p. 16.
21. Baker, W. K.; Weiner, S. A.; Howe,
E. D.: Univ. Calif., Sea Water Conv.
Lab. Rept. no. 64-2 (1964) .
22a. Stephan. D. G.: Proc. Am. Inst. Chem.
Eng.—Inst. Chem. Eng. Joint Meeting,
Section 9 London (1965) p. 25.
22b. Koen, J.; Mandersloot, W. G. B.:
S.A.C.S.I.R. Rept. C. Chem. no. 79
(1965).
23. Seko, M.: Dechema Monogr. no. 47
(1962) p. 575.
24. Forgacs, C; Matz, R.: Dechema
Monogr. no. 47 (1962) p. 601.
25. Hoeting, W. A. G.: Paper read at the
Milano meeting of Europ. Fed. Chem.
Eng.. Water Desalting Working Party
(June 1965) .

469
 26. Olie, J. R.: Paper read at the Milano
meeting of Europ. Fed. Chem. Eng.,
Water Desalting Working Party (June
1965).
27. Wilson, J. R.; Carman, P. C.- "De-
mineralization by electrodialysis", But-
terworths, London (1960) .
28. Volckman, O. B.: Adv. Chem. Series
no. 38 (1963) p. 133.
20. Wilson, J. R.: Trans. Inst. Chem. Eng.
no. 41 (1963) p. 3.
SUMMARY OF DISCUSSION
It was asked what materials were used for
the perimeter gaskets and electrodes and
how the perimeter gaskets were fabricated.
The reply stated that stainless steel was
used for the cathode and that platinized
titanium was used for the anode. With re
spect to the perimeter gaskets, it was stated
that the material was Klingerite steam
jointing ordered from the Klingerite Com
pany in England and that this company
punched both the holes and the slots in
accordance with dimensional tolerances
established by SACSIR.
It was asked if an investigation had been
Limitations du Dessalement de L'Eau
Par Electrodialyse
Membranes Permoselectives
Conditions Requises Pour
L'Equipment D'Electrodialyse
W. G. B. Mandersloot
Afrique du Sud
Lorsque Ton discute le dessalement clec-
trodialytique, il faut tenir comptc du fait
qu'un certain nombre de procedes se pro-
duisent simultancment. Le transfert de
l'eau affectc enormement l'efficacitc d'en-
semble dans le cas de larges gammes de
dessalement. comme pendant la conversion
de l'eau de met. La diffusion en retour des
470
SO. Wilson, J. R.; Carman, P. C: "De-
mineralization by electrodialysis, But-
terworths, London (1960) p. 256.
31. Solt. G. S.: Proc. Am. Inst. Chem. Eng.
—Inst. Chem. Eng. Jo nt Meeting, Sec
tion 9 London (1965) p. 7.
32. Hicks, R. E.; Mandersloot, W. G. B.:
"Electrical leakage in electrodialysis
units", SACSIR Report, in prepartion.
33. Hicks, R. E.; Mandersloot. W. G. B.:
"SACSIR Mark III electrodialysis unit",
SACSIR Report, in preparation.
made of the current distribution across the
electrode face and whether or not a full -face
electrode was used. The reply stated that
current distribution had not been checked
in the SACSIR Mark III design but that
earlier laboratory tests made with smaller
stack designs had shown that the distribu
tion will tend to even out quickly. There
fore, it is not believed that this presents a
problem in the Mark III design, particu
larly when intermediate pack construction
is used. The author also said that a full-
face electrode is not used.
Avec Des
et
sels est le procede le plus detrimental a de
faibles concentrations d'electrolyte.
La presence de substances formant des
precipit£s ou des poisons, soit des ions
mineraux, soit des ions qui sont fortement
ou mcme irreversiblement absorbs par la
resine echangeuse d'ions, soit des matieres
colloidales (par exemple, argile. silice) , et
des ions organiques qui ne sont stables
que dans une gamme spécifique de pH (par
exemple, matière protéinacée) peut inter
férer avec le bon fonctionnement du
procédé.
La polarisation de la concentration est
un autre facteur limitatif dans l'électro-
dialyse. L'efficacité du support de la mem
brane pour encourager le transfert convectif
des sels vers la surface de la membrane
est une considération importante dans la
construction du compartiment (cellule) . Le
rapport entre la densité limitative du
courant, la concentration de l'électrolyte
dans le dialysat et la vélocité du courant est
donné par l'équation:
illm/Cii» nm ~ к • Ve
dans laquelle n est une caractéristique pour
le courant de transition (d'une valeur entre
0,5 et 0,8) .
Les caractéristiques désirables de l'équipe
ment électrodialytique sont:
(A) Aspects mécaniques
(1) Utilisation de l'aire superficielle de
la membrane;
(2) Peu de pièces par paire de comparti
ments (cellules) ;
(3) Matière à joint d'une disponibilité
facile, sans fiuage (déformation à
froid);
(4) Support de membrane avec proprié
tés adéquates de dépolarisation;
(5) Fuites négligeables à l'intérieur du
système;
(6) Position à plat de la membrane
pour faciliter l'utilisation de mem
branes fragiles et bon marché;
(7) Faible pression de scellement et
structure de support légère;
(8) Subdivision en "blocs" de membranes;
(9) Dimension de compartiment (cel
lule) pouvant convenir pour diffé
rentes marques de membranes.
(B) Aspects hydrodynamiques
(1) Distribution du liquide le long des
bords des compartiments (cellules) ;
(2) Distribution du liquide dans l'en
semble des compartiments (cellules);
(3) Distribution du liquide dans tous les
canaux à travers le bloc de mem
branes;
(4) Faible chute de pression (point
critique: introduction du liquide
dans les compartiments [cellules]) .
(C) Aspects électriques
(1) Petits canaux de saumure;
(2) Résistance électrique élevée en liai
son entre les compartiments (cel
lules) et les canaux;
(3) Petit nombre de compartiments
(cellules) de saumure reliés à un
jeu de canaux.
L'appareil SACSIR Mark III incorpore la
plupart des caractéristiques désirables.
L'alimentation des compartiments (cellules)
se fait par des rainures coudées étroites qui
empêchent les fuites entre courants et
donnent une haute résistance électrique
dans les connexions entre canaux et com
partiments (cellules) . L'utilisation de la
surface est élevée (80%) , ce qui a pu se
faire en plaçant les distributeurs à l'exté
rieur des plaques intermédiaires. Ceci, à
son tour, permet des plaques intermédiaires
minces. La chute de pression dans le sys
tème n'est que d'environ 0,28 kg/cm! à une
vélocité de liquide de 8 cm/sec dans les
compartiments (cellules) .
Le dessalement électrodialytique ne peut
trouver que des applications commerciales
limitées à cause des limitations électriques,
physico-chimiques et hydrodynamiques. Il
y a donc plus de place pour la cooperation
que pour la concurrence dans ce domaine.
471
 Недостатки Опреснения Воды Путем
Электродиализа с Селективно
Проницаемыми Мембранами
и Требования, Предъявляемые
к Электродиалитическому Оборудованию
У. Г. Б. Мандерслут
Южная Африка
При обсуждении опреснения посред
ством электродиализа надо иметь в ви
ду, что там ряд процессов протекает ются:
одновременно. При широких пределах (А) С механической точкк зрения
обессоливания перенос воды сильно
влияет на общий коэффициент полез
ного действия, как например при опре
снении морской воды. При низких кон
центрациях электролита обратная диф
фузия соли является наиболее важным
процессом в смысле своей вредности.
Правильная работа процесса может
быть нарушена, когда в воде находят
ся образующие осадки или ядовитые
вещества; неорганические и такие ионы,
которые сильно или Даже необратимо
абсорбируются ионообменными смола
ми; коллоидная материя (например,
глина, двуокись кремния) и органичес
кие ионы, которые стабильны (напри
мер, белковая материя) только в спе
цифических пределах pH.
Концентрационная поляризация слу
жит еще одним ограничительным фак
тором электродиализа.
При проектировании ячеек важным
условием является эффективность опо
ры мембраны, ускоряющей перенос со
ли к поверхности мембраны путем кон
векции.
Зависимость между предельной плот
ностью тока, концентрацией электроли
та в диализате и скоростью потока
дается уравнением:
I пред. _к.у.
С1п средн.
где п = 0,5 - 0,8 = характеристика, от
носящаяся к промежуточному потоку.
472
Желаемыми характеристиками элек-
тродиалитического оборудования явля
(I) Использование площади по
верхности мембран
(II) Малое количество составных
частей в каждой паре ячеек
(III) Легко находимый в продаже
материал для прокладок, не
подвергающийся деформаци
ям при низких температурах
(IV) Опорное устройство мемб
ран, обладающее хорошими
деполяризационными свой
ствами
(V) Незначительные утечки вну
три системы
(VI) Плоское расположение мем
бран, при котором можно
свободно пользоваться де
шевыми хрупкими мембра
нами
(VII) Низкое давление при уплот
нении пленки и легкая кон
струкция опоры
(VIII) Подразделение на мембран
ные группы
(IX) Размеры ячеек, подходящие
для мембран различной вы
работки
(Б) С гидродинамической точки зрения
(I) Распределение (растекание)
жидкости вдоль краев ячеек
(II) Распределение жидкости по
всем ячейкам
 (III) Распределение жидкости по
всем каналам, проходящим
через группу мембран
(IV) Низкий перепад давлений
(критическая точка: при
входе жидкости в ячейку)
(С) С электрической точки зрения
(I) Малые каналы для рассола
(II) Высокое электрическое со
противление в местах соеди
нения ячеек с каналами
(III) Малое количество ячеек для
рассола, соединенных с од
ной группой каналов
Конструкция SACSIR Марка III со
держит большую часть рекомендуемых
характеристик. Питание ячеек произ
водится с помощью узких изогнутых
Limitaciones de la Desalinizacion de
Agua por Electrodialisis
branas Permeables
Requerimientos de Equipo de
Electrodialisis
W. G. B. Mandersloot
Africa del Sur
Cuando se discute la desalinización por
electrodiálisis debe tenerse en cuenta que
ocurren simultáneamente un número de
procesos. La transferencia de agua afecta
significativamente la eficiencia global cuan
do se trata de un alto grado de desaliniza
ción como en el caso de agua de mar.
Difusión de sal en sentido contrario, es uno
de los procesos perjudiciales más impor
tantes a bajas concentraciones de electrólito.
La presencia de sustancias capaces de
formar precipitados o venenos, ya sea iones
inorgánicos o iones que son absorbidos
tenaz o irreversiblemente por la resina de
intercambio iónico, o materia coloidal (por
ejemplo, arcilla, silice) , e iones orgánicos
que son estables solamente en un determi
nado intervalo de pH (por ejemplo, mate
прорезов, которые предохраняют от
междупоточных утечек и обладают вы
соким электрическим сопротивлением в
местах соединения каналов и ячеек.
Использование площади высоко (80%),
что можно достичь, размещая трубы
вне промежуточных тарелок. В свою
очередь, это дает возможность пользо
ваться тонкими промежуточными та
релками. Перепад давлений в системе
достигает только 4 фунтов/кв. дюйм
при скорости жидкости в ячейках 8
см/сек.
Из за электрических, физико-хими
ческих и гидродинамических недостат
ков коммерческое опреснение посред
ством электродиализа ограничено. От
того в этой области больше призывают
к сотрудничеству, чем к конкуренции.
con Mem
Selectivas y los
rias proteicas) pueden interferir con el
funcionamicto normal del proceso.
Otro factor limitante en la electrodiálisis
es la polarización de concentración. La
efectividad del soporte de la membrana en
promover la transferencia de sal por con
vección hacia la superficie de la membrana
es una consideración mayor en el diseño del
compartimiento. La correlación entre la
densidad de corriente límite, concentración
del electrólito en el disalizado y la velocidad
de flujo está dada por la ecuación.
4im/cln medio = k. v"
en la que n es un valor característico del
flujo de transición (con valores entre 0,5
y 0,8) .
Las características deseables del equipo
de electrodiálisis son:
473
 (A) Aspectos Mecánicos
(1) Un área de utilización de la super
ficie de la membrana mayor del 80%;
(2) Pocos elementos por par de compar
timientos;
(3) £1 material de empaquetadura debe
ser fácilmente obtenible y no debe
tener flujo en frío;
(4) El soporte de la membrana debe
tener propiedades de despolarización
en grado suficiente;
(5) Pérdidas despreciables entre los sis
temas;
(6) Posición plana de las membranas
para facilitar el uso de membranas
quebradizas baratas;
(7) Presión de sellado baja y estructuras
de soporte livianas;
(8) Subdivisión en conjuntos de mem
branas;
(9) Tamaño de compartimientos conve
nientes para membranas de distintos
fabricantes.
(B) Aspectos Hidrodinámicos
(1) Distribución del liquido sobre el
borde de los compartimientos;
(2) Distribución del liquido en todos los
compartimientos;
(5) Distribución del líquido en todos los
canales a través del conjunto de
membranas;
474
(4) Poca calda de presión (Punto critico:
introducción del liquido en los com
partimientos) .
(C) Aspectos Eléctricos
(1) Canales de salmuera pequeños;
(2) Resistencia eléctrica alta en las co
nexiones entre compartimientos y
canales;
(3) Bajo número de compartimientos de
salmuera conectados a un conjunto
de canales.
El diseño SACSIR Mark III incorpora la
mayoría de las características deseadas. La
alimentación de los compartimientos es
efectuada con canales curvos estrechos que
previenen pérdidas entre corrientes y dan
una alta resistencia eléctrica en las cone
xiones entre canales y compartimientos. El
área de utilización es alta (80 por ciento)
lo que pudo ser logrado colocando los
múltiples fuera de las placas intermedia
rias. Esto, a su vez, permite placas inter
medias delgadas. La caída de presión en el
sistema es solamente de alrededor de 4
lb/pulg. cuad. a una velocidad del líquido
de 8 cm/seg. en los compartimientos.
La desalinización por electrodiálisis pue
de ser comercialmentc aplicada en forma
limitada debido a las limitaciones eléctri
cas, físico-químicas e hidrodinámicas. Por
lo tanto, la cooperación es mucho más
necesaria que la competencia en este campo.
 Utilization of Desalinated Water

in Japan

Masao Hashizume

Nowadays, many cities in Japan fre Moreover, the concentration of the popu
quently shut off the supply of water, lation in cities and the prosperity of indus
making the need for water more serious. tries accelerate the shortage of water. We
Japan has approximately 1,600 mm (60 cannot overlook the fact that, in spite of
inches) of rainfall a year, but over 80 per its large rainfall, the amount of water per
cent of the water is used for the cultivation capita in Japan is less (1/6) than that in
of rice. the United States.
TABLE LXm. Average Rainfall of the TABLE LXV. Rainfall Per Capita
World (per year)
Rainfall Rainfall
Country mm/year Country mm/year Country (mm/year) (m*/man)
England 1,170 Italy 600 Japan 1,620 6,600
France 770 U.S. 760 England 1.170 5.550
Germany 680 Brazil 1,590 France 770 9,620
Norway 900 China 700 Germany 630 3.460
Sweden 630 India 920 Italy 600 8,100
Spain 650 Japan 1,620 U.S. 750 40,800
Switzerland 1.200 Sweden 630 38,800

To solve the water shortage, people are

TABLE LXIV. Utilization of Water making an effort to increase the utilization
in Japan of rain water, but it is not easy. The utili
zation of desalinated water seems difficult,
Total rainfall because its production cost (about 100
used for: 6,600 x lOW 100% % yen/m', or $1/1,000 gals) is greater than
Agriculture 600 9.1 84.8 that of city water (20 yen/m*) , industrial
Industry 64 1.0 9.0
City water 44 0.6 6.2 water (5 yen/m*) , or agricultural water (2
Total 708 10.7 100.0 yen/m1) .

TABLE LXVL Examples of Water Rates

City water Industrial water
Basic Excess Basic Excess
City water rates 'ater rates water rates water rates
Tokyo 140y/10m*/mo 20y/m« 4.6y/m» 8y/m«
Kawasaki 160y/10m«/mo 25y/m* 6.6y/m» 12y/m*

However, by taking advantage ot a special method of using desalinated water is ex

condition for practical use, we could utilize plained.
desalinated water in our country. In the As Japan has a very humid climate, it is
following paragraphs, Japan's particular difficult to produce salt by natural evap-
oration. In salt fields we get brine of about tory of the three is the Mitsubishi—Sakito
15 per cent sodium chloride from ordinary salt factory, Nagasaki prefecture, Japan
sea water. In order to manufacture salt from (ref. 9) . which has been supplying 2,000
the brine thus obtained, evaporating sys m* of desalinated water to 15,000 people
tems, mainly vacuum evaporation systems, for ten years.
are used. The evaporation systems are all
operated by coal or electricity. We call one TABLE LXIX. Salt Factories Utilizing
system a "flow down salt field system- Desalinated Water
vacuum evaporation system".
The other system is a direct evaporation Name Quantity mVday No. of
people
method which does not depend upon salt Desali Other Total supplied
fields. By this method, salt is manufactured nated water
water
directly from sea water which is evaporated 15.000
in thermocompression and vacuum evap Mitsubishi— 2,000 1.000 3,000
Sakito
oration systems. In these methods, the pro Nio (Kagawa 160 200 860 2.600
duction costs are very high. However, to prefecture)
Setoda 400 2.600 8.000 16.000
comply with the strong national demand (Hiroshima
for a national self-sufficiency in alimentary prefecture)
salt as an indispensable necessity of daily
life, the government has adopted a monop This desalinated water is sent from the
oly system. Thus, the control of domestic factory to a reservoir (60,000 m*) which
salt and the whole operation concerning can store enough water for one month. It
alimentary salt were taken over by the is aerated there and mixed with pond
Japan Monopoly Corporation. Theoretically, water. Afterwards, the pond water is
through the salt-field system—vacuum evap pumped up to the cleaning bed on a hill,
oration system, we can get about 6 to 7 m* and later supplied as city water. This usable
of pure water to one ton of salt; through water is of a good quality.
the direct evaporating system, about 40 m* The Sakaide Marugame salt-field region.
to one ton of salt. Kagawa prefecture, uses 15.000 m* of in
dustrial water a day. About 200.000 tons of
TABLE LXVn. Desalinated Water salt are produced there, and we can calcu
Per Ton of Salt late about 3,000 m* of pure water a day as
byproduct and waste. If the salt produced
Density of Quantity of the desalinated in this district were manufactured through
original water water per one ton salt a direct evaporating method, about 20,000
•B* KL m* of water a day would be obtained inex
8.0 42.7 pensively. Approximately 3500,000 tons of
8.5 86.4
14.0 7.8 industrial salt are imported at the price of
16.0 6.6 about $10 per ton. If the industrial salt
16.0 6.0
needs were supported by using a direct
evaporation system, 40 m* of desalinated
In both cases, we get water as a by water per ton of salt could be utilized.
product, and the original cost is free. The Thus in Japan the production of desal
total amount of salt produced domestically inated water first occurred as a residual
is about 900 thousand tons per year, and product (derivative) of the special method
there are 26 manufacturing factories equip of salt manufacture. With the increasing
ped with the above-mentioned system. need for city water in coastal cities, the
study of desalinated water derivation was
TABLE LXVHX Supply of Salt in Japan begun. Although our main cities are loca
ted in the coastal regions of a mountainous
Salt Supply No. of manufacturing country and river water is conserved in
(1964) factories everv way possible, the demand is rapidly
Domestic 896,747 t Salt-field evaporat Direct exceeding the supply. This is because of
method—22 overpopulation in the cities and industrial
ing;
method—4 areas: an analysis of the statistics for 15
Most of the Imported cities disclosed that their average popula
Imported 3,773.000 t salt is used for tion is increasing at about 4 to 5 per cent
industry annually. This is the greatest single cause
for the shortage of city water. If we make
Three of these factories supply desalin up this deficiency with desalinated water,
ated water to inhabitants. The largest fac the estimated cost of which is ISO yen/m*.
 MSHEET
SALT
FLOW
STEAM
178.
FIGURE
FOF
ITASUCBITSHOI-RSAYKI.TO

MSokito
of
Factory
Salt
FiSteam
ltos-wubsihsehit

OOO60
 the increase in water rates will be one yen
per capita for an average day. That is only
$1 per man per year. As a result, we be
lieve that we can economically solve the
water shortage problem by using the de
478
salinated water derived as a byproduct of
the salt manufacturing process and thereby
satisfy the greater needs of the coastal
cities.
Calculating equation of cl and c2:
d: (Q.F.D — Qo) Ce + Co
FJJ (1)
d Present water rate (yen/man/
day)
F Size of family (per man)
Q Quantity of water supplied (m*/
man/day)
D SO days
Qo Quantity of the basic water rate
Ю Cc : Cost of desalinated water
Ce Excess water rate (yen/m*)
SUMMARY OF DISCUSSION
It was asked if water shortages are being
expected in Japan and if salt is not the
primary product and water the byproduct
Utilisation de L'Eau Dessalee
au Japon
Masao Hashizume
Japon
En dépit des chutes de pluie importantes,
le Japon se trouve avec une alimentation
en eau potable en diminution dans ses
grandes villes en raison de la surpopulation
urbaine. Les statistiques pour 15 princi
pales villes montrent que la pénurie d'eau
est principalement due à la densité démo
graphique (avec une augmentation mo
yenne annuelle de 4 à 5%) .
Une méthode unique de production de
sel est utilisée au Japon, laquelle produit
également, à titre de sous-produit bon
marché, une eau dessalée. Trois usines de
fabrication de sel produisent maintenant
cette eau à un coût nominal. Dans le
Co : Basic water rate (yen)
c2: ClPo + Ce. P.Q
Po + P (2)
C2 : Cost of mixing desalinated water
(yen/man/day)
Po : Water supply population
(per man)
P : Excess water supply population
(per man)
(yen/m»)
of the scheme described in this paper. The
answer to both questions was affirmative.
proche avenir, d'autres usines pourront
également produire de l'eau commerciale
ment pour les villes de la côte, quand le
besoin s'en fera sentir.
On espère que si l'on compense la pé
nurie d'eau avec de l'eau dessalée, on
pourra également enrayer la hausse du prix
de l'eau. Théoriquement, ce prix est d'en
viron 1 yen par personne et par jour
(environ $1 par personne et par an) . Nous
croyons que cette méthode résoudra à la
fois le problème de la pénurie d'eau et
celui de la hausse des tarifs de distribution
d'eau.
479
 Использование Опресненной Воды
в Японии
Вследствие перенаселенности боль
ших японских городов, их запасы пи
тьевой воды, несмотря на обилие осад
ков, уменьшаются. Статистика, относя
щаяся к 15 главным городам, указы
вает, что недостаток воды преимуще
ственно вызывается густотой населе
ния (при ежегодном его приросте от
4 до 5 процентов).
В Японии вырабатывают опреснен
ную воду в качестве дешевого побоч
ного продукта, получаемого при един
ственном в своем роде методе добычи
соли. В настоящее время такая вода
производится по номинальной цене на
Utilización de Agua
en Japon
Masao Hashizume
Japon
A pesar de las intensas lluvias, Japón
tiene una fuente de abastecimiento decre
ciente de agua potable en las grandes
ciudades debido a una población urbana
desproporcionada. Las estadísticas de 15
ciudades mayores muestran que la escasez
de agua se debe fundamentalmente a la
concentración de habitantes en ellas (con
un crecimiento demográfico promedio entre
4 y 5% anual) .
Un método singular de producción de
sal usado en Japón también produce como
subproducto barato agua desalinizada. Tres
fábricas manufactureras de sal la están pro
duciendo a costo nominal. En un futuro
480
трех соляных заводах. В недалеком бу
дущем и по мере надобности другие
тоже смогут ее поставлять прибрежным
городам на коммерчески выгодных
условиях.
Предполагается, что рост цен на во
ду удастся остановить при пополнении
недостатка за счет опреснения. Теоре
тически приходится 1 йена на человека
в день (приблизительно 1 доллар на
человека в год). Мы думаем, что этот
метод не только разрешит проблему
недостатка воды, но и вопрос повыше
ния ее стоимости.
Desalinizada
cercano, otras fábricas serán capaces de
suministrar comercialmente agua para ciu
dades costeras, a medida que la necesidad
se incremente.
Se anticipa que si la escasez de agua
puede satisfacerse mediante agua desalini
zada, el incremento de precio del agua
también puede ser disminuido. Teórica
mente, es alrededor de 1 yen por hombre
diariamente (aproximadamente un dólar
por hombre por año) . Creemos que este
método resolverá tanto el problema de las
limitaciones actuales de las fuentes de
abastecimiento como el costo creciente del
precio del agua.
 Conversion of Sea Water by
Evaporation
Michio Nakayama
Japan
Besides water, the most useful compon
ents of sea water are sodium salt, potas
sium salt, magnesium salt, and calcium salt.
Ordinarily, we can utilize sodium salt as
sodium chloride and sodium sulfate, potas
sium salt as potassium chloride, magnesium
salt as magnesium chloride, magnesium sul
fate, magnesium hydroxide, and magnesium
oxide, and calcium salt as calcium carbon
ate and calcium sulfate.
Except for deposits of calcium carbonate,
underground sources of the above-
mentioned salts are very scarce in Japan.
Thus, sea water has been used as the only
source of many kinds of salt. As sea water
contains only about 2.6 per cent of sodium
chloride, 40 tons of fresh water must be
SALT FIELD AND VACUUM EVAPORATION METHOD
The first step is to concentrate sea water
into brine (about 15 per cent salt content)
by vertical concentration in a flowing-down
salt field. In Japan, it is difficult to produce
salt by solar evaporation alone because of
heavy rainfall and high humidity.
The second step is to crystallize salt from
DIRECT EVAPORATION METHOD
The direct evaporation method is based
on concentration by an evaporator. Two
different groups of salt factories use this
method. One group uses a thermocom
pression evaporation system throughout the
concentration and crystallization processes.
Another group uses a thermocompression
system for concentration and a vacuum
system for crystallization.
In both groups a forced-circulation evap
evaporated to obtain 1 ton of common salt.
Thus, making salt from sea water amounts
to the same thing as conversion of sea
water.
The Japan Monopoly Corporation (JMC)
regulates the production and marketing of
all domestic salt. Research on the concen
tration of sea water is performed at three
JMC laboratories: the Central Research
Institute (Tokyo) , the Odawara Salt Ex
perimental Station (Kanagawa prefecture) ,
and the Hofu Salt Experimental Station
(Yamaguchi prefecture) .
Some methods of making salt in Japan
are briefly described in the following
sections.
the brine by vacuum evaporation. Almost
all the evaporators are of the standard
calandria type. A salt factory usually has
four to six vacuum pans. These vacuum
pans run to quadruple-effect or steam-jet
thermocompression evaporator plus triple-
effect.
orator with an external heating element is
used for concentration; the standard
calandria-type evaporator is used for crystal
lization. This method is quite free from the
influence of weather conditions. Factories
using this method are in areas where elec
tricity or coal is abundant. Fresh water
drained from the evaporator is supplied as
drinking water to people in neighboring
districts (see report by Mr. Hashizume at
481
this conference) .
We are now performing research on the
following subjects in order to improve
PREVENTION OF SCALE
Whenever sea water is concentrated in
any way, scale deposits (composed mainly
of calcium salt) occur. Thus, scale preven
tion is one of the main challenges in treat
ing sea water. In the conversion of sea water
by evaporation and in making salt from
sea water, scale prevention is comparatively
difficult. However, scale prevention is more
difficult in salt-making than in the conver
sion of sea water. In salt-making, sea water
must be evaporated until it is saturated
with common salt; scaling increases sud
denly when brine concentration reaches IS
per cent to 14 per cent or more.
On the other hand, in the conversion of
sea water, the sea water may be blown
down in low concentration. Thus, in the
TABLE LXXI. Chemical Composition of Scale in Preheater
Operating conditions
Factory Brine Brine
concentration temperature
Fuao 14.6'Be 70°C
Aichi 12.4 90
Alchl 12.4 72
Niahino 16.8 68
Naroto 1S.0 75
Scale deposition increases in winter and
the continuous run of a preheater becomes
impossible after a month. The method (ref.
1) of continuously injecting sodium hexa-
metaphosphate into brine to a level of
about 10 to 15 ppm has been widely
adopted for prevention of scale. By adopt
ing this method to a preheater, we will be
able to operate it continuously for 6 months
even in winter, and the heat efficiency of
the preheater will increase to twice that
obtained in the case of nonaddition. About
70 per cent of the phosphate added to the
brine by the sodium hexametaphosphate
remains in the mother liquor, about 20 per
cent is found in the common salt, and the
residue is found in the scale.
SCALE PREVENTION IN CONCENTRATOR
The "crystal seed" method of scale pre
vention is used for the concentrating stage
of a direct or vacuum evaporation system.
The scale deposited at this stage consists
methods of concentration and conversion of
sea water,
research on salt-making from sea water in
Japan, we have long been making great
efforts to improve scale prevention tech
niques. At present, prevention techniques
are well advanced for all phases of salt-
making. Therefore, it would contribute to
the development of sea water conversion
to introduce here our techniques for scale
prevention in salt-making.
SCALE PREVENTION IN PREHEATER
Brine obtained through a flowing-down
salt field and a vertical concentration was
warmed by drips in a preheater before
being fed to a vacuum pan. Table LXXI
shows the composition of scales deposited
under various operating conditions.
Chemical composition
CaCOi CaSO. M>(OH)i
86.8 8.88 0.14
14.6 79.1 1.62
80.6 4.98 1.12
7».0 2.88 4.66
88.8 8.42 0.67
of calcium sulfate and is very hard. Scale
prevention at this stage is the most critical
in the entire salt-making process.
The principle of the crystal seed method
(ref. 2) is as follows. When many crystal
seeds are suspended in brine, the ionit
products of CaSOi will be maintained to
the solubility product and never exceed
this value. Therefore, scale deposit occurs
not on the heating surface but on the added
crystal seeds. If crystal seeds are not sus
pended in brine, the ionic products of
CaSO, become supersaturated and abun
dant deposits of scale appear on the heat
ing surface. Therefore, the crystal seeds
used must have a large capacity for growth.
The crystal seed method is applied as
follows.
(1) Concerning the water of crystalliza
tion of calcium sulfate hydrate, the
same hydrate as crystallized under its
evaporating conditions is the most
effective. Calcium sulfate has three
 forms: anhydrite, dihydrate, and
hemihydrate. Anhydrite generally de
posits at high liquid temperature
and high concentration. Dihydrate
deposits at low liquid temperature
and low concentration. In the evap
orating pan at the same liquid tem
perature in a direct evaporating
system, anhydrite deposits in every
concentrator. In a vacuum evapora
tion system, however, crystal forma
tion differs in each pan. Anhydrite
is crystallized in the first effect, an
hydrite or hemihydrate in the second
effect, hemihydrate in the third effect
and dihydrate in the fourth effect.
(2) Even if the waters of crystallization
of seed crystal were of the same type,
the effect of preventing scale differs
considerably because of the differ
ence of the characteristics.
(3) 20 grams of seed crystals are added
per liter of brine.
(4) As to the size of the seed crystals, the
smaller they are the better.
(5) As to the influence of dihydrate
mixed in anhydrite, the contents of
dihydrate might be permitted up to
20 per cent by weight. The relation
ship between the liquid temperature
and the kind of seed crystal is sum
marized in Figure 179. The most un
favorable temperature range for ap
plication of this method is from 85°
to 70°C; hemihydrate is relatively
effective in this range but its effect
is somewhat unstable.
(6) The crystal form deposited from
brine can be changed to some extent
by adding enough seed crystals (see
"Multieffect vacuum evaporation sys
tem") .
MULTIEFFECT VACUUM EVAPORATION
Brine from the salt field is fed in parallel
to each stage in a quadruple-effect evap
orator. The "Kuju-chuka" method is used
to prevent scaling on the heating tubes;
therefore, the total boiling point elevation
increases, and the effective temperature dif
ference of heat transfer decreases.
DROPWISE CONDENSATION TO IMPROVE HEAT TRANSFER
Dropwise condensation is generally recog
nized as ? method of improving the heat
transfer coefficient of a heat exchanger (ref.
The higher mercaptans (for example.
FIGURE 179. EFFECTS OF
VARIOUS KINDS OF SEED
CRYSTALS ON SCALE FOR
MATION.
(7) The amount of scale deposited on a
heating tube increases inversely to
the circulating velocity in it.
SCALE PREVENTION IN CRYSTALLIZED
If the crystal seed method is applied in
a crystallizer, it may be difficult to separate
the seed crystals from crystallized common
salts; so we cannot apply this method. To
prevent scale in a crystallizer (for direct
or vacuum evaporation) the "Kuju-chuka
method" is widely used in Japan. The
procedure is as follows. First a crystallizing
pan is filled with bittern whose concentra
tion is about 33°Bé. Then steam is intro
duced. When the liquid temperature nears
the boiling point, brine is fed to a crystal
lizer, and then evaporation and crystalliza
tion occur while the concentration of liquid
is maintained at 27°Bé or more.
When this method is applied to a crys
tallizer, the scale deposited on a heating
tube is hardly noticeable even after a long
run. Therefore, this is the best prevention
method for the crystallizer, in spite of the
defect in thermal economy.
To solve this defect, we are studying use
of a forward series feeding system, applying
the crystal seed scale-prevention method.
Experiments have been made with a seven-
effect vacuum evaporation system (ref. 3) .
The results are shown in Table LXXII.
octyl-, dodecyl- and cetyl-mercaptan) are
selected from basic experiments as excellent
promotion agents of dropwise condensation
to a copper heat-exchange tube. The effect
483
 TABLE LXXII. Operating Results of a Seven-Effect Cacuum Evaporation System
Evaporator
Unit No. 1 No. 2 No. 8 No. 4 No. 6 No. 6 No. 7
Area of heat transfer m"
•c 17.6 16.0 16.0 16.0 16.0 16.0 16.0
Brine temperature 116.7 109.6 102.8 96.2 ILt 70.S 47.0
Brine concentration °B*/15*C
8.3 M IM 16.2 20.2 M.1 S1.6
Flow velocity in m/sec 0.4 0.7 M •J 8.T M 0.6
heating tube
Concentration of Vol-% M 1.1 T.4 •J 16.7 0.0
crystal needs in
brine
Overall coefficient kcal/ 2160. 2072. 1827. 1689. 1240. MO. 6S6.
of heat transfer m"hr*C
•c
Effective temperature 4.1 4.7 M M T.1 M 14.0
Evaporation speed kc/m'hr 1«J 18.4 1T.1 IM 1«J 1U 1U
Amount of scale g-CaSO< 68.6 6.4 6.88 8.41 0JI 0.00
deposited /m«
Dissolved CaSO. % 0.267 0.286 0.229 0.208 0.177 0.149 0.0
in brine
Other operating conditions: Running time, 288 hours; concentration and quantity of feed brine,
6.7*B«/16*C and 1.86 kl/hr.

is fulfilled by adding about 1 gram of into the calandria after drying the heating
meicaptan per square meter of heating; surface by stopping the introduction of
area in a vapor pipe. Although the effect
differs according to the various liquid side
conditions, the overall heat transfer co XK)S
efficient with dropwise condensation gen
erally increases 10 to SO per cent a* _
compared with that of filmwise condensa 7
tion. The effect of dropwise condensation CLEAR / /
continues about 1,000 hours (Fig. 180). 6
PIPEv/
In salt factories, the condensing surface
of heating tubes is usually covered with o -
corrosion. Moreover, in vacuum evapora 0
tion the condensing temperature of intro OS
-
duced steam in each evaporator varies //DIRTY
widely. Therefore, the selection of promot /\ PIPE
ing agents is very important for the appli -
i 3
cation of dropwise condensation. o
General information on the use of pro - 2
moting agents is as follows: (1) when the
condensing temperature is under 80°C and
the condensing surface is dirty, it is neces
sary to use octyl- or dodecyl-mercaptan:
(2) when the condensing surface is clean, «C 1 i i i i
any of the mercaptans (octyl-, dodecyl-, or 0 12 3 4 5XIO*
cetyl-) may be used; (3) when the con ITf (KCAL/m2 HR°C)
densing temperature is above 80°C, it is
preferable to use cetyl-mercaptan. FIGURE 180. RELATIONSHIP
The adsorption to the heating surface can BETWEEN THE 0_ VALUE
be accomplished by either of two methods.
One is to inject mercaptan into the steam WITH DROPWISE ttJd) AND
while running; the other is to vaporize it WITH FILMWISE (Uf).

ION-EXCHANGE RESIN MEMBRANE METHOD

This method of obtaining brine of 15 to
17 per cent and separating common salt
from sea water has been researched in
Japan during the past ten years. It is too
expensive to separate fresh water by this
method; moreover, brackish water or under
ground water is scarce in Japan. Three sail
factories in this country produce brine by
this method instead of the production in
salt field (see report of Dr. Tsunoda at this
conference) .
Research (ref. 5) on such subjects as the
synthetic method of ion-exchange mem
brane, mechanism of selective concentration
of ions, equipment and its operation, pre-
treatment of raw sea water, and the mecha
nism of scale deposition on the membrane
and its prevention is being carried out at
the Central Research Institute and the
Odawara Salt Experimental Station of the
Japan Monopoly Corporation.
Two kinds of electrodialytic stacks, the
vertical filter-press type and the unit cell
type, have been operated at current density
of 2 to 3.5 Amp/dm*. These stacks have
200 to 300 pairs of ion-exchange membranes
whose area is about 1 square meter. Meth
ods of supplying raw sea water, structures
of gaskets, shape of spacers, distribution of
electric current in the stack, prevention of
leakage current, etc. are being studied to
find ways to operate safely without the
deposition of magnesium hydroxide or cal
cium carbonate induced by the concentra
tion polarization.
Microsuspended matter in sea water ad
heres to the membrane, mainly to the anion
membrane, and causes the concentration
polarization. Various methods for prevent
ing this phenomenon by pretreating raw
sea water, such as the sand filter method,
the coagulation method by the addition of
ferric chloride solution, and the diato-
maeceous filtration method were compared.
Our conclusion was that the sand filter is
FLASH EVAPORATION METHOD
The flash evaporation equipment ot an
indirect heat transfer system which has six
stages, each having a heating area of one
square meter, is located in the Odawara
Salt Experimental Station.
The factors related to the heat economy
in the multistage flash evaporation method
were analyzed using this equipment, and
the following formulae were obtained (ref.
6) on the performance coefficient (E) on
the requisite input of the heat energy for
flash evaporation (p kcal/kg of fresh water)
and on the concentration ratio (c/co) in
the multistage flash evaporator in which
the heat of flashed vapor is used to impart
heat to the supplied water stream.
For the one-pass system
N { H - (g. + ym)
H{l + (1-^)(N+1)}
2 TJm
[kcal/kg of fresh water]
necessary as a minimum pretreatment for
ordinary sea water.
Scale deposition on the membrane is
closely related to the character of membrane
used. One of the most important problems
is to find a way to prevent the stack from
scaling.
The concentration ratio of sulfate ions to
SO is usually about 05.
chloride ions (T^j1)
Using the anion membrane for the con
centration of sea water, calcium dihydrate
deposits on the anion membrane when the
concentration of brine becomes nearly 15
per cent or more. To prevent this phen
omenon, the hard permeable anion mem
brane of sulfate ion, whose concentration
SO is less than 0.1, and the hard
ratio Т£р
permeable cation membrane of calcium ion,
Ca
whose concentration ratio T..
Na is less than
OS, are produced. The former is generally
used in salt factories in Japan.
The total electric power consumption
necessary to produce 15 per cent brine
equivalent to 1 ton of common salt is about
400 to 500 kwh; this is half (or less) that
of the thermocompression system.
If the permselectivity against the par
ticular ion is given to the membrane, we
can select the particular ion from sea water.
We are now carrying out research on such
permselective ion-exchange membranes.
С l
Cc7 1 _ 4„ • Cpw (T. - T„)
As for the brine recirculation system, the
experimental result was also obtained.
Where
N = number of stages
H — range of total operating
temperature CO
7jm = mean heat efficiency multi
stage flash evaporator
i)a = heat efficiency of feed heater
T„ — TN = range of flashing tempera
ture (ec)
am = mean temperature differ
ence between brine tem
perature and condensate
temperature in stages ("C)
ym : mean approach temperature
in condensers (°C)
485
 ra = latent heat of vapor in flash
chamber of the last stage
(kcal/kg)
LIQUID-LIQUID HEAT TRANSFER
We have not been able to overcome the
problem of scaling when we heat sea water
and brine by means of heat transfer
through metal surfaces.
So, we are carrying out research on
liquid-liquid heat transfer (ref. 7) at the
Hofu Salt Experimental Station. We are
TABLE LXXIII. Physical Properties of Trichlorodiphenyl
Unit.
Density «/m«
Viscosity sr/cm • sec
Specific heat kcal/kg • °C
Vapor tension mmHff
Surface tension dyne/cm
Thermal conductivity kcal/m • hr • °C
GAS HYDRATE PROCESS
We have a bench-scale model of the gas
hydrate process at the Hofu Salt Experi
mental Station. This equipment can pro
duce 125 kg of fresh water from sea water
per hour, and we can test the whole cycle
of the gas hydrate process with this unit.
Freon 21 (CHCl.F) is used as a hydrate
agent at present, but it is not a satisfactory
agent. Therefore, we are looking for a
better hydrate agent (ref. 8) .
Problems to be solved are the selection of
the hydrate agent, the growth of the hy
drate crystal, the recovery of the hydrate
UTILIZATION OF BYPRODUCTS
Methods for separation of byproducts are
classified into two groups. One group sepa
rates them directly from sea water: the
other separates them from the brine or
bittern.
In the first group, magnesium hydroxide,
magnesia clinker, and bromine are sepa
rated on an industrial scale. Research on
the separation of potassium by various
methods was carried out. Methods studied
include the deposition by addition of
picril-2 • 4 dinitronaphthylamine (solubility
of its potassium salt in sea water is one
tenth that of dipicrylamine) , the extraction
method by addition of both an organic
solvent such as nitrobenzene and a deposit
486
Cpw — specific heat of supplied sea
water and recyde-feed mix
ture (kcal/kg, °C)
using trichlorodiphenyl for the heat trans-
fer medium, but we do not consider it
satisfactory (see Table LXXIII) . The most
important key for the development of this
process is to discover how to prevent forma
tion of emulsion of the heat transfer me
dium and the brine.
atS0*C at 100*C
1.886 1.816
0.888 x 10-" 0.08 x 10-*
0.296 0.818
0.008 0.9
60.0
0.0997
agent, etc. Recovery of the hydrate agent
is especially important because the cost of
fresh water is highly influenced by the
degree of recovery. The problem of recover
ing the hydrate agent, however, is incon
sistent with the problem of the growth of
a hydrate crystal. To obtain high recovery
of a hydrate agent, its solubility in brine
must be as little as possible. On the other
hand, the solubility of a hydrate agent must
be fairly large to build the hydrate crystal
rapidly.
ing agent such as dipicrylamine, and the
selective concentration method by the use
of univalent ion selective cation exchange
membrane.
In the second group, calcium sulfate
dihydrate and hemihydrate, magnesium
sulfate, magnesium chloride, magnesium
hydroxide, magnesia clinker, magnesium
carbonate, mixed salt of potassium and
magnesium "Kuju-kali-salt", bromine, and
sometimes potassium chloride are utilized
on an industrial scale.
Underground sources of potassium are
scarce in Japan, so the bittern is an im
portant source. However, the production
cost of potassium chloride by the rarnalitc
process is more expensive than imports. To
solve this problem, research in the separa
tion of potassium as sulfate salt directly
from bittern was carried out and a new
basic triple salt, "NS salt B", was found
(ref. 9) . Chemical composition of NS salt
В is K.SO. • 2MgSO. • Mg (OH) , • 2H.O. It
is crystallized easily by heating the bittern
to about lOO'C after the addition of mag
nesium hydroxide. This salt can be used as
basic potassium-magnesium fertilizer. More
over, we can separate potassium or mag
nesium sulfate by hydrolyzing it if necessary.
NS salt was named after the initials of its
REFERENCES
1. Sugi. J.; Shimizu, K.; Sugita, S.: Nippon
Shio Gakkai-shi no. 1} (1961) p. 3;
ibid. no. 17 (1963) p. 69.
2. Sugi, J.: Aoki, T.; Harada. T.; Shimizu,
Y.; Nakayama, M.: ibid. no. 9 (1955) p.
29.
Sugi, J.; Shimizu, K.; Shimizu, Y.: ibid,
no. 10 (1956) p. 39.
Sugi, J.; Inagawa, T.; Harada, T.;
Saito, S.; Yamashita, S.: ibid. no. 10
(1956) p. 60.
Sugi, J.; Shimizu, K.; Shimizu, Y.;
Murakami, M.: ibid. no. 12 (1958) p.
96.
3. Okamoto, H.; Chuman, T.; Egawa, T.;
Yamane, Y.: Hofu Shikenjo Hokoku
no. 17 (1964) pp. 8-19.
Okamoto, H.; Egawa, T.; Kishino, Y.;
Yamashiro, T.; Tabuchi, J.: Nippon
Shio Gakkai-shi no. 16 (1962) p. 181.
4. Suwa, K.; Nishimoto, T.; Nagaoka, Y.;
Aida, S.: ibid. no. 15 (1961) p. 153.
SUMMARY OF DISCUSSION
In answer to a question about the fre
quency with which the surfaces had to be
repromoted in the dropwise condensation
discoverers, M. Nakayama and J. Sugi.
Appendix A or В indicates their compo
sitions as shown below:
NS salt A:
Na,SC\ • 2MgSO, • Mg (OH) , • 4H.O
NS salt B:
K..SO, • 2MgSO, • Mg (OH) , • 2H,0
NS salt C:
(NH.) ,SO, . 2MgSO, • Mg (OH) , • 2H.O
NS salt D:
RbtSO, • 2MgSO. • Mg (OH) , • 2H.O
Crystallization in the system KCl-KjSO,-
MgCl.-MgSO.-MgSO.-MgiOHb-HjO at
100°C and 50°C was also studied.
Suwa, K.; Nagaoka, Y.: Aida, S.: Oda-
wara Shikenjo Hokoku no. 6 (1961)
p. 35; ibid. no. 8 (1963) p. 123.
5. Many reports are found in Odawara
Shikenjo Hokoku vol. 7 (1962) ; vol. 8
(1963; vol. 9 (1964) .
6. Ishikawa, T.: Nippon Shio Gakkai-shi
no. 17 (1964) p. 298.
7. Hashizume, M.; Okamoto, H.; Motoki,
Y.: Kagaku Kogaku no. 29 (1965) p. 2.
8. Saito, S.; Yamanaka, H.; Hashimoto, T.:
Nippon Shio Gakkai-shi no. 18 (1964)
p. 184.
9. Nakayama. M.: ibid. no. 1) (1959) p.
319; ibid. no. 14 (1960) pp. 22 and 135.
Nakayama, M.; Matsuo, T.: ibid. no. 14
(1960) p. 168.
Sugi, J.; Nakayama, M.: Bull. Agr.
Chem. Soc. Japan no. 22 (1958) p. 208.
Nakayama, M.: ibid. no. 21 (1959) p.
46; ibid. no. 24 (1960) pp. 147 and 362.
promotion experiments presented in this
paper, the author stated that this infor
mation will be available later.
487
 Conversion de L'Eau de Mer Par

Evaporation

Michio Nakayama

Comme le sel gemme et l'eau saumâtre On discute la condensation sous forme de

de puits sont tres rares au Japon, l'eau de gouttelettes comme méthode pour améliorer
mer a été utilisée comme source principale le coefficient de transmission de chaleur
du sel commun. La Régie des monopoles d'un échangeur de chaleur en cuivre. On
japonais (JMC) contrôle la production et a choisi comme agents activants des octyl-,
la vente de tout le sel domestique. Différentesdodécyl-, et cétyl-mercaptanes. On donne
recherches sur les techniques de concentra des renseignements généraux sur l'utilisa
tion de l'eau de mer ont été effectuées dans tion de ces agents. Le coefficient d'échange
les laboratoires de la JMC. Ces travaux de de chaleur d'ensemble avec condensation
recherche sont exposés dans ce rapport. sous forme de gouttelettes est généralement
de 10 à S0% supérieur à celui avec con
PRÉVENTION DE L'ENTARTRAGE densation laminaire.
Prevention de l'entartrage dans le ré- Méthode par membrane à résine d'échange
chauffeur. La méthode d'injection continue ionique. Cette méthode a été étudiée depuis
d'hexamétaphosphate de sodium dans la plus de dix années au Japon pour obtenir
saumure, à environ 10 à 15 ppm, est dis des saumures de 15 a 17% à partir de l'eau
cutée. Cette méthode est utilisée avec succès de mer afin d'en séparer le sel commun.
clans les usines de fabrication du sel. On s'est servi de deux sortes d'ensembles
Prevention de l'entartrage dans le con électrodyalitiques (le type vertical de filtre-
centrateur. Le tartre dans un réservoir de presse et le type à cellule unitaire) à une
concentration se compose principalement de densité de courant de 2 à 3,5 amp/dm*.
sulfate de calcium et est très dur. Л ce Différents travaux de recherche sur la con
stade la prévention contre l'entartrage est struction de l'équipement de fonctionne
très critique pour la totalité du procédé ment, l'influence des matières en suspens
de fabrication du sel. La méthode par en dans l'eau de mer brute, les méthodes de
semencement de cristaux pour empêcher prévention de l'entartrage, etc. sont effec
l'entartrage est utilisée à ce stade. On tuées en utilisant cet équipement. Les ré
discute le principe de cette méthode et les sultats des essais sont discutés.
renseignements généraux concernant son Méthode par évaporation instantanée. On
application (tels que les genres, quantités discute des facteurs se rapportant à l'éco
et dimensions des cristaux d'ensemencement nomie thermique dans l'évaporation instan
à utiliser et l'influence de la vitesse de tanée p\ étages multiples (en utilisant un
circulation dans un tube de chauffage) . système d'échange de chaleur indirect à six
Prévention de l'entartrage dans le cristal- étages avec une surface de chauffage dans
lisateur. La méthode "kuju-chuka" est très chaque étage de 1 m*) .
utilisée pour empêcher l'entartrage dans le
cristallisateur. On décrit le procédé pour Echange de chaleur liquide-liquide. Le
cette méthode. trichlorodiphényle est utilisé comme moyen
Evaporation sous vide à effets multiples. d'échange (porteur) de chaleur. Le prob
On discute les résultats expérimentaux lème le plus important pour le développe
d'une évaporation sous vide à 7 effets d'un ment de ce procédé est de découvrir
système d'alimentation en série à courant comment empêcher la formation d'une
direct en appliquant la méthode de préven émulsion du porteur de chaleur et de la
tion contre l'entartrage par ensemencement saumure.
de cristaux. Procédé à l'hydrate de gaz. On discute la
Condensation sous forme de gouttelettes séparation et l'utilisation d'un nouveau sel
pour améliorer la transmission de chaleur. triple basique appelé sel "NS-B". Sa
488
composition chimique est K.SO, 2MgSO, •
Mg (OH), • 2HJ0. Ce sel se cristallise facile-
ment depuis la saumure, si bien que le
Опреснение Морской Воды с Помощью
Выпаривания
Мичио Накаяма
Так как каменная соль и соляные
родники встречаются в Японии очень
редко, морская вода стала главным
источником поваренной соли. Джапан
Монополи Корпорейшон (т.е. Японское
монопольное общество) заведует про
изводством и продажей всей туземной
соли. В лабораториях ДМК ведутся
разные исследования концентрации
морской воды, которые в общих чер
тах описаны в настоящем докладе.
ПРЕДУПРЕЖДЕНИЕ ОБРАЗОВАНИЯ
НАКИПИ
Предупреждение образования накипи
в подогревателе. Обсуждается метод
непрерывного впрыскивания в рассол
гексаметафосфата натрия в количестве
10-15 мг/л. Он успешно применяется
на соляных заводах.
Предупреждение образования накипи
в концентраторе. Накипь в чрене для
концентрирования главным образом
состоит из сульфата кальция и очень
тверда. Поэтому на протяжении всего
процесса солепроизводства борьба с
накипью в этой стадии является самой
критической. Во время нее для борьбы
с накипью пользуются методом «за
травочных кристаллов». Обсуждаются
принципы этого метода и общие сведе
ния относительно его применения (как
например, разновидности, количество,
размер применяемых затравочных кри
сталлов и влияние скорости циркуля
ции в нагревательной трубке).
Предупреждение образования накипи
в кристаллизаторе. Для предотвраще
ния образования накипи в кристалли
заторе широко применяется метод «куд-
жу-чука», который здесь поясняется.
potassium peut être séparé sous forme de
sel de sulfate directement depuis la sau-
mure.
Многоступенчатое испарение под ва
куумом. Обсуждаются результаты опы
тов 7-ступенчатого испарения под ва
куумом при прямоточном питании и
применении затравочных кристаллов
для предотвращения образования на
кипи.
Капельная конденсация для улучше
ния теплопередачи. Обсуждается ка
пельная конденсация, применяемая для
повышения коэффициента теплопереда
чи теплообменника, сделанного из ме
ди. В качестве промоторов применяют
ся октил-, додекил- и цетил-меркаптан.
Приводится общая информация о при
менении этих промоторов. Общий ко
эффициент теплопередачи при капель
ной конденсации на 10% -30% выше,
чем при пленочной конденсации.
Метод ионитовых мембран. Этот ме
тод изучался в Японии более 10 лет,
чтобы получить из морской воды 15-
17-процентный рассол для выделения
поваренной соли. Работы производи
лись ^ двумя типами электродиалити-
ческих сборок (типа вертикального
фильтрпресса и типа ячеичного) при
плотности тока 2-3,5 амп/кв. дцм. С
их помощью производятся различные
исследования производственного обо
рудования, влияния взвеси, находящей
ся в необработанной морской воде, ме
тодов борьбы с накипью, и т.д. Обсуж
даются результаты испытаний.
Метод испарения с мгновенным вски
панием. Обсуждаются факторы, отно
сящиеся к экономии тепла при много
ступенчатом испарении с мгновенным
вскипанием (пользуясь шестиступенча-
той системой непрямой теплопередачи
с поверхностью нагрева 1 кв.м. в каж
дой ступени).
489
 Жидкостно-жидкостная теплопереда
ча. В качестве теплоносителя применя
ется трихлородифенил. Самым важным
этапом для развития этого процесса
явится открытие способа, как преду
предить образование эмульсии из теп
лоносителя и рассола.
Conversion de Agua de Mar por
Evaporación
Michio Nakayama
Dado que la roca de sal y la salmuera
de pozo son muy ecasas en Japón, el agua
de mar ha sido usada como fuente impor
tante de la sal común. La Corporación dr
Monopolio Japonesa (JMC) (Japan Monop
oly Corporation) regula la producción y
comercialización de toda la sal de produc
ción nacional. En los laboratorios de la
JMC se realizan varías investigaciones sobre
las técnicas de concentración de agua de
mar. Este informe presenta un resumen de
dichas investigaciones.
PREVENCIÓN DE INCRUSTACIONES
Prevención de incrustaciones en el pre-
calentador. Se discute el método de inyec
ción continua de hexametafosfato de sodio,
a 10-15 ppm, en las salmueras. Este método
se usa con éxito en las fábricas de sal.
Prevención de incrustaciones en el con
centrador. La incrustación en un recipiente
concentrador consiste principalmente en
sulfato de calcio y es muy dura. Por lo
tanto, la prevención de incrustaciones en
esta etapa es la más crítica en todo el
proceso de producción de sal. El método de
semillas cristalinas, para prevenir las in
crustaciones, se usa en esta etapa. El prin
cipio en el que se basa este método se
discute en el trabajo conjuntamente con la
información general con respecto a su apli
cación (tipo, cantidad y tamaño de las
semillas cristalinas a ser usadas y la influen
cia de la velocidad de circulación en los
tubos de calentamiento) .
Prevención de incrustaciones en el crista
lizador. El método "kuju-chuka" es amplia
490
Газогидратный процесс Обсуждается
выделение и использование вновь от
крытой тройной соли "NS соль В". Ее
химический состав — KjSOj • 2MgS04.
Mg(OH)2 • 2Н20. Эта соль легко вы
кристаллизовывается из рапы, так что
можно выделить калий непосредствен
но из рапы в виде сульфатной соли.
mente usado para prevenir la formación
de incrustaciones en un cristalizador. Se
discute el procedimiento de aplicación de
este método.
Evaporación al vacio en múltiple efecto.
Se discuten los resultados experimentales de
evaporación al vado en un equipo de
múltiple efecto con siete evaporadores del
tipo de alimentación directa aplicando el
método de semillas cristalinas para la pre
vención de incrustaciones.
Condensación de gota para mejorar la
transferencia de calor. La condensación de
gota, como método para mejorar el coefi
ciente de transferencia de calor de un
intercambiador de calor de cobre, se discute
en el documento. Como agentes promotores
han sido seleccionados octil-, dodecil- y
cetil-mercaptano. Se da información general
sobre el uso de estos agentes. El coeficiente
global de transferencia de calor con con
densación de gota es generalmente 10 a
30% mayor que en el caso de condensación
en película.
Método de membrana de resina inter
cambiadora de iones. Este método ha sido
estudiado en Japón por más de 10 años
para obtener salmueras de 15 a 17% a
partir de agua de mar a los efectos de
separar la sal común. Dos tipos de cuba
de electrodiálisis (el tipo de filtro prensa
vertical y el tipo de célula) han sido
usados a densidades de corriente entre 2 y
3,5 amp/dm'. Usando este equipo, se han
desarrollado varias investigaciones sobre la
construcción de equipo de operación, la
influencia de materias extrañas suspendidas
en el agua de mar sin purificar, métodos
de prevención de incrustaciones, etc. Se
discuten los resultados de los experimentos.
Método de evaporación instantánea. Se
discuten los factores relativos a la economía
de calor en equipo de evaporación instan
tánea de varias etapas (usando un sistema
indirecto de transferencia de calor de seis
etapas, con un área de calentamiento en
cada etapa de I m") .
Transferencia de calor líquido-liquido.
Como medio de transferencia de calor se
usa triclorodifenilo. La clave más impor
tante para desarrollar este proceso es des
cubrir como prevenir la formación de una
emulsión del medio de transferencia de
calor y la salmuera.
Proceso de gas hidratado. Se discute la
separación y uso de una sal básica triple
recientemente encontrada ("NS salt B") .
Su composición química es KjSO, • 2MgSO, •
Mg(OH), • 2HOH. Esta sal cristaliza fácil
mente en las aguas madres, de manera que
el potasio puede ser separado directamente
de las aguas madres como sulfato.
491
 Objectives of the United Kingdom

Research and Development Program

for Desalination

H. Kronberger. O.B.E., F.R.S.

United Kingdom

INTRODUCTION
It is perhaps not widely recognized that salination. Starting from early maritime re
there are severe local water shortages in the quirements, Britain has developed desalting
United Kingdom and that with the increas plants over the last 70 years, leading to the
ing demand for water the position is rapidly very large land-based plants now in opera
deteriorating. Although the amount of rain tion. Moreover, Britain has recently estab
fall in England and Wales is about 96,000 lished economic nuclear power as a major
mgd (VS.) , of which 50,000 could be made source to meet her demand for energy and
available, only one-eighth of the latter is has, therefore, brought the possibility of
caught for use. The water shortage arises using nuclear energy for producing fresh
from the fact that areas of high rainfall are water from brine one step nearer.
in the northwest, and centers of population Recognizing the importance of this. Her
tend to concentrate in the southeast. The Majesty's Government, through the Minister
cost of opening new natural resources of of Technology, has directed the United
water is being investigated at the moment, Kingdom Atomic EneTgy Authority to as
but it certainly will involve high transport sume responsibility on behalf of the Gov
cost; moreover, it will be difficult to find ernment for research and development of
room for new reservoirs in the populated methods of desalination. In accepting this
areas, and we are anxious to preserve the responsibility, the U.K.A.EA. fully appre
beauty of the unpopulated areas. The ciates the achievements which industry has
Water Resources Board, formed over a year already gained in this field. The modern
ago, is considering two main alternatives multistage flash distillation process, which
for increasing the water supplies in the forms the basis of most large desalination
coming decade: (i) damming of river estu plants, was invented by Frankel and Silver
aries to form reservoirs and (2) desalina in the U.K., and, in fact, over two-thirds of
tion of sea water. In the latter they are the world's desalination equipment has
being assisted by The Water Research Asso been built by British firms. A. C. Smith in
ciation, which is surveying all possible his paper, "Some British Achievements in
methods. Desalination", outlines the history and ex
Apart from the possible national require perience in the design, construction, and
ments for large desalination plants, Britain operation of large desalination plants. It is,
is well aware of the current and future therefore, the policy of the U.K.A.E-A. to
need for water throughout the world, and combine the practical experience of U.K.
feels that it has a major part to play in industry in the design, construction, and
alleviating the world water shortage by the operation of desalination plants, with the
provision of technology, plant, and equip skills and facilities of specialists drawn from
ment. the wide range of activities of the Atomic
The United Kingdom feels that it has a Energy Authority.
special role in sponsoring work on de The Upited Kingdom Research and De-

493
 velopment Program falls into three divisions:
(1) exploitation of the development poten-
tial of flash distillation; (2) the combina-
MULTISTAGE FLASH DISTILLATION
It is generally accepted that, in the next
ten years, the majority of large desalination
plants required for sea water conversion
will be of the multiple flash evaporation
type. Therefore, the first objective of the
program is to review, consolidate, and de
velop the potential of multiple flash evap
oration in order to obtain the minimum
cost of water by this method. The program
is a joint venture between the U.K..A.E.A.
and Weir Westgarth, Ltd. The largest
multiflash distillation plant operating at
present was built by Weir Westgarth and
has an output of 1.7 mgd (U.S.) . In col
laboration with the U.K.A.E.A. they have
now completed a design for a 36 mgd
(U.S.) plant consisting of three integrated
12 mgd (U.S.) units. The design is based
on the best present-day technology: the
plant could be built immediately without
further development work. The objective
of this design study was twofold: first, to
provide a design for a large plant which
coy Id be offered for immediate construc
tion, and second, to identify the high cost
areas on which development and design
work should be concentrated.
Some of the studies are fairly obvious.
For instance, where the requirement is
essentially water rather than power and a
cheap supply of fuel is available, it would
be of advantage to raise the top tempera
ture of the plant beyond the currently
accepted value of about 200°F. However,
beyond this temperature the deposition of
calcium sulphate scale becomes a serious
problem. The program, therefore, includes
kinetic studies on sea water scaling and on
methods intended to eliminate the scale
problem.
The effect of raising the plant top tem
perature immediately highlights the de
ficiency of fundamental design information
related to the physical and chemical prop
erties of salt water concentrates in the range
250° to 350°F. A program has, therefore,
been initiated to measure vapor pressure,
density, specific heat, viscosity, and thermal
conductivity of sea water concentrates in
the temperature range of 250° to 350°F.
The detailed program is outlined in Dr.
Grunberg's paper, "Some Properties of
Water and Salt Solutions".
In the above temperature range, there is
also a lack of information on the corrosive
494
tion of flash distillation with nuclear power
plants; and (3) a study of alternative de-
salination processes.
properties of sea water concentrates, and a
program has, therefore, been initiated at Har
well, the Reactor Materials Laboratory Cul-
cheth, and Weir Westgarth, to test the cor
rosion of a variety of construction materials
in sea water under operational conditions.
In current designs of flash distillation
plants, 40 per cent of the product cost is
attributed to the steel work of the flash
chambers. The design geometry of a flash
chamber must be optimized to allow an
efficient flashing process and to ensure effec
tive disentrainment of brine from the
vapor; yet the size and cost of each chamber
should be kept small. If the top tempera
ture of a multiple flash evaporator can be
raised, a development program is necessary
to find the best geometry for the new con
ditions. A large chamber in which the
geometry can be altered by moving the
walls has been in operation to determine
optimum arrangements for temperatures up
to 200°F. A high pressure rig is now being
constructed in which the optimization can
be carried out empirically up to a tempera
ture of S50"F; all these experiments use
natural sea water.
The work is supplemented by more fun
damental investigations into the mechanism
and thermodynamics of flashing. At the
Atomic Energy Establishment in Winfrith
we are using the expertise of the reactor
heat transfer teams to study the factors
which promote bubble nucleation, bubble
growth, and release. At Heriot-Watt Col
lege, Edinburgh, Professor Silver is de
veloping the thermodynamics of the flashing
process. Jn particular he has shown that
by releasing the excess energy content near
the orifice, more energy is available for
driving the flow of water. This is described
in Professor Silver's paper, "Some Problems
and Research in the Multistage Flash Dis
tillation Process", which also includes new-
developments in the theory of condensation.
Reactor and plant control specialists of
the U.K.A.E.A. are investigating the sta
bility of large multistage distillation plants
on a mathematical model and will check
the results against an operating plant.
Apart from the currently accepted flow
sheet for multistage flash distillation, we
are investigating alternative schemes, such
as a vertical flashing plant involving an
intermediate heat transfer fluid.
 COMBINED NUCLEAR POWER AND DESALINATION PLANTS
The U.K. is in the unique position of
having the world's largest nuclear power
program, and having to date generated
more nuclear electricity than the rest of the
world. It is, therefore, natural that particu
lar attention is being paid to the use of
nuclear power for desalination. The opti
mization of a combined power and water
producing plant is strongly dependent on
local conditions, such as the relative re
quirements of power and water, load fac
tor, and financial ground rules; there is no
single steam cycle nor reactor type which
METHODS ALTERNATIVE TO FLASH DISTILLATION
Although the main emphasis of our work
is on flash distillation, some effort is being
devoted to alternatives. On reverse osmosis
our object is to investigate the mechanism
of the separation process in the membrane,
the manufacture of membranes, as well as
membrane characteristics. In his paper, "On
the Mechanism of Osmotic Desalting with
Porous Membranes", Dr. Glueckauf from
the U.K.A.E.A. applied the theory of de
pletion of plane surfaces to the case of a
pore in a dielectric membrane and de
veloped expressions for the separation per
COST OF PROGRAM
The full cost of the U.K.A.E.A. program
is about $5.5 million for the first 3-year
phase, but provision has been made to ex
pand the work rapidly during this phase
if the situation demands it. We have tried
to keep the costs low by combining with
SUMMARY OF DISCUSSION
It was asked whether the United King
dom has investigated single-purpose, low-
temperature reactors. The reply stated that
United Kingdom problems of disposing of
large blocks of electricity have been ex
amined and that nuclear energy supplied
systems, which would produce more water
than electricity, are now being considered.
The author stated further that electricity
is much easier to transport than steam, so
will be the best for all conditions. Consid
erable effort is being devoted to the eco
nomic study of a combined plant for a range
of conditions; some of this work is being re
ported to this Symposium in the paper by
S. Chambers and A. Hitchcock, "Reactor
Steam Cycles for Desalination". This paper
outlines a general method for optimizing
a combined plant. Detailed designs of large
combined desalination and nuclear power
plants are being prepared by British in
dustry.
formance which agree reasonably well with
the experimental results of Sourirajan. The
work gives a lead in the search for im
proved membranes.
A survey paper on experience in the field
of electrodialysis is given by Mr. G. S. Solt
of William Boby and Co., Ltd. The
T.KA.E.A. is also interested in this field;
there are plans for a development program
intended to improve the mechanical detail
design of equipment and the consequential
long-term reliability of an electrodialysis
plant.
industry (which already has a good deal of
experience in the design and construction
of large desalination plants) , by making
use of existing facilities in the laboratories
of the U.K.A.E.A.. and by concentrating on
key features in the development.
flexibility is provided for dual -product pro
duction at sea water locations.
In answer to the question about past and
present United Kingdom projects to further
sea water desalination technology, it was
stated that the United Kingdom Govern
ment finances water resources board studies
and that a single-team effort is now being
formulated under the coordination of the
offices of the Minister of Technology.
495
 Objectifs du Programme de Re

cherche et de Développement du

Royaume-Uni en Matière de

Dessalement de L'Eau

H. Kronberger, O.B.E., F.R.S.

Le Royaume-Uni revendique d'importan du programme national de dessalement.

tes realisations dans le domaine du dessale
ment de l'eau. C'est à l'industrie britan
nique que l'on doit l'invention et la mise au
point du procédé moderne de distillation
à multiples effets et vaporisation par dé
tente, tandis que la majeure partie (plus
des deux tiers) de la capacité de dessale
ment actuellement installée dans le monde
a été construite par des entreprises britan
niques.
Dernièrement le Gouvernement britan
nique a décidé de soutenir et d'accroître les
nouveaux efforts de mise au point des
méthodes de dessalement. C'est ainsi qu'il
a demandé à la United Kingdom Atomic
Energy Authority d'assumer, pour le
compte du Gouvernement, la responsabilité
Les grandes lignes du programme sont
indiquées dans l'exposé. Ce programme
allie l'expérience pratique de l'industrie
britannique en matière de conception et de
construction d'importantes installations de
dessalement à la compétence professionnelle
et aux moyens spécialisés dont disposent les
services de recherche et de développement
de l'U.K.A.E.A.
En outre, Ги.К.А.Е.А. étudie le groupe
ment de grandes installations de dessalement
et de centrales nucléaires. Le Royaume-
Uni possède une vaste expérience acquise
séparément dans ces deux domaines, et les
travaux reposent en premier lieu sur une
technologie éprouvée.

Цели Соединенного Королевства

в Области Исследования и Развития

Программы по Опреснению Воды

Г. Кронбергер, Кавалер ордена Британской Империи (3-ей степени),

член Королевского общества

Соединенное Королевство

Соединенное Королевство имеет испарения и постройку установок, пре

большие достижения в области опрес
нения воды. Британская промышлен
ность ответственна за изобретение и
усовершенствование современного мно
гоступенчатого процесса мгновенного
496
вышающих 2/3 сооруженной во всем
мире опреснительной ёмкости.
Совсем недавно Британское прави
тельство решило начать оказывать под
держку и способствовать дальнейшему
усовершенствованию методов обессо-
ливания, поручив Комиссии Соединен
ного Королевства по атомной энергии
руководить от имени Правительства
национальной программой опреснения
воды.
При сем прилагается общее описание
программы; она объединяет практиче
ский опыт Британской промышленности
в области проектирования и построойки
больших опреснительных установок со
специальными знаниями и оборудова
нием, имеющимися в распоряжении
научно-исследовательских учреждений
Комиссии Соединенного Королевства
по атомной энергии (U.K.A.E.A.).
Кроме того, U.K.A.E.A. изучает во
прос объединения больших опресни
тельных установок с силовыми стан
циями, работающими на ядерной энер
гии. Соединенное Королевство приоб
рело широкий опыт в каждой из обеих
областей отдельно и теперь в первую
очередь работа сосредотачивается на
проверенной технологии.

Objetivos del Programa Británico

de Investigación y Desarrollo en

Materia de Desalinizacion

H. Kronberger, O.B.E., F.R.S.

Unido

En el Reino Unido se sostiene haber grama nacional de desalinización.

logrado realizaciones de importancia en
materia de desalinizacion. A la industria
británica se debe la invención y perfeccio
namiento del sistema moderno de destila
ción instantánea en etapa múltiple, asi
como la construcción de más de dos tercios
de los medios de desalinización instalados
actualmente en el mundo medidos por su
capacidad.
En fecha más reciente, el Gobierno de la
Gran Bretaña decidió apoyar y dar incre
mento al ulterior desarrollo de los métodos
de desalinización y ha encomendado al
Organismo de la Energía Atómica del
Reino Unido (United Kingdom Atomic
Energy Authority: UKAEA) que se haga
cargo, en nombre del Gobierno, del pro
Se ofrece un esquema del programa. En
el mismo se combinan la experiencia prác
tica de la industria británica en cuanto al
diseño y construcción de vastas instalacio
nes de desalinización, con la competencia
y medios especiales existentes en las insti
tuciones de investigación y desarrollo del
Organismo de la Energía Atómica del
Reino Unido.
Además, este organismo tiene en estudio
la combinación de grandes centrales de
desalinización con usinas nucleares. El
Reino Unido ha adquirido gran experiencia
en ambos campos separadamente y, en lo
que respecta al primero, el trabajo se con
centra, en primer lugar, en la tecnología
de resultado comprobado.

497
Low Capacity Nuclear Desalination

Plants

K. K. Polushkin, Yu. L Koryakin, S. P. Kuznetsov, I. L Grozdov, A. P.

Sirotkin, A. A. Loginov, V. D. Khoroshavin, P. Ye. Gasnikov and
Yu. N. Alekesenko

Union of Soviet Socialist Republics

INTRODUCTION
In addition to nuclear large-scale de Among very promising heat carriers for
salination devices whose economic indicators mobile reactors of the low power nuclear
are most favorable for economic compe desalination devices are organic fluids. The
tition with the conventional approaches for active reactor zone using moderators and
satisfying the needs in fresh water, it is of heat carriers can be made sufficiently
considerable interest to study the use of compact.
nuclear desalination devices of relatively The low vapor pressure of organic fluids
low power (with a capacity of distillate permiis the maintenance of pressures not
between 150 to 500 t/hr) . The usefulness of exceeding 3 to 4 atm abs at relatively high
such units is determined by the geographic temperatures within the first loop of the
and economic peculiarities of certain re device. The low heat carrier pressure sim
gions and locations which make the trans plifies the construction and assures a high
portation of fresh water difficult, and the reliability of operation of all the elements
supply of conventional fuel for the desalina of the nuclear device. Insignificant corrosive
tion of salt water and the production of action of the organic heat carrier on the
electrical energy cumbersome and expensive. building materials, particularly on the fuel
The Soviet Union has such regions, and element covers, makes the use of aluminum
they may also be found in other countries. alloys within the active zone of the reactor
The preliminary engineering-economic cal possible and the first loop can be built
culations showed that in such regions the from inexpensive low carbon steels which
use of relatively low power nuclear de secure a correspondingly favorable neutron
salination devices is technically feasible andbalance within the active zone and a com
economically justified. paratively low cost of first loop equipment.
Sometimes the nuclear desalination device The negligibly low induced activity within
may have a single goal, i.e., it may be ear the organic heat carrier allows one to
marked only for the production of distil completely omit the biological protection
late. The production of electric energy is in around the first loop: this reduces the cost
this case needed only for use within the of the device and makes servicing the
nuclear desalination device. equipment considerably simpler and easier.
Such devices must, in general, satisfy the Although organic fluids have basic ad
following requirements: vantages, such heat carriers are not without
(1) A minimum net cost of the distillate; flaws. They exhibit worse heat-physical
(2) Simplicity of construction and high properties than other types of heat carriers
reliability of operation of all elements;
and demand the use of sufficiently large
(3) Simplicity of servicing; heat exchange surfaces. They are also sus
(4) Mobility and the possible mounting ceptible to radiation-thermal decomposition
of the complete device from separate which leads to a maximum permissible
blocks built and tuned at the pro heat carrier temperature and a need for its
duction plant. regeneration.

49<)
 Presently, the USSR is experimentally
operating an atomic electric station with an
organic heat carrier (hydrostabilized gas-
oil) , ARBUS-1. The experimental run of
this atomic electric station showed that all
the equipment of the first loop operates in
a reliable manner and can be easily serviced
since the induced activity of the heat carrier
is insignificant. Investigations of the fuel
elements (uranium-aluminum alloy) which
were dispersed within aluminum dies in the
gas-oil medium showed that even in the
case of intentional puncturing oF otherwise
hermetically closed containers, the escape of
gaseous fission fragments into the heat
carrier loop is, for all practical purposes,
nonexistent. Thus the operation of\ the
atomic electric station ARBUS-1 indicates
quite high operating characteristics. In spite
of certain shortcomings of the organic heat
carrier, this atomic energy station can be
used in nuclear devices of various types
(refs. 1, 2) one of which is the desalination
unit.
As a heat carrier in nuclear desalination
units, one can use hydroterphenyl (HTP)
—a mixture of incompletely hydrogenated
terphenyls. We prefer hydroterphenyl be
cause of its radiation-thermal stability as
compared with gas-oil, its capability of
operating at higher temperatures (up to
S50°C in the core within the first loop
flow) , and better thermophysical properties.
Tests of the radiation-thermal stability
and thermophysical properties of HTP
seem to indicate that this heat carrier is
one of the most promising organic heat
BASIC DIAGRAM OF THE DEVICE
The use of the organic heat carrier per
mits the omission, within the desalination
device, of the intermediate loop, and one
can use the organic fluid directly as the
heating medium within the first evaporator
stage. This approach is dictated by the tech
nological scheme of the device, the con
struction of the first stage of the evaporator,
and the low difference in the pressures
within the media. After the condensation
of the first stage steam in the second evap
oration stage, the condensate is led into a
special tank in which quality is carefullv
and constantly controlled. Another constant
control which has been contemplated is
checking the condensed water arriving from
the first stage of the evaporator. During the
study and experimental run of the ARBUS
device, it was found that the induced ac
tivity within the organic heat carrier con
sists almost completely of the ^-activity of
500
carriers (ref. 2) .
The present paper investigates nuclear
desalination devices with reactors of 15, SO,
and 70 mw of capacity. The use of organo-
organic type reactors is most expedient in
the case of reactor devices with relatively
low thermal powers (up to 30 mw) . For
reactors with heat capacities above 30 mw,
the economic considerations connected with
the magnitude of the absolute outlays for
the makeup of the organic heat carriers
indicate that reactors with organic heat
carrier containing solid moderators are the
more efficient ones.
In reactors with a heat capacity of 15 and
30 mw, the electrical generator supplies
only the amount of electrical energy needed
by the device itself.
In the case of a reactor with a heat
capacity of 70 mw, we used the organic
HTP heat carrier and a solid graphite mod
erator. In this case, the electric generator
not only covers the unit's electric power
requirement, but also produces a surplus of
electric energy. In this way the device with
a thermal reactor power of 70 mw is a
dual-purpose device.
In general, nuclear desalination devices
with organic heat carriers can be built
without any generators to supply electric
energy to the device itself when they are
earmarked for work in regions where such
energy is available. Obviously, the economic
applicability of the single- or dual-purpose
nuclear desalination devices must be deter
mined individually in each particular case.
the phosphorous-S2 and appears almost
fully bound within the high boiling prod
uct of the radiolytic polymerization. Conse
quently, the gaseous products of the radi-
olysis and the low boiling fractions in all
cases under investigation appeared inactive.
This fact, in conjunction with the high re
liability of the hermetically-sealed fuel ele
ment chosen, gives rise to the hope that
even in the case of punctured heat trans
mission tubes and the entrance of the
organic heat carrier into the water, the
probability of a transfer of radioactive com
ponents of the organic fluid by the vapor
is practically nil.
In case the organic liquid enters the con
densate, the latter does not go to the con
sumer but proceeds into the drain. This is
accompanied by a simultaneous repair
which should remove the troubles in the
first evaporation stage. It should be empha-
sized lhat the probability of the occurrence
of such a situation is almost completely
eliminated.
Figure 181 shows the basic diagram of the
nuclear desalination device with direct
use of organic heat carriers within the first
evaporation stage.
which secures the electric power needed by
the device and supplies a portion of this
power to the consumer. After leaving the
steam generators, the organic heat carrier
proceeds to the first evaporation stage. Fol
lowing the transfer of the heat to the salt
water, the heat carrier proceeds to the

FIGURE 181. BASIC DIAGRAM OF THE NUCLEAR

DESALINATION DEVICE.
1 -Evaporator-first stage; 2-Condenser tubing; S-Tubing of the first loop; 4-Gas piping;
5-Receiver; 6-Control valve; 7-Nitrogen bombs; 8-Reactor; 9-Steam generator; 10-Steam
piping; 11 -Feeder pump; 12-Turbine with reductor and generator; 13-Condenser; 14-Cir-
culation pump; 15-Pump of the forced circulation; 16-Breakdown turbopump; 17-Cermet
filter; 18-Condensed water tubing; 19-Salt water tubing; 20-Deaerator; 21-Evaporator;
22-Volume compensator; 23-Main circulation pump; 21 Overflow tank; 25-AuxiFary pip
ing of the first loop; 26-Makeup pump of the first loop; 27-Recirculation filter; 28-Water
supply to the consumer; 29-Feeder pump; 30.Setting tank-condenser; 31-Preheater; 32-
Periodic overflow to the consumer; 33-Special storage; 34-Throttles; 35-First loop heat
carrier regeneration block; 36-Overflow pump; 37-Water disposal.

The circulation of the heat carrier of the
first loop is maintained by two circulation
pumps along two parallel circuits. The heat
carrier proceeds from the reactor into the
steam generators. Within the steam gen
erators the heat of the organic heat carrier
of the first loop is transferred to the vapor-
water loop which generates a steam of 2.3
atm of pressure and temperature of 150°C.
The steam from the steam generators pro
ceeds into a turbine-generator combination
volume compensator which also acts as the
degassing unit. From the volume compen
sators the heat carrier is collected by the
circulation pumps and returned to the re
actor. The pressure within the first loop
is maintained constant at about 3 to 4
atm abs by means of gases liberated during
the radiolysis and pyrolysis of the heat
carrier, and the surplus of gases is led
through the pressure regulator into the
atmosphere. At the time of the start of the

501
device, the pressure within the volume com
pensator is built up by nitrogen. The puri
fication of the heat carrier is accomplished
by cermet filters collecting suspended par
ticles larger than 1 5 to S p (ref. 3) . The
filters are located in bypass circulation
pumps. The polymers and unsaturated com
pounds formed as a result of the radiation-
thermal decomposition of the heat carrier
are removed by a special system of regen
eration added to the device.
The heat carrier regeneration is carried
out within a hydrogénation reactor where
the hydrogénation of unsaturated complexes
and the destruction of polymers is carried out
within an aluminum-cobalt-molybdenum
catalyst under hydrogen pressure.
As a result of the heat carrier regenera
tion one obtains compounds which in their
physicochemical properties are close to the
original heat carrier. The diversion of heat
carriers for regeneration is carried out
within the first loop line, while the regen
erated product is discharged into the over
flow tank.
The device utilizes the direct flow se
quence of multieffect evaporation of the
salt water in vertical units with the use of
seeding. This method was adopted because
of the state-of-the-art as compared with the
flash evaporation technique, in spite of the
fact that the latter may prove to be more
advantageous in the future. The method
was adopted in its semieffect version. Six
low pressure stages are carried out using
the natural circulation of the salt water.
The first stage, the high pressure stage con
REACTORS
The 30 and 70 mw reactors are developed
on the basis of existing units and parts of
the organo-organic reactor of 15 mw of
power. The reactor vessels having 15 and
30 mw of heat capacity are made of welded
cylindrical containers 4,365 mm in height
and 1,340 and 1,470 mm in diameter, respec
tively. The 70 mw reactor utilizes a solid
moderator (graphite) to reduce the radioly-
tic and pyrolytic losses of the organic heat
conductor by means of its partial elimina
tion from the active zone; this makes the
use of the regeneration block of the 15 mw
reactor for this 70 mw reactor possible.
A short description of the construction of
the 15 mw heat capacitor reactor is given
in Figure 182. At the upper part of the
reactor vessel is a flange together with sup
porting clamps and connecting pipes, the
lower four of which serve for the introduc
tion and the upper four for the removal of
taining the organic heat carrier, operates
with the multiple forced circulation of the
salt water with the aim of reducing the
size of the device. The water circulation is
maintained by two axial pumps with low
pressure and high capacity. The water boil
ing point is reached after the exit from
the heat exchanger tubes, thus reducing the
salt deposits on the heat transfer surfaces.
The first-stage steam which was con
densed in the second evaporation stage is
led into a tank containing a quality con
trol. If there are no organic admixtures
found, the product is given to the con
sumer; otherwise, the condensate goes into
the drain. Prior to the introduction of the
salt water into the aerator, part of the
initial water (approximately 20 per cent)
heated up to a temperature of 36* to 40°C
is discarded; subsequently, a certain amount
of condensed water coming from the set
tling tank -condenser with concentrated seed
is added to the basic current of the initial
water supply. (This scheme provides for the
deaeration of the salt water; however, to
reduce the cost of the device, it would be
desirable to eliminate deaeration although
the feasibilty of its elimination from the
technological process is not yet sufficiently
justified.) The mixture of the original water
containing the seed is then led into the
deaerator and subsequently distributed over
the evaporation stages.
The nuclear desalination device whose
basic diagram is shown in Figure 181 may
be adapted to units of varying capacity.
the heat carrier. The irradiation of the
upper vessel is reduced by lateral and bot
tom screens mounted within the vessels. An
internal vessel organizes the flow of the
heat carrier and also acts as the framework
of the structure of the active zone. The
uniformity of the heat-carrier flow distribu
tion prior to the active zone is achieved by
means of perforated plates with openings
located at the lower part of the interior
vessel and serving simultaneously for the
support and centering of the heat-releasing
cells. These cells are fixed by SUZ sleeve
tubing, or by manual control mechanisms
supported by the reactor cover. Along the
periphery of the active zone there is an
aluminum sector which diverts the organic
liquid. The lateral reflector consists of a
I50-mm thick layer made of aluminum sec
tors and the heat carrier surrounding the
inner vessels.

FIGURE 182. CROSS-SECTIONAL
VIEW OF THE REACTOR.
1-Heat carrier exit; 2-Hcat carrier intake;
S-Reactor vessel; 4-Inner vessel; 5-Dis-
placer; 6-Lateral screen; 7-Supporting
plate; 8-Lower screen; 9-Heat generating
cell; 10-Actuator mechanism of the man
ual regulator; 1 1-SUZ sleeve pipe; 12-Cover
with the thermal and biological protec
tion screens.
The active zone of the reactor contains
414 heat generating units distributed over
a triangular lattice with a 35 mm step and
joined into 69 heat-generating cells (Fig.
183) with an active part length of 1,200 mm.
Each unit consists of two concentrically
distributed heat elements: the outer hex
agonal one and the inner cylindrical one.
The heat elements are covered by the D-20
aluminum alloy with a reduced copper
content. The cylindrical fuel element con
tains the displacer. Six fuel element units
are joined within a cell by lower and upper
collars. The lower collar is rigidly con
nected with the stem while the upper is
connected with the cap of the cell by means
of a spring which permits the independent
heat expansion of each unit. Uranium-
aluminum alloy serves as fuel, and its use
within the organic fluid medium excludes,
for all practical purposes, the escape of
fission products into the heat carrier loop
in case the fuel element cover develops a
break.
The reactor is controlled by means of
cylindrical rods which can be displaced
within the active zone. The control unit
can carry out group or individual rod dis
placements. The compensation of the tem
perature effect and the poisoning effect is
accomplished by 32 rods made of boron -
containing steel. Of these, two rods are
earmarked for automatic control (AC) and
four are connected pairwise for breakdown
protection (PP) . The burn-up effect is
compensated by means of 37 rods, which
can be placed in either of two positions,
and by burning-up absorbers.
The control, regulation, and protection
of the reactor at a given power level are
carried out by means of neutron flux meas
urements carried out by a compensation
ionization chamber. The chambers are lo
cated within hermetically-sealed fixtures
located in the space between the shaft and
the vessel of the reactor. The control and
protection system is based mostly on mag
netic amplifiers. The automatic reactor
starter brings the reactor from the (10"'
to 10-5) per cent level of the nominal
power to (1 to 10) per cent of the given
power over a given period. Within this
range the automatic starting device also
secures a protection by sensing the rate of
increase of the power. The overall power
controller specifies the compensation cur
rents for all AC and PP amplifiers and also
permits a smooth change in the reactor
power. The simultaneous setting specifica
tion for all amplifiers simplifies the work
of the operator and eliminates false actua
tion of the PP device. The reactor control
is carried out by a single automatic regu
lator which is at constant standby. The
stability of the given power level U ± 1 per and reactor protection system confirm the
cent. simplicity, reliability, and expediency of its
Experimental runs of the given control use for low power nuclear devices.
 EQUIPMENT COMPONENTS OF THE NUCLEAR DESALINATION DEVICE
Figure 184 represents the overall view of
the nuclear 15 mw desalination device
which differs from units having 30 and 70
mw only in the dimensions of the produc
tion buildings and evaporation columns.
FIGURE 184. GENERAL VIEW OF THE NUCLEAR
DESALINATION PLANT.
The combination of elements of the 30
and 70 mw devices follows exactly the com
bination of the 15 mw unit.
Equipment and elements of the device are
brought to the construction site in the form
of separate fully-mounted blocks already
subjected to checks at the producing fac
tory. The weight and size of the blocks
broken down into mobile units make pos
sible their transportation to the construc
tion site by water, land, or air. The weight
of the mobile sections is not greater than
20 tons. The mounting of the equipment
and the putting into operation of such a
device may be completed in 3 to 5 months.
The equipment for the first loop and the
associated auxiliary systems is located in a
quickly assembled housing-shielding struc
ture. The electrolyzer, discharge capacities,
and some of the equipment related to the
desalination of water are mounted within
the structure.
The housing-shielding structure (Fig. 185)
of the device is divided into four sections
which require different amounts of ventila
tion, air-conditioning, and fire and radiation
protection. The heat and dosimetric control
devices as well as those for the control and
regulation of the entire setup are concen
trated at the operator's panel.
The electric equipment power supply
during the starting and cooling of the re
actor is provided by Diesel generators which
make the entire device fully autonomous.
The device is amplified by a refueling
system (which allows the refueling of the
reactor by the operating personnel in ap
proximately 15 days, taking into account
the time needed for the cooling of the
reactor) , a storage space for the burned up
cells, SUZ tubing with the rods, and the
manual regulators. The storage capacity is
designed for two reactor refuelings. The
necessary operations connected with the
reactor refueling are carried out by means
of a light bridge crane located within the
reactor compartment.
505
 FIGURE 185. DISTRIBUTION OF THE BLOCKS WITHIN THE
MAIN STRUCTURE OF THE NUCLEAR DESALINATION DEVICE.
1-Reactor block; 2-First-stage evaporator block; S-Steam block; 4-Regeneration
block; 5-Dcacrator block; 6-Condenser block; 7-Turbine ; 8-Diesel generator; 9-Con-
trol panel.

The entire personnel consists of 24 per
sons, 14 engineer-technicians and 10 work
ers. (Even with devices having 30 and 70
mw reactors, the number of personnel re
mains unaltered.)
The equipment, armatures, and tubing
of the first loop are made of carbon-steel.
The first loop of the nuclear desalination
unit has no biological protection. The bio
logical protection of the reactor is made of
ordinary shielding material (concrete, gra
phite, polyethylene, and iron) .
The existing data concerning the opera
tion of the ARBUS-1 device indicate that
the area immediately adjacent to the equip
ment of the first loop is 10 p bar/sec. The
activity of gases discarded into the ventila
tion system is of the order of 10-12 Curie/1.
The overall magnitude of gas activity dis
carded by the entire device is approximately
equal to 12 • 10"* Curie/day. In this man
ner, a device of the given type can be
located in the immediate vicinity of the
salt water sources as well as of the fresh
water consumers. The equipment and the
units of the devices presented in this paper
were developed on the basis of experience
with the ARBUS-1 device.
The evaporator of the first stage of the
water desalination system is of the aug
mented reliability type with forced circula
tion. The evaporation column of the sub
sequent stages, the water intake, discharge
channels, water storage reservoirs, and
power equipment of the device are in most
cases standard units utilized in the rest of
the industry.

ENGINEERING—ECONOMIC INDICATORS
Table LXXIV lists the physical character
istics of the active zones of the nuclear de
salination devices under discussion. During
the calculation of the physical characteristics
we took into account the experimental data
gathered during the operation of the
organo-organic reactor ARBUS-1 and of
other setups. Using the experience gained
during the experimental production and
mounting of the ARBUS-1 device, we de
termined the economic indicators of the
nuclear desalination low power devices
under discussion. The calculation of the
cost of electric energy and of the distillate
follows the methods described by Koryakin.
et al (réf. 4) . The basic engineering-
economic indicators of various devices are
listed in Table LXXV. The cost of electric
energy and distillate also covers the ex
penditures for the makeup of the hydro-
terphenyl consumed by the loop. These ex
penditures represent an insignificant portion
of the total value of the constant yearly
outlay for the operation of the nuclear
desalination devices.

506
 TABLE LXXIV. Physical and Engineering Characteristics of the Active Reactor Zones
Characteristic Setup version
I П Ш
Thermal power, mw 16 80 70
Heat carrier HTP HTP HTP
Moderator HTP HTP graphite
Amount of HTP (daring the work
at the intake 160 160 150
at the exit 170 170 170
Height of the active zone, em 120 120 210
Diameter of the active zone, em 80 110 210
Number of celia 69 151 850
Load of U"». kg 88 69 160
Enrichment, per cent
initial 86 21 21
final 28 11.5 12
Run, dayi 780 780 780
Heat carrier temperature, *C :
of the regeneration block) , kg/day 170 830 810

TABLE LXXV. Engineering—Economic Indicators of the Devices

Characteristic Setup version
I II Ш
Heat power of the reactor, mw 15 80 70
Useful electric power, kw 1.600
Power consumed by the device, kw 400 760 1,600
Heat consumption for the desalination of salt water,
kcal/hr 11.0 • 10* 22.0 • 10« 48.8 • 10*
Specific heat consumption for the production of
distillate, kcal/kg 88.7 86.7 88.7
Distillate production, t/hr 127.5 256.0 606.0
Number of hours of rated power utilization, hr/year 7.000 7,000 7,000
Coat of electric energy, kop/kwh 68 67 42
Cost of distillate, kop/t (figures not given

Expenditures for versions I and II repre (in contradistinction to electrical energy)

sent approximately 8 to 10 per cent of total
expenditures and for version III approxi
mately 4 to 6 per cent.
The magnitude of the coefficient of rated
power has a substantial effect on the net
cost of the products of the nuclear de
salination plant. The fact that the distillate
represents a product which can be stored
predetermines the feasibility (in principle)
of operation of nuclear devices with a maxi
mum possible utilization coefficient. How
ever, the seasonal needs of fresh water
must be considered. Consequently, in our
calculations we assumed the number of
hours of rated power utilization to be
7,000 hr/year.

CONCLUSION
A study of the problem of the impending
construction of a nuclear low power desali
nation device, having acceptable engineering-
economic indicators and sufficiently high
operating characteristics, showed that nu
clear devices with organic heat carriers
satisfy all the requirements imposed on de
vices of a similar type. The high working
capability of the entire basic equipment of
a nuclear device with organic heat carrier
was confirmed by the experimental opera
tion of the atomic energy station ARBUS-1 .
The reactor of the desalination device may
be built on the basis of existing elements
and parts and, consequently, the produc
tion and operation of the entire equipment
may be achieved in a sufficiently short
period of time. The nuclear desalination
device can be brought to the building site
in the form of separate, fully-mounted
mobile elements and blocks, the weight and
size of which permit their transportation
by various types of carriers. This offers the
possibility of an autonomous utilization of
nuclear desalination devices in different
regions and significantly shortens the size
and schedules of construction and mount
ing operations.

REFERENCES
Polushkin, K. K.; Vemel'yanov, I. Ya., with organic heat carrier and moder
et al: "Atomic electric station ARBUS ator", Contribution no. 307 to the

507
 Third International Conference on
Peaceful Uses of Atomic Energy (1964) .
2. "Study of the use of organic heat car
riers—moderators in power reactors",
Moscow, Atomizdat (1964) .
S. Tokarev, Yu. I.; Bogdanov, F. F., et al:
Atomnaya energiya no. 18 (1965) p. 5.
4. Koryakin, Yu. I.; Loginov, A. A., et al:
Atomnaya energiya no. 19 (1965) p. 2.
Loginov, A. A.; Koryakin, Yu. I., et al:
"The analysis of the engineering—eco
nomic indicators of nuclear power
desalination devices", Contribution pre
sented at the First International Sym
posium on Water Desalination, Wash
ington, D. C. (1965) .

SUMMARY OF DISCUSSION
There was no discussion.

Usines Nucléaires de Dessalement a

Faible Capacite

К. К. Polushkin, Yu. I. Koryakin, S. P. Kuznetsov, 1. 1. Gruzdov,

A. P. Sirotkin, A. A. Loginov, V. V. Batov, V. D. Khoroshavin
et P. £. Gasnikov

Union des Republiques Socialistes Soviétiques

L'expérience acquise en URSS dans la l'installation de dessalement à un seul

conception et l'exploitation de petites cen
trales électriques à énergie nucléaire, avec
un porteur de chaleur organique, rend pos
sible l'établissement d'installations nuclé
aires de dessalement à faible capacité.
Ce mémoire présente une description et
une analyse économique comparative d'in
stallations nucléaires de dessalement à un
seul usage, installations qui peuvent être
mises au point à la centrale nucléaire
d"'Arbus", ainsi que des réacteurs avec
porteur de chaleur organique, d'une puis
sance thermique de l'ordre de 15 à 70 MW.
On donne des schémas fondamentaux
d'usines de dessalement à un seul usage et
à double usage, ainsi que leurs principaux
paramètres. Le mémoire discute la possi
bilité, en principe, de la suppression du
profil intermédiaire de vapeur dans des
usines de dessalement à un seul usage avec
des réacteurs à porteur de chaleur orga
nique, en raison de la faible pression du
profil I et de l'absence presque complète
d'activation du porteur de chaleur orga
nique.
La conception de la partie réacteur de
usage, mise au point à la centrale nuclé
aire d"'Arbus", est examinée et on décrit
l'équipement essentiel de l'installation et
son arrangement.
On donne les caractéristiques des condi
tions d'exploitation, de la sécurité de radia
tion et de la viabilité de fonctionnement
des installations du type considéré, sur la
base de l'expérience disponible.
Le mémoire considère la possibilité de
l'établissement d'un certain nombre d'usines
avec des réacteurs à porteur de chaleur
organique, en utilisant des ensembles et
de l'équipement d'une installation du type
"Arbus".
Des indices techniques et économiques
sont donnes pour des usines de capacités
diverses, ainsi que des estimations des frais
d'investissement et du prix de revient de
l'eau potable. On discute les perspectives
économiques de l'utilisation d'installations
nucléaires, à porteur de chaleur organique,
pour le dessalement, tout comme pour la
production combinée d'énergie électrique
et d'eau potable.

508
 Ядерные Опреснительные Установки
Малой Мощности
Полушкин К. К., Корякин Ю. И., Кузнецов С. П., Груздов И. И;,
Сироткин А. П., Логинов А. А., Батов В. В., Хорошавин В. Д.-,
Гасников П. Е.
СССР
Имеющийся в СССР опыт проекти
рования и эксплуатации малых атомных
электростанций с органическим тепло
носителем позволяет создать ядерные
опреснительные установки небольшой
мощности.
В настоящем докладе дается описа
ние и сравнительный экономический
анализ одноцелевых опреснительных
ядерных установок, которые могут
быть разработаны на базе АЭС «Арбуо
и реакторов с органическим теплоно
сителем, в диапазоне тепловой мощно
сти от 15 до 70 Мвт.
Даны принципиальные схемы опрес
нительных установок одноцелевого и
двухцелевого назначения и их основ
ные параметры. Рассмотрена принци
пиальная возможность отказа от про
межуточного парового контура в опре
снительных установках одноцелевого
назначения с реакторами на органиче
ском теплоносителе, обусловленная
низким давлением 1 контура и практи
ческим отсутствием активации органи
ческого теплоносителя.
Рассмотрена конструкция реакторной
части одноцелевой опреснительной
установки, разработанной на базе АЭС
«Арбус», с описанием основного обо
рудования установки и его компонов
ки.
На базе имеющегося опыта приве
дены характеристики условий эксплуа
тации, радиационной безопасности и
надежности работы установок рассма
триваемого типа.
В докладе рассмотрен вопрос воз
можности создания ряда установок с
реакторами на органическом теплоно
сителе с использованием блоков и обо
рудования установки типа сАрбуо.
Приведены технико-экономические
показатели для установок различной
мощности с оценкой капитальных за
трат и себестоимости отпускаемой пре
сной воды. Даны экономические перс
пективы использования ядерных уста
новок с органическим теплоносителем
как для целей опреснения, так и для
комбинированного производства элек
троэнергии и пресной воды.
509
 Plantas Nucleares de Desalinizacion

de Baja Capacidad

K. K. Polushkin, Yu. I. Koryakin, S. P. Kuznetsov, 1. 1. Gruzdov,

A. P. Sirotkin, A. A. Loginov, V. V. Batov, V. D. Khoroshavin,
y P. E. Gasnikov

Union de Repúblicas Socialistas Soviéticas

La experiencia disponible en la URSS en reactor de una planta de desalinización de

el diseño y funcionamiento de estaciones fin único, desarrollado en la base de
atómicas de energía eléctrica con un refri "Arbus" AEPS y se describe el equipo
gerante orgánico, hace posible establecer básico de la planta y su ensambladura.
plantas nucleares de desalinización de baja Se dan las características de las condicio
capacidad. nes de funcionamiento, de seguridad de
Este trabajo presenta una descripción y radiación, y de la seguridad de funciona
un análisis económico comparativo de miento de plantas del tipo considerado,
plantas de desalinización de fin único que sobre la base de la experiencia disponible.
pueden ser desarrolladas en la Estación El trabajo considera la posibilidad de
Atómica de Energía Eléctrica "Arbus" y de establecer un número de plantas con reac
reactores con un refrigerante orgánico de tores con un refrigerante orgánico utilizando
una escala de capacidad térmica entre 15 unidades y equipos de una planta del tipo
y 70 Mw. "Arbus".
Se dan diagramas básicos de plantas de Se dan Indices técnicos y económicos
desalinización de fin único y de doble fin. para plantas de diferentes capacidades
El trabajo discute la posibilidad, en prin junto con estimados de inversiones de ca
cipio, de eliminar el perfil intermediario pital y del costo de producción de agua
de vapor para plantas de fin único con potable. Se discuten las perspectivas eco
reactores con un refrigerante orgánico, en nómicas del uso de plantas atómicas con
vista de la baja presión del perfil I y, refrigerante orgánico tanto para desaliniza
prácticamente, de la ausencia de activación ción como para la producción combinada
del refrigerante orgánico. de energía eléctrica y agua potable.
Se examina el diseño de la parte del

510
 Desalination of
Electrolysis — Selection
Current Density
V. A. Klyachko, G. G. Pervov, L. D. Ushakov
Union of Soviet Socialist Republics
Desalination of water by electrodialysis
in multichamber baths with semipermeable
ion-exchange membranes is being used ever
more widely in water supply systems in the
USSR. The possibility of completely auto
mating the process and making the de
salination installation autonomous (i.e.,
independent of reagent supply) makes elec
trodialysis installations very suitable for use
in water supply systems in sparsely popu
lated areas, farms, watering places at dis
tant pastures, as well as for expeditions and
exploring parties in regions deprived of
fresh wajer but having underground or
surface salt water.
However, the area in which it is eco
nomically sound to use electrodialysis de
salination installations has not been deter
mined with sufficient accuracy. In addition,
the processes of polarization and depolari
zation of the membranes in desalination
installations have not received sufficient
attention; therefore, considering the ion
composition of salts dissolved in the water
to be desalinated, it is impossible to accu
rately evaluate the desalination installation.
In recent years, investigations have been
performed at the VODGEO Institute [All-
Union Scientific Research Institute of Water
Supply, Sewerage, Hydraulic Engineering
Structures, and Engineering Hydrogeology]
on the process of desalinating water by
electrodialysis. and the operation of de
salination installations designed according
to the results of the investigations were
also studied.
In this article, the economic aspect of the
work performed, that is, the determination
of the optimum current density prescribed
Saline Water by
of Optimum
in designing the electrodialysis desalination
installation, is examined.
The current density for the electrodialy
sis installation may be chosen after deter
mining the parameters for its design, since
the quantity of salt eliminated and the
output of product water per unit mem
brane surface and per unit time depends
upon the current density.
An increase in current density for a con
stant output of the installation makes it
possible to decrease the necessary membrane
area and the size of the desalination in
stallation. Here, however, the voltage in the
bath is increased, and, to prevent polariza
tion of the membrane, the flow rate must
be simultaneously increased in the bath's
cells. This naturally implies an increase in
the consumption of electric power for de
salination and for circulating the water in
the cells. Therefore, in each case it is
necessary to determine the current density
corresponding to a minimum cost for con
structing and operating the electrodialysis
desalination installation.
In this article, an analytic attempt is
made to determine the optimum current
density in a general form and, using the
relationships thus obtained, to compute the
economical current density for some charac
teristic conditions of desalination.
The calculation is based on the assump
tion that the total cost of building and
operating the electrodialysis installation is
represented with a high degree of accuracy
in the following manner:
P = Pa. + P. + P., (1)
where Pdc is the cost of the energy required
511
 for electrodialysis, I'„ is the cost of the
membranes taking into account their life
time and subsequent replacement, and P,e
is the cost of the energy consumed in circu
lating water on both sides of the membrane.
The cost of the technological equipment
—tubing, pumps, reservoirs, armatures, con
trol devices, and automatic equipment—
and the salaries for the working personnel
are only slightly dependent upon the cur
rent density. To simplify the problem,
these factors are not considered in estimat
ing the cost of desalination. Therefore, fac
tors allowing for the effect of the output of
the installation on the cost of desalination
are also excluded from the calculation.
It is clear that the greater the output of
the plant, the lower is the cost of desalina
tion. The wages of the personnel and the
costs of construction will be about the same
for installations having different outputs,
but the relative proportion of these ex
penses in the cost of desalination will be
high for installations with small outputs
and low for installations with large outputs.
Therefore, in this article we will not con
sider cost factors which depend on the
output of the installation or on the cost of
the equipment.
Calculation of the cost of the electrical
energy used in the electrolysis process is
based on Faraday's law and on certain
known parameters of the electrodialysis
installation.
A general expression for the cost of d-c
current consumed by water purification,
taking into account the cost of (he electrical
energy P. (in kopecks per kwh) and a
current efficiency of 0.9 for a one-hour de
salination cycle of the installation*, is
P«.,= GV • T • P. • N =
. If)-1
.1 1 • 10-' • P, • j • FN • Nkop(2)
The net working area F„ of the mem
brane may be given as a function of the
gross area F, and the porosity of the sepa
rator network (taken as 0.87) .
In baths of small area, a large fraction
of the total surface of the membrane is
occupied by the frames. An analysis of the
construction of frames of different heights
for an identical width of 0.5 m (width of
membranes manufactured industrially in
the USSR) makes it possible to obtain a
value of the coefficient for F, to determine
the working membrane surface:
,r = 0.51 lgF,_ 1.4 (S)
* All notations are given at the end of the
512
The working voltage in the electrodialy
sis bath, V, consists of the voltage drop
across the electrodes, the voltage drop across
the membranes including the concentration
polarization, and the voltage drop across
the cells:
V = E. + 2E_ • N + G • N • R„ (4)
The magnitude of the electrode poten
tial, E„ is slightly dependent upon the
working current density and, according to
our data and the data of certain other in
vestigators, it may be taken to be constant
and equal to approximately 5 v.
The value of the average bath current
for a corresponding average value of ohmic
resistance of the cells may be determined
from a diagram of the desalination cycle in
a circulating system (Fig. 186) .
This diagram is based on data from the
trial operation of the EOSKh-2M installa
tion with an output of 120 m*/day. In the
desalination cycle lasting t hours, the con
centration of salt in the water is reduced
from C„ to C(ia over the line a-b-c. To
decrease the total salt content to 14 mg-eq/l.
(1 g/l.) , the relationship c = f (t) is al
most linear and may be given by the line
a-d-c.
It is desirable to maintain the salt con
tent in the brine channel at a maximum
in order to reduce the cell resistance. How
ever, remembering that in natural water
(here is always a significant quantity of
Ca** and SO, " ions, the brine concentra
tion limit must not exceed the limit of
CaSO, solubility.
The brine concentration coefficient Kc
may be determined from the equation
_ / Sr,
(5)
where Sr.,,,, is the soluhilitv product of
CaSO, (anhydrous) , 6.1 -lO"': f is the activity
coefficient of the Ca** and SO,"" ions. 0.17;
Cct and Cso, are the ion concentrations of
Ca** and SO,"" in g-mol/1.
Thus, in circulating systems operating
with continuous discharge from the brine
channel, the salt concentration must be
KC-CN.
Hence, the average concentration in the
bath cells is
C* + 14
+ KCCN
C„ = 2
Cx (0.25+0.5K,) +3.5 (6)
The specific conductivities, as functions of
the total salt content, are different for dif-
 C/ng-equ //.
T.a
J$£h BRINE KcCh

FIGURE 186. DIAGRAM OF THE CHANGE IN PURIFIED WATER

AND BRINE CONCENTRATIONS PER DESALINATION CYCLE
ON THE ELECTRODIALYSIS CIRCULATING SYSTEM.

ferent solution compositions. Determination it pcisible to give empirical relationships

of the specific conductivity of four types of for the specific conductivities as functions
salt water (diagrams of their hypothetical of their dissolved salt concentrations,
composition are given in Figure 187) make

513
514
 For ocean water, this relationship has
the form
f=wOM1-CM1 (7)
For water in the Caspian Sea, we have
f1 = -S-^rOM-1
2500 ■ CM-1 (8)'
For water in Wells No. 1 and 2 (Kazakh
SSR) it is
st = -^-OM
2750 ' • CM-1 (9)
x brane surface on the salt solution side by
The difference in the values for the spe
cific conductivities for different solution
compositions indicates that in determining
the average cell resistance it is necessary to
make a specific analysis of the water.
The current in the desalination cycle
(Fig. 186) changes over the line «-l-g.
The relationship T = f (r) is nonlinear
this is explained by the nonlinearity of the
function f = f (c) . Therefore the mean
current strength per cycle may be defined
as the quotient resulting from dividing the
quantity of electricity used per desalination
cycle (in ampere-hours) by the duration of
the cycle (in hours) .
The quantity of electricity required for
a desalination cycle of r hours is graphi
cally shown as the area «-l-g-q-p in the
figure.
By processing the test data obtained at
the EOSKh-2M installation, we established
the fact that the area of this figure is close
to the area of the rectangle m-n-q-p whose
ordinate Tm,,« corresponds to the average
salt concentration Cmo.„ determined from
Equation (6) .
By using this assumption, we may sim
plify calculation considerably while main
taining the accuracy within 5 per cent, as
experimental data showed.
Due to a difference in concentrations in
the diluate and brine channels, there is
a potential difference between the solutions
on both sides of the membrane—the so-
called membrane potential. It is always
directed counter to the electric field, reduc
ing the total potential difference. Its value
is determined from the equation
K„=(tA_tB)^,n£i£.(,0)
(a±)D
Assuming that the activities of the brine
and diluate, (a±)br and (a±)dll, are pro
portional to the concentrations, Ct,r and
CD, and remembering that the electrolysis
numbers of the counter-ion for industrially
manufactured membranes are (on the aver
age) 0.90, we obtain
E» = 0.046 lg (11)
after substituting numerical values into
Equation (10) for t = 15°C.
When current flows through the solution-
membrane-solution system, the phase inter
face is subjected to concentration polariza
tion owing to the difference in electrolysis
number. The concentration polarization con
siderably increases the concentration differ
ential on both sides of the membrane,
increasing the concentration at the mem
AC and decreasing it by AC on the diluate
side when hydrodynamic conditions are
identical on both sides of the membrane.
The concentration polarization effect in
creases the membrane potential which,
owing to the large quantity of membrane
in the bath, makes up a considerable
portion of the voltage across its electrodes.
The quantity AC is a complex function
of the current density, rate of motion of
the water in the cells, turbulizer type (sep
arator network) , and solution concentration.
On the basis of data from our laboratory
investigations for almost optimum condi
tions and control data obtained while
running the EOSKh-2M installation, we
may use for economic calculation roughly
a two-fold increase in membrane potential
under the effect of concentration polari
zation.
Then the value for the membrane poten
tial, taking into account the concentration
polarization, is determined from the equation
Em = 0.11g-^ (12)
The mean ohmic resistance of the cell
may be determined from the equation
(IS)
By determining the necessary number of
cells from the general equation resulting
from the Faraday law:
FwPN=26-8-10--.Q(C*-l4) (14)
iv
and substituting all values into the general
equation for voltage which was given
earlier (Eq. (4) ) , we obtain an equation
in expanded form for the voltage across
the bath:
y-5j 53frl0-*-AQ(C.,-14)
~ + jnFNN
5S.6-10-«-dQ (CN— 14)
r.mFsN (15)
53.6.10-'-C,.-rQ (C„-14)
+
515
 Here The equation for the electrical energy
cost consumed by the circulation of the
A = lg^- = lg (18) purified water and the brine during a one-
When the number of cells in the bath is hour desalination cycle, taking into account
not greater than 200 units, we obtain an the assumptions that the pressure drop in
equation for the cost of the d-c current the circulation pipelines, .distributor, col
in the distillation process lectors, and bath cells must not exceed 15 m
of water with respect to the purified water
Pfc=K,(C_14) +KI(C_14) lgi^i- + and brine channels, is
C+14 P.,= 1 .68 • 10-* Vdn P. (28)
Kj (C-14)
[C (0.25+0.5Kc) +35}p -(- K,j (C-14) The water flow rate in the bath cells
(17) must not be less than the critical depolari
after substituting V and A in Equations zation rate whose general equation is
(15) and (16) and the corresponding trans
formations in Equation (2) . In the follow V„= cm/sec (29)
ing equations Values for the coefficient KT depend upon
K,=7.45 • 10'-^- P. (18) the type of turbulizer (separator network).
V In our experiments, using a vinyl-plastic
K,=5.95 ■ io-«-2-p. (19) corrugated separator network, the values
V obtained for KT at d = 02 cm were some
what higher than the values of K, given
K.=5.95 • 10'G.*r — P. (20) by Wilson and Cook.
Remembering that the value for the
Values for the coefficient K, and the expon critical rate turns out to be a minimum for
ent p depend upon the salt composition of a minimum concentration in the purified
the input water. water channel, i.e., for C, = 14 mg-eq/1.,
Thus, for example, for ocean water the critical rate may be determined with
K.,=49.3 • lO-'d -2- P. and 0=0.93 sufficient accuracy by the expression
1 (21) V,r=6.0 • 10-' -L cm/sec (S0>
For water in the Caspian Sea
Substituting this value and the value for
K,= 16.4 • lO-'d SL P. and 0=0.705 N from Equation (14) into Equation (28) ,
* (22) we obtain
For water in Wells Nos. 1 and 2 (salt com P..=K.(C-14) (31)
position given in Figure 187)
where
K.= 16.4 • 10-M — P. and 0=0.705 (23) 27 • 10-'
if K.= i-„r.n.MKF„r-i.t) ' ^ P* (S2)
The general equation for the cost of (he The total cost of the water desalination
membranes, taking into account their life process will be
time 0 in hours and their price Pm in
kopecks/cm", may be represented in the P=(CN-14)[KI+K,.g-^gL +
form
P»=2pNFbr 4" P-kop (24) K.j
[C (0.25+0.5K.) +3.5]0
Here, substituting the value of N from (33)
Equation (14) and making the correspond
ing transformations, we obtain It is clear from the conditions for oper
Kr,(CN—14) (25) ating the desalination process that the co
p„= efficients K„ K„ K„ K,, K|, and K. are
The numerical value of the coefficient K3 positive numbers. An analysis of Equation
depends upon the membrane lifetime. Thus, (33) shows that for every determined initial
for example, for a probable three-year life salt concentration, at determined values of
time for the membrane the functional parameters, the distillation
20.4 • 10-' process cost curve P = f (j) has a minimum.
^P„ (26) This fact is illustrated in Figure 188 which
5 - 0.5 1gFbr_1.4 r, shows four cases of water with different
and for a probable two-year lifetime salt composition but with identical values
30.6. 10-' for all construction and cost parameters.
Ks = — P„ (27) The current density corresponding to a
0.5 lg F.,,-1.4 v
516
minimum cost function will also be the specified in designing the circulating elec-
optimum current density which should be trodialysis installation.
F> Kopek!

220

200

I 80
>

I 60
/
f

I 40 —\

20

I 00
/
/
80

^2
60

40

^3
20

^4

Q0I 0.02 O03 0.04 Q05 0.06 0O7 0.08 009 j,o/cm*
FIGURE 188. CONDITIONAL COST OF PROCESSING PER m3 OF
WATER FOR DIFFERENT COMPOSITIONS, USING THE ELEC-
TRODIALYSIS CIRCULATING SYSTEM WITH THE FOLLOW
ING PARAMETERS.
Fg = 7500 cm»; d = 0.2 cm; r£ - 50 ohm-cm3; n = 0.7; Membrane lifetime - 2 years;
1 -Ocean water, C = S5.03 g/1.; 2-Caspian Sea water, C = 1S.59 g/1.; 3-Water from Well
No. 1; C — 6.09 g/1.; 4-Water from Well No. 2; C = 2.92 g/1.
517
 P, KOPEKSf

/
/
//

y
rr
1 /A 3
\6
- 1I
II \9
11

i #

*
it -<</
/ /
/A * ^ 2
//
•V V 10

.
—••
V\ \,
4
^7

FIGURE 189. CONDITIONAL COST OF DESALINATION PER ms

OF WATER FROM CASPIAN SEA, USING THE ELECTRO-
DIALYSIS CIRCULATING SYSTEM FOR DIFFERENT VALUES
OF THE SPECIFIC COSTS OF ELECTRIC ENERGY AND MEM
BRANE (THE PARAMETERS OF THE INSTALLATION ARE
THE SAME AS IN FIG. 188.
1 - P. 0.5 kop/kwh
2 - P. — 1.0 kop/kwh
3 • P. = 2.0 kop/kwh (for 1 - S, Pm — 63 rub/m2)
4 - P. 0.5 kop/kwh
5 • P. — 1.0 kop/kwh
6 - P. 2.0 kop/kwh (for 4 ■ 6, Pm : 12.6 rub/m1)
7 - P. — 0.5 kop/kwh
8 - P. — 1.0 kop/kwh
9 - P. 2.0 kop/kwh (for 7 - 9, P„ = 25.2 rub/m")

518
 The value for the optimum current den For the same type of water, the optimum
sity may be found by differentiating Equa current density depends to a great degree
tion (33) with respect to j and equating upon the ratio of the specific cost of the
the first derivative to zero: electric power P. and of the membrane Pm.
dP :(C-14) The graph in Figure 189 illustrates some
relationships for P = f (j) at different
-K. values of P. and Pm for the case of desalin
L[C„(0.5>5+0.5Kt)+3.5]/> +• K. j ] (34) ating Caspian Sea water in an EOSKh-2M
installation (Fg — 7,500 cm*; d = 0.2 cm) .
Neglecting the trivial case when C„ — 14
mg-eq/1., we obtain the equation for Below is a table of the calculated op
optimum current density timum current densities for desalinating
waters of different composition by electro-
K,[C,, (0.25+0.5K..+3.5]/? ~ dialysis. The salt composition in these
-4K.+K,[C (0.25+0.5K.) +3.5]/3 waters is given in Figure 187.
(35)
TABLE LXXVI. Calculated Current Densities for Desalinating
Waters of Different Composition by Electrodialysis
Conditional specific cost jopt, a/cm'
for membrane and
electric energy Ocean water, Caspian Sea water, Water from Water from
P. = P., Cn = 86.08 g71. Ck = 18.89 WeU No. 1, WeU No. 2,
rublea/m* kop/kwh Cn = 6.09 Cn = 2.92 B/l.
0.6 0.0148 0.0144 0.0136 0.0186
6.9 1.0 0.0106 0.0102 0.0097 0.0096
2.0 0.0074 0.0072 0.0066 0.0067
0.6 0.0210 0.0204 0.0194 0.0192
12.6 1.0 0.0149 0.0144 0.0136 0.0136
2.0 0.0106 0.0102 0.0096 0.0096
0.6 0.0297 0.0288 0.0272 0.0271
26.2 1.0 0.0211 0.0204 0.0194 0.0192
2.0 0.0148 0.0144 0.0136 0.0186

NOTATION
ip — Faraday constant, 96500 coulombs/ T — current in bath, Amperes
g-equiv V — voltage across bath electrodes, Volts
K — universal gas constant—8.316 j/deg j — current density, A/cm
T — absolute temperature, °K f — specific conductivity, ohm-1 • cm"1
Q — flow rate of device, l./hr r^J — mean specific surface resistance of
v — flow rate in cells, cm/sec membrane, ohm • cm"
d — distance between membranes in cell, C — salt content of water, mg-eq./l.
cm t4 — electrolysis number of counter-ion
p — width of cell in the direction per in membrane
pendicular to the flow rate tB — electrolysis number of K„ ion in
n — number of cells in bath, units membrane
N — number of parallel baths in device, F» — gross area of membrane, cm"
units F„ — net working area of membrane, cm'
T — desalination cycle time, hr r) — current efficiency
H — circulation pump head, m

SUMMARY OF DISCUSSION
An inquiry was made concerning the
types and costs of membranes used in the
analysis presented in this paper. The reply
stated that calculations given in this paper
were made for three membrane costs of 7,
12. and 25 rubles per square meter. The
cheapest membrane, costing 7 rubles per
square meter, is a heterogeneous type that
uses polyethylene backed with nylon fiber,
and the selectivity of this particular
membrane is relatively poor. It is intended
that membranes of improved properties
(which will, of course, be higher in cost)
be developed. Economic calculations will be
made weighing the effect of these improved
membrane properties versus the membrane
cost.
The question was raised as to whether or

519
 not scaling problems were experienced
using Hemodialysis in the USSR. The
reply stated that in the USSR the major
problem with scaling was due to iron in the
underground water, that alkaline earth
scales such as Mg (OH) , were controlled by
acid, and that calcium sulfate scale was
prevented by maintaining a low concentra
tion factor in the brine stream.
Dessalement de
Electrodialyse
V. A. Klyachko, G. G. Perov et L. D. Ushakov
Union des Republiques Socialistes Soviétiques
On a effectué des études des procédés de
polarisation et de dépolarisation des mem
branes d'échange ionique d'installations de
dessalement par électrodialyse, sans tur
bulence du diluant et avec sa turbulence
par l'introduction des filets métalliques on
dulés de profils divers dans l'espace entre
les membranes.
Les potentiels des membranes furent
déterminés pour différentes conditions de
fonctionnement des installations à électro
dialyse.
On a examiné les aspects économiques
de la construction d'usines de dessalement
par électrodialyse, des types à recirculation
Опреснение Солоноватых Вод
Электродиализом
В. А. Клячко, Г. Г. Перов, Л. Д. Ушаков
СССР
Исследованы процессы поляризации
и деполяризации ионитовых мембран
электродиализных опреснительных ус
тановок без турбулизации дилоата и
при его турбулизации в результате
введения в пространство между мем
520
The question was asked as to the type
and design of the separators used in
USSR electrodialysis stacks. The reply stated
that two basic designs of separators had
been evaluated. The first design was a cor
rugated, round hole separator made from
PVC. The second type of separator used
was toweling made from "Kapron". a mono-
meric fiber woven in the form of loops.
L'Eau Saline Par
ou à courant direct, pour des eaux de
salinités différentes.
On a déterminé des valeurs optimales
pour les densités du courant et les vitesses
d'écoulement du diluant et de la saumure
dans des cas de dessalement d'eau saumâtre
souterraine (teneur en sels, de 3 à 10 g/1),
pour des coûts différents de l'énergie élec
trique (de 0,5 à 2 kopecks/kwh) et pour
des coûts variables des membranes d'échange
ionique (de 6 à 18 roubles/m1) .
On donne des descriptions d'installations
de dessalement par électrodialyse, porta
tives et fixes, conçues sur la base des études
ci -dessus.
бранами гоффированных сеток различ
ного профиля.
Определены мембранные потенциалы
в различных условиях работы электро
диализных установок.
Рассмотрены экономические аспекты
проектирования электродиализных оп
реснительных установок циркуляцион
ного и прямоточного типов при опрес
нении вод различных соленостей.
Установлены величины оптимальных
плотностей тока и скоростей протока
дилюата и рассола для случаев опрес
нения подземных солоноватых вод (со-
лесодержание от 3 до 10 г/л) при раз
Desalinizacion de
Electrodialisis
V. A. Klyachko, G. G. Perov y L. D. Ushakov
Union de Repúblicas Socialista» Soviéticas
Se han desarrollado investigaciones de los
procesos de polarización y despolarización
de membranas de intercambio iónico en
plantas de desalinización por electrodiá-
lisis sin turbulencia de diluente y con
turbulencia del mismo mediante la intro
ducción de mallas corrugadas de distintos
perfiles en el espacio entre las membranas.
Se determinaron potenciales de las mem
branas para diferentes condiciones de fun
cionamiento de plantas de electrodiálisis.
Se examinan los aspectos económicos del
diseño de plantas de desalinización por
electrodiálisis del tipo de flujo circulante y
del tipo de flujo directo para aguas de
личной стоимости электроэнергии (от
0,5 до 2,0 коп/квт/час и различной
стоимости ионитовых мембран (от 6
до 18 р/м2).
Приведено описание стационарных и
передвижных опреснительных электро
диализных установок, спроектирован
ных с учетом описанных исследований.
Agua Salada por
distintas salinidades.
Se han establecido valores para densida
des óptimas de corriente y velocidades
óptimas de flujo del diluente y de la sal
muera en casos de desalinización de aguas
salobres subterráneas (con contenido salino
de 3 a 10 g/lt) para costos variables de
energía eléctrica (de 03 a 2,0 copecks/
Kwh) y para costos variables de membra
nas de intercambio iónico (de 6 a 18
rublos/m*) .
Se dan descripciones de plantas de desali
nización fijas y móviles diseñadas sobre la
base de las investigaciones indicadas.
521
 Intensification of Heat Exchange
in Evaporator Installations
V. B. Cheraozubov, A. A. Bolotov, S. I. Golub, V. N. Chadov,
F. P. Zaostrovskii, V. A. Chemezov, L. A. Minukhin, and L. S. Mrezhin
Union of Soviet Socialist Republics
Water desalination in modern industrial
plants requires extensive utilization of metal
for heat exchange surfaces. Consequently,
an intensification of heat exchange would
lead to a considerable reduction in the cost
of fresh water production.
Studies of heat exchange intensification
were carried out using the following ap
proaches:
(1) Removal of the harmful influence of
THE REMOVAL OF HARMFUL INFLUENCES OF NONCONDENSABLE GASES
In multieffect evaporation desalination
units, one (or several) of the last stages
operates in a vacuum. During operation, it
is practically impossible to completely avoid
trapping air and other noncondensable gases
in the heated steam. Since this reduces the
heat exchange intensity, special care should
be taken in the design of the heat exchange
chamber to keep the negative effects of these
admixtures to a minimum.
As is well-known, the negative effects of
noncondensable gases in vapors are caused
by their concentration near the heating sur
face; this creates a layer through which the
vapor must diffuse before it can condense
(ref. 1) . As a result, in addition to the
condensate layer resistance there is a new
diffusion resistance.
The diffusion resistance can be consider
ably reduced by partial destruction of the
vapor-gas layer. This may be achieved by
increasing the turbulence of the flow, i.e.,
increasing the vapor velocity. The feasibility
of a significant heat exchange intensification
by this method was fully confirmed by ex
periments carried out in conjunction with
the study of vapor condensation from a
noncondensable gas admixtures in the
heating steam on the heat transfer
coefficient during condensation.
(2) Insuring droplet vapor condensation
on the heating surfaces.
(3) Development of sufficiently economi
cal methods for an increase in the
heat transfer coefficient by the liquid
in heat exchange devices.
vapor-air mixture moving through a verti
cal pipe cluster.
The dependence of the heat generation
coefficient on the air content for various
weight velocities of the vapor is shown in
Figure 190. A sharp reduction of the heat
transfer coefficient with the increase of air
concentration for low vapor velocities and
a comparatively slight influence in the
region of high velocities is noted. For in
stance, for a vapor weight velocity of 0.05
kg/m' • sec, an increase in air concentration
from 0 to 5 per cent reduces the heat trans
fer coefficient to one-third of the original
value; however, at a velocity of 0.38 kg/m* •
sec, the heat transfer coefficient is decreased
by only 17 per cent.
Excessive vapor velocity increases must be
avoided since the resulting losses in pressure
within the tube cluster lead to a decrease
in the useful temperature gradient.
In designing heating chambers, one must
insure sufficient vapor velocities and, at the
same time, provide for a directed flow and
avoid creating regions with slow vapor con
densation. In such regions, air would ac
cumulate and create a thick vapor-gas layer
523
 FIGURE 190. THE HEAT TRANSFER COEFFICIENT (oc) AS A
FUNCTION OF THE AIR CONTENT OF THE STEAM (£) FOR
VARIOUS WEIGHT VELOCITIES OF THE MIXTURES (wy, kg/
m2, sec).
near the condensation surface; this layer
would almost completely prevent the ap
proach of the heating vapor to the surface
in question.
The correct choice of the place for the
removal of noncondensable gases is of great
importance. It must be located where the
air concentration is maximum and where
the fresh vapor can not be mixed with the
vapor-air mixture already enriched with air;
such mixing would increase the air concen
tration within the entire heating chamber
volume.
From the point of view of the require
ments discussed above, the simplest and
most widespread type of vertical shell-and-
tube heat exchangers exhibit fundamental
drawbacks.
One form of such heat exchangers is
shown in Figure 191a. The heating steam is
introduced at the upper section of the shell
directly into the cluster of tubes. The non-
condensable gases are removed through a
connecting pipe located at the upper and
lower tube grid. The introduction of the
steam directly into the cluster leads to high
input resistances because of the sharp re
duction in size at the cross section of the
passage at this point. As the vapor con
denses, the speed of the mixture decreases
to a minimum in the region where the air
content is the largest and where this speed
should be especially high.
524
The vapor should flow rapidly through
the tube cluster, but this method of intro
ducing the steam and the location of the
pipe which removes the gases create stag
nant zones, i.e., sections with a slow-moving
air-enriched mixture. Consequently, the
heat exchanger is not very efficient even
when comparatively little noncondensable
gas is mixed with the incoming steam.
Thus, its use under vacuum is not ex
pedient.
For evaporators operating under vacuum,
we developed and investigated a new heat
ing chamber design which took into account
the above-mentioned requirements. One of
these designs is shown in Figure 191b. Be
tween the shell and the tube cluster, there
is an annular space not filled with tulies.
In the center of the tube cluster, we placed
a tube with openings through which we
removed the noncondensable gases. The
heating steam enters the collector, crosses
the grids, and is uniformly distributed over
the annular space. Subsequently, the mix
ture moves into the depth of the cluster
toward the place where the nonconden
sable gases are removed. This insures a
directed flow of vapor from the input into
the tube cluster and to the outlet. In ad
dition, the design has a low hydraulic re
sistance; (the velocities are not much higher
at the input into the tube cluster than
along the short passage) . As the amount of
 FIGURE 191. THE HEATING CHAMBER CONSTRUCTION.
the mixture decreases during condensation,
the cross section becomes smaller, and this
maintains the required speed.
A heating chamber of this design with
a heat exchanger surface of 1,000 m3 was
used in a pilot plant. The heat transfer
coefficient in the vacuum stages was close
to the heat transfer coefficient during the
condensation of pure vapor. This particular
design is not the only solution. Another
THE STUDY OF DROPWISE CONDENSATION
During our studies of dropwise condensa
tion, we considered the development of in
dustrial methods for the utilization of this
process in large heat exchange units. A
single application of any known water-
repelling agent on the heating surfaces can
not insure a sufficiently prolonged dropwise
condensation principally because industrial
vapors contain mixtures of insoluble sub
stances which gradually cover the heating
surface and disrupt the action of the drop
let stimulator. A continuous dropwise con
densation may apparently be attained only
after repeated, periodic applications of
the water repellent to the surfaces.
Under industrial conditions, the stimu
lator of dropwise condensation must satisfy
the following requirements:
(1) Sufficiently good adhesion to clean
contaminated metallic surfaces;
interesting design is the heating chamber
with horizontal partitions shown on Figure
191c. Placing horizontal partitions in the
tube cluster permits sufficiently high vapor
velocities along the entire path of the flow
from its entrance into the tube cluster to
the point where the noncondcnsable gases
are removed. Heating chambers of this type
are very useful for devices operating with a
low heat load region.
(2) Feasibility of periodic reestablishment
of dropwise condensation by simple
and inexpensive methods (preferably
without shutting off the device) ;
(S) Los cost, availability, and safety in
operation.
In the case of desalination devices, the
water-repelling agent must also be nontoxic,
and should not generate an aftertaste or
odors in the condensate.
We investigated certain silicon-organic
CH,
I
liquids ([QHsSiHO],,. [-Si -0-]n) . These
I
ONa
silicon-organic liquids may form hydro
phobic lavers 10"* cm thick on the metallic
surface. Within these layers the molecules
become oriented. The organic radicals of
the molecules form an outer layer, the "Lang
525
 muir palisade", generating the hydrophobic
properties of the material with part of the
Si —O— molecule oriented toward the water
repellent surface. The hydrophobic layers
are connected to the metal by chemical
bonds (refs. 2, S) . The chemical bonding of
the silicon-organic liquid with this water-
repellent surface can be schematically repre
sented in the following manner:
R R R The device consisted of three single-tube
-O-s'i-O-ii-O-ii-O-
¿ A A
..i. .1 — 1..
Material
The goal is stable, prolonged dropwise
condensation in the presence of the mono-
molecular layer or a layer a few molecules
in thickness. Such a layer could probably
be created by introducing the water-repel
ling agent into the steam in the form of
small droplets or even molecular groups.
As a result of laboratory investigation, we
established that prolonged dropwise con
densation (hundreds of hours) can be
achieved by passing the heating steam
through a condensate layer with a small
water-repellent mixture (less than 1 per
cent) or by heating with steam boiled out
of such an emulsion. The laboratory device
included several heat exchangers each of
which was made of a metallic tube 10 to 40
mm in diameter and 250 to 400 mm high,
placed in a shell of heat-resistant glass.
The action of the dropwise condensation
stimulator was tested on surfaces made of
different metals, e.g., copper, the MNZh5-l
alloy, brass, stainless steel (type 18-8) , and
others. The condensation characteristics
were checked visually. The device was sup
plied with pure vapor boiled from a dis
INTENSIFICATION OF HEAT EXl IANGE FROM THE LIQUID SIDE
Studies of the intensification of heat trans
fer by the liquid in evaporators followed
a trial method. Several methods for increas
ing the heat transfer coefficient during con-
vective heat exchange are: (1) heat libera
tion stimulation by ultrasound (ref. 4) ; (2)
the introduction of surface-active substances
into the liquid (ref. 5) ; (3) heat exchange
in high intensity electrical fields (ref. 6) ;
(4) the introduction of the liquid onto
the heating surface as a high speed current
(up to 14 m/sec) (ref. 7) . We studied this
last approach whose industrial applications
do not encounter any fundamental techno
logical difficulties.
The experiment concerning heat exchange
526
tillate. The investigation confirmed the
feasibility of a repeated reestablishment of
dropwise condensation. Copper tubes proved
to possess the best characteristics as far as
the duration of water-repellent action is
concerned.
Subsequent investigations were carried out
on larger experimental units supplied by
contaminated steam from industrial mains.
heat exchangers with a heating surface of
0.15 m*. The overall view is shown in Figure
192. During the investigations, the heat
transfer coefficient was measured in parallel
with the visual observations, and these
measurements served as the basic criteria
for the efficiency of the stimulator action.
During these experiments we achieved
multiple reestablishment of dropwise con
densation by introducing a water-repelling
agent into the bubbler (Fig. 19S) . However,
the contamination of the heating surface by
mechanical admixtures led to a sharp reduc
tion in the stimulator action period. Surface
condensation started to expand over a
major portion of the heating surface after
only 20 to 24 hours of operation. The heat
transfer coefficient during this period
dropped from (200 — 120) • 10* kcal/m* •
hr • degree at the time the water-repellent
agent was introduced to (30 — 10) • 10*
kcal/m" -hr • degree as the dropwise con
densation decreased. To prevent disruption
of dropwise condensation, the water repel
lent must be introduced more often through
the heating chamber or pass a portion of
the heating steam through the bubbler con
taining the water repellent. It is also im
portant to find the minimum water re
pellent consumption; consequently these
problems are the subject of further investi
gations.
during the jet application of the liquid
to the heated surface was carried out on
a single-tube model of the heating chamber
of the evaporator. The construction scheme
of the jet spray is shown in Figure 194. The
surface spraying was carried out by apply
ing the liquid through a perforated tube
with openings of 0.5 mm diameters and
by distributing in a checkerboard fashion
with 20 mm spacing. The length of the
heater tube was 1.12 m, and its interior
diameter was 34 mm. Tests showed the
feasibility of a heat transfer coefficient in
crease up to (30-35) • 10* kcal/m" • hr
• degree with a jet efflux velocity of 7 to 9
m/sec. A subsequent increase in velocity
FIGURE 192. THE OVERALL VIEW OF THE EXPERIMENTAL
DEVICE FOR THE STUDY OF DROPLET CONDENSATION.

527
 о
20 40 60 80 100 120 ИО 60
TIME, HOUR.
FIGURE 193. CHANGES IN THE HEAT TRANSFER COEFFICIENT
DURING DROPLET CONDENSATION (WATER REPELLANT
[C^SiHO],,).

(up to 13.5 m/sec) aiming at a further

intensification of the heat exchange did not
lead to the desired results. This may be
explained by the fact that an increase in
the amount of liquid supplied to the device
caused the layer of liquid flowing down the
surface to become so thick that the liquid
jet, in spite of its increased efflux velocity,
was washed out within this layer. The heat
transfer coefficient for the given case will
approach the coefficient obtained in evap
orators with an inclined plate, i.e.. (10 -
12) • lO* kcal/m" • hr • degree.
Our experiments are preliminary in char
acter. For the solution of the problems
connected with industrial utilization of
methods for the intensification of the heat
exchange under investigation, more de
tailed experiments must be carried out and
the most rational constructive scheme ap
plicable to evaporators must be developed.

FIGURE 194. THE CONSTRUC

TION DESIGN OF SURFACE
SPRAYING.

528
 REFERENCES
1. Berman, L. D.: Teplœnergetika (Ther
mal Power Engineering) no. 5 (1954) .
2. Bazhant, V.; Khvalovskii, V.; Ratouski, I.:
Silikony (Silicons), Moscow, Goskhimiz-
dat (1960).
3. Bass, R. L.: Chemistry and Industry
(1959) p. 29.
4. Tret'yakov, A. P.: "Ch'eng hua-ting",
Teploenergetika no. 11 (1960).
5. Stroebe, G. W.; Baker, E. M.; Badger,
W. L.: Trans. Am. Inst. Chem. Engrs.
no. 35 (19S9) p. 17.
6. Alad'ev, I. T.; Efimov, V. A.: Inzhenemo-
Fizicheskii Zhurnal (Journal of Engineer
ing Physics) vol. VI, no. 8 (1963) .
7. Petrovskii, Yu. V.; Fastovskii, V. G.:
Sovremennye Effektivnye Teploobmen-
niki (Modern Efficient Heat Exchangers),
Moscow, Gosenergoizdat (1962) .

SUMMARY OF DISCUSSION
There was no discussion.

Intensification de L'Echange de

Chaleur Dans Les Installations

a Evaporateurs

V. B. Chernozubov, A. A. Bolotov, V. N. Chadov, F. P. Zaostrovsky,

S. I. Golub, L. A Minukhin, L S. Mrehzin

Union des Républiques Socialistes Soviétiques

On a étudié la possibilité de l'intensifica des nombres de Reynolds et du débit du

tion de l'échange de chaleur dans les in
stallations de dessalement par évaporation,
en encourageant la condensation de la
vapeur sous forme de gouttelettes, par son
barbotage à travers une suspension aqueuse
de substances hydrophobes, par l'évacuation
de gaz non condensés, par l'augmentation
liquide en contact avec la surface de
l'échangeur de chaleur sur le côté eau.
On démontre la possibilité d'augmenter le
coefficient d'échange de chaleur de la vapeur
pour le porter jusqu'à 100.000-180.000
kcal/myh/°C et celui du liquide à 30.000
kcal/myh/°C.

529
 Интенсификация Теплообмена

в Испарительных Установках

В. Б. Чериозубов, А. А. Болотов, В. Н. Чадов, Ф. П. Заостровский,

С. И. Голуб, Л. А. Минухин, Л. С. Мрежин

СССР

Исследованы возможности интенси Рейнольдса и скорости потока жидко

фикации теплообмена в испарительных
опреснительных установках путем про-
мотирования капельной конденсации
пара барбатажем его через водную
суспензию гидрофобизируюших ве
ществ, путем отвода неконденсирую
щихся газов, путем повышения чисел
сти, омывающей поверхность теплопе
редачи с водной стороны.
Показана возможность увеличения
коэффициента теплопередачи пара до
100000-180000 ккал/м2 час "С и жид
кости до 30000 ккал/м2 час вС

Intensificación del Intercambio de

Calor en Instalaciones de Evaporación

V. В. Chcrnozubov, A. A. Bolotov, V. N. Chadov, F. P. Zaostrovsky,

S. I. Golub, L. A. Minukhin, L. S. Mrezhin

Union de Repúblicas Socialistas Soviéticas

Ha sido investigada la posibilidad de in tacto con la superficie del intercambiador

tensificar la transferencia de calor en
plantas de desalinización mediante promo
ción de la condensación de vapor en gotas
por burbujeo a través de una suspensión
acuosa de sustancias hidrófobas, por des
carga de gases no condensados, por incre
mento de los números de Reynolds y de
la velocidad del flujo del liquido en con
de calor sobre el lado del agua.
La posibilidad de incrementar el coefi
ciente de transferencia de calor del vapor
hasta 100.000-180.000 kCal/m* por hora por
grado centígrado y del líquido hasta
30.000 kCal/m! por hora por grado centí
grado se muestra en el trabajo.
Slit and Point Corrosion (Pitting)

of Stainless Steels in Chloride Solu

tions at Temperatures up to 100° C

M. N. Fokin, M. M. Kurtepov, V. K. Zhuravlev, and V. I. Oreshkin

Union of Soviet Socialist Republics

INTRODUCTION
The use of stainless steels as corrosion-
resistant structural materials in corrosive
media is based on the highly protective
properties of the surface (oxide) film of
the alloy in the passive state. The localized
character of the failure, which occurs due
to the corrosion of stainless steels in sea
water, is seen as the result of a partial
breakdown in passivity.
The concept of the pitting corrosion of
metal, which has been accepted with respect
to stainless steels in chloride solutions, has
been treated with sufficient completeness
in the work of Uilig (ref. 1) . The neces
sary condition for the development of this
type of failure is the combination of the
chlorine ions in the solution with the
increased oxidizing properties of the me
dium, which bring about an anodic dis
turbance in the passive state of the steel.
In addition, it is known that the process
of localized corrosion in stainless steels may
be accelerated in stagnant sea water under
conditions of overgrowth, under packings,
in fissures and gaps, etc. Among the factors
not related to the composition of the stain
less steels are the successive processes of
deoxygenation of the solution in a narrow
gap and the work of differential aeration
pairs which play a major role in the
initiation of crevice corrosion. These two
factors lead to the acidification of the solu
tion in the anodic electrode gap of the
fissure. In contrast with pitting type failure,
localized crevice corrosion is the result of
the acid-reducing activation of the passive
state of stainless steels in chloride solutions.
The failure in steel in the case of acid-
reducing activation is usually gradual. Lo
calized pitting on the surface of stainless
steels can be found under packings or in
narrow fissures with corrosion in sea water.
The presence of this pitting seems to con
tradict the facts given above; however, this
is not a real contradiction. The selective
failure of the metal in the fissure is the
result of the localized character of the
acidification of the solution in the fissure
which, in turn, is due to the development
of an electrochemical dissimilarity in the
system. Ulanovskii and Korovin (ref. 2)
made direct measurements of the pH of the
solution under packings with self-dissolu
tion of stainless steel in sea water and of
the pH of the anolite after external anodic
polarization of the steel in a narrow gap.
These measurements showed that the local
ized acidification of the solution in the
fissure attains pH values of 3.0 and even 2.3.
The relatively low pH values of the solu
tion in the fissure which were obtained in
experiments cannot yet be considered as
limiting; because of the method of determi
nation used, true readings for the layer
near the electrode may be distorted by the
readings for the contents of the initial
neutral solution. Acidification of the solu
tion in the fissure is limited by the natural
buffering products of anodic dissolution.
The theoretical limit of this acidification
should be refined, and the acid-resistant
steel should also be more resistant to crev
ice corrosion in neutral media.

531
 EXPERIMENTS AND DISCUSSION
OF THE RESULTS
CREVICE CORROSION centrations of salt in the solution, and tem
perature which follow.
As a criterion for the evaluation of the From the characteristic parameters, in
tendency of stainless steels to crevice cor addition to pH„ it is necessary to note the
rosion, we took the critical value of the maximum (critical) density of the anodic
pH solution (pHer) initiating the acid- passivating current in the polarization loop
reducing activation of the passive state of of active dissolution (i„) and the puncture
the steels. The potentiostatic method of potential .F,, which is the anodic disturb
electrochemical investigation was used to ance potential of the passive state), at the
study the effect of the acidification-reducing beginning of which a strong increase in the
properties of the medium on the rate of anodic corrosive current is observed. The
anodic dissolution of the passivated alloys. magnitude of E,„ is interpreted from полу
The design of the potentiostatic installa on as a parameter in the evaluation of the
tion used in the polarization measurements tendency of stainless steels to pitting cor
and the construction of the electron poten - rosion.
tiostat have been previously described. The control polarization measurements
Measurement of the electrode potential was carried out on sodium chloride solutions in
made relative to a saturated calomel elec a nitrogen atmosphere (with preliminary
trode and recorded relative to a hydrogen passage through a solution of gaseous nitro
electrode. Platinum was used as an auxiliary gen for 5 hours) have shown that the de-
electrode in the thermostated cell. Sodium aeration of the solution does not directly
chloride solutions imitating sea water were facilitate the anodic process in stainless
acidified with hydrochloric acid and used steel within the range of electrode poten
in a separate senes of tests in order to tials investigated and up to potential Гр„
obtain a comparative evaluation of the Under conditions of deaeration, only a
crevice effect. deterioration of the stationary electrode po
The series of potentiostatic polarization tential is
curves for the steel lKhl8N10T in a 3 per
cent solution of sodium chloride was re
corded in the interval of pH values from IMa/CM t-20*
1.8 to 0.9 at IC0"C (Fig. 195) and is typical
for obtaining the required information on
the changes in the characteristic parameters
for the variations in steel composition, con-

Evod,b

.KMN2M3T
2 8 24 20 1.6 #12 08 04 0 pH

4 8 12
l.matrrr t 2Л 2.4 2.0 L6 12
l-pH'1.8; 2-pH=l.4,3-pH = l.2¡4-pH-0.9
FIGURE 196. DEPENDENCE OF
FIGURE 195. POTENTIOSTATIC k ON pH IN A 3% SODIUM
POLARIZATION CURVES FOR CHLORIDE SOLUTION FOR
STEEL Khl8N10T IN A 3% SO VARIOUS STAINLESS STEELS
DIUM CHLORIDE SOLUTION AND DIFFERENT TEMPERA
AT lOO'C. TURES.
532
 Experimental data on the effect of tem
perature on the acid-reducing activation of
stainless steels in a 3 per cent solution of
sodium chloride are shown in Figures 196
and 197.
IMa/CM I U I mental method (ref. 2), the concentration
2A 22 20 IB 16 14 1.2 10 08 Q6 pH
1-STEELKhBNIOT,
05 NaO, 2-STEEL NoQ
KM7NBM3T,
SATURATED
FIGURE 197. DEPENDENCE OF
i„ ON pH IN SODIUM
CHLORIDE SOLUTIONS.
At 20°C the less acid-resistant steel,
Khi 7, taken for a single comparison, was
subject to acid-reducing activation upon
reaching the pH value 3.1; but a greater
acidification of the solution, up to pH
values of 1.4 and 0.34 respectively, was
required for the steels Khl8N10T and
Khl7N13M3T. With a temperature in
crease to 80°C, the onset of acid-reducing
activation for the steel Khl8N10T remains
at approximately the same level (pH„ =
1.4) . For steel Khl7N13M3T under identi
cal conditions, the passive state is not dis
turbed up to pH„ — 1.1. The most reliable
experimental data show that at a tempera
ture of 100°C and a pH of 1.8, the acid-
resistance of steel Khl7N13M3T is 6 times
greater than that of steel Khl8N10T (Fig.
196) . In order to evaluate the effect of a
possible concentration of chlorine ions in
the layer near the electrode of the corrod
ing metal on the acid-resistance of the
metal, we studied the critical current den
sity (i„) as a function of pH for the two
steels tested on a background of a saturated
sodium chloride solution. As can be seen
from Figure 197, in this case the beginning
of the activation of the steel occurs earlier,
i.e., with a somewhat lowered acidification
of the solution.
According to the obtained data, notice
able crevice corrosion in steel Khl8N10T
can occur only in the case of a localized
acidification of the solution near the elec
trode up to a pH value of 1.4 (at 80° C)
and a pH value of 1.8 (at 100°C), while
crevice corrosion in steel Khl7N13M3T
occurs with a somewhat greater acidification
of the solution. In the first approximation,
using the previously mentioned experi
(activity) of the hydrogen ions of the
initial neutral anolite in the narrow one
mm gap under current at 60° and 80°C
will attain pH values close to 2.4 as a limit.
In addition, on the basis of the data on
the corrosion permeability of stainless steel
in a model evaporating-recirculating in
stallation, the acidification of the solution
in a narrow gap proceeds substantially
farther.
In a vertical block made of four pipes
heated from the outside (two made from
steel KhlSMOT and two from steel
Khl7N13M3T) , the connection to the upper
water collector was made of rubber sleeve-
packings, creating an actual circular gap
between the pipe and the packing nut
(Fig. 198). After 150 hours of operation of
the installation in a recirculating 3 per
cent buffered (pH = 4) solution of sodium
chloride at 100°C, a clearly visible crevice
corrosion with a permeability of 30 to 40
mm/year was noted in the zone of the
circular gap for the steel KhlSNlOT, while
no corrosion was observed in the same zone
for the steel Khl7N13M3T. Comparing the
results obtained with electrochemical data
(Fig. 197), the narrow range of the rela
tively acid pH values of 1.5 to 1.7, which
can be attained in the fissure space, was
evaluated. However, in the calculation of
the maximum depth index of corrosion
(0.85 mm/150 hrs) in the circular gap of
the pipes made from steel Khl8N10T,
the maximum localized acidification of the
solution attains pH values of 15 for the
current. Such a substantial lowering of the
pH of the solution in the fissure cannot be
explained by an anodic acidification of the
hydrolysis type without taking into account
the additional effect of the concentration of
salts in the narrow gap on the increased
activity of hydrogen • ions (ref. 4). The cal
culations of the maximum values of corro
sion permeability for stainless steels in
crevice corrosion, given maximum possible
acidification of the solution in the fissure
(and vice versa), are sufficiently accurate
and do not depend on the relationship
between the surfaces of a macrocell (i.e., on
the relationship of the metal surface out
side the fissure (cathode) to the metal
surface in the fissure (anode) ) , since the
work of this pair is controlled by the anodic
533
 process, the maximum rate of which (i„)
at a given temperature is almost entirely
dependent on the pH of the solution.
disturbance of the passive state iErai for
steels Khl8N10T and Khl7N13MST in a
3 per cent concentrated sodium chloride
solution. The molybdenum steel showed
greater resistance to pitting under all testing
conditions, although in both steels the tend
ency to pitting increased with increasing
temperature and with increasing concentra
tion of chlorine ions in the solution.

05nNaO

NaaSotuvtod

100 f,C

FIGURE 199. TEMPERATURE

DEPENDENCE OF THE
CHANGE IN THE POTENTIAL
OF ANODIC DISTURBANCE
OF THE PASSIVE STATE
(Epn).
Steel Khl8N10T
FIGURE 198. DIAGRAM OF PIPE Steel Khl7NlSMST
CONNECTION WITH UPPER
WATER COLLECTION IN As demonstrated by further experiments,
MODEL EVAPORATING RE- with acidification of the sodium chloride
ClUCULATORY INSTALLA solution up to a pH value of 1.5, the poten
TION. tial of the anodic disturbance of the passive
1 - Pipes investigated state of the steels (Ep„) remains practically
2 ■ Solution receptacle unchanged (Fig. 200) . The molybdenum
S ■ Areas of corrosion in steel EYalT steel in this case displays a greater resist
4 • Rubber packing ance to pitting than does steel Khl8N10T,
5 - Electric heater especially in the acid region. In slightly acid
6 ■ Gap between pipe wall and nut (. .— and neutral solutions, these advantages de
0.5 ■ 0.8 mm) crease somewhat as the temperature rises
7 - Packing nut to 80°C. But with a further temperature
increase to 100°C, the steel Khl7N13M3T
again displays greater relative resistance to
PITTING CORROSION pitting corrosion than steel Khl8N10T.
The electrochemical evaluation of the In stainless steels, increased temperature
tendency of stainless steels to pitting cor stimulates pitting more effectively than
rosion in the temperature interval up to increased acidity. This holds true only when
100°C was carried out in the first series of the acidifying properties of the medium,
tests in neutral sodium chloride solutions. which can be measured from the magnitude
Figurel99 shows the temperature dependence of the stationary electrode potential, remain
of the change in the potential of the anodic unchanged. With increased acidity the acid

534
ifying properties of the solution (both with
respect to oxygen and hydrogen ions) in
crease, thus increasing the tendency of
stainless steels to pitting. In accordance with
the experimental data on the kinetics of the
establishment of the potential (over a period
of two hours), the stationary potentials of
the steels Khl8N10T and Khl7NlSMST
were practically identical under all test
ing conditions prior to the disturbance
of the passive state (both of an acid-
reducing character and with an excess of
oxidizer) .
FIGURE 200. DEPENDENCE OF
THE STATIONARY POTEN
TIAL (3.4) AND POTENTIAL
OF ANODIC DISTURBANCE
OF PASSIVE STATE (Epu) OF
STAINLESS STEELS IN A 3%
SATURATED SODIUM CHLO
RIDE SOLUTION, ON THE
pH OF THE SOLUTION.
1 - Steel Khl8N10T
2 - Steel Khl7NlSM3T
The magnitudes of the stationary poten
tial and of the potential of the anodic
REFERENCES
1. Uilig, H. H.: Corrosion Handbook (1948).
Korroziya Metallov (Metal Corrosion)
vol. 1, edited by V. V. Skorcheletti, Mos
cow, Goskhimizdat (1952) p. 62.
2. Ulanovskii, I. В.; Korovin, Yu. M.:
Zhurnal Fizicheskoi Khimii (Journal of
Physical Chemistry) no. 33 (1959) p.
1414; ibid no. 31 (1958) p. 1S66.
disturbance of the passive state (Epo) for
steel Khl8N10T, obtained under isothermic
conditions in freshly prepared sodium chlo
ride solutions of various concentrations
were compared (Fig. 200) . This comparison
showed that at first, the pitting does not
occur at temperatures below 80°C and
that the tendency to pitting is greatest in a
saturated solution. In time, there is a
gradual accumulation of the products of
corrosion, and the crevice effect (i.e., the
localized acidification of the solution) ap
pears in the presence of the thermodynami-
cally high oxidizing properties of the oxy
gen dissolved in the water. Time seems to
be the decisive factor in the localized im
provement in potential, which enhances the
anodic disturbance of the passive state. In
fact, in the more acid sodium chloride
solutions, the values of the stationary po
tential and of the puncture potential
overlap (Fig. 200) , showing the possibility
of pitting formation under these conditions.
Acidification of the solution due to the
crevice effect may lead to pitting before
the acid-reducing activation occurs. This
is the link between two essentially différent
processes of the disturbance of the passive
state of stainless steel.
It also follows from the dependences shown
in Figure 200, that the greatest probability
of the occurrence of pitting is found in
concentrated solutions in the presence of
temperature drops along the metallic struc
ture. The work of thermogalvanic pairs may
be very effective in such cases. As seen
from the analysis of subsequent tests, the
maximum depth of pitting on the inner
surface of heating pipes made from steel
1KM7N13MST in a model installation was
always smaller, but comparable with the
data for steel lKhl8N10T whose corrosion
permeability under actual conditions (with
aerated sea water fed to the input) is esti
mated to be 1.8 to 2.0 mm/year (for the
first three months) and 0.6 mm/year for
two years of operation of the pipes in an
experimental desalination plant.
S. Fokin. M. N.; Kurtepov, M. M.; Zhurav-
lev, V. K.; Vinogradov, A. F.: Zavod-
skaya Laboraloriya (Plant Laboratory)
no. 2 (1960) p. 219.
4. Schwabe, К..: Zeitschrift für Physikalische
Chemie, Neue Folge, по. 41 (1964)
p. S68.
535
 SUMMARY OF DISCUSSION
There was no discussion.

Corrosion Par Fissuration et Piqûre

de L'Acier Inoxydable Dans Des

Solutions de Chlorure a 'Des

Temperatures Allant Jusqu'à 100°C

M. N. Fokin, M. M. Kurtepov, V. K. Shuravlcv, V. L Oreshkin

Union des Republiques Socialistes Soviétiques

Dans ce rapport on a effectué une com
paraison de la susceptibilité des aciers
inoxydables IXI8HIOT et IXI7HISM3T à
la corrosion par fissuration et piqûre dans
des solutions saturées de chlorure de sodi
um a 3% et avec des changements dans le
pH de l'ambiance de 0,3 à 7,5 et des tem
pératures de la solution de 20 à 100°C.
Une connaissance des limites de résistance
des aciers examinés a rendu possible de
prédire leur utilisation efficace.
La comparaison du potentiel d'équilibre
et du potentiel de dislocation anodique de
l'état passif des aciers examinés a indiqué
que dans des solutions suffisamment con
centrées de chlorure de sodium, de faible
acidité, avec augmentation de la tempéra
ture au-dessus de 80°C, les propriétés
d'oxydation de la solution aérée sont suffi
santes pour l'apparition et la croissance de
piqûres en raison de l'action à la fois des
micro-cellules ainsi que des macro-cellules
thermogalvaniques.
La profondeur maximum de corrosion
des tubes de chauffage en acier IXI7HI3M3T
dans une installation modèle a toujours été
moindre, mais comparable avec les données
pour l'acier IXI8HIOT, dont la pénétration
de la corrosion est estimée dans des condi
tions de fonctionnement réel, avec injection
dans l'entrée d'eau de mer aérée, être a
un niveau de 1.8 à 2 mm par an (pour les
trois premiers mois) et à 0,6 mm par an
pour deux années de fonctionnement des
tubes dans une usine expérimentale de
dessalement.

536
 О Щелевой и Точечной Коррозии
Нержавеющих Сталей в Растворах
Хлоридов при Температурах до 100°С
Фокин M. Н., Куртепов M. М., Журавлев В. К., Орешкин В. И.
СССР
В работе проведена сравнительная
оценка склонности нержавеющих ста
лей IXI8HIOT и IXI7HI3M3T к щелевой
и точечной коррозии в 3%-ном и на
сыщенном растворах хлористого натрия
при изменениях pH среды от 0,3 до 7,5
и температурах раствора от 20 до
100-С.
Знание границ устойчивости иссле
дованных сталей позволило прогнози
ровать их рациональное применение.
Сопоставление значений стационар
ного потенциала и потенциала анодного
нарушения пассивного состояния ис
следованных сталей показало, что в
слабокислых, достаточно концентриро
ванных растворах хлористого натрия с
Corrosion Crateriforme
Inoxidable en Soluciones de Cloruros
a Temperaturas
M. N. Fokin, M. N. Kurtepov, V. К. Zhuravlev, V. I. Oreshkin
Union de Repúblicas Socialistas Soviéticas
En este informe se hace una comparación
de la susceptibilidad de los aceros inoxida
bles lKhl8N10T y IKhl7N13M3T a la
corrosión crateriforme en soluciones de
cloruro de sodio saturadas y al 3%, con
cambios en el pH del medio desde 0,3 a 73
V la temperatura de la solución de 20
a 100°C.
Un conocimiento de los límites de resis
ростом температуры выше 80'С оки
слительные свойства аэрированного
раствора являются достаточными для
возникновения и развития точечной
коррозии за счет работы как микропар,
так и термогальванических макропар.
Максимальная глубина коррозии гре
ющих трубок из стали IXI7HI3M3T на
модельной установке всегда была
меньшей, но соизмеримой с данными
для стали IXI8HIOT, коррозионная про
ницаемость которой в реальных усло
виях при подаче на вход аэрированной
морской воды оценивается на уровне
1,8-2,0 мм/год (за первые 3 месяца)
и 0,6 мм/год за 2 года работы трубок
на опытной опреснительной установке.
de Acero
Hasta de 100° С
tencia de los aceros examinados hace po
sible predecir sus eficiencias de utilización.
La comparación del potencial de equili
brio y el potencial de dislocación anódica
del estado pasivo de los aceros examinados
indica que en soluciones ligeramente ácidas
y suficientemente concentradas de cloruro
de sodio, con temperaturas mayores de
80°C, las propiedades de oxidación de las
soluciones aereadas son suficiente para la
aparición y propagación de corrosión cra
teriforme debida a la acción de la micro-
célula y de la macrocelula termogalvánica.
La profundidad máxima de la corrosión
de tubos de calentamiento de acero
!Khl7N13MST en una instalación modelo
fue siempre menor que, pero comparable
con los valores para acero lKhl8N10T,
cuya penetración de corrosión se estima
bajo condiciones de operación, con inyec
ción en la entrada de agua de mar aereada,
a un nivel de 1,8-2,0 mm/p.a. (para los tres
primeros meses) y a 0,6 mm/pj. en los
tubos usados en una planta experimental
de desalinización por un período de dos
años.
Prevention of Scale Formation in

Distillation Desalination Plants

by Means of Seeding

V. B. Chernozubov, F. P. Zaostrovskii, V. G. Shatsillo, S. I. Golub,

E. P. Novikov and V I. Tkach

Union of Soviet Socialist Republics

Scale deposited on heat exchange surfaces
during the distillation of sea water may
consist of calcium sulfate, calcium car
bonate, and magnesium hydroxide. Depend
ing on the conditions of heating and evap
oration, one, two, or all three of these
components become part of the scale.
It is possible to construct a multistage
evaporation system so as to avoid crystalliza
tion of calcium sulfate by using the inverse
dependence of solubility on temperature.
To do that, the boiling point should be
lowered successively from one stage to the
other in proportion to the increase in the
concentration of salts without going over
the solubility limit in any one evaporation
stage. Then the task of combating scale is
reduced to preventing deposits of calcium
carbonate and magnesium hydroxide.
Those conditions are completely satisfied,
for example, by continuous multistage evap
orating equipment in which, without risk
ing sulfate crystallization, sea water can be
concentrated three to rive times at a boiling
point of about 40°C in the last stage.
Preventing calcium sulfate deposits in flash
evaporators with closed circulation of sea
water is more complex since in this equip
ment sea water with a maximum salt con
centration passes through the entire range
of temperatures.
Several methods of preventing scale have
been proposed. The best-known and most
practicable methods are the following:
(1) Continuous treatment of sea water
with acids to decompose bicarbonates;
(2) Softening of the arriving sea water
before distillation by sodium cation-
exchange;
(S) Thermochemical softening of the sea
water.
All of these methods require operating
expenditures for reagents, steam, and the
like, or special unwieldy equipment, or
both. The authors of the present report
have taken a less known but, from their
point of view, more promising method of
preventing scale by introducing seed crys
tals into the evaporator (the so-called
seeding method).
In the seeding method a finely dispersed
substance corresponding in composition to
that of the separated scale is introduced
into the sea water to be evaporated, and
the scale compounds crystallize on the
seed crystals. Thus the heat exchange sur
faces remain free of scale. The seed crystals
carried out of the evaporator with the con
centrated sea water can be collected by
clarifying equipment and returned to the
system.

TESTING THE SEEDING METHOD

The seeding method was tested for the Pacific Ocean. During the concentration
first time by the authors in 1954-55 in of this water in experimental evaporators,
conducting experimental work on obtain scale formed intensively; to combat this
ing sodium chloride from the water of the problem, seed crystals of calcium carbonate

539
 and sulfate were introduced into the evap
orator.
The experiments were conducted on two-
stage evaporators built of vertical long tube
units with a heat exchange surface of
2.5 sq m. The design permitted operation
with natural and forced circulation, with
or without boiling in the heating tubes.
The boiling point of the sea water in the
apparatus was held in the range of 100°
to 1S0°C, and the salt concentration was
increased seven or eight times.
It was found that with boiling inside
the heating tubes and without seeding,
the heat transfer coefficient decreased by
half in seven to eight hours of continuous
operation; in an apparatus with boiling
outside the tubes, it decreased by half in
nine to eleven hours. When seed crystals
were introduced, the formation of scale
was retarded. However, it was still consid
erable if the sea water boiled in the heating
tubes. A completely different picture was
observed when seed crystals were introduced
into the evaporating apparatus with boiling
outside the tubes: no drop in heat transfer
was detected by the instruments over a
period of 10 to 14 days. Examination of
the heat exchange surfaces showed almost
no scale. Thus, an effective method of
combating scale during the evaporation of
sea water was developed.

LABORATORY OBSERVATK OF SCALE DEPOSITION

Work on the creation of sea water
evaporators operating without scale forma
tion was resumed in 1960. To study the
distillation of sea water and, primarily, to
solve the problem of preventing scale, a
great deal of experimental work was car
ried out. The main part of this work
was carried out on experimental equipment
on a seraiindustrial scale built on the
coast of the Caspian Sea.
Before stating the results of three years'
investigations with that equipment, we will
describe a laboratory study of scale deposi
tion during boiling, since that work gave
an idea of the character of scale deposition
and of the influence of boiling the solution
on the intensity of deposition on the heat
exchange surface. The experiments were
conducted with laboratory equipment (Fig.
201) which was a vertical glass bath with a
vertical heating element made of stainless
steel piping placed in it. Inside the ele
ment was an electric heater. In contrast with
other analogous work in which calcium
sulfate served as the scale-former (refs.
I, 2), the authors investigated the formation
of scale mainly from a solution of calcium
bicarbonate, since that was precisely the
substance contained in the sea water which
presented the problem in the given case.
Whereas calcium sulfate scale forms as FIGURE 201. OVERALL VIEW
a result of crystallization when the solu OF THE LABORATORY
bility limit is exceeded, scale formation EQUIPMENT.
during the heating and evaporation of
bicarbonate solution occurs as a result of leads to intensified scale deposition at the
thermal decomposition shown as points of boiling as compared with simple
Ca (HCO.) j-frCaCCvfHjO+CO,. heating of the solution. Shtumper, for ex
Practically insoluble CaCO, is deposited ample, had already pointed this out (ref.
as scale. Carbon dioxide readily goes from S) , and experiments have confirmed the
the solution into the vapor phase during fact. Even one or two hours after the
boiling. Elimination of one of the reaction equipment is started, scale appears on the
products increases the reaction rate and heat exchange surface at the places where
540
vapor bubbles formed. Soon after the form
ation of these initial scaling foci, the
entire heat exchange surface is covered with
a very thin deposit whose thickness in
creases with time. This indicates that, to
facilitate scale prevention, the solution on
the heat exchange surface must not be
allowed to boil.
It was discovered that, in addition to
thin deposits of scale, there were sections
with a greater intensity which spread in
a narrow path upward from the center of
vapor formation to the surface, reproducing
the path of a chain of bubbles floating
upwards after breaking away. Consequently,
increased deposition occurs not only dur
ing the formation of vapor on the metal
EXPERIMENTS WITH LARGE-SCALE EQUIPMENT
The basic experimental work on desal
ination of sea water by evaporation with
seeding was done with large-scale experi
mental equipment built on the coast of
the Caspian Sea at Shevchenko. The equip
ment (Fig. 202) , with a productivity of
four to five tons/hr of distillate, consisted
of three stages connected as a continuous
flow evaporating battery.
The sea water entered the first evap
orator, was transferred from one evaporator
to another, and gradually evaporated into
a concentrate. Then the sea water concen
trate with the suspended seeds went from
FIGURE 202. SCHEMATIC DIAGRAM OF EXPERIMENTAL
CONTINUOUS EQUIPMENT.
surface but also during the movement of
vapor bubbles close to the surface. There
fore the prevention of scale by seeding is
evidently difficult in any apparatus with
boiling of the solution in the heating tubes,
even in units with a dropping film in
which, in the opinion of some authors,
the formation of vapor bubbles on the
walls of the heating tubes does not occur
because of intensive turbulent heat trans
fer from the tube wall to the liquid
film-vapor interface.
The described investigations were explor
atory and helped to determine possibilities
for the creation of large distillation desal
ination equipment operating without scale
formation.
the third evaporator into a settling tank.
The seed crystals were returned in the
form of a dense slurry to the first evapora
tor and the clarified concentrate was dis
charged into the sewer. The first evaporator
was heated by steam from a boiler. The
secondary steam was used to heat the
second evaporator, etc. The secondary
steam of the third evaporator was directed
into a surface condenser. The distillate from
the heating chambers of the second and
third evaporators and from the condenser
was directed into small measuring tanks
and then into a storage tank. The seed
541
 crystals were introduced into the evapora
tors at the start of each experiment when
the equipment was started up.
Two types of units were selected for the
tests. Standard vertical long tube evapora
tors with natural circulation and boiling
of the solution in the heating tubes were
used in the second and third stages, and
an evaporator with natural circulation and
a boiling zone remote from the tubes was
used in the first stage. Boiling in the heat
ing tubes was avoided by lowering the
heating chamber under a layer of solution
so that the solution, moving upward
through the tubes, was only superheated
in the tubes and started boiling after
coming out of the tubes into a so-called
riser (refs. 4, 5). Three temperatures of
sea water boiling were investigated in the
first stage: 90°, 100°, and 1I5°C. The boil
ing point in the second stage was 60° to
75°C, depending on conditions, and 40°
to 45°C in the third stage. The sea water
was evaporated to a salt content of 50 to
60 grams/liter. At a higher concentration,
there was a danger of calcium sulfate
crystallization in the third stage.
During each experiment, which lasted
from 10 to 30 days, the working conditions
of the equipment were kept constant, and
the state of the heat exchange surfaces
(i.e., the presence or absence of scale) was
FIGURE 203. GRAPH OF HEAT TRANSFER COEFFICIENT
IN CONTROL EXPERIMENTS.
1, 2, and 3 - in stages 1, 2, and 3 respectively;
4 • salt content of evaporated sea water.
542
checked by the changes in the heat transfer
coefficients (Fig. 203) . At the conclusion
of alternate experiments, the units were
opened and the heat exchange surfaces were
examined for scale.
In the first series of experiments it was
found that seeding with calcium carbonate
in the form of finely ground natural chalk
was an effective means of combating scale
formation. Even at a boiling point of 115°C
in the first evaporator, scale deposits on
the heat exchange surface were almost com
pletely prevented; however, under those
conditions, mainly magnesium hydroxide
was precipitated. It should be noted that,
in this case, the seeds circulating in the
system were gradually enriched with
Mg(OH)„ which became the predominant
component in a few days after start-up. In
spite of noncorrespondence of the chemical
composition of the seeds and the separating
solid phase in the initial period of opera
tion, the heat exchange surface remained
free of scale. Therefore, since there are
natural surface deposits of chalk on most
seashores, this is an inexpensive and easily
available material for seeding.
When introduced into the units, the
seeds consisted of panicles 20 to 100 microns
in size. In the first five to seven days, the
seeds were gradually pulverized, and then
a definite semidispersed composition char
acterized by particles 10 to 40 microns in
size was established.
In the first experiments it was established
that seeding does not prevent scale forma
tion in all evaporators. In the first stage
evaporator, the unit with boiling outside
the heating tubes, operated without scale
formation, despite the fact that the water
temperature was maximal and the fact that
the entering fresh sea water contained a
very large amount of scale-forming compon
ents; however, in the second stage evap
orator, the unit with boiling in the tubes,
there was a slow deposition of calcium
carbonate scale on the heat exchange sur
face even with high concentrations of the
seeding material (up to 20 to 25 grams/
liter). Before continuing the experiments,
the second and third evaporators of the
experimental equipment were replaced with
units in which boiling occurred outside
the tubes. After this, scale formation ceased
in all units.
Thus, in order to prevent scale forma
tion by seeding, it is necessary to prevent
evaporation of sea water on the heat ex
change surface in addition to using seed
crystals.
A special series of experiments was set
up to determine the minimum concentra
tion of seeding necessary to prevent scale
in an evaporator with boiling outside the
tubes. It was found that for the operating
conditions of the first stage at a boiling
point of 90°C, the necessary concentration
of chalk seeding in the sea water inside
the apparatus is a minimum of 5 kg/cu m.
During operation, the concentration should
be kept within the limits of 8 to 10 kg/
eu m. At a boiling point of 115°C, the
concentration of seeding should not be less
than 15 kg/cu m.
It should be pointed out that the volume
of sea water in the evaporator plays a
considerable role in the prevention of
scale. The larger the volume, the longer
the contact of the seeding with super
saturated sea water and the more com
pletely the scale-forming substance is sep
arated on the seeding away from the heat
THE PREVENTION OF CALCIUM SULFATE SCALE
The described method, which has been
developed and organized on an industrial
scale, permits concentrating the sea water
by a factor of 4 or 5. Greater concentra
tion, which in a number of cases would
provide the economic advantage of obtain
ing crystalline products, such as sodium
chloride, sodium sulfate, and other readily
exchange surface.
The values of the minimum concentra
tion of seeding obtained are valid only for
the volumes of liquid relative to the pro
ductivity of the apparatus used. A decrease
in the relative volume of liquid in the
apparatus requires an increase in the con
centration of seeding and vice versa.
The cycle of investigations was com
pleted by prolonged control tests of the
experimental equipment. The boiling point
was 95°C in the first stage, 65°C in the
second stage, and 43 °C in the third stage.
The salt content in the evaporated sea
water was kept within the limits of 45
to 50 kg/cu m, and the concentration of
seeding in the first stage was kept at 10
to 12 kg/cu m. The equipment worked
90 days under these conditions with no
change in the heat transfer coefficients.
After completion of the tests, there was no
trace of scale on the heat exchange sur
faces, and the heating tubes preserved their
metallic luster. These results prove that
scale formation can be prevented during
prolonged distillation desalination.
On the basis of these results, an indus
trial desalination plant was constructed on
the coast of the Caspian Sea and has been
successfully operated since 1963; it is a
four-stage continuous flow evaporating bat
tery with a chalk seeding recirculation
system. The distillate goes into the drinking
water supply system of the city of Shev-
chenko. The plant has an experimental
purpose as well as an industrial one; a
process using the heat from a nuclear
reactor for a large-scale water desalination
plant is being developed.
The basic equipment of the plant is an
evaporator with the boiling outside the
tubes (Fig. 204) . The vertical long tube
evaporators with natural circulation have
approximately the same intensity of heat
transfer as those with a dropping film. As
a result of special investigations, the design
principles have been worked out and the
optimum ratios of the dimensions of the
circulation system of the equipment have
been determined.
soluble salts, from the brine is also of
interest. However, this involves the separa
tion of calcium sulfate in the distillation
process.
Calcium sulfate crystallizes according to
temperature (in proportion to its rise) in
three main forms: (1) dihydrate (CaSO< •
2H,0) , (2) semihydrate (CaSO, • i/2HaO) ,
543

FIGURE 204. EVAPORATING
APPARATUS WITH REMOTE
BOILING ZONE.
and (S) anhydrous (CaSO,) . Each form has
its own crystalline structure. Evidently, the
seeding method can also be used to prevent
calcium sulfate scale, as well as any other
crystalline scale.
In preliminary tests the theoretical possi
bility of preventing calcium sulfate scale by
introducing seeding with the composition of
the scale was shown. Further investigations
were made on desalination of water of the
Caspian Sea. The same experimental three-
stage equipment was used as in the in
vestigation of carbonate scale prevention.
The equipment could operate either as a
continuous or a countercurrent system of
evaporation. The main purpose of the work
was to determine the conditions for pre
venting calcium sulfate scale in a multi
stage evaporating installation (at different
temperatures and concentrations by stages) .
The first experiments gave the following
results:
(I) The operation of a continuous evap
orator with remote settling and recirculation
of the seeding, consisting of CaSO, • 2H,0,
CaSO, • i ;Н.О and CaSO,, was accompa
nied by intensive scale formation in the
last (third) evaporation stage which oper
ated at a boiling point of 40" to 45°C and
544
a salt concentration in the sea water of 140
to 200 kg/cu m (a concentration of 10 to
14 times) . The scale consisted mainly of
calcium sulfate and had mixtures of
Na,SO, and CaCO,.
(2) The operation of a continuous evap
orator with the same system of seeding
recirculation (Fig. 205) was accompanied by
the formation of anhydrous CaSO, scale in
the first stage, which operated at a tem
perature of 110°C and at salt concentrations
of 140 to 200 kg/cu m. The seeding in
these tests was a mixture of CaSO,, CaSO,
• i .,H.O. and CaCO,. The seeding was
somewhat enriched with Mg (OH) , in the
process of the work. With time the crystal
line structure of the sulfate components of
the seeding (CaSO, and CaSO, • 1/2Н,0)
became less distinct; under a microscope
the seeding appeared to be an amorphous
mass, whereas the scale from the tubes of
the first stage evaporator had the fairly
distinct structure characteristic of the an
hydrous (alt.
SEA »«TER
CONDEКБДТЕ
FIGURE 205. SCHEMATIC DIA
GRAM OF EXPERIMENTAL
COUNTERFLOW EVAPORA
TING EQUIPMENT.
This effect may, in part, explain the dep
osition of the anhydrous salt on the tubes
in the presence of that form of the seeding.
Possibly the cvclical variation of tempera
ture in the range of 40° to U0°C during
circulation of the seeding through a closed
circuit leads to a partial transformation of
the seed crystals of calcium sulfate from
one crystal form to another. In the transi
tion from low temperature stages to high
temperature stages, the semihydrate tends
to change to the anhydrous salt; when the
seeding is returned from the remote settling
tank to the stage with the lowest tempera-
ture, the anhydrous salt tends to change to
the semihydrate and dihydrate forms. After
many cycles, the seed crystals may acquire
a distorted structure and become insuffi
ciently active crystallization centers.
Starting from this hypothesis it was
necessary to abandon the system of recir
culation of the seeding in the evaporating
battery. Another system was tried in which
seeding with the composition of the appro
priate scale was introduced into each evap
oration stage and kept there. In this case,
the seeding was under isothermal condi
tions and the mutual transformation of
modifications of CaSO, was eliminated.
In one of the evaporators, the conditions
of each stage of the countercurrent three-
stage evaporating equipment were worked
out in turn. These conditions are given
in Table LXXVII. The stages are numbered
along the course of the steam.

TABLE LXXVII. Operating Conditions of Stages of the

Experimental Countercurrent Evaporating Equipment

Bollini Concentration of salta, Composition of seeding

Stage no. •c point, ker/cu m
1 108-112 140-200 CaSO» + CaSO. • 1/2H.0 + CaCOa
2 65-70 80-40 CaCO.
> 40-45 20-25 CaCO.

Scale formation was prevented under all TABLE LXXVIII. Content of the Princi
conditions. pal Components in Ocean and Caspian
The results were checked by testing the Sea Water Content, kg/cu m
experimental three-stage equipment accord In Caspian In ocean water
ing to a countercurrent plan with indi Components
Sea water
vidual seeding in each evaporator. For this Na* 8.86 10.8
purpose, compact clarifiers were installed Mg-** 0.80 1.8
inside the evaporator. After 15 days of con Ca** 0.36 0.41
tinuous operation, no scale had formed. CI 6.54 19.4
SC— 8.17 2.7
Thus, the conditions for. preventing calcium HCOi- 0.22 0.16
sulfate scale by seeding during the distilla co«-- 0.0185 -
tion of sea water were found. The data ob Total salts 18.6 35.0
tained can be used in designing industrial
plants, since the experimental equipment In spite of the increased total salt content
was on a large scale (a productivity of about of ocean water due to NaCl, the Caspian
100 ai m of distillate per day and a heat Sea water contains, on the average, the
exchange surface of each apparatus of 20 same amount of scale-forming components:
sq m) . somewhat less Ca4* and Mg** and more
All the stated results were obtained in HCO; and SO" ". Consequently the data
the desalination of Caspian Sea water. Since obtained can be used in the construction of
it differs considerably from ocean water in plants for the desalination of ocean water.
its salt composition (Table LXXVIII) , it is Only a slight correction of the individual
necessary to analyze the applicability of indicators of the working conditions, espe
the results of the investigations for the cially of the degree of concentration, is
desalination of ocean water. required.

REFERENCES
1. Golightly, D. R.; McCartney, E. R.: The
Chemical Engineer, no. VI (1963) p.
169.
2. Banchero, Dzh. T.; Gordon K. F.: (trans
literated) In the Collection: Salt Water
Desalination, trans, from English, For
eign Literature Publishing House (1963).
3. Shtumper. R.: Fiziko-Khimicheskie os-
novy obrazovania i predotvrashchenia
nakipi (Physicochemical Principles of
Scale Formation and Prevention) in Rus
sian) , GEI (1933) .
4. Ushatinskii, N. A.; Golub, S. I.; Cher-
nozubov, V. В.: Trudy NllKhlMMash
no. 3S (1960).
5. Levin, R. E.: Novyi vyparnoi apparat
(A new evaporating apparatus) , Metal-
lurgizdat (1957) .

545
 SUMMARY OF DISCUSSION
There was no discussion.

Protection Contre L'Entartrage, Par

Ensemencement, Dans Les Installa

tions de Dessalement Par Distillation

»

V. B. Chernozubov, F. P. Zaoetrovsky, V. G. Shatsillo, S. I. Golub,

E. P. Novikov, V. I. Tkach

Union des Républiques Socialistes Soviétiques

On a étudié le processus de la formation jusqu'à un point où la concentration des

du tartre pendant la distillation d'eau de
la Mer Caspienne.
Il a été démontré que l'injection de l'en
semencement dans l'eau en cours d evapora
tion, sous forme de craie en poudre fine,
empêche complètement la formation du
tartre, avec une concentration de l'eau par
evaporation de près de trois fois, sans ébul-
lition sur les surfaces de transmission de
chaleur.
En concentrant l'eau, par evaporation,
sulfates et du calcium dans l'eau dépasse
le point de solubilité de l'anhydrite, on
obtient la prévention de la formation du
tartre par l'injection dans chacun des étages
de l'évaporateur de semences d'une struc
ture cristalline qui correspond à la struc
ture cristalline du tartre se formant dans
cet étage de l'évaporateur à la température
et au degré correspondants de concentration
par évaporation de l'eau d'alimentation.

Предотвращение Накипи

в Дистилляционных Опреснительных

Установках с Помощью Затравки

В. Б. Чернозубов, Ф. П. Заостровский, В. Г. Шацилло, С. И. Голуб,

Е. П; Новиков, В. И. Ткач

СССР

Исследован процесс накипеобразова- отсутствии кипения на поверхностях

ния при дистилляции воды Каспийско
го моря.
Показано, что введение в испаряе
мую воду затравки в виде тонкомоло
того мела практически полностью пре
дотвращает накипеобразование при
почти трехкратном упаривании воды и
546
теплопередачи.
При упаривании воды до степени,
когда концентрация сульфатов и каль
ция в воде превышает произведение
растворимости ангидрита, предотвра
щение накипи достигается в результа
те введения в каждую из ступеней ис
парителя затравки такой кристалличе- разующейся на этой ступени испари-
ской структуры, которая соответствует теля при соответствующей температуре
кристаллической структуре накипи, об- и степени упаривания исходной воды.

Prevención de Incrustaciones en

Plantas de Desalinizacion por

Destilación Mediante el Processo de

Siembra

V. B. Chernozubov, F. P. Zaostrovsky, V. G. Shatsillo, S. I. Golub,

E. P. Novikov, V. L Tkach

Union de Repúblicas Socialistas Soviéticas

El proceso de formación de incrustacio tración de los sulfatos y el calcio en el

nes durante la destilación de agua del mar
Caspio ha sido estudiado.
Se demostró que la inyección, en el agua
a ser evaporada, de semillas en la forma
de polvo fino de tiza, impide completa
mente la formación de incrustaciones du
rante una concentración por evaporación
de agua, casi al triple, sin ebullición en la
superficie de calentamiento.
En la concentración de agua por evapo
ración hasta el punto en el cual la concen
agua excede el producto de solubilidad de
la anhidrita, la prevención de incrustacio
nes se logra por inyección, en cada una de
las etapas de evaporación, de semillas de
una estructura cristalina que corresponde
a la estructura cristalina de la incrustación
en el correspondiente evaporador, a la
temperatura de operación y a la con
centración por evaporación del agua de
alimentación.

547
 The Corrosion-Resistance of
Materials in Sea Water
E. V. Konstantinova, L. S. Semenova, A. A. D'yakov
Union of Soviet Socialist Republics
With the development of desalination
plants, it became necessary to find structural
materials capable of high corrosion-resistance
at high temperatures, in the presence
of salt, and also at a high velocity of sea
water.
In order to accomplish this, the corrosion-
resistance of structural materials in sea
water was tested in situations similar to
the operating conditions of evaporating in
stallations. Also investigated were the effect
of temperature, increased salt content, the
combined and individual effect of the basic
aggressive ions in salt water on the corrosion-
resistance of carbon-steel St. 3 and of the
copper-based alloys LO70-1, MNZh5-l and
LA77-2. The state of corrosion in experi
mental and industrial evaporation plants,
in which stainless steel Khl8N10T was the
basic structural material, was kept under
constant observation.
The mechanism^of the corrosion of these
materials in Caspian Sea waters is deter
mined by the water's high oxygen content
(up to 8 mg/liter): under these conditions,
all the metals and alloys investigated cor
roded with oxygen depolarization (refs. 1 , 2).
Corrosion with oxygen depolarization is
usually accompanied by diffusion control;
because of this, an increase in the velocity
of sea water is one of the main factors in
the acceleration of the corrosion process
(ref. 1).
The initial sea water has a mild alkaline
reaction (pH — 7.8 to 8.2) . With heating,
however, the bicarbonate ions are subject to
dissociation with the formation of carbonate
ions (ref. S) . The latter, undergoing
hydrolysis, alkalyze the water (ref. 4) :
t"
2HCC",-» CO", + H.O
CO", + H,0 = 20H' -|- CO,
As a result, under the working condtions
of the desalination plant, the pH of the
water increases to 8.8 to 9.0; this increase
is one of the factors contributing to in
creased corrosion-resistance in many struc
tural materials, especially steels (ref. 5).
An increase in the temperature of the sea
water influences the corrosion process in
two ways. On the one hand, it increases the
speed of the electrochemical reactions, thus
increasing corrosion; on the other hand, it
lowers the degree of solubility of the oxygen
in the electrolyte, which lowers the velocity
of the process of corrosion occurring with
oxygen depolarization. This explains the
often observed fact that the temperature de
pendence of the velocity of corrosion in sea
water passes through a maximum (refs. 1,
6-9) .
It must be kept in mind that under the
working conditions of distilling-type de
salination plants without preliminary de-
aeration (as in the experimental unit) or
with incomplete deaeration (as in the first
industrial unit), the manifestation of all the
processes involved in the development of
corrosion, which are related to oxygen de
polarization, may be expected to occur only
in the first unit, where boiling takes place
for the first time in the system and, conse
quently, full deaeration of the sea water
occurs. Analysis has confirmed the absence
of oxygen in the following units, where
cathodic depolarization is apparently real
ized as a result of the reduction of the ions
or molecules of the water in accordance
with the reactions
Fe ■ + e -» Fe
2H,0 + e -» H, + 20H' (1)
These processes are not verv effective (in
significant content of trivalcnt iron ions in
the water, reduction of the water molecules
549
with the formation of hydroxyl ions in the be strongly inhibited in comparison with
medium having a pH value of 9) : there- the working conditions of the first unit,
fore, it may be assumed that corrosion will

THE CORROSION-RESISTANCE OF STAINLESS STEEL

On the basis of the results of preliminary the stripping of the pits in the process of
corrosion tests, the evaporation units of ex cleaning the pipes. None of the heating
perimental and industrial plants were made pipes in the experimental plant had to be
mostly from the stainless steel Khl8N10T. taken out of operation due to pitting dur
Under laboratory conditions it is difficult ing the entire period of operation.
to recreate all the factors affecting pitting No pitting was observed on the surface
in stainless steel in sea water. As a result, the of the pipes in the second and third units
main sources of information on the behavior which, as was already noted, were operat
of steel Khl8N10T were the distilling-type ing under more favorable conditions. Some
desalination plants in operation. areas of the walls of the experimental and
Pitting was observed along the entire industrial desalination plants showed pit
length of the heating pipes of the first unit. ting, but it was shallow (less than 02 mm)
The maximum depth of the pitting after and did not require any preventive meas
two years of operation was I mm. It is ures. The heating pipes of the indus
characteristic that with increasing duration trial installation are generally made of steel
of operation, the depth of the pits does not Khl7N13M2T. After 18 months of opera
increase. This is probably connected with tion, there were no signs of pitting.

THE CORROSION-RESISTANCE OF CARBON-STEEL

Stainless steel displays high corrosion- ucts. In this solution the corrosion increased
resistance in the working conditions of uninterruptedly in time, in contrast to the
desalination plants; however, stainless steel behavior of the same steel in a sodium
is very expensive. From 'the point of view chloride solution. In a solution of sodium
of reducing cost, it is expedient to study chloride, the same specimens at the same
the possibility of using less expensive ma temperature were covered with a firm and
terials such as carbon-steel, which could be shiny 'film which was obviously endowed
used for the manufacture of housings, ducts, with protective properties since after 190
and other parts, and the copper-based hours the corrosion ceased to increase.
alloys, whose high heat conductivity makes In a solution of 25 g/1. of CI' + 15 g/1.
them desirable for the manufacture of heat of SO'\ at a temperature of 120°C, the
ing pipes. same degree of corrosion as in a solution of
Special attention was devoted to a study sodium chloride can be seen; but with time,
of the corrosion of carbon-steel and copper the corrosive action of the sulfate ion evi
alloys in contact with each other, since such dently begins to predominate, and the de
contact is possible in the installations. The gree of corrosion after 690 hours is approxi
corrosion tests were carried out with natural mately equal to the average value of the
sea water, both under laboratory conditions magnitude of the corrosion in both solutions.
and in a special installation which made it The curve of the temperature dependence
possible to duplicate the operating con of the velocity of corrosion of the steel St. 3
ditions of a desalination plant (Fig. 206) . in sea water (in the static state) displays
In addition, we investigated under labora a maximum at 90°C (Fig. 208.) The absolute
tory conditions the effect of temperature magnitude of the corrosion of steel St. 3
(within the range of 20° to 120°C). of the does not exceed 0.2 mm/year.
salt content of the sea water, and of the The presence of a maximum on the curve
more aggressive ions found in sea water on of the temperature dependence of corrosion
the corrosion-resistance of the materials. of the sea water is determined from the
Tests on carbon-steel in solutions with juxtaposition of the manifold data found
different contents of chlorine and sulfate in the literature. This is explained by the
ions showed that the sulfate ions are the effect of two opposite factors on corrosion:
most dangerous for the steel (Fig. 207) . In a (1) the change in the rate of the electro
solution containing 15 g/1. of SO", at a chemical reaction occurring with tempera
temperature of 120°C, the specimens were ture changes, and (2) the solubility in
covered with a soft film of corrosion prod water (refs. 1 , 6-9) . In static tests of the
 FIGURE 206. DIAGRAM OF INSTALLATION FOR THE
CORROSION TESTING OF MATERIALS.
steel St. 3, it seems that a temperature of
90°C corresponds to the complete expendi
ture of the dissolved oxygen for the cathodic
reaction. A further temperature increase
does not lead to increased corrosion, since
the oxygen content of the water decreases.
During boiling, the corrosion of steel is at
a minimum.
The corrosion of steel St. 3 in the water
phase during boiling is almost independent
of the concentration of the solution (degree
of evaporation of the sea water) (Fig. 209).
It must be noted that the corrosion is sub
stantially greater in the steam phase than
in the water phase and increases up to a
certain point with the degree of evapora
tion. This is due to an increase in the con
centration of salt molecules in the steam
phase during concentration of the solution
(ref. 10) . As the thin condensation film
covering the specimens in the steam phase
increases, so does the salt concentration and
the electrical conductivity which, to a
certain degree, determines the rate of the
electrochemical reactions on the metal. But
even in the steam phase, the rate of cor
rosion of steel St. 3 does not exceed 0.4
mm/year. Thus, under static conditions,
steel St. 3 has a low rate of corrosion in sea
water; however, the picture is not so favor
551
 CURVES
IST.
Na2S04
AND
NaCl
COR ONSION
207.
FIGURE
TIME
VS
STEEL
FOR
S

TIME.HOURS
TIME.HOURS

120°
TEMPERATURE
SOF
TOEMLPUERTAITOURNES
AT
120°C.
AND
40°

i
 TABLE LXXIX. Comparative Data on Cor-
i Under Static ana Dynamic Conditions
Temperature Static Rate of
CO) state movement
1.2 m/sec
70 0.12 1.2S
90 0.18 0.77
100 0.09 0.38

As can be seen from the table, the move

ment of the solution increases the rate of
corrosion 4 to 10 times due to the intensive
supply of oxygen to the corroding surface.
FIGURE 208. TEMPERATURE The deleterious effect of mixing is also
DEPENDENCY OF THE COR apparent in the curves of the corrosion
ROSION RATE (MM/YEAR) current versus the ratio of the surfaces in
OF STEEL ST. 3 AND OF NON- the galvanic element St. 3-copper alloy
FERROUS METALS IN SEA (Fig. 210) .
WATER (UNDER STATIC
CONDITIONS). DURATION
OF TESTS 500 HOURS.

able in a situation imitating the working

conditions of desalination plants, of which
the most important is the movement of the
sea water.

MTie or c»TNaM-*aoM »

FIGURE 210. DEPENDENCE

i s k> is CO OF ANODIC CURRENT DEN
OEGREE OF CONCENTRATION, n TIMES SITY IN GALVANIC PAIRS ON
• STEEL ST 3; LA77-2 THE RATIO OF THE SUR
< MNZhS-l 1070-1
FACES IN SEA WATER, AT A
TEMPERATURE OF 90°C.
FIGURE 209. DEPENDENCE
OF CORROSION RATE (MM/
YEAR) OF STEEL ST. 3 AND
NONFERROUS ALLOYS ON It is noteworthy that, in addition to the
CONCENTRATION OF SOLU general increase in the rate of corrosion of
carbon-steel with intensive movement of the
TION IMITATING SEA sea water, the corrosion under static con
WATER, AT BOILING TEM ditions at 90°C (which corresponds to the
PERATURE. corrosion maximum under static conditions)
is found to be less than that at 70°C with
movement of the sea water. It is apparent
Comparative data on corrosion understatic in the curve of the temperature-dependent
and dynamic conditions are given in Table change of the corrosion current in the gal
LXXIX. Tests were conducted in a model vanic element St. 5-copper alloy that the
installation with mixing at a rate of \2 corrosion current maximum takes place at
m/sec for 100 days, and without mixing in 70°C (Fig. 211) . This temperature is obvi
the retorts with return coolers for 20 days. ously the least favorable for the working

553
 conditions of desalination plants. In the
case of mixing, the shift of the maximum
along the corrosion versus temperature
curve in the direction of lower temperatures
is apparently linked to a greater rate of
corrosion in moving sea water, the corrosion
being controlled by diffusion factors. Be
cause of this, the moment of the full utili
zation of the dissolved oxygen and the
subsequent drop in the curve k-t° take
place at a lower temperature.
300
STEEL ST 3 IN CONTACT WITH BRASS LOTO-I X *
STEEL ST3 M CONTACT WITH ALLOY MNZhS'l • -*
STEEL ST.3 M CONTACT WITH BRASS LA77-2 » »
FIGURE 211. CHANGES OF
CORROSION CURRENT DEN
SITY IN GALVANIC PAIRS
(RATIO OF SURFACES 1:5)
AS FUNCTIONS OF THE
TEMPERATURE OF THE SEA
WATER, AT MIXING RATE
OF 1.2 M/SEC.
Figure 212 shows the results of a 100-hour
test of the carbon-steel St. 3 in contact with
a copper alloy (LO70-1 or MNZh5-l) or
with the stainless steel Khl7N13M3T, at
different ratios of the cathode-anode sur
faces (from 1 to 10) in sea water at a
temperature of 70" to 100°C and a water
speed of 1.2 m/sec. (The tests were carried
out in a model plant (Fig. 206)). As can be
seen from these curves, in the case of
carbon-steel, the copper-based alloys are
generally better cathodes than stainless
steel. However, when much of the surface
is in contact with the carbon-steel, the
degree of steel corrosion will be practically
the same regardless of the material of the
cathode.
Under the most adverse conditions (at a
temperature of 70°C and a cathode-anode
surface ratio of 10) , the rate of corrosion
of the steel was approximately 3 mm/year,
which was more than twice the correspond-
554
ltS48S7SS>0
RATO OF CATHOCC-ANCOE AREAS
A—» STEEL ST 3 M CONTACT *ITM ALLOY MNZhS'l
X—»< STEEL ST 3 H CONTACT WITH BRASS L070 -I
• > STECL STS IN CONTACT «TH STEEL Khl TNI3H2T
FIGURE 212. PENETRATION
(MM/YEAR) OF STEEL ST. 3
IN SEA WATER AS FUNG
TION OF THE AREA OF THE
MATERIAL IN CONTACT
WITH IT. RATE OF MIXING
1.2 M/SEC.
ing rate of corrosion for steel St. 3 not in
contact with an electropositive material (15
mm/year) .
These tests made possible certain con
clusions about the possibility of using
carbon-steel as a structural material in de
salination plants:
(1) When designing parts or units made
from steel St. 3, it is necessary to avoid their
contact with more electropositive materials;
(2) Steel St. 3 cannot be used in units
operating at a temperature of 70"C and
with intensive movement of the "water, with
out deaeration.
At temperatures of 900, to 100°C and sea
water velocities of 1.2 m/sec, it is possible
to use carbon-steel even without deaeration
(since under such conditions the oxygen
content is close to zero); however, it is nec
essary to plan for maintenance with respect
to an even corrosion (approximately 0.8
mm/year) . With deaeration of the sea
water and no contact with nobler metals,
there are no serious objections to the use
of steel St. 3.
The first industrial desalination plant
using carbon-steel St. 3 was equipped with
water-transfer pipes </> 350 between the
evaporating devices. Concentrated sea water
deaerated in the first unit with a primer
at a temperature of 65° to 95°C flows at
a rate of 1.2 to 1.5 m/sec through these
pipes. After eighteen months of operation,
the pipes were in good condition and dis
played only an even surface corrosion.
 TEMPERATURE 120° С
70-1 1 1

60

0 100 200 300 400 500 600 700

TIME.HOURS
x X x L070 "I
a a * MNZH5-I

TEMPERATURE 40°C
70 ( -Г-

0 100 200 300 400 500 600 700

TIME.HOURS

FIGURE 213. CORROSION VS TIME CURVES OF BRASS LO70-1

AND ALLOY MNZh5-l IN NaCI AND Na2S04 SOLUTIONS, AT
TEMPERATURE OF 40° AND 1200C.

555
 THE CORROSION-RESISTANCE OF COPPER ALLOYS
The effect of temperature on the corro When comparing the results of tests on
sion-resistance of copper-based alloys is copper alloys in stagnant and moving sea
similar to the effect of temperature on steel water, it was noticed that they display less
St. 3: with the temperature increasing to corrosion with mixing than under static
80°C (no tests were conducted at 90°C) , conditions. This is most apparent in the
corrosion increases; with a further tempera case of alloy MNZh5—1.
ture increase, corrosion decreases, especially This is probably due to the difference in
at the boiling temperature (Fig. 208) . The the duration of the static and dynamic
temperature dependence of corrosion is, on tests (20 and 100 days respectively) . It can
the whole, less than for steel St. 3: the depth be assumed that with large outputs and a
of penetration for alloy MN7.h5-l and brass continuous supply of oxygen (with mixing) ,
LO70-1 varies within the limits of 0.02 to the specimens will become covered with
0.09 mm/year; for the more resistant brass films made of (he products of corrosion and
alloy LA77-2, the variation is from 0.01 to that these films will inhibit the further
0.03 mm/year. The corrosion of copper development of the process of corrosion. A
alloys is practically independent of the visual inspection of specimens made from
degree of concentration of the sea water copper -based alloys after corrosion supports
with boiling both in the liquid and gas this assumption; after prolonged tests in
phases (Fig. 209) . Table LXXX gives the moving sea water, the specimens were cov
comparative data relative to the corrosion - ered with dense oxide films which do not
resistance of copper alloys at a temperature form in static tests.
of 70° to 100°C under static conditions and
with movement of the sea water at a rate The corrosion tests of copper alloys in
of 1.2 m/sec. solutions of NaCI and NajSO, at tempera
tures of 40° and 120°C have shown that
the chlorine ion is more corrosive for these
TABLE LXXX. The Permeability of alloys than the sulfate ion which slightly
Copper Alloys in Sea Water at inhibits corrosion (Fig. 213) .
Different Temperatures, (mm/year)
The corrosion tests confirm the high
Alloy Test -Temperature (*0) degree of corrosion-resistance of these
conditions 70 copper-based alloys. As a result, they can be
90 100 highly recommended as a structural mate
MNZhB-1 Static 0.07 0.09 0.09 rial for heating pipes and heat exchange
Dynamic O.OB 0.04 0.02 units. The first unit of the industrial in
LO70-1 Static 0.08 0.08 0.08 stallation has several dozen heating pipes
Dynamic 0.08 0.07 0.06
made of brass LO70-1. After 18 months of
LA77 2 Static 0.02 0.08 0.02 operation, no damage due to corrosion has
Dynamic*
• The tests of brass LA77-2 under dynamic been observed.
conditions are still in progress.

CONCLUSIONS
Among the least expensive and most read the sea water and no contact with electro
ily available structural materials recom positive materials;
mended for desalination plants are the (2) Copper-based alloys LO70-1, MNZh5-l.
following: and LA77-2 (for the heating pipes) .
(1) Carbon-steel St. 3 with deacration of

REFERENCES
1. Tomashov, N. D.: Corrosion Theory ical Bases of the formation and Preven
and the Protection of Metals, Moscow, tion of Scale, Moscow. Gosenergoizdat
Publishing House of the Academy of (1953) .
Sciences of the USSR (1959). 4. Nerkasov, B. V.: General Chemistry
2. Akimov, G. V.: Fundamentals of Cor Course, Moscow-Leningrad, Goskhim-
rosion and the Protection of Metals, izdat (1952).
Moscow, Mctallurgizdat (1946). 5. Mamet, A. P.: The Corrosion of the
3. Shtumpcr, R.: The Physicial and Chem Thermal Power Equipment of Power
 Plants, Moscow-Leningrad, Gosenergoiz-
dat (1952).
6. La-Ke, F.: In the collection: Metal Cor
rosion, Edited by G. G. Ulig, (Trans
lation under the editorship of V. V.
Skorchelleti), Moscow-Leningrad, Gos-
khimizdat (1952).
7. Akimov, G. V.: Theory and Methods
for Investigating the Corrosion of
Metals, Moscow, Publishing House of
the Academy of Sciences of the USSR
(1945) .
This paper was submitted for publication only.
Resistance Des Matériaux a la
Corrosion Dans L'Eau de Mer
V. B. Chernozubov, E. V. Konstantinova, L. S. Semenova, A. A. Dyakov
Union ta Republiques Socialistes Soviétiques
On a effectué des études de la résistance
à la corrosion des matériaux de construc
tion dans des installations pilotes fonction
nant avec de l'eau de mer naturelle ainsi
que dans des conditions de laboratoire.
I^s métaux suivants ont été analysés:
acier au carbone Ct.3, aciers inoxydables
XI8HIOT. XI7HI3M3T, et X2IH5T, aciers
au chrome, alliages à base de cuivre
MH5-1 . MH70-30, J1O70-1 , JIA77-2 et égale
ment nickel H-I, aluminium A-I; titanium
BTI et zirconium.
Les résultats des recherches sur la cor
rosion dans l'exploitation des installations
d'évaporation indiquent la possibilité
d'utiliser des aciers inoxydables X18HIOT
et XI7HI3M37 ainsi qu'un certain nombre
d'alliages de cuivre comme matériaux de
construction pour des usines de dessalement
par evaporation de l'eau de mer.
La corrosion de l'acier Ct.3 dans l'eau de
8. Akimov, G. V.; Trusova, E. F.: Works
of the VIAM (All-Union SdentiBc Re
search Institute for Aviation Materials)
(1945).
9. Gerasimov, V. V.: Dissertation of the
IFKh (Institute of Physical Chemistry)
of the Academy of Sciences of the USSR
(1955) .
10. Gel'perin. N. I.: Evaporation Installa
tions, Moscow, Goskhimizdat (1947).
mer est en général d'une nature uniforme.
L'acier au carbone peut être utilisé comme
matériau de construction pour les usines
d'évaporation pourvu que les conditions
suivantes soient strictement observées:
1. désaération de l'eau de mer d'alimen
tation;
2. éviter le contact d'appareils fabriqués
en acier au carbone avec des compo
sants fabriqués de matériaux plus
électro-positifs (acier inoxydable, alli
ages de cuivre, etc.) .
Le nickel, le zirconium, le titanium et
leurs alliages dont l'utilisation n'est pas
encore économique, montrent de bonnes
résistances à la corrosion dans les conditions
étudiées.
On ne peut recommander les aciers au
chrome (sans nickel) à cause de leur sen
sibilité élevée à la corrosion par piqûre.
557
 Коррозионная Стойкость Материалов
в Морской Воде
В. Б. Чернозубов, Е. В. Константинова, Л. С. Семенова, А. А. Дьяков
СССР
Исследование коррозионной стойко
сти конструкционных материалов про
водилось на производственных модель
ных установках, работающих на при
родной морской воде, и в лаборатор
ных условиях.
Испытаниям были подвергнуты сле
дующие металлические материалы:
углеродистая сталь Ст. 3, нержавею
щие стали XI8HIOT, XI7HI3M3T.
Х21Н5Т, хромистые стали; сплавы на
мерной основе МНЖ5-1, МН70-30.
ЛО70-1, ЛА77-2, а также никель
H - 1, алюминий А - 1, титан ВТ1 и цир
коний.
Результаты исследований коррозии
эксплуатируемых испарительных уста
новок указывают на возможность ис
пользования в качестве конструкцион
ных материалов для испарительных
установок опреснения морской воды
нержавеющих сталей XI8HIOT и Х17-
HI3M37 и ряда медных сплавов.
Коррозия стали Ст. 3 в морской во
Resistencia a la Corrosion de
Materiales en Agua de Mar
V. В. Chernozubov, Е. V. Konstantinova, L. S. Semenova, A. A. Dyakov
Union de Repúblicas Socialistas Soviética*
Se investigó la resistencia a la corrosión
de materiales de construcción en instala
ciones experimentales, funcionando con
agua de mar, así como en condiciones de
laboratorio.
Se sometieron a prueba los siguientes me
tales; acero al carbono St. 33. aceros inoxida
558
де носит, в основном, равномерный ха
рактер. Углеродистая сталь может быть
использована в качестве конструкцион
ного материала для испарительных
установок при обязательном соблюде
нии двух условий:
1) деаэрация исходной морской во
ды;
2) предупреждение контакта узлов,
выполненных из углеродистой ста
ли, с деталями из более электро
положительных материалов (не
ржавеющие стали, медные сплавы
и т.п.).
Хорошую коррозионную стойкость
в исследованных условиях показали
никель, цирконий, титан и их сплавы,
использование которых пока неэконо
мично.
Хромистные (безникелевые) стали не
могут быть рекомендованы вследствие
повышенной их чувствительности к
язвенной коррозии.
bles Khl8N10T, Khl7N13M3T y Kh21N5T.
aceros al cromo; aleaciones a base de
cobre, MNZhS-I. MN70-30, LO70-I, LA77-2.
as( como níquel N-I, aluminio A-I. titanio
VTI y circonio.
El resultado de las investigaciones acerca
de la corrosión en las instalaciones de eva
poración en funcionamiento sugiere la
posibilidad de utilizar aceros inoxidables
Khl8NI0T y KM7NI3M37, así como algu
nas aleaciones de cobre, como materiales
de construcción para las centrales de desali-
nización por evaporación de agua de mar.
La corrosión de acero St.3 en agua de
mar es de índole fundamentalmente uni
forme. £1 acero al carbono puede utilizarse
como material de construcción para las
centrales de evaporación, siempre que se
observen al pie de la letra los dos requi
sitos siguientes:
1. Desairear el agua de mar que entra;
2. Evitar que hagan contacto los ele
mentos hechos de acero al carbono
con los componentes hechos de mate
riales más electropositivos (acero in
oxidable, aleaciones de cobre, etc.) .
El níquel, el circonio, el titanio y sus
aleaciones, cuyo empleo no resulta aún
económico, demostraron buena resistencia
a la corrosión en las condiciones que se
investigaron.
Los aceros al cromo (sin níquel) no
pueden recomendarse por su gran suscepti
bilidad a la corrosión en forma de
picaduras.
559
 Use of Ion-Exchange Membranes

for Desalination

A. B. Pashkov, Z. V. Klimova, M. A. Zhukov, N. S. Tikhomirova,

V. I. Serenkov, B. N. Laskorin, N. M. Smirnova, E. L. Semenova,
and Yu. I. Tisov

Union of Soviet Socialist Republics

The desalination of saline waters by the
method of electrodialysis with the use of
ionite membranes is, from the point of
view of power consumption, very economi
cal in comparison with the methods of
evaporation or freezing.
Electrodialytic equipment is simple to
operate and has a low metal content and
relatively small dimensions. These advan
tages permit one to expect that the cost of
desalinated water will be lower than with
the other methods. The practical realiza
tion of these fundamental advantages of
electrodialysis depends on the degree of per
fection of the designs for electrodialyzers
and their main part—the ionite membranes,
as well as on the price of the designs,
which constitutes an appreciable portion of
the cost of desalinated water.
In this report we present the results of
our work on the creation of heterogeneous
and homogeneous membranes for water de
salination (refs. 5, 10, 11-15, 17) and on the
investigation of their properties both in lab
oratory and in operating conditions. Meth
ods described in the literature (ref. 16)
were generally used to determine the rela
tive electrochemical and mechanical prop
erties of membranes.

HETEROGENEOUS MEMBRANES
At the present time, in the desalination membranes are used. The principal proper
of water with a starting salt content of ties of these membranes arc presented in
4 to 15 grams/liter, reinforced MK-40 Table LXXXI (ref. 5) .
cationite membranes and MA-40 anionite

TABLE LXXXI. The Principal Properties of Heterogeneous

MK-40 and MA-40 Membranes with a Thickness of 0.6 mm
Indicators MK-40 MA-40
Static exchange capacity (dry membrane) , mg-equivalents/hr 2.3+2.6 8.0-4.4
Selectivity in 0.01-0.2N NaCl 0.95-0.97 0.98-0.95
Electrical resistivity, ohms x cm 160-180 180-220
Surface electrical resistance, ohms/cm* 9-M1 11-18
Swelling: capacity in thickness, % 116-130 120-180
Swelling* capacity in area, % 110-126 110-126
Sixe, cm 150x60 160x50
Tensile strength, kg/cm9 130-160 180-180

As is evident from Table LXXXI, MK-40 sures as well as in portable equipment.

and MA-40 membranes have completely Lengthy investigations of these mem
satisfactory electromechanical and good me branes by sanitary and hygienic institutes of
chanical properties; this permits using them the USSR have shown that they are harm
in electrodialyzers working at elevated pres less to health and do not form harmful

561
 mixtures in the course of operation. There that the MK-40 and MA-40 membranes have
fore, their use for the production of drink sufficiently good electrochemical indicators
ing water is allowed (ref. 1). At the present and preserve them in the course of lengthy-
time sufficient experimental material on the operation. In a control inspection of the
prolonged operation of these membranes membranes after one year of operation it
has been accumulated. was found that the condition of all the
We will present some of the results ob membranes, except those directly adjacent
tained in one of the EOU-NIIPM-12 elec- to the electrode chambers, was good and
trodialytic installations with a through- that the membranes were suitable for fur
flow system, which is used to produce drink ther operation.
ing water (ref. 2). The two membranes which were adjacent
Composition of the starting water: to the electrodes were partially destroyed:
the damage was greater on the anode side.
Total salt content 3.8288 grams/liter Those membranes were replaced, and after
Ca" 296.6 mg/liter that the equipment worked normally. The
Mg" 116.7 reason for the more rapid aging of the
Na 7915 membranes adjacent to the electrodes is
HCO; 329.5 the action of the aggressive mediums which
CP 758.8 form in those chambers. The membranes
SO," 1586.0 do not form harmful mixtures during
pH 7.65 operation, and therefore the taste of the
Composition of desalination water: desalinated water remains good. The water
completely satisfied the requirements of
Total salt content 1.0 gram/liter All-Union State Standard No. 2761-57 for
Ca" 58 mg/liter drinking water. Analogous results were ob
Mg" 25.6 tained at a current density of 100 amps/sq m.
Na 250.9 On the basis of these data it is possible
HCO~ 146.4 to guarantee a two-year period of operation
CP 200.0 of the membranes and to assume that the
SO«" 278.0 real service life of the membranes will be
pH 7.6 greater. The prospective cost of reinforced
Productivity 16 cum/day MK-40 and MA-40 membranes, if electro-
Current density 21 amperes/sq m dialysis is introduced on a large scale, will
As a result of operation of the mem be 5 to 7 rubles per sq m.
branes for two years, it was established that Membranes adjacent to the anode cham
the mean electric power consumption per ber should have great chemical stability.
cu m of desalinated water was 1.3 kwh Membrane MA-41 has considerably better
(without consideration of power consump chemical stability than membrane MA-40
tion for pumping the solutions) and re (Table LXXXII) (ref. 3) . which permits
mained unchanged during the entire period working it much longer.
of operation. This is the basis for assuming

TABLE LXXXII. The Principal Properties of Heterogeneous MA-41

Membrane with a Thickness of 0.6 mm
Indicators of
Static exchange capacity, mg-eq/liter 1.8 - 2.2
Selectivity in 0.01-0.2N NaCl 0.90 - 0.96
Electrical resistivity in IN NaCl, ohms x cm 160 - 200
Surface electrical resistivity, ohms/sq cm 9-12
Swelling capacity in thickness, % 120 - 180
Swelling capacity in area, % 110 - 115
Tensile strength, kg/sq cm ISO - 160

As is evident from Table LXXXII, the
MA-41 membrane can also be used as a
main anionite membrane in the electro-
dialysis process.
In the course of subsequent investigations
it was established that there are consider
able possibilities for further improvement
of membranes of this type. Thus, reducing
the thickness of the membranes permits
considerable improvement of their electro
chemical and mechanical properties (Tables
LXXXIII and LXXXIV) .

562
 TABLE LXXXIII. Change in the Properties of the MK 40 Membrane
as a Function of Thickness
Membrane Thickness, mm
Indicator*
0.3 0.4 0.6 0.6
Static exchange capacity, mg-eq/liter 1.68 1.60 1.67 1.70
Selectivity in 0.01-0.1N NaCI 0.96-0.98 0.95-0.98 0.96-0.98 0.95^-0.98
Electrical resistivity in IN NaCI.
ohms x cm 160-180 180 180 180
Surface electrical resistance, ohms/cm" 4.2-6.1 7.4 9.0 11.0
Swelling capacity in thickness, % 182 188 130.8 133.0
Swelling capacity in area. % 118 116 120.0 118.0
Dimensions, cm 150x60 160x50 150x50 150x60
Tensile strength, kg/cm» 200 198 224 126

TABLE LXXXIV. Change in the Properties of the MA-40 Membrane

as a Function of Thickness
Membrane Thickness, mm
Indicators
0.8 0.4 0.6 0.6
Static exchange capacity, mg-eq/liter 2.88 2.6 2.6 8.2
Selectivity in 0.01-0.1N NaCI 0.93-0.95 0.98-0.96 0.93-0.95 0.93-0.90
Electrical resistivity in IN NaCI,
ohms x cm 180-220 220 220 200
Surface electrical resistance, ohms/em9 5.4-6.0 7.9 10.8 12
Swelling capacity in thicknesB, % 185 181
Swelling capacity in area, % 115 129 118 122
Dimensions, cm 120x50 150x50 160x50 160x60
Tensile strength, kg/cm1 172 168 128 119

It is evident from the data of Table The electrodialytic equipment is assem

LXXXIII that in their principal electro bled in the form of a compact unit mounted
chemical properties membranes with a thick on a supporting frame. The dimensions of
ness of 0.3 to 0.4 mm are similar to known the equipment are: 6.5 meters in length,
homogeneous membranes but surpass them in 2.5 meters in width, 2.8 meters in height
mechanical properties. In addition, reduction (without the circulation loop). The weight
of the thickness makes them still cheaper. of the equipment when in operation is 17
Water of the Caspian Sea (Table LXXXV) tons. The equipment is arranged in a
was desalinated on MKK and MAK mem single-story building 12 meters long, 6
branes (0.25 to 0.44 mm thick) to a residual meters wide, and 4.5 meters high. A batch
salt content of 1 gram/liter; electrodialysis process of desalination is used. Every 20
equipment of the circulating type which minutes, 1,300 liters of desalinated water
had a productivity of 100 cu m/day was are obtained. The brine continuously runs
used. off into the sewer. The equipment is com
pletely automated. A silicon rectifier serves
TABLE LXXXV. Salt Content of Water as the direct current source. The desalin
of the Caspian Sea (oxidizability 18.6, ated water and brine circulate across mem
pH = 7.6, total hardness 79.5 mg eq/liter, brane packets. Two membranes placed in
temporary hardness 3.55 mg eq/Iitcr.) a row form the desalination or concentra
tion chamber. The chambers are confined
Components Content of component by rubber gaskets on their outer contours.
mo/liter Between the membranes are separator grids
1. Cations
Sodium 3.846.8 which assure a constant distance (1 mm)
Potassium 70.0 between the membranes. The liquid is dis
Magnesium 745.6
Calcium 857.4 tributed inside the membrane packet over
Iron 0.11 the chamber on the filterpress principle.
Zinc 0.06 The 1,616 ionite membranes used in the
Copper 0.07 equipment were assembled into two assem
$ Anions
Carbonate 18.6 blies, each containing eight membrane
Chlorine 5,548.7 packets. Each membrane packet contains
Sulfate 8.165.8 101 membranes (50 anionite and 51 cation -
Bicarbonate 215.9
Bromine 7.6 ite) . The dimensions of the membranes arc
Iodine 0.085 1 .000 x 400 mm. A schematic diagram of the
Fluorine 0.26
Silicic acid 27.0 operating process is shown in Figure 214.
Dry residue 13.860.0 All parts of the equipment which are in

563
 sea water was desalinated at various volt
ages and current strengths. The velocities
in the systems were set as follows:
In the system of
dialysate 42 cu m/hour
In the system of
condensate 50 cu m/hour
In the system of
wash water 1.5 cu m/hour.
During the investigations, the length of
the desalination cycle, the volume of dialy
sate obtained, and the voltage and strength
of the direct current were measured. Be
cause the conductometric cell (saltmeter)
FIGURE 214. SCHEMATIC DIA opened a pneumatic valve on the discharge
GRAM OF THE ARRANGE line at a content of 1 gram/liter of salt in
MENT OF ELECTRODIALYSIS the dialysate, the salt content in the ob
EQUIPMENT. tained dialysate was measured for several
but not all of the experiments. The pH
values in the concentrate and wash water
contact with aggressive liquids were made were checked periodically. The principal
of corrosion -resistant materials: vinyl plas results of a number of these experiments
tic, rubberized steels, and cast iron. The are presented in Table LXXXVI.

TABLE LXXXVI. Principal Results of Investigations of Desalination of Water

of the Caspian Sea*
Voltage. Current strength, amps Mean Productivity Electric Mean
V current of the power con- current
density, equipment. sumption per yield, %
Initial Final Mean amps/m* mVhour m* of desali
nated water,
kwh
468 60 80 60 111 4.86 6.88 87.8
440 80 24 62 96.1 4.18 6.46 96.7
416 76 24 60 62.6 8.70 6.62 88.8
8»0 74 22 48 86 8.84 6.68 88.6
* Volume of dialyzate obtained in each experiment, 1,300 liters

The current density was calculated on As a result of the investigations, optimum

the basis of the average current strength in working conditions of the equipment were
the course of a desalination cycle and the found which are characterized by the fol
working area of the membrane, which was lowing parameters:
0.27 sq m. The current yield (as %) was Productivity (in de
calculated for the mean gram-equivalent of salination from 14 to
salts in sea water with the formula: 1 gram/liter) 4.18 cum/hour
_ nr 26.8 -100 Electric power consumption:
' — 75.8 • I • t • 800 (1) directly on de
salination 5.5kwh/cum
where m is the quantity of transported total 9.0 kwh/cu m
water, in grams; 26.8 is the Faraday unit,
in amperes x hours; 75.8 is the mean gram- Current yield 835 to 96.7%
equivalent of salts in sea water, in grams; Length of desalination
I is the mean current strength during a cycle 20 minutes
cycle, in amperes; t is the cycle length, in Voltage on the
hours; 800 is the number of desalination electrodes 440 V
chambers. Mean current strength 52 amperes
As follows from the data presented in Mean current
Table LXXXVI, with an increase of the density 96.1 amperes/sq m
voltage fed to the electrodes the current Consumption of 10%
density rises, the productivity of the equip HC1 on acidification
ment increases, and the length of the of water in the washing
desalination cycle is shortened. system of the electrode
 chambers (per cu m of
desalinated water) 3 to 5 liters
Discharge of brine
into sewer 2 cum/hour
Salt content of brine 50 grams/liter
Cost per eu m of de
salinated water 60 kopecks
The investigations conducted showed that
ionite membranes MKK and МАК are very
effective for the desalination of sea water
THE METHOD OF CROSS-LINKAGE OF
HETEROGENEOUS IONITE MEMBRANES
The question of creating a strong bond
between a hydrophilic ionite and a hydro
phobic polymer, which combine poorly, in
a heterogeneous ionite membrane is of sci
entific and technical interest.
To create a bond between the polymer
and ionite (a cross-linkage) , that is, to
give the ionite the properties of a so-called
"activated" filler (such as oxidized carbon
blacks in mixtures with rubbers), it is
necessary to bring the molecular properties
of the surfaces of the particles of ionite and
polymer close together (ref. 18) . When a
surfactant is introduced, the ionite acquires
the properties of an activated filler.
The surfactants are attached to the sur
face of the ionite by their polar hydrophilic
groups. The hydrocarbon chains, directed
into the medium of the polymer, hydro-
phobize that surface, increasing its affinity
to the nonpolar polymer.
With surfactants it is possible to change
the nature of the surface of the particles
of ionite, to regulate the force of the inter
action between them and the polymeric
medium, and, consequently, to control the
processes of cross-linkage. V. A. Kargin,
P. A. Rebinder, and their coworkers (refs.
19, 20, 27) have studied the cross-linkage
of polymeric materials. Both Soviet and
foreign scientists have made detailed stud
ies of methods for improving the properties
of filler systems (refs. 19-21). The main
efforts have been directed toward improv
ing the combination and reaction of the
polymer with the surface of the filler. For
this purpose the filler has been modified
by various methods. The significance of this
modification is the reaction of the polymer
with the filler, which occurs after the intro
duction of various surfactants. The me
chanical properties of the entire system
improve when an optimum quantity of sur
factant is introduced (refs. 22, 23).
In a filled polymeric system such as a
heterogeneous membrane, a complex struc
containing up to 15 grams/liter of
Improving the membrane process and ceas
ing to reinforce materials will permit a
sharp reduction in the cost of ionite mem
branes. This in turn will reduce the cost
of water desalination by electrodialysis. One
way to reduce the cost of the membranes
is the method of cross-linkage, which con
sists of introducing surfactants into the
composition of a heterogeneous ionite mem
brane (ref. 17).
ture results from the primary directing
structure of the particles of the activated
filler and from the secondary directed struc
ture of the polymer which forms on the
first as on a skeleton (refs. 19, 24, 25) .
When there is a low degree of volumetric
filling of the polymeric medium by the
activated filler, the particles of the filler
are separated by the polymeric phase and
cannot form a coagulation structure, i.e.,
chains and space lattices of particles of
fillers separated by thin interlayers—bridges
of the adsorption-strengthened polymer.
When there is a gradual increase in the
concentration of the filler, the probability
of its particles meeting increases, and if
their surface has been sufficiently hydro-
phobized, separate chains form which are
later united in a complex branched chain
structure of the solid phase (refs. 19, 24).
The strength of the system increases with
the development of these chain structures.
In the presence of an excess of filler, the
character of the structure changes, and
large aggregates form which lead to the
formation of local overstresses and danger
ous defects (ref. 20) .
The general regularities of the modifica
tion of fillers and of the processes of cross-
linkage in mixtures of fillers with polymers
in a broad range of concentrations of sur
factant* have been studied (refs. 21, 23).
However, the theoretical concepts have still
not been adequately generalized. Therefore,
it is necessary to determine the optimum
ratio of the components for each new
polymer-filler-surfactant combination.
This section deals with the modification
of heterogeneous ionite membranes by sur
factants. Specimens of membranes with the
prescribed composition were prepared by
the described method of V. S. Titor (ref.
26) . High density polyethylene was used
as the binder for KU-2 and EDE-IOP
ionites. The surfactant was introduced into
a mixture of ionite and polyethylene on
565
 rollers in the form of aqueous or acetone tants on the properties of membranes was
solutions. The influence of various surfac- investigated (Table LXXXVII) .

TABLE LXXXVII. The Influence of Surfactants on the Properties of Ionic Membranes

(surfactant, 3x10'' moles/gram of ionite)
Electrical
No. of Static Moisture Coefficient resistivity
•urfac- Surfactant exchange content, of swelling in IN NaCl
tant capacity, % In water, % solution.
•ample mg-eq/gram
Starting resin. KU-2 2.95 88.2 10.6 1.960
1. Primary amine 2.64 38.0 16.0 800
2. Trioctylamine 2.84 39.6 12.6 220
3. Dialkyldimethyl-
ammonium chloride,
Cit-Cjo 2.2 84.8 18.7 190
4. Alkyltrimethylammonium
chloride, Cio-Cia 2.8 86.2 11.2 286
6. Dimethylalkylbenzyl-
ammonium chloride,
Cio-Cr. 2.7 40.2 12.8 220
6. Dimethylalkylbenzyl-
ammonium chloride,
On-Cb* 2.6 42.2 16.0 140
7. Dialkylmethylbenxyl-
ammonlum chloride,
Cit-C» 2.56 40.5 11J 160
8. n-Alkybenzylpyridine
chloride (Katapin) 2.87 86.4 12.5 285
Starting resin,
EDE-IOP 4.66 86.6 10.0 10.000
9. Oleic acid 3.92 36.5 10.5 640
10. Secondary nlkyl sulfate
"Progreaa" 4.25 82.0 8.76 686
11. Alkylbenzol sulfonate
"Sulfanol NP-1" 8.99 80.2 7.6 600
12. Primary amyl sulfate, Cu 4.08 82.1 8.7 600
18. Alkyl sulfonate (molten),
Cu-Cu 4.4 86.5 8.76 860
14. Fatty carboxyllc acids,
ClT-ClO 8.96 87.8 10 560

The influence of the quantity of trioctyl change is noted in the properties of the
amine on the characteristics of cationite membrane in a broad range of compositions.
membranes is shown in Figures 215 and 216.
The presence of a sharply expressed optimum
of activity of the surfactant, corresponding
to a specific degree of hydrophobization of
the ionite by the adsorption layers of the
surfactant, is characteristic for all the curves.
The position of the maximum (or mini
mum for the electrical resistivity) on the
curves corresponds to C10rf — 5 x 10"*
moles/gram of ionite, after which a rapid
decrease in strength elasticity, swelling
capacity, exchange capacity, and selectivity
of the membranes and an increase in their
electrical resistivity are observed. These data
confirm the regularities found by a number T
of authors in the processes of structure QUANTITY OF TMOCTVLAMNE,
MOLO/WANl OF lOWTl
formation in the presence of an adsorption
layer contributing to the development of
coagulating lattice structures (ref. 23). FIGURE 215. TENSILE
The cross-linking action of surfactants in STRENGTH AND RELATIVE
such systems depends to a considerable ELONGATION OF MEM
degree on the quantity of activated filler BRANES AS A FUNCTION OF
in the volume of the polymeric phase. THE CONCENTRATION OF
When the surfactant is introduced, a TRIOCTYLAMINE.

FIGURE 216. CHEMICAL AND
ELECTROCHEMICAL PROP
ERTIES OF MEMBRANES AS
A FUNCTION OF THE CON-
CENTRATION OF TRIOCTYL-
AMINE.
The greatest reduction in electrical resist
ivity takes place at a small content of
the ionite (40 to 50 per cent) , when the
effect of cross-linkage is very distinctly
reflected (Fig. 217a) . To judge by the physi
cal and mechanical characteristics of the
membranes, additions of surfactant start to
exert a cross-linking effect at a content of
the ionite greater than 67 per cent. The
maximum elasticity is reached at a 75 per
cent content of the resin (Figs. 217b and
217c). It is clear from Figure 217d that at
any composition the modified membranes
have less exchange capacity than the un
modified ones. This is explained by the fact
that part of the nonionogenic groups has
been taken up by molecules of trioctylamine
adsorbed on the surface of the ionite. How
ever, the losses of capacity are slight and do
not exceed 10 per cent.
The cross-linking action of various sur
factants was investigated to clarify the pos
sibilities of their wide use to improve the
properties of heterogeneous ionite mem
branes. The. results of the investigations,
which are presented in Table LXXXVII,
show that all the investigated surfactants are
good cross-linking additives which improve,
in turn, the electrochemical properties of the
membranes. In such case the nature of the
surfactant itself (molecular weight, the
character of the polar groups, the size of
the alkyl radical) exerts a substantial
influence.
The reduction in exchange capacity dur
ing modification of the membranes confirms
the conclusion that a part of the ionogenic
groups reacts with the surfactant. Losses
in the capacity of cationite membranes is
observed to a greater degree when addi
tives with large alkyl radicals are used
(specimen 3, Table LXXXVII), which form
a denser adsorption layer. The selectivity of
membranes increases when a surfactant is
introduced, which is also indicative of the
emergence of structural formations in the
volume of the polymer.
Nonionogenic surfactants in aqueous solu
tion do not form ions. Their solubility is
caused by functional groups which have

TABLE LXXXVm. The Influence of Nonionogenic Surfactants

on the Properties of Membranes

Static Electrical
Noniogenic Surfactant« Tensile Relative exchange Coefficient resistivity
and ionlt« strength, elongation capacity, of swelling in IN NaCl
kg/cm' at break, % zng-eq/gram In water, % solution,
ohms X em
Starting ionite*
KTJ-2 47.6 2.96 10.6 1.960
EDE-IOP 62.6 12 4.66 10 11,000
Coconut oil diethanolamine
KU-2 46.4 18 2.71 12.6 186
EDE-IOP Б9.Б 10 4.6 10 460
Monoalkylolamines,
Cu-Ou
KU-2 42.6 1.6 2.46 11.26 280
EDE-IOP 67.0 8 4.62 10 420
OP-7 KU-2 62.6 2 2.4 16.2 176
Polyhydroxyethylene
eater of alkylphenol
EDE-IOP 62.6 2 4.4 10 260

567

9001-
CONTENT OF KU-2 RESIN
FIGURE 217. CHANGE IN THE PROPERTIES OF MEMBRANES
AS A FUNCTION OF THEIR IONIC CONTENT.
a strong affinity to water. The introduction
of noniogenic surfactants into the mem
branes also leads to structure formation.
It is evident from Table LXXXVIII that
when nonionogenic surfactants are intro
duced the properties of cationite and
anionite membranes also improve.
The cross-linking action of nonionogenic
surfactants is equally well expressed on
either cationite or anionite membranes. The
effect of cross-linkage upon the introduc
tion of surfactant additives is very distinctly
expressed in the case of the use of high
density polyethylene with a high molecular
weight as the binder. Membranes made on
the basis of such polyethylene without sur
factant additives have a high electrical re
sistivity (Tables LXXXVII and LXXXVIII),
cationite ones up to 2,000 ohms x cm,
and anionite ones up to 10,000 ohms x cm.
56°
2
<->90h
When surfactants are introduced, the elec
trical resistance of the membranes decreases
by a factor of 10 to IS, the effect of cross-
linkage being manifested more strongly with
increase in the size of the alkyl radical of the
cation active additives. Thus, when surfac
tants are introduced in to the ionite polymer
system a double effect is achieved. On the
one hand, adsorption activity of the inonite.
that is, increase in its affinity to the polymer
and the creation of coagulation structural
formations in the system, is assured. On the
other hand, cross-linkage, the orientation
of molecules of polyethylene where the sur
factant plays the role of an intermolecular
lubricant, assures a more uniform distribu
tion of the dispersed phase of the ionite in
the polymer (ref. 27).
Further improvement of ionite mem
branes and the designs of electrodialyzers
 based on them is connected with making
rigid membranes with a developed surface.
This will permit giving up separator grids,
HOMOGENEOUS MEMBRANES
It is known that the selectivity of mem
branes noticeably decreases when the con
centrations of the solutions increase; this
complicates the use of electrodialysis for the
desalination of highly mineralized water (of
the oceanic type) (ref. 4) . This effect can
be counteracted by increasing the concen
tration of the ion-exchange groups in the
membrane.
It appeared to us that the increase could
be achieved by creating homogeneous mem
branes in which the ion-exchange capacity
TABLE LXXXIX. Principal Properties of Homogeneous Membranes
(chemically grafted)
Indicators
Static exchange capacity, mg-eq/gram
Selectivity In 0.01-0.2N NaCl
Electrical resistivity In IN NaCl,
ohms X cm
Swelling capacity in thickness. %
Swelling capacity in area, %
Tensile strength, kg/cm*
Those membranes can also be used to
produce drinking water, since the tests con
ducted at sanitary and hygienic organiza
tions of the USSR have given positive
results. However, the water should be
passscd through an absorbent (activated
carbon) after electrodialysis to remove
micromixtures which give the water an
unpleasant odor and taste.
Homogeneous membranes, which have
good electrochemical and mechanical prop
erties, can be successfully used for water
desalination. However, the increase in the
concentrations of ionogenic groups in com
parison with heterogeneous membranes has
not been successfully achieved. Increase in
the capacity of such membranes is accom
panied by increase in mechanical strength.
Work in that direction is being continued.
Anionite membranes which are better in
their exchange capacity have been obtained
by grafting monomers to polyethylene.
Radiationally grafted copolymers suitable
for ion-exchange membranes were obtained
by a method described earlier (refs. Я,
lead to a considerable simplication of the
assembly of electrodialyzers, and also im-
prove the reliability of their operation.
could be considerably increased by reducing
the amount of the inert constituent. There
fore, over a number of years, the Institute
of Plastics has worked on the creation of
homogeneous membranes, having selected
methods of chemical and radiational graft
ing. As a result of chemical grafting, the
MK-100 cationite and the MA-100 anionite
membranes were formed (ref. 6) . The prop
erties of these membranes are presented in
Table LXXXIX (ref. 7) .
MK-100 MA-100
2.6 + 2.8 2.0 - 2.85
0.97 - 0.98 0.97 + 0.98
120 - ISO 160 + 180
2.1 -t 5-6
- -
110-115 112 - 115
120 - 1Б0 120 - 140
9) . The membranes were made by subse
quent chemical processing of grafted chain
copolymers.
The properties of a cationite membrane
based on polyethylene-polystyrene (RMK-
100) and an anionite membrane based on
polyethylene-2.5-vinylmethylpyridine (RMA)
al an optimum value of the grafting are
presented in Table XC.
Depending on the amount of grafting of
2.5-vinylmethylpyridine on the polyethylene
film, the exchange and electrochemical
properties of the membrane vary (Table
XCI) . The least electrical resistance (20
ohms x cm) is that of membranes with a
grafting of 450 per cent with preservation of
strength in the range of 40 kg/cm and
a high relative elongation. Anionite mem
branes based on polyethylene and 2.5-vinyl
methylpyridine with grafting of 50 to 650
per cent can also be recommended for
various purposes depending on the require
ments set for them. The toxic properties
of the given membranes are being in
vestigated.
569
 TABLE XC Principal Properties of RMK-100 Cationlte
and RMA Anionite Membranes
Indicator* RMK-100 RMA, 0.1 mm thick
(0.3 mm thick) (200% grafting)
Static exchange capacity, mg-eq/gram 1.88 6.0
Selectivity in 0.01-0.2N NaCl 0.96
Electrical reactivity, ohms x cm 208 104
Surface electrical resistance, ohma/cm' 6.86 U
Swelling capacity in thickness, % 120 -
Swelling capacity in area, % 121 24
Tensile strength, kg/em' ISO 80
Relative elongation. % 110 160

TABLE XCI. RMA Anionite Membranes (0.1 mm thick

with various amounts of radiational grafting)
Properties of films swollen in O.IN HsSOi
Amount of Static exchange Tensile
grafting, % Linear capacity in strength, Elongation at
swelling. % 0.1N HC1 kg/em9 break. %
mg-eq/gram
16 2.8 0.98 160 400
70 9.8 2.90 140 160
160 16.0 4.80 120 160
260 24.6 6.14 70 160
800 26.0 6.86 42 170
460 27.0 £.80 40 170
660 28.6 6.20 14

CONCLUSIONS
As a result of scientific research conducted
by the authors in the course of a number
of years, an assortment of heterogeneous
and homogeneous membranes suitable for
water desalination has been created. The
synthesized membranes are characterized by
good electrochemical and mechanical prop
erties which permit using them efficiently
to obtain desalinated water.
Experience in the operation of mem
branes of a heterogeneous type has been
accumulated and studied. The good oper
ating properties of such membranes in elec-
trodialytic processes have been established.
The suitability of these membranes for
obtaining drinking water has been deter
mined.
Ways have been found to improve the
qualitative characteristics of heterogeneous
membranes; the most promising method is
cross-linkage. A prospective cost of hetero
geneous membranes has been determined
which permits improving the economic in
dices of the process of water desalination.

1. Shtukovskaya, O. A., et al: Gigiena i 5. Saldadze K. M., et al: Ionoobmennye

Sanitariya (Hygiene and Sanitation),
no. 6 (1962) p. 29.
2. Saldadze, K. M., et al: Elektroionoitovyi
metod opresneniya vody razlichnogo
solesoderzhaniya Electroionite Method
of Desalination of Water of Various
Salt Contents), Collection, Academy of
Sciences USSR, "Nauka" (Science) Pub
lishing House (1964) p. 119.
S. Ganulevich, N. E., et al: USSR Author's
Certificate No. 146,940 (1961). Byulleten'
izobretatelya (Bulletin of the Inventor),
no. 9 (1962).
4. Whalley, C. H.: Chem. Ind. no. 1
(1958) p. 8.
570
vysokomolekulyarnye coedineniya (High
Molecular Ion-Exchange Compounds),
Goskhimizdat (State Chemical Publish
ing House) (1960).
6. Granulevich, N. E., et al: USSR Au
thor's Certificate No. 148,906 (1962).
7. Pashkov, A. B., et al: In the Collection:
Tezisy dokladov na soveshchanii po
proizvodstvu i primeneniyu ionoobmen-
nykh polimerov v promyshlennosti
(Subjects of Reports at the Conference
on the Production and Application of
Ion-Exchange Polymers in Industry),
Moscow, GOSNITI (1964) p. 17.
 8. Klimanova, R. S., et al: Trudy II Vseso-
yuznogo soveshchaniya po radiatsionnol
khimii (Proceedings of the Second All-
Union Conference on Radiation Chem
istry), USSR Academy of Sciences Pub
lishing House, Moscow (1962) p. 501.
9. Tikhomirova, N. S., et al: Plasticheskie
massy (Plastics), no. 3 (1964) p. 4.
10. Titov, V. S.; Pashkov, A. B.: USSR
Author's Certificate No. 102,135 (1955) .
11. Titov, V. S.: Byulleten' tsvetnoi metal-
lurgii (Bulletin of Nonferrous Metal
lurgy), vol. 4, no. 105 (1958) p. 29.
12. Pashkov, A. B.; Titov, V. S.: Khimi-
cheskaya promyshlennost' (Chemical In
dustry), vol. 5, no. 10 (1958) p. 270.
13. Titov, V. S., et al: USSR Authors Cer
tificate No. 106383 (1956) ; Byulleten'
izobretenii, no. 6 (1957) .
14. Titov, V. S.: Plasticheskie massy, no. 3
(1959) p. 45.
15. Titov, V. S.: Khimicheskaya nauka i
promyshlennost' (Chemical Science and
Industry), vol. 4, no. 1 (1959) p. 137.
16. Laskorin, B. N., et al: Ionoobmennye
membrany i ikh primenenie (Ion-Ex
change Membranes and Their Applica
tion), Gosatomizdat (State Atomic Pub
lishing House) (1961) .
17. Laskorin, B. N.: USSR Author's Certifi
cate No. 172,485 (1965) ; Byulleten' izo
bretenii, no. 13 (1965) .
18. Yampol'skii, B. Ya., et al: Doklady AN
This paper was submitted for publication only.
Utilisation Des Membranes
D'Echange Ionique Pour
Le Dessalement de L'Eau
F. T. Shostak, N. Ya. Lyubman, O. D. Savenko, S. M. Serikbaeva
Union des
On a mis au point des methodes de syn
theses des membranes d'echange ionique
destinies a etre utilisees dans les usines de
dessalement par electrodialyse.
A la suite des etudes exploratoires effec-
tuees, on a montre que l'une des tendances
les plus effectives dans la synthese des mem
branes est la combinaison moleculaire de
SSSR, vol. 1, no. 42 (1962) pp. 3-633.
19. Rebinder, P. A.: Zh. Vses. khim. obshch.
im. Mendeleeva (Journal of the All-
Union Chemical Society imeni Mende
leev), vol. 8, no. 2 (1963) p. 162.
20. Rebinder, P. A.: In the Collection:
Uglegrafitovye materialy i ikh primen
enie (Graphitic Carbon Materials and
Their Application), Profizdat (Trade
Union Publishing House) (1958) .
21. Trapeznikov, A. A.; Shcherbakov, R. N.:
Zh. fit. khim. (Journal of Physical
Chemistry), vol. 38, no. 25 (1964) p.
512.
22. Neimark, I. E., et al: Vys. soed. (High
Molecular Compounds), vol. 3, no. 5
(1961) p. 711.
23. Taubman, A. B., et al: Doklady AN
SSSR, vol. 142, no. 2 (1962) p. 407.
24. Dogadkin, B. A.; Lukomskaya, A. I.:
Trudy 111 Vses. konf. po kail. khim.
Proceedings of the Third All-Union
Conference on Colloidal Chemistry),
USSR Academy of Sciences Publishing
House, Moscow (1956) pp. 363, 371.
25. Kasatochkin, V. L.; Lukin, B. V.: Zh.
tekhn. fiz. (Journal of Technical Physics),
no. 19 (1950) p. 76.
26. Titov, V. S.: USSR Author's Certificate
No. 117,450 (1959).
27. Kargin, V. A.: Koretskaya, T. A.: Vys.
soed., vol. !, no. 11 (1963) p. 1729.
polyelectrolytes avec des polymeres thermo-
plastiques inertes. En consequence, les me
thodes suivantes ont ete developpees:
1. Combinaison moleculaire de polyole-
fines et autres thermoplastiques avec des
composes aromatiques de polyvinyle avec
reticulation ulterieure et introduction de
groupes ionogenes.
571
 2. Utilisation de nouvelles reactions de
certains types de résines de carbo hydrate-
formaldehyde qui conduisent a l'obtention
de polyélectrolytes tri-dimensionnels (réac
tion de réticulation sulfurisante et autres)
dans des conditions flexibles.
S. Imprégnation des pellicules polymé-
riques inertes avec différents monomères
Ионитовые Мембраны для Опреснителей
Соленых Вод
Шостак Ф. Т., Любман Н. Я., Савенко О. Д., Серикбаева С. М.
СССР
Разработаны методы синтеза ионо
обменных мембран, предназначаемых
для применения в электродиализных
опреснительных установках.
В результате проведенных поиско
вых исследований показано, что одним
из наиболее эффективных направлений
в синтезе мембран является молеку
лярное совмещение полиэлектролитов
с инертными термопластичными поли
мерами. В соответствии с этим разра
ботаны следующие методы:
1. Молекулярное совмещение поли-
олефинов и иных термопластов с по-
ливинилароматическими соединениями
с последующей сшивкой и введением
ионогенных групп.
572
vinylaromatiques avec polymérisation ulté
rieure et introduction de groupes ionogenes.
4. Combinaison moléculaire de thermo-
plastiques inertes (polyethylene, chlorure
de polyvinyle et autres) avec des produit!
de condensation de différentes amines et
d'épichlorhydrine avec formation ultérieure
de pellicules.
2. Использование новых реакций не
которых типов углеводородформаль-
дегидных смол, ведущих к получению
в мягких условиях трехмерных поли
электролитов (реакция «сшивки-суль-
фирования> и др.).
3. Пропитка инертных полимерных
пленок различными винилароматически-
ми мономерами с последующей поли
меризацией и введением ионогенных
групп.
4. Молекулярное совмещение инерт
ных термопластов (полиэтилен, поли-
нилхлорид и др.) с продуктами кон
денсации различных аминов и эпихлор-
гидрина и последующим формованием
пленок.
El Uso de Membranas
cambio Iónico en
de Agua
F. T. Shostak, N. Ya. Lyubman, O. D. Savenko, S. M. Serikbaeva
Union de Repúblicas Socialistas Soviéticas
Se han perfeccionado métodos para sinte
tizar las membranas de intercambio iónico
que se intenta utilizar en las centrales de
desalinizacion por electrodiálisis.
Como resultado de las investigaciones
preliminares que se llevaron a cabo, se ha
revelado que una de las tendencias más
efectivas en la síntesis de membranas es la
combinación molecular de polielectrólitos
con polímeros termoplásticos inertes. En
conformidad con esto, se han perfeccionado
los siguientes métodos:
1. La combinación molecular de polio-
lefinas y de otros termoplásticos con com
puestos polivinil-aromaticos, con la poste
rior formación de enlaces cruzados e intro
ducción de grupos ionogénicos.
de Inter
la Desalinizacion
2. La utilización de nuevas reacciones
en algunos tipos de resinas de formaldehido
carbon idratado que conduce a la obtención
de polielectrólitos tridimensionales (reac
ción de sulfurización con formación de
enlaces cruzados y otras) en condiciones
flexibles.
3. La impregnación de películas polimé-
ricas inertes con diferentes monómeros
vinil-aromáticos, con la posterior polimeri
zación e introducción de grupos ionogénicos.
4. La combinación molecular de termo-
plásticos inertes (polietileno, cloruro de
polivinilo y otros) , con los productos de
condensación de diferentes aminas y de
epiclorhidrina, con la subsiguiente forma
ción de película.
573
 Water Desalination by the
Ion-Exchange
V. N. Smagin
USSR
The ion-exchange method of deminerali-
zation is widely applied in the power,
chemical, and other industries to obtain
highly desalinated water from natural waters
containing dissolved salts in the range of 1 to
1.5 g/1, (réf. 1).
In demineralization (partial desalination)
of salt waters, the opinion was formed as
to the absolute unprofitable—the use of the
ion-exchange method for water containing
more than 2 to 3 g/1. of dissolved salts is con
sidered unprofitable (refs. 2, 3). This opinion
is based on theoretical considerations con
cerning the increased effect of the counter-ion
which inhibits deionization with an increase
in the salinity of water processed on the
cation-exchanger. However, this assumption
is correct only for the simplest scheme of de-
mineralization with two stages of deioniza
tion (H-anionization) , in which the possi
bilities of the ion-exchange method are far
from being fully utilized (refs. 2, 4) .
In order to establish general patterns and
develop a better industrial process for de
ionization of highly mineralized waters for
drinking and industrial purposes, we carried
out theoretical and experimental investiga
tions of the ion-exchange method.
As a result of these investigations which
were begun in 1958. a multistage industrial
process for deionization was proposed (ref.
5) . This proposal was based on the follow
ing premises:
(1) Achievement of a high degree of
utilization of the exchange capacity of the
cation-exchanger by successive two-stage
H-Na- and H-cationization of highly miner
alized water without taking any special
• Under present conditions the anlon-exchanger
KDE IOP acte aa a strongly basic anion resin.
Method
measures to decrease the counter-ion effect;
(2) Utilization of the exchangers to sepa
rate cations and anions and to unite these
ions in a new combination. Using a strongly
basic anion-exchanger in the HCO,-form, we
can effect not only demineralization, equiva
lent to the acidity of H-cationized water, but
also the conversion of noncarbonate salts to
bicarbonate alkali;
(3) Utilization of the alkali formed on
the anion resin for leading the counter-ion
in a reversible process whereby we achieve
thorough utilization of the exchange capacity
of the following H-cation resin in the plant;
(4) Application in the terminal stage of
desalination of the sulfonic cation-exchanger
in the H-Na form under the conditions of
"starvation" regeneration to eliminate alkali
(ref. 6).
Figure 218 shows flow diagrams of the
multistage ion-exchange desalting units for
natural waters with a dissolved salt content
of 2 to 6 and 7 to 11 g/1. The scheme for
demineralization of water containing 11 g/1.
consists of: (1) • three cation-exchange filters
with a strong acid cation resin, K.U-2-8
(refs. 7-9) (of the sulfostyrene-divinylben-
zene type) , and weak acid sulfonic cation
resin regenerated with sulfuric acid; (2)
two anion -exchange filters with medium-
basic anion resin, EDE-IOP* (condensation
product of polyethylene polyamine and
epichlorohydrin) (refs. 7-9) , regenerated
with calcined soda; (3) degasifier for the
removal of CO,; and (4) a marble filter for
stabilizing the water. With a decrease of the
salt content in the initial water, the scheme
is simplified. At 2 to 6 g/I. salt content,
the manufacturing scheme is shortened by
two stages of deionization.
575
 7-llg/l 9
_1C
INITIAL
WATER

WATER,05fl/l

2-6g/l
INITIAL
WATER
i rr

WATER, Q5qfl
FIGURE 218. BASIC DIAGRAMS OF MULTISTAGE
ION-EXCHANGE UNITS.
K — 1, 1', J — strong add filters;
H — cation-exchange filters;
A — 2, 4 — strong or medium — basic anion-exchange niters;
SC — S, 5 — weak acid sulfonic resin niters for
M — 4, 6 — marbli filters;
D — degasifier with termediate reservoirs;
V — ventilator;
C — collector of rinse waters.

OPERATION OF THE FILTERS OF THE INDUSTRIAL PLANT

ACCORDING TO STAGES OF DEIONIZATION
The first stage of deionization (filter 1)
represents a used-up H-cation resin filter
of the second stage, which is switched over
to the first stage when the breakthrough of
metal cations reaches 80 per cent. In the
filter, the metal tons (chiefly calcium and
magnesium) present in the initial highly
mineralized water are exchanged for the
hydrogen ions which remain in the lower
layers of the filter and for sodium ions
which were absorbed during the previous
working cycle (the process of H-Na-cation-
ization) .
Because of the natural alkalinity of the
initial water, the hydrogen ions react with
bicarbonate ions to form carbonic add
which decomposes when water and free car
bon dioxide are formed. Thus, as a result of
partial H-cationization and secondary proc
esses, the demineralization in the first filter
is equivalent to the natural alkalinity of
the initial highly mineralized water. The
bulk of sodium ions, as well as the chloride
ions and sulfates, pass into the second stage
of deionization. In general, the process of
576
H-cationization of the water in the first
stage is expressed by the following equation:
I Me' (m) / T \
+ m( Me* I A- );±Ri~
H* (n - m) \ 1 /
J Me* (n) + (n-m^H ^A-^ (1)
where R°" is the complex radical of the
cation resin, an organic support,
practically insoluble in water,
which plays the part of a fixed
T is a sign pointing to the ability
I of all electi iolvtes participating
J- in the reaction to ionize by elec
trolytic dissociation;
n~ is the valence of the solid phase
of the cation resin which plays
the role of an anion;
m is the number of cations which
enter the cation resin from proc
essed water in exchange for
hydrogen ions;
 (n - m) is the acid concentration in H
cationized water.
In the second stage of deioniiation (filter
!'), in the freshly regenerated strong acid
cation-exchanger, KU-2-8, incomplete H-
cationization of water softened by a primary
¡>r ein stalled filier takes place. Even with
incomplete H-cationization of water in the
second stage, the resulting filtrate can be
fed to strong base anion-exchanger filters
without risking precipitation of calcium
carbonate and magnesium hydroxide. Owing
to the additional use of the used-up
H -cation resin filter ll, as a filter for the first
stage of deionization, a high total exchange
capacity of cationite KU-2-8, which is
more than 1,000 g-eq/m" is achieved. The
process of H-cationization in the first stage
of ionization may be expressed by the fol
lowing equation*:
Rî"J H* (n) + m
J H* (n - m)
(2)
Me* (m)
where [m] is the acid concentration in
H-cationized water after the second stage
of ionization, which is equivalent to the
number of metal cations exchanged for
hydrogen cations. Other designations are
the same as in Equation (1) .
Due to the insufficient degree of regenera
tion, as well as to oppositely -charged ion
effects caused by the high acidity of H-
cationized water, there is a considerable
leakage of the metal cations (Me*) in the
process.
In the third stage of deionization (in filter
2, loaded with a medium-basic anion-
exchanger EDE-IOP) the exchange of
anions of strong acids, formed upon H-
cationization of the initial water during the
first and second stages of deionization, oc
curs.
Some of the chloride anions and prac
tically all of the sulfate ions which passed
through the first and the second filters, are
exchanged for (OH") and (HCO~,) anions,
which are taken up by the filtered water
from the anion-exchanger. The exchange
anions and the hydrogen ions form water and
slightly dissociated carbonic acid, which
leads to a deionization of the equivalent
acidity of H-cationized water.
The sodium ions, taken up after two
* Equations (1) and (2) present simplified de
scriptions of processes which take place at the
cation resins without taking into account leakage
stages of ionization, pass through the anion-
exchanger, uniting chiefly with bicarbonate
ions to form sodium bicarbonate, according
to the equation
RÏ'JhCO, +Na
lsoj-
cl
+ Na* I HCO,
iso* I (3)
where R"* is the complex radical of the
anion-exchanger, an organic support, prac
tically insoluble in water, which plays the
part of a fixed cation.
The alkalinity of the filtrate changes de
pending on the degree of H-cationization
of the water; this alkalinity disappears
upon complete exchange of sodium for
hydrogen and increases with the increase
of sodium concentration in the filtrate of
the second stage of deionization (filter l1) .
In general, the process of anion-exchange
is expressed by the following equation:
ТОН (n'-m')
+m (H* I A-)
(HCOi) , I
+ (q+P) (Me*
cJa-) -К"» J
A;,+ mH20+ (m'-P)CO,+P
i'-P)CO,H
e^HCO,)
(Me* I НСО", ) + qq(Me*J
(Me* I A") (4)
where n' is the valence of the solid
phase of the anion resin, which plays
the part of a cation, i.e., it has a certain
positive charge;
m is the acidity of H-
cationized water which enters the anion-
exchanger to be processed;
(q -)- P) is the metal cation content
of the water processed in the anion-
exchange;
q is the number of anions
which were not taken up by the anion-
exchanger from the processed water but
passed through the anion resin filter;
P is the number of metal cat
ions in the processed water, which de
termines the bicarbonate alkalinity of
tiie filtrate, as a result of the anion-
exchanger;
n' and
(n' — m") are, correspondingly, the
number of HCO^ and OH" exchange
anions in an anion resin particle.
577
 In accordance with this equation, the
alkalinity of the filtrate has its highest
value at the beginning of the working cycle
of the filter, when the regenerated anion-
exchanger is richest in exchange bicarbon
ate anions. By the end of the working
cycle, the chlorine anions are getting
through the filter in ever greater numbers,
while the alkalinity of the filtrate decreases.
The fourth stage of water processing
(filter )) is the repetition of the H-
cationization stage, using a strong acid
cation-exchanger in which deionization
equivalent to the alkalinity formed in the
previous stage is achieved, as well as an ad
ditional exchange of sodium ions for hydro
gen ions. In general, the mechanism of the
exchange of metal cations (chiefly of sodium)
contained in anionized water for the hydro
gen ion, follows Equation (2) .
For desalination of water with mineraliza
tion of 2 to 6 g/1., this stage of deionization
is not required.
The fifth stage of deionization (filter 4)
is the repetition of anionization using a
medium-basic anion-exchanger. Here, as in
the third stage, the anions of strong acids
are exchanged, while sodium chloride is
converted to sodium bicarbonate.
The process of anion-exchange takes place
in accordance with Equation (4) . As with
the previous stage, this stage is not required
in the desalination of water with a miner
alization of 2 to 6 g/1.
The sixth stage of deionization (filter 5)
completes desalination in the H Na-form
using a weakly acid sulfonic cation resin
(refs. 7, 10) under the conditions of "star
vation" regeneration. In this stage a de-
mineralization of water equivalent to the
alkalinity of the anionized water takes place.
Despite the fact that the sulfonic cation
resin is not fully converted into the hydro
gen form, the hydrogen ions are exchanged
for the cations contained in the processed
water until the alkalinity disappears from
it. The presence of a certain reserve of un
displaced sodium ions in the charged cation-
exchanger imparts buffer properties to the
sulfonic-type filter. If breakthrough of acid
water occurs during operation of the anion-
exchanger filter due to untimely switching
it off for regeneration), the sulfonic resin
does not let it pass through the filter. In
this case, the exchange of the hydrogen
ions from acid solution for sodium ions
will occur. The action of the sulfonic resin
in the removal of alkalinity and acidity is
expressed by the following equations:
Ih* T t Na*
Na+Na^COs^RrJNa
+H.O+CO, t (5)
ri'In..+h Icr-R*K
+Na*Jcr (6)
The completion of water desalination by
the sulfonic cation-exchanger filter is ex
pedient because the exchanger, being chem
ically stable, not only does not contaminate

TABLE XOl. Changes in Ionic Composition of the Initial Water

with 2 g/1. of Dissolved Salts to Stages of Deionization

Content, Initial water Deionitation stage

mg-eo/1. mg-eq/l.
1 2
H-Na cation- H-cation- OH-HCOi H-Na
exchanger exchanger anion- sulfonic
exchanger cation-
exchanger
Sodium ) 28.4 28.0 8.8
Potassium! 8.8 4.4
Calcium J 0.9 0.9
Magnesium) 0.6 0.6 0.6 0J
Sum of metal cations 29.9 28.9 9.4 9.4 46
Chlorides 18.8 18.8 18.8 4.5 4J
Sulfates 11.1 11.1 11.1 0.1 0.1
Bicarbonates 6.0 4.8
Sum of anions 29.9 24.9 24.9 9.4 4.6
Acidity 1 16.5 -
(1+14.5)
Alkalinity 6.0 4.8
Compact residue, 2,000 1,680 1.800 660 250
mg/L
578
the water with its decomposition products,
but also absorbs the potential dissolution
products of the anion-exchanger which have
alkaline properties.
Tables XCII through XCV present the
average (per working cycle) chemical com
position of the filtrate after each stage of
deionization upon desalination of natural
waters with various dissolved salt contents.
In these tables, the acidity of processed
water, the value of H-cationization) is equal
to the sum of the alkalinity taken up by the
cation-exchanger and the acidity of its fil
trate. The value of the anionization of H-
cationized water is equal to the sum of the
acidity of water entering the anion-
exchanger filter and the alkalinity of its
filtrate.

TABLE XCIII. Changes in Ionic Composition of the Initial Water

with 3.5 g/1. Content of Dissolved Salts to Stages of Deionization

Content, Initial water. Deionization stage

mg-eq/1.
1 2 8 4
H-Na cation- H-cation- OH-HCOi H-Na
exchanger exchanger anion- sulfonic
exchanger cation-
exchanger
Sodium 1
Potassium] 60.9 36.6 9.6 9.6 6
Calcium 8.2 1.2 0.6 0.6 0.2
Magnesium 2.1 1.1 0.2 0.2 0.1
Sum of metal cations 66.2 41.9 10.8 10.8 6.8
Chlorides 36.2 86.2 86.2 6 6
Sulfates 18.7 18.7 18.7 0.3 0.3
Bicarbonates 2.8 - - 6.0 -
Sum of anions 66.2 68.9 63.9 10.3 6.8
Acidity _ 12 48.6 _ _
Alkalinity 2.8 - - 6.0 -
Compact residue, 3.600 8,140 2.600 700 800
mg/l.

TABLE XCIV. Changes in Ionic Composition of Initial Water

with 5 g/1. Content of Dissolved Salts to Stages of Deionization

Content, Initial water, Deionization stage

mg-eq/1. mg-eq/1.
1 2 3 4
H-Na cation- H-cation- OH-HCO. H-Na
exchanger exchanger anion- sulfonic
exchanger cation-
exchanger
Sodium J 78.66 68.66 12 12 6.6
Potassium)
Calcium 4.11 2.61 1.6 1.6 0.6
Magnesium 2.60 1.60 2.6 2.6 1.6
Sum of metal cations 80.36 62.86 16 16 8.6
Chlorides 68.60 68.60 68.60 7.6 7.6
Sulfates 19.26 19.26 19.26 1.0 1.0
Bicarbonates 2.6 - - TJ -
Sum of anions 80.86 77.86 77.86 16 8.6
Acidity _ 16 61.86 _ _
(46.86+16)
Alkalinity 2.6 - 7.6 _
Compact residue, 6,000 4,600 8,600 1.080 480
mg/l.

579
 TABLE XCV. Changes in Ionic Composition of Initial Water
with 10.87 g/1. Content of Dissolved Salts to Stages of Deionixation

Deionixation stage
Content* Initial 1 2 8 4 6 6
nur-eq/l. msr-eq/l. H catioo- OH HCOi H-Na-
H-Na- H-cation- OH-HCOt exehangrer
anion-
eation- exchanger exchanger anion- cation-
exchanger exchanger exchaiurer
Soduim J 1X8.4 128.4 60 60 10 10 4
Calcium 28.7 8 4 4 % 2 1
Magnesium 22.6 8 • • 8 8 8
Sum of cations nt.t 146.4 70.0 70.0 16.0 15.0 7.8
Chlorldas 108.0 108.0 108.0 80 80 t *
Sulfates 81.8 61.6 61.6 88 26 1 1
Hydrocarbonatra 8.0 0 0 16 • 11 S
Bum of anions 176.8 169.6 168.6 70.0 6S.0 16.0 7.0
Acidity _ 24.2 08.6 - 40 - -
Alkalinity 8.0 - - 16 - 11 2
Compact residue. 10.870 io,oao 8.480 4.710 2.S20 1.1S0 478
msVl.

REGENERATION OF ION-EXCHANGE FILTERS AND CATION-EXCHANGE

(STRONG AND WEAK ACID) FILTERS
When the exchange capacity of the H-
cation resin or sulfonic resin is exhausted,
it is regenerated by a sulfuric acid solution
which restores the reserves of hydrogen
ions.
The time for renegeration of strong acid
resins is determined from the indices of
filtrate acidity and hardness; the time for
regeneration of the sulfonic resins is deter
mined from the breakthrough of alkalinity
and the increase of salt content in the ni
trate (more than 1.2 g/1.) .
The regeneration cycle for cation-
exchangers consists of four successive opera
tions:
(1) Loosening the ion-exchanger with
the initial mineralized water by backwash-
ing at 3 to 5 l./sec/m* for 20 minutes. This
operation is terminated after washing off
suspended particles and degraded resin
(finer than 0.25 mm) . If the filter resistance
at the usual rate of filtration (before re
generation) is 8 to 10 mm of water, then
no loosening is required.
(2) Conversion of the cation-exchanger
material, which is saturated with calcium, to
the Na-form by treating it with regenerative
"waste" effluents of anion-exchange filters,
whose alkalinity does not exceed 100 mg-
eq/1. and whose sulfate content does not
exceed 120 mg-cq/1., to avoid the formation
of compounds which are not easily soluble.
The feeding of sodium salt solution to
the filter is continued until analysis of the
filtrate shows a calcium hardness of 50
mg-eq/1.
The cation resin will then be freed from
calcium ions and will be in the Na-form:
the danger of gypsumizing the filter will
thus be averted.
The conversion of cation resin to the
Na-form is performed only for strong add
filters, usually after completion of a filter
ing cycle in the first stage of deionization.
In general, this process can be expressed by
the following equation:
RvTMem,+m> <NaTA■> - R»T Na
1 1 ±Me*,.__,
+mi(Me* J A-) (7)
where m, is the number of sodium cations
which enter the cation -exchanger from the
processed water in exchange for Ca** and
Mg*» cations.
Other designations are the same as in
previous equations.
(3) Regeneration, i.e., passing a solution
of sulfuric acid with a concentration from
5 to 10 per cent, prepared with the use of
initial water, through the layer.
After regeneration, the hydrogen ions,
contained in acid solution, displace the
Na* and Me4 cations, retained during the
working cycle of filtering, from the cation-
exchanger into the solution.
The process of cation resin regeneration
in the ionic form is expressed by the fol
lowing equation:

580
 K*-JmN"Ä +пхН,ЛГ|н:
+nMe*+n (Х-1) H* (8)
where х is a coefficient, equal to 2, which
shows that hydrogen ions (H*) are being
spent for regeneration in an amount higher
than the stoichiometric ratio for the dis
placement of cations (Me*) and insuring
the proper course of the reaction from left
to right.
The expenditure of hydrogen ions in юте
excess, an increased concentration of sul
furic acid in the regeneration solution, and,
consequently, a high specific hydrogen ion
content in the solution, permit us to
achieve a high degree of regeneration and
a high value for the exchange capacity of
the H-cation-exchanger.
Usually, the excess of hydrogen ions, in
troduced with acid, is lost down the drain.
In the deionization scheme under discus
sion, the acid is expended in an amount
close to the one theoretically required for
regeneration of all cationic filters, strong
acid and sulfonic resins, i.e., not more than
49 to 60 g of 100 per cent H.SO. per
g-eq of Me* cations absorbed by the resin
during the filtering cycles preceding regen
eration. Therefore, the cation-exchange
filter loaded with KU-2-8 and the cation-
exchange filter of the sixth stage, which is
loaded with sulfonic resin, are regenerated
simultaneously even when not completely
spent.
Both medium acid and weak acid cation-
exchangers are regenerated with one acid
portion which is passed through the filters
until an acid reaction appears after the
second filter.
Thus, there is nb excess acid in the
system which is not being used for desal
ination of water, and there is no acid
drainage.
The neutralized solution, following the
exchange of hydrogen ions of the acid for
the sodium cations contained in KU-2-8
resin and then the acid filtrate (excess of
acid) from the H-cation-exchange filter,
which entered the weak acid filter, bring
about the following successive processes:
ANION-EXCHANGE FILTERS
When the exchange capacity of the
anionic filter is exhausted, it begins to yield
an acid filtrate. The anion-exchange filter is
then regenerated with a 4 to 5 per cent solu
tion of calcined soda.
The regeneration cycle of anion-exchange
conversion of the sulfonic resin to the
Na-form and the exchange of a consider
able fraction of the sodium cations for the
hydrogen ions of the acid.
The process of regeneration of the sul
fonic resin coincides with the washing of
the strong acid cation-exchange filter.
(4) The products of regeneration, com
posed mainly of sodium sulfate and
the unexpended regeneration solution, are
washed off the H-cation resin with the
highly mineralized input water.
The washing of the highly acid H-cation-
exchange filter is complete when the de
crease of the acidity of its filtrate is
equivalent to the sum of the cations in the
initial water; after this, the filter is switched
back into the working cycle.
With the completion of the washing of
the H-cation-exchange filter, the regener
ation of the sulfonic resin filter is termi
nated, and this filter is washed with
anionized water.
The washing is continued until the salt
content of the filtrate is 1 g/1. The specific
expenditure of the initial water for the
washing of the strong acid H-cation-
exchanger filter constitutes no more than 1.5
m* per m" of the load.
The specific expenditure of anionized
water for washing the weak acid sulfonic
resin is equal to 1.1 to 15 m* per m* of
the load, if the expenditure of the acid
for its regeneration does not exceed the
amount theoretically required.
In the case of a deeper regeneration of
the sulfonic resin, when the acid spent is
in excess of stoichiometric ratios, it has
the capacity not only to remove the excess
alkalinity from the processed water, but
also to convert neutral salts to the corre
sponding acids.
The washing of the sulfonic resin must
be performed with anionized water with an
increased alkalinity (up to SO mg-eq/I.),
in which case the specific expenditure of
water will be no more than 1-1.5 m* per
m* of the filter load.
The washing is checked by a salinity
meter and is terminated when the salt con
tent of the filtrate drops to 1.0 to 15 g/1.
filters consists of three successive operations:
(1) Loosening with softened H-cationized
water or with the washed off waste waters
of anion-exchange filters. The other param
eters correspond to those adopted for the
H-cation-exchange filters.
581
 (2) The regeneration is the passing of
the solution of calcined soda at a concentra
tion of 4 to 5 per cent (40 g/1.) . Usually
the solution is prepared with the input
water and is clarified from the residue by
settling: however, it would be more ex
pedient to prepare the regeneration solu
tion from the initial Na-cationized water,
i.e., highly mineralized water passed through
the cation-exchange filter (loaded with
KU-2-8) after a filtering cycle in the first
stage of deionization.
With this procedure, the specific expendi
ture of soda is reduced and the, reagent
procedures are simplified, since there is no
longer any need to settle the solution and,
consequently, there is also no need for fre
quent cleaning of the reagent tanks. The
rate of the passing of soda solution through
the anion-exchange filter should be 3 to
4 m/hr.
The specific expenditure of calcined soda
amounts to 75 to 85 g of 100 per cent soda
per 1 g-eq of anions absorbed by the anion
resin (i.e., approximately one and one-half
excess over the stoichiometric ratios) during
the filtering cycle preceding regeneration.
The process of regeneration may be de
scribed in general by the following
equation:
A.-. + -J" (Na;■I CO|") + "T
OH- (n'- m')
(H- OH) *r J (HCO,- )-'
I
+ n'(Na* A-) + (-f — )co« t 0)
I
582
(Designations are the same as in the previ
ous equations.)
(3) The products of regeneration and
the excess reagent are washed off the anion-
exchange filters with H-cationized water
after feeding the necessary amount of soda
solution to the filter. The washing is per
formed at a rate of S to 5 m/hr. The
specific expenditure of H-cationized water
for washing is li lo 2 m' per m* of anion-
ite. All washed off waters (as well as all
regeneration waters) are collected in tanks
for subsequent use in cation- and anion-
exchange filters.
The washing of the anion-exchange filler
of the first stage of deionization is termi
nated when the content of dissolved salts
in the filtrate has decreased to about 50
per cent of the initial amount, and that
of the filter of the second stage with min
eralization has decreased to SO per cent of
the initial one. After washing, the anion-
exchange filter is switched into the working
cycle.
Table XCVI gives the basic data for de
signing units for desalination of highly
mineralized water (11 g/.) according to the
multistage scheme.
 o » a3 «4
6"
a pi) 4. 4 26 * oop "1 3 M *P »
a Q e' B 2
e so H gc 5«
? =5 1
|B J < B
d ot
<M «±2 ■* S o' g S OQ lA IO OP
3 4 "
S 3

toM
2 o2 t s 04I OP
3- Z
lis
II I «** 4!
i! !nf I
M oo o S| j|S ©Ob
1 iii
1 " ■» _ -fro
J is1 2 21 12 -•81

a
< .2». a
«2P 3 11 M* «li
P S3 S N3
II I
5 0-3
«"
00 a«
J. 3 l| i
b 2
-I8 »| oo Tit C«
s- Si J3 •
il £<S- ™3 a" ^«
3 8 fl? S| |
5 ■8 -£ 6 a PC c8 £S<3
,2o
5^ £■* X£7* 8 "s e<
S S
S 1-5 8*5 Sto ofeJ » °£ if- =B 8*
o 8-2 •s"s I *' s 0 3 B
1 11 Jf§ 65 ill gl|S|-§ ~ ii
8k >> «5 1 i! £ g m SB J5 a £ o

583
 TECHNICAL AND ECONOMICAL INDICES
None of the known methods for desalina of waste waters, etc.
tion of salt waters can be considered as The shortcoming of the ion-exchange
universal. The economical expediency of the method is the need for reagents. However,
selected method of desalination should be in the industrial system just described, the
determined for each water supply, taking expenditure of reagents has been limited to
into consideration the local conditions (e.g., a minimum.
the existence of power sources, degree of The specific expenditure of sulfuric acid
mineralization of the initial water, its is 49 to 60 g per g-eq of retained cations.
amounts, and the required output of the The specific expenditure of calcined soda
desalination unit) . In some cases, the ion- is 75 to 80 g per g-eq of retained anions.
exchange method may prove to be the only Figure 219 shows a gTaph of specific ex
acceptable system for obtaining fresh water penditures (per m* of desalinated wateT)
from salt water. The ion-exchange method of reagents for the regeneration of ion-
has a number of advantages: the simplicitv exchangers, depending on the dissolved salt
of equipment, small expenditure of initial content of the water being desalinated.
wateT for plant needs (up to 15 to 20 The cost of water desalinated by a multi
per cent of the output of the unit) , small
expenditure of electric power, small volume stage system of deionization. depending on
the initial salt content and performance of
the desalination unit, is given in the graph
in Figure 220.

0 12345678,
EXPENDITURE OF ACID (100% HgSO^.kg/nr
1 I I I I 1 1 J 1 1 1 I— 1000 5000 IOOOO 6000
I 2 3 4 5 6 7 8 9 10 II 12 OUTPUT Of UMTS, m^'24H0URS
EXPENDITURE OFSODAOOOItNOgCOjJ.kg/m3
FIGURE 220. COST OF PAR
FIGURE 219. REAGENT OUT TIALLY DESALINATED
LAY FOR REGENERATION WATER USING MULTISTAGE
OF ION-EXCHANGERS DE DEIONIZATION SYSTEM (INI
PENDING ON SALT CON TIAL WATER FROM 2 TO
TENT OF INITIAL WATER. 11 g/L).

REFERENCES
1. Shkrob, M. S.; Prokhorov, F. G.: Vodo- cow, Publ. House of the Acad, of Sci
podgotovka i vodnyi rezhim parotur- ences (1959).
binnykh elektrostantsii (Water Treat 3. Nachod, F.; Shubcrt, D.: lonoonbmen-
ment and Water Regime of Steam- naya tekhnologiya (Ion-Exchange Tech
Turbine Power Stations), Moscow- nology), transl. from the English, ed.
Leningrad, Gosenergoizdat (1961). by B. N. Laskorin, Moscow, Matallur-
2. lonnyi obmen i ego primenenie (Ion- gizdat (1959).
Exchange and Its Application), Mos 4. Kunin, R.; Maiers, R.: Ionoobmennye

584
 smoly (Ion-Exchange Resins), transi,
from the English, ed. by Prof. G. S.
Perov, Moscow, Publ. House of Foreign
Literature (1952).
5. Smagin, V. N., et al: Author's Certifi
cate no. 146248.
6. Subbotina, N. P.: "On the use of
H-cationization with starvation regen
eration and methods of chemical desal
ination of water", Teploenergetika, no.
5 (1961).
7. Saldadze, K. M.; Pashkov, A. B.; Titov.
V. S.: lonoobmennye vysokomolekuly-
arnye soedineniya (Ion-Exchange High
Molecular Weight Compounds), Mos
cow, Goskhimizdat (1960) .
8. Drachev, S. M.: "Hygienic evaluation
of water quality desalinated by some
SUMMARY OF DISCUSSION
Information was requested concerning the
extent of loss in ion-exchange capacity re
sulting from the use of rinse waters having
a concentration of 1 to 3 grams per liter.
It was stated that this loss was held to a
minimum by using a small amount of rinse
water (1 to 1 \A volumes) , and that this
loss is included in the performance figures
and costs given in this paper.
It was asked if the high amount of
Dessalment de L'Eau Par La Méthode
D'Echange Ionique
V. N. Smagin
Union des Republiques Socialistes Soviétiques
La méthode d'échange ionique pour la
déminéralisation est devenue d'une utilisa
tion fréquente dans différentes branches de
l'industrie en tant que procédé de dessale
ment de haute pureté des eaux naturelles
avec une teneur en sel de 1 à 15 g par
litre. En tant que résultat d'expériences
pratiques dans le dessalement partiel de
l'eau, on a constaté que la méthode
d'échange ionique n'était pas économique
lorsque l'eau possédait une teneur en sel de
plus de 2 à 3 g par litre. Ceci était basé sur
des considérations théoriques au sujet de
l'effet croissant des contre-ions qui empêch
forms of ion-exchangers", Cigiena i
Sanitariya no. 2 (1956).
9. Markaryan, M. K.; Shtannikov, £. V.:
"Manufacturing of drinking water from
highly mineralized waters of Central
Asia with the aid of some domestic
ion-exchange resins", Gigiena i Sanita
riya no. 10 (1959) .
10. Apel'tsin, I. E.; Klyachko, V. A.; Lur'e,
Yu. Yu.; Smirnov, A. S.: lonity i ikh
primenenie (Ionites and Their Appli
cation), Moscow, Standartgiz (1949) .
11. Kastal'skii, A. A.: Proektirovanie usta-
novoh dlya khimicheskogo obessoliva-
niya vody (Designing of Installations for
Chemical Desalination of Water), Mos
cow, Gosstroiizdat (1964).
sulfuric acid required to regenerate the
cation resin caused problems with calcium
sulfate precipitation. The reply stated that
this type of scaling is not a problem. Before
the cation resin columns are regenerated,
the resin is first converted into the sodium
form using waste water from the anion
resin columns. In this manner, calcium
levels are sufficiently lowered to prevent
calcium sulfate precipitation from occurring.
ent le procédé de déionisation avec l'aug
mentation de la salinité de l'eau traitée
sur l'échangeur cationique.
Le présent rapport montre que ceci est
vrai pour les procédés les plus simples de
déminéralisation avec deux étages ionisants.
11 présente les résultats d'études sur la
méthode d'échange ionique pour la dé
minéralisation et des données sur l'exploi
tation des installations de dessalement con
firmant le bien-fondé technique et l'effica
cité économique de cette méthode dans le
dessalement d'eau avec une teneur en sel
allant jusqu'à 10 et 11 g par litre. On y
585
 discute du mécanisme du procède d'échange
ionique qui a lieu dans l'échangeur d'ions
dans des conditions dynamiques tout en
déminéralisant l'eau
Опреснение Соленых Вод Методом
Ионного Обмена
в. н.
СССР
Ионообменный метод деминерализа
ции получил широкое применение в
различных отраслях промышленности
как процесс глубокого обессоливания
природной воды с содержанием солей
1 + 1,5 г/ л. В практике опреснения
(частичного обессоливания) соленых
вод сложилось мнение нерентабельно
сти ионообменного метода при обра
ботке воды с содержанием солей более
2-3 г/ л. Это основывалось на теоре
тических соображениях о возрастании
влияния противоиона, тормозящего
процесс деионизации с ростом солено
сти обрабатываемой воды на катионите.
В докладе показано, что такое поло
жение справедливо для простейшей
Metodo de Desalinizacion
por Intercambio Iónico
V. N. Smagin
Union de Repúblicas Socialistas Soviéticas
El método de desmineralización por in
tercambio iónico se generalizó mucho en
varias ramas de la industria como procedi
miento de desalinización de gran pureza
de aguas naturales con un contenido de sal
de 1 a 13 g/1. Como resultado de la expe
riencia práctica en la desalinización parcial
de agua, se descubrió que el método de
intercambio iónico no resulta económico
586
Le rapport présente également des dis
positions technologiques d'usines de dessale
ment par échange ionique à étages
multiples.
схемы деминерализации с двумя ста
диями ионирования. Приводятся ре
зультаты исследовательских работ по
ионообменному методу деминерализа
ции и данные по эксплуатации опрес
нительных установок, подтверждающие
техническую целесообразность и эко
номическую эффективность применения
этого метода для опреснения воды с
содержанием соли до 10-11 г/л. Рас
сматривается механизм процессов об
мена ионов, протекающий на ионитах
в динамических условиях при демине
рализации соленых вод.
Приводятся технологические схемы
многоступенчатых ионообменных опре
снительных установок.
de Agua
cuando se somete a tratamiento agua con
un contenido salino mayor de 2 a 3 g/1.
Esto se basa en consideraciones teóricas
acerca del efecto gradual de los contra
iones, que obstaculizan el proceso de desio
nización al aumentar la salinidad del agua
tratada con el intercambiador catiónico.
En este informe puede verse que esto
sucede cuando se trata del procedimiento
más simple de desmineralización con dos
etapas de ionización. En él se presentan
los resultados de las investigaciones del
método de desmineralización por intercam
bio iónico y se ofrecen datos sobre el
funcionamiento de centrales de desalinea
ción que confirman la conveniencia técnica
y la eficiencia económica de este método
en la desalinización de agua con un conte
nido salino de hasta 10 a 11 gramos por
litro. Se trata también acerca del meca
nismo del procedimiento de intercambio
iónico que se desarrolla en el intercam
biador iónico bajo condiciones dinámicas,
mientras se desmineraliza el agua salina.
Se presentan los planos tecnológicos de las
centrales multigraduales de desalinización
por intercambio iónico.
587
 Dropwise Condensation
Robert A. Erb and Edmund Thelen
United States of America
INTRODUCTION
The outlook on dropwise condensation
has changed considerably in the last several
years. Since 1930, with the publication of
the pioneering work of Schmidt, Schurig,
and Sellschopp (réf. 1) , it has been known
that much faster heat transfer occurs when
dropwise condensation takes place on a
condenser surface than with the usual film-
wise condensation. The basic problem has
been to develop a system which is perma
nently dropwise, has high thermal conduct
REVIEW OF THE FUNDAMENTALS
Dropwise condensation is an interesting
process as observed visually. There is inces
sant activity as drops form, grow with many
mergers, and sweep down a surface. Studies
of the various phenomena occurring have
been made by a number of investigators.
A basic reason for the great increase in
heat transfer (and the condensation rate)
with dropwise condensation appears to be
that the steam can be cooled directly on the
bare metal areas between the drops. This
is in contrast to the case with filmwise
condensation, where a film of liquid water
(which has low thermal conductivity)
covers the entire surface.
PRIMARY DROP FORMATION
There has been some confusion in the
literature as to the mechanism of the
formation of primary drops (i.e., the first
drops on a bare surface before merging
takes place) , and, indeed, as to the mech
anism whereby drops grow. In 1935 Tam
mann and Boehme (ref. 3) observed that
drops formed repeatedly at the same sites
in a condensation-evaporation-condensation
cycle. This suggests that there are specific
ance, and is economically feasible. From
the literature on the subject up until 1964
(ref. 2) , the general impression that would
be gathered is that the problem has not
been solved. However, recent developments
in dropwise condensation, particularly those
involving the use of very thin films of noble
metals and very thin films of vapor-
deposited polymers on condenser surfaces,
have changed this situation for the better.
sites for nucleation at which the drops
form.
In 1936, however, Jakob (ref. 4) pro
posed a mechanism of drop formation in
which a thin layer of steam or water forms
on a surface, grows to a certain thickness
and then "rolls itself together to form
droplets". Fatica and Katz (ref. 5) in 1949
also stated a belief that "the droplets are
formed as the result of the breakup of a
more or less continuous film or film patch
on a hydrophobic surface". As part of their
support for this, Fatica and Katz cited
experimental studies with superimposed
motion picture sequences of drops at the
same stage of development in consecutive
condensation cycles wherein the drops were
not found to be in repeatable locations
("condensation centers were not evident in
one case investigated in this work") . As Erb
(ref. 6) has noted, however, Fatica and
Katz were working at low magnifications
and were not observing primary drops at
all. but rather drops after a number of
generations of merging, which would ran
domize the observed drop positions. Welch
and Westwater (ref. 7) in 1961 also fol
589
 lowed che mechanism of drop formation
by a fracturing liquid film, and estimated
the "critical film thickness" to be 0.5
micron. However, the low magnification
used did not permit direct resolution of
primary drops, and they apparently mistook
the cause of darkening of a metal surface
at the beginning of a condensation cycle
as the formation of a thin liquid-water
film; whereas, as Erb (ref. 6) has shown,
based on higher resolution observations,
such darkening under specular illumination
is actually due to the diffuse reflection from
a field of small drops. The film-splitting
mechanism was also considered by Rucken-
stein and Metiu (ref. 8) in 1965 to be one
mechanism operative in dropwise condensa
tion and was used by them as the basis
of further analysis of heat transfer.
In the light of the most recent evidence,
however, no liquid film does exist between
growing drops, and the film-splitting mech
anism is basically in error. Erb and Har
rington (ref. 6) have reported that in
observations of nucleation and drop forma
tion on gold and silver surfaces at 1240X
magnification there is no evidence of a
fracturing liquid film. When a liquid film
remained in a state of evaporation, inter
ference fringes could be easily seen, but
without any darkening such as occurs with
the diffuse reflection by small drops. Umur
and Griffith (ref. 9) very recently provided
the remaining piece of evidence needed to
discredit the film-splitting theory. They
showed experimentally, with a technique
using elliptically polarised light and a gold
condensing surface, that no film greater
than a monolayer in thickness exists on the
area between the drops.
It should be pointed out here that the
statement of Tammann and Boehme (ref.
3) , that the number of primary drops
per unit area is independent of the differ
ence in temperature between the saturated
vapor and the substrate, is incorrect. Erb
(ref. 6) found that the density of primary
drops is strongly dependent on the differ
ence between vapor and substrate tempera
tures, with the area densities of drops on
one silver surface ranging from less than
0.5 x 10* cm-1 to greater than IS x 10*
cm*1, as the supersaturation ratio was in
creased from slightly over 1.0 to 1.7. Some
nucleation sites are active for primary drop
formation at very low supersaturations,
while drop formation at others will occur
only at higher supersaturation levels.
590
THE PATH OF HEAT TRANSFER AND
THE MICROCONDENSATION PROCESS
Many conflicting theories on where the
steam condenses and how the heat is trans
ferred in dropwise condensation have been
supported by various workers in the field.
Those supporting the film-splitting mech
anism have usually suggested that heat is
transferred from the steam by way of the
thin, condensing film to the cooled metal
substrate. If such a film does not exist,
however, how does the heat get to the
cooling surface? Some (ref. 9) have sug
gested, since no net condensation takes place
on the area between the drops, that nearly
all the energy transferred to the cooling
surface is transferred through the drops.
This would not seem to be a satisfactory-
mechanism in view of the low thermal
conductivity of water (which evidences it
self in the low heat transfer coefficients
with filmu i.se condensation) , although
Trefethen (ref. 10) has suggested that
there would be active internal circulation
from thermally-caused differences in surface
tension.
The most satisfactory mechanism for heat
transfer would appear to involve a two-
step process: (1) a given mass of vapor
is supercooled by heat transfer with the
condenser surface; (2) part of this mass
of supercooled vapor is condensed on a
growing drop surface and the remaining
part ' is heated by the released heat of
vaporization to approach a saturated condi
tion. The saturated vapor, with further
vapor added, recycles through the cooling
and condensing process. Emmons (ref. 11)
suggested in 1939 that there are violent
local eddy currents in the vapor between
the drops in dropwise condensation. This
active motion of the vapor near the bare
metal cooling surface could explain the
high heat transfer coefficients observed.
Figure 221 is a schematic illustration of
the movement of vapor during active con
densation when growing drops are present.
Saturated vapor moves toward the cooled
substrate, becomes supersaturated, and con
denses in part at the liquid-vapor interface.
This causes a local reduction in pressure
which in turn induces further movement of
supersaturated vapor to the interface. Fig
ure 222 shows approximately the supersatu
ration levels near a cooling surface and
growing drops as might be obtained in
the vapor moving as in Figure 221. with a
substrate temperature of 100°C and a satu-
rated steam temperature of 104°C. (This
would correspond to a maximum super-
saturation ratio of 1.15 in the absence of
condensation.) In the mechanism sup-
ported here, the surface of the liquid drop
is maintained at essentially the saturated
steam temperature; deviations are self-
correcting by condensative (warming) and
evaporative (cooling) exchange with the
vapor.

FIGURE 221. SECTIONAL DIAGRAM OF FLOW PATTERN OF

WATER VAPOR DURING DROP-GROWTH PHASE OF DROP-
WISE CONDENSATION.

FIGURE 222. SECTIONAL DIAGRAM SHOWING ISO-SUPERSAT-

URATION LINES IN WATER VAPOR DURING DROPGROWTH
PHASE OF DROPWISE CONDENSATION (APPROXIMATED FOR
STEAM AT 104°C AND WALL AT 100°C).

591
 A number of theoretical analyses of heat
transfer with dropwise condensation have
been presented by various authors; illustra
tive of a more comprehensive study is thai
of Sugawara and Michiyoshi (ref. 12) in
1956. Unfortunately, a number of the analy
ses in the literature appear to be marred
by incorrect basic assumptions relating to
the physical description of the system and
the nature of the microcondensation process.
There is a definite need for further theo
retical analysis of heat transfer with
dropwise condensation, based on a better
understanding of the microcondensation
phenomena.

ADSORBED ORGANIC PROMOTERS

Much of the practical history of drop-
wise condensation for the past 30 years
could be related to attempts to promote
dropwise condensation for extended periods
by treatment of the metal condenser surface
with organic materials which would chemi-
sorb on the metal to form a hydrophobic
surface. The history is, in part, a record
of failure to reach the ideal goal of a
surface which is permanently dropwise from
an initial treatment. Table XCVII lists the
results of some of the major investigations
on the durability of various types of organic
promoters in the dropwise condensation of
steam. In general the compounds studied
would be those which can be chemisorbed
(attached with a chemical bond) to the
substrate material. For copper-containing
substrates these include organic acids (e.g.,
oleic acid) and organic sulfur compounds
(e.g., dibenryl sulfide) .

TABLE XCVTI. Durability of Adsorbed Organic Promoters

Under Conditions with f
Maximum]
dropwise
Type of
Year <hn)
Drew, Nacle, ft Smith (ref. 18) 1985 Cu;Ni:Cr:steel Mineral oils <24
Cu:Ni;Cr;brass:S.S. Oleic acid >24
Mone!;steel: AI <24
Cu;brass;S.S. Stearic acid >24
Ni <24
Cu:S.S. Beeswax >24
Al <24
Bran Diethyl sulfide <24
Cu :brasa ;monel Benzyl mercaptan >M
Cu;brass K-amyl xanthate >24
Monel <24
Cu;brasa Dithiophosphates >24
<M
Monel;bra»s;Cr a-naphthylamine <24
(raf. 14) 1955 Brass Oleic acid 2-2H |
Benzyl mercaptan 8-10
Mixture of above 2 16-24
S.S. Oleic acid/lube oil
Cr
Blackman, Dewar, & Hampson (ref. 16) 1957 Bran 16 larae-moleeule >600
sulfur compounds
Dibenzyl sulfide >1.780
S-ethyl octadecyl >1,850
xanthate
SS-decamethylene > 1.680
di (octadecylxanthate)
Glycerol tri-(ll-ethoxy >8.6S0
thiocarbonyl)
thioundecanoate
Dodecyltrisethylthio >1.850
silane
Watson. Blrt, Honour, ft Ash (ref;i16) 1962 CuNi alloy Montan wax 100
Irish peat wax >60
Beeswax 40
CandeliDa wax 40
Carnanba wax M
Tanner, Pope, Potter, ft West (ref. 17) 1964 Cr Montanic add I

592
 Many of the materials listed have short
lifetimes and the treated surface reverts to
filmwise condensation within 2 or 3 days.
Some of the large, sulfur-bonded com
pounds have reported lifetimes of up to
several thousand hours without breakdown
under laboratory conditions. In later stud
ies with similar materials, Osment, Tudor,
Speiers, and Rugman (ref. 18) found much
shorter lifetimes with the use of industrial
steam instead of pure steam (their explana
tion: failure due to fouling of the promoted
surface, probably by impurities deposited
out of the steam, and by corrosion or
oxidation of the surface) and with inter
mittent, instead of continuous, steam-
condensing conditions (with failure probably
caused by oxidation of the metal surface) .
POLYMER FILMS
That many organic polymers have hydro
phobic properties is well known. Many
polymers also have good mechanical prop
erties and are resistant to high temperature
steam. It is natural, therefore, to look to
polymer coatings as a means of producing
dropwise condensation on condenser sur
faces. Because of the low thermal conduc
tivity of polymers, however, it is necessary
to use a very thin coating, less than about
0.0004 inch (10 micron) , in order to realize
increases in heat transfer from the dropwise
condensation. Thicknesses in the range of
0.000010 to 0.000100 inch (0.25 to 2.5
micron) would be more desirable from the
heat transfer viewpoint. There are at least
two difficulties connected with such thin
coatings: the first is the difficulty in prepar
ing such a thin, surface coating free of
defects (about an order of magnitude
thinner than usual organic protective coat
ings) , and the second is related to main
taining the desired adhesional barrier and
mechanical properties with such a thin
coating.
Two classes of polymer materials which
have been considered in the literature for
producing dropwise condensation are the
silicone resins and the fluorocarbons. A
patent issued in 1949 to Hunter (ref. 19)
describes the treatment of a condensing sur
face with an organo-silicon halide under
controlled conditions so as to form a thin
adherent polymer film on the surface. After
48 hours of continuous condensation with
low pressure steam, the condensation mode
was dropwise on steel, copper, brass, and
glass substrates which had been treated
with diethyl silicon dichloride or monoethyl
silicon trichloride. Kullberg and Kendall
Other workers have sidestepped the prob
lems of permanence that occurs with the
single-treatment approach by the periodic
(e.g., daily) injection of promoter into the
steam. Such materials as copper (II) oléate
and octadecylamine have been used with
this approach. Claims have been made of
indefinite lifetime of resulting dropwise
condensation, based on laboratory tests of
some thousands of hours in duration. Peri
odic or continuous injection of organic
promoter into the steam may indeed be
suitable for certain applications. For some
applications, however, such as multistage
distillation plants for saline water conver
sion, the injection process does not appear
to represent a practical solution to the
problem of obtaining dropwise condensation.
(ref. 20) described in 1960 the use of
a baked-on silicone resin (Dow-Corning
R-671) to produce dropwise condensation
on copper tubes. Dropwise condensation
was continuing after 1500 hours condensa
tion on panels coated with a silicone film
0.0004 inch (10 micron) in thickness.
Tetrafluoroethylene polymer (such as
duPont Teflon TFE) has attracted the inter
est of a number of investigators. In 1955
Topper and Baer (ref. 21) reported that
water, ethylene glycol, nitrobenzene, and
aniline condense in a dropwise manner on
a coating of Teflon 0.00008 inch (2 micron)
thick on a brass substrate. This coating
was applied from a diluted TFE dispersion
(about 0.6 per cent solids) . Additional
studies with Teflon films for promotion of
dropwise condensation have been reported
by Eibling and Hyatt (ref. 22) , Bucking
ham (ref. 23) , and Depew and Reisbig
(ref. 24) . The greatest concern of the
investigators appears to be related to find
ing practical methods for forming Teflon
films in the desired thicknesses.
More recently, some basically different
approaches to the formation of extremely
thin polymer films have become available.
These involve the formation of the polymer
directly on the substrate from a gas phase.
This approach may be of very great inter
est in dropwise condensation because films
0.00001 inch (0.25 micron) and greater
in thickness, with high mechanical strength
and few voids, can be readily formed.
Two types of vapor-deposited polymers,
which have been studied for producing
dropwise condensation at The Franklin In
stitute Research Laboratories, are glow-
discharge polymers and the parylenes.
 In one experiment, a glow-discharge poly
mer film from hexafluorobenzene was de
posited on a copper flat; condensation of
steam at 101 С was carried out for over
1000 hours on this surface. The condensa
tion was dropwise at first, but after a few
days the surface became partially wetted
out. This appeared to be associated with
oxide formation on the substrate, which
became discolored even under the polymer
film. This behavior suggested to us that
such thin polymer films would be more
effective for producing dropwise condensa
tion on substrates which would not form
gross oxides in steam in which there might
be occasionally small traces of air. (An
earlier study of ours with a thin film of
Teflon FEP laminated to a 90-10 copper-
nickel surface also showed some discolora
tion of the metal under the film.)
The parylenes were next considered. Pary-
lene N, a polymer of para-xylylene vapor-
deposited by the process of Union Carbide
FIGURE 223. (LEFT TO RIGHT) CONDENSATION ON:
0.25 micron parylene N on 90-10 Cu-Ni;
I micron parylene N on 90-10 Cu-Ni;
0.25 micron parylene N on Cr-plated 90-10 Cu-Ni;
1 micron parylene N on Cr-plated 90-10 Cu-Ni.
After 24 hours in steam at 114° С
594
Corporation, was studied for producing
dropwise condensation on bare and chro
mium-plated surfaces of 90-10 copper-nickel
tubes. Two thicknesses of the parylene were
used on each substrate: 0.000010 inch (025
micron) and 0.000040 inch (1 micron) .
Figure 223 shows the appearance of these
four samples after 24 hours of condensation
in steam at 11 1С. The thinner film sample
on the bare 90-10 alloy has filmwise con
densation, while the condensation on the
other three is dropwise. Table XCVIII lists
the effects of the coatings on condensation
rate and overall heat transfer coefficient after
24 hours of condensation. At 9.75 ft/sec
velocity of cooling water, a 38 per cent
increase in overall heat transfer coefficient,
compared with the untreated 90-10 control,
was obtained with the thicker coating on
the bare 90-10 substrate and with the
thinner coating on the chromium-plated
90-10 substrate.
 TABLE XCVIII. Heat Transfer Refaits with Parylene N Coatings
After 24 Hours Condensation in Steam at 114°C
Cooling water at в ft/tee
Overall heat
transfer
Sample coefficient
(Btu/ff-hr-'F)*
90-10 CuNi control 675
10 microinch parylene N
on 90-10 CuNl «70
40 microinch parylene N
on 90-10 CuNI 860
10 microinch parylene CR
on 90-10 880
40 microinch parylene CR
on 90-10 800
•1.000 But/ft4>r-°F = 4,880 kcal/m"-hr-°C
After 44 hours, the 0.000040 inch parylene
film had peeled off of part of the 90-10
surface, with the bared area being filmwise.
The parylene coatings on the chromium -
plated tubes were intact and 100 per cent
dropwise after 2,300 hours of continuous
condensation, with the test still continuing.
The use of a corrosion-resistant plating
(such as chromium) over copper-alloy tubes
is advisable when considering the use of ex
tremely thin polymer films to promote
dropwise condensation. Other tube mate
rials such as stainless steel, titanium, or
zirconium may be coated directly with
selected vapor-deposited polymer films to
provide effective long-term dropwise con
NOBLE METALS AND OTHER INORGANIC, HYDROPHOBIC SYSTEMS
PREVIOUS REPORTS OF DROPWISE
CONDENSATION ON METALS
In their pioneering work on dropwise
condensation, Schmidt, Schurig, and Sells-
chopp (ref. 1) suggested that condensation
of water on highly polished chromium
was inherently dropwise in nature. Drew,
Nagle, and Smith (ref. IS) showed this
not to be the case. The generally filmwise
nature of the condensation of water on
chromium surfaces has been confirmed in
the work of: Hampson and Ozisik (ref.
25) ; Lustenader, Richter, and Neugebauer
(ref. 26) ; and Tanner, Pope, Potter, and
West (ref. 17) . One generally useful prin
ciple related to the results of Schmidt et
al is that better quality dropwise conden
sation is usually seen on a smooth, rather
than on a rough, surface of a given mate
rial. • (This has been seen in our work with
materials on which water has an advancing
contact angle of between 45° and 90° on
the plane surface) . Some investigators have
noted hydrophobic behavior with chromium
when noncondensable gases were present in
Cooling water at 9.75 ft/tec
Overall heat
Condensation transfer Condensation
rate coefficient rate
(ее/tee) (ee/tee)
0.61 78Б 0.64
0.67 880 0.71
0.87 1.080 0.91
0.80 1.080 0.91
0.77 1,080 0.87
densation. There appear to be potentially
profitable areas for study with ultrathin
polymer systems for obtaining long-term
dropwise condensation.
The cost of raw material for a coating
of parylene 1 micron thick would be
approximately $0.23/ ft2, based on the devel
opment price of $l,000/lb for the para-
xylylene dimer. For a projected price of
dimer of $100/lb, the raw material cost
would amount to about $0.023/ft". A total
system cost, including the cost of the
chromium underlayer might then be in the
$0.15 to $0-20/ft» range. This approach to
permanent dropwise condensation appears
to be very attractive economically.
the system; this behavior may be related
to possible enhanced effects of traces of
organic contamination under these circum
stances.
There" have been references in the lit
erature to inherent dropwise condensation
characteristics of water on certain other
metals. These include the references of
Russell (ref. 27) in 1941 to zirconium and
tantalum, of Eibling and Hyatt (ref. 22)
to titanium in 1958, and of Venkatram and
Kuloor (ref. 28) to stainless steel in 1964.
We have run extended condensation tests
with each of these materials in high purity
steam and found that water consistently
condenses in a filmwise fashion on them.
Titanium was studied with various rolled
and mechanically polished finishes without
effect on the filmwise condensation mode.
It should be noted, however, that when
noncondensable gas, either oxygen or Argon,
was added to the closed, refluxing system
in 0.3 per cent concentration, the mode
of condensation on the titanium would
become mixed (the water existing in a
595
 branch-like pattern on the condensing
surface) .
DROPWISE CONDENSATION ON
NOBLE METALS
In 1962 a research program (ref. 29)
was undertaken at The Franklin Institute
under the sponsorship of the Office of
Saline Water to study the dropwise con
densation characteristics of water on raetal-
si 1 1 I'm If surfaces. Particularly of interest in
this program were copper (I) sulfide and
silver sulfide, which were known to have
extremely low solubility in water and to
be fairly hydrophobic. Two condensing ap
paratus for long-term tests were constructed
simultaneously on 42 (later reduced to 16)
sample flats in one apparatus and 8 sample
tubes in the other, with steam generated
from high purity water (redistilled from
alkaline permanganate solution) or from
sea water. Sulfide films formed by reaction
of copper-alloy surfaces with moist hydro
gen sulfide, did promote good quality drop-
wise condensation in a number of cases,
but only for condensation periods up to
about 700 hours. Silver sulfides exhibited
dropwise condensation for longer periods
in some cases, but usually failed before 1000
hours. (However, one silver sulfide sample
on a mild steel substrate has shown good
dropwise condensation for considerably
longer periods.)
Selenides of copper and silver were also
studied and found to behave very similarly
FIGURE 224. DROPWISE CONDENSATION ON SURFACE OF
GOLD (NO. 72), RHODIUM (NO. 105), AND PALLADIUM AFTER
10,770 HOURS (450 DAYS) OF EXPOSURE TO CONTINUOUS
CONDENSATION OF STEAM AT 101 °C.
596
to the sulfides in condensation tests.
In the experimental program, an unex
pected behavior was observed: the unsul-
fided silver control samples produced better
dropwise condensation of steam than did
the sulfided samples. This behavior was
contrary to the widely held belief that a
clean, high energy surface is inherently
wettable by water. The complete wettability
of glass and titanium samples in the same
apparatus helped to confirm the feet that
the behavior of the silver was not caused
by organic contamination.
By considering the position of silver in
the periodic table (Cu-Ag-Ag in Group
IB) , we predicted that gold also should
produce dropwise condensation. This was
tested and verified with various solid and
electroplated gold specimens. The inher
ently hydrophobic nature of clean gold
has also been determined by White (ref.
30) under different experimental conditions.
A general explanation for the observed
nonwettability of silver and gold is that
there is a lack of surface oxide present
under the continuous condensing condi
tions, and that the water is less strongly
bonded to the metal than to a surface
oxide. With this concept in mind, we
extended our consideration of metals which
should be inherently dropwise to include
all the noble metals. Condensation studies
were made on rhodium, palladium, and
platinum, each of which was found to
exhibit dropwise condensation under long
term conditions with high purity water.
Contact angles of water on these surfaces
were measured during active condensation
(ref. SI) ; some average advancing angles:
gold, 55-85"; rhodium, 65-82°; palladium,
74°; platinum, 50°. Thelen (ref. 32) showed
that these contact angles relate to the co
hesive energy densities of the metals. Some
of these surfaces have exhibited dropwise
FIGURE 225. FILMWISE CON
DENSATION ON RHENIUM
(312 HRS).
condensation for more than 13,600 hours
of continuous exposure. Figure 224 shows
dropwise condensation on gold, rhodium,
and palladium surfaces after 10,770 hours
(1.23 years) of condensation.
Results with other metals tend to con
firm our thinking with respect to oxides
and wettability. Water has been found to
exhibit filmwise condensation on the fol
lowing metals: titanium, zirconium, niobi
um, tantalum, chromium, molybdenum,
tungsten, rhenium, type 316 stainless steel,
nickel, 90-10 copper-nickel, cadmium, 65-35
tin-nickel, and lead, as well as microscope-
slide glass and fused quartz. Figure 225
shows a typical filmwise sample, rhenium.
Certain nonnoble metals, such as lead and
copper which are below hydrogen in the
emf series, will show a washing off of oxide
to form bright areas under condensing con
ditions with air-free steam, with dropwise
condensation sometimes occurring in these
areas. If a small amount of oxygen is
introduced into the system, however, these
areas quickly darken and wet out.
Condensation rate and heat transfer
measurements have been made on various
tube samples coated with noble metal sys
tems. Table XCIX is a compilation of some
of these result? taken from different test
runs. The increases in condensation rates
and overall heat transfer coefficients are
very substantial in some cases. For example,
at 9.75 ft/sec velocity of cooling water,
the gold coating on 90-10 copper-nickel
increased the overall heat transfer coeffi
cient by 58 per cent, and palladium on
90-10 increased it by 82 per cent in another
test.

TABLE XCIX. Heat Transfer Results with Noble Metal Coatings

on Vertical Bayonet Tubes (1.3 an diam., 13 cm length)

Condensa- Condensation Overall heat transfer

tion rate (cc/sec) coefficient at
exposure at coolant* (Btu/ffLhr-F)
to 114*C Dropwise velocity of coolant velocity of
steam or
Sample description (hrs) filmwise 6 ft/sec 9.7Б ft/sec 6 ft/see 1.76 ft/see
90-10 CuNl control 26601 F 0.488 0.БББ 476 884
18« Cr on 25д Ni on 90-10 P 0.518 0.Б71 507 684
1.3д Au on 7.6/1 Ni on 90-10 D 0.741 0.87 800 1082
13д Ag on 18/1 N1 on 90-10 D 0.741 0.80 800 1080
0.25/1 Rh on 2.5a Au on 90-10 D 0.687 0.789 702 »82
Type 816 stainless steel control F 0.417 0.50 476 686
18д Ar over Type 816 S.S. D 0.808 0.718 672 785
90-10 CuNl control ББ00 F 0.485 0.50 410 688
1.8/« Au on 7.8/1 Ni on 90-10 D 0.588 0.8» 887 »88
90-10 CuNi control» О 0.784 1.18 865 1880
1.8/« Pd on 7.6/. N1 on »0-10* 720
M F 0.81 0.84 575 786
D 0.95 1.25 1025 1480
L 2000 hours in steam from distilled water, followed by 680 hour• in steam from sea water
(including 0.8 per cent Oi for 2 days before bleeding)
2. After cleaning inside of condenser tube
8. Cooling; water (mineral free) input temperature, 26"C; outlet • 40* to 7643
4. Tubes nickel-plated on the inner surface

597
 The increases in condensation rate and (4) The use of multiple depositions from
heat transfer coefficients with the systems different electrolytes to obtain the
coated with noble metals, combined with noble metal topcoat;
the potentially permanent nature of the (5) The use of an oxide film (e.g., alumi
dropwise promotion, make the noble metal num oxide, titanium dioxide) beneath
systems an attractive possibility in the de the noble metal topcoat to minimize
sign of future generations of distillation diffusion of base metal ions into the
plants for the conversion of saline water. noble metal film; this might require the
A question arises about the economics of use of a process other than electro-
the process, however. A number of the deposition to form the topcoat (e.g..
experimental systems described above would vacuum deposition or chemical deposi
not be economically feasible in a condens tion) .
ing system with very low cost per unil Figures 226 through 230 show dropwise
area of condensing surface. condensation of steam at 101 °C on some of
In the study of means for lowering the the systems being presently studied, using
cost of effective noble metal dropwise some of the above five approaches. Approxi
systems, first it should be noted that silver, mate cost per square foot of surface area
even though it does have inherently good is shown for each coating system; included
dropwise condensation characteristics, is not in this estimate is the cost of the noble
satisfactory for use as an outer layer because metal plating materials plus $0.10/ft* for
(as seen in our experiments) its surface the miscellaneous costs of the electrodeposi-
becomes roughened when condensing steam tion process (which would be carried out
which is generated from sea water. This as an automated process, considering that
phenomenon, which also happens much millions of square feet of condenser tubing
more slowly with steam which is generated might be coated for one large saline water
from distilled water, leads to a partial distillation plant) . Also listed by number
wetting out of the roughened areas. How
ever, gold and the other noble metals have
not exhibited this type of behavior.
Secondly, dropwise condensation does not
seem to be effectively produced in general
with the usual electrodeposited noble metal
coatings, if they are less than about 0.000015
inch (0.38 micron) thick directly over a
base metal, such as nickel. This may be due
to the transport of wettable material
through imperfections in the film to the
surface or, possibly, to long-range contri
butions of energy from the substrate metal
to the surface of the film.
The following five approaches are pres
ently being studied in our program to
optimize the performance per unit thickness
of noble metal used (primarily gold and
palladium) :
(1) The use of plating systems which pro
duce noble metal films of relatively
low porosity;
(2) The use of silver as the coating imme
diately below the thinner noble metal
topcoat; e.g., 0.000005 inch (0.13) mi
cron) or gold over 0.0005 inch (13
micron) silver over 0.0005 inch (13
micron) nickel;
(3) The use of an electrodeposited gold- FIGURE 226. SAMPLE 133: 0.5
silver alloy for a topcoat (e.g., a 75-25 MICRON HG BRIGHT GOLD*
Au-Ag alloy, which is approximately ON 13 MICRON NI ON 90-10
two-thirds the cost of pure gold for a CU-NI.
given thickness) ; ♦TECHNIC, INC.

598
from the above paragraph are the ap would be encountered in saline water dis
proaches used for each sample: tillation practice. A question has arisen,
Sample Approx. cost Performance/cost for example, about the possible effects of
no. ($/ff) approaches inundation of lower tubes from upper tubes
in a horizontal bundle (though Watson,
133 1.28 1 Brunt, and Birt (ref. 33) have reported that
135 1.02 1,2 the effect of inundation may be ignored for
146 0.70 1,4 tube bundles of less than 40 rows high) ;
147 2.12 1,4 we expect to investigate this with the
153 0.90 1,2,3 noble metal systems with a pilot (scale)
Systems which cost $1.00/ft2 and increase plant, using seawater.
the condensation rate by 50 per cent could Present indications with noble metal
provide very significant savings in construc systems are good, and it appears that for
tion of condensers for saline water distilla the first time dropwise condensation of a
tion plants. permanent nature will be able to be in
Further work is planned in developing corporated as an element of design for
high performance low cost noble metal coat distillation plants for the conversion of sea
ings and in studying these dropwise con water.
densation systems under conditions, such as

FIGURE 227. SAMPLE 135: 3.13 FIGURE 228. SAMPLE 146: 0.13
MICRON OROSENE 999* ON MICRON OROSENE 999* ON
13 MICRON AG ON 13 MIC 0.13 MICRON HG BRIGHT
RON N1 ON 90-10 CU-NI. GOLD* ON 13 MICRON N1 ON
♦TECHNIC, INC. 90-10 CU-NI.
* TECHNIC, INC.

599
 FIGURE 229. SAMPLE 147: 0.13
MICRON OROSENE 999* ON
0.13 MICRON RH SULFATE
TP* ON 0.1 S MICRON HG
BRIGHT GOLD* ON 13 MIC
RON N1 ON 90-10 CU-NI.
* TECHNIC, INC.
CONCLUSION
The solution appears to be in sight for
the long standing problem of obtaining
permanent dropwise condensation on con
denser surfaces. The two approaches of
greatest interest are: (1) extremely thin
polymer films polymerized in situ from the
vapor state on a corrosion-resistant base
layer, and (2) systems with extremely thin,
noble metal films as the outer layer. (The
latter is of greater interest at the moment
and, as a result, is the subject of extensive
REFERENCES
1. Schmidt, E.; Schurig, W.; Seilschopp, W.:
Technische Mechanik und Thermody
namik vol. 1, no. 53 (1930) .
2. Erb, R. A.; "Bibliography of the litera
ture on dropwise condensation, 1930-
1964", Saline Water R&D Progr.
Rept. no. 119 Clearing House for Fed
eral Scientific and Technical Informa
tion, Springfield, Va. 22151; Rept. no.
PB 166269, $1).
600
FIGURE 230. SAMPLE 153: 0.13
MICRON ALAUTRONIX 18**
ON 13 MICRON SILVREX**
ON 13 MICRON N1 ON 90-10
CU-NI.
**SEL-REX CORPORATION.
laboratory studies.)
With the increased heat transfer coeffi
cients and condensation rates obtained with
dropwise condensation, a substantial reduc
tion in condenser size and overall cost for
a given fresh water production output
should be realized. Since the condenser
system is the largest cost item in a distilla
tion plant, this could lead to a significant
reduction in the cost of fresh water pro
duced.
3. Tammann, G.; Boehme, W.: Ann Phy
sik no. 22 (1935) p. 77.
4. Jakob, M.: Mechanical Engineering no.
58 (1936) p. 729.
5. Fatica, N.; Katz, D. L.: Chemical En
gineering Progress no. 45 (1949) p. 661.
6. Erb, R. R.: "Heterogeneous nucleation
on single-crystal silver and gold sub
strates in cyclic condensation of water
vapor". Ph.D. Dissertation, Temple Uni
 versity (May 1, 1965) ; to be available
from University Microfilms: Erb, R. A.;
Harrington, G. W.: Paper Presented at
the 150th National Meeting, American
Chemical Society, Atlantic City, N. J.
(Sept. 1965) .
7. Welch, J. F.; Westwater, J. W.; Inter
national Developments in Heat Trans
fer, Part II (1961) p. S02.
8. Ruckenstein, £.; Metiu, H : Chemical
Engineering Science no. 20 (1965) p.
173.
9. Umur, A.; Griffith. P.: Trans. Amer.
Soc. of Mech. Engrs. (Journal of Heat
Transfer) no. 87, Series C275 (1965) .
10. Trefethen, L. M.: GEL Rept. no.
58GL47, General Electric Corp., Schen
ectady. N. Y. (Feb. 3, 1958) .
11. Emmons, H.: Trans. Amer. Inst. Chem.
Engrs. no. 35 (1939) p. 109.
12. Sugawara, S.; Michiyoshi, I.: Memoirs
Faculty of Engrg. Kyoto Univ. no. 18
(1956) p. 84.
13. Drew, T. B.; Nagle, W. M.; Smith.
W. Q.: Trans. Amer. Inst. Chem. Engrs.
no. 31 (1935) p. 605.
14. Hampson, H.: Engineering no. 179
(1955) p. 464.
15. Blackmail. L. C. F.; Dewar, M. J. S.:
Hampson, H.: /. . Appl. Chem. no. 7
(1957) p. 160.
16. Watson, R. G. H; Birt, D. C. P.;
Honour, C. W.: Ash, B. W.: /. Appl.
Chem. no. 12 (1962) p. 539.
17. Tanner, D. W.; Pope, D.; Potter, C. J.;
West. D.: /. Appl. Chem. no. 14 (1964)
p. 439.
18. Osment, B. D. J.; Tudor, D.; Speiers,
R. M. M.; Rugman, W.: Trans. Instn.
Chem. Engrs. no. 40 (1962) p. 152.
19. Hunter, J. B.; U. S. Patent 2,469,729
(1949).
SUMMARY OF DISCUSSION
There was no discussion.
20. Kullberg, G. K.; Kendall, H. B.: Chemi
cal Engineering Progress vol. 56 no. 1
(1960) p. 82.
21. Topper, L.; Baer, E.: /. Colloid Sci.
no. 10 (1955) p. 225.
22. Eibling, J. A.; Hyatt, D. L.: Chemical
Engineering Progress vol. 54 no. 10
(1958) p. 84.
23. Buckingham, W. T.: U. S. Patent
2,923,640 (1960).
24. Depew, C. A.; Reisbig, R. L.: Indus
trial and Engineering Chemistry Process
Design and Development no. 3 (1964)
p. 365.
25. Hampson, H.; Ozisik, N.: Proc. Inst.
Mech. Engrs. B IB (1952) p. 282.
26. Lustenader, E. L.; Richter, R.; Neuge-
bauer, F. J.: Trans. Amer. Soc. of Mech.
Engrs. (Journal of Heat Transfer) no.
81, Series C (1959) p. 297.
27. Russell, H. W.; U. S. Patent 2548,909
(1941).
28. Venkatram, T.; Kuloor, N. R.: Indian
J. Tech. vol. 2 no. 3 (1964) p. 73.
29. Erb, R. A.; Thelen, E.: "Dropwise con
densation on hydrophobic metal and
metal -sulfide surfaces", Paper presented
at 149th National Meeting of the Amer
ican Chemical Society (Apr. 1965) ;
Industrial and Engineering Chemistry,
vol. 57, no. 10 (1965) p. 49.
30. White. M. L.: J. Phys. Chem. no. 68
(1964) p. 3083.
31. Erb, R. A.: /. Phys. Chem. no. 69
(1965) p. 1306.
32. Thelen, E.: to be published.
33. Watson, R. G. H; Brunt, J. J.; Birt,
D. C. P.: International Developments
in Heat Transfer, Part II, Section A
(1961) p. 296.
601
 Condensation
Robert A. Erb et Edmund Thelen
Etats-Unis d'Amérique
D'après les développements au cours des
dernières années, la condensation perma
nente en gouttelettes de vapeur sur des
surfaces de condenseurs, avec les augmenta
tions connexes dans l'échange de chaleur,
semble maintenant être une réalité pratique.
L'une des principales techniques concerne
l'utilisation de pellicules très minces de
métaux nobles sur les surfaces des con
denseurs.
Le mécanisme de la condensation par
gouttes est un sujet ayant un certain in
térêt. Des suggestions ont été présentées par
certains analystes à savoir que la formation
primaire de gouttelettes se produit par la
rupture d'une mince pellicule d'eau liquide
sur la surface. Des preuves récentes indi
quent cependant que le mécanisme de
rupture de la pellicule est essentiellement
une erreur. Des études de grossissement
très fort de la nucléation par Erb et des
études ellipsométriques par Umur et Grif
fith ont montré qu'il n'existe aucune
pellicule liquide sur le substrat entre les
gouttes.
Il existe un certain nombre de théories
contradictoires en ce qui concerne le méca
nisme d'échange de chaleur dans la conden
sation en gouttelettes. Cependant, tout
porte à croire qu'un mécanisme proche de
celui décrit par Emmons serait le plus
près de la réalité; c'est-à-dire, la vapeur
est refroidie et devient sursaturée par le
transport de chaleur sur le substrat nu;
une partie de cette vapeur sursaturée se
condense à la surface d'une gouttelette et
une partie restante à un niveau de sursa
turation réduit est recirculée dans les
courants locaux actifs mis en oeuvre par
l'élimination de la vapeur par condensation.
Depuis plus de trente années, on étudie
les promoteurs organiques de condensation
par gouttelettes, bien qu'apparemment sans
avoir atteint l'objectif idéal d'une surface
qui, après un traitement initial, soit pro
ductrice de gouttelettes d'une façon perma
nente. Les promoteurs organiques sont
généralement des matières qui sont chimi-
sorbées sur le substrat. Pour des substrats
en alliage de cuivre, ceux-ci comprennent
en Gouttelettes
des acides organiques (par exemple, acide
oléique) et des composés organiques à base
de soufre. Selon l'information disponible,
la durée de service de ces matières, relative
à la formation des gouttelettes de vapeur
pure, varie entre plusieurs heures pour des
acides organiques et plusieurs milliers
d'heures pour des composés au soufre. On
indique que ces durées sont moindres avec
de la vapeur impure ou dans le cas d'un
fonctionnement intermittent. Dans certains
systèmes, l'injection continue de promoteurs
dans la vapeur s'est révélée utile, mais cette
méthode ne serait probablement pas pra
tique, pour provoquer la condensation par
gouttes, dans les installations de distillation
en étages multiples pour la conversion de
l'eau saline.
Pour la production de la condensation
en gouttelettes sur les surfaces métalliques
des condenseurs, on a également proposé
dans la littérature des revêtements de poly
mères. D'après les conditions requises, on a
besoin des pellicules extrêmement minces
(à peu près moins de 10 microns, en raison
de la faible conductivité thermique des
polymères) , ayant une bonne résistance a
la vapeur, une bonne adhérence et étant
relativement exemptes de défauts. On a
mentionné des études sur la condensation
en gouttelettes avec des revêtements minces
de polymères de silicone et de polytétra-
fluoroéthylène (Teflon) .
Les progrès récents dans la préparation de
pellicules de polymères extrêmement minces,
relativement exemptes de défauts, par for
mation directe du polymère sur le substrat
en partant d'une phase gazeuse, sont intéres
sants. Deux de ces types de polymères, qui
ont été étudiés au laboratoire de recherche
du Franklin Institute, en vue de leur utili
sation pour encourager la formation des
gouttelettes dans le procédé de condensation,
sont des polymères à décharge par incan
descence et les parylènes. Sur un substrat
de cuivre, une pellicule d'hexafluoroben-
zine, polymère à décharge par incande
scence, produit au début une condensation
par gouttes, mais le cuivre s'est noirci
(oxydé) sous la pellicule et la surface s'est
 partiellement humidifiée. Ceci suggère
l'utilisation d'une couche intermédiaire de
chrome ou matière similaire qui ne forme
rait pas d'oxyde brut dans la vapeur avec
des impuretés occasionnelles de l'air.
On a étudié le parylène N (polymère de
p-xylylène, déposé sous forme de vapeur
par le procès d'Union Carbide) à des épais
seurs de 0,25 et 1 micron sur des tubes
90-10 cuivre-nickel nus et chromés. Le
revêtement de 0,25 micron sur 90-10 a pro
duit une condensation laminaire dans les
vingt-quatre heures et le revêtement de 1
micron sur 90-10 s'est partiellement détaché
après quarante-quatre heures. Cependant
après 305 heures, les deux revêtements
étaient intacts sur la surface chromée et
produisaient une bonne condensation en
gouttelettes avec l'essai encore en cours.
Avec le revêtement de 0,25 micron sur le
chrome, à une vélocité de 3,9 m/seconde de
l'eau de refroidissement, on a obtenu une
augmentation du coefficient d'ensemble de
l'échange de chaleur de 38%, par compa
raison avec un tube 90-10 non-traité. Il est
établi qu'il est préférable d'utiliser un sub
strat résistant à la corrosion lorsque l'on
considère l'utilisation de pellicules très
minces de polymère pour produire une
condensation en gouttelettes.
Des caractéristiques inhérentes d'encou
ragement des gouttelettes ont été attribuées
à certains métaux par différents auteurs; ces
métaux comprennent le chrome, le zirco
nium, le tantale, le titanium et l'acier
inoxydable. Dans des études avec de la
vapeur très pure au Franklin Institute on
a cependant trouvé que chaucun de ces
métaux produisait une condensation lami
naire.
En 1962, un programme de recherches fut
entrepris au Franklin Institute sous le
patronnage de l'Office of Saline Water pour
étudier les caractéristiques de condensation
par gouttes des surfaces de sulfures de
cuivre et de sulfures d'argent. Des surfaces
de sulfure, formées par réaction de sub
strats d'alliages de cuivre et d'argent avec
du sulfure d'hydrogène humide, dans des
conditions contrôlées, encouragèrent la con
densation en gouttelettes mais généralement
leur durée était inférieure à 1.000 heures.
Une découverte utile dans ce programme
a été que l'argent non sulfuré encoura
geait indéfiniment la condensation en
gouttelettes dans la vapeur pure, ce qui est
contraire à certaines généralisations dans
la littérature au sujet de l'humidification
des surfaces à haute énergie. On a trouvé
également que l'or, et plus tard les métaux
de platine étaient à condensation par
gouttes parfaite dans des conditions de
fonctionnement continu. Une des explica
tions de la non-humidification se trouve
dans la faible liaison de l'eau avec une
surface métallique exempte d'oxyde. La
condensation en gouttelettes continue sur
des surfaces d'or, de palladium et de rho
dium, après plus de 11.000 heures d'exposi
tion continue à la condensation. Dans la
même appareil, la condensation laminaire
s'est produite sur plus d'une douzaine de
métaux non nobles.
Des mesures de taux de condensation et
de transfert de chaleur ont été effectuées
sur des échantillons de tubes revêtus de
systèmes de métaux nobles. On a obtenu
des augmentations substantielles des taux
de condensation et des coefficients d'en
semble de transfert de chaleur (58% et
82% dans deux exemples) par l'application
d'un revêtement de métal noble.
Les études continuent pour arriver au
maximum de rendement avec un coût mini
mum pour les systèmes de revêtement avec
des pellicules superficielles extrêmement
minces de métal noble. L'argent ne peut
pas être utilisé comme revêtement extérieur
parce qu'il devient rugueux par exposition
à la vapeur (particulièrement la vapeur
de l'eau de mer) , et une pellicule ordinaire
d'or ou d'autre métal noble ne peut pas
être amincie indéfiniment sans humidifica
tion à cause de l'influence de la matière de
substrat humidifiable à travers les pores ou
autrement. Un certain nombre de méthodes
sont utilisées avec un certain succès, telles
que l'utilisation d'argent comme couche im
médiatement au-dessous du revêtement su
périeur extrêmement mince en métal noble,
et l'utilisation de dépôts ultérieurs de
métaux nobles pour diminuer les pores.
Les considérations économiques actuelles
et les études de rendement en laboratoires
sont favorables. Des plans ont été faits pour
des essais sur une grande échelle dans des
conditions simulants celles des installations
de distillation pour la conversion de l'eau
saline.
Les indications actuelles sont qu'une con
densation permanente en gouttelettes peut
être obtenue sur une base économiquement
attractive. Ces systèmes de condensation en
gouttelettes, lorsqu'ils sont incorporés dans
la conception d'usines de distillation dans
l'avenir, pour la conversion de l'eau de
mer, pourront fournir un abaissement im
portant du prix de revient de l'eau douce
produite.
603
 Капельная Конденсация
Роберт А. Эрб и Эдмунд Телен
Соединенные Штаты Америки
Благодаря усовершенствованиям, про
изведенным за последние несколько
лет, долговременная капельная конден
сация пара на поверхностях конденса
тора н связанное с этим повышение
теплопередачи сейчас кажутся практи
ческой реальностью. Основной техни
ческий метод состоит в покрытии по
верхностей конденсатора очень тонки
ми пленками, состоящими из благород
ных металлов.
Механизм капельной конденсации ин
тересен сам по себе. Некоторые иссле
дователи создали гипотезу, что пер
вичное образование капли происходит
благодаря дисперсии на поверхности
конденсатора тонкой пленки жидкой
воды. Однако, последние данные указы
вают, что это предположение, касаю
щееся разрыва пленки, является в ос
нове ошибочным. Изучение образова
ния центров кристаллизации, проведен
ное Эрбом при большом увеличении,
и эллипсометрические исследования,
произведенные Умиром и Гриффитом,
показали, что на субстрате между кап
лями не существует никакой жидкой
пленки.
В литературе имеется ряд противо
речивых теорий, относящихся к меха
низму теплопередачи при капельной
конденсации. Однако, есть основания
предполагать, что механизм, похожий
на описанный Эммонсом, является на
иболее близким к действительности;
согласно нему, пар охлаждается и ста
новится пересыщенным благодаря пе
реносу тепла к голому субстрату; часть
этого пересыщенного пара конденси
руется на поверхности капли, а осталь
ная часть при пониженном уровне пе
ресыщения рециркулируется в местные
активные потоки, возникающие благо
даря удалению пара с помощью кон
денсации.
Органические промоторы капельной
конденсации изучались более 30 лет,
хотя идеальная цель, в виде поверхно
сти, которая с момента своей первич
ной обработки все время способствует
образованию капель, видимо и не была
604
достигнута. Органическими промотора
ми обычно являются материалы, хемо-
сорбирующиеся на субстрате; при суб
стратах из медных сплавов к ним отно
сятся органические кислоты (например,
олеиновая кислота) и органические сер
нистые соединения. Описанные сроки
службы каплеобразования при чистом
паре на поверхностях этих материалов
колебались в пределах от нескольких
часов для некоторых органических ки
слот до нескольких тысяч часов для
некоторых сернисто-связанных соеди
нений. Было замечено, что эти сроки
службы сокращаются при неочищен
ном паре и при работе с перерывами.
Для некоторых систем оказалось по
лезным непрерывное инжектирование
промоторов в пар, но повидимому это
практически не оправдывается на мно
гоступенчатых установках морской во
ды с капельной конденсацией.
В литературе, для образования ка
пельной конденсации, было предложе
но покрывать металлические поверхно
сти конденсаторов полимерами. Нуж
ны весьма тонкие пленки (менее 10
микронов, вследствие низкой удельной
теплопроводности полимеров), хорошо
противостоящие действию пара, проч
но сцепляющиеся и сравнительно мало
подверженные повреждениям. Имеют
ся исследования, касающиеся капель
ной конденсации, при тонких полиси-
локсановых и политетрафторэтилено-
вых (Тефлон) покровах.
Интересно последнее усовершенство
вание методов изготовления полимер
ных пленок, почти не имеющих изъя
нов, при котором полимер образуется
из газовой фазы непосредственно на
субстрате. К двум типам таких поли
меров, изученных Исследовательскими
лабораториями института им. Франкли
на в целях получения капельной кон
денсации, принадлежат полимеры с
тлеющими разрядами и парилины.
Пленка полимера с тлеющим разрядом,
сделанная из гексафторобензола и на
ходясь на медной субстрате, вначале
содействовала капельной конденсации,
но затем медь под пленкой потемнела
(окислилась), а поверхность стала ча
стично смоченной. Это навело на мысль
применить промежуточный слой из хро
ма или подобного материала, который
бы при случайных воздушных загряз
нениях не образовывал значительных
окисей в паре.
Парилин N (полимер р-ксилилина,
осажденный паром согласно процессу
Компании Юнион Карбайд), толщиной
0,25 и 1,0 микрон, был изучен на голых
и покрытых хромом медно-никкелевых
трубах состава 90-10. 0,25-микронный
покров на сплаве 90-10 через 24 часа
вызвал пленочную конденсацию, а 1,0-
микронный покров на сплаве 90-10 ча
стично облупился через 44 часа. Одна
ко, на поверхности из хрома оба по
крова, хорошо способствуя капельной
конденсации, остались по прошествии
305 часов неповрежденными, после че
го опыт продолжался. По сравнению с
необработанной трубой из сплава 90-
10, при 0,25-микронном покрове на по
верхности из хрома и скорости потока
охлаждающей воды 9,75 фут/сек, бы
ло достигнуто 38-процентное увеличе
ние общего коэффициента теплопере
дачи. Установлено, что при употребле
нии для капельной конденсации очень
тонкой полимерной пленки, желатель
но применять субстрат, который сопро
тивляется коррозии.
Согласно различным литературным
источникам, способность вызывать ка
пельную конденсацию присуща неко
торым металлам: к ним относятся хром,
циркон, тантал, титан и нержавеющая
сталь. Однако, при исследованиях, про
веденных в Институте им. Франклина с
чистым паром, было обнаружено, что
они способствуют пленочной конден
сации.
В 1962 г. Институтом им. Франклина
под покровительством Управления по
опреснению соленых вод была проведе
на серия работ для изучения капельно-
конденсационных характеристик по
верхностей из сернистой меди и серни
стого серебра. Сернистые поверхности,
образованные с помощью реакции мед
ных сплавов и серебряных субстратов
в присутствии увлажненного сероводо
рода и при регулировании общих усло
вий, вызывали капельную конденсацию,
но обычно она продолжалась менее
1.000 часов.
Благодаря этой программе было сде
лано ценное открытие, что при чистом
паре непросульфидированное серебро
всегда способствует капельной конден
сации, что противоречит, некоторым об
щим выводам, указанным в литературе
и относящимся к смачиваемости высо
ко-энергетических поверхностей. Потом
было найдено, что золото, а затем и
платина, вызывают образование капель
при непрерывных конденсационных
условиях. Несмачиваемость объясняет
ся более слабой связью воды с поверх
ностью не имеющего окиси металла.
Капельная конденсация не прекраща
ется на поверхностях из золота, палла
дия и родия после непрерывной кон
денсационной работы, превышающей
11.000 часов. В том же аппарате при
испытании более дюжины неблагород
ных металлов появлялась пленочная
конденсация.
Были произведены измерения скоро
стей конденсации и теплопередачи на
образцах труб, покрытых различными
благородными металлами. При покро
вах из благородных металлов было до
стигнуто значительное повышение ско
ростей конденсации и общих коэффи-
циентев теплопередачи (58 процентов
и 82 процента в двух опытах).
В целях достижения максимальной
производительности при минимальных
затратах продолжаются исследования
различных покровов с чрезвычайно
тонкими поверхностными пленками из
благородных металлов. Для образова
ния наружного слоя нельзя пользовать
ся серебром, потому что оно грубеет
под действием пара (особенно полу
ченного из морской воды); а обыкно
венную пленку из золота или другого
благородноге металла нельзя беспре
дельно утончать, так как возникает
смачиваемость, благодаря воздействию
через поры и иными путями со стороны
смачивающегося материала субстрата.
Успешно пользуются рядом методов
для уменьшения пористости, как на
пример применением слоя серебра не
посредственно под крайне тонким на
ружным покровом из благородного ме
талла, а также последовательным на
слоением' благородных металлов.
Результаты последних экономических
анализов и лабораторных испытаний
производительности благоприятны. На
мечены планы для опытов большого
масштаба, симулирующих условия ра
боты установок, опресняющих соленую
воду.
В настоящее время имеются указа
ния на то, что удастся достичь эконо
мически выгодной капельной конден
сации долговременного действия. Вклю
чение этих капельных систем в проекты
605
 будущих дистилляционных установок
для морской воды, вероятно сможет
Condensación en Gotas
Robert A. Erb y Edmunde» Thelen
Estados Unidos de America
Como resultado de los perfeccionamientos
realizados durante los últimos años, la
condensación permanente en gotas del
vapor sobre las superficies del condensador,
acompañada de aumentos en la transmisión
de calor, parece ser ahora una realidad
práctica. Una de las técnicas principales
consiste en el uso de películas muy delga
das de metales nobles en las superficies del
condensador.
El mecanismo de la condensación en
gotas es un asunto que reviste algún inte
rés. Ciertos investigadores han insinuado
que la formación primaria de gotas ocurre
a causa de la fragmentación de una película
delgada de agua liquida en la superficie.
Sin embargo, últimamente se ha eviden
ciado que el mecanismo disgregador de
películas es fundamentalmente erróneo. Los
estudidos de alta amplificación de la nu-
cleación, efectuados por Erb, y los elipso-
métricos, por Uraur y Griffith, han demos
trado que no hay ninguna película líquida
en el substrato entre las gotas.
En la literatura de la especialidad apete
cen muchas teorías contradictorias acerca
del mecanismo de la transmisión de calor
en la condensación en gotas. Sin embargo,
hay indicios de que un mecanismo seme
jante al descrito por Emmons podría ser el
correcto; es decir, el vapor se enfría y se
toma sobresaturado por la transmisión de
calor al substrato descubierto; parte de
este vapor sobresaturado se condensa en la
superficie de una gota y la parte restante,
a un grado más bajo de sobresaturación,
se vuelve a circular en las corrientes locales
activas producidas por la supresión del
vapor por condensación.
Desde hace más de 30 años se están
estudiando las activadores orgánicos de la
condensación en gotas sin que al parecer
se haya logrado la finalidad ideal de obte
ner una superficie donde se formen las
gotas ininterrumpidamente, a partir de un
606
значительно снизить стоимость опрес-
ненного продукта.
tratamiento inicial. Los activadores orgá
nicos son, por lo general, substancias que se
absorben o adsorben químicamente en el
substrato; tratándose de substratos de alea
ción de cobre, estas substancias comprenden
ácidos orgánicos (v.g., el ácido oleico) y
compuestos orgánicos de azufre. Según se
ha dado a conocer, la duración total en
forma de gotas de estas substancias con
vapor puro ha sido desde varias horas, en
el caso de algunos ácidos orgánicos, hasta
varios miles de horas en el caso de algunos
compuestos ligados con azufre. Se ha dado
a conocer que estas duraciones se han acor
tado a causa de vapor impuro o de la
operación intermitente. Se ha comprobado
que la inyección continua de activadores
en el vapor es de utilidad en ciertos siste
mas, .pero probablemente no sería una
solución práctica para proporcionar conden
sación en gotas en las instalaciones de
destilación en etapa múltiple para la con
versión de agua salada.
En la literatura se han propuesto reves
timientos de polímeros como el medio de
producir condensación en gotas sobre las
superficies metálicas de los condensadores.
Lo que hace falta son películas en extremo
delgadas (de menos de unos 10 micrones,
debido a la baja conductividad térmica de
los polímeros) , que tengan buena resisten
cia al vapor, buena adhesión y carencia
relativa de defectos. Se han dado a conocer
estudios acerca de la condensación en gotas
con revestimientos delgados de polímeros
de siliconas y de politetrafluoretileno
(Teflon) .
Son interesantes los perfeccionamientos
realizados últimamente en la preparación
de películas poliméricas sumamente delga
das, relativamente exentas de defectos,
mediante la formación del polímero direc
tamente sobre el substrato, desde una fase
gaseosa. Dos de esos tipos de polímeros
que han sido estudiados con el fin de pro
ducir condensación en gotas, en los labora
 torios de Investigación del Instituto
Franklin, son polímeros de descarga lumi
niscente y los parilenos. Una película de
polímero de descarga luminiscente de
hexafluorobenceno produjo condensación
en gotas inicialmente cuando se hallaba
sobre un substrato de cobre, pero el cobre
se obscureció (proxidación) debajo de la
película y la superficie se humedeció par
cialmente. Esto sugirió el empleo de una
capa intermedia de cromo u otro material
semejante que no formara óxidos densos
en el vapor con impurezas ocasionales de
aire. El parileno N (polímero de p-xilileno,
depositado al vapor por el procedimiento
de la Union Carbide) , se estudió en tubos
de cobre-níquel 90-10 cromados y sin reves
timientos, en espesores de 0,25 y 1,0
micronès. El revestimiento de 0,25 micrón
en el tubo de cobre-níquel 90-10, produjo
una condensación pelicular dentro de las
24 horas y el revestimiento de 1,0 micrón
en el tubo de cobre-níquel 90-10 se des
cascaró parcialmente en 44 horas. Sin em
bargo, al cabo de 305 horas los dos revesti
mientos sobre la superficie cromada se
hallaban intactos y produciendo una buena
condensación en gotas, continuándose la
prueba. Con el revestimiento de 0,25 micrón
sobre cromo, a una velocidad de flujo de
9,75 pies/segundo de agua de enfriamiento,
se logró obtener un aumento de 58 por
ciento en el coeficiente total de transmisión
de calor, en comparación con un tubo de
90-10 sin tratamiento. Se llegó a la conclu
sión de que es aconsejable un substrato
resistente a la corrosión cuando se consi
dera el uso de películas poliméricas muy
delgadas para promover la condensación
en gotas.
En varias publicaciones de consulta se
atribuye a ciertos metales características
que favorecen la condensación en gotas;
entre estos metales figuran el cromo, el
zirconio, el tantalio, el titanio y el acero
inoxidable. Sin embargo, en estudios efec
tuados en el Instituto Franklin se comprobó
que estos metales, en presencia de vapor
de alta pureza, favorecían la condensación
pelicular.
Bajo los auspicios de la Oficina de Agua
Salada, el Instituto Franklin emprendió en
1962 un programa de investigaciones con
el- objeto de estudiar las características de
condensación en gotas de las superficies de
sulfura de cobre y sulfuro de plata. Las
superficies sulfuradas, formadas por la re
acción de substratos de plata y aleación
de cobre con sulfuro de hidrógeno húmedo,
en condiciones reguladas, sí promovieron
la condensación en gotas, aunque por lo
general la duración fue de menos de 1000
horas.
En el curso de esas investigaciones se
realizó el valioso descubrimiento de que la
plata sin sulfurar favorecía indefinidamente
la condensación en gotas en vapor puro, lo
cual contradice algunas generalizaciones
publicadas acerca de la humectabilidad de
las superficies hiperenergéticas. Se com
probó también que el oro, y más adelante
que los metales del platino se condensaban
en gotas cuando la condensación era con
tinua. Una explicación de la falta de hu
mectabilidad fue que la cohesión del agua
en una superficie metálica exenta de óxido
era más débil. La condensación en gotas
continúa en las superficies de oro, paladio
y rodio después de más de 11.000 horas de
estar expuestas a una condensación con
tinua. En el mismo aparato, la condensa
ción pelicular ocurrió en más de una do
cena de metales no nobles.
Se realizaron mediciones de la velocidad
de condensación y de la transmisión tér
mica en muestras de tubos revestidos de
metales nobles. Se lograron aumentos en
la velocidad de condensación y en los coefi
cientes totales de transmisión térmica (de
58 y 82 por ciento en dos ejemplos) por
medio de la aplicación de revestimientos
de metal noble.
Se prosiguieron los estudios destinados a
lograr un rendimiento máximo por un
costo mínimo con los sistemas de revesti
miento con películas superficiales de metal
noble en extremo delgadas. La plata no
puede utilizarse como capa exterior porque
se pone áspera cuando está espuesta al
vapor (especialmente el de agua de mar) ,
y el espesor de una película ordinaria de
oro u otro metal noble no puede reducirse
indefinidamente sin producirse humecta
ción, a causa de la influencia que ejerce
el material humectable del substrato a
través de los poros o de otra manera. Se
ha obtenido éxito con algunos métodos en
sayados, tales como el empleo de plata para
la capa aplicada inmediatamente debajo de
una capa superior sumamente delgada de
metal noble, así como con las aplicaciones
sucesivas de metales nobles para reducir
los poros a un mínimo.
Tanto las consideraciones económicas
como los estudios de laboratorio actuales
sobre el rendimiento, son favorables. Se han
trazado planes para la realización de pruebas
en mayor escala en condiciones semejantes
a las de las instalaciones de desalinizacion
para la conversión de agua salada.
A juzgar por las indicaciones actuales, la
condensación permanente en gotas puede
607
 obtenerse en bases económicamente atracti lación para la conversión de agua de mar,
vas. Una vez que estos sistemas de con es muy probable que contribuyan a reducir
densación en gotas se incorporen en el apreciableraente el costo del agua dulce
diseño de las futuras instalaciones de desti producida.

608
 Solar Distillation — A Review of

Battelle Experience

J. W. Bloemer, J. A. Eibling, J. R. Irwin, and G. O. G. Löf

United States of America

INTRODUCTION
This paper summarizes the results ob
tained in an extensive research program on
solar distillation of sea water conducted by
Battelle Institute for the Office of Saline
Water, United States Department of the
Interior (refs. 1-3) . This program has now
been completed. Solar stills of various
designs were built and operated at a re
search station near Daytona Beach, Florida
Concurrently, analytical and experimental
studies were conducted at Battelle's Colum
bus, Ohio, laboratories.
The objectives of this program were to
obtain realistic data on the construction,
performance, and maintenance of solar
stills, and to use this information to reduce
the cost of solar distilled water. Two ap
proaches were taken: (1) exploring ways
to decrease the cost of constructing and
operating the stills and (2) studying means
of increasing productivity.
Essentially, a solar still consists of a
shallow basin of water covered with glass
or transparent plastic. Solar radiation trans
mitted through the cover warms the water
in the basin. Part of this water evaporates
and then condenses on the underside of
the cooler, sloping cover. The condensate
runs down the cover to a trough, and then
flows from the still. The unevaporated
water is replaced periodically with fresh
sea water to prevent crystallization in the
basin.
One modification of this basic concept
is to replace the basin with a wick, which
can be either vertical or tilted toward the
sun. The wick, in effect, represents a very
shallow basin, which is desirable from the
standpoint of high thermal efficiency. An
other modification is to replace the wick
with a series of small, shallow trays through
which the sea water cascades.

FLORIDA STATION
Figure 231 is a view of the solar distilla
tion research station located on U. S. Coast
Guard property near Daytona Beach. Flor
ida. The station was operated from June
1958 to June 1965. A fenced-in area of
approximately 0.7 acre was available for
still construction. A partially underground
shelter, shown near the center of the photo
graph, contained instruments used in the
still evaluation program. Feedwater cf ap
proximately 32,000 ppm dissolved solids was
drawn from the nearby tidal river.
FIGURE 231. SOLAR DISTIL
LATION RESEARCH STATION.
 STILLS EVALUATED AT FLORIDA STATION
Following are descriptions of the various
stills constructed and operated at the Flor
ida station (Figs. 232-237) . Some of the
stills were developed by the Battelle team;
others were designed by various other or
ganizations contributing to the Office of
Saline Water program. In the latter in
stances, the designer or manufacturer is
identified in the description of the still.
- in large droplets, causing reflux into the
a
b and then shipped to the Florida station
FIGURE 232. GLASS-COVERED
BASIN-TYPE STILLS,
a. Original still b. New still
INFLATED PLASTIC STIUS
Figure 238 shows an inflated plastic still
which was constructed at the Florida sta
tion in cooperation with the E. I. du Pont
Company. It consisted of grooved concrete
curbs laid 3 feet apart to form 15 bays
each 60 feet long. This gave a total basin
area of 2,300 sq ft. The edges of the plastic
basin liner and the clear plastic cover were
inserted in grooves in the curbs. The cover
was inflated to about one-fourth inch of
water pressure by means of a small fan.
Figure 239 shows an inflated plastic still
610
which was constructed later at the Florida
station by the Church World Service. The
total basin area of this still was about 1,600
square feet. This design was a modification
of the original inflated still design men
tioned previously. The use of wide, low
bays was made possible by a special treat
ment of the Tediar plastic cover to make
it wettable. With nonwettable surfaces, the
distillate tends to accumulate on the cover
brine and increasing reflection of solar
radiation from the cover. Butyl rubber
sheeting was found to be one of the most
suitable basin liner materials.
Figure 240 shows the performance of the
Church World Service still which had a
basin depth of about three-fourths inch
and had 1 inch of sawdust insulation be
neath the basin.
EXPENDABLE PLASTIC STILLS
The stills described so far can be classi
fied as permanent or semipermanent, de
pending on their relative service lives. The
glass-covered, basin-type stills are considered
in the permanent category inasmuch as they
are built entirely of long-life materials. The
inflated plastic and tilted -wick stills have
components such as plastic covers or wicks
which would have to be replaced periodi
cally. Thus, they are considered as semi
permanent. Another type is the so-called
expendable still, which, hopefully, is so low-
in cost that when any part of the still
fails, the entire unit can be discarded.
Figure 241 shows a single-tube expendable
still. The still was completely prefabricated
where it was unfolded on level ground,
inflated, and partially filled with sea water.
Such units could be mass produced at low
cost, the cost being primarily that of the
plastic film. They could be used singly or
in groups. It was found that with these
stills the ground must be leveled reason
ably well to prevent low spots in the dis
tillate troughs. Also, the stills must be
anchored securely to prevent damage by
wind.
VERTICAL-ENVELOPE STILLS
Figure 242 shows one of four vertical-
envelope stills that were evaluated. These
units were constructed by Bjorksten Re
search Laboratories and shipped prefabri
cated to the Florida station. The design of
these stills was different from that of the
usual wick-type still in that evaporation

FIGURE 233. CROSS SECTION OF GLASS-COVERED
BASIN STILL.
0 500 1000 2000 3000
Solar Radiotion, Btu/(«q ft) (doy)
FIGURE 234. PRODUCTIVITY
OF BASIN-TYPE STILL WITH
12-INCH BASIN DEPTH.
occurred from both sides of the wick and
condensation occurred on two surfaces—the
transparent cover and the opaque back.
These features appeared attractive at the
time the stills were built. However, sub
sequent work showed that increased con
densing area is not necessarily beneficial to
productivity. Because of the poor wetting of
the wicks and damage to the stills by even
moderate winds, the stills did not operate
long enough for full evaluation of their
productivity.
MATERIALS EVALUATION STILLS
Several special stills were built for the
purpose of evaluating construction mate
rials. Four different basin liner materials
were evaluated: butyl rubber sheeting,
asphalt-impregnated jute mat, prefabiicated
Precast
concrete pad
asphaltic mat with a PVC core, and asphalt
paving.
The asphalt paving leaked excessively
and, therefore, was considered unsatisfac
tory. The asphalt-impregnated jute rotted
through in about one year. The asphaltic
mat and the butyl sheeting both appeared
promising.
Several different methods of glass install
ation and various distillate trough materials
were also evaluated on these stills. It was
found that thin, continuous, stainless steel
strips, shaped in place made excellent dis
tillate troughs and that single-strength
window glass sealed with asphaltic cement
was satisfactory for the cover.
ADDITIONAL INVESTIGATIONS
Slime formation on the liners of the
basin stills created a problem. Analysis of
the growth showed that it was not an alga
but that it consisted primarily of suspended
matter from the feedwater contained in a
web of either fungi or bacteria. The growth
would thicken on the liner and large sec
tions of it would break loose and float to
the surface. There was evidence that this
floating slime could reduce the productivity
of the still. Several chemical treatments,
including the addition of chlorine, potas
sium permanganate, and copper sulphate to
the feedwater were found to actually accel
erate the growth. Toward the end of the
program, the feedwater was filtered through
sand to remove the suspended matter. This
appeared to be a solution to the problem,
but there was not sufficient time to defi
nitely establish the success of the method.
Transparent plastic films which might be
611
FIGURE 235. TILTED-WICK STILL.
suitable for covers on solar stills were also
evaluated. The films were stretched over
water-filled buckets so that they were
exposed to the weather and had water con
densing on the lower surface as in a solar
still. Du Pont's Tediar and Weatherable
Mylar films and Allied Chemicals' Aclar
films appeared the most promising. They
lasted about 4 years under these exposure
conditions.

0.14

500 1000 1500 2000 2500

Solar Radiation on Plane of Still, Btu/(sq ftl(day)

FIGURE 236. PRODUCTIVITY OF TILTED-WICK STILLS.

FIGURE 237. DURABLE CON

STRUCTION TILTED-WICK
STILL.
FIGURE 238. DU PONT IN
FLATED PLASTIC STILL.

613
 FIGURE 239. CHURCH WORLD SERVICE INFLATED
PLASTIC STILL.

614
0.18

0.16

FIGURE 240. PRODUCTIVITY OF CHURCH WORLD SERVICE

STILL.
COVER FILM
INTERMITTENT HEAT SEALS
AIR-SUPPORTED

////////////////.

FIGURE 241. SINGLE-TUBE EX-

PENDABLE-TYPE STILL.

615
 drain

FIGURE 242. VERTICAL ENVELOPE STILL.

 SUPPORTING STUDIES
In addition to the construction and oper
ation of solar stills at the Daytona Beach
station, supporting studies consisting of
computer studies (refs. 5, 6) and the oper
ation of a laboratory still were carried out
at the Columbus, Ohio, laboratories.
Figure 243 is a photograph of the labora
tory still which was heated electrically
rather than with solar energy. In an actual
solar still, most of the solar radiation passes
through the water in (he basin and is ab
sorbed by the basin liner; the water then
being heated by the warm liner. Thus, in
the laboratory still it was possible to simu
late solar still operation by heating the
water from below with a blanket-type elec
tric heater. The still was so constructed
that design and operating parameters such
as basin depth, cover slope, cover-to-brine
distance, outside air temperature, outside
wind speed, energy input rate, and thermal
insulation beneath the basin could be va
ried independently. Some (rials were con-
FIGURE 243. LA
STILL.
ducted under steady-state conditions and
others were conducted with variable energy
input to simulate solar heating. The results
clearly indicated that, aside from energy
input, the only factors significantly alfecting
solar still performance are basin depth and
the use of insulation beneath the basin.
Figure 244 shows the performance of the
laboratory still as it varied with basin
depth and insulation for two different
energy input rales corresponding to a clear
summer day and a winter day. The energy
input rates shown are the equivalent solar
radiation inputs. The actual energy sup
plied by the electric heater was about 15
per cent below the values shown to account
for the losses that would occur in a solar-
operated still by way of reflection from the
cover, brine surface, and basin liner and
absorption by the cover. It is evident from
Figure 244 that for insulated basins, the
productivity increases rapidly at shallow
depths as the basin depth is further de
creased. As the basin depth is decreased,
the average daily and maximum brine tem
peratures increase because of the lower
thermal inertia. At a higher temperature,
the air circulating between the brine and
the cover can carry more water vapor,
thus increasing the rate of distillation. The
magnitude of the gain is sufficient to more
than offset the increase in thermal losses
resulting from the higher temperatures.
The performance of the laboratory still
and the Florida basin stills under the same
conditions was identical, showing that the
laboratory still was a good simulation of a
solar still.
From these results, one is tempted to
conclude that the use of insulated basins,
made as shallow as possible, is the best
design approach. However, if shallow basins
are used, they must be leveled accurately
lo prevent dry spots; otherwise the liner
may be damaged by the attendant high
temperatures. This more accurate leveling
increases costs; consequently, an economic
optimum depth must be determined. The
cost of the thermal insulation must also
be justified by the expected increase in
productivity.
617
 SOLA* DISTILLATION ECONOMICS
Solar distillation, if a basin-type still is
used, has a number of economic character
istics which are different from those of
other sea water conversion processes:
(1) Unit construction cost is not affected
appreciably by still size.
(2) Power requirements are negligible.
(3) The skill is constructed on-site using
unskilled and semiskilled labor.
(4) Operation and maintenance can be
handled by people with little tech
nical training.
(5) Construction materials are durable
and readily available.
(6) The still design is essentially modu
lar; capacity of an existing still can
be increased by any desired incre
ment with practically no cost pen
alty.
Solar distillation should have excellent
possibilities in a situation where these char
acteristics are important considerations and
where there is adequate solar radiation and
a need for relatively small quantities of
fresh water. Remarkably, many regions of
the world present this situation, including
the developing countries where, in many
cases, energy costs are high, labor costs are
low, and populations are not highly con
centrated.
Table C presents the estimated material
costs and labor requirements for construct
ing a basin-type still. The material costs
are representative of U. S. prices, but, be
cause of the nature of these materials,
costs probably would not vary substantially
throughout the world. However, because
hourly labor rates vary greatly, labor re
quirements are given in terms of man-hours.
The liner and glass costs in Table C in
clude generous allowances for shipping and
wastage during construction.
Table CI presents the estimated capital
costs for a 50,000 gpd basin-type solar still.
A productivity of 0.085 gal/ft'/day at a
solar radiation intensity of 2,000 Btu/ft'/day
for a two-inch deep, uninsulated basin was
assumed. The labor cost of $050 per man-
hour is fairly typical of many developing
areas.
Table CII presents the estimated operating
costs for this same still. The standardized
cost procedure of the U. S. Office of Saline
Water was followed as much as possible in
preparing Tables CIII and CIV, except for
some items for which estimates more ap
propriate to solar stills were included.
 Figure 245 shows a comparison of the cost In preparing Figure 245, it was assumed
of water produced by solar distillation and that the solar radiation intensity averages
by two commercially successful conversion 2,000 Btu/ft'/day and local labor costs $0.50
processes—vapor compression and multiple- per man-hour. The prices of fuel and power
effect flash distillation. indicated on the curves are for units of
TABLE C Typical Basin-Type Still Costs
Material. Labor, man-hours/
Item 1/1,000 BQ ft 1,000 m ft
of basin area of basin area
Layout, {trading, compacting, and roil sterilization 10 20
Asphalt mat liner 80 40
Concrete blocks 60 10
Precast concrete beams 190 26
Glass and asphaltic cement 210 26
Distillate trough materials 60 6
Miscellaneous piping and pumps 70 1
Storage tank 60 6
Totals 8720 ~185

TABLE CI. Basin-Type StiU Capital Costs TABLE cn. Basin-Type StUl Operating
(Dollars; 50,000 gpd capacity; 550,000 ft*) Costs (Dollars per day; 50,000 gpd capacity)
Basio still materials 896,000 Power 1.86
(80.72 per ft») Supplies and maintenance materials 7.00
Erection and assembly 89,600 Operating labor (80.60 per man-hour) 8.00
(80.60 per man-hour) Payroll extras 1.80
Instruments 6,000 General and administrative overhead 2.80
Feedwater supply 600 Amortisation 110.00
Contingencies 20.000 Taxes and insurance 28.00
Engineering 4,000 Interest on working capital 1.10
Construction Interest 26,600
Site 1,600 Total dally cost 169.06
Total plant investment Cost per 1,000 gallon* 8.18
492,200

5.00 1 1 1 1 1 1 1 1 1 1 1 1 1 1 III'
c
O Solar : Basin still, 2000 Btu/(sq ft)(day)
o
o> VC: Vapor compression
O 4.00
o \ Flash: Multiple-effect flash
o
a.
\- 3.00
D
O
\ Nr"^" "— power
O 2.00 -
(J ^^*-*-^ Finch |i 0n -
QJ
O
-

000 1 1 1
10,000 100,000 1,000,000
Capacity, gallons per day

FIGURE 245. COST OF DISTILLING WATER BY

SEVERAL METHODS.

619
one million Biu ana one kwh. The fuel
costs shown are equivalent to about $0.06
and $0.14 per U. S. gallon. Capital costs
and energy requirements of the vapor com
pression and flash distillation plants were
based on recent estimates of the manufac
turers (ref. 7) . Solar still costs were based
on Tables C, CI, and CII assuming a still
with a two-inch deep uninsulated basin.
In all cases, the estimates include the costs
of installation of the plants, feedwater
supply, product water storage, construction,
interest, and operating and maintenance
labor. A 20-year amortization period with
4 per cent interest was assumed for all
plants.
The curves of Figure 245 indicate clearly
that, for the conditions assumed, solar dis
REFERENCES
1. Bloemer, J. W.; Collins, R. A.; Eibling.
J. A.: "Study and field evaluation of
solar sea water stills". Office of Saline
Water R&D Progr. Rept. no. 50 (Sept.
1961).
2. BloemerJ. W.; Irwin, JR.; Eibling. J. A.:
"Second two years' progress on study
and field evaluation of solar sea water
stills". Office of Saline Water Summary
Rept. (Sept. 25, 1964) .
3. Bloemer, J. W.; Eibling, J. A.: "A
progress report on evaluation of solar
sea water stills". Paper no. 61-WA-296.
presented at ASMF. Winter Annual
Meeting, New York, New York (Nov.
26 Dec. 1, 1961).
4. Bloemer, J. W.; Irwin, J. R.; Eibling,
SUMMARY OF DISCUSSION
The presentation of the efforts in de
veloping solar distillation gave rise to ques
tions concerning aerodynamic stability of
the simple stills, severe damage due to hur
ricanes, and the height of wind velocity
that dilfercnt types of solar stills will with
stand. The reply stated that l>ccaiise of the
severe effect of wind in many locations,
the Bal telle group favored glass as the
material for covering solar stills and that
these glass covers had survived three hur
ricanes with winds of up to 70 mph. It
was found that plastic covers were affected
by winds of 20 mph: and even though air-
inflated stills showed better resistance to
wind, they were not as good as glass.
It was staled that the tilted solar sills
were designed for l>etter utilization of the
tillation is preferred when fresh water
quantities of 50,000 gpd or less are required.
The product water cost of $3 per 1.000
gallons may appear to be high by conven
tional standards, but there are many places
in the world where drinking water, often
of marginal or very poor quality, is now-
supplied at considerably higher cost. In
these localities solar distillation is an eco
nomically feasible method of producing
fresh water.
Some new designs have been proposed
which - anticipate using very inexpensive
plastics of relatively short life. These show-
promise of reducing product water costs
almost 50 per cent. Successful development
of this type of still would greatly extend
the applicability of solar distillation.
J. A.: "Design of a basin-type solar
still". Office of Saline Water R&D
Progr. .Rept. no 112 (June 1965) PB
181697.
5. L6f, G. O. C: Eibling. J. A.; Bloemer.
J. W.: "Energv balances in solar dis
tillers", AlChE Journal, vol. 7, no. 4
(Dec. 1961).
6. Bloemer. J. W.; Eibling. J. A.: Irwin,
J. R.: Lof, G. O. C: "Analog computer
simulation of solar still operation",
Paper no. 63-WA-313, presented ASME
Winter Annual Meeting, Philadelphia.
Pennsylvania (Nov. 17-22, 1963).
7-. "Water desalination in developing
countries". United Nations Publication.
Sales no. 64II.B.5 (1964) .
sun's energv than that of the flat still, and
it was asked how the dust later affected the
efficiency of the still. The reply stated that
the glass stills in Florida were not cleaned
over a period of two years; however, since
glass is self-cleaning, it was found that
transmission was not seriously affected.
In answer to a question of what happens
to inflated stills which arc deflated during
a power failure, it was stated that since
the plastic is in danger of being torn by-
high winds, it is deflated and covered with
water during a severe storm. It was pointed
out that steel wire reinforced plastics will
resist wind damage and that covers re
inforced in this way may also be handled
easily without tearing the plastic material.
It was asked whether solar systems
powered by fossil fuels had been considered.
The author replied that this system had
been considered but that the studies had
not been sufficiently advanced to draw any
Distillation Solaire — Examen de
L'Expérience de Battelle
J. W. Bloemer, J. A. Eibling, J. R. Irwin, et G. O. G. Löf
Etats-Unis d'Amérique
Cet exposé résume les résultats d'un pro
gramme de recherches poussées sur la dis
tillation solaire de l'eau de mer effectuées
pour le Département de l'Intérieur des
Etats-Unis, Office of Saline Water, par le
Battelle Institute.
Les objectifs de ce programme étaient
d'obtenir des données réalistes sur la con
struction, le rendement, et l'entretien de
distillateurs solaires et d'appliquer ces ren
seignements pour réduire le prix de revient
de l'eau distillée par l'énergie solaire. Des
distillateurs solaires de conception différente
furent construits et étudiés à la Station de
recherches près de Daytona Beach, Florida.
En même temps, à l'appui des travaux sur
les lieux, des études analytiques et expéri
mentales furent effectuées aux laboratoires
de Battelle, Columbus, Ohio.
Les plus économiques des distillateurs
(alambics) construits à la Station de re
cherche, en ce qui concerne le prix de
revient de l'eau produite, étaient les dis
tillateurs du type bassin couvert de verre.
Deux ensembles de 230 m* chacun furent
construits. Le second ensemble incorporait
des améliorations de construction qui rédui
sirent le coût de construction à un quart
de celui du premier ensemble et améliorèrent
la durée de service. Les deux évaporateurs
fonctionnent sur le principe de l'énergie
solaire passant à travers la couverture trans
parente et chauffant l'eau dans le bassin.
Une partie de l'eau s'évapore, se condense
sur le dessous de la couverture du refroi-
disseur, et s'écoule dans des chéneaux
récepteurs.
Une variante du distillateur recouvert
de verre est un distillateur au bassin de
150 m* avec des couvertures en plastique
gonflé qui a été construit en 1959 en co
opération avec Du Pont Company. Le
conclusion. It was remarked that for capa-
cities of up to 50,000 gpd, a fossil fuel plant
would have to be very cheap and very
efficient to compete with solar distillation.
Church World Service a construit plus
récemment un distillateur amélioré de ce
type à la Station de Floride, en tant que
prélude à la construction de tels distilla
teurs en Grèce. Un gain important de
rendement a été obtenu par l'utilisation de
couvertures humidifiables Tediar.
Un distillateur à bassin produit plus
d'eau potable lorsque le profondeur du
bassin est faible. Une conception qui, en
fait, approche d'une profondeur zéro du
bassin est le distillateur du type à mèche,
qui est généralement construit avec la
mèche inclinée vers le soleil. Vingt de ces
distillateurs, chacun de 2,3 m1, furent
conçus par Dr. Maria Telkes et construits
par la Curtiss-Wright Corporation. Ceux-ci
ont très bien fonctionné pendant plusieurs
années, sauf que la durée de la mèche
était limitée à environ six mois.
Un autre distillateur du type à mèche a
été construit par les laboratoires de re
cherches Bjorksten. Ceux-ci utilisaient une
mèche verticale suspendue entre une cou
verture de plastique transparent et une
partie arrière opaque. La mèche était
humide sur les deux côtés et la condensa
tion se produisait sur la couverture et la
partie d'arrière. Une des difficultés de ce
genre de construction était sa sensibilité
au vent.
Plusieurs petits distillateurs, complète
ment préfabriqués, entièrement en plas
tique furent également construits par
Battelle dans le but d'illustrer le concept
d'un distillateur très bon marché construit
en usine, qui pourrait être monté rapide
ment et dont on pourrait se débarrasser
lorsqu'il n'est plus utilisable.
D'autres distillateurs à .bassin couvert de
verre furent construits dans le but d'évaluer
62 i
 les matériaux de construction et lea va
riantes de conception.
Pour compléter le programme d'essai sur
les lieux et pour mieux comprendre l'in
fluence de la construction et des facteurs
ambiants sur la performance, deux activités
a l'appui du programme furent effectuées:
une étude théorique utilisant des calcula
teurs digitaux et analogues et des expéri
ences avec un distillateur de laboratoire
où la radiation solaire était simulée par la
chaleur électrique.
Le distillateur de laboratoire était conçu
de façon à ce que d'importantes variables
telles que la profondeur de bassin, la pente
de la couverture, l'espace entre la couver
ture et la surface de saumure, la tempéra
ture extérieure de l'air, la vitesse du vent,
l'isolement, le taux d'entrée d'cnérgie, puis
sent être variés de façon indépendante. La
disposition de chauffage permettait soit un
fonctionnement à l'état stationnaire avec
un apport de chaleur fixe, soit un fonction
Солнечная Дистилляция — Обзор Опыта,
Полученного в Институте Им. Баттелл
Дж. У. Блёмер, Дж. А. Эйблинг, Дж. Р. Ирвин и Г. О. Г. Лёф
Соединенные Штаты Америки
В настоящем докладе дается краткий
отчет о результатах обширной исследо
вательской программы, касающейся ди
стилляции морской воды посредством
солнечной энергии, которая была про
ведена Институтом им. Баттелл по по
ручению Управления по опреснению
соленых вод Министерства внутренних
дел Соединенных Штатов.
Целью этой программы было полу
чение точных данных о постройке,
производительности и эксплуатации
солнечных дистилляционных установок,
чтобы использовать эти сведения для
снижения стоимости опресняемой во
ды. На исследовательской станции око
ло Дейтона Бич, шт. Флорида, были
построены и изучены перегонные уста
новки различных конструкций. Одно
временно, в виде дополнения к рабо
там в поле, проводились аналитические
и эмпирические исследования в Лабо-
622
nement intermittent pour simuler les varia
tions typiques de l'énergie solaire.
Les résultats des analyses théoriques et
des expériences sur le distillateur de labo
ratoire montrent que l'apport d'énergie, la
profondeur du bassin et l'utilisation d'isole
ment au-dessous du bassin étaient les seuls
variables ayant un effet signiftcateur sur
le rendement -du distillateur.
Des études d'ordre économique ont dé
montré que le distillateur du type bassin
couvert de verre est le plus pratique de
tous les alambics solaires. Dans certaines
régions du monde, des distillateurs durables
et pratiques pourraient être construits dès
maintenant en vue de produire jusqu'à
200 m* d'eau par jour à un prix inférieur
& celui de tout autre procédé de distilla
tion. Les progrès réalisés à l'avenir dans
la conception des distillateurs à couverture
en plastique et utilisant de nouvelles ma
tières plastiques devraient encore améliorer
la rentabilité de la distillation solaire.
раториях Баттелл в г. Колумбус, шт.
Огайо.
Среди построенных на исследова
тельской станции дистилляционных
групп, наиболее экономичными в смы
сле стоимости опресненной воды ока
зались покрытые стеклом выпарные
бассейны. Было сооружено два агрега
та по 2.500 кв. футов каждый. Благо
даря усовершенствованию конструкции,
стоимость постройки второго агрегата
была снижена до одной четверти по
сравнению с первым и увеличена про
должительность срока его службы. Оба
агрегата работают с помощью солнеч
ного излучения, проходящего через
прозрачное покрытие и нагревающее в
бассейне воду. Часть воды испаряется,
конденсируется на нижней стороне бо
лее прохладного покрытия и стекает
вниз в собирательное лотки.
Вариантом дистиллятора со стеклян-
ным покрытием явился выпарной бас
сейн площадью 1.600 кв. футов с на
дутыми воздухом покрытиями из пласт
массы, который был построен в 1959 г.
в сотрудничестве с Компанией Дю
Понт. После этого организация Чёрч
Уорлд Сервис построила на Флоридской
станции вновь спроектированную уста
новку такого же типа, перед сооруже
нием аналогичных перегонных агрега
тов в Греции. С помощью смачиваю
щихся покрытий из «Тедлара» была
значительно повышена производитель
ность.
Выпарной бассейн производит боль
ше опресненной воды, когда он имеет
малую глубину. У проекта дистилляци-
онной установки фитильного типа глу
бина бассейна приближается к нулю, а
фитиль обычно наклонен в сторону
солнца. Двадцать таких установок, по
25 кв. футов каждая, были спроекти
рованы Доктором Мариа Телкес и по
строены фирмой Кёртисс-Райт Корпо-
рейшон. Они несколько лет находи
лись в эксплуатации и имели хорошую
производительность, с тем только ис
ключением, что срок службы фитиля
был ограничен шестью месяцами.
Другая установка фитильного типа
была построена Исследовательскими
лабораториями Бйоркстен. На ней при
менялся вертикальный фитиль, подве
шенный между прозрачным покрытием
из пластмассы и светонепроницаемой
задней стенкой. Фитиль был смочен с
обеих сторон и конденсация происхо
дила, как на покрытии, так и на стенке.
Единственным недостатком этой кон
струкции являлась ее плохая сопротив
ляемость ветру.
Институт им. Баттелл также построил
несколько маленьких, полностью сбор
ных и сделанных целиком из пластмас
сы опреснительных установок, чтобы
дать представление об очень дешевых
дистилляционных агрегатах заводского
изготовления, поддающихся быстрому
монтажу и сносу за ненадобностью.
С целью испытания строительных
материалов и проектных вариантов бы
ли построены и другие опреснительные
бассейны, покрытые стеклом.
В качестве дополнения к опытной
программе в поле и для лучшего пони
мания влияния конструкции и окружа
ющей среды на производительность
были проведены два вспомогательных
мероприятия: теоретические исследова
ния с помощью цифровых, моделирую
щих счетных машин и опыты с лабора
торным перегонным аппаратом, при ко
торых солнечное излучение симулиро
валось нагреванием посредством элек
тричества.
Лабораторный опреснительный аппа
рат был спроектирован таким образом,
что представлялось возможным от
дельно менять столь важные парамет
ры, как глубину бассейна, наклон по
крытия, расстояние между покрытием
и уровнем рассола, наружную темпера
туру воздуха, скорость ветра, изоля
цию и расход поглощаемой энергии.
Система нагрева позволяла работать
либо при стационарных условиях и рав
номерном поглощении энергии, либо
нестационарно, чтобы симулировать ти
пичное непостоянство солнечного излу
чения.
На основании теоретических анализов
и лабораторных испытаний было обна
ружено, что потребление энергии, глу
бина бассейна и изоляция под ним яв
ляются единственными параметрами,
которые оказывают значительное влия
ние на производительность дистилля-
ционной установки в виде функции глу
бины бассейна при двух различных
суточных расходах энергии, с примене
нием и без применения изоляции.
Экономические исследования показа
ли, что в настоящее время опреснитель
ный бассейн, покрытый стеклом, явля
ется наиболее практичной установкой
среди применяющих солнечное излуче
ние. В некоторых частях мира можно
теперь строить удобные солнечные оп
реснительные установки, с длительным
сроком службы, для производства
50.000 галлонов воды в сутки, которая
обходится дешевле, чем при любом
другом дистилляционном процессе.
Ожидается что будущий прогресс в
области конструкций опреснительных
усановок с покрытиями, сделанными из
вновь усовершенствованных пластмасс,
еще больше повысит экономичнось сол
нечной дистилляции.
623
 La Destilación por
un Análisis de la Experiencia
de Battelle
J. W. Bloemer, J. A. Eibling, J. R. Invin y G. O. G. Lof
Estados Unido» de Norteamérica
Este trabajo sintetiza los resultados de
un vasto programa de investigaciones sobre
la destilación solar del agua de mar llevado
a cabo por el Instituto Battelle por cuenta
de la Oñcina de Agua Salada del Departa
mento del Interior de los Estados Unidos.
Las finalidades de este programa fueron
las de obteneT datos prácticos acerca de la
construcción, funcionamiento y manteni
miento de instalaciones destiladoras solares
y utilizar estos datos para reducir el costo
del agua destilada por energía solar. En
una estación de investigaciones cerca de
Daytona Beach, Florida, se construyeron y
estudiaron instalaciones destiladoras solares
de varios diseños. Simultáneamente, y en
apoyo del trabajo en el terreno, se llevaron
a cabo estudios analíticos y experimentales
en los Laboratorios de Battelle en Colum
bus, Ohio.
Los alambiques más económicos con
struidos en la estación de investigaciones,
en lo que al costo del agua producida se
refiere, fueron los alambiques de depósitos
cubiertos de vidrio. Se construyeron dos
unidades de 2.500 pies cuadrados cada una.
En la segunda se incorporaron majoras de
diseño que redujeron su costo a una cuarta
parte del de la primera y aumentaron su
durabilidad. Ambos alambiques funcionan
de acuerdo con el principio de que la
energía solar atraviesa la cubierta trans
parente y calienta el agua en el depósito.
Parte del agua se evapora, se condensa en
la cara inferior de la cubierta que está a
menor temperatura y se escurre por ella
hasta caer en las cubetas colectoras.
Una variación del alambique cubierto de
vidrio fué el alambique de depósito, de
1.600 pies cuadrados, con cubiertas plásti
cas infladas con aire construido en 1959
con la colaboración de la compañía du
Pont. Más recientemente, el Servicio Mun
dial de Inglesias construyó un alambique
rediseñado, de este tipo, en la estación de
624
Energía Solar —
Florida como etapa previa a la construc
ción de esos alambiques en Grecia. Se logró
una mejora importante en su rendimiento
mediante el empleo de cubiertas humecta-
bles de Tediar.
Un depósito produce aún más agua po
table cuando es poco profundo. Un diseño
con un depósito que, en efecto, se aproxi
ma a la profundidad nula, es el alambique
de mecha que por lo general se construye
de modo que la mecha se incline en direc
ción al sol. Veinte alambiques de este tipo
de 25 pies cuadrados cada uno fueron
proyectados por la Dra. María Telkes y
construidos por la Curtis-Wright Corpora
tion. Estos alambiques funcionaron durante
varios años con buen éxito, salvo que la
duración de las mechas se limitaba a unos
seis meses.
Otro alambique del tipo de mecha fué
construido por los Laboratorios de In
vestigaciones Bjorksten. En este alambique
se utilizó una mecha vertical suspendida
entre una cubierta plástica transparente y
un respaldo opaco. La mecha estaba hume
decida en ambos lados y la condensación
tenia lugar tanto en la cubierta como en
el respaldo. Una de las dificultades de este
diseño consistió en que era susceptible a
dañarse por la acción del viento.
El Instituto Battelle construyó también
varios alambiques pequeños completamente
plásticos y prefabricados, con el objeto de
ejemplificar el concepto de un alambique
de precio muy bajo y producido en la
fábrica que podría instalarse fácilmente y
desecharse cuando dejara de ser útil.
Se construyeron otros alambiques con de
pósito, forrados de vidrio, con el propósito
de estudiar los materiales de construcción
y las variaciones de diseño.
Con el objeto de complementar el pro
grama de pruebas sobre el terreno y de
lograr un mayor entendimiento de la in
fluencia que ejercen el diseño y los factores
ambientales en el rendimiento, se llevaron
a cabo dos actividades auxiliares de apoyo,
a saber: un estudio teórico por medio de
computadores digitales y otros análogos, y
experimentos con un alambique de labora
torio, para el cual se simuló la radiación
solar con calentamiento eléctrico.
£1 alambique de laboratorio se proyectó
en forma tal que pudieran variarse inde
pendientemente las variables importantes
tales como la profundidad del depósito, el
declive de la cubierta, la distancia entre
la cubierta y el agua salada, la temperatura
de aire exterior, la velocidad del viento,
la aislación y el régimen de energía absor
bida. El sistema de calentamiento permitía
el funcionamiento constante con una radia
ción calórica fija o el funcionamiento dis
continuo para simular la variabilidad
característica de la energía solar.
Los resultados de los análisis teóricos y
de los experimentos con el alambique de
laboratorio revelaron que la energía ab
sorbida, la profundidad del depósito y el
empleo de aislación debajo de este último,
eran las únicas variables que ejercían un
efecto notable en el rendimiento del
alambique.
Los estudios económicos revelaron que
el alambique de depósito, cubierto de
vidrio, es actualmente la instalación desti
ladora solar más práctica que se conoce.
En algunas partes del mundo podrían fabri
carse hoy instalaciones destiladoras prácticas
y duraderas para producir hasta 50.000
galones de agua por día a un costo más
bajo que con ningún otro procedimiento de
destilación. Se espera que los futuros ade
lantos en el diseño de alambiques cubiertos
con materiales plásticos de desarrollo re
ciente, contribuyan a mejorar aún más la
economía de la destilación solar.
625
 Solar Distillation in Greece
A. Delyannis and £. Piperoglou
Greece
The scale of the water supply problems
which must be faced in Greece differs ac
cording to the three sizes of communities:
(1) Large cities, like Athens, which expect
to face water shortages of 50 to 100,000
m* (12 to 25 million gallons) per day
in a few years. There is no doubt that
dual-purpose plants will be the only
answer for such cities (ref. 1) .
(2) Medium-sized communities which need
500 to 4,000 m" (125 thousand to 1
million gallons) per day. It is not yet
clear which desalting methods are best
adapted for the various local condi
tions.
(S) Small communities with a daily need
of 20 to 100 m1 (5,000 to 25,000 gal
lons) . Solar distillation of sea water
appears to be the best answer for the
water problems of small communities
on arid islands.
Several hundred islands in the Greek
Archipelago are completely arid and depend
on rain for their natural water supply.
Rain collected from roofs during winter is
stored in cisterns for drinking, cooking, and
household use for the rest of the year.
Every house has an individual cistern, and
many islands have large community reser
voirs.
Water is towed to some islands in plastic
containers, (500 to 1,000 tons capacity) at
a cost of $5 per 1,000 gallons. This is a
commercial operation used only by a few
islands which can afford to pay such a
STILLS ERECTED BY CHURCH WORLD SERVICE
The first program for erecting commercial
solar stills in Greece was sponsored bv
Church World Service and its anonymous
donors.
In October 1964 the first solar still was
dedicated on the Dodecanese Island of
high price for water. When the cisterns
on other islands run empty, the government
sends water tankers; there is no charge
for the water, but the cost to the govern
ment is even higher than S3 per 1,000
gallons.
About 10 years ago, the availability of
free energy made solar distillation one of
the favorite methods of desalination. How
ever, in the following years this interest
decreased because of natural limitations of
this method. Nevertheless, solar distillation
seems to be the only method well suited
for small communities and individual fam
ily stills, from the point of view of invest
ment per gpd and operating cost.
A clear sky for about 300 days per year,
low humidity, and high radiation values
make the Greek islands a favorite place for
conversion of sea water by solar distillation.
In all cases cited in this paper, plant erec
tion costs have been furnished by grants;
thus, the small and poor communities are
not burdened with capital charges and only-
have to provide for the cheap and simple
operation of the solar stills.
Three independent programs in Greece
cover the field of solar distillation. Two of
them focus on .the erection of commercially
operated solar stills. The third focuses on
pure and applied research. Through these
solar distillation programs, Greece is pur
suing the course believed to be best suited
for supplying small communities with fresh
water.
Symi (ref. 2) . Symi, with 3,000 inhabitants,
is one of the many Greek islands which
depend completely on collection and stor
age of rainwater for their water supply-
The Symi still is of the plastic covered
design, with an air-supported cover of
627
 Tedlar-film: it i> very similar to the still
built in Florida a few years ago by Frank
Edlin.
Plastic solar stills have many advantages.
However, the inflated design is not the
design best suited for Symi because of the
need for continuous power to run the
ventilators. In Symi, as on many other small
islands, power is available only during part
of the day.
The specially installed diesel generators
and the attendants needed to operate venti
lators and pumps make the still operation
in Symi very expensive. Thus, plans are
being considered to replace the original
STILLS ERECTED BY THE GREEK GOVERNMENT
The second program for erecting com
mercial solar stills in Greece is more im
portant. Upon the initiative of the Minis
try of Industry, the Greek Government aims
to supply most small islands with solar
stills to make them more or less independ
ent of rain as an exclusive source of water.
The previously described still design de
veloped at the Technical University of
Athens has been adopted for this program.
Four stills now being erected will be com
pleted early next year (1966) on the fol
lowing islands: Rimólos and Nisyros (about
2300 m* or 27,000 sq ft each) , Patmos
(8.000 m" or 86.000 sq ft) , and Symi (200
m" or 2,000 sq ft) .• More solar stills will
be erected on other islands during next
year. Each of these stills will also collect
628
inflated cover with a plastic cover, held in
V-shape by a load lying along the full
length of each bay.
During the past summer, three more
plastic stills were erected by Church World
Service. A small still was erected on the
roof of the restaurant at the Y.M.CA,
camp on the island of Salamis; it covers
an area of 500 m: (5,400 aq ft) . A second
still was erected in the community of
Perdika on the island of Aegina (1300 m*
or 16,000 sq ft) and a larger one on the
island of Santorini (4.000 m* or 43,000
sq ft) . Aqua-Sol, Inc., St. Paul, Minnesota,
is the contractor for all C.W.S. stills (ref. 3) .
rain falling on its surface, thereby increas
ing the average yield per year.
Whereas on Rimólos and at the hotel in
Symi there is nothing special to be reported,
an attempt is being made in Nisyros, a
volcanic island, to use geothermal energy
by feeding the still with water from hot
springs. The Patmos still is the largest in
the world; it is about twice the size of the
frequently cited Las Salinas still in Chile
and of the Church World Service still on
Santorini.
Thus, during 1966 Greece will have at
least eight commercially operated solar
stills, having a total of about 22,000 m* or
235,000 sq ft. The map in Figure 246 shows
locations of the solar stills.
 SOLAR EXPERIMENT STATION ON SYMI
Last year the Technical University of
Athens erected a Solar Experiment Station
on the island of Symi. A grant of the
Wemyss Foundation enabled the station to
expand considerably last summer. A 4-year
program for various applications of solar
energy is being established. Up to now
research has been restricted to solar dis
tillation. The station tests various designs
for solar stills and evaluates construction
materials.
It is too early to make an extensive report
of our work. However, the following is an
outline of the present scope of research.
To meet the needs of the many small
communities in the Greek islands, an at
tempt was made to develop a solar still
which was simple in design and easy to
assemble from prefabricated parts by un
skilled labor. It is a shed-type still, having
a glass cover supported at an angle of 12*
by an aluminum frame.
In the design (Fig. 247) , condensate col
lecting gutters, having a special profile, are
used as the main frame. Precut and drilled
glass supporting structures are riveted on
the main frame at the erection site. The
aluminum frame rests on concrete walls,
which form the basin, and does not come
in contact with sea water. Butyl rubber
sheeting is used for lining the basin. A
black orlon butting, Boating on the surface
of the water, serves as the heat collector.

1 3 I
4
•
2

FIGURE 247. SHALLOW AND DEEP BASIN DEVELOPED AT

THE TECHNICAL UNIVERSITY OF ATHENS.
1. Concrete walls of the basin & Distillate- collecting gutters
2. Leveling with sand or earth 7. Aluminum supporting structure
S. Butyl rubber sheeting 8. Glass covers
4. Orion butting as black body 9. Tubular condenser
5. Shallow basin level 10. Deep basin level
 While the construction described here is
the standard design, improvements in oper
ation are being investigated.
One handicap in the operation of every
solar still is the predetermined ratio of the
evaporating and the condensing surface. It
is expected that an increase of the con
densing surface will result in increased
evaporation and better still performance.
Thus, internal tubular condensers were used
to increase the condensing surface. As
shown in Figure 247, the condenser is
adapted to the steep side of the shed \to
minimize shadow when the still is oriented
from east to west. Extensive experiments
were performed at Symi with two solar
stills having a 13.4 m* (144 sq ft) and
24.3 m1 (261 sq ft) evaporating area respec
tively. The same stills were operated suc
cessively as:
(a) Shallow basin: water depth of about
10 mm (0.4") or 12 mm (0.5")
(b) Deep basin: water depth of about
TABLE СШ. General Relationship of the Various Ways
of Operating the Symi Experimental Still
Total radiation 6,460 kcal/m'/day
2.380 Btu/sq ft/day
A. Shallow basin 10 mm (0.4")
B. Deep basin 50 mm (2")
C. Cooling and shallow basin 10 mm
D. Cooling and deep basin 50 mm
Total radiation 5,620 kcal/m'/day
2,078 Btu/sq ft/day
A. Shallow basin 12 mm (0.5")
B. Deep basin 60 mm (2.4")
C. Cooling and shallow basin 12 mm
D. Cooling and deep basin 60 mm
The figures of this table show the general relation of the various ways of operating the Symi experi
mental stills.
OPERATION AS SHALLOW AND DEEP BASIN STILL
The next step leads to the saving of the
heat accumulated in the cooling water by
using the warm water to feed the still.
Thus, the following method of operation
was adopted.
Early in the morning the basin is allowed,
bv the overflow arrangement, to contain a
shallow layer (about 1 cm) of water. As
soon as the water temperature rises enough
to insure considerable evaporation, cooling
water is circulated through the condensers.
Additional distillate is produced. The cool
ing water shows an increase in tempera
ture (At about 25° to 30°C) and the pre
heated water is fed into the basin of the
still at a temperature of about 50° to 55°C.
The still, which in the morning hours
had a shallow basin, showing a produc
tivity similar to curve A, progressively be
comes a deep basin still. The additional
50 mm (2") or 60 mm (2.4")
(c) Shallow basin with added cooling
by internal condensers.
The results for two mean radiation values
are shown in Table СШ. The curves of Fig
ure 248 correspond to a radiation of 5,620
kcal/m'/day (2,073 Btu/sq ft/day) . Curve
Л shows the distillate production per hour
of still operation as a shallow basin and
Curve В as a deep basin. The difference
in productivity is self explanatory. Curve С
in Figure 248 shows distillate production of
the still with additional cooling by the
internal condensers, compared with the
normal shallow basin operation (Curve A) .
In the present case the warm cooling water-
was not used in order to show the effect
of the cooling operation alone. The figures
show a large increase in production during
daylight hours. During the early morning
and late afternoon, the water temperature
in the basin is equally low, and there are
no great differences, in distillate output.
Distillate output Distillate
kg/m'/day lb/sq ft/day yield
4.64 0.950 100.0 %
4.29 0.878 92.6 %
5.24 1.078 112.9 %
5.76 1.177 123.9 %
Distillate output Distillate
kg/m'/day lb/sq ft/day yield
4.01 0.821 100.0 %
8.66 0.749 91.2 %
4.23 0.866 105.6 %
4.55 0.931 118.6 %
cooling water, fed to the still during the
operation, does not permit the temperature
of the basin to rise to the level expected
in the operation of a simple shallow basin
still.
Therefore, no great increase of distillate
output could be observed before noon.
Early in the afternoon, the still reaches
its maximum depth. As the temperature
of the cooling water in the condensers begins
to decrease, no more water is fed into the
basin, but it seems advantageous to continue
cooling until the evening. During the fol
lowing night, the still is operated as a
normal deep basin still. Curve D in Figure
248 shows the distillate output of the still,
operated alternatively as a shallow and as a
deep basin still.
To attain a higher basin-water tempera
ture, the cooling water was given a second
631
632
preheating before being fed into the still.
Parabolic solar collectors were used for
this purpose. Sufficient experimental data
were not yet available. Nevertheless, higher
productivity is anticipated.
A comparison of the results obtained
under the described operating conditions
showed that distillate output increased con
CONCLUSIONS
In recent years the interest in desalination
has been directed to large and sometimes
to giant plants, in order to lower the cost
of product water. As a result, citizens of
large towns will have the privilege of wast
ing more water and paying less.
Millions of farmers, fishermen, and in
habitants of coastal villages can expect little
help from the processes under development,
which assume large production figures.
Most of these people have no piping for
water distribution or sewage. They do not
waste precious water. Water is a matter of
life for them. These are the people we are
REFERENCES
I, Delyannis, A.: "The development of the
electrical energy demand in Greece and
of the water supply of the Athens
area", Presented at the 5th Meeting of
the I.A.E.A. Desalination Panel, Vienna
(April 1965) .
SUMMARY OF DISCUSSION
In answer to several questions, it was
stated that the area of the stills is about
22,000 square meters and that the rent for
the land is not included in the operations;
however, an idea of what the rent would be
could be indicated by a plot of ground
which supports five houses and is rented
siderably when additional condensing surface
was used. By means of the internal coolers
some of the heat, otherwise lost to the air
through the cover, may be utilized. The
thermal performance of the still improves
accordingly. Storage of the preheated cool
ing water and the deep basin operation at
night leads to further improvement.
concerned about.
Solar distillation might be the right
answer to the water problem of the many
small and isolated communities. We feel
that research on solar distillation has been
somewhat neglected as a method of small-
scale desalination for small-scale needs.
Many improvements can be expected when
research on solar distillation is intensified.
In Greece we will continue to supply
small communities with solar stills and to
attempt to improve designs and methods of
operation.
2. Delyannis, A.: "Solar stills provide an
island's inhabitants with water", Sun
at Work, vol. 10. no. 1 (1965) pp. 6-8.
3. Eckstrom, R. M.: "Design and construc
tion of the Symi still", Sun at Work,
vol. 10, no. 1, (1965) p. 7.
for $5 per month.
It was asked how feed water is delivered
to a solar still. The answer stated that the
still is about six feet above sea level, that
the feed water is delivered by pumping, and
that the town has built a reservoir for the
product.
633
 Distillation Solaire en Grèce
A. Delyannis et £. Piperoglou
Grèce
Plusieurs centaines d'Iles de la mer Egée
sont complètement arides et elles comptent
uniquement sur la pluie pour leur alimen
tation en eau. Pendant l'hiver, la pluie est
recueillie lorsqu'elle coule des toits et
emmagasinée dans des citernes. L'eau est
transportée dans des réservoirs en plastique
à raison de $0,75 environ par m* aux
quelques Iles qui peuvent se permettre de
payer un prix aussi élevé pour leur eau.
Le Gouvernement fournit l'eau gratuite
ment par bateaux-citernes aux autres îles,
mais à un coût encore plus élevé.
Les ties grecques, en raison du niveau
élevé des radiations solaires, constituent un
endroit idéal pour la conversion de l'eau
de mer par distillation solaire. Les frais de
construction des installations sont couverts
par des subventions; ainsi, les frais d'inves
tissement ne constituent pas une charge pour
les petites agglomérations peu prospères
qui n'ont qu'à s'occuper du fonctionnement
des alambics solaires.
Il existe trois programmes indépendants
en Grèce qui couvrent le domaine de la
distillation solaire. Deux se concentrent sur
la construction des alambics solaires ex
ploités commercialement. Le troisième s'oc
cupe de recherche pure et appliquée.
Grâce à ces programmes de distillation
solaire, la Grèce s'est donc engagée sur la
voie qui, à son avis, convient le mieux
pour procurer de l'eau douce aux petites
agglomérations.
Le premier programme prévoyant la con
struction d'alambics solaires commerciaux
est patronné par le Church World Service
et ses donateurs anonymes.
En octobre 1964, le premier alambic
solaire a été inauguré dans l'Ile de Symi
qui dépend entièrement sur la captation et
le stockage de l'eau de pluie. L'alambic de
Symi est du type à couverture de matière
plastique avec revêtement en pellicule
"Tedlar" supportée par l'air; il ressemble
beaucoup à l'alambic construit en Floride
il y a quelques années par Frank Edlin.
Au cours de l'été dernier, trois autres
alambics, tous du type à revêtement en
plastique, ont été construits par le Church
634
World Service. Un petit alambic a été
construit sur le toit du restaurant dans le
camp de 1"Y.M.CA. dans l'île de Salamine.
Un deuxième alambic a été construit à
Perdika dans l'Ile d'Egine et un dernier,
plus important, dans l'île de Santorin. La
surface totale couverte par le programme
du Church World Service est d'environ
8.600 m'.
Le deuxième programme prévoyant la
construction d'alambics solaires en Grèce
est plus important. Sur l'initiative du
Ministère de l'Industrie, le gouvernement
grec a pour objectif de fournir des alambics
solaires à la plupart des petites Iles.
Le type d'alambic mis au point à l'Univer
sité technique d'Athènes a été adopté pour
ce programme. Quatre alambics, actuelle
ment en voie de construction, seront ter
minés à la fin de l'année dans les îles
suivantes: Kimolos. Nisyros, Patmos; un
petit alambic sera également construit sur
le toit d'un hôtel à Symi. D'autres alambics
solaires seront construits dans d'autres Iles
au cours de l'année prochaine. Chacun de
ces alambics captera également toute la
pluie tombant sur sa surface, augmentant
ainsi son rendement annuel moyen.
On essaie à Nisyros d'utiliser l'énergie
géothermique en alimentant l'alambic avec
de l'eau provenant de sources chaudes.
L'alambic de Patmos, avec ses 8.000 m", sera
le plus grand du monde. La superficie
totale couverte par le programme du Minis
tère de l'Industrie est d'environ 13500 m".
L'année dernière, l'Université technique
d'Athènes a installé une station d'expé
riences sur l'énergie solaire dans l'Ile de
Symi. Une subvention de la Fondation
Wemyss permettra d'agrandir considérable
ment la station cet été. Jusqu'à maintenant,
les recherches se sont limitées à la distilla
tion solaire. La station effectue des essais sur
différentes conceptions d'alambics solaires
et évalue le matériaux de construction. Un
alambic du type hangar, ayant un revête
ment de verre supporté à un angle de 12°
par un bâti en aluminium, a été mis au
point. Le distillateur solaire est d'une con
ception simple et d'une construction facile
 à partir d'ensembles préfabriqués montés à
l'aide d'une main-d'oeuvre non spécialisée.
Le bâti principal est constitué par les
gouttières de recueil du condensât. Des
structures en aluminium, coupées et percées
à l'avance, sont rivées au bâti principal au
lieu même de la construction. Le bâti en
aluminim repose sur les murs en béton qui
forment le bassin, mais il n'entre pas en
contact avec l'eau de mer. Des feuilles de
caoutchouc de butyl sont utilisées pour le
revêtement du bassin. Un abuttement en
orlon noir, flottant à la surface de l'eau,
sert de collecteur de chaleur.
Un des obstacles rencontrés dans le
fonctionnement de tout alambic solaire est
le rapport prédéterminé surface d'évapora-
tion/surface de condensation. Un second
obstacle est la perte de la chaleur de con
densation à l'air. De nombreux essais ont
été effectués pour mettre au point des
alambics solaires à étages multiples afin de
conserver la chaleur en utilisant le con
denseur pour le chauffage préalable de
l'eau d'alimentation.
Le bassin profond constitue encore une
autre méthode de stockage de la chaleur.
L'optimisation de la distillation solaire
conduit à un fonctionnement avec un bassin
peu profond pendant la journée et avec un
bassin profond pendant la nuit.
Des essais poussés ont été effectués à Symi
avec un distillateur solaire, qui a fonc
tionné successivement de la façon suivante:
a) bassin peu profund: profondeur de
l'eau, environ 1 cm;
b) bassin profond: profondeur d'eau
d'environ 5 cm;
c) bassin peu profond avec refroidisse
ment supplémentaire par condenseurs
internes.
La prochaine étape conduit à l'économie
de la chaleur accumulée dans l'eau de
refroidissement en utilisant l'eau chaude
pour alimenter l'alambic. Le matin de
bonne heure, le bassin contient une couche
peu profonde d'eau (environ 1 cm) . Dès
que la température de l'eau s'élève suffi
samment pour assurer une evaporation
considérable, l'eau de refroidissement circule
à travers les condenseurs. L'eau de refroidis
sement présente une augmentation de
température (environ 25 à 30°C) et l'eau
ainsi préchauffée est alimentée dans le
bassin à une temperature d'environ 50 à
55°C. L'alambic qui, pendant les heures
de la matinée, possède un bassin peu pro
fond devient progressivement un alambic à
bassin profond.
Au début de l'après-midi, l'alambic atteint
sa profondeur maximale. On n'ajoute plus
d'eau dans le bassin, mais il semble avan
tageux de continuer le refroidissement
jusqu'au soir. Pendant la nuit suivante,
l'alambic fonctionne comme un alambic â
bassin profond normal.
Pour atteindre une température plus
élevée d'eau de bassin, on a donné un
second chauffage préalable à l'eau de re
froidissement avant de la faire passer dans
l'alambic. Des collecteurs solaires parabo
liques ont été utilisés dans ce but. On ne
dispose pas encore de données expérimen
tales suffisantes. Néanmoins, on s'attend à
une productivité plus élevée.
CONCLUSIONS
En comparant les résultats obtenus, on
peut en conclure que la production de
distillât augmente considérablement en uti
lisant une surface de condensation supplé
mentaire et que l'on peut utiliser une
certaine partie de la chaleur autrement
perdue à l'air à travers la couverture. Le
rendement thermique s'améliore de façon
correspondante. Le stockage de l'eau de
refroidissement préalablement chauffée et le
fonctionnement en bassin profond pendant
la nuit constitue une nouvelle amélioration.
Afin d'abaisser le prix de revient de l'eau
produite au cours des dernières années l'in
térêt sur le dessalement s'est porté sur de
grandes installations, parfois géantes. Il
s'ensuivra que les habitants des grandes
villes auront le privilège de gaspiller plus
d'eau et de payer moins.
Des millions de fermiers, de pêcheurs et
d'habitants des villages côtiers n'ont pas de
canalisations pour la distribution de l'eau,
ni d'égouts. Ils ne gaspillent pas l'eau
précieuse. L'eau est pour eux une question
vitale. C'est d'eux que nous nous occupons.
Il se peut que la distillation solaire soit
la bonne solution pour venir à bout du
problème de l'eau dans les petites agglomé
rations, ainsi que dans les agglomérations
isolées. Nous estimons que les recherches
sur la distillation solaire ont été négligées
en tant que méthode de dessalement à
petite échelle dans les cas où les besoins
sont moindres. On peut s'attendre â de
nombreuses améliorations lors de l'intensifi
cation des recherches sur la distillation
solaire.
En Grèce, nous continuerons à équiper
les petites agglomérations avec des alambics
solaires et à essayer d'en améliorer la con
struction et les méthodes de fonctionnement.
635
 Дистилляция в Греции с Помощью
Солнечной Энергии
А. Делыганис и Е. Пипероглу
Греция
Несколько сот островов Греческого
архипелага совершенно безводны и в
смысле естественного водоснабжения
исключительно зависят от дождя. Зи
мой дождевая влага собирается с крыш
и сберегается в цистернах. К несколь
ким островам, которые в состоянии
платить такую высокую цену за воду,
как 3 доллара за 1.000 галлонов, она
доставляется на буксирах в сосудах из
пластмассы. К другим островам прави
тельство бесплатно подвозит воду в на
ливных судах, но она обходится еще
дороже.
Благодаря сильному солнечному из
лучению греческие острова находятся
в благоприятном положении в смысле
опреснения морской воды посредством
солнечной энергии. Стоимость построй
ки установок покрывалась субсидиями;
поэтому небольшие и бедные общины
не обременены капитальными затрата
ми и должны только заботиться об
эксплуатации выпарных, работающих с
помощью солнечного излучения, агре
гатов.
В Греции к области этой дистилля
ции относятся три независимые про
граммы. Две из них сосредотачивают
свое внимание на постройке, функци
онирующих на коммерческих началах
солнечных дистилляционных установ
ках. Третья занимается теоретической
и прикладной исследовательской рабо
той. Считают, что с помощью этих про
грамм Греция придерживается наибо
лее правильного курса в вопросе снаб
жения небольших общин пресной во
дой.
Первая программа, относящаяся к
постройке в Греции солнечных выпар
ных агрегатов коммерческого назначе
ния, субсидируется Мировым советом
церквей и его анонимными жертвова
телями.
В октябре 1964 г. была торжественно
открыта первая солнечная выпарная
установка на острове Сими, который
636
целиком зависел от сбора и хранения
дождевой воды. В конструкции уста
новки Сими применена пластмасса с
покрытием поддерживаемым воздухом
из пленки Тедлар; она очень похожа
на установку, построенную несколько
лет тому-назад Франком Эдлин во
Флориде.
Этим летом Мировым советом церк
вей были построены еще три установ
ки, все сделанные из пластмассы. Ма
ленький выпарной аппарат был смон
тирован на крыше ресторана в лагере
Христианской ассоциации молодых лю
дей на острове Саламис. Второй вы
парной аппарат был построен в общине
Пердика на острове Эгине и большая
установка была сооружена на острове
Санторини. Полная площадь построй
ки, входящая в программу Мирового
союза церквей, достигает примерно
8.600 кв. метров или 92.600 кв. фут.
Вторая программа постройки в Гре
ции солнечных дистилляционных уста
новок является более важной. Грече
ское Правительство по инициативе Ми
нистерства Промышленности намерева
ется снабдить солнечными выпарными
агрегатами большинство маленьких
островов.
Для этой программы была одобрена
конструкция выпарной установки, раз
работанная Афинским техническим уни
верситетом. Четыре теперь строющих-
ся агрегата будут закончены в конце
года на следующих островах: Кимо-
лос, Нисирос, Патмос, и небольшой
выпарной аппарат будет построен на
крыше гостиницы в Сими. В течение
будущего года будут смонтированы ди-
стилляционные установки и на других
островах. Все эти агрегаты будут так
же собирать дождевую влагу, попадаю
щую на их поверхность тем самым уве
личивая их среднюю годовую произ
водительность.
В Нисирос производится попытка
использовать геотермическую энергию,
 питая выпарочный агрегат водой из В Сими были произведены простран
горячих источников. Патмосская сол ные опыты с солнечным выпарным ап
нечная дистилляционная установка с паратом, который успешно работал,
площадью 8.000 кв. метров (86.000 кв. имея:
фут) является самой большой в мире. а. мелкий бассейн: глубина воды около
Вся площадь, входящая в программу 1 см (0,4 дюйма),
Министерства Промышленности, со б. глубокий бассейн: глубина воды
ставляет примерно 13.200 кв. метров около 5 см (2 дюйма),
или 142.000 кв. фут. в. мелкий бассейн с дополнительным
В прошлом году Афинский техниче охлаждением с помощью внутренних
ский университет смонтировал на остро конденсаторов.
ве Сими Солнечную экспериментальную Второй шаг для сбережения накопив
станцию. Субсидия со стороны фонда шегося в охлаждающей воде тепла ве
им. Вемисс даст возможность ее зна дет к использованию теплой воды для
чительно расширить этим летом. Пока- питания дистилляционной установки.
что исследовательская работа была Рано утром бассейн содержит тонкий
ограничена дистилляцией, производи (около 1 см) слой воды. Лишь только
мой с помощью солнечной энергии. температура воды достаточно поды
Станция испытывает различные кон мется, чтобы обезпечить сильное испа
струкции солнечных выпарных устано рение, через конденсаторы начинает
вок и производит техническую оценку пропускаться циркулирующая охлаж
строительных материалов. Был разра дающая вода. Температура охлаждаю
ботан агрегат навесного типа со стек щей воды повышается (примерно на
лянным, под углом 12° покрытием, под 25°-30°С) и подогретая вода при тем
держиваемым алюминиевой рамой. Он пературе около 50°-55°С поступает в
конструктивно прост и, состоя из ча виде питания в бассейн дистилляцион
стей заводского изготовления, удобен ной установки. Постепенно она обра
для сборки неквалифицированными ра щается в установку с глубоким бас
бочими. сейном, в то время как утром ее бас
Собирающие конденсат желоба ис сейн был мелким.
пользуются, как главные рамы. Пред Вскоре после полудня глубина воды
варительно нарезанные и просверлен достигает максимума. После этого пи
ные алюминиевые компоненты склепы тание бассейна прекращается, но явля
ваются с главной рамой на месте мон ется выгодным продолжать процесс
тажа. Алюминиевая рама лежит на бе охлаждения до самого вечера. Затем в
тонных стенках, которые образуют бас течение ночи агрегат работает, как
сейн, и не приходит в соприкосновение нормальная дистилляционная установка
с морской водой. Для облицовки бас с глубоким бассейном.
сейна применяется обшивка из бутило Для большего повышения темпера
вой резины. Черное покрывало из ор- туры воды бассейна, охлаждающая во
лона, держащееся на поверхности во да до впуска ее туда в виде питания,
ды, служит в качестве собирателя теп была второй раз подогрета. С этой
ла. целью были использованы параболиче
Одной из помех в работе каждого ские коллекторы солнечного излучения.
солнечного выпарного аппарата явля Пока еще нет достаточных эксперимен
ется заранее определенное соотношение тальных данных.
между испарительной и конденсирую
щей поверхностью. Второй помехой ЗАКЛЮЧЕНИЕ
служит потеря конденсационного тепла Сравнивая полученные результаты,
в окружающую атмосферу. Было сде можно сказать, что продукция дистил
лано много попыток разрабоки много лята значительно увеличивается при
ступенчатых солнечных дистилляцион- увеличении площади конденсации и
ных установок для сохранения тепла, использовании части тепла, которое
пользуясь конденсатором для подогре иначе было бы потеряно через покры
ва исходной воды. тие в окружающую атмосферу. Терми
Другим методом аккумулирования ческая производительность выпарного
тепла является устройство выпарного агрегата соответственно улучшается.
агрегата с глубоким бассейном. Опти Дальнейшее улучшение достигается ак
мизация солнечной дистилляции ведет кумулированием подогретой охлаждаю
к работе с мелким бассейном в течение щей воды и применением ночью глу
дня и глубоким бассейном в течение бокого бассейна.
ночи. В течение последних лет интерес в

637
 области опреснения был направлен в
сторону крупных, а иногда и громад
ных, установок для того, чтобы снизить
стоимость выработанной воды. Поэто
му жители крупных городов будут
иметь привилегию расходовать зря
больше воды и меньше за нее платить.
Миллионы фермеров, рыбаков и оби
тателей прибрежных деревень не име
ют трубопроводов для распределения
воды и канализации. Они не тратят зря
драгоценную воду. Вода для них явля
ется вопросом жизни. Вот те люди, о
которых мы заботимся.
Дистилляция с помощью солнечной
энергии может быть правильным отве
том на водяные проблемы многих ма
Distilacion Solar en Grecia
A. Delyannis v E. Piperoglou
Greda
Varios cientos de islas del archipiélago
griego son completamente áridas y de
penden exclusivamente de la lluvia para
su abastecimiento de agua potable. La
lluvia se recoge de los techos durante el
invierno y se conserva en cisternas. El agua
se transporta en recipientes de plástico, a
un costo de aproximadamente $3 por
millar de galones, a unas pocas islas que
pueden pagar este alto precio. El Gobierno
suministra agua con tanques a otras islas,
sin cobrar por ella, pero a un costo
también alto.
Altos valores de radiación hacen de las
islas griegas un excelente lugar para tratar
agua de mar mediante la destilación solar.
Los costos de construcción de plantas han
sido cubiertos mediante donaciones, de tal
manera que las comunidades pobres y pe
queñas no tienen que afrontar los costos
de inversión y solamente tienen que cubrir
los gastos de operación de los destiladores
solares.
Tres programas independientes se apli
can, en Grecia, al campo de la destilación
solar. Dos de ellos enfocan la construcción
de unidades de destilación solar operadas
coraercialmente. El tercero enfoca la investi
gación científica y aplicada. Mediante estos
programas de destilación solar, Grecia está
siguiendo el curso que se considera más
conveniente para suministrar agua potable
638
леньких и изолированных общин. Нам
кажется, что на исследование этой ди
стилляции, как метода опреснения ма
лого масштаба при потребностях мало
го масштаба, не обращалось должного
внимания. Если посвященные ей иссле
дования будут проводиться более ин
тенсивно, то можно будет ждать мно
гих усовершенствований.
В Греции мы будем продолжать снаб
жение маленьких общин выпарными
агрегатами, работающими с помощью
солнечного излучения, и будем про
должать наши старания, направленные
к улучшению конструкций и методов
технической эксплуатации.
a pequeñas comunidades.
El primer programa para construir uni
dades comerciales de destilación solar en
Grecia es auspiciado por el Church World
Service y sus donantes anónimos.
En Octubre de 1964, el primer destilador
solar fue inaugurado en la isla de Symi
que dependía completamente de la colec
ción y almacenamiento de aguas de lluvia.
El destilador Symi es del diseño de cubierta
de plástico con una cubierta, sostenida por
aire, de una película de Tediar; es muy
similar al destilador construido por Frank
Edlin en Florida hace unos pocos años.
Durante el verano pasado, tres destila
dores más, de plástico, fueron construidos
por el Church World Service. Un pequeño
destilador fue construido en el techo del
restaurante del campamento de la Asocia
ción Cristiana de Jóvenes, en la isla de
Salamis. Un segundo destilador fue con
struido en la comunidad de Perdika, en la
isla de Aegina, y uno de gran tamaño en
la isla de Santorini. El área total cubierta
por el programa del Church World Service
es de aproximadamente 8.600 ma ó 92.600
pies*.
El segundo programa para construir de
stiladores solares comerciales en Grecia es
el más importante. Por iniciativa del Mini
sterio de Industria, el gobierno griego
proyecta proporcionar destiladores solares
 a la mayoría de las islas pequeñas.
Para este programa ha sido adoptado el
diseño de destiladores desarrollado en la
Universidad Técnica de Atenas. Cuatro de
stiladores actualmente en construcción serán
completados a fin de año en las siguientes
islas: Kimolos, Nisyros, Patmos, y un pe
queño destilador sobre el techo de un hotel
en Symi. Más destiladores solares serán
construidos en otras islas durante el año
próximo. Cada uno de estos destiladores
también recogerá toda la lluvia que caiga
sobre su superficie, por lo que se aumen
tará la producción anual.
En Nisyros se hace un intento para usar
energía geotérmica mediante la alimenta
ción de los destiladores con aguas prove
nientes de fuentes termales. El destilador
de Patmos con sus 8.000 m" (86.000 pies*)
es el más grande del mundo. El programa
del Ministerio de Industria cubre un área
total de aproximadamente 1S.200 m" ó
142.000 pies'.
El año pasado, la Universidad Técnica
de Atenas construyó una Estación Experi
mental Solar en la isla de Symi. Una dona
ción de la Fundación Wemyss permitirá
que la estación se expanda considerable
mente este verano. Hasta el presente la in
vestigación se ha limitado a la destilación
solar. La estación prueba varios diseños de
destiladores solares y evalúa los materiales
de construcción. Se desarrolló un destilador
de tipo cobertizo, teniendo una cubierta de
vidrio sostenida a un ángulo de 12" me
diante un marco de aluminio. El destilador
solar es de diseño simple y fácil de ensam
blar, a partir de partes prefabricadas, por
obreros no adiestrados.
Las cañerías de colección del condensado
son usadas como parte fundamental de la
estructura. Estructuras de aluminio precor-
tadas y agujereadas son remachadas sobre
la parte fundamental de la estructura en
el sitio de instalación. El armazón de alu
minio descansa sobre paredes de concreto
que forman el estanque y no entra en con
tacto con el agua de mar. Para recubrir
el estanque se usan planchas de caucho
sintético (butilo) . Una base de orlón negro,
flotando sobre la superficie del agua, sirve
como un colector de calor.
Una limitación en la operación de todo
destilador solar es la relación predetermi
nada de la superficie de evaporación y con
densación. Una segunda limitación es la
pérdida del calor de condensación en el
aire. Se han hecho muchos intentos para
desarrollar evaporadores solares de etapas
múltiples con el fin de conservar el calor,
usando el condensador para precalentar el
agua de alimentación.
El evaporador de base profunda, es otro
método para conservar el calor. La optimi
zación de la destilación solar conduce a una
operación con base de poca profundidad
durante el dia y a una operación de base
profunda durante la noche.
En Symi se ha desarrollado una experi
mentación amplia con un destilador solar
que ha sido usado sucesivamente como:
a. base poco profunda: profundidad del
agua aprox. 1 cm (0,4") ,
b. base profunda: profundidad del agua
aprox. 5 cm (2") ,
c. base profunda con enfriamiento agre
gado, por condensadores internos.
El paso siguiente conduce a la utilización
del calor acumulado en el agua de enfria
miento mediante el uso del agua calentada
para alimentar el destilador. Temprano en
la mañana, la base contiene una capa poco
profunda (aprox. 1 cm.) de agua. Tan
pronto como la temperatura del agua se
eleva suficientemente para asegurar una
condensación considerable, se hace circular
agua de enfriamiento a través de los con
densadores. El agua de enfriamiento mues
tra un incremento en temperatura (a
cerca de 25 a S0°C) y el agua precalentada
se utiliza como alimentación de la base
del destilador a una temperatura de
aproximadamente 50 a 55°C. El evaporador,
que en las horas de la mañana tiene una
base poco profunda progresivamente se
convierte en un evaporador de base pro
funda.
Temprano en la tarde, el evaporador
alcanza su profundidad máxima. No se
alimenta con más agua, pero parece venta
joso seguir enfriando hasta el atardecer.
Durante la noche siguiente, el evaporador
es operado como un evaporador de base
de profundidad normal.
Para alcanzar una temperatura más alta
del agua de la base, el agua de enfria
miento- sufre un segundo precalentamiento
antes de ser introducida en el destilador.
Colectores solares parabólicos fueron usados
con tal fin. Aún no se dispone de suficientes
datos experimentales. Sin embargo se anti
cipa una productividad más alta.
CONCLUSIONES
Comparando los resultados obtenidos,
puede resumirse que la producción de desti
lado incrementa considerablemente cuando
se usa superficie de condensación adicional
y que puede utilizarse algo del calor que
de otra manera se pierde en el aire a través
de la cubierta. La eficiencia térmica del
evaporador se mejora consecuentemente. La
conservación del agua de enfriamiento pre
calentada y de la operación nocturna como
639
 de base profunda conduce a mejores
mayores.
En años recientes, el interés en la desa
lineación se ha orientado hacia grandes,
y casi gigantes, plantas a los efectos de
reducir el costo del agua producto. Como
resultado, pobladores de grandes ciudades
disfrutarán el privilegio de desperdiciar
más agua y pagar menos.
Millones de agricultores, pescadores y
habitantes de las villas costeras no cuentan
con cañerías para distribución de agua po
table ni colección de aguas servidas. Ellos
no desperdician agua que les resulta co
stosa. El agua es un asunto vital para ellos.
Esta es la clase de gente que a nosotros
640
nos preocupa.
La destilación solar puede ser la solución
correcta para el problema del agua de
muchas comunidades pequeñas y aisladas.
Consideramos que la investigación de la
destilación solar ha sido descuidada como
método de desalinización en pequeña escala
para necesidades pequeñas. Pueden espe
rarse muchas mejoras cuando la investiga
ción de la destilación solar se intensifique.
En Grecia continuaremos suministrando
a las comunidades pequeñas destiladores
solares y continuaremos nuestros esfuerzos
para mejorar diseños y métodos de opera
ción.
 The Freezing Processes for Water
Conversion in the United States
Allen J. Barduhn
United States of America
The systematic study of freezing processes
for converting sea water to fresh water has
been underway in the United States for over
15 years. The beginning was modest, but
today at least five companies have built
pilot plants to produce about 15,000 gpd
(U.S.) fresh water and one plant designed for
200,000 gpd has been constructed. A con
siderable amount of more basic research on
the thermodynamics and kinetics of ice for
mation has also been pursued at several
universities in this country. The processes
are still in their infancy and no great body
HISTORY
One of the earliest investigators of freez
ing of sea water in this country was the
late Dr. T. G. Thompson of the Depart
ment of Oceanography at the University of
Washington (refs. 29, 50) . His work was
begun in 1947 and was followed by Hen
drickson and Moulton (ref. 11) at the same
institution, who made a study of conven
tional ice making machines for producing
fresh water from saline feeds. They quickly
saw that brine-ice separation was important
but difficult; they studied centrifuging,
gravity drainage, filtration, and compression
(squeezing) as a means of making the
separation. They also looked briefly at
washing, but none of the methods were
entirely satisfactory, although compression
appeared the most promising. They made
economic calculations on various processes,
including direct contact refrigeration and
vacuum flashing, but concluded on a pessi
mistic note as to the cost of fresh water
produced by freezing. Their contributions
were important, however, since they dis
posed of the possibility of using indirect
heat transfer for freezing and pointed out the
of design and operating experience is yet
available, such as is the case with the dis
tillation processes; still the economics of
desalting by freezing appear quite favor
able, especially in the smaller plant sizes
ranging from 50,000 gpd to 5 mgd. These
encouraging economics have kept several
industrial firms actively interested, and
the Office of Saline Water of the U. S.
Department of the Interior has financed a
considerable portion of the research and
development to date.
importance of the ice-brine separation step.
Rose and Hoover (ref. 22) studied the
formation of small ice crystals by freezing
salt water in beaker sized equipment, and
learned much about crystal sizes and shapes
produced; they found that 3.5 per cent
NaCl solutions gave results very similar to
those using sea water. This has allowed
synthetic feeds to be used in many pilot
plants where sea water is not available.
They studied the problem of separating ice
and brine on a small scale.
In the middle 1950's, Carrier Corporation
first worked on freezing and later reported
results from a pilot plant in which a
freezer and washer were operated continu
ously and simultaneously (refs. 3, 4) . The
freezer was of the vacuum flash type, the
washer a moving bed countercurrent design,
and ihe capacity was 300 gpd of fresh
water, although no melter was used. Melt
ing was studied separately. The water vapor
was absorbed rather than compressed. The
results were used to design a 15,000 gpd
plant using LiBr absorption of the water
vapor. This plant was built in 1959 and
641
operated successfully. The economic analy
ses from the data of the 300 gpd plant made
freezing appear attractive again. The im
porta nee of the Carrier work was that the
continuous washing of ice was developed
to a point at which it was efficient and eco
nomical; flash freezers were studied exten
sively through many design variations, and
the design for a complete pilot plant based
on extensive engineering data and experi
ence was first reported (ref. 5) .
At about the same time other groups in
this country, including those at Cornell
under Wiegandt, at Blaw-Knox under Kar-
nofsky, and at Struthers-Wells under Svanoe,
were working on freezing. Fairbanks-Morse
(now part of Colt Industries) and Rocket-
dyne Division of North American Aviation
became interested in freezing in the late
1950s, but no published accounts of their
work are available.
Wiegandt (refs. 32, 33) and Blaw-Knox
(ref. 15) were both interested in the use
of direct contact secondary refrigerants.
Wiegandt studied freezing, washing, and
melting extensively and made valuable con
tributions, especially in his concept of a
full scale plant in which freezing, washing,
and melting were all conducted in a single
vessel. Blaw-Knox adapted their Rotocel
extractor for use as freezer and washer and
combined their efforts with those of Wie
gandt to design and build a pilot plant
NATURE OF FREEZING PROCESSES
Due to the combined efforts of these
many people, we now have a much better
picture of the freezing processes than we
had even 5 years ago: where they are most
competitive, what their economics are, how
to design their components, etc. Even so,
the experience has been entirely with pilot
plants and no one has yet designed a small
plant in which the best features have been
used in all components. This is probably
so because each company has concentrated
its efforts on some features and neglected
others. Also there is the feeling that al
though "a freezer" or "a melter", etc. can
be designed and will be workable, there is
probably much improvement still possible
in the near future and that small changes
or radically new designs may cut costs
appreciably. In spite of this situation we
can make many useful general statements
about freezing.
First let us look at the processes with a
broad view. All the freezing processes make
ice as small crystals, separate them from
the adhering brine, and melt them to pro
near St. Petersburg, Florida, in which sev
eral of these design concepts were tested.
Struthers' initial work concentrated main
ly on the freezing step. They studied the
formation of large ice crystals in the bu
tane freezing process (ref. 27) ; this has
been their most valuable contribution
since they have produced larger and better
shaped ice crystals than any so far reported.
The larger crystals simplify the ice-brine
separation step. They subsequently com
bined their knowledge with that of Rocket-
dyne and of Dr. Umano of Japan and have
built two pilot plants at Wrightsville Beach.
North Carolina.
Fairbanks-Morse (Colt) joined efforts
with the Israeli Government (Zarchin proc
ess) to study and build a vacuum flash
evaporation pilot plant at Eilat, Israel, con
sisting of 4 modules and having a total
capacity of about 250,000' gpd. They have
contributed most significantly in the area
of low pressure (3 to 5 mm Hg) compressor
design and of compact inexpensive heat
exchangers. They are now constructing a
75,000 gpd pilot plant at Wrightsville
Beach, North Carolina.
Some of the above companies have made
contributions to this Symposium and these
can he consulted for a detailed statement
of their more recent work. Curran (ref. 7)
has calculated the energy consumption for
several idealized freezing schemes.
duce fresh water.
(a) Flash freezing consists of removing
heat by evaporating water under vacuum
and simultaneously producing ice. The
water vapor may be compressed (Colt)
or absorbed (Carrier) .
(b) Instead of using the water vapor as
the refrigerant, an insoluble secondary
refrigerant may be introduced and evap
orated in direct contact with the sea water.
This may be butane which is cheap but
inflammable (Blaw-Knox and Struthers) ,
or octafluorocyclobutane which is expen
sive but nonflammable and has a better
vapor pressure than butane (Carrier) .
The following characteristics are pre
sented to help place freezing processes in
perspective with respect to other processes
such as distillation and electrodialysis. All
the characteristics are not advantageous it)
every situation and many factors must be
considered when choosing a process for
making fresh water. These include the na
ture of the saline feed, the production rate
required, the method and cost of disposing
of the brine, the availability and cost of
power and heat, etc.
Freezing processes have the following
characteristics:
(1) They operate at low temperatures
thus minimizing scale and corrosion prob
lems. Low temperature plants may be ex
pected to last longer than those operating
at high temperatures.
(2) In the freezing and melting steps,
heat transfer is accomplished without inter
vening metal surfaces, and in product-feed
heat exchange, where such surface is not
critical, the transfer of heat may be accom
plished in any of several ways. The great
advantages of transferring the latent heat of
phase change by direct contact between
phases are that scale formation is unimpor
tant and that temperature differences re
quired for heat transfer are small. In
distillation scaling and corrosion limit oper
ating temperatures and thus thermodynamic
efficiency. In electrodialysis the presence of
materials which precipitate requires feed
pretreatment and periodic membrane clean
ing. Many natural brackish waters are nearly
saturated with salt and thus present treat
ment and scale problems for all but the
freezing process.
(3) For brackish waters containing more
than about 8,000 ppm dissolved solids, freez
ing appears very attractive for small- and
medium-sized plants up to about 5 mgd.
Electrodialysis is not considered economical
for feeds above this concentration and dis
tillation costs are not much lower than those
of sea water operation. The latter fact is
due partly to the low boiling point rise
compared to the freezing point lowering for
aqueous solutions, and partly to the smaller
overall temperature differences needed to
transfer heat in direct contact freezing. De
creasing feed concentration from that of
sea water to some lower concentration thus
reduces the temperature lift required in
heat pumping by a significant amount for
freezing and a smaller amount for vapor
compression distillation. On sea water, freez
ing appears at least as inexpensive as dis
PLANT CAPACITY LIMITATIONS
In the vacuum flash process, it is the
nature of the compressors that, when lim
ited to 60-cycle speeds of 3,500 rpm, 1,750
rpm, etc., they fix the capacity of the
entire plant within rather close limits. Thus
a 3500 rpm compressor must have a rotor
about 6 ft in diameter which will serve
a plant producing about 60,000 to 75,000
gpd of product. A 1,750 rpm unit will have
tillation in the proper size ranges, and it
thus would be considerably cheaper on
brackish waters. Freezing may compete with
electrodialysis on brackish water even at
feed salinities well below 8,000 ppm, espe
cially if scaling problems are severe or penal
ties are associated with large volumes of
reject brine.
(4) Freezing processes can be designed
for practically any feed from dilute brackish
water to sea water.
(5) Freezing processes operating on brack
ish waters can economically convert a larger
fraction to product than can electrolysis. On
a 1500 ppm feed the Webstre, South Dakota
demonstration plant converts 51 per cent to
fresh water while a freezing process operat
ing at its optimum conversion for this feed
would probably convert about 90 per cent.
Using these figures and comparing two
plants each making the same amount of
fresh water, one finds the electrodialysis
unit producing over 8 times the volume of
brine. Brine disposal is a serious problem
for inland communities unless it can be
discharged to surface waterways and this
may not be permissable in the future.
(6) Freezing is the only developed proc
ess which man use electrical power to desalt
sea water. This allows plants to be built
where cheap steam is not available in quan
tity. Electrical power may be transported
hundreds of miles, but steam must be used
near its source. When economics are favor
able, the use of other forms of mechanical
energy are quite suitable, e.g., gas or diesel
engine drives.
(7) Due to the nature of the equipment
used in freezing, the process appears (at this
stage of its development) to be most com
petitive in the size range 50,000 to 5 mgd.
Flash freezing covers the lower end of this
range and secondary refrigerant freezing,
the upper. Freezing may never compete with
distillation of sea water in the 100 mgd
range. This size limitation statement may
not be agreed to by some companies, and
it may be proved incorrect in the future,
but today it appears valid.
a diameter of about 12 ft; such a design
is untested. If such a machine can be made
to work well, it will serve a plant produc
ing roughly 300,000 gpd. Flash plants de
signed to produce water at rates other
than these must use more than one primar)'
compressor and scale-up beyond 5 mgd
appears difficult. Some economies may be
made by having one freezer or washer, etc..
643
 served by several compressors. Also when
more than one compressor is required, the
economies of staged freezing are attractive.
When adsorption of the water vapor is
used rather than compression, the size
limit for a single freezer -absorber appears
to be on the order 165,000 gpd product,
and multiple units are again required for
larger plant capacities.
In the secondary refrigerant processes the
primary compressors limit plant capacities,
but the requirements are not so stringent
as in water vapor compression. Nearly any
plant capacity up to about one-half mgd
ECONOMICS OF FREEZING
The cost of fresh water from freezing
process is not yet well established since
the basic data are from plants of small size.
These are the pilot plants of Carrier and
Struthers at Wrightsville Beach. North Car
olina, of Blaw-Knox at St. Petersburg, Flor
ida, and of Colt in Beloit, Wisconsin, and
Eilat, Israel. Struthers' 200,000 gpd plant
has not yet operated well, and the 240,000
gpd Colt-Israeli plant is essentially four
60,000 gpd units which can be run singly.
Cost estimates from the various companies
do not vary widely and they are shown on
Figure 249 without reference to the sources
since the data are unpublished. The band
of costs is somewhat irregular since each
company made independent estimates and
considered plants of different sizes. They
include both flash freezing with vapor com
pression and secondary refrigerant freezing
plants. These costs should probably not be
extrapolated to capacities beyond 5 mgd
since the designs are more tentative in the
larger sizes.
Some older cost data from Struthers are
available, but they have not been shown
because they are somewhat out of date
(ref. 25) .
For comparison, Figure 249 also shows
cost estimates for water from the multistage
flash evaporation process (MSF) , the long
tube vertical multieffect distillation process
(LTV) , and the electrodialysis (ED) proc
ess. The freezing and distillation costs are
based on sea water feed and the electro-
dialysis costs are based on a 1,500 ppm
brackish water feed. The comparison
costs are taken from the Bechtel Corpora
tion (ref. 2) , and are based on successful
operating and design experience in demon
stration plants of 0.25 to 1.2 mgd sizes.
Bechtel has an experienced engineering
staff and has no commercial interest in any
of these processes. The cost figures on freez-
644
can be designed with a single primary com
pressor; the use of multiple compressors is
necessary for larger plants. Axial -flow com
pressors have to be multistaged for either
the vacuum flash or butane process. Freez
ing, washing, and melting vessels cannot be
increased in size indefinitely, and modules
are again necessary when designing in the
few million gpd range.
Multiplying modules of a basic plant
design does not lead to reduced water costs
as fast as does increasing the size of impor
tant components.
ing may be less reliable than those on the
other processes. All estimates have been
made using the Office of Saline Water cost
procedure, with minor modifications in
some cases.
Gilliland, in this symposium, gives actual
cost data on water from the 650.000 gpd
electrodialysis plant at Buckeye, Arizona.
Over a 3-year period, the operating and
maintenance costs have been |0.42/1,000
gals and the principle and interest charges
appear to add $058 to this figure making
the total water cost $0.70/1,000 gals. The
feed is a brackish water containing about
2300 ppm salts.
All the above cost data are for single-
purpose plants, i.e., those designed to pro
duce water only. Dual-purpose plants to
produce both power and fresh water by
distillation have been designed and the
estimated water costs are shown for large
plants using fossil fuel (ref. 6) .
More recent data on water costs from
MSF plants operating at elevated tempera
tures (250°F instead of 200°F) and on LTV
plants (270°F instead of 235°F) show that
reductions of about 23 cents per 1,000 gal
may be achieved in both cases for plants
of 1 to 2 mgd capacity (ref. 12) .
Unpublished cost estimates on freezing
with a 5,000 ppm brackish water feed have
recently been made by interested companies,
and they show the water cost to be 17 to
20 cents per gallon less than the costs
with sea water feed.
While all the freezing cost estimates
have some elements of speculation in them,
they are based on the l>est knowledge of anv
one company to date. The costs may be
optimistic for the plants as designed,
but no estimate incorporated the best
known designs for all unit operations, and
this tends to counteract the natural tend
ency for an engineer to estimate liberally
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the cost of water from his own process.
Every design had elements which could be
improved upon with no further research.
From Figure 249 it can be seen that water
costs depend strongly on plant capacity.
It is not meaningful, for example, to com
pare the cost of water from a freezing plant
with that from a distillation plant unless
the two plants have the same capacity.
A cost of $1.35/1,000 gallons for water from
a freezing plant producing 150,000 gpd
of product may appear high when pne hears
of estimates of $0.75 or $0.50/1,000 gallons
for water by a distillation process, but the
latter estimates are only for much larger
plants. Distillation costs in a 150,000 gpd
plant may be considerably greater than
THE REFRIGERANT FOR DIRECT CONTACT
The refrigerant is chosen to give oper
ating pressures near and preferably slightly
above atmospheric, to be insoluble in water,
and not to form a hydrate. Ideally, it should
also be nontoxic, nonflammable, inexpen
sive, and highly stable. Normal butane has
most of these attributes and is commonly
used. It is, of course, flammable and re
quires operating pressures slightly below
atmospheric. Octafluorocvclobutane (C-318)
is being seriously considered by Carrier
since it has all the required attributes
except that it is expensive ($2.00/lb) . Its
nonflammability. complete absence of tox
icity (it can be used as an aerosol agent
with foods) , and vapor pressure which
allow operation at slightly above atmo
FREEZER DESIGNS
The means by which ice is formed in
a freezer are critical since the subsequent
operations of ice-brine separation and melt
ing are affected strongly by the size and
shape of the particles formed. A freezer
must perform the functions of (1) allowing
the proper amount of new nuclei to form,
(2) providing adequate residence time to
grow crystals of reasonable size, (3) pro
viding space for separation of vapor with
out entrainment of liquid spray, (4)
preventing ice clusters from building up
and causing irregular slurry flow, and
(5) creating adequate interfacial area and
agitation for good heat and mass transfer
to occur.
Generally, these problems have been
solved in rather different fashions by those
using vacuum flash and those using a sec
ondary refrigerant. Vacuum flash freezers
$1.35/1,000 gallons.
A recent published cost estimate of water
from a vacuum absorption freezing plant
has been made by Carrier (ref. 9) but is
not included in Figure 249. The predicted
water cost from a 165,000 gpd plant was
$1.93/1,000 gallons, and possible process im
provements were predicted to bring this
down to $1.74/1,000 gallons. These high
costs are partly due to the fact that absorp
tion freezing requires both electrical energy
(46 kwh/1,000 gab) and steam (557 lbs/
1 ,000 gals) . This is also a disadvantage in
that plant locations are limited to those
areas where both power and steam are
available at reasonable costs.
spheric pressure, make it look desirable.
Isobutane ' has a better vapor pressure
than n-butane, but it forms a hydrate at
+ 2.1 °C. A mixture of iso + normal
butane is now used by Struthers. although
there is an energy penalty associated with
mixed refrigerants since the temperature
lift for the abstracted heat is increased by
a small amount. The increase is the differ
ence between the dew point of the vapor
and the bubble point of the liquid. Hy
drates apparently give no trouble with
80 per cent iso + 20 per cent normal
butane, and the operating pressures are
above atmospheric. Butane-1 was also used
by Struthers in some early pilot freezer
work.
tend to be designed as agitated tanks with
provision for increasing the liquid surface
area considerably by sprays or fountains.
The vertical walls may be washed with
recirculated brine to prevent ice build up.
Brine recirculation holds the ice content of
the slurry to about 10 per cent. Carrier also
recirculates slurry, returning it through
standpipes overflowing in the vapor space
to insure adequate interfacial surface
where heat is being removed by vaporiza
tion. The Carrier vacuum Rash-absorption
plant and its successful operation are yvell
described in a recent report (ref. 9) .
All operators have observed that ice
crystal sizes increase as the salinity of the
freezing mixture decreases, even though the
overall driving forces be made constant.
This is true for both flash and butane
freezers, but no convincing explanation of
 this phenomena has been made. It implies
that freezing of brackish water will yield
larger crystals than sea water. It will also
be a factor to consider when specifying
the fraction of the feed to be converted to
fresh water, i.e., the salt content of the
brine.
Crystal sizes are measured in different
ways by different contractors and care
should be taken in interpreting such data.
Carrier measures a mean equivalent diam
eter which is equal to the diameter of a
sphere having the same surface to volume
ratio as the crystal collection, and it is
determined by permeability measurements
using the Carman-Kozeny equation to inter
pret the results. They obtain an equivalent
diameter for their particles of 95 microns
under optimum operating conditions. If
the particles are disc shaped with a diam
eter to thickness ratio of 4, then the disc
diameter is twice the equivalent diameter.
Thus the mean disc diameter of the Carrier
particles would be 190 microns. Measuring
the same particle collection by observing
sizes under the microscope will not neces
sarily give the same values as the perme
ability test, but no comparisons have been
made. If a wash column is used for separa
tion, the permeability test is very useful in
itself, since it determines directly the rates
at which ice may be pushed through the
column without flooding of the wash water
which flows countercurrently under gravity.
The mean disc diameter of the Colt crystals
is 20 to 40 per cent larger than the Carrier
crystals, although the diameters were meas
ured by observation under a microscope
instead of by permeability measurement.
The nominal residence time of the liquid
in the freezer, i.e., the liquid volume in
the freezer divided by tHe volumetric input
rate of feed, recycle brine, and slurry is
on the order of 2 to 3 minutes. The signifi
cance of this time in these flash freezers
is not clear, since much of the heat and
mass transfer must take place at the
interface which exists between the liquid
and vapor, and this will not be proportional
to the liquid volume present, since much
of this surface is in the spray and on the
wetted walls and standpipes. The mean
time of growth of any one crystal is thus
probably less than the nominal residence
time and this could account for the small
crystals produced.
The distribution of residence times of
individual crystals in a freezer will be very
difficult to determine since it will be affected
both by the flow patterns of the fluid
through the vessel and also by the nature
of the nucleation. The interpretation of
such information, if it were available, would
also be complicated since each location in
the vessel would be associated with different
growth rates depending on the local degree
of subcooling. Thus a final crystal size
would be a function not only of its resi
dence time but also of its path through
the vessel.
It seems important that an increase of
crystal size produced in flash freezers be
attempted by modified vessel design or im
proved agitation methods. Generally, this
may lead to more capital cost in the freez
ing vessel but it will be attended by de
creased washing costs and smaller wash
columns, and the net effect is likely to be
beneficial. Smaller wash columns will help
make larger capacity freezing plants more
practical.
Some of the heat removed in the freezer
must be rejected to the atmosphere in the
secondary refrigeration cycle and one meth
od of doing this is to remove additional
heat from the precooled feed before intro
ducing it to the freezer. This is thermo-
dynamically advantageous since the required
temperature lift is reduced, but it also
has an effect on freezer operation. Colt
has tried a conventional flake ice machine
to do this which not only precools but also
forms some ice in the feed, and it is found
that the main freezer produces a crystal
product with a smaller mean size when
flake ice is present in the feed than without
it. This should be studied in more detail
since the adverse effect on crystal size might
be eliminated by modified design. Colt is
also studying other methods of feed pre-
cooling.
Freezers in the secondary refrigerant
processes tend to be patterned more after
a tubular reactor than a stirred tank. The
Struthers vessels are long and horizontal
with feed put in at one end and slurry
removed from the other. The liquid depth
is kept modest to prevent excessive hydro
static head at the bottom. Liquid butane is
introduced on top of the aqueous phase
and agitators cause the butane to be mixed
gently with the brine. The object is to hold
a low degree of subcooling so that nucle
ation is moderate and crystal growth can
predominate. Residence time in the liquid
phase varies from 20 minutes in the 15.000
gpd plant to 5 minutes in the larger plant.
Too little operating experience has been
gained from these plants to state results
with certainty, although the small plant has
produced ice crystals which have high per
meability indicating large-sized particles. No
published material is yet available on the
647
Operation of either of the Struthers pilot
plants.
The Blaw-Knox pilot plant has gone
through several modifications since it first
started. The idea of using the Rotocel ex
tractor has been abandoned, and Wiegandt's
column has been modified mainly to elimi
nate the freezer. The most recent and suc
cessful freezer is a unit separate from the
wash and melt column which consists of
a horizontal torus-shaped vessel in which
butane and feed circulate rapidly. Liquid
butane is sprayed in below the liquid
surface. The spraying, vaporization, and
liquid circulation around the torus all con
tribute to agitation. The residence time in
the liquid phase is 10 to 15 minutes, but
it is not yet known whether this is opti
mum. Circulation around the torus is rapid
so that the behavior is somewhat like a
stirred tank, although the vessel appears
more like a tubular reactor bent into a
circle. Blaw-Knox will have a formal report
published by the Office of Saline Water in the
near future which will describe their plant
and its operation in more detail; the com
bination of the Blaw-Knox process and the
Wiegandt process is called the Cornell
process.
Driving force temperature differences used
in the various freezers vary but little and
are close to 2°F. This is an overall tem
perature difference for heat and mass trans
fer and represents the difference between
the actual bulk brine temperature, as
measured with a thermometer in contact
with the aqueous phase, and the saturation
temperature of the refrigerant at the pres
sure in vapor space in the freezer. Struthers
ICE-BRINE SEPARATION
The present freezing pilot plants employ
only two methods for separating ice and
brine: (1) countercurrent washing in a
vertical moving bed and (2) centrifuging.
Л third method is now used in the propane
hydrate pilot plant of Sweet Water Devel
opment Company at Wrightsville Beach,
North Carolina. The latter method uses
liquid cyclones to separate hydrate crystals
from brine after slurrying the mixture with
liquid propane. The plant has not been
on-stream long enough to test this separa
tion system. Other methods have also been
studied (ref. 10) .
Struthers Scientific used centrifuges in
both their original pilot plants, and con
fidence in them was based on their suc
cessful use for separation by Umano in
Japan and by the Germans (ref. 8) , Yugo
perhaps uses an overall Д1 of less than 2CF.
but they point out that the temperature
difference between the ice crystal and the
brine is the critical one and that this is
much smaller than 2°F (probably less than
0.2°F) . This latter temperature difference
is divided between heat transfer, mass trans
fer, and crystal growth; assuming the last
to be small, a method has been worked out
by Sherwood and Brian (ref. 24) to deter
mine the individual driving forces.
The important temperatures in a freezer
are:
(1) That of the saturated refrigerant at
the pressure in the vapor space,
(2) The bulk liquid refrigerant,
(S) The bulk aqueous phase,
(4) The equilibrium freezing temperature
of the bulk brine leaving the freezer,
and
(5) The brine-ice interface temperature.
Any pair of these may be used to describe
a driving force, and care must be taken in
interpreting data on temperature differ
ences.
Generally, freezer design is still a pure
art. Little has been done to describe the
processes mathematically because they are
so complex and intractable. In his work
on optimizing the entire freezing process,
Orcutt (ref. 20) attempted a mathematical
description of a freezer, but the results are
only preliminary. He had to have a mathe
matical model of a freezer which included
the effects of nucleation, crystal growth, and
heat and mass transfer between phases
(there are 4 phases present in butane
freezers) , and he found it difficult with
the data available.
slavs (ref. 21) , and others (ref. 19) . The
large Struthers plant has been operating
now for over a year and the small one for
over two years, but generally the separation
of ice and brine by centrifuge has been
unsuccessful. In the large plant some
equipment other than centrifuges has given
trouble; and in the small plant which has
produced good ice crystals, though inter
mittently, the centrifuge was necessarily
oversized because machines of an adequately
small size had not been manufactured. The
problems with the centrifuges have mainly
been due to ice building up in the rotating
baskets and not moving continuously and
uniformly through the machine.
Wash columns have been used and devel
oped very satisfactorily by Carrier, Blaw-
Knox. and Colt. The Office of Saline Water
has also built a wash column and put it 1n
service on the 15,000 gpd Struthers plant
where it has performed well.
The first analyses of the countercurrent
washing and the hydraulics in wash col
umns were reported by Wiegandt (refs. 32,
S3) and by Barduhn (refs. 4, 5) . The de
scriptions there of the ice bed moving up
ward vertically due to frictional forces from
the cocurrent brine flow are still valid, but
better means have been found to describe
the mass transfer in the counterflow sec
tion, to design columns, and to analyze the
hydraulics.
Both Carrier and Blaw-Knox built col
umns of rectangular cross section when it
was found that circular columns are more
difficult to analyze and can not be scaled-up
without changing design. A sketch of a rec
tangular countercurrent wash column with
screens in the vertical wall is shown in
Figure 250. Slurry of 5 to 25 per cent solids
UNCONSOLIDATED
SLURRY
u
T
ICE LIQUID FLOW
MOVEMENT PATTERN
FIGURE 250. WASH COLUMN MECHANICS.
concentration is introduced into the bottom
and it flows upward. The ice consolidates
at some level and brine is filtered through
the ice and leaves, in the horizontal direc
tion, through screens on two opposite walls.
The ice continues vertically past the screens
and meets a descending stream of wash
water which removes the salt and leaves
with the brine. Ice and entrained water
emerge from the liquid, some water drains
off and a scraper removes the washed ice
at the top. The height of a wash column
is thus the sum of the heights needed to
perform these several functions.
From the inlet at the bottom to the
screens, the distance must be adequate to
provide the force necessary to push the
ice column upward. The required force is
estimated from the net weight of the ice,
the buoyant force of the ice in the brine,
the weight of the wash water, and the
frictional forces between the sides of the
C/Cin I
AXIAL SALT CONCENTRATION
GRADIENTS
649
 column and the ice. The depth of the ice
below the screen adjusts itself to give the
proper pressure drop to the brine flowing
through the ice bed to provide this net
force. The ice permeability and porosity
determine this depth. An allowance below
the bottom of the consolidated ice is made
to provide for variability in particle sizes,
variation in slurry densities, misoperation.
etc.
Fluid streamlines in the column have been
pictured by Mixon (ref. 18) and are shown
roughly on Figure 250. These are for a
column with rectangular cross section and
with screens on two opposing walls. The
flow field thus approximates two dimen
sional flow and Laplace's equation is as
sumed to describe both the pressure
potential field and the streamlines.
The height above the screens must pro
vide space for the "brine hump" in the
center, allow adequate washing, and pro
vide height for drainage and some con
tingency for misoperation. The difficulty
with scale-up of circular columns stems
from the fact that the brine flow is not
only vertical but has an important hori
zontal component in the vicinity of the
screens. To provide the potential to force
the brine in the lateral direction, the
liquid level builds up in the center of the
column. A reasonable "brine hump" height
of several inches can be maintained if the
screens are only a few feet apart. Scale-up
of a rectangular column is thus conceptu
ally simple if the distance between screens
is fixed and the other horizontal dimension
is increased in proportion to the desired
capacity. Annular column cross sections
have also been proposed by several de
signers.
Batch washing experiments in ice beds
and other porous media all show that the
breakthrough curves may be well repre
sented, using a simple axial dispersion co
efficient. Assuming that it is permissible
to use a similar model for steady state
counterflow, the following analysis of the
washing section is useful and turns up some
very interesting results. It was first suggested
by Mikesell (ref. 17) .
The assumptions and nomenclature are
(Fig. 251) :
(1) The liquid flow is one dimensional
and vertical. This is obviously not accu
rate since in the wash section some flow
is toward the screen and this has a hori
zontal component. The results will thus
be more qualitative than quantitative.
(2) Lateral concentration gradients are
small even in the pores, i.e., Taylor type
650
diffusion exists (refs. 1 , 28) . С is the
function of X only.
(S) x is the distance measured upward
from the bottom of the wash section where
the salt concentration in the brine is
С = С,.
(4) The net convective velocity, v, is
constant. It represents the difference be
tween the downward velocity of the wash
liquid and the upward velocity of the
liquid carried with the ice, both measured
with respect to the wall. All velocities are
superficial, i.e., equal volumetric flow rates
divided by total column cross section.
When the net wash is positive, v is posi
tive. (Measured in opposite direction from
x for convenience.)
(5) x — L at the top of the wash section
where С = С..
(6) Salt moves only by convection and
axial dispersion, and D is the axial dis
persion coefficient.
The differential equation describing this
set of conditions is:
d*C dC л
D^i-+v-dx-=° «
with boundary conditions
C(0) =C„
(2)
C(L) =Coot
The solution is:
_ (vL/D) (x/L)
C, -C 1 -e
c-c - -vL/D
1-е (S)
and is plotted on Figure 252 for various
values of vL/D. The curves show that when
the net wash is positive (vL/D > O) , most
of the concentration change takes place
near the bottom of the wash section and
when negative, near the top. For zero
net wash Equation (3) is indeterminate but
yields a linear gradient when the indeter
minacy is lifted. Even small deviations of
the net wash from 0 yield the above
picture of the major concentrations change
taking place in one end or the other of the
section. Thus, the condition of having zero
net wash with a linear salt gradient is not
very stable and will tend to revert to one
of the other two possible concentration
patterns with only slight perturbations in
operating conditions. Furthermore, while
a negative wash rate can yield salt -free ice
it requires that the concentrated brine be
very near the top of the wash section and
this would also be a difficult operating con
dition, since small changes in flow rates
could quickly bring concentrated brine up
with the harvested ice.
C-C.H, x-L

x=0
volumetric net wosh rote
+ V 3 total column cross section area .«

0 «axial dispersion coefficient for

porous media

J2C L dC
D-TT + V -—
dx2 dx

C(0) = C,
C{L)»C.
FIGURE 251. AXIAL DISPER
SION MODEL OF WASHING
SECTION FOR SALT TRANS
FER.
One may estimate the vertical distance
over which most of the concentration
change takes place, say from 0 to 90 per
cent of the total change. Dispersion coeffi
cients (D) in porous media have been
measured by many investigators, (refs. 24,
31) , and collected (ref. 16) . It is found that
the Peclet number formed by using this D
is independent of the Reynolds number
and is roughly a constant having a value
between 0.5 and 1, depending on the
investigator. Thus assume for this demon
stration:
Pe — d,u/D = 1
where d, = the particle diameter
and u = the superficial velocity meas
ured with respect to the ice bed.
-Ç~§"B Accomplished Fractional Concentration Change
FIGURE 252. PREDICTED
AXIAL CONCENTRATION
GRADIENTS IN WASH COL
UMNS.
The relation between u and v is:
u = v + v, (5)
where v, is the linear ice velocity measured
positive upward with respect to the wall.
Some calculations show that v is on the
order of 1 per cent of V| for many operating
conditions, and thus, for evaluating D from
Equation (4) , it is suitable to take
u = V, (6)
For evaluating the possible range of vL/D
the following two extreme conditions are
assumed:

651
 Lars« particles Small partieUê
at high i at low waah
0.07 em Hp = limn 0.02 cm
particle site
1,000 lbe/hrft« Ice washing 130 lba/hr ft'
rat*
0.5 = Ice por- 0.6
oaity
0.81 егл/аас ti = (calcu + 0.0009 cm/sec
lated)
76% % ice in 60%
harvested
product
+ 1% ratio: net + 6%
wash/wash
rate
+ 0.0009 em/все V (calculated) 4 0.0009 cm/aee
100 cm L (aaaumed) 100 cm
+« vL/D (cal. + 110
culated)
The last value is estimated from:
vL dFu V L
T3 D~ "ÏT ' d¡¡
and from Equations (4) and (6) .
From the above one finds that the vertical
distance over which 90 per cent of the con
centration change takes place is about 2 cm
for the small particles at low wash rates.
Assuming values of L = 10 cm and 1,000 cm
(instead of 100 cm) does not change this
value appreciably. For the large particles at
high wash rates, this distance is 9 cm for L =
10 cm, and about 55 cm for L = 100 or
1,000 cm or larger. For many operating
conditions the calculated height over which
the required concentration change takes place
is a foot or less, and this has been verified
by engineers who have operated wash col
umns. Thus, most of the height of a wash
column is needed for purposes other than
washing.
While Equation (3) gives only a qualita
tive picture of the washing section, it does
provide insight into the countercurrent
washing process. The equation is not direct
ly useful for design since С is predicted
only if both L and C0 are known, although
since results are insensitive to L when
(vL/D) is greater than about 10. estima
tions may be made. The most adverse as
sumption is probably that the velocity field
is one dimensional. It should be noted that
Ce is a weighted mean of the composition
of the wash water and the liquid adhering
to the harvested ice, and that C, is a
weighted mean of the brine from the freezer
and that leaving the filtration screens.
Large ice particles which yield a highly
permeable bed require taller wash columns
since a longer section is required below the
screens to provide the necessary pressure
drop. They are no more easily washed than
smaller particles and even less so according
to the rough analysis above. They have a
distinct advantage, however, due to their
permeability because a much higher ice
652
flux may be used without flooding. Accord
ing to Darcy's law and the Carman-Kozeny
equation the column area should be in
versely proportional to the permeability and
thus also to the particle diameter squared.
i.e.,
A. = C/dJ
The height of the column is the sum of
the height needed for adequate pressure
drop to be created for ice movement, H.
plus an assumed constant height for all the
other wash column functions, he. Thus:
V = A.(H + h„)
H should be directly proportional to perme
ability and thus to dj . The column volume
is thus calculated as:
V = С, + C/d'
The term d represents the volume between
the bottom of the ice bed and the screens.
It is independent of the permeability of the
ice, i.e., as the particle size increases the
height of this section increases, but the cross
section area decreases at the same rate leav
ing the volume of the section fixed. The
term C/dJ represents the volume of the rest
of the column. It decreases rapidly as par
ticle size is increased because the required
cross sectional area is reduced.
Some limited data indicate that the allow
able throughput rate in a wash column is
linear in the particle size (refs. 9, 13) in
which case there is an optimum particle
size for minimum wash column volume.
Data on the throughput rates of wash
columns in various plants are given below.
The wide variation is due mainly to the
differences in the nature of the ice produced
and not in the wash column design itself.
It is also due partly to the fact that some
rates are the maximum possible rates and
others are operating or design rates. The
data are not firm nor strictly comparative.
Ice rate in
Wash column Ibs/hr ft'
Blaw-Knox 700
(■rectangular)
Colt 300
Carrier 165
Office of Saline Water Col 1,000
umn on Strulhers plant
The wash water may be applied to the
top of a column at a rate controlled to
yield low salt product, and the top section
of ice will then be draining normally dur
ing its upward passage. Ambient pressure
will exist in the continuous gas space in
the pores down to the liquid level. This is
a "drained" column. The wash water may
also be applied in excess to the ice so that
much water is harvested with the ice. In
this case the "flooded" column wash water
consumption is controlled by varying the
back pressure on the screens. Either method
of operation is workable, but some oper
ators think the drained column is simpler
to operate (Carrier) and others prefer the
flooded column (Blaw-Knox) .
MELTERS
Two general melter designs are used. One
condenses compressed refrigerant vapor
directly onto the washed and drained ice
(Colt, Blaw-Knox) . The other contacts the
warm vapor with a slurry of ice in a column
with splash trays (Struthers) . Condensing
of vapor onto ice directly is not as fast as
condensation onto a cooled heat transfer
surface, since two liquid films form. Colt's
design provides mechanical arms to distrib
ute and move the melting ice, and Blaw-
FEED-TO-PRODUCT HEAT EXCHANGERS
So far four types of equipment have been
studied for feed-to-product heat exchangers:
(1) conventional tubular exchangers; (2)
direct contact types (DCHE) , using an
insoluble secondary fluid; (3) compact
special design exchangers; and (4) multi
stage flash evaporation of the feed. A
method using an immiscible secondary fluid
which vaporizes and condenses rather than
simply exchanging sensible heat as in the
DCHE, has been described and studied
recently (ref. 10) .
The conventional exchanger is very useful
in an experimental pilot plant since it is
easily available; but most important, it is
relatively trouble-free and does not compli
cate the operation obthe rest of the plant.
The surface is expensive, however, and it is
probably not economical for use in produc
tion plants. Cheaper surface and higher
heat transfer rates allow closer temperature
approaches, and this improves the thermo
dynamics of the refrigeration cycle, especially
in the energy requirement for the secondary
compressors.
Recent studies on DCHE's indicate that
they may be cheaper than conventional sur
faces and they should be investigated for
their usefulness in the freezing process.
Struthers has them installed in both their
pilot plants but they are not simple to
operate and problems of carryover, inade
quate and low heat transfer rates, and
holdup have appeared. The refrigerant itself
is the logical fluid to use as the immiscible
heat transfer agent in freezing. Study of
Only in the vacuum flash freezing with
absorption is the wash column open to the
atmosphere at the top and easily accessible
for observation and sampling. In the flash
compression process and in the secondary
refrigerant process using butane, the col
umn is sealed-in, the former at about 5 mm
absolute and the latter at about 800 mm.
Knox dumps ice into a chamber and allows
it to stand until melted. The latter put all
the vapor from the primary compressor into
the melting chamber and let the excess
sweep through the ice to eliminate stag
nant regions where noncondensables ac
cumulate. They claim that melting ice in a
dead end vapor space does not work well.
Melter design is an art like freezer de
sign, but no serious problems have arisen
with existing units.
these DCHE's is better undertaken as a
separate independent project.
Due to lack of any new and suitable de
signs from the heat exchangers industry,
Colt has developed a simple, inexpensive,
compact, true countercurrent, aluminum
heat exchanger on its own, and Carrier is
investigating a multistage flash system for
precooling the sea water (ref. 14) . The
lack of a vigorous heat transfer industry at
the present time in this country has been
pointed out by Philip Sporn (ref. 26) . He
believes the opportunities for such an in
dustry are great at this moment. Certainly
there is a strong need for more ingenious
and economical heat exchanger designs to
assist in cutting costs in all water conver
sion processes.
The Colt heat exchanger design is pro
prietary, but they will probably disclose
and patent it in the near future. They claim
to be able to operate the exchangers eco
nomically with approach temperatures less
than 2°F.
The Carrier idea is to use a several stage
vacuum flash on the feed with the cold
products flowing countercurrently in a simi
lar fashion to the flash distillation process.
The surface for heat transfer would prob
ably be tubular but high heat transfer
coefficients can be expected with condensing
steam on one side, thus reducing the area
required below that for straight liquid-
liquid exchange. Another benefit which ac
crues to this system is that additional fresh
water is produced in the flashing. This
653
mitigates the penalty of high feed tern-
peratures that all freezing processes have.
The hotter the feed the more fresh water
DEAERATORS
All pilot plants built so far except that
of Blaw-Knox have deaerators for the feed.
The object is twofold: (1) To reduce
corrosion by free oxygen and (2) to remove
noncondensable gases for improving re
frigerant condensation.
The reduction of oxygen in feeds to high
temperature equipment is of unquestioned
importance, but little work has been done
on the dissolved oxygen effect in sea water
at low temperatures. The effect may or may
not he important, and the use of inex
pensive construction materials might be
REFERENCES
1. Ananthakrishnan, V.; Gill, W. N.; Bar-
duhn, A. J.: "Laminar dispersion in
capillaries—Fart", A. 1. Ch. E. Journal,
accepted for publication (1965) .
2. Bechtel Corporation: Office of Saline
Water R&D Progr. Rept. no. 72 (1963) .
3. Bosworth, C. M.; Carfagno, S. S.; San
dell, D. J.. Jr.: O. S. W. R&D Progr.
Rept. no. 23 (Jan. 1959) .
4. Bosworth, C. M.; Carfagno, S. S.; Bar-
duhn. A. J.; Sandell, D. J., Jr.: O. S. W.
R&D Progr. Rept. no. 32 (July 1959) .
5. Bosworth, C. M.; Barduhn, A. J.; San
dell, D. J., Jr.: Advances in Chemistry
no. 27 (1960) p. 90 Am. Chem. Soc..
Washington, D. C.
6. Catalytic Construction Co. and Nuclear
Utility Services, Inc.: O. S. W. R&D
Progr. Rept. no. 124 (Nov. 1964) .
7. Curran, H. M.: Advances in Chemistry
no. 27 (1960) p. 56 Am. Chem. Soc.
Washington, D. C.
8. Doge, F.: Dechema-Monographien Nr.
781-814 vol. 47 (1962) p. 829.
9. Hahn, W. J.; Burns, R. C; Fullerton,
R. S.; Sandell, D. J., Jr.: O. S. W. R&D
Progr. Rept. no. 113 (June 1964).
10. Harriott, P.; Wiegandt, H. F.: A. 1.
Ch. E. Journal vol. 10 H964) p. 755.
11. Hendrickson, H. M.; Moulton, R. W.:
O. S. W. R&D Progr. Rept. no. 10
(Aug. 1956) .
12. Jebens, R. H.; Dykstra, D. I.: Paper
presented at A. I. Ch. E. Meeting, Hou
ston (Feb. 7-11, 1965) .
13. Johnson, C. A., et al: Carrier Corpora
tion Report to O. S. W. on Contract
318, Phase I (May 1963) .
is produced. With normal feed tempera-
tures the additional product ranges between
4 and 10 per cent.
stimulated if we knew more about this
phenomenon.
Blaw-Knox has stated that the cost of a
deaerator may be unwarranted from the
standpoint of removing noncondensables.
They suggest that in a butane freezing
plant it is easier to remove these gases by
venting in the secondary condenser.
In the vacuum flash freezing process it is
much more necessary to deaerate the feed
since removal of noncondensables at 5 mm
is difficult, and the adverse effects of air in
the melter are more pronounced.
14. Johnson, C. A.; Sandell, D. J., Jr.: Car
rier Corporation Report to O. S. W. on
Contract 318, Phase II (July 1964) .
15. Karnofsky, G.; Steinhoff, P. F.: O. S. W.
R&D Progr. Rept. no. 40 (July 1960) .
16. Levenspiel, O.: "Chemical reaction en
gineering", John Wiley, New York
(1962) p. 275.
17. Mikesell, R. D.: Post-Doctoral Fellow,
Dept. of Ch. E. & Met., Syracuse Uni
versity (May 1965) .
18. Mixon, F. O.: Report to O. S. W. on
Contract 379 (Sept. 18. 1964) .
19. Okabe, T.: Dechema-Monographien JVr.
781-834 vol. 47 (1962) p. 815.
20. Orcutt, J. C: Report to O. S. W. on
Contract 379 (July 6, 1964) .
21. Pankovic, Z.: Dechema-Monographien
Nr. 781-8)4 vol. 47 (1962) p. 805.
22. Rose, A.; Hoover, R. B.: O. S. W. R&D
Progr. Rept. no. 7 (Sept. 1955) .
23. Sandell, D. J., Jr.; Johnson, C. A.:
"Direct freezing—wash separation proc
esses", First International Symposium
on Water Desalination (Oct. 3-9. 1965) .
Washington, D. C.
24. Sherwood, T. K.; Brian, P. L. T.: Re
port to O. S. W. on Contract 295 (Oct.
31, 1964) .
25. Sinek, J. R.; Ganaris, N.: Engrs. Soc. of
W. Pa., Proc. Int'l. Water Conference
(Oct. 28, 30, 1963) Pittsburgh, Pa.
26. Sporn, Philip: "Fresh water from saline
waters", Am. Elect. Pwr. Co., New York
(March 11, 1965) .
27. Svanoe, H.: Swigcr, W. F.: O. S. W.
R&D Progr. Rept. no. 47 (June 1961) .
28. Taylor, G. I.: Proc. Roy. Soc. vol. 219A.
 no. 186 (1953) ; vol. 22)A, no. 446
(1954) ; vol. 225Л, no. 47) (1954) .
29. Thompson, T. G.; Nelson. K. H.: Re-
frigeration Engr. no. 62, (July 1954)
pp. 44-48, 90.
SO. Thompson, T. G.; Nelson, К. H.: Sears
Foundation J. Marine Research no. 13
(Nov. 1954) p. 166.
SUMMARY OF DISCUSSION
It was asked if there is work going on in
the United States utilizing the hydraulic
piston bed principle on a large scale. In
affirmation it was stated that the Blaw-Knox
Company has projected a horizontal type
piston bed design for commercial-size plants
and that the Carrier Corporation has de
signs for 165,000 gpd modules. It was asked
if a staged process had been suggested. The
reply was affirmative and further stated
that for 1,500 ppm water, a 90 per cent
recovery would be expected.
Comments were requested concerning the
Les Procedes de Congelation Pour la
Conversion de L'Eau Aux Etats-Unis
Allen J. Barduhn
Etats-Unis d'Amérique
L'étude systématique des procédés de
congélation pour la conversion de l'eau de
mer en eau douce a été entreprise aux Etats-
Unis depuis plus de quinze ans. Le début a
été modeste, mais aujourd'hui au moins
cinq sociétés ont construit des installations
pilotes, chacune pour produire environ
60 m9 d'eau douce par jour et une installa
tion conçue pour 750 m* par jour a été
construite et est en exploitation. Plusieurs
universités de ce pays poursuivent des
quantités importantes de recherches plus
fondamentales sur la thermodynamique et
la cinétique de la formation de la glace.
Les procédés en sont encore à leurs débuts
et l'on ne possède aucune ressource impor
tante de conception et d'expérience de fonc
tionnement comme c'est le cas dans les
procédés de distillation; pourtant, du point
de vue économique, le dessalement par con
gélation semble tout à fait favorable, spé
31. von Rosenberg, D. U.: A. 1. Ch. E.
Journal no. 2 (1956) p. 55.
32. Wiegandt, H. F.: О. S. W. R&D Progr.
Rept. no. 41 (Aug. 1960) .
S3. Wiegandt, H. F.: Advances in Chem
istry no. 27 (1960) p. 82 Am. Chem.
Soc, Washington, D. C.
centrifuge. The concept of centrifugal sepa
ration, introduced by Dr. Umano of Japan,
is a process which was designed to produce
brine and for that purpose worked very
well. There was data to show that potable
water could be made using centrifugal sepa
ration; however, experiments with this
method have been unsuccessful. The author
said that Struthers Scientific, which used
the centrifugation method without success,
is presently experimenting with the wash
column.
cialement dans les dimensions plus petites
d'usines allant environ de 200 m' à 20.000
m" par jour. Ces résultats économiques
encourageants ont réussi à maintenir actif
l'intérêt de plusieurs maisons industrielles,
et l'Office of Saline Water du Département
de l'Intérieur des Etats-Unis a financé une
proportion considérable des travaux de re
cherches et de développement jusqu'à
maintenant.
On donne un bref historique du déve
loppement des procédés de congélation aux
Etats-Unis et des contributions de plusieurs
groupes de recherches et sociétés intéres
sées dans les procédés industriels.
Les avantages du procédé de congélation
sont énoncés et discutés. Parmi ceux-ci, on
note la faible température de fonctionne
ment et l'utilisation de transmission de
chaleur directe, ce qui élimine les pro
blèmes d'entartrage et permet le fonctionne
655
 économique sur tous le* genres d'ali-
depuis l'eau saumllre diluée
jusqu'à l'eau de mer. que des éléments de
formation de tartre soient présents ou non
Dans l'état actuel du développement, il
semble que l'on puisse étudier des procédés
de congélation pour des capacités allant
jusqu'à environ 20.000 m* par jour et la
nature des installations plus importantes
reste spéculative. On discute la raison de
cette limitation des dimensions.
On présente des estimations des prix de
revient de l'eau provenant des usines par
congélation, montrant qu'ils peuvent con
currencer la distillation dans la gamme des
dimensions considérées, à la fois pour les
eaux saumàtres et pour l'eau de mer. La
Процессы Вымораживания
для Опреснения Воды в Соединенных
Штатах
Аллеи Дж. Бардун
Соединенные Штаты Америки
В Соединенных Штатах уже более 15
лет производится систематическое изу
чение процессов вымораживания для
опреснения морскоой воды. Начало бы
ло скромным, но сейчас по крайней ме
ре пять компаний построили пробные
установки, каждая с производительно
стью по 15.000 американских галлонов
опресненной воды в сутки, а одна уста
новка, спроектированная на 200.000 гал
лонов в сутки, была построена и на
ходится в эксплуатации. В нескольких
университетах страны было проведено
значительное количество теоретических
исследований, касавшихся термодина
мики и кинетики образования льда.
Эти процессы до сих пор еще находят
ся в стадии раннего развития и по
сравнению с дистилляцией пока-что от
сутствует большой конструктивный и
эксплуатационный опыт; тем не менее
опреснение с помощью вымораживания
подает с экономической точки зрения
большие надежды, особенно для не
больших установок с производитель
ностью в пределах от 50.000 до 5 мил
лионов галлонов в сутки. Вследствие
656
congélation peut également concurrencer
rélectrodialyse lorsque la concentration de
sels dans l'alimentation est supérieure à
8.000 ppm ou peut-être pour toute eau
saumâtre s'il se pose des problèmes d'entar
trage difficiles et si le volume de résidu de
saumure doit être faible.
On présente des discussions de la concep
tion technique et de l'application pratique
sous les titres suivants: réfrigérant pour
contact direct, conception de congélateurs,
séparation glace-saumure, fondeurs, échange
de chaleur alimentation/eau produite, et
dégazeurs. Ceci comprend à la fois la congé
lation instantanée sous vide et la congéla
tion par contact direct avec réfrig^érant.
благоприятных экономических возмож
ностей оно продолжало активно инте
ресовать несколько промышленных
фирм, а Управление по опреснению со
леных вод Министерства внутренних
дел США до настоящего времени фи
нансировало значительную часть иссле
довательской и проекционной работы.
В докладе приводится краткая исто
рия развития процесса вымораживания
в Соединенных Штатах и отмечаются
заслуги нескольких исследовательских
групп и компаний, заинтересованных в
коммерческих методах.
Перечисляются и обсуждаются пре
имущества процесса вымораживания.
К ним относятся низкая рабочая тем
пература и прямая передача тепла, ко
торая устраняет проблемы образования
накипи и тем самым дает возможность
экономично работать при всех видах
питания, начиная слабо солоноватой и
кончая морской водой, несмотря на то,
есть ли там образующие накипь эле
менты. При настоящем уровне развития
создается впечатление, что процессы
вымораживания могут быть применены
для производительности до 5 миллио
нов галлонов в сутки, тогда как для
более крупных установок этот вопрос
еще на разрешен. В докладе обсужда
ется причина необходимости ограни
чить размеры.
Представлены сметы стоимости опре
сненной вымораживательными установ
ками воды, из которых видно, что в
указанных пределах они могут конку
рировать с дистилляцией, как солоно
ватой, так и морской воды. Вымора
живание сможет также конкурировать
с электродиализом не только при со-
лесодержании питания, превосходящем
8.000 мг/литр, но даже, вероятно, и при
Los Procedimientos
Para la Conversion
EE.
Allen J. Barduhn
Estados Unidos de Norteamérica
Desde hace más de 15 años se lleva a
cabo en los Estados Unidos el estudio siste
mático de los procedimientos de congela
ción para convertir agua de mar en agua
dulce. Aunque el principio fué modesto, ya
cinco empresas, por lo menos, han estable
cido instalaciones experimentales para pro
ducir cada una alrededor de 15.000 galones
americanos por día (gpd) y también se
ha construido y puesto en marcha una in
stalación proyectada para producir 200.000
gpd. Igualmente se ha realizado una canti
dad de trabajos de investigación de una
orientación más básica en varias universi
dades de este pals, en relación con la
termodinámica y la cinética de la formación
de hielo. Sin embargo, estos procedimientos
se hallan aún en sus etapas preliminares
de desarrollo ya que no se cuenta todavía
con la experiencia en el diseño y en el
funcionamiento como ocurre en el caso de
los procedimientos de destilación. A pesar
de ello, la economía de la desalinización
por congelación parece ser muy favorable,
especialmente cuando se trata de las instala
ciones más pequeñas que producen de
50.000 gpd a 5 millones gpd. Esta alenta
dora economía ha contribuido a que las
любой солоноватой воде, если суще
ствует серьезная проблема образования
накипи, а объем сбросного рассола
должен быть небольшим.
Обсуждение технического проекти
рования и практических сторон дела
приведено под заглавиями: Холодиль
ный агент для прямого контакта, Кон
струкции вымораживателей, Отделение
льда и рассола, Плавильники, Тепло
обмен между исходной и опресненной
водой и Деаэраторы. Приводятся све
дения, касающиеся как мгновенного
вымораживания под вакуумом, так и
вымораживания с помощью прямого
контакта.
de Congelación
de Agua en los
UU.
diversas empresas industriales se mantengan
interesadas en el proyecto activamente, y
por otra parte, la Oficina de Agua Salada
del Depto. del Interior de lo EE. UU. ha
financiado una proporción considerable de
los trabajos de investigación .y desarrollo
ejecutados hasta ahora.
En este trabajo se presenta un historial
conciso acerca del desarrollo del procedi
miento de congelación en los ЕЕ. UU. y se
da cuenta de la colaboración prestada por
varios grupos y empresas de investigación
que se interesan en los procedimientos co
merciales.
Se enumeran y discuten los procedi
mientos de congelación. Entre ellos figuran
el de baja temperatura de trabajo y el que
emplea transmisión directa de calor los
cuales evitan las dificultades producidas por
las incrustaciones y permiten la operación
económica con cualquier tipo de agua de
alimentación, desde agua salobre diluida
hasta agua de mar, con la presencia de
elementos formadores de incrustaciones o
sin ella. Existe actualmente la impresión
de que en su actual estado de desarrollo
los procedimientos de congelación pueden
proyectarse para una producción de hasta
 5 millones gpd, y que la índole de instala
ciones más grandes es puramente especula
tiva. Se discuten las causas que limitan el
tamaño.
Se presentan los costos del agua prove
niente de las instalaciones de congelación,
demostrándose que compiten con los de la
destilación, dentro de los tamaños consi
derados tanto para el agua salobre como
para el agua de mar. La congelación com
pite también con la electrodiálisis cuando
la concentración de sal en el agua de ali
mentación es mayor de 8000 ppm, o tal vez
con cualquiera agua salobre cuando el pro
658
blema de las incrustaciones es serio y la
cantidad de agua madre de descarte tiene
que ser pequeña.
El estudio de los proyectos y prácticas
de ingeniería se presenta bajo los siguientes
títulos: El Refrigerante para Contacto Di
recto, Diseños de Congelador, Separación
de Hielo y Aguas Madres de Salmuera,
Fundidores, Intercambio Térmico entre el
Producto y la Alimentación, y Desaeradores.
Se incluye tanto la congelación instantánea
al vado como la congelación con refrige
rante de contacto directo.
 Operational and Future Aspects of
Vapor-Compression Distillation
Paul L. Geiringer
United State* of America
INTRODUCTION
The vapor-compression evaporation proc
ess is one of the oldest methods used to
secure potable water from salt water.
The Roswell Demonstration Plant is the
newest of the four demonstration plants
constructed by the Office of Saline Water.
It has the great advantage of requiring less
space and also has a favorable energy
balance.
The Roswell vapor-compression plant was
constructed not only to prove that this
method of desalination of water was pos
sible, but also to study the problems en
THE BRACKISH WATER OF NEW MEXICO
At the time of construction of the Ros
well Plant, the following article appeared
in the January 22-, 1962, issue of CHEMI
CAL ENGINEERING:
"Water desalting engineers are now
ready to undertake their toughest job
so far—producing fresh water continu
ously from underground brine that is
pregnant with scale forming calcium
sulfate ... the plant will check out the
feasibility of such an operation. To be
located at Roswell, New Mexico, it will
be the fourth demonstration plant au
thorized under Public Law 85-883.
"Designed to produce 1 mgd of fresh
water, this plant will evaporate brine
that, uncontrolled, could deposit 10
tons/day of scale on heat transfer sur
faces. Although Roswell brine is only
two-thirds as saline as sea water, it
contains twice as much calcium, one-
fifth more sulfate and one-third more
carbonate. Therefore, some experts feel
countered in desalting highly brackish
water.
The water to be purified, the design con
cept and its equipment, the difficulties en
countered and their remedies, and the
future aspect of the operating cost and the
possible design improvements of this desalt
ing method are all discussed in this paper.
It is hoped that this survey of the vapor-
compression evaporation systems will show
the low operating costs which can be ex
pected by utilizing the design concepts sug
gested.
that, if the proposed plant can extract
fresh water successfully from such a
feed, distillation or evaporation can
successfully desalt almost any source."
GENERAL
New Mexico has about 15 billion acre
feet of saline ground waters. These range
from brackish to brine, and could, if de
salinated, supply New Mexico's water de
mands for thousands of years (ref. 1) .
Furthermore, water similar to Roswell brine
is distributed widely in the arid Southwest
and in a broad belt extending north into
the Dakotas.
As it now stands, New Mexico is very
much in need of fresh water. Several com
munities are using substandard water for
drinking purposes. For example, the city of
Roswell water has 1,900 ppm of dissolved
solids (ref. 2) . This was one of the factors
which determined the choice of Roswell
as the site for the demonstration plant.
659
 The most important factor in selecting the
location, however, was the abundance of
easily accessible saline water.
The city of Roswell is required to de
liver saline water to the plant at a rate of
600.000 to 2.400.000 gpd.
As the location for this conversion plant,
Roswell obtained a supply of fresh water
at a cost of between 40 and 60 cents per
1,000 gallons. By tapping the saline water,
the pressure in the large saline reservoirs
underground was reduced; this reduction in
pressure helped to reduce the danger of
contamination of the relatively small fresh
water supply from encroachment by the
saline water supply. Previously, as the fresh
TABLE CIV. Comparison of Roswell Brackish Water
Roswell
dni«n
(ref. 8)
PH 7.1
HCOt ppm 16S
COi ppm 0'
Ca ppm 996
Us ppm 224
SOi ppm 8,200
Silica ppm IS
Ma ppm 7.780
CI ppm 11.820
Total solids ppm 24,470
The Roswell brackish water is more diffi
cult to process than sea water since both
the calcium and the sulfate ion concentra
tions are higher. The Roswell plant was
originally designed to process water with a
calcium content of 936 ppm and a sulfate
content of 3,200 ppm, but the water source
was changed. A typical analysis of the water
used for the present operation shows a
calcium content of 588 ppm and a sulfate
content of 1,490 ppm.
Sea water has a calcium content of ap
proximately 400 ppm and a sulfate content
of approximately 2,600 ppm. The Roswell
design requires that the feed be acidulated
with sulfuric acid before entering the vacu
um degasifier. This adds approximately 300
ppm of sulfate ion to the feed.
The high concentration of calcium and
sulfate ions increases the chance of calcium
sulfate scale formation on the inside of the
second effect evaporator tubes, since the
brine concentration factor in the second
effect evaporator is 4:1 or 3:1. Depending
on the mode of operation, the temperature
of the brine is approximately 216°F at the
point of highest concentration.
The Freeport, Texas, Sea Water Conver-
660
water was withdrawn, the salt water flowed
into the fresh water.
ROSWELL BRACKISH WATER AND ITS
COMPARISON WITH SEA WATER
The plant was originally designed for a
brackish well water shown in Table CIV,
Column 1. Later it was found that this well
could not be used and new wells were
drilled. Finally, the water shown in Column
2 was selected for desalination. Column 3
shows a "standard" sea water analysis de
veloped by W. L. Badger Associates. Inc.
(ref. 5) , and Column 4 shows a sea water
analysis from the Atlantic coast (ref. 6) .
Atlantic Coast
Roswell "Standard" sea water
operation Bea water North Carolina
(ref. 4) (ref. 6) (ref. 6)
8.0
206 148 140
0 0 0
688 408 446
161 1.298 1.810
1,4(0 2.702 2.740
IS .02 to 4 0
4,970 10,7(8 10,600
8,040 1»,861 10,700
16,400 86,176 86,200
sion Demonstration Plant # I was originally
designed for a concentration factor of 4:1.
It is presently operating at 3:1. However,
this high concentration factor reached at
the twelfth stage is obtained where the
brine temperature is only 120°F. The solu
bility of calcium sulfate in water is approxi
mately 0.202 grams per 100 grams of water
at 122°F and 0.1619 grams per 100 grams
of water at 212T (ref. 7) . Calcium sulfate
is approximately 25 per cent more soluble
at 122° than at 2I2°F.
The first and second Point Lorna, Califor
nia, multistage flash evaporation plants have
been designed to operate at a maximum
concentration factor of 2:1 with the tem
perature of brine in the last effect of less
than 100°F. The solubility of calcium sul
fate in water is approximately 0.2097 grams
per 100 grams of water at 104°F and 0.1619
grams per 100 grams of water at 212°F
(ref. 7) . Calcium sulfate is nearly 30 per
cent more soluble at 104° than at 212T.
Due to the higher concentration factor and
temperature, the Roswell plant is more
susceptible to calcium sulfate scale than
both the sea water desalination plant at
Freeport. Texas, and at the original Point
 Loma, California, plant.
Calcium sulfate solubility increases as
sodium chloride concentration increases
(ref. 10) . Sea water has a much higher
sodium chloride concentration than the
Roswell brackish water. This further re
duces the scaling potential of calcium sul
fate in a sea water conversion plant as
compared to the Roswell brackish water
plant.
The Roswell plant processes brackish
water with a silica content of 15 ppm (reT.
3) . Sea water has a negligible (if any)
silica content. It has been reported that an
appreciable amount of the scale in the
evaporator tubes at Roswell consists of
silicates (refs. 8, 9) .
THE ROSWELL CYCLE AND DESIGN
THE CYCLE OF OPERATION
The Roswell plant is a forced circulation-
vapor compression brackish water conver
sion plant designed to produce one mgd of
water of not more than 50 ppm at concen
tration factors of 3:1 up to 4:1.
The plant is equipped to prevent scale
formation in the evaporator tubes with ion-
exchange equipment as well as apparatus
for slurry recycle.
Plant Operation Using the Ion-Exchange
Equipment (Fig. 253) : The ion-exchange
» equipment is designed to remove 75 to 90
per cent of the calcium ions in the cold
feed by passing the brackish water feed
through cation ion -exchangers, using as
resin Nalco HCR-W. The ion-exchangers
are regenerated with blowdown brine, de
rived from the second effect, and brine
prepared by using purchased salt.
The softened feed, leaving the ion-
exchangers, is split into two parallel streams
recovering heat from the product and blow-
down streams in heat exchangers 608
and 609.
The two feed streams are combined
downstream of heat exchangers 608 and
609, acidified with 66° Baume H,S04 to a
pH of about 4.0 before entering the vacuum
degasifier, where carbon dioxide and oxvgen
are liberated. The bicarbonates in the feed
are removed when the carbon dioxide is
liberated.
The degasified feed is neutralized up to a
pH of between 7.5 and 8.0 in the bottom
of the vacuum degasifier by adding NaOH.
The feed is then pumped through heat
exchanger sets 605 and 606 to recover heat
from the product and blowdown streams.
The feed is heated further by passing
In summary, the Roswell plant operation
is more difficult than any of the sea water
conversion plants because the chance of
scale formation is greater since:
(a) Roswell Plant water has a much
lower concentration of sodium chloride
than sea water.
(b) Roswell feedwater has a higher cal
cium and higher sulfate content.
(c) Roswell feedwater contains silica,
while sea water does not.
(d) The last effect of the Roswell Plant,
containing the highest brine concentra
tion, operates at a much higher tempera
ture than the last effect of sea water
conversion plants.
through the second effect vent-condenser
602A and first effect vent-condenser 601A.
It then enters the downcomer of the first
effect evaporator and mixes with the recircu^
lating brine solution.
The brine in the first effect is pumped
through the inside of 7,200 vertical 1-inch
diameter tubes of the evaporators by a low
head, high volume pump of about 90,000
gpm capacity. Approximately one pound of
liquid is vaporized for every 260 pounds of
brine being circulated. The brine is heated
by steam passing on the outside of the
1-inch aluminum-bronze tubes. Vaporization
of brine in the tubes should be prevented
by keeping the brine between an 8-foot
minimum and 11 -foot normal level above
the upper tube sheet.
The steam which heats the brine in the
first effect evaporator (601) comes from
the vapor dome of the second effect evapo
rator (602) and is compressed from 16 psia
to 23 psia in a large axial-flow vapor com
pressor. The superheat in the steam dis
charged from the compressor is removed bv
the injection of condensate into a destiper-
heater derived from the second effect.
A portion of the brine circulating in the
first effect, after passing a level control, is
sent to the downcomer of the second effect.
The concentration factor of the brine leav
ing the first effect is 1.6:1.0 when the
concentration factor in the second effect
reaches 4:1.
The brine in the second effect is circu
lated through this effect in the same way
as the brine is circulated in the first effect,
and the same amount of steam is produced
in this evaporator. The brine is heated by
steam, condensing on the outside of the
661
FIGURE
FORCED
253.
CUSING
OPIRCRMUEPLORATCAEIOSTEN-IVSAOPNR

IOENQ-UEXICPHAMNEGNT.
THE
663
 cubes. The steam is derived from the vapor
dome of the first effect evaporator.
The combined condensate from the first
and second effects becomes the total product
stream. The product is pumped through
feed heat exchangers 605 and 608 and into
a product water tank where it is cooled.
Frpm there it is pumped into the city main.
Л portion of the brine circulating in the
second effect is sent, after passing a level
control, to the blowdown system. The con
centration factor of the blowdown can be
adjusted to maintain 4:1, or down to 5:1
concentration, in order to reduce the scaling
potential. The blowdown is fed through
heat exchangers 606 and 609 and into a
regenerative brine tank, No. 818. It can
then be pumped either to the makeup
sump, where it can be enriched with pur
chased salt, or pumped to storage tank No.
831. This tank serves as storage for the
brine used in the regeneration of the ion-
exchange resin. The brine is pumped from
the regenerative brine tank to the cation
ion -exchangers during the regeneration
cycle: after leaving the ion-exchangers, it
passes into a disposal tank and is then
pumped to a large brine disposal pond.
Operation Using the Slurry Recycle Sys
tem (Fig. 254): The slurry recycle method of
operation is based on circulating a slurry
of calcium sulphate crystals through the
brine contained in the two evaporators.
Scale is inclined to form on the inside of
the evaporator tubes. Scale formation should
be prevented by the preferential attachment
of the dissolved calcium sulphate contained
in the brine on the calcium sulphate
crystals of the slurry, rather than by coating
the evaporator tubes. The finite size and
quantity of calcium sulphate crystals in the
slurry are continuously controlled.
The process operates as follows: The
brackish water feed bypasses the ion-
exchange equipment and flows directly to
the heat exchangers 608 and 609. The
process flow of the feed stream is identical
to that explained above for the ion-exchange
method of operation, except that the feed
bypasses the ion-exchangers and goes di
rectly into heat exchangers 608 and 609.
The product water process flow is iden
tical to that explained for the ion-exchange
method of operation.
The hot blowdown leaving the second
effect evaporator is pumped directly to the
hydroclone #3412A, where a slurry con
taining the large calcium sulphate crystals
discharges as underflow. The separation has
to be performed hot since calcium sulphate
has an inverse solubility curve (less soluble
664
hot than cold) . The slurry containing the
enlarged crystals passes through a continu
ous ball mill #5412C to reduce the crystals
to micron size. The discharge from the ball
mill is continuously monitored for viscosity
by the addition of brine feed water. The
slurry containing the micron size crystals
is pumped (by pump 945) to the first effect
feed stream just upstream of the first effect
level control valve.
The overflow from the hydroclone is
pumped- by pump 935 through feed heat
exchangers 606 and 609 and into a thick
ener, No. 3412B. The overflow from the
thickener passes into the disposal tank.
No. 833.
The underflow from the thickener. No.
3412B, which contains some calcium sul
phate crystals, passes into a surge tank. No.
842, and is pumped (by pump 931) into a
seed preparation tank. No. 828, to store
calcium sulphate slurry for start-up pur
poses. The excess slurry from the underflow-
is pumped into the disposal tank. No. 832.
ROSWEU EQUIPMENT DESIGN—
MAJOR COMPONENTS
Ion-Exchangers: There are 6 ion-exchange
vessels (tanks) , supplied by Cochran Divi
sion, Crane Company, each 6'6" O.D. by
8'6" long, tangent to tangent, of carbon-
steel with Apexior No. S lining.
The ion-exchangers are filled with Nalco
HCR-W resin. At any one time 4 ex
changers are softening feed and 2 exchangers
are 'being regenerated. A typical cycle will
take 75 minutes and consists of the follow
ing steps:
(a) Softening (down flow)
(b) Regeneration with blowdown brine
(down flow-)
(c) Regeneration with purchased brine
(down flow)
(d) Displace with feed water (down flow)
(e) Rinse with feed water (down flow)
(f) Back wash (up flow)
The operation of the ion-exchangers is
automatically controlled by flow pulse
counters, timers, cam-operated switches,
solenoid valves, and pneumatic valves.
Feed Heat Exchangers: The feed recovers
heat from the blowdown stream in heat
exchangers 609 and 606, and from the
product stream in heat exchangers '608 and
605. These heat exchangers are of the float
ing head, nonremovable bundle type, with
carbon-steel shells and 5^" O.D. by 18 bwg
tubes of aluminum-bronze. Each shell has
2 tube and 2 shell passes. These heat ex
changers are further described in Table CV.
 TABLE CV. Feed Heat Exchangers Description
Number Surface per shell Total surface
'"bo- Description of shells (sqft) (soft)
60S Product water I 2.980 8.940
exchangers
toe Blowdown exchangers S 944 2.882
60S Product water s 4.U9 12.417
Preheat exchangers
Blowdown preheat 4 1.142 4.968
609

Acidification, Vacuum Degasification, and inlet cone, piping, and a recirculation low
Neutralization System: The system consists head, high volume pump.
of an acid mixing chamber, degasifier vessel, The Two Evaporator Recirculation Pumps
two vent-condensers, two vacuum pumps, a and Motors 901 and 902: The brine in the
sulphuric acid pump and storage tank, and evaporators is recirculated by pumps 901
a caustic pump and storage tank. Sixty-six and 902, which are type HLTL, horizontal
degree Baume sulphuric acid (98 per cent) shaft, 56-inch propeller type, Bingham
is injected into the feed in the acid mixing pumps. They are designed for 90,000 gpm
chamber, and oxygen and carbon dioxide at 6 feet head operating at 200 rpm. Casings
are removed. The elimination of bicarbon- are made of carbon-steel, and the impellers
ates reduces the potential for calcium car are monel.
bonate scale formation. The pumps are driven by 250-hp,
The acid mixing chamber consists of a 1,770-rpm, 440-volt, 3-phase, 60-cycle, Allis-
12-inch diameter pipe 9 ft long. The orig Chalmers totally-enclosed, fan-cooled motors.
inal chamber was stainless steel, but was The gear reducers are Falk No. 100625.
replaced by a rubber-lined carbon-steel pipe. They reduce the motor speed of 1,720 rpm
The degasifier vessel is 6' O.D. by 23'6" to the pump speed of about 200 rpm.
overall length. It is constructed of rubber- Vapor Compressor: An axial-flow vapor
lined carbon-steel with two packed sections compressor compresses and simultaneously
of Maspac polypropylene ribbed Berl superheats the steam derived from the dome
saddles. of the second effect (820) from 16 psia to
In the bottom of the degasifier vessel, the 23 psia. Injection of condensate into the
feed is collected and neutralized by addition desuperheater located in the compressor
of NaOH to 7.0 to 7.5 pH. discharge line reduces the steam tempera
The Two Vertical Tube Forced Circula ture to a level slightly above the saturation
tion Evaporators: The two evaporators are temperature. The compressed steam is piped
of equal size and utilize a pressure increase to This
the first effect steam chest.
machine is one of the largest axial-
of about 7 psi, resulting from the operation flow compressors
of the compressor. They are arranged in Chalmers and is rated ever built by Allis-
series, each evaporating about 175,000 lb J_j91Q_ rpm. It is supplied at 75.500 CFM at
of water per hour. with manually
adjustable inlet guide vanes for capacity
The vertical 12-ft diameter tube bundle adjustments. The steel casing is horizontally
is crowned by a 28-ft diameter pera-shaped split, permitting removal of rotor and stator.
vapor dome. The compressor motor is an Allis-
Forming the heating area are 7200, 1-inch Chalmers induction type, rated at 2300 hp,
O.D., 18 bwg aluminum-bronze tubes 1,185 rpm, 3 phase, 60 cycle, 4,000 volts, and
(52,700 sq ft) . is weather protected.
Brine is recirculated at about 6 ft/sec Motor and compressors are connected
velocity and a rate of 90,000 gpm through through a Falk type "Q" high speed unit
the inside of the tubes. There is a log mean capable of increasing the motor speed of
temperature difference of 5.42°F for the 1,185 rpm to 4,870 rpm.
first effect and 5.05°F for the second effect. The compressor and gear system are pro
A water level controller maintains a level vided with a forced lubrication system with
of about 1! to 13 feet about the upper oil reservoir, main and standby lubricating
tube sheet. oil pumps, oil heaters, and coolers.
Each evaporator is equipped with a Package Steam Boiler: Auxiliary steam
liq'uid recirculation system consisting of an required for start-up purposes, for space
665
 heating in winter, and freeze protection of
the equipment is furnished by a fire tube
package steam generator of about 10,000 lb/
hr output for 150 psig and operated at 30
psig, burning number 4 or lighter fuel oil.
Hydroclone No. M12A: The hot blow-
down from pump 926, while operating with
the slurry recycle system, flows into hydro-
clone No. S412A, which is a Dorr-Oliver
type FR dorrclone, 12-inch size, designed
for 232 gpm, and a separation range of
36 to 46 microns. The feed enters tangen-
tially into the upper section of the dorr-
clone at sufficient pressure to support the
vortex action of the slurrv in the unit.
Centrifugal forces in the vortex throw the
coarser particles in the feed to the walls of
the cone, where they collect and pass down
ward and out of the unit through the apex
valve and tailpipe. The fine particles move
to the inner spiral of the vortex, and to
gether with most of the liquid, are dis
placed upward into the vortex finder and
OPERATIONAL EXPERIENCE
At Roswell several operational difficulties
were experienced which led to modifications
of the original equipment. From these in
adequacies some experience for future de
signs can be obtained. The greatest number
ION-EXCHANGERS
DIFFICULTIES ENCOUNTERED
(1) The monel screens supporting the
resin beads pulsed and finally ruptured due
to fatigue failure. The high pressure (125
psig) of the well pump furnishing the brine
and the cyclic operation of the ion-
exchanger unit, together with inadequate
support, were the causes.
(2) The diaphragm control valves on the
ion-exchanger's flow lines often jammed
and seized, stopping operation. The reason
was the inability of the valve stems to hold
lubrication on their surfaces and somewhat
weak valve operators.
666
out the overflow pipe.
Ball Mill No. 3412C: The underflow from
hydroclone No. 3412A flows into ball mill
No. 3412C. The ball mill, filled with 4.150
pounds of one-half inch diameter by one-
half inch long Burundium high density
grinding cylinders, reduces the size of the
calcium sulphate crystals from larger than
36 microns to about 5 microns. The mill is
60-inch diameter by 48-inch length, with
a capacity of 469 gallons, and is lined with
two and one-half inch thick white, high
density formed block.
Clarifier Thickener Tank: The thickener
is 45 feet in diameter and 12 feet high and
has a flat bottom and open top. The thick
ener paddle, operating at 0.145 rpm. fur
nished by Eimco Corporation, spans the top
of the tank and has rotating arms that
sweep the settled sludge toward the center
discharge. The motor drive and reduction
gear are located on a superstructure above
the thickener.
of modifications was needed in the degasifier
and the ion-exchange units. Below is an
outline of the major difficulties encountered
and the remedy or improvement.
IMPROVEMENT OR REMEDY
The monel screens were reinforced with
subway grating to cut down the pulsing
and flexing of the screens. Grating was in
stalled on both sides of the screens and
held in place by cross angle supports.
(Fig. 255).
In addition, two stages were removed
from the raw brine well pump to reduce
the inlet pressure to the ion-exchanger
from 125 to 90 psig. Also a pressure control
valve was installed.
These three modifications have solved the
screen problem. It is significant to note that
the strength of these screens may determine
the maximum limiting pumping pressure
when designing an ion-exchange tank.
This was solved by having the valve stems
pressure-coated with molybdenum sulphide.
When oiled, molybdenum sulphide retains
oil on its surface, which then acts as a
lubricant.
 DIFFICULTIES ENCOUNTERED
(3) The ion-exchange system did not
remove 75 per cent of the calcium ions as
originally intended. This was due to un
satisfactory flow arrangement by which the
blowdown brine was able to dilute the pur
chased salt regenerating fluid. Another
cause was the contamination of the resin
by iron contained in the regenerant brine.
(4) The present operation of the ion-
exchanger still leaves room for improvement.
DEGASIFIER (FIG. 257)
DIFFICULTIES ENCOUNTERED
(1) The choice of porcelain Raschig
rings was unfortunate since they could not
withstand the surging of the feed. They
broke into small pieces, which were un-
usable, and plugged the outlet holes. The
broken rings allowed channeling and a
decrease in area of 40 to 50 per cent.
(2) The surface of the overhead con
denser was too small.
(3) The vacuum pump did not have
sufficient capacity.
IMPROVEMENT OR REMEDY
FIGURE 255. SKETCH OF NEW
HOLD-DOWN GRATING IN
COCHRANE ION-EXCHANGE
UNIT.
The iron contamination of the resin was
removed by washing with oxalic acid.
Internal headers were installed and a
new control center was installed, which
made the primary regeneration a down-
flow regeneration instead of upflow. This
increased the contact between resin and salt
in the brine. New headers were installed
a few inches above the resin to decrease
dilution produced by the volume of water
above resin level (Fig. 256) .
It should be noted that regeneration was
the chief problem encountered with the
exchange system and is of prime importance
for the proper functioning of the ion-
exchange unit, and for the system as a
whole.
New tests are continually made and it is
hoped that an increased removal of calcium,
magnesium, and sulfate ions can soon be
achieved.
IMPROVEMENT OR REMEDY
The Raschig rings were replaced by
Maspac, a trade name for polypropylene
ribbed Berl saddles. No further trouble
with breakage occurred.
A second condenser with a surface of 92
sq ft was installed above the old condenser.
A second vacuum pump was installed
parallel to the old pump. Its capacity, 260
CFM, brought the total to 400 CFM. (It may
667
 DIFFICULTIES ENCOUNTERED IMPROVEMENT OR REMEDY
be noted here that the indication is that
items 2 and 3 were the critical and marginal
componentes of the degasified design.)

(4) The few distributing pipes did not
distirbute evenly over the whole area of the
upper piping.
The modified system has a monel pipe
which delivers the feed to a perforated
plate. Л few inches of water build up on
the plate, and this allows for even
distribution.

(5) The acid-brine mixing chamber and
injection nozzle were made of stainless steel,
which corroded quickly. Also, the original
design of baffles did not effect proper
mixing.
Injection nozzle for the H,SO, was
changed to teflon and decreased to a mini
mum diameter of 0.1 inch. The acid mixer
was set up with three orifice mixers made
of monel, 18 inches apart, with two to five
psi drop across each. It was made of rubber-
lined steel.

REGENERANT
SERVICE IN BLOWfXMM IN
RINSE IN BACKWASH OUT
DISPLACE IN

LIQUID

.PURCHASED SALT
i SOLUTION IN

NEW SPRAY HEADER

SIN

GRATING (TYP)
.SCREEN (TYP)
GRATING (TYP)

LIQUID

BACKWASH IN SERVICE OUT

PURCHASED SALT SOLUTION OUT
DISPLACE OUT
RINSE OUT
REGENERANT SLOWDOWN OUT

FIGURE 256. CUTAWAY VIEW OF ION-EXCHANGER WITH

PRESENT OPERATING CYCLE.
 DIFFICULTIES ENCOUNTERED
(6) The placement of a flow regulator at
the outlet rather than at the inlet of the
degasifier led to pulsating in the degasifier
which caused an unsteady performance.
PIPING
DIFFICULTIES ENCOUNTERED
(1) The application of fiber cast piping
at many locations in the plant seems to
have been incorrect as most of it leaked
or broke up during surging or high pres
sure use.
(2) The return bends of heat exchangers
eroded and corroded in a relatively short
time because of highly turbulent flow con
ditions.
EVAPORATORS (FIG. 258)
DIFFICULTIES ENCOUNTERED
(1) The lower half of the evaporator
domes corroded; they should have been
coated by a preventive agent.
(2) The evaporator allowed entrained
liquid to reach the vapor-compressor; this
could have pitted or otherwise damaged the
blades of the compressor and made neces
sary continual cleaning at short intervals.
(3) The water level in the evaporator
was too low and thus vapor formed within
the tubes.
VALVES
DIFFICULTIES ENCOUNTERED
(1) Rubber seal rings around moving
discs of butterfly valves dislodged. This was
due to the action of brine on the rubber
seal and caused the seals to swell. In the
case of such valves operated by diaphragm
motors, the valve stems failed in shear.
IMPROVEMENT OR REMEDY
A surge tank was placed before the 906
pump, serving two purposes. First, it ab
sorbed the pulses from the cyclic operation
of the ion-exchanger, and second, it served
as a constant supply for the 906 pump.
The flow control was put on the outlet
of the 906 pump to give constant flow rate
to the degasifier.
IMPROVEMENT OR REMEDY
The fiber cast piping was for the most
part replaced by steel piping.
The return bends were lined with penton
resin,
IMPROVEMENT OR REMEDY
The evaporator bottoms were cleaned
down to the metal and painted with epoxy
resin.
A fine wire mesh with no straight path
through it was installed. The entrained
droplets collect on the mesh and eventually
drop back into the evaporator. A baffle to
force the vapor through the demister and a
spray to wash away the salt from the mesh
pad were also installed.
The set point on the evaporator level
control was adjusted so that the level was
increased to 11 feet above the upper tube
sheet. We have found that even this higher
level is not fully sufficient to eliminate all
vapor formation in the tubes.
IMPROVEMENT OR REMEDY
These rubber-sealed butterfly valves were,
for the most part, replaced by gate valves,
669
 iNFW I
Or
rrj-i

modification?
I. NEW PACKING MASPAC So. HOOFED ACD-FEED MIX CHAMBER
WfJH ORFICE MIXERS
2. NEWSURWOE 5b. NEW ADDEXTENDtJG
-FEED NOZZLE MADECPJFC£
OF
92 SOFT TEFLON TO FTRST
1 NEW VACUUM PUMP PUKED FLOW CONTROL VALVE AT
DISCHARGE OF PUMP 90
FEEDPIPE
4b. NEW
TRAYPERFORATED
ALSO HOLDS DISTRIBUTION
DOWN PACKING

FIGURE 257. SKETCH SHOWING MODIFICATIONS

TO DEGASIFIER.

670
 COMPRESSOR
DIFFICULTIES ENCOUNTERED
(1) Misalignment of the compressor was
the major cause for shutdown. It caused 'he
moving blades to foul the moveable vanes.
Iron chips mixed in with the grouting,
which supports the foundation plates, were
found to be responsible, because some of
the iron was converted to ferric oxide which
has a much larger volume.
(2) One coil on the 2,500 hp motor
burned out. Insufficient monitoring of the
motor coils, which could have exposed
operating difficulties in the motor, was the
cause.
SLURRY RECYCLE SYSTEM
DIFFICULTIES ENCOUNTERED
(1) Before the installed slurry recycle
system could be used, pilot plant studies
(ref. 11) revealed that the installed system
probably would not work satisfactorily be
cause the operation temperature was too
low.
THE FUTURE ASPECTS OF THE VAPOR-COMPRESSION SYSTEM
INTRODUCTION
To assess the future of this type of
evaporation system, it is necessary to cor
relate it with respect to investment and
operations costs with the other two systems
for which demonstration plants have been
built. These are the multiflash evaporation
system and the multieffect evaporation
system.
The investment and operating costs of
these three systems have to be compared,
and an evaluation made on an equal basis
of the capital costs and operating costs.
This will determine whether one system
alone, or a combination of several methods,
would represent the best solution for de
salination.
In discussing the investment and opera
tion costs, various cycle and equipment
improvements which can be expected in the
near future and their effect on the cost
picture will be discussed and assessed.
CAPITAL COSTS
Table CVI shows the tabulation of the
capital cost of various sizes of normalized
IMPROVEMENT OR REMEDY
The grouting under the compressor was
replaced by an aluminum compound which
does not "grow" with time.
Additional temperature detection devices
were installed which automatically shut off
the motor before burning out could occur.
IMPROVEMENT OR REMEDY
The slurry recycle system was therefore
completely reconstructed so that it received
the brine at a higher temperature. It uses
blowdown brine from second effect at a
temperature of approximately 216° instead
of 80° F as before. The increase of tempera
ture was necessary because of inverse solu
bility of calcium sulfate in brine. The
present design has been discussed before.
plants similar to the:
(1) Former Point Loma sea water multi
stage flash evaporation system;
(2) Freeport sea water multieffect evapo
ration system;
(3) Roswell brackish water compression
evaporation system.
The investment cost for plants larger
than 1 mgd are considerably smaller per
production unit. These construction costs
have -been escalated to sizes of 8, 10, 14,
and SO mgd (refs. 13.15). The unit cost
per gallon per day of water produced may
reach a level of $0.75/gpd for the 50 mgd
size plant (Table CVI) .
No plant of this size has yet been built.
However, the cost estimates are fairly accu
rate and can be used as a basis for cost
evaluation.
A breakthrough greatly reducing these
investment costs can be expected only when
considerable improvement of the evaporat
ing capacity of the surfaces installed can be
achieved. A great reduction can also l>e
expected, however, from a standardization
of the design. Manufacturing the compo
nents in large quantities in factories and
 FIGURE 258. SKETCH OF MODIFICATIONS TO EVAPORATOR
DOME, SECOND EFFECT.
transporting them in large units to the
building site would be an important step
toward lowering investment costs.
A number of cost studies for the 50 mgd
plant size (ref. 15) are available. Most of
them, however, intertwine the cost evalua
tion with power production so that the
figures given in that report are somewhat
lower as compared to those given for 8
and 14 mgd size plants (ref. 13) .
672
OWNING AND OPERATING COSTS
The present owning and operating costs
of a normalized plant of 1 mgd capacity
are given in Table CVII.
In comparing the costs for these normal
ized plants of 1 mgd, it can be seen that
the multiflash system apparently has the
lowest operating ' costs. This is somewhat
misleading because it seems to indicate that
a multiflash type normalized plant has
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674
lower total cost, maintenance cost, and
energy requirements than the other types,
which is not actually the case.
Only the utility costs in these three plants
differ greatly. The majority of the power
was produced at San Diego in back pressure
with a very low heat cost so that the unit
cost of the power produced was less than
half of that which is charged in Roswell.
Therefore, at present Roswell has to bear
considerably higher power costs.
Roswell is further loaded with high
chemical costs which are peculiar only to
this brackish water plant. It is hoped that
these additional costs for chemicals can be
eliminated in the very near future.
FUTURE ASPECTS FOR REDUCING THE
OWNING AND OPERATING COSTS
An economic evaluation of the cost figures
for 1,000 gallons of potable water produced
by a normalized vapor distillation system
shows that at present for a plant capacity
of 1 mgd, the following apportioning can be
expected (Table CVIII) .

TABLE CVIII. Apportionment of Owning and Operating Costs Plant Size: One mgd
Total owning and operating: costs for producing 1,000 gallons of
potable water from saline sea water
Group Coat group Cost Percent
(Cents/1,000 gal)
I Cost of utilities, energy, power and beat 44.3 81.40
II Cost for chemicals to be used in the process 1.6 1.18
III Cost for labor, administrative functions, 42.5 80.10
supervision and maintenance
rv Cost for amortization and interest for 52.9 37.87
capital invested—taxes, insurance
Total expense per 1,000 gallons 141.3 100.00

The figures of this table are taken from the owning and operating costs for produc
the cost figures of LTV plant shown in ing 1,000 gallons of potable water from
Table CVII (See also ref. IS) . saline sea water are shown in Table CIX.
For a multiflash plant of 50 mgd capacity,

TABLE CIX. Owning and Operating Costs for a 50 mgd Plant

Cents Per cent
Group I Utilities and energy (power and heat) 20.6 81.61
Group II Chemicals 2.7 4.16
Group III Labor and management 6.7 10.83
Group IV Amortization, taxes and insurance 35.0 63.90
Total expense per 1,000 gallons 64.9 100.00

The figures of Table CIX are taken from
reference 15. These cost groups also reflect
the fact that the design of the large plants
will be somewhat more refined than the
present ones. They will have more stages,
more chemical pretreatment of the water,
and higher operating temperatures.
Table CIX shows that the cost relation is
greatly changed and that the cost factors
of the different groups receive different
weights.
The cost for labor assumes a small role,
and the mai.i load is placed on the cost of
the utilities (Group I) and on the cost for
amortization, taxes and insurance, etc.
(Group IV) , which mainly depends on the
investment cost, the design, and conse
quently the evaporation capacity of the
units. It is obvious that design improve
ments are very important factors, since
they reduce the overall investment and in
this way decrease the amortization. The
cost factor for the energy consumption,
however, is of equal importance.
From Table CIX it can be seen that the
cost for labor maintenance and management
Incomes rather small and is reduced more
and more when the size of the plant is
enlarged. For countries other than the
United States, this figure assumes an even
smaller value.
The cost of chemicals has an increased

675
 rate and will reach a level of about 2.7 efficiency of about 70 per cent so that the
per cent for large sea water conversion heat required for 1 kw can be equated to
plants and an even higher level for brackish 5.000 Btu/hr of heat consumption. For
water plants having more undesirable condensation about twice this heat, or about
constituents. 10,000 Btu/hr in fuel heat, would be
The aspect of utility or energy costs needed. Since large modern plants supply
reduction is discussed in the next para ing energy for water conversion will be
graphs. The aspect of cost decrease by cycle built combining power and heat, the figure
and equipment improvement is also of 5,000 Btu per kwh can be assumed as
sufficiently correct for our purposes.
expounded.
Fixed Charges
COMPARISON OF THE UTILITIES OF THE
MAJOR EVAPORATION PROCESSES The fixed charges for the power produc
ON AN EQUAL BASIS tion equipment are found, assuming:
The energy for conversion of saline water Load factor: operating time
to potable water is needed in the form of (SSOdays) x (24 hr) = 7,920 hr/year
power and also in the form of heat. Both Investment cost for power
forms of energy can be either purchased or equipment without heat
produced in a combined power-heat plant source $80.00/kw
erected simultaneously with the water con Fixed charges: amortization—
version plant. The expected investment and 20 vears at 4 per cent
operating cost of the energy so produced interest equal to: 7.4%
will be established. The power and heat
requirements of the three types of evapora Taxes, etc. 2.0%
tion systems will be shown in Table CX. Supplies 05%
The cost of energy for the three types of Total fixed charges 9.9%
evaporation systems are shown in Tables
CXI and (All A comparison of these costs _Power cost. : Fixed charges
2— —
will ascertain which system has the lowest per kwh
utility expenditure.
$80.00 x 0-099 = 0Momu
For this comparison, the energy consump 7520
tion of normalized 1 mgd demonstration
plants can be used. These data are taken Heat Production
from the operation reports of the 1 mgd
size plants. Fuel
The production cost of heat depends on
Owning and Operating Cost of Power and the fuel price. Assuming a fuel cost of $050
Heat Produced in a Utility Plant Adjacent per million Btu for large plants and an
to a Saline Water Conversion Plant: These average production efficiency of 80 per cent,
costs are establshed here for steam power it can be assumed that the cost per million
plants. They will not be greatly different Btu is therefore $0.25/million Btu. For the
for gas turbine plants with boilers heated low pressure steam with 1.000 Btu/lb, the
by the exhaust of the gas turbines. No labor cost is 25.0 ccnts/1,000 lb of steam.
costs were included in these computations,
assuming that labor and management are Fixed Charges
furnished by the saline water conversion
plant. The cost for labor and management The fixed charges for the heat produced
changes considerably with the size and load can be computed assuming:
factor of the plant. The charges for this Load factor: operating time
group of costs for the size of plants under (SSOdays) x (24 hr) = 7,920 hr/ycar
discussion are rather small—about 5 per Cost of heat equipment, piping.
cent or less of the total cost of energy. control, buildings: $9,000
Power Production Cost per million Btu/hr of heat
produced.
Fuel Fixed charges: amortization—
The most economical method for power 20 vears at 4 per cent
production is, of course, the combination interest equal to: 7.4%
of power with heat production. For most Taxes, etc. 2.0%
conversion plants this combination is Supplies 05%
feasible. It can be assumed that power in
back pressure can be raised with an overall Total fixed charges 9.9%

676
 TABLE CX. Evaluation of the Energy Requirement! of the
Three Major Evaporation Processes Presently in Use
Energy per 1,000 gallons of water
Type of energy Heat Btu/lb Power Heat
Type of system of product kwh Btu
Multistage flash
evaporation system Power _ IS _
86 stages -
San Diego Plant I Heat 100 883.000
Multieffect LTV
evaporation system Power _ 9 _
12 stages
Freeport Heat 100 - 838.000
Multieffect vapor _
compression system Power 70
2 Btages
Roswell Heat 2.88 - 24,000

Heat production: fixed charges — in back pressure using a heat rate of 5,000
$9,000 x 0 099 Btu/kwh.
7,920 „ , 0.3625 Per kwh
Fuel: 5,000 x 10* 0.18125 cents
= 1155 cents/million Btu
Fixed charges 0.100 cents
Total Cost of Heat Production per
Million Btu Total 0.28125 cents
Fuel $0.25 per million Btu with other incidentals,
Fixed charges 0.1125 per million Btu total cost 0.30 cents/kwh
Total $0.3625 per million Btu Comparison of the Major Systems: Com
equal also to 36.25 cents per 1,000 lb of low- paring the three distillation systems with
pressure steam. respect to the cost of energy consumption,
we find the following energy cost per 1,000
Total Cost of Power Production per kwh gallons of production, based on the experi
It is assumed that the power is produced ence obtained when operating a 1 mgd plant.

TABLE CXI- Energy Costs for One mgd Normalized Plants

Energy requirements per
1,000 gallons Cost per 1,000 gallons
Price 0.3 cents 86.25 cents
Type of Btu Power units kwh 1 million Btu
normalised in Total
plant lb kwh* Heat* energy power heat total
kwh Btu Btu cents cents cents
Multistage flash
(1) evaporation 16 76,000 4.5
system 908,000 34.8
36 stages 833.000 29.8
(San Diego) 100
Multieffect
(2) evaporation plant 9 45,000 2.7
12 stages 878,000 29.8 82.5
(Freeport) 100 833.000
Double-effect
(8) vapor compres 70 350.000 21.0 21.87
sion plant 874.000 0.87
(Roswell) 2.88 24,000
* One kwh assumed equal to 5,000 Btu.

It should be poaible to achieve for larger energy figures. It can be assumed that for
plants a reduction in Btu/lb of water pro 50 mgd normalized plants, the cost of
duced and arrive for large plants at lower energy will be as shown in Table CXII.

677
 TABLE CXII. Energy Requirements and Their Costs for 50 mgd Normalized Plants
Energy requirements per
1,000 gallons Cost per 1.000 gallons
Price 0.3 cents 86.25 cents
Type of Btu Power unit* kw 1 million Btu Total
normalized in Total
plant lb kwh Beat energy power heat
kwh Btu Btu cents cents cents
Multistage flash
(1) evaporation 15 76.000 4.5
system 576,000 22.62
66 stages 60 500.000 18.16
Multieffect
(2) evaporation 9 674.770 20.82
system 618.770 23.52
16 effects 6* 46.000 2.7
Triple-effect
(8) vapor- 65 275,000 16.6
compression 289,000 17.00
system 1.68 14.000 0.60

Basis: Heat costs S6.25 cents/million Btu
(includes fixed charges). Amortiza
tion and interest—7.4 per cent over
20 years at 4 per cent interest rate,
0.5 per cent for supplies, and 2.0 per
cent for taxes.
Total fixed charges 9.9 per cent.
Operating time—7.920 hr/year (350 days).
Power cost 0.3 cents/kwh (including fixed
charges) .
FUTURE ASPECT FOR REDUCTION
OF THE ENERGY COSTS OF
DESALINATION SYSTEMS
The Use of Power Produced: Hitherto,
the main attack on the energy costs was
made by combining these plants with power
producing plants and a credit for power
production was assumed in order to reduce
the operating cost per thousand gallons.
Extensive computations for this combina
tion were prepared (refs. 13, 17, 18) .
The purpose of this combination of
power and heat is to produce the power in
back pressure at a heat rate of 5,000 Btu/
kwh or less.
In the effort to reduce the overall opera
tion costs, power production and also the
sale of power had to be coupled with water
desalination. This is an approach which is
not always practical or feasible from a com
mercial and/or other points of view.
Combination of Vapor-Compression with
Otlier Evaporation Systems: The vapor-
compression system has the lowest heat rate,
provided the power is produced at a heat
rate not to exceed 5,000 Btu/kwh.
The comparison with other systems,
which was given in Tables CX through
CXII, has shown this. It is, therefore, often
fi78
preferable to utilize the power produced in
back pressure not for sale to the outside to
consume it but within the desalination plant
itself and to produce part of the potable
water by means of a vapor-compression
process. This vapor-compression system can
be operated in parallel with a multi-effect
or mukifiash evaporation system.
This combination is feasible for power
production when either gas turbines or
steam turbines are used (Fig. 259) .
It is important that the energy consump
tion of the two systems be arranged so that
the power and heat consumption of both
systems is balanced relative to each other.
The power used must then be produced
at a heat rate not to exceed 5.000 Btu/kwh.
This low rate can be achieved when all
steam or heat exhausted by the turbine is
usefully utilized in both evaporation
systems.
The Jet Compression System (Figs. 260 and
261: The greatest part of the capital cost
of a mechanical vapor-compression system
is the power producing machinery together
with the compressor.
Another approach can be suggested by-
substituting the vapor-compressor and its
drive by a high pressure boiler and a jet
compression system. More economical than
using high pressure steam for this purpose
is utilizing high temperature, high pressure
water of 1,000 to 1500 psi to compress the low
pressure steam exhaust from and an evapo
rator effect of a lower stage to the pressure
level of a higher stage. The excess steam
produced by this compression process will
serve as a steam source for feeding a multi-
effect evaporation, or multistage flash evap
oration system.
 The high pressure water produced for
driving the jet is raised from a temperature
level of only 550° up to 600°F. It is, there
fore, still possible to produce a considerable
amount of power by topping gas turbines.
The use of high temperature water when
compared to steam is found to be 15 to 20
per cent more economical for compressing
steam or air over a relatively small pressure
range. The high temperature water develops
steam and, due to its high density, it will
attain a lower velocity compared to that of
superheated steam. The water contained in
the steam is separated, collected, and refed
to the high pressure boiler.
This system, for which process patents

AIR
GAS
ELECTRIC GENERATOR
PRODUCING POWER
FOR PUMPS

WASTE K
BOILER
MULTI EFFECT VAPOR
OR MULTI FLASH COMP
STEAM EVAPORATOR SYSTEM
TEMS
SYSTEMS
T
PRODUCT PRODUCT

ELECTRIC GENERATOR
PRODUCING POWER FOR PUMPS

HIGH STEAM .
PRESS
BOILER TURBINEA I

VAPOR
COMP
MULTI EFFECT SYSTEM
OR MULTIFLASH
EVAPORATOR
SYSTEMS

PRODUCT PRODUCT

FIGURE 259. GAS TURBINE POWER PRODUCTION UNIT.

STEAM TURBINE POWER PRODUCTION UNIT.
 have been applied, has the greatest advan
tage, when compared to a mechanical vapor-
compression system in that investment costs
are much lower and consequently the
amortization charge is greatly reduced.
Maintenance is equally diminished since
power machines are replaced by boilers
and jets.
Figure 261 illustrates system design and
Tables CXIII and CXIV illustrate the heat
balance.
The design of the combined system shown
in Figure 261 and its heat balance were
prepared using the heat balance figures of

HOT FEED FROM HEAT

FIGURE 260. DESIGN OF TWELVE-EFFECT LTV EVAPORATOR

SYSTEM WITHOUT JET.
HOT FEED FTOM
HOT FEED FROM HEAT EXCHANGERS
38»,7WfHR, 2K>°F

-PRODUCT STAGES I TO XII 397, 568>/HR

-ADDITIONAL PRODUCT 274,951 '/HR

FIGURE 261. DESIGN OF TWELVE-EFFECT LTV EVAPORATOR

SYSTEM WITH JET.
680
the present Freeport plant for the fourth
through twelfth effects. This was done in
order to illustrate the increased heat econ
omy obtained by this system in comparison
to an ordinary twelve-effect multidistillation
system.
In Table CXIII a resume of the heat
balance for the twelve-effect system, with
and without jet, is given.

TABLE CXIII. Mass and Energy Balance 12-Effect LTV Evaporator System
with and without Jet
lt-etage lt-ttage
eyatem
without with
water jet TOTAL PRODUCT water jet
0 Additional product from stages I, II, III 274,981 lb/hr
397,668 lb/hr Product from stages I to XII 897,568 Ib/hr
397.568 lb/hr Gross product 672,499 lb/hr
81,600 lb/hr Purchased steam 0
886,068 lb/hr Net product 672,499 lb/hr
Appro*. 1 med Total net product 1.96 mgd
MASS BALANCE
IN
0 Additional brine feed 489,768 lb/hr
489,800 lb/hr Present brine feed 489.800 lb/hr
489,300 lb/hr Total mass in 929,068 lb/bi
OUT
866,068 lb/hr Total net product 672,499 lb/hr
122,832 lb/hr Blowdown from evaporator I to XII . 0
0 Blowdown from evaporator I to III . 183,887 Ib/hr
0 Blowdown from evaporator IV to XII 122.332 lb/hr
900 lb/hr Steam 900 lb/hr
489,300 lb/hr Total mass out 929,068 Ib/hr
HEAT NEEDED
For 12-stage For jet
Steam system system 1,000 psi
81,500 lb/hr @ 1,272 Btu/lb = water 121.694 lb/hr ® 642 Btu/lb =
40,068,000 Btu/br 65.903,948 Btu/hr
ЯДА Г RETURNED
31,600 lb/hr @ 71.6 Btu/lb = Water from separator 82,724 lb/hr 208 Btu/lb
2,252,226 Btu/hr Product water 88,870 lb/hr 71.5 Btu/lb
121,594 lb/hr 164.6 Btu/lb
20,014,372.4 Btu/br
NET HEAT NEEDED
40,068.000 Btu/hr 65,903,948 Btu/hr
2,262.226 Btu/hr 20,014.872.4 Btu/hr
87.816.775 Btu/hr 45,889.576 Btu/hr
HEAT CONSUMPTION PER POUND OF PRODUCT
87.815.776 Btu/hr = 103.3 Btu/lb 45,889,676 Btu/hr = 68.24 Btu/lb
866,068 lb/hr 672,499 lb/hr -
POWER BALANCE
Generator 6,000 kw
Feed pump to heater 200 kw
Gas compressor 150 kw
Other fans, etc 150 kw
Net available 4,600 kw

TABLE CXIV. Comparison of 12-Effect LTV Evaporator System

with and without Jet
HEAT CONSUMPTION PER POUND OF PRODUCT
Per cent Heat
Net product total consumed Btu/lb
12 stage system
without jet 366,068 64.4 87,816,775 108.8
Additional
(with jet) 306,431 46.6 8,078,801 26.4
Total 672.499 100.0% 46,889,676 68.24

681
 TABLE CXV. Comparison of Heat Consumption of a 12-Effect Evaporation System
with and without the High Temperature Water Jet
Water
Typ« of Production production Heat consumption
system increase (%) (ft/hr) total net Btu/Ib needed
1. 12 effects 100.0 868.088 87.81Б.775
without Jete (basis) 1.0x10« kpS
2. First 3 effects of 808,481
a 12-effect system 82.7 0.8x10* rod 8.078.801
with jet
2. Total system 188.7 672.499 46.889,676
with Jet 1.8x10« rod

Tabic CXV illustrates the savings in heat
obtainable, which are in this case 33.9 per
cent over the previous rate. To this heat
rate, a power consumption rate of 9 kwh
per 1,000 gallons has to be added.
Of course, if the evaporation system is
extended in the temperature range up to
500°F or in the number of effects (16
instead of 12) , the high temperature water
jet principle is equally well applicable and
will show considerable savings.
Table CXVI shows the energy cost of the
jet part of the steam alone. These figures are
given only as an illustration to indicate
how the combination of the jet design with
a multieffect system reduces the combined
energy costs.

TABLE CXVI. Energy Consumption and Operating Costs of Jet System

per 1,000 Gallons
Energy requirements per Cost per 1,000 gallons
1,000 gallons
Price 0.8 cents 86.25 cents
Type of Type of Btu Power Heat unita kwh 1 million Btu Total
system energy lb In kwh power heat
Kwh Btu cents cents cents
High Power • 46,000 2.7
temperature
water jet Heat 28.8 240,000 8.87 11.87

Total 286,000
Note: Basis of this table saine as for Table CXII.

EXTENSION OF A COMBINED JET MULTI- Per cent

EFFECT SYSTEM BY A MECHANICAL
VAPOR-COMPRESSION SYSTEM
The relatively moderate temperature level
of the high temperature water between
500° and 6O0°F permits the use of gas
turbine exhaust gases for producing the
high temperature, high pressure water. The
power produced by the gas turbines can be
used for raising more water in a mechanical
vapor-compression system or by sale of the
power, if this possibility prevails.
If it is decided to use the power energy
produced for additional water conversion,
then a plant design as shown in Figure 262
could be used.
In the arrangement of Figure 26?, the
distribution of production would be about
as follows:
682
26.3 1.0 mgd by multieffect evapora
tion system when no jet is used.
21.0 0.8 mgd added when high tem
perature water jet is added.
52.7 2.0 mgd added when mechanical
vapor compressor is added.
100.0 3.8 mgd.
All power would be produced in back
pressure, permitting maximum utilization
of the heat of the fuel.
The average energy cost of such a com
bined system would be reduced to 11 to 12
cents for fuel costs alone and 15 to 16 cents
per 1 ,000 gallons, including fixed charges.
The correct balancing of the vapor-
compression part of this desalination system
with the evaporation part, utilizing the
latent heat of the steam, permits reduction
 GAS
COMPRESSOR
ELECTRIC GENERATOR
PROOUONG POWER FOR
4 PUMPS
AIR

GAS
TURBNE

COOLED WASTE
GAS
v VAPOR

HEATER

fW4—kv\A

PREHEATER HIGH TEMP WATER>

WATER ,

WATER
SEPARATOR

A LARGER SMALLER 2 TO 4
HIGHER MULTI- MULTI - MULTI-
EFFECT LOWER
PRESS PRESS EFFECT EFFECT
STEAM EVAP'S STEAM EVAP EVAP
MMC UP-

PRODUCT PRODUCT
263% 527%

FIGURE 262. COMBINED HIGH TEMPERATURE WATER JET

VAPOR-COMPRESSION PLANT WITH A MULTIEFFECT EVAP
ORATION SYSTEM.

683
 of the energy of this combined desalination
system to a low level, which can hardly be
achieved in any other way.
FUTURE ASPECT OF REDUCING THE
FIXED CHARGES BY REDUCTION OF
INVESTMENT COSTS
Reduction in investment costs can be
achieved by increasing the output of the
evaporating surfaces. This means that the
same heat transfer surfaces would be able
to evaporate or condense more steam, either
by increasing their effectiveness or by
keeping them clean. Further approach to
the cost reduction has to be found in pre-
fabrication and normalization of the com
ponents.
The heat transfer coefficient of all surfaces
is affected by scale formation. The problem
of avoiding scale is of paramount impor
tance. Numerous studies have been made
to achieve this end, and the long list should
not be repeated in this paper.
Preventing Scale Formation
In judging methods to inhibit scale
deposits, the solubility product principle
has to be considered. Let us focus our
attention on the compound calcium sulfate,
consisting of calcium cations and sulfate
anions. The concentration of sulfate ions
times the concentration of calcium ions
must be less than a constant or precipita
tion (scale formation) will occur. A cation
exchanger which removes 60 per cent of
calcium ions is only half as effective as one
which removes 80 per cent:
[ca"] [soy] <K
Due to the solubility product principle,
it would appear that the removal of anions
subsequent to the removal of cations would
be beneficial. Work on this idea has been
done by the University of California (ref.
19) . The anion -exchange resins were pro
duced earlier than the cation -exchange
resins, but since they are not fully stable
they have not often been used. If a full
regeneration of cation- and anion-exchange
resins without purchased salt (with only
concentrated blowdown brine) were possible,
it would mean a great step in the right
direction.
Another approach for excluding scale
formation is the use of chelating agents.
There are a few such agents available, but
in general this material is rather expensive.
Tests are still under way to determine
whether this approach is feasible.
684
Addition of Surface Active Scale
Preventatives
Trace quantities of scale preventive
(surface active chemicals) could be added
to the feed to prevent scale-forming ions
from forming precipitates which adhere to
heat transfer surfaces. A scale preventive
was added to the feed at Roswell. This
appeared to stop scale formation (ref. 20) .
This scale preventive is absolutely nontoxic
and was approved by the U.S. Department
of Health. Very few satisfactory scale
preventives satisfy this condition and are
available at reasonable cost.
Increasing Heat Transfer Surface
Effectiveness
The heat transfer surface effectiveness
can be increased by increasing the inside
heat transfer coefficient (brine side) and
the outside heat transfer coefficient (steam
and condensate side) .
Inside Heat Transfer Coefficient
of Brine
The heat transfer coefficient inside the
tubes has been maximized by increasing
the velocity within the tubes. An investiga
tion (ref. 21) to determine the most eco
nomical velocity in forced circulation plants
considering all power and investment costs,
has ascertained that a velocity of seven to
seven and one-half feet per second seems
to Be the optimum for one-inch diameter
tubes. Eight feet per second is perhaps, in
some cases, slightly more advantageous.
However, the danger of erosion at these
velocities and small diameters is already
considerable. A velocity of seven to seven
and one-half feet per second, however,
produces high heat transfer coefficients for
brine at 212°F in one-inch O.D., 16 gauge
tubes of 2.440 to 2370 Btu/hr/ft'/°F and
for 160°F temperature these figures are
reduced to 1,970 to 2,090. A velocity between
7 and 8 feet can be considered as an opti
mum brine velocity for vapor evaporation
forced circulation plants.
Outside Heat Transfer Coefficient
of Condensing Steam
The possibility of increasing the conden
sation coefficient for steam was subjected to
a large number of investigations over the
last 30 to 40 years. Nusselt, Jacob, and
numerous leading men in the thermo
dynamic field have shown ways of improving
the condensation coefficient.
A very thorough investigation was made
about ten years ago at Yale University
 (réf. 22) . The investigation at Yale found
that it 'is possible, by adding dropwise
condensation promoters, to increase the
condensation heat transfer coefficient for
one-inch O.D. tubes to 5,000 or even 9,000
Btu/hr/ft'/T. The overall heat transfer
coefficient could, therefore, be increased by
50 to 80 per cent if a dropwise condensation
promoter is introduced. The main diffi
culty using the condensation promoter
method of operation is that it would be
difficult to select a promoter which is
acceptable for human consumption. The
Yale study used lard oil as their condensa
tion promoter.
Conclusion of Investment Cost Reduc
tions: There are many methods to reduce
the investment costs of desalination plants.
It is anticipated that the review of the
operating data from the demonstration
plants and the research work sponsored by
the Office of Saline Water and other organi
zations will continue to make desalination
REFERENCES
1. The Proceedings of the Eighth Annual
New Mexico Water Conference (July
1-2, 1963) .
2. Specifications for Demonstration Plant
No. 4, Roswell, New Mexico, Specifica
tion no. 224 PB 181116.
3. Specification for Demonstration Plant
No. 4, Roswell, New Mexico, Specifica
tion no 224 PB 181116, pp. 5-11.
4. Roswell, New Mexico, Demonstration
Plant No. 4, U.S. Geological Survey
Water Analysis (Dec. 29, 1964) .
5. Properties of Sea Water and Its Concen
trates Extended Range, Supplement to
Report no. 43B, W. L. Badger Associ
ates, Inc. (June 22, 1960) .
6. Wrightsville Beach, North Carolina,
Water Analysis (Aug. 4. 1964) W. R.
Lab. no. NC42018.
7. Chemical Engineers Handbook, 4th
Edition, pp. 3-92, Tables 3-138.
8. Management and Operating Contrac
tor's Monthly Report of February 1965.
Saline Water Demonstration Plant No.
4, Roswell, New Mexico.
9. Management and Operating Contrac
tor's Monthly Report of May 1965. Sa
line Water Demonstration Plant No. 4,
Roswell, New Mexico.
10. University of California, Rept. no. 64-5,
Scale Formation in Saline Water Evap
orators, January 1964, Water Resources
Center Contribution no. 84, Figure 8.
11. Final Report, Seeding for Prevention of
plant investment costs lower.
CONCLUSION
The future aspects of vapor -compression
systems can be found in:
(A) Reduction of the energy require
ments by:
(1) Combining under one. roof differ
ent types of evaporation plants
where power and heat require
ments complement each other.
(2) Introduction of the high tempera
ture water jet principle for vapor
compression.
(B) Reduction of fixed charges by increas
ing the effectiveness of the evaporative
surfaces through scale elimination and
overall heat transfer coefficient in
crease.
If these favorable circumstances were
achieved, large plants would have consider
ably lower operating costs.
CaSO, Scale in LTV Evaporators at
SOOT, Results of Harbor Island Pilot
Plant Test (May-Dec, 1963) ; Rept. no.
486, by W. L. Badger and Associates,
Inc. (Dec, 1963) .
12. Report on Division of Demonstrations
Plants, by R. H. Jebens, Chief Engi
neering Services Division, Office of Sa
line Water, U.S. Department of the
Interior, OSW Washington Saline Water
Conversion Report for 1962.
13. A Study of Large-Size Saline Water
Conversion Plants, Bechtel Corp., San
Francisco, OSW Rept. no. 72 (Mar.
1963).
14. Second Yearly Report on the Operation
of the Roswell Vapor Compression
Plant (June, 1964) .
15. Cost Studies of Large Multistage Flash
Saline Water Conversion Plants, OSW
R&D Rept. no. 116.
16. Second Yearly Report on the Operation
of the LTV Plant at Freeport (June
1962 to June 1963) p. IV-5.
17. Pacific Southwest Water Plant, Office
of Saline Water, U.S. Department of
the Interior.
18. Dual -Purpose Water and Power Pro
duction Plants, R. H. Jebens, Office of
Saline Water, U.S. Department of the
Interior (April 7, 1964) .
19. Ion-Exchange Equilibrium Data in the
Design of a Cyclic Sea Water Softener
Process; Gerhard Klein, et al, Industrial
685
 and Engineering Chemistry, Process
Design and Development, vol. S. no. S
(1964) p. 280.
20. Management and Operating Contrac
tor's Monthly Report of January 1965,
Saline Water Demonstration Plant No.
4, Roswell, New Mexico.
21. Economic Evaluation Study of Distilla
tion of Saline Water by Means of
Forced-Circulation Vapor Compression
SUMMARY OF DISCUSSION
In answer to a question concerning the
cost of water at the plant at Roswell, New
Mexico, it was replied that the cost is about
$1.39/1,000 gal. Questions were asked con
cerning scale formation and whether or not
the size of the compressor could lie in
creased. The reply stated that scaling would
take place but that it is controlled by
Aspects D'Exploitation et Avenir de
la Distillation Par
Vapeur*
Paul L. Geiringer
Etats-Unis d'Amérique
L'usine de Roswell à compression de
vapeur, la plus nouvelle de quatre usines
de démonstration, a été construite pour
démontrer la possibilité de ce qui suit:
(1) La conversion d'eau saumâtre d'une
haute salinité en eau potable.'
(2) L'exploitation avec des concentrations
élevées de décharge.
(3) L'étude de deux méthodes de pré
vention de l'entartrage: échange io
nique et recirculation des matières en
suspension (boucs) .
(4) Le fonctionnement de machines de
compression de grande dimension.
(5) L'exploitation à des températures
d'évaporation de 110°C.
La première partie de l'exposé indique
que cette eau saumâtre contient 588 ppm
de calcium, 1.490 ppm de sulfate, 161 ppm de
• Tous les chiffres et numéros de tableaux se
rapportent à l'exposé principal.
686
Distillation Equipment; Office of Saline
Water, R&D ProgT. Rept. no. 21,
Dr. Dodge and Dr. Eshays.
22. Forced Circulation and Dropwise Con
densation Techniques for Improving
Heat Transfer Rates for Vapor Com
pression Evaporators; Office of Saline
Water, R&D Progr. Rept. no. 8, Yale
University.
ion-exchange and pH methods. It was also
stated that the 2,500-hp compressor can be
increased to 10.000 hp. A question was
asked about the removal of iron and organic
materials from the feed water. The answer
stated that there are no organic materials
present and that iron must be removed from
the resin bed by washing with oxalic acid.
Compression de
magnésium et 13 ppm de silice. Cette quan
tité de produits chimiques est devenue
spécialement difficile dans la conversion
car la concentration de NaCl atteignait
seulement 1,3% contre 3% pour l'eau de
mer, diminuant de cette manière la solubi
lité de ces produits chimiques indésirables.
Le cycle et l'équipement de Roswell sont
discutés dans la deuxième partie.
Les défauts rencontrés dans le passé et
les disposilions prises pour y remédier sont
le sujet de la troisième partie. L'expérience
acquise des difficultés rencontrées et les
manières d'y remédier peuvent être d'une
grande valeur pour les ingénieurs d'étude
de ce type d'équipement.
Les améliorations et l'éxpéricnce ac
quises sur l'équipement d'échange ionique,
ainsi que les travaux importants de labora
toire effectués, peuvent avoir une valeur
considérable dans l'avenir pour l'élimina
 tion de l'entartrage dans le fonctionnement
des installations futures. Les travaux pra
tiques et de laboratoire continuent et
semblent assez prometteurs.
L'aspect d'avenir des systèmes à compres
sion de vapeur est discuté dans la partie
IV.
L'investissement, les frais en matière de
droits de propriété et d'exploitation des
usines futures sont des facteurs essentiels.
Le coût de la construction influence
l'amortissement et le taux de financement
en augmentant les charges fixes ce qui
augmente le coût d'exploitation.
Le coût d'exploitation peut se résumer
en quatre groupes principaux:
Groupe I. Combustible et électricité.
Groupe II. Produits chimiques.
Groupe III. Main-d'oeuvre, entretien et
gestion.
Groupe IV. Charges fixes (amortissement,
taxes, assurance, etc.) .
Plus la dimension de l'installation
augmente, plus l'investissement, ainsi que
les frais d'intérêt et d'exploitation, dimi
nuent en proportion. Le coût de la produc
tion de l'eau potable est dominé par deux
facteurs principaux du prix de revient:
(1) Coût du combustible et de l'électri
cité (Groupe I) .
(2) Coût des charges fixes (Group IV) .
Par comparaison, tous les autres facteurs
de coûts n'ont qu'une importance assez
faible.
On a calculé et comparé le coût de la
chaleur et de l'énergie électrique pour les
trois principaux systèmes d'évaporation sur
une base égale (vaporisation instantanée en
étages multiples, effets multiples et com
pression de vapeur) .
Le taux d'énergie des trois systèmes d'éva
poration en cause a été déterminé d'après
les données d'exploitation des installations
d'essais et de démonstration de l'Office of
Saline Water de 3.800 m' par jour.
Si une centrale thermique est construite
près d'une usine de dessalement, l'énergie
pourrait être produite par des turbines, et
la chaleur d'échappement serait utilisée
pour fournir l'énergie thermique au sys
tème d'évaporation des usines type 1 (va
porisation instantanée en étages multiples)
ou type 2 (effets multiples) . L'énergie
pourrait être produite de cette manière à
un taux thermique ne dépassant pas 1,250
KcaykWh.
En suposant que ce taux thermique par
kWh soit maintenu, le système par com
pression de vapeur possède théoriquement
et pratiquement de loin les besoins d'éner
gie les plus faibles.
Afin d'arriver à des taux thermiques aussi
faibles par kWh d'énergie produite, il a été
souvent suggéré que les usines de dessale
ment du type 1 (vaporisation instantanée en
étages multiples) et 2 (effets multiples)
devraient être combinées avec une installa
tion de production d'énergie; ainsi l'énergie
en excès produite est vendue sous forme de
courant électrique à un service de distribu
tion proche. La combinaison de la vente
d'énergie avec le dessalement peut ne pas
toujours être pratique, car certaines raisons
économiques ou autres peuvent la rendre
impossible.
En général, il est donc plus pratique
d'utiliser un faible coût d'énergie pour la
production d'eau supplémentaire. On sug
gère que le programme total de production
d'eau d'une usine proposée soit étudiée en
sorte qu'une partie des besoins totaux en
eau soient couverts par un système du type
1 (vaporisation instantanée en étages mul
tiples) ou du type 2 (à effets multiples)
et une autre partie par un système à com
pression de vapeur (type 3) . On peut
obtenir des économies beaucoup plus élevées
par un équilibre correct des systèmes (voir
paragraphe 4.6 dans l'exposé principal)
que ceux qu'on peut obtenir par la vente
d'énergie à une installation de distribution.
Une autre méthode de réduction impor
tante des dépenses d'exploitation est d'em
ployer des compresseurs à jets d'eau à
haute température pour rendre plus dense
la vapeur s'échappant d'un étage d'évapo
ration inférieur si bien qu'elle peut être
utilisée pour le chauffage d'un étage plus
élevé. L'excès de vapeur produite dans ce
procédé est alimenté à un système d'évapo
ration à vaporisation instantanée a étages
multiples ou à effets multiples. On
peut de cette manière obtenir des écono
mies d'énergie de 35 à 50%. La consomma
tion de chaleur d'un système d'évaporation
à douze effets est réduite de 57 Kcal/kg à
environ 38 KcalДg d'eau produite.
L'eau à haute température, sous pression
de 70 à 105 kg/cm', utilisée pour entraîner
le jet, comparée à la vapeur surchauffée à
haute pression, fournit une économie accrue
de 10 à 20%.
Le niveau de production de température
pour élever l'eau à haute température de
93°C à 288 ou 315°C est relativement
modéré, si bien que l'on peut utiliser
l'échappement des turbines à gaz dans ce
but. Ceci permet en outre la production
simultanée d'énergie à un faible taux
thermique d'environ 1.250 Kcal/kWh.
La production d'énergie supplémentaire
bon marché rend possible l'utilisation d'un
système combiné d'injection, d'effets mul
687
 tiples et de compression de vapeur méca
nique. La proportion de production d'eau
potable d'une telle usine combinée serait
approximativement 263% du système d'éva-
poration à effets multiples. 21% du système
à éjecteur, et 52.7% du système multiple à
compression de vapeur.
Avec un coût de combustible de 80 cents
par million de Kcal, le coût d'énergie pour
le combustible utilisé pour le système
combiné serait d'environ 2.9-3,1 cents par
m* pour des usines importantes. Si les
charges fixes pour l'usine de production
d'électricité sont ajoutées au coût de l'éner
gie pour le combustible, les charges pour
l'électricité ne devraient pas dépasser
4-4,2 cents par m*.
L'équilibre correct des trois parties de ce
système lors de l'étude permet une réduc
tion des coûts d'énergie à un niveau faible
qu'il est difficile d'obtenir par tout autre
moyen.
Enfin, l'aspect d'avenir de la réduction
des frais d'exploitation pour la production
d'eau potable devrait inclure la réduction
des charges fixes qui peuvent provenir
d'une réduction de l'investissement néces
saire par kilo d'eau évaporée.
Une double attaque sur ces charges fixes,
qui devrait rendre une telle réduction d'in
vestissement possible, comprend:
(1) L'élimination de l'entartrage.
(2) L'augmentation du rendement des
surfaces d'évaporation en augmentant
la différence de température et en
augmentant le coefficient d'ensemble
de la transmission de chaleur.
ELIMINATION DE L'ENTARTRAGE
Pour de faibles concentrations de saumure
et de faibles températures (au-dessous de
93°C) la plupart des eaux salines ont
simplement besoin d'être traitées avec de
l'acide sulphurique et dégazées pour éli
miner l'anhydride carbonique et l'oxygène.
Le retrait de l'anhydride carbonique élimine
le danger de formation de dépôt de carbo
nate de calcium.
L'eau saline à des températures élevées
allant jusqu'à 135 ou 150°C et les facteurs
de concentration de la décharge de 3 pour 1
ou de 4 pour 1 et plus élevés, exigent un
prétraitement plus complet de l'alimenta
tion. Les systèmes d'échange ionique avec
régénération du résidu semblent être les
plus prometteurs. L'utilisation de sel acheté
dans des buts de régénération ne semble pas
pratique car le coût de ce sel est trop
élevé. On étudie également l'application
d'agents chélatiques et de matières anti
688
tartre tensioactives. Les systèmes de recircu
lation des matières en suspension (boues)
n'ont pas encore été suffisamment essayés si
bien qu'il n'est pas possible pour le moment
de juger de leur valeur.
AUGMENTATION DU RENDEMENT
DE LA SURFACE D'ÉVAPORATION
L'amélioration de l'échange de chaleur
a pour condition préliminaire l'élimination
de la formation du tartre aux températures
élevées. Si on est assuré de la non-formation
de tartre à ces températures plus élevées,
alors on peut augmenter le nombre d'étages
et le prix de revient de la production peut
diminuer par l'étalement accru de la
température et par la prise de production
supplémentaire des mêmes surfaces en raison
des plus grandes différences de température.
L'amélioration du coefficient de trans
mission de chaleur n'est possible que par
une augmentation du coefficient de trans
mission de la pellicule sur le côté saumure
et sur le côté vapeur. Le coefficient de
pellicule sur le côté saumure (intérieur
des tubes) peut être augmenté en augmen
tant la vitesse d'écoulement. Une vitesse
d'écoulement de 2,25 à 2,40 m/sec semble
être la vitesse d'écoulement optimale du
liquide lorsque l'on équilibre le danger
d'érosion et les coûts d'énergie. En utili
sant des vitesses d'écoulement de cet ordre
de grandeur, on peut s'attendre à des co
efficients de pellicule de saumure supérieurs
à 2.0OO aux températures au-dessus de
9S°C. Le coefficient de pellicule sur le
côté vapeur peut être augmenté par l'utili
sation des promoteurs de condensation par
gouttelettes. On a également à l'étude
d'autres méthodes telles que des tubes can
nelés lesquels, A l'heure actuelle, ne sont
pas d'une fabrication économique prouvée.
En bref, on peut dire que des augmenta
tions dans la température et le coefficient
amélioré de transmission de chaleur, ainsi
que des surfaces exemptes d'entartrage,
pourraient réduire les charges fixes de 20
à 30%. La réduction dans le coût de l'éner
gie à un niveau d'environ 3 cents pour le
combustible et d'environ 4 cents pour les
coûts d'énergie totaux, par m", et l'amélio
ration dans la prévention de l'entartrage et
l'échange de chaleur, ainsi que des tempé
ratures plus élevées, pourraient permettre
des chiffres de prix de revient de 8 à 9
cents par m' pour de grandes usines à
combustible fossile. Ceci constitue l'aspect
d'un avenir "prochain" des usines de con
version par évaporation.
 Эксплуатационные Стороны Дистилляции
со Сжатием Пара и Ее Виды на Будущее
Поль Л. Гейрингер
Соединенные Штаты Америки
Росуэллская установка со сжатием
пара, новейшая среди четырех показа
тельных агрегатов, была построена для
демонстрирования осуществимости ни
жеследующей программы:
(1) Превращение солоноватой воды
с большим солесодержанием в
питьевую;
(2) Работа с более высокой концен
трацией продувки;
(3) Исследование двух методов борь
бы с накипью: ионный обмен и
рециркуляция взвеси;
(4) Работа с крупным компрессор
ным оборудованием;
(5) Работа при температуре испаре
ния 235°F.
В Части I доклада указано, что вы
шеупомянутая солоноватая вода содер
жит 588 мг/л кальция, 1.490 мг/л суль
фата, 161 мг/л магния и 13 мг/л дву
окиси кремния. Это количество химика
лий сильно затрудняет опреснение, так
как концентрация хлористого натрия
достигала только 1,3% по сравнению
с 3,0% в морской воде, уменьшая та
ким образом растворимость других не
желательных элементов.
Росуэллский цикл и оборудование
обсуждаются в Части II.
Встретившиеся в прошлом недостат
ки и их исправление являются предме
том Части III. Полученный опыт, бла
годаря встретившимся затруднениям, и
их исправление могут оказаться очень
полезными для проектировщиков обо
рудования этого типа.
Достигнутые при совместно прове
денной большой лабораторной работе
улучшения и опыт в области ионооб
менного оборудования, могут стать в
будущем весьма ценными для борьбы
на установках с образованием накипи.
Лабораторная и практическая работа
продолжается и подает довольно боль
шие надежды.
Виды на будущее для систем со сжа
тием пара подробно отмечены в Ча
сти IV.
Для будущих заводов расходы, свя
занные с капиталовложением, владени
ем и эксплуатацией, представляют
большую важность. Стоимость построй
ки влияет на амортизацию и финансо
вые ставки, увеличивая накладные сто
имости, что повышает стоимость экс
плуатации.
Примечание: Все номера чертежей и
таблиц относятся к главному докладу.
Эксплуатационные расходы можно
разделить на четыре главные группы:
Группа I. Энергия (горючее и элек
тричество).
Группа II. Химикалии.
Группа III. Рабочая сила, ремонты и
администрация.
Группа VI. Накладные стоимости
(Амортизация, налоги,
страхование и т.д.).
При увеличении размеров установки
расходы, сопряженные с капиталовло
жением, владением и эксплуатацией
уменьшаются. На стоимость производ
ства питьевой воды влияют два глав
ных фактора:
(1) Стоимость энергии (Группа I).
(2) Накладные стоимости (Группа
IV).
По сравнению с этими двумя группа
ми все остальные факторы стоимости
второстепенны.
Для трех главных дистилляционных
систем (с многократным мгновенным
вскипанием, многоступенчатых и со
сжатием пара) были подсчитаны рас
ходы энергии (тепла и электроэнер
гии) и сравнены между собой на одной
общей базе.
Расход энергии трех обсуждаемых
выпарных систем был определен на
основании рабочих данных показатель
ных опытных установок (на один мил
лион галлонов в сутки каждая) Управ
ления по опреснению соленых вод.
689
 Если вблизи от опреснительного за
вода будет сооружена тепло-силовая
установка, то сбросное тепло от тур
бин, производящих энергию, может
быть использовано для выпарной си
стемы Типа 1 (с многократным мгновен
ным вскипанием) или Типа 2 (много
ступенчатой). При таких условиях мож
но было бы производить энергию при
расходе тепла не выше 5.000 Б.Т.Е./ки-
ловатт-час.
В предположении этой постоянной
затраты тепла на киловатт-час, что те
оретически и практически система со
сжатием пара имеет самый низкий рас
ход энергии.
Чтобы достичь столь низких затрат
тепла на киловатт-час получаемой
энергии, часто предлагалось комбини
ровать опреснительные заводы Типа 1
(многократного мгновенного вскипа
ния) и Типа 2 (многоступенчатого) с
установкой, производящей энергию, из
лишек которой, в форме электрическо
го тока, можно было бы продавать со
седней электрической компании. Одна
ко, совмещение продажи электричества
с производством опресненной воды не
всегда бывает практичным и по эконо
мическим и другим причинам иногда
становится невозможным.
Поэтому использование дешевой
энергии для выработки дополнительной
воды обычно является более целесооб
разным. Рекомендуется так планиро
вать общую программу производства
воды на предполагаемой установке,
чтобы удовлетворить общий спрос на
воду, применяя частично систему Ти
па 1 (с многократным мгновенным
вскипанием) или Типа 2 (многоступен
чатого) и частично систему со сжатием
пара (Типа 3). При правильном равно
весии систем (см. параграфы 4, 6 глав
ного доклада) можно добиться гораз
до более крупных экономий, чем при
продаже тока электрической компании.
Другой метод резкого снижения
эксплуатационных расходов основан на
применении высокотемпературных во
доструйных компрессоров для уплот
нения пара, выпускаемого из более
низкой испарительной ступени, и его
использовании для нагрева более вы
сокой ступени. Производимый с по
мощью этого процесса избыточный пар
доставляется в выпарную систему с
многократным мгновенным вскипанием
или во многоступенчатую. Таким обра
зом можно получить энергетическую
экономию в размере 35-50%. Расход
тепла в 12-ступенчатой испарительной
690
системе снижается со 103 Б.Т.Е. до при
мерно 68 Б.Т.Е. на фунт опресненной
воды.
Применение при манометрическом
давлении 1.000-1.500 фунтов на кв.
дюйм струи горячей воды вместо пе
регретого пара высокого давления дает
дополнительную экономию в размере
10-20%.
Температурный уровень источника
нагрева для повышения температуры
горячей воды с 200°F до 550°-6Ó0°F
сравнительно невысок, так что выхлоп
газовых турбин может быть использо
ван для этой цели. Таким образом воз
никает возможность одновременно про
изводить дополнительную энергию
при малой затрате тепла, около 5.000
Б.Т.Е. на киловатт-час.
Выработка дополнительной дешевой
энергии делает возможным устройство
струйно-многоступенчатой комбиниро
ванной системы с механическим сжа
тием пара. Пропорциональное распре
деление продукции питьевой воды на
такой комбинированной установке бы
ло бы приблизительно следующим: со
стороны многоступенчатой испаритель
ной — 26,3%; со стороны струйной си
стемы — 21%; со стороны системы мно
гократного сжатия пара — 52,7%.
При стоимости горючего — 20 центов
за миллион Б.Т.Е., на больших установ
ках комбинированной системы расход
на горючее для выработки 1.000 галло
нов опресненной воды составит 11-12
центов. Если к стоимости горючего бу
дут добавлены накладные расходы, то
издержки на энергию не должны пре
взойти 15-16 центов на 1.000 галлонов.
При правильной конструктивной
уравновешанности трех частей системы
можно снизить стоимость энергии до
такого низкого уровня, который вряд-
ли иначе достижим.
Наконец, для снижения в будущем
эксплуатационных издержек, связанных
с производством питьевой воды, необ
ходимо снижать накладные расходы,
уменьшая капиталовложение, приходя
щееся на каждый фунт опресненного
продукта.
Атака в двух направлениях на на
кладные расходы для достижения ука
занной цели, включает:
(1) устранение образования накипи;
(2) увеличение производительности
испарительной зоны посред
ством повышения температурно
го перепада и общего коэффи
циента теплопередачи.
УСТРАНЕНИЕ ОБРАЗОВАНИЯ
НАКИПИ
При низких концентрациях рассола и
низких температурах (ниже 200°F) со
ляного раствора обыкновенно нужна
только его обработка серной кислотой
и дегазирование для устранения дву
окиси углерода и кислорода. Удаление
двуокиси углерода устраняет опасность
образования накипи, состоящей из кар
боната кальция.
Соленая вода, при высоких темпера
турах порядка 275°-300°F и факторах
концентрации продувки 3 : 1 до 4 : 1 и
выше, нуждается в дополнительной
предварительной обработке. Ионооб
менные системы с рекуперацией про
дувки видимо сулят наилучшие резуль
таты. Употребление для рекуперации
покупной соли является непрактичным,
ввиду ее слишком высокой стоимости.
Изучается также применение хелатных
агентов и поверхностно-активных ма
териалов предназначенных для борьбы
против накипи. Системы рециркуляции
взвеси не были достаточно испытаны,
так что в настоящее время невозмож
но оценить их применимость.
УВЕЛИЧЕНИЕ ПРОИЗВОДИТЕЛЬНО
СТИ ИСПАРИТЕЛЬНОЙ зоны
Предпосылкой улучшения теплопере
дачи является устранение образования
накипи при высоких температурах.
Если при этих условиях удастся осво
бодиться от накипи, то представится
возможность увеличить число ступеней
и снизить стоимость производства по
средством распространения повышен
ной температуры и получения благода
ря большим температурным перепадам
дополнительной продукции с той же
самой поверхности.
Повышение коэффициента теплопере
дачи возможно только при увеличении
коэффициента передачи пленки на сто
роне рассола и пара. Коэффициент
пленки на стороне рассола (внутри
труб) может быть повышен путем уве
личения скорости. 7,5-8 футов в секун
ду видимо является оптимальной ско
ростью жидкости, так как приходится
считаться с опасностью эрозии и сто
имостью энергии. При таких больших
скоростях и температурах, превосходя
щих 200°F, можно рассчитывать на по
лучение коэффициентов пленки выше
2.000. Повышение коэффициента плен
ки на стороне пара можно достичь с
помощью промоторов, вызывающих
капельную конденсацию. Изучаются
также другие методы, как например
трубы с канавками (рифлением), кото
рые пока-что экономически не оправ
дываются.
В виде резюме можно сказать, что
повышение температурного уровня и
коэффициента теплопередачи, при сво
бодных от накипи поверхностях, смо
жет на 20-30% уменьшить накладные
расходы. Снижение стоимости энергии,
приходящейся на горючее, до уровня
11-12 центов, а всей ее стоимости до
15-16 центов на 1.000 галлонов про
дукта, повышение теплопередачи и ра
бочих температур, совместно с улуч
шением борьбы с накипью, приведут
на больших установках потребляющих
органическое горючее, к ценам на воду
в размере 30-35 центов за 1.000 галло
нов. Это является для дистилляционных
опреснительных установок перспекти
вой «близкого» будущего.
691
 Aspectos Funcionales y
de la Destilación
Vapor*
Paul L. Geiringer
Estados Unidos de America
La planta Roswell de compresión por
vapor, que es la más reciente de las cuatro
instalaciones para fines de demostración,
fue construida con el objeto de demostrar
la viabilidad de lo siguiente:
(1) Convertir agua salobre de alta sali
nidad en agua potable.
(2) Operar a una más alta concentración
de purga.
(3) Investigar los dos métodos de pre
vención de incrustaciones, a saber: el
de intercambio de iones y el de
recidar la mezcla.
(4) Operar maquinaria de compresión
grande.
(5) Operar a temperaturas de evapora
ción de 235°F.
La Parte I del trabajo indica que esta
agua salobre contiene 558 ppm de calcio,
1.490 ppm de sulfato, 161 ppm de magnesio
y 13 ppm de silice. Esta cantidad de sub
stancias químicas causó algunas dificultades
en la conversión porque la concentración
de NaCl sólo llegó a 1,30%, en compara
ción con la del agua de mar que llegó
a 3,0%, reduciéndose así la solubilidad de
estas substancias químicas indeseables.
En la Parte II se trata sobre el ciclo y
equipo de Roswell.
Las deficiencias encontradas en el pasado
y su corrección son tema de la Parte III.
La experiencia que se obtuvo de las difi
cultades encontradas y de su solución puede
ser de gran utilidad para los diseñadores
de este tipo de equipo.
Tanto las mejoras como la experiencia
logradas con el equipo de intercambio
iónico, asf como los trabajos extensos de
laboratorio que se han efectuados, podrían
ser de valor incalculable en el futuro para
eliminar las incrustaciones en la operación
de plantas futuras. Los trabajos de labora-
* Todos loa números de las tablas se refieren al
texto del trabajo.
692
Perspectivas
por Compresión a
torio y de práctica continúan y parecen
ser muy promisorios.
El aspecto futuro de los sistemas de com
presión por vapor se discute en la Parte IV,
La inversión, la propiedad y loe cosía
de explotación de las futuras plantas son
factores importantes. El costo de construc
ción influye en la amortización y en la tasa
de financiamiento al aumentar los gastos
fijos que a su vez aumentan el costo de
explotación.
Los gastos de explotación pueden divi
dirse en cuatro grupos principales, a saber
Grupo I. Servicios (de combustible y
electricidad) .
Grupo II. Productos químicos.
Grupo III. Mano de obra, conservación
y administración.
Grupo IV. Gastos fijos (amortización,
impuestos, seguro, etc.) .
A medida que aumenta el tamaño de la
planta, disminuyen tanto la inversión como
los costos de propiedad y de explotación.
El costo de producción de agua potable se
rige por dos factores de costo principales,
a saber:
(1) El costo de los servicios públicos
(Grupo I) .
(2) El costo de los cargos fijos (Grupo
TV).
En comparación con estos dos grupos de
costos, los demás factores de costo son poco
importantes.
Para los tres sistemas de evaporación
principales (de etapas múltiples instantá
neas, de multiefectos y de compresión por
vapor) los servicios (de calentamiento т
electricidad) se computan y comparan entre
si sobre una base igual.
La tasa de energía eléctrica para los tres
sistemas de evaporación de que se trata
se ha calculado de acuerdo con los datos
funcionales de las instalaciones experimen
tales para demostraciones, con rendimiento
de un millón de galones por día, de la evaporación de 12 efectos se reduce de 103
Oficina de Agua Salada. BTU/lb. a 68 BTU/lb. del agua producida.
Si se construye una planta de energía y El agua de alta temperatura a presión
calefacción adyacente a una planta de de- de 1.000 lppcg a 1.500 lppcg utilizada para
salinización, podría producirse electricidad impulsar el chorro, en comparación con el
con turbinas, mediante las cuales el calor vapor sobrecalentado de alta presión, ofrece
de escape se aprovecha para suministrar una mayor economía de 10% a 20%.
energía térmica al sistema de evaporación El nivel de la temperatura de producción
de las plantas de Tipo 1 (de etapas múlti para elevar el agua de alta temperatura de
ples instantáneas) o de Tipo 2 (de multi- 200° F a 550° F o 600° F, es relativamente
efectos) . De esta manera, la energía podría moderado, do modo que el gas descargado
producirse con un consumo calorífico no por las turbinas puede utilizarse para este
mayor de 5.000 BTU/Kvh. fin. Además esto permite la producción
Suponiéndose que se mantenga esta tasa simultánea de energía a una tasa baja de
de calor, teórica y prácticamente el sistema calor de unas 5.000 BTU/Kvh.
de compresión por vapor es el que requiere La producción de energía adicional a
menos energía. costo bajo facilita el uso de un sistema
Para lograr tales tasas bajas de calor por combinado de compresión a vapor, de
Kvh de energía producida, se ha sugerido chorro, de efecto múltiple y mecánico. La
con frecuencia que se combinen las plantas distribución del agua potable producida
de Tipo 1 (de etapas múltiples instantá por una planta combinada de esa especie
neas) y Tipo 2 (de efectos múltiples) con sería de más o menos 28,3% del sistema
una planta que produzca energía, mediante de evaporación de efecto múltiple; 21%
lo cual el exceso de energía producida del sistema de chorro; y 52,7% del sistema
podría venderse como corriente eléctrica a de compresión por vapor múltiple.
alguna empresa de servicio público de las Siendo el costo del combustible de 20
inmediaciones. Tal vez no sea siempre prác centavos por millón de BTU, el costo de
tico combinar la venta de energía eléctrica la energía para combustible utilizado en
con la desalinización, pues podría ser im un sistema combinado será de 11 a 12
posible por razones económicas o de otra centavos por 1.000 galones en el caso de
índole. plantas grandes. Si se añaden los cargos
Por lo tanto, generalmente resulta más fijos de la planta de servicio público al
práctico utilizar la energía de costo bajo costo de la energía para combustible, los
para producir más agua. Se sugiere que el cargos por servicio no excederán de 15 a
programa de producción total de agua para 16 centavos por 1.000 galones.
una planta proyectada se elabore de ma El equilibrio correcto de las tres partes
nera que una parte de las necesidades de este sistema en el diseño permite reducir
totales de agua sean satisfechas por un los costos de la energía eléctrica a un
sistema del Tipo I (de etapas múltiples nivel bajo, cosa que difícilmente se logra
instantáneas) o Tipo 2 (de efectos múlti en ninguna otra forma.
ples) y la otra parte por un sistema de Finalmente, el futuro aspecto de la re
compresión a vapor (Tipo S) . Mediante un ducción de los gastos de explotación para
equilibrio exacto de los sistemas (véase el producir agua potable deberá incluir la re
párrafo 4.6 en el trabajo principal) po ducción de
drían realizarse economías mucho más de reducir lalosinversión gastos fijos que resultaría
de dinero necesaria
grandes que las que se pueden obtener
mediante la venta de energía eléctrica a por libra de agua evaporada.
una empresa de servicio público. Hay dos maneras de atacar el problema
Otro método para reducir radicalmente de esos gastos fijos que posibilitarían tal
los gastos de explotación consiste en apli reducción de la inversión de que se trata,
car compresores de chorro de agua a alta a saber:
temperatura para densificar el vapor des (1) La eliminación de las incrustaciones.
cargado de una etapa de evaporación más (2) El aumento en la producción de la
baja, de modo que pueda utilizarse para zona de evaporación mediante el in
calentar en una etapa más alta. El exceso cremento de la diferencia de tem
de vapor producido por medio de este peraturas y el aumento del coeficiente
procedimiento pasa a un sistema de evapo total de transmisión térmica.
ración de etapas múltiples instantáneas o
de efecto múltiple. De esta manera puede ELIMINACIÓN DE LAS INCRUSTACIONES
ahorrarse del 35% al 50% de la energía. A concentraciones bajas de salmuera y
El consumo térmico de un sistema de a bajas temperaturas (inferiores a 200° F) ,

693
 ta mayor parte del agua salina sólo tiene
que tratarse con ácido sulfúrico y desgasi
ficarse para extraer el anhídrido carbónico
y el oxigeno. Al extraer el anhídrido car
bónico se elimina el peligro de que se
formen incrustaciones de carbonato de
calcio.
El agua salina a temperaturas elevadas
hasta de 275° F a 300° F y con los factores
de concentración de purga de 3 a 1 hasta
\ a 1 y mas altos, requiere un pretrata-
miento ulterior de la corriente de alimenta
ción. Los sistemas de intercambio iónico con
regeneración de purga parecen ser los más
promisorios. El empleo de sal comprada
para los fines de regeneración no parece
ser práctico porque el costo de esta sal
es muy elevado. También se estudia la apli
cación de agentes de quelación y de mate
riales para evitar la formación activa de
incrustaciones en la superficie. Los sistemas
de recirculación de la mezcla semifluida no
se han sometido a suficientes pruebas y por
eso no es posible apreciar su valor por el
momento.
EL AUMENTO DE PRODUCCIÓN EN
LA ZONA DE EVAPORACION
El mejoramiento de la transmisión térmica
tiene como prerrequisito la eliminación de
la formación de incrustaciones a tempera
turas elevadas. Si se asegura la inmuniza
ción contra incrustaciones a estas tempera
turas más elevadas, entonces podrá aumen
tarse el número de etapas o reducirse el
costo de explotación diseminándose más la
temperatura y obteniéndose mayor produc
ción de la misma zona superficial, debido a
mayores diferencias de temperatura.
694
El mejoramiento del coeficiente de trans
misión térmica sólo se logra cuando aumen
ta el coeficiente de transmisión de la
película en el lado de la salmuera y del
vapor. El coeficiente de la película en el
lado de la salmuera (dentro de los tubos)
puede aumentarse acelerando la velocidad.
Una velocidad de 7i/¡ a 8 pies/segundo
parece ser la velocidad óptima del líquido
cuando se equilibran el peligro de corrosión
y el costo de la energía eléctrica. Cuando
se emplean velocidades de este orden,
puede esperarse que los coeficientes de la
película de salmuera sean mayores de
2.000 a temperaturas superiores a 200°F. El
coeficiente de película en el lado del vapor
puede aumentarse utilizándose aceleradores
de condensación en goticulas. También se
tienen bajo estudio otros métodos, tales
como el uso de tubos estriados que hasta
ahora no han demostrado ser económica
mente viables.
En resumidas cuentas, puede decirse que
los aumentos de temperatura y el mejora
miento del coeficiente de transmisión tér
mica, junto con superficies exentas de
incrustaciones, podrían reducir los cargos
fijos en 20% a 30%. La reducción del costo
de la energía a un plano de 11 a 12 centavos
por el combustible y de 15 centavos a 16
centavos por el costo total de la energía por
cada 1.000 galones, asi como el mejoramien
to de la protección contra incrustaciones
y de la transmisión térmica, acompañados
de aumentos de temperatura, producirán
cifras de oosto de 30 a 35 centavos por
1.000 galones en las plantas grandes que
consumen combusibles fósiles. Este es el
aspecto de las plantas de conversión por
evaporación para el futuro "próximo".
 Removal of Scale Formers with
Byproduct Recovery
Murrell L. Salutsky and Phil Messina
United States of America
The formation of scale on heat transfer
surfaces greatly reduces the efficiency of
distillation equipment used for the produc
tion of fresh water. The scale which is
deposited from heated sea water is primarily
a mixture of calcium and magnesium com
pounds, particularly calcium carbonate,
magnesium hydroxide, and calcium sulfate.
To avoid scale formation, distillation
equipment has often been operated at lower
temperatures (190°-210°F) than optimumly
desired; sometimes small amounts of poly
phosphates (réf. 1) were added to help
complex the calcium and magnesium. More
recently sea water has been pretreated with
acids (ref. 2) to prevent the formation of
calcium carbonate and magnesium hydrox
ide and allow operating temperatures up to
270°F. Still higher operating temperatures
are difficult (or impossible) to achieve with
acids alone because of the formation of
calcium sulfate which has an inverse solu
bility with temperature. Temperatures above
270°F will require, not only the acid treat
ment, but also that part of the calcium be
removed from the sea water prior to distil
lation. Very high temperatures (above
300°F) will probably require the removal
of magnesium as well as calcium.
Pretreatment methods which remove
calcium from sea water utilize ion-exchange
(refs. 3, 4), sludge recycle (ref. 5) , carbon
ate precipitation (refs. 6, 7) , and phosphate
precipitation (refs. 8-10) . With the pos
sible exception of the sludge-recycle method,
all of these methods for removing calcium
cost more than the acid treatment, either
in raw materials or processing costs or both.
Since the acid treatment requires about one
pound of sulfuric acid for each 1 ,000 gallons
of sea water treated, the cost per 1,000
gallons of fresh water produced amounts
to 3 to 5 cents, depending on factors such
as the location of the plant, brine concen
tration or blowdown ratio, etc.
Because of the stringent economics asso
ciated with the desalination of sea water,
almost any cost for pretreatment is prohib
itive—even the 3 to 5 cents per 1,000 gallons
for acid treatment. Pretreatment at no cost
could be achieved only if a byproduct were
simultaneously produced and if the by
product could be sold at sufficient profit to
pay the cost of the pretreatment. Since
scale consists of calcium and magnesium
compounds, the byproduct would have to
be a calcium or magnesium compound.
Low cost sources of calcium are so wide
spread that the prospect of producing a
profitable calcium product is not promis
ing. Magnesium is different. It is already
largely obtained from sea water. However,
the conventional process of adding lime to
sea water to precipitate magnesium hydrox
ide is not suitable as a pretreatment method
because it greatly increases the calcium
concentration of the sea water. The use of
other precipitating agents, such as caustic
soda and ammonia rather than lime, would
have difficulty competing because of cost.
Therefore, the byproduct approach to
pretreatment at no cost requires the pro
duction of a magnesium compound without
the addition of lime to the sea water. The
value of the product must not be seriously
depressed by contamination with calcium,
which must simultaneously be removed
from the sea water. There must be a large
market (or potential large market) for the
product. Profit from the sale of the product
must be sufficiently large to pay for the
pretreatment so that no charges are assessed
against the production of fresh water. A
pretreatment process (refs. 8-10) . which
695
 produces a byproduct consisting of magne fertilizers, has promise for fulfilling these
sium ammonium phosphate and other requirements.
phosphates for use in the manufacture of

REMOVAL OF SCALE FORMERS BY PHOSPHATE PRECIPITATION

A simplified flowsheet of a process for ammonia utilized are stoichiometric to the
the removal of the scale formers from sea magnesium and calcium concentrations in
water, with the simultaneous production of the sea water as needed for the precipitation
a phosphalic byproduct suitable as a raw of magnesium ammonium phosphate and
material for the manufacture of fertilizer, dicaldum phosphate according to the fol
is shown in Figure 263. lowing equations:
MgCl, + H.PO, -I- 3NH, + 6H.O -*
SE* WATER MgNH^PO, • 6HtO+2NH,Cl (1)
HjPO, ± CaCl, + H.PO, + 2NH, + 2H.O -»•
NHj CaHPO, • 2H.O + 2NH.C1 (2)
8-5)
Essentially all the magnesium is precipitated
at pH 7, but a pH of 8.5 (requiring about
10% excess of ammonia) is necessary for
SETTLER _TREATED SEA WATER the precipitation of the dicaldum phos
To Desalnation Plant! phate.
PHOSPHATE SLURRY In the dehydrator, the phosphate slurry
is digested at a high temperature (195°F)
DEHYDRATOR to convert magnesium ammonium phosphate
|195°F| hexahydrate to the monohydrate according
to the following reaction:
195°F
MgNH«PO. • 6H.O »
MgNH«P04 • H.O + 5H.O (3)
FILTER
This is done to increase the plant nutrient
concentration (i.e., N and P,0,) of the
PHOSPHATE FILTER CAKE phosphates and substantially increase thdr
[To Farbhm Manufacture! value to the fertilizer manufacturer. Dehy
dration cannot be carried out with the dry
hexahydrate because the compound decom
FIGURE 263. REMOVAL OF poses when heated dry with the simulta
SCALE FORMERS FROM SEA neous loss of ammonia and water. The
WATER BY PHOSPHATE monohydrate is considerably more stable to
PRECIPITATION (SIMPLI heat.
FIED PROCESS FLOWSHEET). The process was initially developed in a
small bench-scale unit operating continu
ously at a flow rate of about 5 gallons per
Phosphoric add is added to sea water hour. All processing steps performed well,
and then sufficient ammonia to produce a indicating rapid reaction, settling, and fil
slurry of pH 8.5. The mixture of precip tration rates.
itated phosphates and sea water is dis The treated sea water contained 0.3-0.4
charged to a settler. After the phosphates ppm of magnesium and 10 to 11 ppm of
have settled, the clear overflow is pumped calcium. Since the sea water originally con
to the saline water conversion plant. The tained 1,132 ppm of magnesium and 356
phosphate slurry (underflow from the ppm of calcium, the percentages removed
settler) is pumped to the dehydrator and by the process were 99.6 and 97 per cent,
maintained at 195°F for one hour. It is respectively. The residual concentration of
then filtered and the resulting solids are P,05 in the descaled sea water was 66 ppm
sent to the fertilizer plant where they are which corresponds to a phosphate recovery
mixed with potash and other fertilizer in the fertilizer product of 98.5 per cent.
materials, granulated, dried, screened, and The total ammonium ion concentration
finally bagged. The filtrate is recycled to expressed as NH, was 1,800 ppm and the
the settler. free ammonia (also expressed as NH,) was
The amounts of phosphoric acid and 200 ppm.
cm
 The dried filter cake had the following
average composition: 7.3 per cent N, 43 per
cent P,05, 21 per cent MgO, 5.3 per cent CaO,
and 1.4 per cent moisture at 100°C. With effi
cient filtration it was not necessary to wash
the cake since the dried unwashed solids
contained as little as 02 to 0.3 per cent
chloride. Approximately 74 pounds of these
phosphates would be produced for each
1 ,000 gallons of sea water treated.
PILOT PLANT DEVELOPMENT OF PHOSPHATE PROCESS
Л pilot plant designed to treat 10,000 gpd
of sea water was constructed at the Office of
Saline Water Research and Development
Test Station located at Wrightsville Beach,
North Carolina, U.S. Figure 264 is a flow
diagram of the process depicting the items
of equipment, their sizes, and the raw
material usages in the pilot plant.
PROCESS DESCRIPTION
The raw sea water was metered to the
pilot plant through a recording flow con
troller totalizer. The phosphoric acid was
metered into the sea water stream at a
mixing nozzle. The acid was measured by
a weigh tank with a visual flowmeter check.
The amount of acid feed could be varied by
adjustments to the diaphragm pump to
maintain the desired ratio of phosphoric
acid and sea water. Liquid ammonia was
mixed with the acidified sea water in a
reaction tank (70 gallon capacity) having
about 10 minutes retention time at a sea
water flow rate of 10,000 gpd. The ammonia
was metered to the reactor by a weigh tank,
a recording flow controller, and a visual
flowmeter to maintain an 8.5 pH in the
reaction mix. The pH was measured and
recorded by a flow-type electrode.
The solids formed by the chemical reac
tion in the reactor were separated from the
bulk of the sea water in a clarifier (6-foot
diameter by 5-foot depth) . The overflow
from the clarifier was pumped to one of
two storage tanks (2,000 gallons) for evalua
tion in distillation equipment. Concen
trated solids were pumped at selected rates
from the bottom of the clarifier into a
dehydrator (70 gallon capacity) . The de-
hydrator was operated at approximately
200°F with a residence time of about one
hour. Slurry from the dehydrator was fed
into a rotary drum filter. The filtnt» was
returned to the clarifier and the solid sent
to fertilizer manufacture.
The pilot plant was successfully operated
at the design capacity of 10,000 gpd. Upon
increasing the rate, the instrumentation for
Therefore, the laboratory research (ref. 8)
predicted that the process would yield
treated sea water practically free of scale
formers and a phosphate sludge suitable for
fertilizer manufacture. However, pilot plant
development of the process was necessary
before meaningful cost estimates could be
made or the value of the treated sea water
established.
flow control and metering of raw material
streams (sea water, phosphoric acid, and
ammonia) was found to have a limit of
140 per cent of design. Although the clari
fier capacity appeared to have been exceeded
at the input rate of 14,000 gpd, higher
performance is anticipated in future testing
by the use of flocculating agents. The
reactor and dehydrator appeared to func
tion properly at the 140 per cent level.
EQUIPMENT
Feed Systems: Chemical feeds were con
trolled with weigh scales, adjustable feed
pumps, and rotameters. The chemical flows
were measured by weight because small
changes in ambient temperature caused
volume variations in the chemicals which
upset the control of the pilot plant. Some
difficulties were encountered because of the
small feed rates required. However, experi
ence showed that the ammonia stream could
be metered at 13 pounds per hour with
one-half pound variation and the phosphoric
acid at 30 pounds with 1 pound variation.
Larger flows can be handled with better
accuracy.
The automatic system for metering an
hydrous liquid ammonia did not operate as
installed because vaporization or flashing
occurred at the metering constrictions.
Therefore, the system was operated manually
with two metering valves in series to bal
ance pressure drops without flashing.
A number of leaks developed in the
stainless steel (Types 304 and 316) equip
ment and lines for handling the phosphoric
acid (75% H,PO.) . Future equipment for
handling this acid should be fabricated of
rubber-lined steel with catalyzed epoxy
coatings on exterior surfaces or a high
quality plastic lining such as penton.
Neoprene hose with Type 316 stainless steel
hose adapters was suitable for lines and a
plastic container served very satisfactorily as
an acid weigh tank. It was necessary to
install a strainer between the phosphoric
acid storage tank and the metering system
697
698
to prevent solids in the acid from causing
malfunction of the ball check valves of the
metering pump.
Based _ on pilot plant experience, flow
controlling, recording, and totalizing instru
mentation is recommended for plant opera
tion on the raw material streams.
Reactor: The reactor in which the acid
ified sea water was neutralized with ammo
nia was a stirred tank with a working
volume of 71 gallons. Previous laboratory
data (refs. 8, 10) had indicated that a
minimum residence time of 6 minutes was
required and that thorough mixing was
necessary. A residence time-distribution
curve indicated a residence time of 10.13
minutes when the reactor was operated
continuously at a flow rate of 7 gallons
per minute and that excellent mixing was
achieved within the reactor.
It was later found that the reaction could
be carried out in a simple pipeline reactor.
The solids produced in this type of reactor
did not always settle as well as those
produced in the stirred tank unit. However,
a pipeline reaction in which the ammonia-
tion zone was near the bottom of the
clarificr produced effluent water with a
lower concentration of solids than that
obtained with the stirred tank-clarifier
system.
TABLE CXVII. Summary of Clarifier Operation
Clarifier feed Clarifier underflow
dal/day)
10,100
10,100
10,200
•12,000
12,225
17,000
• Clarifier operated with pipeline reactor near its bottom.
The total solids in the underflow stream
were found to increase both with plant
capacity and with a decrease in the rate at
which it was pumped from the clarifier
(Fig. 265) . When the solids content ranged
from 10 to 20 per cent, the bulk density of
the clarifier underflow was relatively con
stant, about 8.7 pounds per gallon. It in
creased when the solids content was above
20 per cent. For example, a bulk density
of 9.4 pounds per gallon at a solids content
of 28.6 per cent was obtained during a
pipeline reactor run in which the clarifier
solids were so mushy and thick that the
underflow could hardly be removed with
The reaction was monitored by measur
ing the pH of the reactor effluent which
was maintained at 8.5. The electrodes,
which were immersed in a stream contain
ing 1.5 per cent solids, required periodic
flushing and monthly clearing with acid.
Clarifier: The clarifier was a rubber-lined
pilot model of Dorr-Oliver. It was 6 feet in
diameter and 5 feet high. The rake was
raised 2 inches from the bottom and oper
ated at a speed of 0518 rpm. A minimum
of 72 hours of operating time was necessary
to achieve steady-state operation. The clari
fier was operated without the aid of floccu
lating agents.
The solids in the overflow streams varied
with the feed rate. The results of runs with
at least the minimum on-stream times to
establish steady-state operation are sum
marized in Table CXVII. The total solids in
the overflow increased with feed rate. For
example, at 17,000 gallons per day the clari
fier overflow contained 760 ppm of solids,
which represents about 10 per cent of the
by-product. The capacity increased about 20
per cent when the clarifier was operated
with a pipeline reactor near its bottom.
The clarifier capacity may also be increased
by maintaining a higher bed height as an
aid for filtering out the fine solid particles
more efficiently or by the use of flocculants.
Clarifier overflow
(lbs/hour) (ppm total dry solids)
448 96
4ST 161
S12 145
882 163
4S8 271
874 760
the diaphragm pump.
Dehydrator: The dehydrator, a 71-gallon
jacketed tank supplied with an agitator,
was used to heat the underflow slurry from
the clarifier to 195° to 210°F and to pro
vide a retention time of one hour. Under
these conditions, the magnesium ammo
nium phosphate hexahydrate (MgNH.PO,
• 6HjO) in the slurry was converted to the
monohydrate. The dicalcium phosphate di-
hydrate (CaHPO, • 2H.O) should not be
affected at these temperatures.
When the pilot plant was processing
10,000 gpd of sea water, the residence time
699
 50
9000 10,000 11,000 12,000 13,000 14,000 15,000 16,000 17,000 18,000
INLET SEA WATER RATE [pt /ёцг)
FIGURE 265. EFFECT OF PLANT CAPACITY AND SLURRY PUMP
RATE ON THE TOTAL SOLIDS IN CLARIFIER UNDERFLOW.
in the dehydrator was 1.37 hours for slurry
pumped from the clarifier at 450 pounds
per hour. When processing 17,000 gpd, the
residence time was 0.71 hour for slurry
pumped at the rate of 874 pounds per hour.
In the latter case, the feed to the dehy
drator contained 16.7 per cent solids
(hydrated basis) and the effluent slurry
contained 10.6 per cent solids. The ratio of
solids in the feed and effluent was 1.58
compared to a theoretical ratio of 1.36. The
temperature was relatively constant at 209°
to 218°F. Under these conditions the dical-
rium phosphate dihydrate was apparently
converted to anhydrous tricalcium phos
phate, Ca, (PO,) „ which may account for
the higher ratio of solids in the feed and
effluent than predicted theoretically. The
MgNH.PO, -бН.О was effectively dehy
drated to MgNH.PO. • H.O.
Filter: A continuous drum filter fitted
with a drum 20 inches in diameter and 12
inches wide, a string discharge, and a wash
assembly was used to filter the byproduct
phosphates. Its effective filtration area was
5 sq ft. A nylon cloth (Feine WNH-
G2E7-HG8) was used. The drum speed
was 0.144 rpm. The operating vacuum was
14 and 16 inches of mercury on the mother
liquor and wash liquor sections, respectively.
Major difficulties were encountered be
cause the filter was oversized. Initial opera
tion with a belt discharge was unsatisfactory.
Meaningful data were obtained using a
700
string discharge, but only when the plant
was treating 17,000 gpd of sea water. At
this throughput the slurry from the de
hydrator amounted to 874 pounds per hour,
which formed a cake 14 to yt inch thick on
the drum.
The slurry fed to the filter contained 6 to
17 per cent solids (dry basis). The filter
cake had an average moisture content of
39.4 per cent. Washing with 1 pound of
water per pound of dry cake lowered the
chloride content from an initial 2 or 25
per cent to about 0.5 per cent. The filtrate,
which was recycled to the clarifier, con
tained an average of 504 ppm of solids (dry
basis) .
OPERATIONAL PROBLEMS
The pilot plant was successfully operated
as designed. Although no serious opera
tional problems were encountered besides
those previously mentioned with the feed
systems, due to the formation of a vapor
lock in the ammonia system and corrosion
of the stainless steel in the phosphoric acid
system, there was a gradual buildup of
solids within the equipment used to chemi
cally pretreat the sea water. This might
eventually lead to trouble, particularly if
the solids are formed as the result of re
hydration of magnesium ammonium phos
phate. Under such a condition a hard crust
can be formed.
After 1J> months of operation solids were
found to have built up on the walls of
both the reactor and dehydrator above the
liquid level and in the overflow pipe of
the reactor. The walls of the clarifier also
had crusty deposits which could be removed
with a brush. The deposits were thin films
up to 1/2 inch thick at the launder over
flow weirs. Operation of the rotary drum
filter was hampered by the buildup of solids
on exposed metal surfaces whose tempera
tures were below 190°F. The magnesium
ammonium phosphate monohydrate would
slowly réhydrate and form hard deposits on
surfaces such as the stainless steel guide
comb and the undercut surfaces of the
drum.
Hoses used as transfer lines contained »
one-fourth inch layer of loose sediment at
the bottom of horizontal sections. These
deposits caused problems at valves, pumps,
and metering points, whenever they were
sluiced down the lines by surges in flow.
The diaphragm in the clarifier underflow
pump was ruptured by solids packing at
the periphery. This problem was solved
by replacement of the diaphragm and occa
sional flushing of the pump head. The cen
trifugal pumps handling the treated sea
water were found to be frozen when left off
the line for more than two days; however,
these units were readily freed when placed
into service.
There was evidence of post precipitation
in the tanks used for storage of the treated
sea water. About 2 per cent of the byprod
uct was found in the storage tanks. This
did not present a serious problem because
residual solids were removed from the
treated water prior to distillation by a
polishing filter. However, it does indicate
the probable need for more contact with
solids in the clarifier (e.g., increased bed
depth) to eliminate supersaturation.
EVALUATION OF THE TREATED SEA WATER
Composition: The composition of the
treated sea water is shown in Table CXVIII.
The table also includes the composition of
treated sea water previously obtained in
the laboratory on a bench scale (ref. 8) .
It is obvious that the composition of the
water produced in the pilot plant is com
parable to that obtained in the laboratory.
The sea water fed to the pilot plant had
a chlorinity which varied between 17.84 and
19.41 per mill. The calcium concentration
in the untreated sea water ranged between
368 and 412 ppm and that of magnesium
between 1,173 and 1,302 ppm. Since the
residual concentrations of calcium and mag
nesium in the treated sea water were less
than 4 ppm and 0.5 ppm, the process can
TABLE CXVni. Composition of Treated
Sea Water
Composition Pilot plant Laboratory
(ppm) (ppm)
Ca» <» 10
Mg« <0.B <0.i
200 ев
NHj (flxed.and free)" 2,600 2,000
Solids 150
• Determined by emission spectrographs an
alysis.
** Approximately 10 per cent of the ammonia
is present as free NHs needed to achieve a pH of
8.5. The remainder is fixed as ammonium salts,
NH.C1 and (NHibSO..
remove approximately 99 and 100 per cent
of these scale-forming elements, respec
tively.
The small differences between the com
position of the treated sea water obtained
in the pilot plant and that under labora
tory conditions are probably attributable to
two factors: (1) the tendency of calcium to
form tricalcium phosphate rather than di-
calcium phosphate under pilot plant oper
ation and (2) the lower chlorinity sea
water used in the laboratory (i.e., 16.6 per
mill) . Because tricalcium phosphate is less
soluble than dicalcium phosphate, its pre
cipitation should decrease the calcium con
centration but increase that of phosphate in
the treated sea water (as was observed) .
The higher chlorinity sea water used in the
pilot plant contained more calcium and
magnesium than the water used in the labo
ratory. Its treatment required more am
monia and the resulting treated sea water
contained more residual fixed ammonia.
Distillation Tests: The treated sea water
(after removal of the free ammonia) was
tested in two types of distillation units, a
Cleaver-Brooks Model DVC-20 vapor-com
pression unit and a Swenson forced circu
lation evaporator. Unfortunately these were
the only units available at the test site and
were not really suitable for a thorough
evaluation of the treated sea water because
they were designed for operation at rela
tively low temperatures and low brine con
centrations. However, they were useful in
preliminary testing of the water and in
establishing whether operational difficulties
would be encountered with this type of
water.
The vapor-compression unit was one of a
type built for the Navy to produce fresh water
from sea water at temperatures just above
the normal boiling point. In normal opera
tion the distilling unit only concentrates
701
 the brine twofold. These units are very
susceptible to scale formation on heat-
transfer surfaces when operated at higher
temperatures and brine concentrations. The
vapor-compression unit was successfully
operated for 500 hours at a brine blow-
down of 3.1 to 3.3 using the treated sea
water as feed. Scale did not form on the
heat transfer surfaces as indicated by a de
crease in the differential pressure across
the boiler and condenser sections from 4.4
to 3.3 psi for the 500 hours of operation
(Fig. 266). Scale formation on the boiling
unit was operated at a liquor temperature
of about 276°F and at a brine concentration
factor of about 6:1. In the initial lest the
treated sea water was not deaerated and
the mild steel tubes in the heat exchanger
were severely perforated and eroded from
oxygen pitting, low pH, and high liquid
velocity conditions. In a later test with
deaerated water and aluminum-bronze
tubes, corrosion was not a serious problem.
Although the test was terminated after 116
hours because of pump difficulties, no scale
was found on the heat transfer surfaces.

6.0

/ RAW SEA WATER FEED

TREATEDjEAWJiS-
50%

TREATED

TEST UNIT: CLEAVER-BROOKS, MODEL DVC-20

1.0

1 _1_
100 200 300 400 500 600
HOURS ON STREAM

FIGURE 266. VARIATION OF DIFFERENTIAL PRESSURE WITH

HOURS ON STREAM FOR VARIOUS TYPES OF FEED WATER.

side of heat-transfer surfaces is normally The distillate contained an average of 130

reflected by an increased steam pressure on
the condensing side for constant evapora
tion rates, as also indicated in Figure 266
for raw sea water and to a much lesser de
gree for a mixture of 50 per cent raw sea
water and 50 per cent treated water. Unlike
raw sea water, no foaming was observed
during the test period with the treated sea
water. Although no major processing prob
lems occurred, the fresh water distillate con
tained an average of 273 ppm of ammonia
and had a pH of 9.4.
The forced circulation evaporator was
used to test the treated sea water at higher
temperatures and brine concentrations. The
ppm of ammonia and had a pH of 9.4. The
blowdown brine, which had been concen
trated by a factor of about 6:1, had a pH
of 4 to 5.
The distillation tests indicate that the
problem with scale formation is probably
eliminated when treated sea water is used
as feed to an evaporator. However, two new
problems are created by utilizing this type
of water, namely, absorption of ammonia in
the fresh water distillate which affects its
potability and the development of a low pH
in the brine which increases its corrosiviiy.
Potability of the Distillate: The previous
tests indicate that the distillate would con

702
 tain about 200 ppm of ammonia. Although
there appear to be no public health restric
tions on the concentration of ammonia in
potable water (other than as an indication
of bacterial activity in polluted streams)
(ref. II), it does affect the taste of the
water and, therefore, should not be present
at more than a few ppm. (One or two ppm
of ammonia are frequently added to drink
ing water to fix chlorine as chloramine.)
Some method for removing ammonia from
the distillate or keeping it out of the dis
tillate would have to be developed before
the water would be potable.
As previously indicated, about 10 per
cent of the total ammonia in the treated
sea water is present as free ammonia. The
free ammonia is needed to raise the pH of
the water to 8.5 and to insure calcium pre
cipitation. The concentration of ammonia
in the distillate is about the same as that of
free ammonia in the treated sea water. Be
cause of its high vapor pressure and high
solubility in water, the free ammonia is
simply carried over with the distillate.
Efficient deaeration of the treated sea water
prior to distillation might solve this prob
lem.
There is another source of ammonia in
the treated sea water, the ammonium salts,
which gradually hydrolyze to liberate am
monia according to the following equations:
N H.CI -(- H.O -NH.OH + HC1 (4)
NH4 OH NH, + H,0 (5)
However, the amount of free ammonia lib
erated by hydrolysis is thought to be small
as compared to that already present in the
treated sea water for pH adjustment.
Corrosion: Because of hydrolysis (Eq. 4)
solutions of ammonium salts are acidic.
When free ammonia is stripped from the
treated sea water (as occurs in an evap
orator) the pH is 5.0 to 55. The pH is
lowered still more as the ammonia pro
duced by hydrolysis is carried over with the
distillate (F.q. 5) . Therefore, the water be
comes corrosive, particularly to steels.
The corrosiveness of the treated sea water
was evaluated by placing a corrosion test
spool in the forced circulation evaporator
at a point 12 inches above the tube sheet
in the heat exchanger effluent stream. The
tubes in the heat exchanger were alumi
num-brass. The evaporator was operated
at an average temperature of 276°F. The
medium velocity in the evaporator tubes
was 13 feet per second. Although the test
was of rather short duration, only 161
hours, it did indicate that certain materials
of construction might be acceptable. For
example, the corrosion rates for copper.
90/10 copper-nickel, admiralty brass, M
bronze, G bronze, and aluminum-bronze
(7%) were all below 0.02 inches per year
with no evidence of pitting or intergranular
corrosion. Corrosion of iron and steel
samples was severe. Therefore, the effect of
this water on the shells of evaporators over
a long period of usage is questionable.
With the exception of the evaporator, no
serious corrosion problems were encountered
with the treated sea water. Corrosion tests
and visual inspection of the various pieces
of equipment in the pilot plant indicated
that most materials, including steel, were
acceptable in the various processing vessels.
BYPRODUCT EVALUATION
No attempt was made to granulate the
phosphates since they would be granulated
during the manufacture of the fertilizer
using the filter cake as a raw material. How
ever, solid spherical granules (—20 -4- SO
mesh) were occasionally formed in the de-
hydrator when it was operated above 210°F.
These were filtered to less than 20 per cent
moisture on the rotary drum filter and were
easily worked free of fines. Future studies
of this phenomenon should be made be
cause granulation within the dehydrator
would significantly lower the cost of fer
tilizer manufacture.
Composition: The analysis of the phos
phate granules is shown in Table CXIX.
Dried filter cakes containing 8 per cent
nitrogen and 45 percent P,05 were contained
in the pilot plant, whereas in the previous
laboratory work (ref 8) the products con
tained about 7 per cent nitrogen and 43 par
centPjO,. Theoretically pure magnesium am
monium phosphate monohydrate contains
9 per cent nitrogen and 45 per cent P,Os.
It is obvious that a more desirable product
was produced in the pilot plant, probably
due to more consistent operating conditions.
TABLE CXIX. Composition of
Phosphate Byproduct
Per cent
Moisture at 100°C 0.42
N a.oo
PiOi 46.20
InBol. PiO.* 4.08
Avail. PjOb" 41.12
Water soluble N <0.05
Mb-O 23.80
CaO 6.81
* Insoluble in neutral ammonium citrate solu
tion according to method of the Association of
Official Agrriculural Chemists (ref. 12).
•• The percentage of PiOi which Is available aa
a plant nutrient (ref. 12).
703
 The very low percentage of water soluble
nitrogen (< 0.05%) is significant. When
magnesium ammonium phosphate is pro
duced commercially from conventional raw
materials, it contains 1 to 2 per cent water
soluble nitrogen and 6 to 7 per cent water
insoluble nitrogen. Although both materials
contain the same total amount of nitrogen
(8%) , the water insoluble nitrogen is more
valuable agronomically.
Phosphate Recovery: High phosphate re
covery is essential because the raw material
cost for phosphoric acid amounts to more
than half the total cost of the process.
Therefore, any loss of phosphate into the
treated sea water adds materially to the
economic burden of the fertilizer. In pre
vious laboratory research (ref. 8). a phos
phate recovery of approximately 98 per
cent was achieved. The amount of phos
phoric acid added was stoichiometrically
equivalent to the calcium and magnesium
in the sea water based on the formation of
magnesium ammonium phosphate and di-
calcium phosphate. A somewhat lower re
covery was obtained in the pilot plant, due
partlv to greater mechanical losses and
partlv to the formation of tricalcium phos
phate rather than dicalcium phosphate. An
assured recovery of 90 per cent of the P,Os
in the byproduct was shown and it appears
that 95 per cent may be reasonably an
ticipated.
Phosphate recovery is improved by oper
ating with less than the stoichiometric
amount of phosphoric acid; however, the
calcium level of the treated sea water in
creases. For example, at addition levels of
P20, close to stoichiometric, magnesium
was almost completely removed (less than
0.4 ppm) and the calcium content was re
duced to less than 10 ppm. With 3 per cent
less than the stoichiometric amount of
P,05, the magnesium concentration was still
very low but the calcium concentration was
56 ppm. If treated sea water with 56 ppm
of residual calcium is adequate for evap
orator feed, a significant savings in by
product cost could be achieved due to high
er phosphate recovery. The optimum level
ECONOMIC CONSIDERATIONS
Preliminary cost estimates (refs. 9, 10)
had shown that raw material costs were
considerably more significant than process
ing costs. Before making a more concise
cost evaluation, two factors were considered
which would improve raw material costs:
(I) on-site production of dilute phosphoric
acid directly in sea water and (2) the re
704
for removing the scale formers from sea
water is at present an unresolved factor
Ammonia Recovery: According to Equa
lion (1) only a third of the ammonia used
to precipitate the magnesium ammonium
phosphate is recovered with the precipitate;
the remainder of the ammonia is left in the
treated sea water as ammonium chloride (or
sulfate) . None ' of the ammonia used to
precipitate the dicalcium phosphate is re
covered with the precipitate (Eq. 2) . Free
ammonia required to attain a pH of 85
also remains in the treated sea wateT. The
maximum amount of ammonia that could
be recovered in the precipitate is approxi
mately 28 per cent of the total. That re
maining in the treated sea water is not lost,
however, since most of it can be recovered
and recycled, as will be discussed later.
Agronomic Value: The agronomic prop
erties of magnesium ammonium phosphate
are quite remarkable. Because of its low
solubility, magnesium ammonium phosphate
in granulated form is a slow release fertilizer.
Interest in this type of fertilizer has been
increasing in recent years. Unlike conven
tional water soluble fertilizers, the release
rate of plant nutrients from magnesium
ammonium phosphate can be controlled bv
granule size (refs. 13, 14) . It does not leach
from sandy or porous soils, will not burn
plants even when used in large overdosages,
and its nutrients remain available to the
plants over a long period of time. Agro
nomic tests indicate that plants utilize the
nutrients from magnesium ammonium phos
phate more efficiently than those from
most conventional fertilizers (refs. 15-17).
Magnesium ammonium phosphate in
granulated form may be placed adjacent to
the bare roots of plants without danger of
burning or damaging the plant. Because
of this property several years' supplv of the
fertilizer may be applied when planting a
small bush or tree. Such accurate place
ment of nutrients, where needed, en
courages rapid growth of the plant without
fertilization of weeds and other competitive
growths.
covery and recycle of ammonia from the
residue brine of the evaporator.
PRODUCTION OF DILUTE PHOSPHORIC ACID
In a conventional phosphoric acid plant,
phosphate rock is reacted with concentrated
sulfuric acid and recycled dilute phosphoric
acid. After sufficient residence time to
insure maximum reactivity, the resulting
slurry is filtered. The filter cake (calcium
sulfate) is washed. Part of the wash (dilute
phosphoric acid) is recycled. The remainder
is combined with the original filtrate and
evaporated until the phosphoric acid con
centration is approximately 54 per cent
P,05. Most phosphoric acid plants produce
and captively use their own sulfuric acid.
The heat liberated by burning sulfur is
utilized to concentrate the phosphoric acid.
The process for removing scale formers
from sea water does not require concen
trated phosphoric acid. There are several
advantages in producing a dilute acid (e.g.,
16% Pj05) . Recovery is higher because the
phosphate rock and sulfuric acid react
more completely. The capital costs and
processing costs are lower because of the
elimination of equipment to concentrate
the acid is unnecessary and because the
calcium sulfate is easier to filter and wash.
Credit may be taken for the heat produced
in the sulfuric acid plant or this heat used
for other purposes (e.g., for the recovery
and recycle of ammonia) .
Research carried out in a laboratory
bench-scale unit operating continuously for
approximately one week indicated that
dilute phosphoric acid (16% P205) could
be produced by reacting sulfuric acid and
phosphate rock in sea water. The recovery
of Pj05 was 98 per cent or better with
indications that the consumption of sulfuric
acid was slightly lower than conventionally
required. Sufficent operating data were ob
tained to permit a cost estimate and plant
design.
The cost estimate indicated that dilute
phosphoric acid could be produced at many
coastal locations adjacent to a desalination
plant for a price equal to or less than that
in conventional phosphoric acid plants pro
ducing concentrated acid. The savings in
capital and processing costs compensate for
the fact that the plant would usually be
smaller and farther from the source of phos
phate rock than a conventional phosphoric
acid plant.
RECOVERY AND RECYCLE OF AMMONIA
As previously shown, the treated sea
water contains about 2,000 ppm of fixed
ammonia and about 200 ppm of free am
monia. Most of the free ammonia would be
stripped from the treated sea water upon
efficient deaeration of the water. The fixed
ammonia would become more concentrated
in the evaporator and would be ejected
with the residue brine. Its recovery and
recycle is important to the economics of the
process since it represents approximately
70 per cent of all the ammonia used.
The recovery and recycle of ammonia
(both fixed and free) from waste brines are
handled with great efficiency and at low
cost in the commercial process for the pro
duction of soda ash (ref. 18) . Yields greater
than 99 per cent are achieved. Free am
monia is recovered by sparging the brine
with steam. Fixed ammonia is recovered by
first treating the brine with lime and then
stripping the resulting free ammonia from
the brine by sparging with steam. The
whole operation is carried out in a specially
designed ammonia recovery tower (ref. 18) .
The feasibility of recovering ammonia from
the waste brines obtained after desalination
of the treated sea water was investigated
using technology similar to that of the soda
ash process. A major soda ash producer
was consulted in making this study.
The study indicated that ammonia could
be recovered in high yield (> 99%) from
the waste brines. The cost is significantly
affected by the quantity of steam needed
and its price. Capital costs are not particu
larly significant because of the large amount
of ammonia to be recovered (as is true for
the soda ash process) . The amount of steam
required depends on the brine concentra
tion factor at which the evaporators oper
ate, because this controls the volume of
rejected brines which must be treated.
Sulfate may present a problem since sea
water brines contain a much higher sulfate
concentration than is normally encountered
with brines used in soda ash production.
If the treated sea water were concentrated
until saturated with salt (concentration
factor of about 10 to 1) , its composition
(with the exception of sulfate) would not
be greatly different from that of the brines
treated in the soda ash process. In this case
the cost to recover ammonia should be low.
Unfortunately, most evaporators currently
operate at brine concentration factors of 2
or 3 to 1 and this greatly increases steam
requirements. Nevertheless, the recovery
and recvele of ammonia are still desirable.
The cost of recovered ammonia would be
about half that of purchased ammonia in
a plant producing 10 mgd of fresh water
from treated sea water, operating at a brine
concentration factor of S to I, and using
steam for ammonia recovery at 55 cents per
1 ,000 pounds.
CAPITAL AND MANUFACTURING COSTS
FOR BYPRODUCT RECOVERY
Capital and manufacturing costs for the
removal of scale formers with byproduct
705
fertilizer recovery were estimated for a
plant treating 15 mgd of sea water and
yielding 10 mgd of fresh water (i.e., operat
ing at a brine concentration factor of 3 to
1) . A Florida location was assumed be
cause firmer prices were available for raw
materials and finished fertilizers than at
other locations. The total complex included
(1) a sulfuric acid plant producing 93 per
cent sulfuric acid, (2) a phosphoric acid
plant producing diluie phosphoric acid
TABLE CXX. Capital and Manufacturing Costs for Removing Scale Formers
with Byproduct Recovery
Sea water treated (epâ)
Fresh water production (gpd)
Brine concentration factor
Fertilizer production (8-48-0), dry basis (tons/day)
Location
Total plant investment:*
Sulfuric acid
Phosphoric acid
Ammonia stripping
Chemical treatment
Distillation
Total (not including distillation)
Manufacturing eoata:
Fertiliser byproduct ($/ton)*>
Treated sea water (i/1.000 gallons)
* Does not include site preparation, terminal dock facilities, or working capital.
** Does not Include granulation costs, G & A. Bales expense, or profit.
The influence of steam costs for ammo
nia stripping is very significant as pre
viously discussed. A value of 55 cents per
1,000 pounds was used for the estimate in
Table CXX. At a steam cost of 24 cents per
1,000 pounds, the manufacturing cost of the
byproduct fertilizer would show a reduction
of $3.09 per ton.
No credit was taken for anv intrinsic
increased value of the treated sea water
produced by this facility, the implicit as
sumption being that sale of the byproduct
would pay for the chemical treating proce
dure (i.e., the treated sea water would be
produced at no cost) . However, if a charge
is assessed to the potable water produced
from such facilities, then for every cent per
1,000 gallons of fresh water produced, the
ACKNOWLEDGEMENTS
This research was carried out by the
VV. R. Grace & Co., Research Division.
Washington Research Center, Clarksville.
Maryland, under Contract No. 14-01 -0001 -323
with the Office of Saline Water, U.S.
Department of the Interior. A large num
ber of people were involved in supplying
(16% P.O.) directly in sea water, (3) an
ammonia stripping plant to recover the
fixed ammonia in the brine concentrate,
and (4) a chemical treatment plant for
removing the scale formers with byproduct
fertilizer recovery. The estimates shown in
Table CXX were based on the best informa
tion available from pilot plant experience
and various engineering and laboratory
studies.
16,000.000
10,000.000
8:1
590
$ 1.900.000
1.900,000
2,600,000
4,200,000
10,600,000
864.20
I
byproduct manufacturing costs would be
reduced by 20 cents per ton.
Under favorable conditions it appears
that the byproduct fertilizer material could
be produced for about $50 per ton not in
cluding granulation which would cost a
few dollars per ton. At this production
cost the finished fertilizer would have to sell
for a 10 to 20 per cent premium (on a
nutritional value basis) over conventional
bulk fertilizers in order to be economically
feasible. There is no question that this
could be done in the specialty fertilizer
markets because of its high quality and
unusual agronomic properties. However,
the large production rate necessitates that
nonspecialty markets, which are primarily
influenced by price, also be tapped.
pilot plant, laboratory, and engineering
information in this study. Credits are due
particularly to C. J. A. Volz, E. T. Wood
ruff, M. G. Dunseth. W. Lutz (The Weston
Process Design Corp.) , Diamond Alkali Co..
and The International Nickel Co.
 REFERENCES
1. Lacy, R. E.; Lang, E. W.; Feazel, C. E.:
"Investigation of chelation as a means
of removing ions from sea water",
Office of Saline Water R&D Rept. no.
42 (Mar. 1961) .
2. Checkovich, A.: U.S. Patent No. 3,1 19,752
(Jan. 28, 1964) .
3. Mcllhenny, W. F.: "Sea water soften
ing by ion-exchange as a saline water
conversion pretreatment". Office of Sa
line Water R&D Rept. no. 62 (May
1962).
4. Hunter, R. F.; Simmons, J. P.; Spinner.
I.H.: "Scale prevention by reciprocat
ing flow ion-exchange", Dept. of Chem
ical Engineering and Applied Chemis
try, University of Toronto, Toronto,
Canada (1965) (Chem. Eng. News. Feb.
22, 1965, pp. 38-41) .
5. Gainey, R. J.; Thorp, C. A.; Cadwal-
lader, E. A.: Ind. Eng. Chem. no. 55
(1963) p. 39.
6. Waters, O. B., Jr.; Salutsky, M. L.:
"Lime-soda softening of sea water".
147th Natl. Meeting, Amer. Chem. Soc..
Philadelphia (1964).
7. Salutsky, M. L.; Dunseth, M. G.; Waters,
O. B., Jr.: "Mineral byproducts from
the sea", Office of . Saline Water R&D
Rept. no. 91 fMar. 1964) pp. 72-84.
8. Dunseth, M. G.; Salutsky, M. L.: Ind.
Eng. Chem. vol. 56, no. 6 (1964) p. 56.
9. Salutsky, M. L.; Dunseth, M. G.; Eason,
W. E., Jr.: "Removal of scale-forming
compounds from sea water", Office of
Saline Water R&D Rept. no. 57 (Feb.
1962).
SUMMARY C
There was no discussion.
10. Ibid., Rept. no. 66 (Sept. 1962).
11. "Standard methods for the examination
of water, sewage, and industrial wastes",
10th edition, American Public Health
Association, Inc., 1790 Broadway, New
York 19. N. Y. (1955) .
12. "Official methods of analysis of the As
sociation of Official Agricultural Chem
ists", 9th edition, W. Horwitz, editor,
Association of Official Agricultural
Chemists, P. O. Box 540, Benjamin
Franklin Station, Washington 4, D. C.
(1960).
13. Bridger, G. L.; Salutsky, M. L.; Star-
ostka, R. W.: /. Agr. Food Chem. no.
10 (1962) p. 181.
14. Lunt, O. R.; Kofranek, A. M.; Clark.
S. B.: J. Agr. Food Chem. no. 12 (1964)
p. 497.
15. Leiser, A. T.; Sanborn, J. M.: "The
efficiency of nitrogen and phosphorus
uptake from magnesium ammonium
phosphate", Abstracts of Papers, 142nd
Meeting of the American Chemical So
ciety, Atlantic City, N. J. (Sept. 1962)
p. 13J.
16. Koritskaya, T. D.; Remen, R. E.: Zh.
Vses. Khim. Obshchestva im. D. I. Men-
deleeva vol. 7, no. 5 (1962) p. 520.
17. Voth, V.; Bringhurst, R. S.; Lunt. O. R.:
California Agriculture (Oct. 1963) pp.
7-8.
18. Hon, T. P.: "Manufacture of soda".
2nd edition, Reinhold Publishing Corp..
New York (1942) pp. 225-250.
DISCUSSION
707
 Elimination Des Générateurs de
Tartre Avec Recuperation Des
Sous-Produits
Murrell L. Salutsky et Phil Messina
Etats-Unis d'Amérique
En raison des économies très poussées
associées avec le dessalement de l'eau de
mer. presque tous les coûts de contrôle de
l'entartrage sont prohibitifs. Le contrôle
de l'entartrage ne coûtant rien pourrait
seulement se faire si un sous-produit était
simultanément produit qui puisse être
vendu avec un bénéfice suffisant pour com
penser le coût de l'élimination des généra
teurs de tartre dans le prétraitement de
l'eau de mer. Comme le tartre se compose
de composés de calcium et de magnésium
et que les sources bon marché de calcium
sont nombreuses, le sous-produit doit être
un composé du magnésium. Sa valeur ne
doit pas être sérieusement diminuée en
raison de la contamination avec le calcium
qui doit également être retiré de l'eau de
mer. Il faut qu'il y ait des marchés im
portants pour le sous-produit. Le retrait
des générateurs de tartre, y compris la
production d'un engrais constituant un sous-
produit, est prometteur pour remplir ces
conditions.
Un procédé de prétraitement basé sur la
précipitation d'un mélange de phosphate
d'ammonium-magnésium et de phosphate
de calcium a été évalué dans une installa
tion pilote conçue pour traiter 400 m"
d'eau de mer par jour. On ajoute de l'acide
phosphorique à l'eau de mer et ensuite
suffisamment d'ammoniac pour produire un
sédiment de pH 8,5. Le mélange est dé
chargé dans un réservoir de clarification
d'où le trop-plain limpide est pompé vers
l'ensemble de conversion de l'eau saline.
Le sédiment de boue de phosphate est
pompé à un déshydrateur et la boue est
maintenue à 90°C pendant une heure
pour convertir le phosphate d'ammonium-
magnésium de son hexahydrate au mono-
hydrate, augmentant ainsi sa valeur en tant
qu'engrais. La boue est alors filtrée à chaud
et les phosphates sont envoyés à une usine
de fabrication d'engrais en vue de les trans
708
former en un produit fini.
L'installation pilote a fonctionné avec
succès comme conçue. Les instruments pour
le contrôle du débit et la mesure des
matières premières ont donné une limite de
140% de la capacité d'étude. Tous les
autres éléments de l'équipement semblent
fonctionner d'une façon satisfaisante au
niveau de 140% avec l'exception possible
du réservoir de clarification où la nécessité
d'un agent de floculation était indiquée.
L'eau de mer traitée, produite dans l'in
stallation pilote, avait de très faibles con
centrations de calcium et de magnésium,
respectivement moins de 4 ppm et 0,5 ppm.
Le procédé est donc capable d'éliminer de
99 à 100% de ces éléments d'entartrage.
Comme les ions calcium et magnésium
étaient remplacés avec des ions ammonium,
l'eau traitée contenait environ 2.000 ppm
d'ammoniac fixé sous forme de chlorure
et de sulfate d'ammonium. En outre, l'eau
contenait environ 200 ppm d'ammoniac à
l'état libre nécessaire pour l'ajustement du
pH. Une concentration résiduelle d'environ
200 ppm de P,Oj a également été observée.
Cette perte a été réduite en diminuant
l'alimentation d'acide phosphorique au-
dessous du montant stoïchimmétrique. L'eau
en résultant contenait une teneur en cal
cium plus élevée (10 à 100 ppm) qui
pouvait être contrôlée pour convenir aux
conditions de l'installation de distillation
tout en réduisant au minimum les besoins
en acide phosphorique.
L'eau de mer traitée a été essayée dans
deux types d'appareils de distillation, un
appareil à compression de vapeur Clcaver-
Brooks modèle DVC-20 et un évaporateur
Swenson à circulation forcée. L'appareil à
compression de vapeur a fonctionné avec
succès pendant 500 heures avec un résidu
de saumure de 3,1 à 3.3 en utilisant l'eau
de mer traitée comme alimentation. Le
tartre ne s'est par formé sur les surfaces de
 transfert de chaleur comme indiqué par
une diminution dans la pression différen
tielle, à travers les sections du condenseur
et de la chaudière de 0,3 à (Ш kg/cm* pour
les 500 heures de fonctionnement. A l'in
verse de l'eau de mer brute, aucun moussage
n'à été observé avec l'eau de mer traitée.
L'évaporateur à circulation forcée a fonc
tionne à une température de liquide d'en
viron 135°C et à un facteur de concentra
tion de saumure de 6:1. Bien que l'essai ait
été interrompu après 116 heures en raison
de difficultés de pompage, on n'a trouvé
aucun entartrage sur les surfaces de trans
fert de chaleur. La corrosion n'a pas
constitué de problème sérieux lorsque l'éva-
porateur a été équipé avec des tubes en
bronze d'aluminium.
Les essais de distillation indiquent que
le problème de la formation du tartre a
probablement été éliminé lorsqu'on utilise
de l'eau de mer traitée pour l'alimentation
de l'évaporateur. Cependant, deux nouveaux
problèmes se trouvent créés par l'utilisation
de ce genre d'eau, à savoir le transfert
d'ammoniac libre dans le distillât d'eau
douce qui affecte son goût et provoque un
faible pH dans la saumure, ce qui aug
mente son pouvoir de corrosion. Dans le
premier cas, un dégazage efficace de l'eau
de mer traitée avant la distillation pourrait
résoudre ce problème en éliminant l'am
moniac libre. Cependant, le pH de l'eau
traitée tombe alors à moins de 6 et devient
plus corrosif, particulièrement pour les
aciers.
L'agressivité de l'eau de mer traitée a été
évaluée en plaçant une bobine d'essai de
corrosion dans l'évaporateur à circulation
forcée. Les taux de corrosion pour le
cuivre, le cupro-nickel 90/10, le laiton de
l'amirauté, le bronze M, le bronze G, et le
bronze d'aluminium (7%) étaient tous bien
inférieurs à 0,5 mm par an sans constation
de corrosion par piqûre ou intergranulaire.
La corrosion des échantillons de fer et
d'acier était sévère.
Le sous-produit obtenue dans l'installa
tion pilote contenait environ 8% de nitro-
gène et 45% de P2Oj et devrait convenir
pour la production d'engrais. Les propriétés
agronomiques du phosphate de magnésium-
ammonium sont tout a fait remarquables.
En raison de sa faible solubilité, le phos
phate de magnésium-ammonium sous forme
granulée constitue un engrais à dégagement
lent. Au cours des dernières années, on a
constaté un intérêt croissant dans ce type
d'engrais. Contrairement aux engrais nor
maux solubles à l'eau, le taux de dégage
ment des sels nutritifs du phosphate de
magnésium-ammonium pour les plantes peut
se contrôler par la dimension des granules.
Il ne s'échappe pas par lixiviation des sols
sablonneux ou poreux, il ne brûle pas les
plantes même lorsqu'il est utilisé dans des
doses trop importantes, et ses sels nutritifs
restent disponibles aux plantes pendant
une longue période de temps.
La récupération du phosphate dans le
sous-produit était de 90% et il semble que
l'on puisse raisonnablement compter sur
une récupération de 95%. Cependant, la
récupération maximum de l'ammoniac dans
le produit est d'environ 28%, la plupart du
reste étant présent dans l'eau de mer
traitée sous forme d'ammoniac fixé. Comme
les estimations de prix de revient prélimi
naires montrent que les coûts des matières
premières sont considérablement plus signi
ficatifs que les coûts du traitement, deux
facteurs ont été considérés que devraient
améliorer les coûts des matières premières:
(1) la production sur les lieux d'acide
phosphorique dilué directement dans l'eau
de mer et (2) la récupération et la re
circulation de l'ammoniac depuis les sau
mures résiduaires.
La première étude indique que l'acide
phosphorique dilué peut être produit à de
nombreux emplacements côtiers proches
d'une installation de dessalement pour un
prix égal ou moindre à celui en cours dans
une usine normale d'acide phosphorique
qui fabrique de l'acide concentré, bien que
l'échelle de fonctionnement soit beaucoup
plus faible. Il en résulte des économies en
ce qui concerne les dépenses en capital et
les dépenses de traitement parce que l'acide
n'a pas besoin d'être concentré. Une petite
augmentation de rendement est également
obtenue.
La seconde étude indique que l'ammoniac
peut être récupéré avec un rendement élevé
(supérieur à 99%) des saumures résiduaires
par un procédé similaire à celui utilisé
dans le procédé Solvay pour la production
du carbonate de sodium. Le coût est affecté
d'une façon significative par la quantité de
vapeur nécessaire et par son prix. Le coût
de l'ammoniac récupéré devrait être la
moitié ou moins de celui de l'ammoniac
acheté dans des installations produisant
400.000 m' d'eau douce par jour depuis de
l'eau de mer traitée en fonctionnant à un
facteur de concentration de saumure de
3 pour 1.
Les frais d'investissement et de fabrica
tion pour l'élimination des générateurs de
tartre avec la récupération d'engrais sous
forme de sous-produit ont été estimés pour
une usine traitant 600.000 m" par jour d'eau
de mer et ayant un rendement de 400.000
m3 par jour d'eau douce. On a supposé un
709
 emplacement en Floride. L'ensemble du
complexe comprenait (I) une installation
d'acide sulfurique produisant un acide à
93%, (2) une installation d'acide prospho-
rique produisant un acide dilué (16% P,Ot)
directement dans l'eau de mer, (3) une
installation d'élimination de l'ammoniac
pour récupérer l'ammoniac fixé dans la
saumure concentrée, et (4) une installation
pour le prétraitement chimique de l'eau
de mer. L'investissement total (non compris
Удаление Образователен Накипи
с Рекуперацией Побочного Продукта
Мёррелл Л. Саллуцкий и фил Мессина
Соединенные Штаты Америки
Ввиду того, что с опреснением мор
ской воды связана жесткая экономика,
почти всякая стоимость борьбы с на
кипью является запретительной. До
биться предотвращения накипи без по
вышения себестоимости можно только
тогда, когда удастся получать побоч
ный продукт и продавать его с доста
точной выгодой, которая бы покрыва
ла затраты, связанные с обработкой
морской воды для удаления образова-
телей накипи. Так как накипь состоит
из соединений кальция и магния, а де
шевые источники кальция широко рас
пространены, то побочным продуктом
должно служить соединение магния.
Нельзя допускать, чтобы его ценность
понижалась вследствие загрязнения
кальцием, который тоже надо удалять
из морской воды. Для побочного про
дукта необходим широкий спрос. Уда
ление образователей накипи с одновре
менной выработкой удобрения в ка
честве побочного продукта сулит воз
можность осуществления этих условий.
Для опытной установки, рассчитан
ной на обработку 10.000 галлонов мор
ской воды в сутки, был произведен
подсчет стоимости процесса предвари
тельной обработки питания, основанно
го на осаждении смеси фосфата магния
и аммония, а также фосфата кальция.
К морской воде добавляется фосфор
ная кислота и достаточное количество
аммиака, чтобы получить взвесь с по
710
l'équipement de distillation) s'élèverait à
environ 10 millions de dollars. Dans des
conditions favorables, il semble que le sous-
produit sous forme d'engrais pourrait être
produit pour environ 50 dollars par tonne-
non compris les frais de granulation. Л ce
prix de production, il faudrait que l'engrais
fini se vende de 10 a 20% de plus que les
engrais en' masse normaux (en raison de sa
valeur nutritive) pour que sa production
soit économiquement possible.
казателем pH = 8,5. Смесь выпуска
ется в отстойник, из которого светлый
слив перекачивается в опреснительный
агрегат. Находящаяся внизу взвесь
фосфата откачивается в дегидратор и
в течение одного часа поддерживается
при температуре 195°F, чтобы превра
тить смешанные фосфаты магния и ам
мония из гексагидратов в моногидраты,
тем самым повышая их ценность как
удобрение. Затем взвесь в горячем со
стоянии фильтруется и фосфаты от
правляются на завод искусственных
удобрений для выработки окончатель
ного продукта.
Как проект, так и эксплуатация опыт
ной установки оказались удачными.
Аппаратура для регулирования потока
и измерения сырья была достаточной
при работе, достигавшей 140% наме
ченной производительности. Все ос
тальные части оборудования повиди-
мому функционировали удовлетвори
тельно на 140% уровне за возможным
исключением аппарата для осветления,
где обнаружилась потребность во
флоккулирующем агенте.
Обработанная на опытной установке
морская вода имела очень низкие кон
центрации кальция и магния, а именно
менее, чем 4 мг/л первого и 0,5 мг/л
второго. Следовательно, процесс мо
жет удалять 99-100% этих образующих
накипь элементов. Так как ионы каль
ция и магния заменялись ионами аммо-
ния, обработанная вода содержала око
ло 2.000 мг/л связанного аммиака в
форме хлорида аммония и сульфата.
Кроме того, вода содержала около 200
мг/л свободного аммиака, нужного для
регулирования pH. Была также замече
на остаточная концентрация Р2Ов в
размере 200 мг/л. Эта потеря была
уменьшена сокращением питания фос
форной кислотой до уровня ниже сте-
хиометрического количества. Произво
димая вода содержала больше кальция
(10—100 мг/л), что можно было регу
лировать и приспособлять к условиям,
налагаемым дистилляционной установ
кой, одновременно доводя до миниму
ма потребность в фосфорной кислоте.
Обработанная морская вода была
испытана в дистилляционных агрегатах
двух типов: Модели DVC-20 Кливер-
Брукса со сжатием пара, и системы
Свенсона, снабженной испарителем с
принудительной циркуляцией. Агрегат
со сжатием пара удовлетворительно ра
ботал в течение 500 часов при продув
ке рассола 3,1-3,3, пользуясь в качестве
питания обработанной морской водой.
Как указано, благодаря снижению в
секциях кипячения и конденсации диф
ференциального давления с 4,4 до 3,3
фунтов на кв. дюйм, в течение пятисот
часовой работы накипь на теплопере-
даточных поверхностях не образовыва
лась. В отличие от естественной мор
ской воды, обработанная морская вода
не пенилась. Испаритель с принуди
тельной циркуляцией функционировал
при температуре жидкости около 276Т
и факторе концентрации рассола 6 : 1.
Несмотря на то, что из за неисправно
стей перекачки через 116 часов при
шлось прекратить испытание, на те-
плопередаточных поверхностях не бы
ло найдено никакой накипи. При испа
рителях с трубами из алюминиевой
бронзы коррозия не являлась серьез
ной проблемой.
Испытания дистилляции указывают,
что при питании испарителя обработан
ной морской водой, проблему образо
вания накипи вероятно можно считать
ликвидированной. Однако, при пользо
вании такой воды возникли две новые
проблемы, а именно, перенос свободно
го аммиака в дистиллят пресной воды,
что влияет на ее вкус, и образование
низкого pH в рассоле, увеличивающего
его коррозийность. В первом случае
эффективная деаэрация обработанной
морской воды до ее дистилляции может
разрешить эту проблему посредством
отгонки свободного аммиака. Однако,
тогда показатель pH обработанной мор
ской воды падает до уровня ниже 6 и
вода становится более коррозийной,
особенно для стали.
Оценка коррозийности обработанной
морской воды была произведена с по
мощью коррозо-испытательной катуш
ки, помещенной в испаритель с при
нудительной циркуляцией. Скорость
коррозии меди, сплава 90/10 меди и
никкеля, адмиралтейской латуни, брон
зы типа М, бронзы типа G и 7%-аллю-
миниевой бронзы была меньше 0,02
дюйма в год без признаков питтинго-
вой или межкристаллитной коррозии.
Коррозия образцов железа и стали, бы
ла весьма сильной.
Побочный продукт получаемый с
опытной установки содержал примерно
8% азота и 45% Р2Ов и казался при
годным для выработки удобрения.
Агрономические свойства смеси фос
фата магния заслуживают большого
внимания. Вследствие своей низкой ра
створимости она в гранулированной
форме является удобрением медленно
го действия. За последние годы инте
рес, вызываемый удобрением такого
типа, продолжает расти. В отличие от
обыкновенных водорастворимых удоб
рений, скорость выделения питающих
растения веществ из смеси фосфата
магния и аммония поддается регулиро
ванию размером отдельных гранулей.
Она не выщелачивается в песчаных или
пористых грунтах, не обжигает расте
ний даже при чрезмерной дозировке, а
ее питательные вещества остаются до
ступными для растений в течение дол
гого времени.
Рекуперация фосфатов в побочном
продукте достигала 90% и можно с
уверенностью ожидать ее повышения
до 95%. Однако, максимальная реку
перация аммиака из продукта состав
ляет примерно 28%, в то время как
большая часть его остатка находится
в обработанной морской воде в свя
занной форме. Так как предваритель
ные сметы указывают, что стоимость
сырья значительно важнее, чем стои
мость обработки, были приняты во вни
мание два фактора, которые могли бы
снизить стоимость сырья: (1) произ
водство разбавленной фосфорной ки
слоты непосредственно в морской воде
на месте установки и (2) рекуперация
и рециркуляция аммиака из остаточных
рассолов.
Первое исследование указало, что
разбавленная фосфорная кислота мо
жет вырабатываться на многих при
711
 брежных участках, примыкающих к
опреснительным установкам, и обхо
диться столько же или даже менее, чем
на обыкновенном заводе концентриро
ванной фосфорной кислоты, несмотря
на то, что испытания производились в
значительно меньшем масштабе. Сни
жение капитальных и эксплуатацион
ных расходов объясняется отсутствием
необходимости концентрировать кисло
ту. Кроме того, получается некоторое
небольшое повышение производитель
ности.
Второе исследование указало, что
имеется возможность рекуперировать
более 999г аммиака из сбросных рас
солов по способу, применяемому в про
цессе Солвея для выработки безводно
го карбоната натрия (кальцинирован
ной соды). Стоимость в значительной
степени зависит от количества потреб
ного пара и его цены. Рекуперирован
ный аммиак обойдется в два и даже
более, чем в два раза дешевле по срав
нению с покупным, на заводе, произ
водящем 10 миллионов галлонов опрес
ненной воды в сутки из обработанной
морской воды при факторе концентра
ции рассола 3 : 1.
Для установки, обрабатывающей 15
миллионов галлонов морской воды в
сутки и производящей 10 миллионов
Extracción de Formadores de Incru
staciones con Recuperación
de Subproductos
Murrell L. Salutsky y Phil Messina
Estados Unidos de America
A consecuencia de los rigurosos factores
económicos vinculados con la desalinización
del agua de mar, casi cualquier costo por
concepto de control de incrustaciones es
prohibitivo. El control de incrustaciones sin
costo alguno sólo podría lograrse si se
produjera simultáneamente algún subpro
ducto que pudiera venderse con una ganan
cia suficiente para sufragar el costo de
pretratamicnto del agua de mar con el fin
de eliminar los formadores de incrustacio
nes. Como éstas últimas consisten en com
712
галлонов опресненной воды, были под
считаны капитальные и эксплуатаци
онные расходы, связанные с удаление*
образователей накипи и рекуперацией
побочного продукта в виде удобрений.
Предполагаемым местом выработки яв
лялся шт. Флорида. В полный комплекс
были включены: (1) завод серной ки
слоты 93-процентной концентрации;
(2) завод фосфорной кислоты, произ
водящий разбавленный продукт (шест-
надцатнпроцентная Р2Ов) непосред
ственно в морской воде; (3) установка
для отгонки и рекуперации связанного
аммиака из концентрата рассола и (4)
химическая установка для предвари
тельной обработки морской воды. Ка
питаловложение, относящееся ко всему
комплексу (за исключением дистилля-
ционного оборудования) примерно со
ставит 10 миллионов долларов. Ожи
дается, что при благоприятных усло
виях стоимость производства побочно
го продукта, а именно удобрения,
обойдется примерно 50 долларов за
тонну, не считая стоимости гранулиро
вания. При такой стоимости производ
ства придется продавать готовые удо
брения, для того, чтобы они окупались,
на 10-20% дороже (беря за основание
питательную ценность), чем обыкно
венные массовые удобрения.
puestos de calcio y magnesio, y como las
fuentes de calcio a costo bajo son tan am
plias, el subproducto tiene que ser un
compuesto de magnesio. No debe permitirse
que baje mucho su valor por haberse con
taminado con el calcio, el cual debe tam
bién eliminarse del agua de mar. Debe
haber una gran demanda de este subpro
ducto en el mercado. La eliminación de los
formadores de incrustaciones con la pro
ducción simultánea de abono artificial como
producto secundario, promete satisfacer esas
necesidades.
En una planta piloto diseñada para
tratar 10.000 galones de agua del mar al
día, se ha evaluado un método de pretrata-
miento a base de la precipitación de una
mezcla de fosfato de amonio magnésico y
fosfato de calcio. Se añade ácido fosfórico
al agua de mar y luego una cantidad de
amoniaco suñciente para producir una
mezcla de pH 83. La mezcla se descarga
en un tanque de sedimentación de donde
el excedente puro que se desborda se
bombea a la instalación de conversión de
agua salina. La corriente subálvea de la
mezcla de fosfato se bombea a un deshidra-
tador, manteniéndose a una temperatura
de 195°F por espacio de una hora para
convertir el fosfato de amonio magnésico
de hexahidrato a monohidrato, aumentán
dose así su valor como abono artificial.
Después se filtra la mezcla aun caliente y
se envían los fosfatos a una empresa pro
ductora de abonos para su transformación
en un producto acabado.
La planta piloto funcionó con éxito de
acuerdo con su diseño. Se comprobó que
los instrumentos utilizados para regular la
con-iente de agua y dosificar las materias
primas tenían un limite de 140% de la
capacidad de diseño. Todos los demás com
ponentes de la instalación parecían funcio
nar satisfactoriamente al nivel de 140%,
con la posible excepción del clarificador,
donde se indicaba la necesidad de un
agente floculante.
El agua de mar sometida a tratamiento y
producida en la planta piloto tenia un
contenido muy bajo de concentraciones de
calcio y magnesio, o sea de menos de 4
ppm y 05 ppm, respectivamente. Por lo
tanto, este procedimiento puede extraer de
99% a 100% de los elementos formadores
de incrustaciones. A causa de que los iones
de calcio y de magnesio fueron reempla
zados por iones de amonio, el agua tratada
contenía alrededor de 2000 ppm de amo
niaco fijo, en forma de cloruro y sulfato
de amonio. El agua contenía, además, unas
200 ppm del amoníaco líquido necesario
para ajustar el valor pH. Se observó tam
bién una concentración residual de unas
200 ppm de P203. Esta pérdida se redujo
disminuyéndose la alimentación del ácido
fosfórico a menos de la cantidad estequio-
métrica. El agua resultante tenía un conte
nido de calcio más alto (10-100 ppm) que
podía regularse para ajustarse a las condi
ciones de la planta de desalinización, mien
tras se reducían al mínimo las necesidades
de ácido fosfórico.
El agua de mar tratada se sometió a
pruebas en dos tipos de instalaciones de
destilación — una compresora a vapor
Cleaver-Brooks, modelo DVC-20 y un eva-
porador Swenson de circulación forzada.
La compresora funcionó con éxito por
espacio de 500 horas, con una purga de
salmuera de 3,1 a 3,3, utilizándose el agua
de mar tratada para la alimentación. No se
formaron incrustaciones en las superficies
de transmisión térmica, como lo indica un
descenso de la presión diferencial, a través
de las secciones de la caldera y del conden
sador, de 4,4 a 3,3 lpc durante las 500
horas de operación. A diferencia del agua
de mar cruda, no se observó ninguna
espuma en el agua de mar sometida a
tratamiento. El evaporador de circulación
forzada se hizo funcionar a una tempera
tura del líquido de unos 276°F y una con
centración de salmuera de 6:1. Aunque la
prueba se suspendió al cabo de 116 horas
a causa de dificultades con las bombas, no
se encontraron incrustaciones en las super
ficies de transmisión térmica. Cuando el
evaporador estaba provisto de tubos de
latón de aluminio, la corrosión no consti
tuía un problema serio.
Las pruebas de destilación indicaron que
probablemente el problema de la forma
ción de incrustaciones se elimina utilizán
dose el agua de mar tratada como alimen
tación para el evaporador. Sin embargo,
al utilizarse este tipo de agua se han
creado dos nuevos problemas, a saber: el
paso del amoniaco libre al destilado de
agua dulce que altera su sabor y el desarro
llo de un bajo pH en las aguas madres
que contribuye a aumentar su corrosividad.
En el primer caso, la desaireación eficaz
del agua de mar tratada, antes de la
destilación, podría resolver ese problema
separando el amoniaco libre. Sin embargo,
el pH del agua de mar tratada bajará
entonces a menos de 6 y será más corrosivo,
especialmente para los aceros.
La corrosividad del agua de mar tratada
se determinó colocándose un carrete de
prueba de corrosión en el evaporador de
circulación forzada. La tasa de corrosión
del cobre, de la niquelina de 90/10, del
latón de aleación, del bronce M, del bronce
G y del bronce de aluminio (7%) fue, en
todos los casos, de menos de 0,02 pulgadas
al año, sin ninguna señal de corrosión
crateriforme o intergranular. La corrosión
era seria en las muestras de hierro y de
acero.
El subproducto obtenido en la planta
piloto contenía aproximadamente 8% de
nitrógeno y 45% de Pc05 y debiera ser
adecuado para la producción de fertilizan
tes. Las propiedades agrónomas del fosfato
de amonio magnésico son muy notables.
713
 A causa de su baja solubilidad, el fosfato
de amonio magnésico en forma granulada
es un fertilizante de emisión lenta. Durante
los últimos años se ha despertado un in
terés cada vez mayor en esta clase de
fertilizantes. A diferencia de los fertilizan
tes solubles en agua, la velocidad de emi
sión de los alimentos nutritivos para las
plantas, provenientes del fosfato de amonio
magnésico, puede regularse por el tamaño
de los gránulos. No se lixivia de los suelos
arenosos o porosos, no calcina las plantas,
aunque se use en cantidades excesivas, y
sus substancias nutritivas pueden ser apro
vechadas por las plantas en un largo
periodo.
La recuperación de fosfato del subpro
ducto fue de 90% y parece razonable
esperar un 95%. Sin embargo, la recupe
ración máxima de amoniaco del producto
es de más o menos 28%, permaneciendo
casi todo el resto en el agua de mar tra
tada, en forma de amoniaco fijo. Como los
cálculos preliminares indican que los costos
de la materia prima son mucho más signi
ficativos que los de elaboración, se tomaron
en consideración dos factores que contri
buirían a reducir los costos de la materia
prima, a saber: (1) la producción al pie
de la obra de ácido fosfórico diluido direc
tamente en agua del mar y (2) la recupe
ración y recirculación de amoniaco de las
aguas madres residuales.
El primer estudio indicó que el ácido
fosfórico diluido podfa producirse en mu
chos lugares contiguos a una planta de
desalinización a un precio igual o más bajo
que el de una fábrica corriente de ácido
fosfórico donde se produzca ácido concen
trado, aunque la explotación fuera en
escala mucho menor. Pueden hacerse aho
rros en los gastos de capital y de elabora
ción porque el ácido no tiene que ser
concentrado. También se obtiene un rendi
miento algo mayor.
714
El segundo estudio indicó que el amo
niaco podía recuperarse con rendimiento
elevado (>99%) de la salmuera residua',
por un método análogo al que se utiliza
en el procedimiento Solvay para la pro
ducción de carbonato sódico anhidro. En
el costo influye notablemente la cantidad
de vapor que se necesite y su precio. E!
costo del amoniaco recuperado sería b
mitad, o menos, del costo del amoniaco
comprado, en una planta que produzca 10
millones de galones por dia de agua dulce
obtenida de agua del mar tratada y que
funcione con un factor de concentración
de salmuera de 3 a 1.
Se calcularon los costos de instalación »
elaboración para eliminar los formadores
de incrustaciones, con recuperación de fer
tilizante como subproducto, en una planta
donde se trataban .15 millones de galones
al día de agua del mar y producían 10
millones de galones de agua dulce. Se
presumió la ubicación en Florida. El com
plejo total constaba de: (1) una planta de
ácido sulfúrico que producía ácido al 95*^,
(2) una planta de ácido fosfórico que
produda ácido diluido (16% P:Oj) direc
tamente en agua del mar. (3) una planta
de separación de amoniaco para recuperar
el amoniaco fijo en el concentrado de
salmuera, y (4) una planta para el pre
tratamiento químico de agua del mar. La
inversión total en las plantas (sin incluir
el equipo de destilación) serla de más o
menos $10.000.000. Según parece, en condi
ciernes favorables el material fertilizante
del subproducto podría producirse por $50
la tonelada, sin incluir los costos de granu
lación. A base de este costo de producción,
el fertilizante acabado tendría que venderse
a premio de 10-20% (a base del valor
nutritivo) por encima de los fertilizantes
corrientes a granel para que resulte econó
micamente viable.
A Pilot Plant Design Based upon a Di

rect Contact Flash Distillation Process

with Liquid-Liquid Heat Exchange

Clyde Don Watson

United States of America

INTRODUCTION
The feasibility of a direct contact flash
distillation process has been demonstrated
in laboratory equipment. Sufficient develop
ment work has been performed on process
and equipment to permit a design scale-up
for pilot studies at the 40,000 gpd level.
This paper explains a proposed pilot
study program currently under considera
tion by the Office of Saline Water. The
direct contact process and the equipment
that has been designed to carry out the
program are described and explained.
The direct contact flash distillation proc
ess is best described by a comparison with
the more familiar multistage flash distilla
tion process. The advantages and disad
vantages of the direct contact process are
discussed in terms of possible improvements
in the conventional process. After a general
description of the process, the specific de
tails of the pilot process and equipment
will be more meaningful.
Many desalting processes in use today
have been advanced sufficiently to warrant
consideration for possible application to the
design of large-scale saline water conversion
plants. Foremost among these processes is
the multistage flash distillation process
which has received a great deal of attention
in the last few years, and is now being
proposed in the design of 50 and 150 mgd
dual-purpose desalting power plants.
The FMC direct contact flash distillation
process is a logical variation of the basic
multistage flash process, wherein all metallic
heat exchange surfaces have been com
pletely eliminated. The primary advantage
of the direct contact process is the promise
of higher thermal efficiency and the absence
of scaling.

COMPARISON OF DIRECT CONTACT WITH

CONVENTIONAL MULTISTAGE FLASH DISTILLATION
The direct contact process differs from
the conventional multistage flash process in
the manner of condensation of product
vapors, and in the heating of the salt water
feed stream.
MULTISTAGE FLASH DISTILLATION PROCESS
In the conventional multistage flash proc
ess, incoming salt water flows through the
tubes of the condenser serving as the cool
ant for condensation of product vapors.
Thus the latent heat of condensation is
recovered in preheating the feed brine.
Process heat must then be supplied to the
brine at the highest temperature level in a
salt water heater. Subsequent flashing of
the brine through a long series of flash
chambers in counterflow to the feed yields
the product vapors, which are condensed
in each stage to produce fresh water and
then conveyed from stage to stage in a
separate stream parallel to that of the
flashing brine stream. This fresh water
stream flashes and recondenses as it passes
from stage to stage and finally leaves the
still in equilibrium with the outgoing
brine.

715
 DIRECT CONTACT RASH flash chambers vary incrementally from hot
DISTILLATION PROCESS to cold.
In the direct contact process, a cool fresh (3) In the third step, the product vapors
water stream is fed to the condenser of the in each stage are condensed by direct con
last stage wherein sufficient surface is ex tact with a cooler fresh water stream
posed to absorb the product vapors from flowing countercurrenlly. Hence, the heat
the evaporator of that stage; then, the and mass of the product vapors are ab-
slightly warmer fresh water stream is moved sorbed into the fresh water stream, resulting
on to the condenser of the next stage where in a heat recovery which is nearly rerombk
it is heated further, and so on throughout when a large number of stages are used
the still, until finally a hot fresh water (4) In the fourth step, the recovered
stream emerges from the first stage, carrying heat is very efficiently removed from the
with it the product and the associated heat fresh water by direct countercurrent contact
of condensation. Process heat is supplied to with the cool, immiscible hydrocarbon from
the fresh water stream either by conven Step 1 in another series of spray column1
tional means or by live steam injection. Hence, as the hydrocarbon is heated, the
In the heat recovery system, the fresh fresh water is cooled to almost ambient.
water stream is cooled by direct contact
countercurrent exchange with the salt water STEP 1 HVDFOCABBO*
feed stream in a liquid-liquid heat ex
changer, utilizing an immiscible hydro
carbon oil as the intermediate liquid. In ' f-
this way the salt water feed stream is
heated continuously from ambient to maxi STtP 2 FLASH CHAMBERS
mum temperature, entirely by direct contact,
and the main salt water heater is elimi
nated. The fresh water stream is cooled
more efficiently by countercurrent heat ex
change than by the irreversible flashing in
the conventional process.
DETAILED DESCRIPTION AND
FLOW DIAGRAM OF THE
DIRECT CONTACT PROCESS
The direct contact flash distillation
process is best understood in terms of four
steps involving three liquid streams and a
number of vapor streams. The three liquids
are brine, fresh water, and a suitable im
miscible hydrocarbon. The flow rates of the
three respective streams are maintained in
inverse proportion to their respective heat
capacities such that equal temperature
changes are experienced by any pair of
interacting streams. Referring to Figure 267:
(1) In the first step, brine is heated from HYDROCARBON
ambient to the upper process temperature
by direct countercurrent contact with a finely
dispersed, hot, immiscible hydrocarbon in a FIGURE 267. FLOW DIAGRAM
series of liquid spray columns. The hydro —FMC DIRECT CONTACT
carbon is cooled in the process of heating FLASH DISTILLATION
the brine. PROCESS.
(2) In the second step, the heated brine
is successively flashed down through a
number of irreversible pressure drops in a Integration of these four steps to form
series of flash chambers wherein product a complete cycle requires addition of suffi
vapors are formed at the expense of the cient process heat to fresh water or oil to
available sensible heat of the brine. The bring the temperature of the oil leaving
residual cooled brine is subsequentlv dis Step 4 up to that required for introduction
charged as blowdown. Temperatures of into Step 1.
the product vapor streams issuing from the The above flow diagram has been over
716
simplified for clarity of explanation. Figure
268 shows the general type of approach
required in the liquid-liquid heat exchanger
system to account for variation in specific
heat of the hydrocarbon. For each column
pair, the flow rate of the oil would be
adjusted for optimum temperature ap
proach in operation.
FIGURE 268. FLOW DIAGRAM-FMC LIQUID-LIQUID
EXCHANGER.
For example, a lower oil rate would be
used at the hot end because the oil heat
capacity is higher. The object is to make
the temperature change of the oil equal to
that of the water, thereby balancing the
temperature approaches at each end of the
individual columns.
CONVENTIONAL MULTISTAGE FLASH—
GENERAL DISCUSSION
The multistage flash process produces
excellent water with good steam economy;
however, the capital investment is appre
ciable, because a great deal of equipment
is required. Much of the cost of the equip
ment is attributable to large amounts of
HEAT
metallic heat exchange surface which must
be composed of alloys resistant to the
corrosive attack of heated brines flowing
inside the tubes.
The multistage flash process requires a
large number of stages, and in turn each
stage requires a large amount of heat ex
changer surface area for condensation of
 product vapors. Additional heat exchange
surface is required for the main brine heater
which supplies the process makeup heat.
Because of a high initial investment and
a large amount of metallic heat exchange
surface, the multistage flash distillation
process depends upon a source of low cost
process steam and an economical and effec
tive means of scale control if it is to com
pete favorably with other processes.
The large quantities of low pressure
turbine exhaust steam available from an
electrical power plant lead to the favorable
economics of dual-purpose power-desalting
plants. Furthermore, since the desalting
plant replaces the main condenser of the
power plant, a portion of the cost of the
desalting plant can be charged against the
condenser it replaces. With the multistage
flash plant, one of the more significant
operating problems is scaling in the main
brine heater, particularly at temperatures
of 250°F and above. The utilization of
lower temperature exhaust steam in the
dual-purpose plant avoids this problem.
Thermal economy is improved by operat
ing at higher temperatures; however, scaling
and corrosion problems increase rapidly as
temperature exceeds 250°F. Hence, costs
begin to rise exponentially, thereby offset
ting the improved steam economy.
For example: The allocable steam cost
increases with temperature or the ability to
do useful work; equipment costs rise with
temperature due to the associated higher
pressures and increased rates of corrosion,
which require heavier vessel walls; main
tenance and operating costs rise due to the
need to control scaling by chemical addi
tives and periodic cleaning. The sum of
these effects results in the exponential
increase in cost at temperatures above
250°F.
Nevertheless, it has been demonstrated
that multistage flash plants can be operated
continuously for extended periods through
the use of adequate scale control techniques.
Examples of successful multistage flash
plants are the 100,000 gpd Cleaver-Brooks
plant of Southern California Edison Com
pany, which was recently moved from
Oxnard, California, to Avalon, Catalina
Island, and the one mgd Point Loma Plant
which was moved by the Navy to Guanta-
namo, Cuba.
Both of the above plants performed so
well in their initial pilot installations that
they were selected to serve as work horses
in places of extreme water shortage. In both
applications, the maximum brine tempera
ture has been limited to about 200°F or
below for long term reliability. The result
718
of this is a reduction in steam economy and
in production rate, but this is offset bv the
convenience of using scale control tech
niques of proven reliability.
ADVANTAGES AND DISADVANTAGES OF
THE DIRECT CONTACT PROCESS
The direct contact flash distillation
process retains most of the advantages of
conventional multistage flash distillation.
Furthermore, it offers the possibility of
preventing scaling problems through elimi
nation of all metallic heat exchange surfaces
upon which scale might form. In addition,
there is a good possibility of handling
troublesome scale products as a liquid
sludge which would be removed continu
ously during operation.
The lower thermal resistance afforded by
direct contact permits closer temperature
approaches and thus higher efficiencies. In
the absence of scaling limitations, a higher
maximum operating temperature will give
higher steam economies. With direct con
tact methods, ultimate thermal efficiency
can be attained because the cost of ample
contact surface area is only slightly more
than that for moderate surface area, whereas,
with conventional surface heat exchangers,
there is an economic limitation to the
efficiency obtainable because of the high
cost of surface.
Direct contact has a few disadvantages.
As with conventional flash distillation, a
large number of stages are required, and
each stage must have considerable surface
area for the condenser. The elimination of
the tubes in the direct contact process re
quires that an intermediate heat exchange
liquid be used to carry heat from product
fresh water to saline feed. This increases
the size of the equipment because allowance
must be made for an additional flow pas
sage. Another consequence of the elimina
tion of physical barriers is that multiple
pumps are necessary for the maintenance of
counterflow, and each pump must carry the
full volume of throughput.
DISPERSION OF THE LIQUIDS
For effective heat and mass transfer, it is
necessary to disperse the liquids to extend
the surface area. Dispersion by spraying,
mixing, or throttling requires considerable
energy. The dissipation of this energy can
result in the formation of very fine disper
sions and emulsions which are difficult to
disengage.
From the standpoint of minimal energy
dissipation, and subsequent ease of disen
gagement, dispersion is best accomplished
by a simple gravity difference across a
perforated plate.
This method has been used in liquid-
liquid spray towers for dispersing oil drops
in water with excellent results.
A similar approach has been used with
deaerators and direct contact condensers;
however, in this case, the dispersion is in
the form of continuous falling water
streams of small cross section surrounded by
vapor.
SIZE OF EQUIPMENT
The size of the equipment is determined
largely by the free or open area of perfo
FEASIBILITY OF DIRECT CONTACT PROCESS
The feasibility of a direct contact flash
distillation process has been demonstrated
in laboratory equipment. Individual studies
have been performed on the major equip
ment, and a limited amount of work has
been done on an integrated pilot unit.
LIQUID-LIQUID HEAT EXCHANGERS
Test results from the operation of liquid-
liquid heat exchangers in the form of
flooded spray columns are presented in
Figures 269 and 270 for 4-inch and 16-inch
diameter columns with mass flow rates of
4,000-5,000 lb/hr/ft'.
FIGURE 269. TEMPERATURE APPROACH AS A FUNCTION OF
OPERATING TEMPERATURE RANGE FOR HEAT RECOVERY
COLUMN.
rated plate required to pass the desired
throughput and the minimum hole spacing
to avoid reduction of surface area due to
coalescing of individual streams.
In general, the fluid velocities in direct
contact equipment are quite small, result
ing in the need for large cross sections to
obtain the desired throughput. Hence, the
size of the equipment will be somewhat
larger than conventional equipment. Never
theless, the simplicity of construction should
lead to a lower cost.
Performance has been indicated by plot
ting temperature approach or log mean At
against temperature change of the liquid
streams. Figure 269 is for the fresh water
cooler or heat recovery column. Observe
that data extend to 44°C for this unit.
Apparently, water can be cooled 30° F at an
approach of under 2°F in a 16-inch diam
eter column.
Figure 270 gives the performance of the
salt water heater column. Operating experi
ence indicates that performance becomes
very inefficient at temperature changes much
greater than 25 °C possibly due to back
 mixing resulting from convection currents.
Under these conditions the log mean Д1
increases by a factor of S or 4 and. due to
a lower efficiency, the temperature change
of the liquid streams is reduced accordingly.
Nevertheless, it appears that brine can easily
be heated 30°F with a 2°F approach and
no disturbance by convection circulation.
DIRECT CONTACT FLASH STILL
Test results from the operation of a five-
stage flash still are given in Table CXXI. The
FIGURE 270. TEMPERATURE APPROACH AS A FUNCTION OF
OPERATING TEMPERATURE RANGE FOR BRINE HEATER
COLUMN.
PILOT STUDY PROGRAM
A pilot plant based upon the direct
contact process has been designed to further
investigate the possible application of direct
contact to large-scale plants.
The information being sought concerns
the practicality and economics of operation
in general and of escalation to large sizes.
In addition, a number of problems must be
investigated and resolved before any definite
conclusions can be made concerning appli
cations to large-scale equipment.
The effect of scale-up to larger diameters
on the thermal performance of the heat
exchangers is not definitely known.
More information is needed on the design
720
working temperature differences illustrated
are in most cases too high to be of interest
here; however, the last two are applicable-
It can be seen that in all but three cases
the net approach difference is less than 1 f-
and, in the last two cases, only 0.35T-
Hence, it is concluded that an overall ap
proach to within 2°F of equilibrium is well
within reason and probably attainable in
practice in a direct contact still. Similar ap
proach differences appear to be attainable
in the liquid-liquid heat exchanger columns.
and performance of direct contact con
densers, particularly as to the effects of
noncondensables and the geometry of
design.
Little is known about the feasibility of
collecting and handling scale products from
sea water as a liquid sludge, although it is
known that the sludge will form. The pilot
unit, as designed, is a coupling of two test
modules capable of being operated over any
60°F section of the temperature range from
250° F to ambient.
One of the modules is the 8-stage still
which can be considered as any 8 stages of
a multistage still. With this unit it will be
 TABLE CXXI. Thermal Data from FMC Five-Stage Direct Contact Flash Still
(all temperatures °F)
Flow Production Stage Approach to Not
Ib/hr Ib/hr/fP working equilibrium BPE approach
Date Gt Xi At AU S At.-«
6/28/62 6.097 4.19 18.27 1.70 0.77 0.93
7/6/62 6,620 8.99 19.21 1.47 0.69 0.78
7/81/62 6,462 8.96 19.27 1.36 0.69 0.67
8/2/62 6.844 3.89 19.8 1.71 0.69 1.02
8/8/62 6,466 4.88 21.27 1.66 0.70 0.96
8/8/62 6.487 4.87 21.8 1.67 0.70 0.87
8/6/62 7,149 6.67 21.03 2.18 0.69 1.44
8/8/62 7,787 6.76 22.47 2.61 0.71 1.90
12/17/62 8.971 1.66 11.01 1.00 0.68 0.82
12/18/62 6,986 1.88 8.86 1.27 0.69 0.68
12/19/62 4,069 1.00 6.66 1.19 0.69 0.60
12/20/62 3,073 0.78 6.69 1.16 0.69 0.46
1/8/68 4,179 1.80 8.26 1.16 0.68 0.48
1/8/68 6,840 1.94 8.86 1.44 0.68 0.76
1/8/68 6,980 2.81 10.4 1.67 0.68 0.89
1/10/68 6,061 2.78 14.29 1.27 0.69 0.68
1/11/68 4,904 2.67 14.8 1.28 0.69 0.69
1/14/63 6,762 3.93 16.6 1.64 0.70 0.94
1/81/68 6,176 1.87 9.6 1.04 0.68 0.86
t/1/63 6,181 1.29 6.66 1.17 0.69 0.48
2/6/68 6.180 0.91 4.67 1.02 0.68 0.84
2/7/68 6,482 0.98 4.64 1.06 0.69 0.86
possible to study and measure temperature from sludge in particular can also be
profiles over the entire operating range, as studied.
well as direct contact mass transfer coeffi It is known that hydrocarbons are ex
cients and the effects of noncondensables. tremely insoluble in water; however, some
The other module is the heat exchanger finely dispersed oil will be lost in the
system consisting of two brine heater outgoing water streams. It is difficult to
columns, a heat recovery column, and estimate this type of loss without measure
process makeup heater. The makeup heater ments taken over extended periods of
simulates a second heat recovery column. operation.
Several of these modules operating in Thermal information from operation of
series would be required in order to cover 5-ft diameter heat exchanger columns will
a large temperature range. The two brine be of considerable interest in predicting
heaters in series permit study of the control the practicality of escalation to larger diam
aspects of series linking of columns. eters. The importance of random mixing,
Sludge formation from scale products and convection currents, and other hydrodynamic
its subsequent collection and removal can factors can be studied under carefully
be investigated at various temperature controlled conditions.
levels. Oil losses in general, and oil recovery

PILOT PROCESS DESIGN

The basis for the design is a 40.000 gpd recovery column E5; then the balance of
plant. Considering the information re the heat is supplied by conventional heat
quired, a process design has been prepared exchanger E6, which is the process makeup
with an 8-stage still, three liquid-liquid heater. Exchanger column E5 is similar to F.3
heat exchangers, and sufficient conventional and E4. The heat exchanger oil flows in a
heat exchangers to stimulate desired test con closed loop through units E3, E4, E5, and
ditions. The process design is illustrated in F.6. The 8-stage direct contact still is pro
Figure 271. vided to obtain information on direct con
Sufficient direct contact heat exchange tact condensers. The still is designed to
capacity has been provided to heat sea
water from the temperature at which scale operate over a temperature range of ap
just begins to form to 250° F. Two units proximately 60°F, with a throughput of
are required to accomplish this heating. 150 gpm. and a production rate of 8.5 gpm.
Figures 27S and 274 illustrate the details of Figure 272 illustrates the important de
construction of the units. The heating step tails of a typical distillation stage. The
is illustrated in Figure 271 where E3 and vertical column is the condenser. Fresh
E4 are the brine heaters. Design throughput water coolant enters at the top. falls from
is 150 gpm of sea water. tray to tray, then is pumped from the sump
The hot oil stream utilized by the sea at the bottom to the top of the next
water heaters is partially heated by heat condenser. The evaporator is at the bottom.

721
\tz
Ma•Ouwo-TvHntxsviroavidax
aranou
 The performance of the still El is illus
trated in Figure 271 where the brine stream
is flashed down from inlet to outlet tem
perature in 8 steps. The fresh water stream,
passing in counterflow, is heated through
the same temperature range as the brine
(At El) , and then goes to the heat recov
ery column E5.
FIGURE 272. TYPICAL DIS
TILLATION CHAMBER.
DESCRIPTION OF EQUIPMENT
DIRECT CONTACT STIU
A cutaway view of one distillation cham
ber is shown in Figure 272.
Brine enters the evaporator through the
variable orifice slot on the lower right. A
V-shaped weir spreads the brine into a
thin film and maintains an interstage liquid
seal. Brine flow out of the evaporator is
regulated to prevent flooding of the weir.
The bottom of the fresh water reservoir in
the top section acts as a splash plate.
Product vapors pass upward through (he
conical vapor uptake and demister to the
condenser section above.
In the condenser, fresh water rains down
ward from tray to tray and collects in the
sump below from which it is pumped to
the condenser of the next stage. The trays
are arranged in disk and donut fashion to
provide a countercurrent vapor path. Non-
A conventional countercurrent heat ex
changer, E2, is piped in series with the
liquid-liquid heat exchanger columns such
that it can be used to absorb all or part of
the heat exchange load of the direct con
tact equipment. The performance of heat
exchanger (E2) is illustrated in Figure 271.
condensable gases will be swept upward by
the vapor from the evaporator and vented
from the top of the condenser, after con
tacting the cool incoming fresh water to
strip out all condensable vapors.
LIQUID-LIQUID HEAT EXCHANGERS
A cutaway view of a liquid-liquid heat
exchanger in operation is shown in Figure
273 and a perspective view in Figure 274. The
water stream is introduced just above the
midsection and distributed uniformly over
the entire column cross section. The water
flows downward through a bed of closely
packed oil drops in the flooded region, then
around the outer edge of the oil dispersion
plate, and through the Raschig ring tray
to the water outlet at the bottom of the
column.
The hydrocarbon oil is introduced, at the
FIGURE 273. LIQUID-LIQUID HEAT EXCHANGER OPERATION.
bottom of the column, below a perforated
dispersion plate. The oil passes upward
through the perforations in tiny jets which
break up into small droplets. These oil
drops rise freely to the flood line where
they pile up and then rise at a restricted
rate. The flooded region extends to a point
just above the water inlet where the oil
drops coalesce into a floating oil layer.
A plastic-coated perforated plate located
just above the water inlet helps stabilize the
interface of coalescence. Oil leaves the
column from the floating oil layer at the
top of the column.
Above the oil is a nitrogen gas blanket
which acts as an accumulator to absorb
surges in the flows. A level control at the
gas-oil interface regulates oil flow out of
the column.
The foregoing operational description i<
general and applies both to salt water
heater and heat recovery columns. If water
is introduced hot, and oil cold, the column
serves as a water cooler. Conversely, when
oil is introduced hot and sea water cold, the
column serves as a brine heater.
The enlarged top section is a decanter
for separation of sludge in the case of
heating sea water above scaling tempera
tures. Scale products will apparently form
FIGURE 274. LIQUID-LIQUID
HEAT EXCHANGER COLUMN.
on the interface between oil and water or
on the outside of the individual oil drops.
As the oil drops rise, the scale particles
become trapped in viscous water films sur
rounding the oil drops and thus are carried
to the top of the column. When the oil
drops coalesce, these films break, but remain
almost intact much like the broken skin of
a grape. These little "deflated and flattened
spheres" are slightly heavier than oil and
 tend to settle by gravity in regions of low
velocity. Such a region has been provided in
the decanter top section.
CONCLUSIONS
The prospect of a saline water conversion
process that requires no metallic heat ex
changer surface is indeed attractive. Studies
completed to date indicate that direct con
tact is basically feasible and very efficient
SUMMARY OF DISCUSSION
In reference to the system presented in
this paper, it was stated that in the United
Kingdom a similar system has been studied
and that it created several problems. When
asked to comment about the complexity of
the system, the author stated that pumps are
a very disturbing thing and that there seems
to be no way to eliminate them. Convection
currents do not seem to arise if the system
is operated under 20°F gradient. The
author stated further that should metals for
heat transfer surfaces become very difficult
to obtain, this system will be more attractive.
It was asked whether sludge will lie
Conception D'Installation
Basée Sur un Procede de Distillation
a Vaporisation Instantanée a Contact
Direct Avec Echange
Liquide - Liquide
Clyde Don Watson
Etats-Unis d'Amérique
La possibilité d'un procédé de distillation
à vaporisation instantanée par contact direct
a été démontrée en équipement de labora
toire. Des travaux de mise au point suffi
sants ont été effectués sur l'équipement et
les commandes du procédé pour permettre
une conception à l'échelle des études pilotes
à un niveau de 150 m" par jour.
L'objectif de cet exposé est d'expliquer ce
726
thermally in small-scale equipment. More
development work and pilot studies on a
larger scale will be required before the
economics and practicality of large-scale
equipment can be predicted with any de
gree of certainty. A pilot program, such as
the one proposed in this paper, will answer
many of the basic questions that exist today
regarding the direct contact process, and
expose those areas where further develop
ment work is needed.
entirely removed by décantation. The reply
stated that experimenters are not sure.
It was asked why oil is not dispersed
instead of water. The author replied that
this is primarily determined by the size
of the drops; with oil, more surface is
obtained due to the larger quantity re
quired; and for safety reasons, nitrogen gas
is used in a breather system. In addition,
the author stated that sea water performs
no differently than fresh water; however, if
pH is much above normal rates, there is
some effect.
Pilote
de Chaleur
procédé ainsi qu'un programme envisagé
d'études pilotes, actuellement soumis à
l'examen de l'Office of Saline Water.
PROCÉDÉ
Il est plus facile de comprendre le pro
cédé de distillation à vaporisation instan
tanée par contact direct en termes de
quatre étapes impliquant trois courants
liquides et un certain nombre de courants
de vapeur. Les trois liquides sont la sau
mure, l'eau douce et un hydrocarbure
approprié immiscible. Les débits de ces
trois courants respectifs sont maintenus en
proportion inverse de leur capacité ther
mique respective si bien que des change
ments de température égaux se produisent
dans chaque paire de courants réagissant
l'un avec l'autre.
1. Dans la première étape, la saumure
est chauffée de la température ambiante à
la température supérieure du procédé
(niveau) par contact direct à contre-courant
avec un hydrocarbure immiscible chaud,
finement dispersé dans une série de colonnes
à vaporisation liquide. L'hydrocarbure se
trouve refroidi dans le procédé de chauf
fage de la saumure.
2. Dans la seconde étape, la saumure
chauffée est évaporée instantanément à tra
vers un certain nombre d'étapes irréversibles
dans une série de chambres à évaporation
instantanée où les vapeurs produites sont
formées aux dépens de la chaleur sensible
disponible de la saumure. La saumure
refroidie résiduelle est ensuite déchargée en
tant que résidu. Les températures des
courants de vapeur produite sortant des
chambres à vaporisation instantanée dimi
nuent petit à petit de chaud à froid.
S. Dans la troisième étape, les vapeurs
produites sont condensées par contact direct
avec un courant d'eau douce plus froid
circulant à contre-courant. Ainsi, la chaleur
et la masse des vapeurs produites sont
absorbées dans le courant d'eau douce, avec
pour résultat une récupération de la chaleur
qui est presque réversible pour un grand
nombre d'étages.
4. Dans la quatrième étape, la chaleur
récupérée est retirée très efficacement de
l'eau douce par contact direct à contre-
courant avec l'hydrocarbure immiscible
froid provenant de (1) dans une autre
série de colonnes à vaporisation. Ainsi, au
fur et à mesure que l'hydrocarbure est
chauffé, l'eau douce est refroidie à presque
la température ambiante.
L'intégration de ces quatre étapes pour
former un cycle complet exige l'addition
d'une chaleur de procédé suffisante à l'eau
douce ou à l'hydrocarbure, pour amener la
température de l'hydrocarbure quittant (4)
à celle requise pour son introduction en (1).
L'avantage primordial du procédé par
contact direct est la promesse d'une haute
économie thermique et l'absence des in
efficacités provoquées par l'entartrage. Ces
avantages sont partiellement annulés par le
besoin d'une installation importante afin
de réaliser l'économie possible. De là, en
dépit de l'efficacité apparente du contact
direct, il faut un grand nombre d'étages
qui, à cause du contact direct, seront néces
sairement plus importants en volume que
les étages correspondants des ensembles à
vaporisation instantanée à étages multiples.
Néanmoins, cet équipement est de construc
tion relativement simple car il ne nécessite
pas de surfaces de tubes métalliques coû
teuses, et ainsi le coût unitaire par rapport
au volume du réservoir diminue au fur et
à mesure que la dimension ou la capacité
augmente.
Les données d'approche de température
d'après les études de laboratoire démontrent
l'avantage thermique de l'échange de chaleur
par contact direct. Ces données provien
nent d'un évaporateur à cinq étages et de
colonnes d'échange de chaleur de 40 cm de
diamètre. On peut facilement obtenir des
différences d'approche aussi faibles que
1,1 °C. Il y a de nombreux cas où les
températures d'approche sont inférieures à
05°C. En général, les besoins de chaleur,
du procédé seront la somme des trois
approches, un BPE, et un étage At.
PROGRAMME D'ÉTUDE PILOTE
Un programme d'étude pilote a été for
mulé pour trouver la réponse à quatre
questions fondamentales concernant le pro
cédé par contact direct. Ces questions sont:
1. L'équipement d'essai peut-il être
agrandi aux grandes dimensions sans perte
significative des avantages thermiques dé
montrés précédemment en équipement de
laboratoire?
2. Le système de distillation par vapori
sation instantanée par contact direct est-il
pratique et économiquement sain?
3. Est-il économique et pratique de
substituer l'échange de chaleur liquide-
liquide par contact direct à l'échange aux
surfaces métalliques?
4. Les matières d'entartrage libérées par
l'eau de mer lors de son chauffage peuvent-
elles être continuellement ramassées et
évacuées sous forme de bouc liquide, évitant
ainsi le prétraitement de l'alimentation
et/ou les arrêts périodiques pour le nettoy
age, qui sont généralement associés avec
des surfaces métalliques d'échange de
chaleur?
EXAMEN DES QUESTIONS
1. Les renseignements disponibles sug
gèrent que l'on peut s'attendre a un rende
ment thermique raisonnable de colonnes
d'échangeur liquide-liquide de chaleur de
diamètres plus importants si elles sont bien
conçues. Donc, des colonnes d'un diamètre
de 130 m seront prévues dans l'installation
727
 pilote d'une confection en permettant une
modification possible.
2. Les renseignements existants sur la
distillation instantanée par contact direct
sont assez rares et il sera donc nécessaire
d'effectuer une bonne vérification expéri
mentale des nombreuses analyses théoriques
(1) et (2) pour tout agrandissement ulté
rieur. Un évaporateur horizontal à huit
étages, avec un condenseur du type à
courant descendant, a été choisi pour cette
échelle intermédiaire.
S. Dans l'installation pilote, une compa
raison directe des échangeurs de chaleur
tubulaires normaux avec les colonnes de
vaporisation liquide-liquide dans des condi
tions similaires de fonctionnement servira
de base pour l'évaluation économique et
l'application des échangeurs liquide-liquide
(1) Othmer, D. L., Vapor Reheat Floth Evapo
ration System, Final Report to O.S.W.. Contract
No. 14-01-001-183. E 162, octobre 1862.
(2) Chens, Sih Y»o, and Woodward, H. T.,
Research on Vapor Reheat Distillation System
Heat Calculations. Report to O.S.W., CE 982»,
en date du 24 octobre IMS.
Проект Опытной Установки,
Применяющей Процесс Дистилляции
со Мгновенным Вскипанием
при Непосредственном Контакте
и Жидкостно-Жидкостном Теплообмене
Клайд Дон Ватсон
Соединенные Штаты Америки
Осуществимость процесса дистилля
ции со мгновенным вскипанием при не
посредственном контакте была нагляд
но доказана с помощью лабораторного
оборудования. Было проведено много
работ, касавшихся усовершенствования
оборудования для самого процесса и
аппаратуры регулирования, так что те
перь имеется возможность составить
проект в увеличенном масштабе, рас
считанный на опытные исследования, с
производительностью 40.000 галлонов
в сутки.
Целью настоящего доклада является
объяснение вышеуказанного процесса
728
a d'autres procédés.
4. Le ramassage et la manipulation de?
produits d'entartrage sous forme de boor
liquide demanderont une quantité impor
tante de travail de mise au point base sut
le fonctionnement sur des gammes impor
tantes de températures et de concentration
des sels. L'installation pilote proposée per
mettra l'étude sur la gamme complete des
températures depuis la température am
biante jusqu'à 120°C. Un système de
recirculation permettra le fonctionnement
pour toute condition désirée de concentra
tion des sels.
L'installation pilote comprendra: un
module d'essai de distillation en huit étages,
une colonne de récupération de chaleur,
deux colonnes de chauffage de la saumure,
et suffisamment d'échangeurs de chaleur
normaux pour permettre la simulation des
conditions finales nécessaires pour étudier
l'un quelconque des huit étages d'une instal
lation de 150 m* par jour fonctionnant sur
une gamme totale de 100"C.
и предложенной программы опытных
исследований, которая в настоящее вре
мя рассматривается Управлением по
опреснению соленых вод.
Процесс
Процесс мгновенной дистилляции не
посредственного контакта легче всего
представить в виде четырех ступеней,
касающихся трех жидкостных потоков
и целого ряда потоков пара. Тремя
жидкостями являются рассол, опреснен
ная вода и подходящий несмешиваю-
щийся углеводород. Скорости протека
ния этих трех соответственных пото-
ков поддерживаются в обратной про
порциональности к их соответственным
теплоемкостям, так что любая пара
взаимодействующих потоков испыты
вает одинаковые температурные изме
нения.
1. На первой ступени рассол, имею
щий температуру окружающей среды,
подогревается до (уровня) высшей тем
пературы процесса, что достигается
путем непосредственного противоточ-
ного контакта (соприкосновения) с
тонко рассеянным, горячим, несмеши-
ваюшимся углеводородом в ряде рас
пыляющих жидкость колонок. Во вре
мя процесса нагревания рассола угле
водород охлаждается.
2. На второй ступени нагретый рас
сол последовательно и мгновенно про
носится через ряд необратимых ступе
ней серии камер мгновенного вскипа
ния, где образуются пары продукта за
счет располагаемой рассолом теплоты
нагрева. Затем остаточный охлажден
ный рассол спускается в виде продув
ки. Температуры потоков пара продук
та, выходящие из камер мгновенного
вскипания, инкрементально меняются
от тепла к холоду.
3. На третьей ступени пары продукта
конденсируются путем непосредствен
ного контакта с потоком холодной
опресненной воды, идущей противото
ком. Таким образом тепло и масса па
ров продукта абсорбируются потоком
опресненной воды, в результате чего
возникает рекуперация тепла, которая
почти обратима для большого числа
стадий.
4. На четвертой ступени рекупериро
ванное тепло очень эффективно уда
ляется из опресненной воды путем не
посредственного противоточного кон
такта с холодным, несмешивающимся
углеводородом из (1) в другой серии
распылительных колонок. Следователь
но, в то время, как углеводород нагре
вается, опресненная вода охлаждается
почти до температуры окружающей
среды.
Для интегрирования этих четырех
ступеней и образования полного цикла
требуется добавление достаточного ко
личества рабочего тепла к опреснен
ной воде или к маслу для поднятия
температуры масла, выходящего из (4),
до той, которая требуется при входе
в (1).
Основным преимуществом процесса
непосредственного контакта является
многообещающая термическая эконо
мия и отсутствие неудобств, связанных
с- образованием накипи. Эти преиму
щества частично сводятся на нет не
обходимостью сооружения большой
установки, чтобы добиться осуществле
ния возможной экономии. Поэтому, не
смотря на кажущуюся эффективность
непосредственного контакта, требуется
большее количество стадий, чем в со
ответственных многоступенчатых уста
новках мгновенного вскипания. Тем не
менее, это оборудование имеет сравни
тельно простую конструкцию, так как
оно не требует дорогих поверхностей
металлических труб, и потому удель
ная стоимость объема сосудов пони
жается при увеличении размеров и про
изводительности.
Данные относительно температурно
го приближения, полученные с помо
щью лабораторных исследований, на
глядно показывают термические преи
мущества теплопередачи при непосред
ственном контакте. Эти данные были
получены на выпарочном аппарате с
пятью стадиями и теплообменными ко
лонками с 16-дюймовым диаметром.
Легко достигаются столь малые диф
ференциалы приближания, как 2°F. Во
многих случаях они меньше, чем 1°F.
В общем, потребность тепла для про
цесса выражается суммой трех прибли
жений, одного повышения точки кипе
ния и одной стадии át.
Программа опытных исследований
Программа опытных исследований
была составлена для ответа на четыре
основных вопроса, касающихся процес
са непосредственного контакта. Они
состоят в следующем:
1. Можно ли увеличить пробное обо
рудование до больших размеров без
значительной потери термических пре
имуществ, которые ранее были нагляд
но показаны на лабораторном оборудо
вании?
2. Является ли практичной дистилля
ция со мгновенным вскипанием и не
посредственным контактом, а также
оправдывается ли она экономически?
3. Является ли это экономичным и
практичным заменить металлические
поверхности жидкостно-жидкостным
теплообменом непосредственного кон
такта?
4. Можно ли непрерывно собирать и
удалять в виде жидкого шламма, вы
деляемую при нагреве морской воды
накипь, тем самым избегая предвари
тельную обработку питания и/или пе
риодическое выключение установки для
729
 прочистки обычно подвергающихся на
кипи металлических теплообменных
поверхностей?
Обсуждение вопросов
1. Имеющаяся информация приводит
к выводу, что от теплообменных, пра
вильно спроектированных жидкостно-
жндкостных колонн больших диамет
ров можно ожидать удовлетворитель
ной термической производительности.
В соответствии с этим, на опытной
установке, намеченной к постройке, бу
дут сооружены колонки 5-футового
диаметра, допускающие возможность
быстрого модифицирования.
2. Существующая информация о ди
стилляции со мгновенным вскипанием и
непосредственным контактом весьма
ограничена, так что требуется хорошая
экспериментальная проверка многочи-
(1) Othmer, D. L., Vapor Reheat Flath Evap
oration System, Final Report to O.S.W., Contract
No. 14-01-001-183, & 162, October 1962.
(2) Cheng, Sih Yao. and Woodward, H. T..
Reecirch on Vapor Reheat Dietillation System
Heat Calculations, Report to O.S.W., CK 9829,
dated Oct. 24, 1968.
Diseno para una
Base en el Procedimiento de Destila
ción Instantánea
Directo con Intercambio
Liquido-Liquido
Clyde Don Watson
Estados Unidos de America
La viabilidad de un procedimiento de
destilación instantánea por contacto directo
ha sido demostrada en el laboratorio. Se
han ejecutado suficientes trabajos experi
mentales con equipos y reguladores de
procedimientos para llevar a cabo amplia
ciones de diseños para estudios piloto con
base en un rendimiento de 40.000 galones
por dia.
Este trabajo tiene por objeto explicar
este procedimiento y un programa pro
puesto para la realización de estudios
piloto, actualmente a consideración de la
сленных теоретических анализов (1) ■
(2) перед дальнейшим увеличением «
масштабов. Для промежуточного пас-
штаба был выбран горизонтальный вы-
парочный аппарат с восьмю стадииз:
и тип конденсатора с падающим пото
ком.
3. Непосредственное, при одинако
вых рабочих условиях, сравнение ви
опытной установке обычных трубчатых
теплообменников и жидкостно-аид-
костных разбрызгивающих колонок,
послужит основой для экономической
оценки и применения жидкостно-жид-
костных теплообменников в других
процессах.
4. Собирание и обработка продуктов
накипи в виде жидкого шламма потре
бует большой исследовательской ра
боты в широких пределах температур
и концентраций соли. Намеченная опыт
ная установка позволит изучить весь
диапозон между температурой окру
жающей среды и 250°F. Система рецир
куляции позволит работать при любом
желаемом солесодержании.
Planta Piloto con
por Contacto
Calórico
Oficina de Agua Salada.
EL PROCEDIMIENTO
El procedimiento de destilación instan
tánea por contacto directo se entiende
mejor en términos de cuatro operaciones
que entrañan tres corrientes de líquido y
varias de vapor. Los tres líquidos son:
salmuera, agua dulce y un hidrocarburo
inmiscible apropiado. El caudal de las tres
corrientes respectivas se mantiene en pro
porción inversa a sus capacidades calóricas
correspondientes, de modo que cualquier
par de corrientes, de acción recíproca, expe mente sencilla porque no requiere super
rimenta cambios de temperatura iguales. ficies metálicas tubulares costosas y por
1. En el primer paso, la salmuera se eso, el costo unitario por volumen de
lleva de la temperatura ambiente a la recipiente baja a medida que aumenta el
temperatura más elevada del procedimiento tamaño o la capacidad.
por medio del contacto directo de la con Los datos obtenidos por medio de los
tracorriente con un hidrocarburo inmiscible estudios en el laboratorio acerca de la
atomizado y caliente, en una serie de co aproximación de la temperatura demues
lumnas de rodo liquido. El hidrocarburo tran las ventajas térmicas de la transmisión
se enfria en el proceso del calentamiento de calor por contacto directo. Estos datos se
de la salmuera. obtuvieron de una destiladora de cinco
2. En la segunda operación, la salmuera etapas y de columnas termointercambiado-
calentada es pasada en forma rápida y no ras de un diámetro de 16 pulgadas. Se
reversible por una serie de cámaras de logran fácilmente diferenciales de aproxi
vacío en cuyo interior se forman vapores del mación hasta de 2°F en la regulación de la
producto a expensas del calor sensible dis temperatura. En muchos casos las aproxi
ponible de la salmuera. Luego se purga la maciones netas de temperatura son infe
salmuera residiual enfriada. Las tempera riores a un °F. En general, los requeri
turas de las corrientes de vapor del pro mientos calóricos del proceso serán la suma
ducto, que salen de las cámaras de vacío, de tres aproximaciones, de un BPE y de
varían progresivamente de calientes a frías. una etapa At.
3. En la tercera operación, los vapores PROGRAMA DEL ESTUDIO PILOTO
del producto se condensan por contacto
directo con una corriente de agua dulce En respuesta a cuatro preguntas funda
más fresca que fluye en sentido contrario. mentales acerca del procedimiento de con
En consecuencia, el calor y la masa de los tacto directo, se ha formulado un programa
vapores del producto son absorbidos por la de estudio piloto. Dichas preguntas son:
corriente de agua dulce, dando por resul 1. ¿Es posible aumentar el equipo de
tado una termorecuperación que es casi ensayo a tamaños grandes, sin menoscabo
reversible durante un número considerable de las ventajas calóricas demostradas ante
de etapas. riormente con los equipos de laboratorio?
4. En la cuarta operación, el calor recu por2. contacto
¿El sistema de destilación instantánea
directo es práctico y econó
perado se substrae con gran eficacia del micamente válido?
agua dulce por medio del contacto directo 3. ¿Es económico y práctico reemplazar
de la contracorriente con el hidrocarburo las superficies metálicas por el intercambio
tibio inmiscible de (1.) en otra serie de calórico líquido-líquido de contacto directo?
columnas de rodo. Por lo tanto, a medida 4. ¿Los materiales formadores de incrus
que se calienta el hidrocarburo, el agua taciones extraídos del agua de mar por
dulce se enfría a casi la temperatura calentamiento pueden reunirse continua
ambiente. mente y extraerse en forma de sedimento
La integrarión de estas cuatro operaciones líquido para evitar de esa manera el pre-
para formar un ciclo completo, requiere la tratamiento del agua de alimentación y/o
adición de suficiente calor operativo al agua el paro periódico para la limpieza que
dulce o aceite para elevar la tempartura del normalmente se hace en las superficies
aceite que sale de (4) al grado necesario metálicas de los termointercambiadores?
para su introducción en (1.).
La ventaja principal del procedimiento CONTESTACIÓN A LAS PREGUNTAS
de contacto directo es la posibilidad de 1. Los datos de que actualmente se dis
lograr una gran economía calórica y la pone sugieren que puede anticiparse resul
ausencia de dificultades a causa de incrus tados calóricos razonables o de las columnas
taciones. Estas ventajas son contrarrestadas intercambiadoras de calor, líquido-líquido,
en parte por la necesidad de contar con de mayor diámetro, siempre que su diseño
una instalación gTande que permita con sea adecuado. De acuerdo con ello, se
cretar la economía posible. De ahí que, a proporcionarán columnas de 5 pies de
pesar de la aparente eficacia del contacto diámetro para la planta piloto, de una cons
directo, se requiere un gran número de trucción que permita su fácil modificación.
etapas que, por causa del contacto directo, 2. Los datos actuales acerca de la desti
serán mayores en volumen que las corres lación instantánea por contacto directo son
pondientes al proceso de destilación instan muy insuficientes, por lo que sería necesario
tánea con etapas múltiples. En todo caso, hacer una buena verificación experimental
este equipo es de construcción relativa de los numerosos análisis teóricos (1) y (2)

731
 para el aumento ulterior del tamaño de las
instalaciones. Para esta escala intermedia
se ha elegido una destiladora horizontal de
ocho etapas con un condensador del tipo
de corriente descendente.
3. En la planta piloto, la comparación
directa entre los intercambiadores tubulares
de calor comunes con las columnas de
rodo líquido-liquido, en condiciones simi
lares de funcionamiento, servirá de base
para la evaluación económica y la aplica
ción de los intercambiadores de calor
líquido-líquido, a otros procedimientos.
4. La reunión y tratamiento de los pro-
(1) Othmer, D. L„ Vapor Rthsat Flash Evap
oration Siintem. Informe Final para la Oficina de
Agua Salada. Contrato No. 14-01-001-183. y 162,
octubre de 1962.
(t) Chena-, Sih Y«o y Woodward. H. T., Re
search on Vapor Reheat Distillation System Heat
Calculations. Informe para la Oficina de Affua
Salada. CE 9829, de facha 24 de octubre da 1968.
732
ductos de incrustaciones como sedimente
liquido requerirán extensos trabajos experi
mentales basados en gamas amplias de
temperaturas y concentraciones de sal. La
planta piloto que se propone facilitara el
estudio de toda la gama de temperaturas
desde la del ambiente hasta la de 250"F
Un sistema de recirculadón permitirá tra
bajar con la concentración de sal que mas
convenga.
La distribución de la temperatura en la
instalación piloto consistirá de un module
de ensayo para la destiladón en ocho
etapas, una columna recuperadora de calor,
dos columnas calentadoras de salmuera y
suficientes intercambiadores de calor, de
tipo corriente, para poder simular las con
diciones finales de necesarias para el estudio
de cualesquiera de las ocho etapas de una
instalación 40.000 gpd que fundone en la
gama total de 180°F.
The Multiple-Phase
Vapor Compressor
Desalination Systems
S. William Gouse, Jr., George F. Harper,
Clarence A. Kemper, John H. Leigh
United States of America
INTRODUCTION
An ejector (sometimes called an injector,
aspirator, jet pump, jet compressor, educ
tor, etc.) is a device in which two fluid
streams are brought into intimate contact at
high relative velocity such that the driving
stream transfers momentum to the driven
stream, thereby increasing its stagnation
pressure. In general, the two fluid streams
are accelerated in separate nozzles before
being brought together in a mixing section.
After mixing, the combined streams are
decelerated as a single stream in a diffuser.
A multiple-phase ejector, hereafter called
an MPE, differs from ordinary ejectors
which employ single-phase streams in that
one or both of the inlet streams are acceler
ated to form a two-phase stream before
being introduced into the mixing section.
While it is possible for one or both of
the streams to contain solid particles, the
streams entering an MPF. will, in general,
be two-phase liquid-vapor streams. In the re
mainder of this paper, only this two-phase
condition will be treated.
The MPE in distillation desalination sys
tems utilizes a two-phase liquid-vapor driv
ing stream to compress a vapor stream to
a higher pressure and corresponding satura
tion temperature. The driving stream enters
the MPF. as liquid and is accelerated in a
converging-diverging nozzle to form a super
sonic liquid-vapor stream. The vapor stream
is accelerated in a separate converging
nozzle and may enter the mixing region as
a liquid-vapor stream or as a pure vapor
stream, depending upon the vapor stagna
Ejector as a
in Distillation
tion state and the vapor-nozzle efficiency.
By proper design, the processes in an MPE
can be made more nearly reversible than in
ejectors which employ single-phase streams;
therefore, it is possible to make an MPE
desalination system which is more efficient
than any desalination system employing
conventional ejector devices.
The reasons that an MPE can be more
efficient than ordinary ejectors may be
understood by considering some major
sources of irreversibility in an ejector;
namely, heat transfer between the streams
due to large temperature differences and
momentum transfer by means of viscous
interaction between the inlet streams due
to large velocity differences. Since the inlet
streams to an MPE are expanded before
mixing to the same static pressure in the
two-phase region, very small temperature
differences exist between the liquid and
vapor phases when the. streams mix.
Furthermore, for the case wherein the
stagnation state of the driving stream is
high pressure liquid, it is possible to choose
the mixing pressure so that the momentum
transfer between streams occurs with a
small velocity difference.
Consider the expansion of the two
streams to a given mixing pressure at which
both streams are in the two-phase region.
When the mixing pressure is equal to the
vapor stagnation pressure, the high pressure
stream which was initially liquid will have
finite velocity, while the vapor stream will
have zero velocity. Further reductions in
733
the mixing pressure will cause the vapor
or high quality stream to increase velocity
much more rapidly than the liquid or low
quality stream, because, for a given differ
ential change in pressure, the change in
velocity of a fluid stream is nearly propor
tional to the ratio of specific volume to
velocity. Thus, at some value of mixing
pressure, the velocity of the two streams
will be the same, and if the streams are in
the two-phase region at the same pressure,
the temperatures will also be the same. In
theory, these two streams can be mixed
reversibly; i.e., without viscous or heat
transfer losses. The pumping action in this
case will occur in the diffuser, because as
the combined two-phase stream is deceler
ated, the vapor will change velocity more
rapidly than the liquid, thus creating a
difference in velocity between the two
phases and permitting momentum transfer
from the liquid to the vapor by means of
viscous drag. If the liquid droplet diameter
is small, the irreversibility in this process
goes to zero as the velocity difference goes
to zero.
When the effects of wall friction, relative
velocity between phases, and temperature
distributions within each phase are con
sidered, the optimum mixing section pres
sure will be different from that calculated
for the ideal case, and, of course, the
processes within the MPE will no longer
be reversible. Even when realistic values
are assigned to the irreversibilities involved,
however, an MPE is far more efficient than
a single-phase ejector.
EVALUATION OF MPE PERFORMANCE
THERMODYNAMIC ANALYSIS
The conservation of mass for the control
volume of Figure 275 is given as:
w — VI' -\- w" (1)
The First Law of Thermodynamics, as ex
Inlet Vapor Flow
Driven Steom
FIGURE 275. CONFIGURATION OF MPE WITH MIXED-PHASE
EXIT STATE.
pressed by the steady flow energy equation
in terms of the stagnation enthalpies,
requires that:
1
Ы+ 1 h." + u>+ 1 h*.
(2)
where
w"
(3)
w*
The Second Law of Thermodynamics
requires that the entropy of the mixture
leaving the MPE must equal or exceed the
total entropy of the two entering streams.
This entropy increase, in terms of the
mixture leaving the MPE, is given by:
AS• =
: V- (-^T s° + 1^T>- )
(4)
The entropy of the exit stagnation state
of the ejector, sor, is determined from the
enthalpy at the same state, h„. and by one
additional thermodynamic property. Since,
in this case the exit stagnation state is an
equilibrium two-phase mixture, the most
convenient additional property to specifv
is the stagnation temperature at the MPE
exit, T0,. The MPE exit stagnation tem
perature is also the condensation temper
ature in the desalination system shown
schematically in Figure 276*.
Since the stagnation ejector-exit fluid
consists of both liquid and vapor phases in
thermodynamic equilibrium, we can write":
h„r = ht (T„) + xor h,f (T„) (5)
s„ = sf (TOT) + x„, s„ (T„) (6)
For a pure substance, the following rela
tionship is exact at anv value of tempera
ture at which a two-phase mixture can exist
in thermodynamic equilibrium:
* Note that corresponding state points are la
beled in Figures 276, 276, 278. 279. and 280.
The notation. hr(Toy), means that the prop
erty, hr. is evaluated at the temperature in
parentheses. Tor.
or

Qs,Heat Input
Liquid Heater
\^,Work Input
FIGURE 276. CONFIGURATION OF MPE DISTILLATION
DESALINATION SYSTEM.
T= h„/st, (7)
Combining Equations (5) , (6) , and (7)
gives the result:
h„ — ht (T0T)
T« = s„ _ sf (T„) (8)
If Equations (2) , (4) , and (8) are com
bined, it is possible to solve for the MPE
inlet flow rate ratio, ш, in the form'
T,T [s; - s, (т.у) ] -
"~IK -h, (T07)]-T„
[h; - h, (T.,) ] + T„7AS
[s;' - s, (T„) 1 - T„As (9)
Equation (9) may be used to calculate
the inlet flow rate ratio, u, which is required
in order for the MPE to accept the inlet
streams having the set of inlet properties
4. !¡¡, h¡. and h", and to deliver these
streams against a back pressure correspond
ing to the exit temperature, T„. under the
handicap of the total entropy rise, As.
If the vapor inlet stagnation state is a
saturated state, as it usually is in the de
salination systems considered, we can write
the following as a special case for the MPE
inlet flow ratio, a.
/"Г0 —T'\
__\ t; /ht.(T?+[h((T„)-htrr;)i
- [K - ht (T.F) ] - T„ [s- - sf (T„)]
- Tor [s( <J„) - s, (T'0) } + T„, As
- T„ As (10)
Liquid Inlet State
Two -Phase Exit
State , oy
The ejector entropy rise, As, must be
evaluated in terras of the various possible
types of losses in the ejector as part of the
process of calculating the required MPE
inlet flow rate ratio, ». The use of the MPE
entropy rise, As, in evaluating the ejector
performance has turned out to be a very
useful MPE design technique. Unlike many
devices such as heat exchangers, turbines,
etc., an MPE does not have energy exchanges
with the environment across its boundaries;
thus its losses cannot be identified by as
sessing such energy exchanges. However, it
is possible to determine the entropy in
creases due to irreversibilities in various
MPE elemente and processes such as the
nozzles, fluid-mixing losses, wall friction,
two-phase shock waves, and the like. The
details of the method of solution are given
below.
MOMENTUM ANALYSIS OF MPE
In general an MPE, as depicted in Figure
275, may be described as having three sec
tions. Section I consists of the stagnation
chambers and nozzles for the entering fluids.
Section II is a mixing section and, although
shown as converging, may be diverging or
of constant area. Section III is a diffuser.
In the preceding thermodynamic analysis,
it was not necessary to consider the details
of the internal processes of the MPE as
these may be accounted for by the entropy
735
 e, As, in Equation (4) . However, be Equation (15)
sides satisfying the First and Second Laws
of Thermodynamics, the processes within 2f-
the MPE must satisfy the conservation of (1 +«) V = wV," + V/_ V,
momentum. The model selected for evalu
ating the mixing process is that of "constant fis;.
pressure" mixing as follows: If we further assume that
V ~ V, (19i
(1) The mixing section is shaped so that the momentum «[nation finally becomes*
either the pressure is constant throughout
the mixing section or the pressure vari V,= «V.4-V,'
ations cancel each other; thus, the net pres („+l) (l+2f-¿-)
sure force on the fluid within the mixing
section is negligible. 1.20.
Our objective at this point is not to pre
(2) The mixing process is complete and dict accurately the wall shear stress in the
the flow is one-dimensional at the exit of constant pressure mixing section, but to
the "constant pressure" mixing section. estimate the effect of friction on the overall
For the control volume around a repre performance.
sentative mixing section as shown in Figure The friction factor in Equation (14) can
277, Newton's second law may be written as be obtained as follows:
follows: f = 0.00140 + 0.125/Re" = (21)
where the Reynolds number. Re. is
g.-^T= ш V," + V/ _ („ + 1) V, (11) mated as
where F, the resultant wall friction forre DV2 wD
Re «
in the x direction, is given as: v>nt (T.) •Vf <T,)
F — JJ WTw Ddlcosi (12) 4\v
rDM (T.) (22)
To get this result we have assumed steady, The average mixture specific volume, v,. is
one-dimensional flow, and uniform pressure approximately
across Sections 1 and II. Previous experience
has shown that cos 0 will be approximately _ <■> Vf (T.)l+ш
+ v. (T.)
V,_ (2S)
unity for the cases to be considered, and
thus we can rewrite Equation (12) as if there is no relative velocity between
F~rDLr. (13) phases and the viscosity, ц. is assumed to
be the liquid viscosity at the mixing section
in which the parameter, D, represents the exit temperature, T,. It is recognized that
average mixing section diameter and г is the actual problem is one of two-phase flow
the wall shear stress due to viscous wall and that this simplified homogeneous flow
friction. An expression for the wall shear model representation is not necessarily the
stress. t„, can be written approximately as best. However, it is simple, and its accuracv
follows: is satisfactory for these purposes.
fp V Nozzles: The nobles constitute an impor
T- = "2ir (14)
tant part of the MPE and thev are analyzed
If we combine Equations (11) , (13) , and by applying the steady flow energy equation
(14) , we obtain the following expression to the sections O'-l and 0"-l of Figure 277.
for the momentum equation: Thus, we can obtain the following results:
V/ = V2goJ(IV_h1'). (24)
2w. = » V," + V/ _ („ + 1) V, (15) and
If, in addition, we make use of the follow V," = V"2g.J(h."-h,"). Œ5Ï
ing continuity and geometric relationships if the flow is steady, one-dimensional, and
at thermodynamic equilibrium. More use
wV (w' + w") V ful results are as follows:
w' (I + „) V Vu» = Ca'Vïg0J(ï
(16) = V2.0j(h'0_h;.) (26)
and * In the absence of friction, f = o, and Eq. 20
reduces to:
A — rD' (17)
1+u
736
 All. Pressure Distributions Uniform
t* Wall Shear Stress

P A
2 2
F Resultant Fr iction Force}

U_|v v,
D ^Average Diameter) 2

1 2
FIGURE 277. MPE MIXING SECTION CONTROL VOLUME.

and be evaluated for the primary stream enter

Vu" = C4" V2g„J(h(>"-h1'').=
V2g.J(h0"_hu") (27)
The parameter, Cd, is the nozzle discharge
coefficient and accounts for irreversibilities
in the nozzle flows; the parameters, (h„'—h,"),
and (h„"—h,") , are the reductions of isen-
tropic flow enthalpy across the nozzles. This
is a convenient form since, if the inlet
stagnation states of the ejector (s„\ h„',
s„", h.") are given conditions, the specifica
tion of the desired mixing section exit
temperature is sufficient to determine the
nozzle flow. The ideal and real nozzle flows
are illustrated in Figure 278. It may be de
sirable to determine if the dimensions of
the resulting nozzle exit areas at the MPE
mixing section inlet are feasible. Assuming
the primary nozzle area, A,', is an annular
ring concentric with the secondary nozzle
exit area, A,", we have
A,' = W/rx V„T (28)
A," = m rf/W v«1 (29)
or
D," = (4A,"/*) * (30)
and
t' = {[ (A,' + A,-) 4/,]* - D,"}/2 (31)
In Equations (28) and (29) , the values
of the densities of the two streams entering
the ejector mixing section at the nozzle exit
plan*1, p,' and p,", are required. These may
ing the nozzle mixing section as follows:
From Equation (26) we can show that
h,.' = h„' - C<" (W - W) . (32)
x,' = [hu' - h, (T.) ]/h„ (T.) (33)
1
Pi' = -v, (T.) +X/V,, (T.) (34)
and
•u' = s, (T.) + s„ (T.) (35)
For the secondary stream entering the
MPE mixing section, the equivalent rela
tions depend on the value of the mixing
chamber exit temperature, T,. Referring
to Figure 278 we can see that the liquid
stream entering the MPE can enter the
MPE mixing section as either a liquid or
a two-phase mixture. We are considering
the two-phase case only. Thus, we have as
above:
h„" = h." - Ct- (h." - h,") . (36)
x," = [hu" _ h, (T.) ]/hfr (T,)i (37)
n_ 1
* ~ vf (T.) + x," v„ (Tt) (38)
s,.- = sf(T1) + x,"sf,(T,) (39)
METHOD OF SOLUTION
As previously mentioned, the object of
the momentum analysis is two-fold: (1) Can

737

H,V
07 Ideal Liquid " Stream *j J
i Nozzle Expansion
Entropy In cr ea se A cr о ss |
*1 ! Liquid Stream Nozzle
So" Soa
Ent ropy
FIGURE 278. SOME THERMODYNAMIC STATES IN WORK-INPUT
MPE DESALINATION SYSTEM ILLUSTRATING NOZZLE
PROCESSES.
the MPE be made to achieve the re
sults called for and yet satisfy the laws of
conservation of mass, momentum, and
energy within the limits of the Second
Law of Thermodynamics; and, (2) if fea
sible, what is the best MPE design (the
least irreversible) ? The best MPE design
would of course be the one with minimum
entropy increase, i.e., no friction and re
versible mixing.
For the conditions of Figure 278, it was
always possible to get a velocity match at
the ejector mixing section inlet. However,
if the liquid stream enters the mixing sec
tion as a compressed liquid, it is possible
to have a velocity match without a temper
ature match. In the case of a mismatch,
one must decide which mismatch or com
bination of velocity and temperature mis
match leads to a minimum entropy increase.
In general we proceed as follows:
(1) The MPE exit stagnation tempera
ture, T„, or the condensing temperature
in the evaporator of Figure 276 is specified.
Since this is a two-phase state by assump
tion, the ejector exit stagnation pressure,
Poj (T0T) , is known, as well as the other
saturation properties such as v, (T„) ,
v. (T„) . h, (T„) , h, (T„) , s, (T„) , and
», (T„T).
738
p
' oy
т -Р-
R ea I Vapor
Stream Nozzle
Expansion
P-SP1
I--Entropy Increase
^ I Across Vapor
, Sir earn Nozzl
,
SQ' S0'oa
(2) The temperature difference in the
evaporator, T„ — T„\ is specified, and this
in turn fixes the evaporating temperature,
T„', and the evaporating pressure, p„' (T„') ,
as well as v, (T„') , v, (T„') , h, (T.') ,
h, (T„') or h.', s, (T.') , and s, (T.-) or
s.'.
(3) The pressure rise across the pump
in the ejector liquid inlet stream, Лр, and
the pump efficiency, Vp, are specified.
(4) The pump inlet temperature, Te. is
specified. At this point h0 and ig can be
determined. Next we can determine h„".
T0" and s0".
(5) The length-to-diameter ratio of the
test section, L/D, and the two nozzle dis
charge coefficients, Cd' and Ct". are specified
to permit the friction losses in the MPE to
be estimated.
(6) At this point, a number of tempera
tures and temperature differences, such as
the sea water inlet temperature and the
minimum temperature difference in the in
let sea water regenerator, are specified.
(7) Finally, the value of a number of
conversion factors, computer control con
stants, computation accuracy limits, and
miscellaneous properties and constants, all
of which are listed and defined in the com
puter program, are given by Joseph Have
and Company (réf. 1) . Once the final minimum entropy increase,
If the preceding momentum analysis is As, and its associated ejector flow rate ratio
examined, one will find that two quantities are determined, the heat and work require
have not yet been specified, namely, the ments can be computed from the appro
total entropy increase across the MPE, As, priate relations in the following sections.
and the mixing section static temperature, If desired, the total entropy increase can
T,. As stated earlier, the object of the also be broken down to determine which
analysis is to determine the ejector mixing contribution is the greatest, the mixing sec
section static temperature, T„ that leads to tion friction, one of the nozzles, or the
a minimum entropy increase, As, across the mismatch in mixing section inlet stream
ejector. In order to start the solution, a trial properties.
value for As, usually 0.0005 Btu/lbm-R,
must be used to calculate a first value for EVALUATION OF SYSTEM PERFORMANCE
the ejector flow ratio, w, from Equation Figure 276 shows the essentials of a desali
(10) . A trial value for T„ the ejector mix nation system using an MPE which could
ing section exit temperature, is selected next. be driven by any desired combination of
The value of T, cannot be greater than heat and work imputs. Figures 279 and 280
show the corresponding state points on a
The selection of Tj allows us to deter temperature-entropy diagram for two limit
mine p (T.) , vf (T.) . h, (T.) , h, (Ts) , ing cases. The incoming saline water enters
sf (T.) , s, (T.) , h,"., and by.. an evaporator substantially at the boiling
Then h„ is calculated from Equation (2) , point (B) , where it receives heat and is
V/. from Equation (26) and V,", from partially evaporated. The vapor flow leav
Equation (27) . It is next assumed that ing the evaporator, w'", (C) , is divided into
there is no friction (f — 0) , and the veloc two streams. The first of these streams,
ity, V„ is computed from Equation (20) . w"':-w', is passed directly into a condenser.
Next we compute V, from Equation (23) , The condensate is circulated out of the sys
Re from Equation (22) , f from Equation tem (J) through the inlet-water regenera
(21) , and an improved value for V, from tor. The second vapor flow stream, w'.
Equation (20) . Finally we determine, h2, enters the MPE (D) from the evaporator
the mixing section exit enthalpy, as follows: and mixes with the two-phase driving
V,' stream, w". The mixture is decelerated be
hs = h„7 _ fore leaving the MPE to higher values of
'2g„J (40) temperature and pressure (oy) than the
Since state 2 is a two-phase state, we can stagnation values of these two properties of
write the following: the inlet vapor stream (o') . Thus, a differ
T.. [s, - s, (T,) ] = [h, - h, (T,) ] ence in temperature is established between
(41) the ejector exit stream and the evaporating
liquid. The exit stream from the ejector is
h, - h, (T2) passed into the condensing side of the
s, = s, (T,) +
(42) evaporator, regeneratively supplying heat
and for the evaporation process.
X, - [s, - s, (T,) ]/[s, (T,) - s, (T.) ] The quantity of heat available from con
densing the MPE exit flow generally ex
(48) ceeds
In the above it is assumed that thermo the quantity of heat required in the
dynamic equilibrium exists at state 2. If, in evaporator to generate the MPE inlet vapor
addition, it is assumed that a reversible flow. In this analysis, the excess heat is used
adiabatic diffuser is used to decelerate the to generate the flow, w'"-w\ which is con
flow from state 2 to state oy, we ran write densed immediately without compression
the following: and removed from the system as product
s„, = S water.
Thus we determine a first calculated value The condensed flow leaving the evapora
for the entropy increase across the ejector. tor (K) is split into two streams. The first
As. This process is now repeated for other of these streams is equal in flow rate to the
values of T, until a minimum value of As vapor stream entering the MPE. This stream
is found. The first minimum value of As is also flows out of the system as product
used in Equation (10) to determine an water through the inlet-water regenerator.
improved value for the ejector flow ratio,
The earlier process is repeated with this desired * This iterative procedure in repeated until the
second value of ш to obtain another mini numerical accuracy in the solution and
all of the controls necessary to assure conver
mum value of As.* gence of the process to a final answer o' desired
accuracy are given in reference 1.
739
 MPE Liquid

Entropy

FIGURE 279. THERMODYNAMIC STATES IN WORK-INPUT MPE

DESALINATION SYSTEM.

Entropy

FIGURE 280. THERMODYNAMIC STATES IN HEAT-INPUT MPE

DESALINATION SYSTEM.

The second stream is recirculated through
a pump and perhaps a water heater to drive
the MPE.
The energy input to the MPE driving
stream, per pound of fresh water produced,
is defined by the relation.
E. = Q. + W. (44)
and may be calculated from
E' = -^[h"„-h, (T.,)] (4¿)
The ratio of the vapor flow rate at the
MPL inlet to the flow rate of fresh water
produced is determined by requiring that
the heat derived from condensing the MPE
exit flow be used to evaporate the vapor
which eventually leaves the system as fresh
water. Thus, we get.
(w + w») [h„, - hf (T„) ] = W" hf, (T'e)
(46)
Combining Equations (1) , (2) , (3) , and

740
(46) , we get E. = « [h"0 - hf (T„) ]
w'
w7" — (T;)-[h((T„)-hf(T;)U
h„ (T'„)
h., (T'„) - [h, (T„) - hf (T'„) ] + * [h» -h, (T.y) ] ) (48)
=— — г—
+ м [П. _. 1J
П, (l.F) ._.
(4/) a The required
aj ^ven MPE inlet(щflowmay
jn Equation ratefe ratio,
sub.
Equation (47) may be substituted into stituted into Equation (48) to give the
Equation (45) to give: result:

To, [s To,) + AS]

E. = hf, (T'0) [h'o-h, (Tor)]
, [s', - s, (Tor) 4- As] T„, [s"„ — s, (Тог) -I- As]
P [h'» - hf (T0,) ] [h"0-hf (T„,)] (49)

The fraction of the energy input to the Q. =0 (51)

system in the form of work is given by the W. = E. (52)
relationship:
h". - hf (T„) = —L-Ap
W /Е - (ДР/Р"") Pt Vp (53)
h"0-h, (T.7) (50) Since, for a simple substance,
Equations (49) and (50) are the basic _dh_ vdp
system performance equations to be used in T ~~ T (54)
further descriptions of the work and heat we can make the following approximation:
input versions of the system.
[s». - s, (TOT) ] ~ -=i— [h"0 - hf (T„,) ] -
(1) Work Input Case:
For this case, the entire energy input is
accomplished by means of a liquid pump. T„p, (55)
The system in Figure 276 is applicable, ex
cept for deletion of the heater following [s».-,, (TW)J«^-. (i^)
the liquid pump. The corresponding ther y 1 »7 P» \ Vp / (56)
modynamic states are shown in Figure 277. Substituting Equations (52) , (53) , and
Thus. (56) into Equation (49) , we get:

[■S'o - s, (Tor) + As]

VV. « h„ (T'.) p [h'„ - hf (Toy) ] -'I
T„ [s'o Sf (Tp,) + As]
[h'„ _ hf (To,) ] ,57)

(2) Heat Input Case:
For this case, given by Figures 276 and 280,
the pump work must be sufficient to assure
that the pump outlet pressure equals or
exceeds the saturation pressure correspond
ing to the desired MPE driving stream inlet
temperature, T"0. If the driving stream
were allowed to evaporate partially, the
input heat would be received at average
temperatures greater than those obtained
when the driving stream is heated just to
the saturation point at the same pressure.
For this reason, one would suspect that
the performance of the system would be
enhanced by partial evaporation of the
driving stream.
The performance equations for the heat
input system are constructed to include this
case. The following relations may be used
in F.quations (49) and (50) :
h"„ = ht (T"„) +x"„h„ T"„ (58)
s"„ - s, (T"„) + x"o s„ (T».) (59)
Ap = p.., (T".) - p„, (T0,) (60)
The fraction of the input energy in the
form of work is usually less than 1 per cent
in the heat-input svstem.
Some typical calculated performance
curves for the work- and heat-input sys
tems, respectively, are given in Figures 281
and 282. In each figure, the ideal perform
ance curves are based on a value for the
MPE entropy rise, As, of zero, and on a
value for the liquid pump efficiency, of
1.0. The remaining performance curves are

741
based on the models selected for the MPE (refs. 1-3) , with a liquid-pump efficiency
losses given by Joseph Kaye and Company of 0.90.

FIGURE 281. CALCULATED ENERGY REQUIREMENTS OF

WORK-INPUT MPE DISTILLATION SYSTEM.
FIGURE 282. CALCULATED ENERGY REQUIREMENTS OF HEAT-
INPUT MPE DISTILLATION SYSTEM.

SUMMARY OF CURRENT EFFORTS

The MPE has been examined for appli
cability in both distillation and freezing
desalination systems. Various other system
configurations are analyzed by Joseph Kaye
and Company (refs. 1-3). A work input dis
tillation system using an ideal MPE in con
junction with an ideal liquid pump has
been found to be slightly better than one
using an ideal vapor compressor, because
the MPE system does not compress vapor
into the superheat region. With losses in
cluded in the analysis, the predicted MPE
system performance is roughly comparable
with that of a conventional vapor com
pression system operating at the same
evaporation and condensation temperatures.
The capital cost of the liquid pump for a
work input MPE system is expected to be
considerably lower than the cost of a con
ventional vapor compressor while the cost
of the MPE itself is expected to be modest.
An unusual aspect of MPE systems is
their ability to operate as work input, heat
input, or combination work and heat input
systems. We believe that no other current
distillation system permits this freedom
within the limitation of using the same
evaporator heat transfer surface in both

743
 work and heal input modes. This aspect
of the MPE system may be an interesting
feature for a combination electric power
plant and desalination system.
Experiments are underway on a small-
scale transparent MPE to test and improve
the performance of the most critical MPE
components, namely, the liquid inlet nozzle
NOMENCLATURE
A cross sectional flow area, ft*
C„ nozzle discharge coefficient, dimen-
sionless
D average mixing section diameter, ft
E, total energy input to system per pound
of fresh water produced. Btu/lbm
f Fanning friction factor, dimensionless
F resultant wall friction force in MPE
mixing section, lbf
g„ 32.174, lbm-ft/lbf-sec"
h specific enthalpy, Btu/lbm
J 778.26, ft lhf/Btu
L mixing section length, ft
p absolute pressure, psia or Btu/ft*
Др pressure rise in liquid pump, psi or
Btu/ft»
Q. heat input to system per pound of
fresh water produced. Btu/lbm
Re Reynolds' number, dimensionless
» specific entropy. Btu/lbm R
Д8 entropy increase of flow in MPE per
pound of flow leaving MPE, Btu/lbm
R refers to MPE exit state
t width of vapor stream annulus at
nozzle exit plane, ft
T absolute temperature, R
V specific volume, ft*/lbm
V velocity, ft/sec
w mass flow rate (signifies total flow
rate leaving MPE when not super
scripted) , lbm/sec
W, work input to system per pound of
fresh water produced. Btu/lbm
X mass fraction of vapor in two-phase
mixture, dimensionless
REFERENCES
1. "Study of multiphase ejectors for dis
tillation desalination systems", Joseph
Kaye & Company (Oct. 21, 1963) Dept.
of Interior, Office of Saline Water Con
tract No. 14-01-0001-329.
2. "Addendum to study of multiphase
ejectors for distillation desalination sys
tems", Joseph Kaye tt Company (Mar.
26. 1964) Dept. of Interior, Office of
Saline Water Contract No. 14-01-0001-
329.
744
and the diffuser. The MPE test system has
been designed so that it can be modified
with minimum effort at a later time to
permit inclusion of an evaporator of the
type used by conventional vapor-compres
sion desalination systems. Results from cur
rent tests will be made available in the next
several months.
ijp efficiency of liquid pump, dimension
less
в half angle of mixing section, degrees
p. viscosity, lbf/ft sec
p mass density, lbm/ft*
pi density of liquid being pumped, lbm/
ft*
tw mixing section wall shear stress, lbf/
ft*
a ratio of MPE inlet flows, w'yw'. di
mensionless
SUBSCRIPTS
refers to actual processes or states de
* fined in Figure 278
refers to saturated liquid state
refers to change of state in evapora
tion at constant pressure
refers to saturated vapor state
refers to stagnation state
refers to isentropic process
" refers to saturation conditions
refers to conditions at entrance to
mixing section
refers to conditions at exit of mixing
section
SUPERSCRIPTS
refers to MPE vapor inlet flow, driven
stream
refers to MPE liquid inlet flow, driv
ing stream
refers to total product water flow
3. "Study of multiphase ejectors for freez
ing process desalination systems". Joseph
Kave Ic Company (May 14, 1964) Dept.
of Interior, Office of Saline Water Con
tract No. 14-01-0001-373.
4. "Condensuctor for deep running tor
pedo—Part I: General analysis and
calculated performance", J. Kaye, E. F.
Kurtz, Jr., S. W. Gouse. Jr., Joseph
Kaye fc Company, Inc.. Rept. N-2. Cam
bridge, Massachusetts (Nov. 1, 1956).
5. "An analytical study of the use of the
condensing ejector in a 300 kw loop
and one-half space power system", G. A.
Brown. Joseph Kaye 8c Company, Inc.,
Rept. 41, Cambridge, Massachusetts
(Aug. S, I960 .
6. "Injector rocket pump study", S. W.
Gouse, Jr., R. H. Eastman. Joseph
Kaye & Company, Inc., Rept. 42, Cam
bridge, Massachusetts (Aug. S, 1961) .
7. "An analysis of performance data from
SUMMARY OF DISCUSSION
There was no discussion.
L'Ejecteur Multiphase en Tant
Compresseur de
Systèmes de Dessalement
Distillation
S. William Gouse, Jr., George F. Harper, Clarence A. Kemper,
John H. Leigh
Etats-Unis d'Amérique
L'éjecteur multiphase dans les systèmes
de dessalement par distillation utilise un
courant moteur en deux phases liquide-
vapeur pour comprimer un courant de
vapeur à une pression et a une température
de saturation correspondantes plus élevées.
Le courant moteur entre dans l'éjecteur
multiphase sous forme de liquide et est
accéléré dans un ajutage convergent/diver-
gent pour former un courant supersonique
liquide-vapeur. Le courant de vapeur est
accéléré dans un ajutage convergent séparé
et peut entrer dans la région de mélange
sous forme de courant liquide-vapeur ou
sous forme de courant de vapeur pure scion
l'état de stagnation de la vapeur et l'effica
cité de l'ajutage vapeur. Grâce à une bonne
conception, les processus dans un éjeetcur
multiphase peuvent être rendus beaucoup
plus réversibles que dans des éjecteurs qui
utilisent des courants à phase unique; il
est donc possible de fabriquer un système
de dessalement à éjecteur multiphase qui
soit plus efficace que tout système de des
the NUOS condensuctor test facility
with a new theory for the variable-area
condensuctor: I -steam -water operation".
G. A. Brown, Joseph Kaye Ic Company.
Inc., Rept. 44, Cambridge, Massachusetts
(lan. 15, 1962).
"Effects of particle-laden stream on
ejector efficiency", R. H. Eastman,
Joseph Kaye & Company, Inc., Rept. 52,
Cambridge, Massachusetts (Mar., 196S) .
Que
Vapeur Dans Les
Par
salement utilisant des dispositifs normaux
à éjecteur.
On peut comprendre les raisons pour
lesquelles un éjecteur multiphase peut être
plus efficace que les éjecteurs ordinaires en
examinant certaines des sources principales
d'irréversibilité dans un éjecteur, à savoir
l'échange de chaleur entre les courants, qui
est dû à une grande différence de tempéra
ture et au transfert de moment au moyen
d'une' interaction visqueuse entre les cou
rants d'entrée produite par de grandes
différences de vélocité. Etant donné que les
courants d'entrée à un éjecteur multiphase
sont détendus avant mélange à la même
pression statique dans la région en deux
phases, il existe des différences de tempéra
ture très faibles entre les phases liquide et
vapeur lorsque les courants se mélangent.
De plus, en ce qui concerne le cas où l'état
de stagnation du courant moteur est du
liquide à haute pression, il est possible de
choisir la pression de mélange de façon à
ce que le transfert de moment entre les
745
 courants se produise avec une faible diffé
rence de viscosité.
Considérons la détente des deux courants
à une pression de mélange donnée à laquelle
les deux courants sont dans la région des
deux phases. Lorsque la pression de mélange
est égale à la pression de stagnation de la
vapeur, le courant à haute pression qui
était initialement liquide aura une vélocité
finie tandis que le courant de vapeur aura
une vélocité nulle. Des réductions ulté
rieures dans la pression de mélange pro
voqueront 1 "accroissement de la vélocité du
courant de vapeur ou courant à haute
qualité, beaucoup plus rapidement que celle
du courant de liquide ou courant à basse
qualité, parce que, pour un changement
différentiel donné dans la pression, le
changement dans la vélocité d'un courant
de fluide est presque proportionnel au
rapport du volume spécifique par rapport à
la vélocité. Ainsi, pour une certaine valeur
de pression de mélange, la vélocité des
deux courants sera la même, et si les
courants se trouvent dans la région des
deux phases à la même pression, les tem
pératures seront également les mêmes. En
théorie, ces deux courants peuvent être
mélangés de façon réversible, c'est-à-dire
Многофазный Эжектор в Качестве
Компрессора Пара в Дистилляционных
Опреснительных Системах
С. Уильям Гауз, младший, Джордж Ф. Харпер,
Кларенс А. Кемпер, Джон X. Лей
Соединенные Штаты Америки
Многофазный эжектор дистилляци
онных опреснительных систем утили
зирует две фазы: рабочий жидкостно-
паровой поток для нагнетания пара до
более высокого давления и соответст
венной температуры насыщения. Этот
нагнетательный поток поступает в
многофазный эжектор в виде жидко
сти и ускоряется в суживаюше-расши-
ряющемся сопле для образования уль
тразвукового жидкостно-парового по
тока. Поток пара ускоряется в отдель
ном суживающемся сопле и может по
ступать в зону смешения в виде жид
746
sans perte de viscosité ou d'échange de
chaleur. L'action de pompage dans ce cas
se produira dans le diffuseur parce que, au
fur et à mesure que le courant combiné en
deux phases est ralenti, la vapeur changera
de vélocité plus rapidement que le liquide,
créant ainsi une différence de vélocité entre
les deux phases qui permettra le transfert
de moment du liquide à la vapeur au
moyen d'un entraînement visqueux. Si le
diamètre de la gouttelette du liquide est
faible, l'irréversibilité dans ce procédé
tendra vers zéro au fur et à mesure que la
différence de vélocité elle-même tendra
vers zéro.
Lorsque l'on considère les effets de frot
tements des parois, de vélocité relative
entre les phases et de distribution de la
température au sein de chaque phase, la
pression optimale de la section de mélange
sera différente de celle calculée pour le cas
idéal et, par conséquent, les processus à
l'intérieur de l'éjecteur multiphase seront
plus réversibles. Même lorsque l'on attribue
des valeurs réalistes aux irréversibilités en
cause, un éjecteur multiphase est de loin
plus efficace qu'un éjecteur en une seule
phase.
костно-парового потока или потока
чистого пара в зависимости от состоя
ния застоя пара и эффективности па
рового сопла. При правильной кон
струкции процессы в многофазном
эжекторе можно больше приблизить к
обратимости, чем в эжекторах, приме
няющих однофазные потоки; поэтому
представляется возможным сделать
многофазную эжекторную систему оп
реснения более производительной, чем
все другие опреснительные системы,
пользующиеся обыкновенными эжек-
торными устройствами.
 Причины ббпыпей эффективности
многофазного эжектора по сравнению
с обыкновенными эжекторами можно
лучше понять, рассмотрев в эжекторе
его главные источники необратимости;
а именно, теплопередачу между пото
ками вследствие больших различий
температуры и передачи момента по
средством вязкого взаймодействия ме
жду впускными потоками ввиду боль
ших скоростных перепадов. Так как
впускаемые в многофазный эжектор
потоки перед смешением расширяются
в двухфазной зоне до одинакового ста
тического давления, то во время сме
шения температурный перепад между
жидкой и паровой фазой бывает очень
малым. Кроме того, в том случае, ко
гда рабочий пар в состоянии застоя
представляет собой жидкость под вы
соким давлением, является возможным
выбрать такое давление смешения, при
котором передача момента между по
токами происходит при малом скорост
ном перепаде.
Рассмотрим теперь расширение обо
их потоков до заданного давления сме
шения, при котором они находятся в
двухфазной зоне. Когда давление сме
шения одинаково с давлением застой
ного пара, поток высокого давления,
который вначале был жидким, имеет
ограниченную скорость, в то время как
скорость потока пара становится рав
ной нулю. Дальнейшее снижение дав
ления смешения будет увеличивать
скорость потока пара, или высокого
качества потока, гораздо скорее, чем
жидкости, или низкого качества потока,
потому что, прй заданной дифферен
циальной перемене давления, перемена
скорости жидкого потока почти про
порциональна отношению удельного
объема к скорости. Таким образом, при
некоторой величине давления смешения
скорость обоих потоков станет одина
ковой, и если потоки находятся в двух
фазной зоне при одинаковом давлении,
температуры тоже будут одинаковыми.
Теоретически эти два потока можно
смешать обратимым образом, т.е. без
потерь на вязкость и теплопередачу. В
этом случае действие накачивания бу
дет происходить в диффузоре, потому
что при уменьшении скорости комби
нированного двухфазного потока пар
будет менять скорость быстрее, чем
жидкость, тем самым создавая перепад
скорости между двумя фазами и воз
можность передачи момента от жид
кости к пару посредством вязкостного
торможения. Если диаметр капелек
мал, необратимость этого процесса
приближается к нулю, в то время, как
и перепад скоростей тоже приближа
ется к нулю.
При принятии во внимание действия
трения о стенки, относительной ско
рости между фазами и температурного
распределения в каждой фазе, опти
мальное давление в секции смешения
будет отличаться от подсчитанного при
идеальных условиях, и, конечно, про
цессы внутри многофазного эжектора
уже не будут обратимыми. Но даже и
при реалистичных величинах в отно
шении необратимости, многофазный
эжектор будет гораздо эффективнее,
чем любой однофазный эжектор.
747
 El Eyector de Fase Multiple
Como Compresor
de Vapor en Sistemas de Desaliniza-
cion por Destilación
S. William Gome, Jr., George F. Harper, Clarence A. Kemper,
John H. Leigh
Estados Unidos de Norteamérica
El eyector de fase múltiple en sistemas
de desalineación por destilación utiliza una
corriente motriz de dos fases, liquido-vapor,
para comprimir una corriente de vapor a
una presión más alta y a la temperatura
de saturación correspondiente. La corriente
motriz entra en el eyector de fase múltiple
como liquido y es acelerada en una tobera
convergente-divergente de manera que for
ma un chorro líquido-vapor supersónico.
La corriente de vapor se acelera en una
tobera convergente separada y puede entrar
en la región de mezcla como una corriente
de líquido-vapor o como una corriente de
vapor puro, dependiendo del estado de
estancamiento del vapor y de la eficiencia
de la tobera de vapor. Mediante el diseño
apropiado, es posible lograr que los proce
sos en un eyector de fase múltiple sean
más reversibles que con eyectores que em
pican corrientes de fase simple; por lo
tanto, es posible construir un sistema de
desalinización con eyector de fase múlti
ple, más eficiente que cualquier sistema que
emplea aparatos eyectores convencionales.
Las razones por las que un evector de
fase múltiple puede ser más eficiente que
eyectores ordinarios se comprenderán si se
consideran algunas de las fuentes de irre-
vcrsibilidad en un eyector; por ejemplo,
transferencia de calor entre las corrientes
debido a grandes diferencias de tempera
tura y transferencia de impulsión por
medio de una interacción de viscosidad
entre las corrientes de entrada, debido a
grandes diferencias de velocidad. Dado que
las corrientes de entrada de un eyector de
fase múltiple son expandidas antes de mez
clarse a la misma presión estática en la
región de doble fase, existen diferencias
muy pequeñas de temperatura entre la fase
748
líquida y la de vapor cuando las corrientes
se mezclan. Además, para el caso en que el
estado de estancamiento de la corriente
motriz es el del líquido a alta presión, es
posible seleccionar la presión de mezclado
de manera tal que la transferencia de
impulsión entre corrientes se produzca con
una pequeña diferencia de velocidad.
Considérese la expansión de las dos cor
rientes a una presión de mezclado dada,
a la que ambas corrientes se encuentran en
la región de doble fase. Cuando la presión
de mezclado es igual a la presión de estan
camiento del vapor, la corriente de alta
presión que inicialmente era líquida ten
drá una velocidad finita, mientras que la
corriente de vapor tendrá una velocidad
cero. Ulteriores reducciones en la velocidad
de mezclado serán motivo de que la corrien
te de vapor, o de alta calidad, incremente
velocidad mucho más rápidamente que la
corriente de líquido, o de baja calidad,
porque para un cambio diferencial dado
en la presión, el cambio en la velocidad
de una corriente flúida es casi proporcional
a la relación del volumen especifico res
pecto de la velocidad. Por lo tanto, a
cierto valor de la presión de mezclado, la
velocidad de las dos corrientes será la
misma, y si las corrientes están en la región
de doble fase a la misma presión, las
temperaturas también serán las mismas. En
teoría, estas dos corrientes pueden mezclarse
reversiblemente, esto es, sin pérdidas de
transferencia de calor o viscosas. La acción
de bombeo en este caso ocurrirá en el
difusor porque a medida que es desacele
rada la corriente de doble fase combinada,
el vapor cambiará velocidad más rápida
mente que el líquido, creando entonces una
diferencia de velocidad entre las dos fases
y permitiendo una transferencia de impul
sión del líquido al vapor, por medio de
resistencia viscosa. Si el diámetro del gotero
de liquido es pequeño, la irreversibilidad
en este proceso va a cero cuando la dife
rencia de velocidad va a cero.
Si se tienen en cuenta los efectos de fric
ción de las paredes, la velocidad relativa
entre las fases y las distribuciones de tem
peratura en cada una de las fases, la
presión óptima de la sección de mezclado
será diferente de la calculada para un caso
ideal y, por supuesto, los procesos dentro
del eyector de fase múltiple ya no serán
reversibles. Aun cuando se adjudican valo
res realistas a las irreversibilidades involu
cradas, un eyector de fase múltiple es mucho
más eficiente que un eyector de fase simple.
749
 On the Freezing Process*
G. Bozza, C. Dassù, G. Giambelli
Italy
Of the several methods proposed for
obtaining fresh water from the sea or
brackish water, the freezing process offers
many advantages, both thermodynamical
and technological: the heat of crystalliza
tion is lower than that of evaporation and
the corrosion of materials by the saline
water is lessened at low temperature. How
ever, there are several problems involved.
Perhaps the most important is the fact that
the mass of ice traps some of the brine
from which it is formed. The ice always
retains some brine even when it is very
compact or dry, as shown by various experi
ments conducted by the authors.
Experiments show that the ice is always
contaminated with salt, whether it is ob
tained from still water, water strongly
agitated by air bubbles, spraying the water
sprayed on the cooling surfaces, or water
flowing as a thin layer on the same.
Also, the contamination cannot be elimi
nated, whether the temperature differential
between the brine and the cooling surfaces
is lower or higher, .but it is smaller in the
first case. An experiment to confirm this
fact is mentioned here for its ingenuity and
easy repetition: a solid cylindrical rod of
copper has a part maintained at a very
low temperature (15° to 20°C below freez
ing) by immersion in a thermostatic bath;
the other part, for a suitable length, is
introduced into the saline solution. Owing
to the temperature gradient along the
cylindrical rod. the temperature of the sur
face in contact with the brine {and sub
sequently with the ice formed from it)
varies continuously between a value very
close to that of the cooling source and a
value very close to that of crystallization
of ice in the brine. The ice formed on the
• The present work has been carried out at
the Politécnico of Milan with a fund Kranted
by "Conaiglio Nationale delle Ricerche" of Italy.
rod is obtained with very different tempera
ture differentials, and samples taken at
various distances from the colder end can
give the influence of the above differentials
on the contamination of the ice.
Those experiments confirmed the fact
that it is practically impossible to obtain
pure ice from solutions more than scantily
concentrated in salts.
It is possible to eliminate the brine from
the mass of ice when the processes of melt
ing the ice and draining the mother liquor
are conducted very slowly. In this case the
first fraction of water has a salt content
very close to that of the brine from which
the ice was formed: the subsequent frac
tions have ver)' quickly diminishing salini
ties. To obtain a sufficient purification, it
is necessary to melt more than half of the
ice. Hence the efficiency of a freezing plant
is greatly reduced. Some students of the
matter have endeavored to obtain the ice
from the brine in the form of compact
crystalline granules large enough to permit
an easy washing of the same. But the oper
ative conditions are very critical and the
process does not appear to be verv promis
ing.
The ice obtained directly from a saline
solution with temperature differences be
tween the cooling surfaces and a brine is
always in very minute crystals, and can
be easily scraped from the cooling surfaces.
For instance, on the surface of a rotating
cooling drum we can normally obtain a
flake clear ice from fresh water, while from
a saline solution, very thin crystals are
formed. These crystals are scraped away bv
blades and, mixed with the mother solu
tion, form a more or less thick slurry. Tak
ing it for granted that the only practical
process when operating with an indirect
heat transfer in the cooling and freezing
is to obtain a slurry, the separation of the
751
 ice from the brine and its thorough wash
ing are the paramount problems to be
resolved.
The very thin crystals have a relatively
thick limiting layer of concentrated solu
tion, and the mobility of the latter is so
low that the elimination of salt can lie
accomplished only by a diffusion mechanism
toward the less concentrated layers.
The centrifugation of the mass or the
filtration leaves a considerable amount of
residual moisture. It is necessary to employ
a substantial quantity of fresh wash water
to remove the brine and there is not suffi
cient time for an effective diffusion effect.
The feasibility of such a process is, eco
nomically, very questionable.
Moreover, the simple displacement of the
adhering solution is by no means complete.
In trying to percolate a flow of pure water,
made visible with a dye, so that the front
of it advances by parallel planes without
mixing phenomena until the entire mass is
pervaded by the color, there is still salt in
the water from the melted ice.
With the granulometry of ice obtained in
our experiments (about 0.1 mm) and the
resulting geometrv of the network of crys
tals, repeated determinations of the relative
quantities of ice, water, and salt in thor
oughly drained samples have given a ratio
of ice to water of about 1 to 1.
The continuous countercurrent washing
of the ice from the original slurry is thus
the obvious technical solution for an eco
nomically feasible process. The washing
water is to be taken as a fraction of the
melted ice, and the economy of the device
requires that the fraction should be small.
However, it is obvious that a small quantity
of countercurrent water requires a large
.surface of diffusion because the mean
difference of concentration between the
upward and the downward streams is less
ened when the washing is reduced. It is
apparent that a calculation of optimization
is required. To achieve this, it is necessary
to analyze the behavior of such a wash
tower.
Its characteristic feature is that the solid
to be washed, the ice, floats in the solution
and rises toward the top of the tower, accu
mulating as a more or less compacted lied
which continuously moves upwards; the
rate of its rising is controlled by the rate
of production and ice melting. If water dis
charged from the top is less than the water
input resulting from the melting of the ice
in the top section (i.e., the mass water dis
charge is less than the mass rate of rising
of ice) , the difference between the two
752
rates decreases as a net downward flow,
contributing to the washing of the ice.
The behavior of a wash tower working
with a continuous rising movement of the
solid phase (ice) and a correlated drive of
the polluting liquid phase can be evaluated
as follows:
In a volume element of the tower there
is a fraction a of ice distributed as a net
work of very small crystalline granules, and
a fraction 1 —a filled with water or saline
solution. The parameter a mav be different
along the tower height, owing to the thick
ening of the ice under the buoyancy forces
due to the inferior parts. Eventually in a
short length a steady condition can be
obtained in which a is about 0.3. so that for
the sake of simplicity we may assume a
constant value for e.
At the bottom of the tower a suspension
of ice crystals in the brine is fed with a
mass ice discharge G for unity of tower
area, or a volume discharge G/ß0, ß„ being
the density of ice. With constant a, and
without melting of ice or freezing of part of
the brine, G remains constant along the
tower; possible thermal effects and their
consequences will be considered separately.
An absolute rising speed of ice. v„ is asso
ciated with the discharge G: and the ice
drags a certain amount of brine toward
the top of the tower. The amount can be
evaluated as follows: The complicated out
line of the water flow in the network of ice
particles can be simplified as an assemblv of
flow tubes parallel to the axis of the tower:
the shape of the tube section can be chosen
at will. The following treatment is perhaps
the simplest. An analogous treatment with
cylindrical channels leads to very similar
results.
Suppose that the system is composed of
ice vertical lamellae (Fig. 283) separated by
layers of water of a thickness 2s: the ice
lamellae will be 2s а/П—a) thick. Thus
we have in the unity of tower area.
(1—a) /2s elementary channels 2s wide and
of unity length. The ice lamellae have the
rising speed v0, and the volume discharge
of ice G//9„ is represented by
V" 12s—аа ' 1 -
2s a = V°
The ice melts at the top of the tower: the
volume of water formed per unity of time
and unity of tower area is
G /3„
ß, being the water density. We extrari
 The total discharge of liquid in the chan
nel is
»c*=»[v-(£)(&)]

to be taken positive when directed toward

the top of the tower.
As a matter of fact, the net discharge in
each section of the tower should be the
amount restituted at top: it is, when we
disregard the density differences,
_ 2 v„ s a p„ (1 - y)
(1 - a) fa
Equating it to the above total discharge,
we can deduce the pressure gradient Ap/Ah

Ah
and the velocity distribution

= M s^[1+T3rx(1-^)]
FIGURE 283. ICE LAMELLAE
SEPARATED BY TWO LAYERS 1+3
1 -. ]l
OF WATER.
The absolute velocity is negative for (x/s)1
between 0 and
from the top every unity of time and area,
the volume W of water: introducing an 1 + 1 -a ft (i-y)
extraction ratio or yield ratio y — W fc/G,
the discharge of water at top is, for each . positive for
elementary channel.
>0(r^)(f)H
2v.s<
1 -a (x/s)* between that value and I.
Calculating separately the upward ^ and
and the amount of water restituted down downward q, discharges, we obtain
ward to the tower is /
(upward)j, q, = — 2 v„•__
s
2v.j. (1 — a) 0i
1 -a 4- Pi |~J_ I [d -a) ft +3 aft, (1-7)7
To investigate the motion in the water |_ 3 \ 3[(1 - a) ft + aft, (1 - y)]
layer in the elementary channel, let the
vertical coordinate be h, with its origin at -a 0.(1 -7/ J
bottom of tower, and the horizontal be x,
perpendicular to the plane of lamellae, with (downward) q, = - 2v„ s
its origin in the axial plane of channel. (1 - a) ft
With constant viscosity y. of brine, we have [(1 -a) ft + 3aft,(l ~7)T
dv 4 3[d - a) ft + a-ft, (1 - y)]
* Ap = " dx~ Ah
and their sum gives the net discharge as
Ap being the drop of pressure along Ah above.
due to the velocity gradient and v the As the velocity v„ can be written
velocity (positive upward) at x. The abso v, = C/o^, and in the unity section we
lute velocity is v„ at x — s, the same as the have (1— a) /2s elementary channels, we
ice wall; so the velocity distribution across can introduce the upward and downward
the channel is unitary discharges (for unity section)
I •ip 1 -a „ 1 -a
 and the adimensional discharges
Q,ft Qsft
~G~ G
They are
(upward) ^ '•— -

—a
sT" ft +»
— (1 - Y)
a Po (I)

(downward) Q»ft
G

So
(2)
1 -,
ft
(net) (Q. + Q.) ft = - (1 - y) (»)
G
Taking for 0„ the value 910 kg/m«, for ft
that of 1,000 kg/m1 (for the sake of sim
plicity, the same for water and brine) , we
have:
Q.ft (1,856 — y)»" for a = 0.3
(3367 - y)
(1,550 -y)1" for a = 0.4
__ (2,650.
(1.867 -y)"1 for a = 0.5
- (2,100 - y)
(1344 - y)"* for a = 0.6
- (1.733 — y) 1/1
The calculated values for 7 from 0 to 1 are
collected in Table CXXII and in Figure 284.
The same reasoning, applied to a cylin
drical instead of a lamellar channel, leads
to similar results: for instance
(downward)
f (1 -«) (ft) -I'
Q.ft _ L (2a) (0.) 7J FIGURE 284. CALCULATED
G (1 - «) (ft) + 1-7 VALUES FOR YIELD RATIO
(a) (ft) (CYLINDRICAL CHANNEL).

TABLE CXXII. Calculated Values for y from 0 to 1

a = 0.8 0 = 0.4 a = 0.6 0 = 0.6
y Qi pi Qi 0i Qi pi Qj 01 Qi 0i Q> 01 Qi0i Otfii
G G G G G G G G
0.0 0.888 1.888 0.187 1.187 0.102 1.102 0.066 1.056
0.1 0.848 1.248 0.194 1.094 0.108 1.008 0.059 0.969
0.2 0.859 1.159 0.202 1.002 0.114 0.914 0.062 0.862
0.8 0.871 1.071 0.211 0.911 0.121 0.821 0.066 0.766
0.4 0.885 0.985 0.221 0.821 0.129 0.729 0.071 0.671
0.6 0.401 0.901 0.232 0.782 0.138 0.638 0.078 0.678
0.6 0.417 0.817 0.246 0.645 0.148 0.548 0.085 0.48S
0.7 0.434 0.784 0.260 0.661 0.160 0.460 0.094 0.S94
0.8 0.462 0.662 0.277 0.478 0.174 0.874 0.106 0.J06
0.9 0.472 0.572 0.296 0.396 0.191 0.291 0.121 0.221
1.0 0.494 0.494 0.817 0.317 0.212 0.212 0.140 0.140

754
 of brine with a concentration c"b, drawn by
the volume discharge G/p„ of ice goes from
the bottom section to the tower.
The balance between the in- and out-
coming quantities, in suitable zones of the
tower, gives <n
(a) In the bottom mixing section
( Q'. + 10,1 = Q". + |Q,|
IQ'.C.+ IQ,! Cb = [Q»0+ |Q,|C„
(b) In a part of tower, including the bot
tom section
<Q'. + IQ.| = Q".+ IQi|
\ c. + IQ.I c = Q",,cb + iq.1 c
(c) For the complete tower, from bottom
to top sections
f/3iQ'. + G = /3,Q/'.-(-7G
(Q'.C. = Q".Cb + y c",
Pi
(d) In the top mixing and melting section
G
'IQ.I + = 10.1 + 7-^-
Pi
l|Qi| C, = |Q,|C", -I- y — c",
Pi
Taking into account C",. the concentration
of salts in the fresh water obtained, the
relationship between the average concentra
tions c" and C of the descending and
ascending flows is
c" = [l-(l_Y)-r£7T-]c<--r
p. 10,1
- c", (4)
.10.1
I 0.1 01 04 0.4 O S 0* 0.7 O.t 0.0 1.0 With a parameter J or freezing ratio as the
fraction of the original saline water trans
IGURE 285. FLOW RELA- formed in ice crystals, J =G/^, Q. we have
TIONSHIP IN THE UNIT the relations
SECTION OF THE TOWER. '•-T^-Pr1)©"-*-
c, — y * c",
the tower, with reference to the unity \-yS
lion, we have the following relations:
bottom there is a continuous feed, in
: unity of time, of the mass G (Fig. 285) G (l-Y»)C„-c.
se volume G/fS,) of ice, and of the vol-
le Q'. of brine with a concentration c*. + frlQ.! «
salts. If the concentration of the original Between c', and c",, in the top section,
ine water is c., we should have there is the relationship
'• = C-(1+
c, = c,
being the density of the brine. C.
From the bottom we have a discharge 1 _ (1 _ y) (5)
ft 10,1
with a concentration cV Into the Dot
al mixing section goes the discharge | Q, | (1) The concentrations of ascending flows are
indicated c', those of the descending* flows c"
brine with a concentration c"», com- The b index characterises the
% from the tower: and the discharge | Q, tower and bottom section, the t in
tween tower and top section.
755
 TABLE CXXIII. of tf and c," Calculated for the a Values 0.3, 0.4, 0.5 t

a -- 0.4 a = 0.5
Q l-(l-Tr). y ft i»
O G G
* fix I Q. I * fix \ Q> ! fix 0,1
0.0 0.000 0.156 0.000 0.092 0.000 0 0S3 0 (00
0.1 0.279 0.081 0.176 0.091 0.107 0.099 0.061 0.1M
0.2 0.310 0.178 0.202 0.200 0.126 0.218 0.074 0.£H
0.1 0.347 0.279 0.232 0.329 0.146 0.366 0.086 C,3«
0.4 0.391 0.406 0.270 0.486 0.177 0.549 0.1O5 0-5*4
0.5 0.444 0.555 0.319 0.681 0.218 0.784 0.135 •ja
0.6 0.509 0.736 0.381 0.928 0.270 1.096 0.175 uu
0.7 0.590 0.958 0.465 1.247 0.348 1.521 0.240 1.m
08 0.693 1.227 0.581 1.674 0.465 2.139 0.S46 2.SIS
0.9 1.572 0.747 2.275 0.657 3.080 O.SKS
1.0 2.023 1.000 8.160 1.000 4.716 1.000 7.1M

Table CXXIII shows the coefficients of C and (1 -yS) [(I -y) C+C".]
c", calculated for the a values 0.3. 0.4, 0.5, (1 - y) c„ + y (\ - 8) c",
and 0.6.
We are assuming that it is possible to = _ ka (1 - y) h 17*
describe the exchange process of salt be ft IQ»! IQ.I
tween the upward and the downward flows When h reaches the full height of r±<
by means of an exchange coefficient k, to be tower, H, the concentration c' becomes c,
determined by experiments, so that we can and is expressed by Equation (5) . The
write height of tower, H, is then
|Q,| dc" = |Qi| dC = - k a dh • (C - <f) _G IQil ft 1Q,! ft
H = 0, ka (1 _ y) " G " G
where a is the total exchange area in the
unity volume (a dh is the area for the layer ( 1 - (1 - y)
of thickness dh and unity surface of tower) In ft!Q»i
and, in the scheme of lamellar channels, 1 -yi
equals (1— a) /s.
+ In [y (1 - 8) + (1 - i)
Since (Eq. (4))
It is reduced to zero when
1-7
c. 1+^(1-S) ftfe
from Equation (6) we have
c",
dc* I _ (1 _ y)
ft 10,1
c", such a ratio of concentrations can be d>
lained without a wash tower, independent'
= _ ka (1 - y) dh, of the exchange phenomena between tlx
ftlQ.| IQ.I two streams of liquid. Rearranging Eqiu
and, by integration, tion (8) , and, if necessary , introducing tin
volume V — H A of the tower having tin
In [C + y-*— C\] = - ka (1 - y) area A, and the total feed of ice P - C i
' I we can write an adimensional ratio chaw
teristic of the behavior of the tower
ft IQ.I !Q.I
with C, an arbitrary constant. IQ.I ft 10. ft
H , V , G " G
At bottom h = 0 and c' = c'b = ~G kaft="p- ka^,= j-—
c. - y 8 c". (» - 0 - y) . Go ) 0 - y
1 - y» ft IQ,
so • In
1 — yi
y (i - 8)
+ •-]
Thus the relationship between the height y
in the tower, h, and the concentration in The parameters affecting the ratio are a 1
the upward flow, c', is 8, c„/c"t: both a and 8 are nearly 6^

756
 О 25 SO 71 100 125 150 175 200 225 250 275 100

FIGURE 286. TOWER ADIMENSIONAL RATIO CHARACTERIS

TICS WITH VOLUMETRIC ICE FRACTION 0.3.

0 25 50 75 100 125 ISO 175 200 225 250 275 300

FIGURE 287. TOWER ADIMENSIONAL RATIO CHARACTERIS

TICS WITH VOLUMETRIC ICE FRACTION 0.5.

757
 (a because it depends upon the thicken
ing of the ice, a because it is not opportune
to increase the quantity of water trans
formed in ice) , so the essential operating
factors in the tower are y and c./c",.
The value of the ratio, calculated fo
a = 0.3, a = 03. a = O.l and for the -
values from 0 to 1 and several values of tie
ratio c./c",, are collected in Tables CXXP
and CXXV and Figures 286 and 287.

TABLE CXXIV. Ratio Values (a — 0J)

y e. T»lu for ——
«"i G K
Um to SO 60 70 100 111 150 176 200 | 250
0.0 3.95 0.TSI 0.014 1.140 1.299 1.460 1.660 1.643 1.71S 1.774 1.874 1JH
0.1 8.84 0.786 0.978 1.226 1.S86 1.668 1.668 1.768 1.828 1.891 1.90S IMi
0.1 8.7* 0.849 1.069 1.S20 1.496 1.682 1.704 1.801 1.971 2.040 2.167 IB*
0.S S.62 0.927 1.160 1.444 1.6S6 1.8S7 1.963 2.064 2.156 2.2SS 2.SSS 2.46*
0.4 3.49 1.020 1.170 1.588 1.708 2.024 1.160 2.177 2.375 2.460 2.600 X.TU!
OS S.ST 1.141 1.426 1.782 1.017 2.277 1.484 2.664 2.680 2.778 2.9S5 ua
o.c 8.15 1.S0S 1.620 2.03S 2.807 2.610 2.800 2.945 3.080 S.186 3.SS0 UM
0.T S.14 1.613 1.908 2.418 2.760 8.126 3.365 8.540 8.700 3.840 4.075 4.J*
0J S.04 1.890 2.410 S.100 3.568 4.060 4.890 4.645 4.860 5.060 S.S84 5*4.5
0.9 2.9S 2.640 S.S60 4.610 6.810 6.186 6.750 7.110 7.610 7.060 8-6*0 »J>10
1.0 2.8S 00 00 00 00 00 00 00 00 OO so

TABLE CXXV. Ratio Values (a = 0.5)

V e« Hk.fr for -fr~ -

o"t G
lira to 80 60 70 100 116 160 175 200 150 too
0.0 10.81 0.069 0.114 0.171 0.208 0.149 0.274 0.294 0.812 0.S16 0.851 ojn
0.1 10.16 0.081 0.180 0.192 0.232 0.276 0.801 0.326 0.844 0.359 0.386 0.4M
0.1 0.60 0.096 0.147 0.213 0.267 0.803 0.382 0.356 0.396 0.894 0.423 0.444
0.8 9.0S 0.108 0.104 0.286 0.284 0.886 0.366 0.392 0.414 0.434 0.465 0.4M
0.4 8.46 0.110 0.101 0.270 0.328 0.878 0.418 0.441 0.466 0.486 0.521 0-545
0.6 7.87 0.164 0.222 0.810 0.369 0.481 0.460 0.500 0.629 0.661 0.591 S.434
0.6 7.S6 0.181 0.268 0.368 0.425 0.496 0.641 0.676 0.608 0.685 0.686 0.TUI
0.7 6.81 0.114 0.816 0.486 0.516 0.699 0.665 0.700 0.7S5 0.768 0.822 UKi
0.8 6.29 0.284 0.39R 0.661 0.664 0.768 0.885 0.893 0.043 0.986 1.057 1J1I
0.0 6.77 0.S98 0.668 0.798 0.063 1.146 1.260 1.368 1.487 1.609 1.630 1-TT
1.0 6.26 00 00 00 00 00 00 00 00 00 00 -

A planned experimental plant was de the numerical value of ka in different

signed to verify theoretical relationships
and, in particular, whether the ka term of
the final formula, which summarizes the
analysis of a wash tower, was a constant.
' From this particular point of view, ka
becomes the operative parameter and we
can generally write ka — f (J, a, H, 0„ p„,
G, y, c„/c",) . Among the numerous param
eters involved, we can assume a and a to be
fixed, the former being the volumetric frac
tion of ice in the slurry, and the latter the
freezing ratio maintained (very small in
practice so that it can be considered equal
to zero) .
For each tower, the height of the porous
ice bed (H) is generally constant: we can
say the same of /3, (fresh water density)
and /9„ (ice density) . The experimental
plant must be sufficiently flexible to permit
the imposition of the value of G (mass rate
of flow of the ice) and of y (extraction
ratio) and to determine the value of the
concentration ratio c0/c",. In this way we
will be able to obtain from Equation (9)
operating conditions.
If we find a constant value of the ka
parameter, we will be optimistic about the
applicability of Equation (9) in designing
freezing plants. In the experimental plant
(Fig. 288) , ice is formed from saline witr
by means of a continuous machine usualfr
employed for ice production (G) . In this
apparatus the ice is formed on a routine
cylinder, cooled by Freon 12 direct expan
sion. Special blades scrape away the lavrr
of ice in form of minute crystals: these art
collected together with the brine, in a tanl
(S) . The resulting slurry is fed by a pump
at the bottom of a separation column (Ti
in which the ice crystals float upwards
while the liquid brine is recycled. The icr
is melted at the top of the tower In mean*
of a heating coil: the rate of melting is
fixed by controlling the supply of power to
the heating device. The fresh water pn>
duccd at the top is partially drawn off M
a peristaltic pump (D) : the residual frac
tion (generally a small amount of the total'
flows downward, washing the ice. In steach

758
conditions, the mass quantity of ice (G)
melted at the top is obviously equal to the
quantity that must be fed in at the bottom
of the tower.
' content c"t of fresh water was measured
FIGURE 288. EXPERIMENTAL
PLANT FOR THE FREEZING
PROCESS.
The extraction ratio is changed by means
of the dosing pump (D) . The experimental
tower was built in plexiglas (lucite—Fig.
289 having an external diameter of 290 mm
(that is an are a of 0.066 m*) and a height
of 2,000 mm. A part of the total height of
the tower, about 1,500 mm, was filled with
ice particles; the inlet of the feed pipe was
250
2.000
FIGURE 289. DIMENSIONAL DATA OF THE EXPERIMENTAL
TOWER.
situated at a distance of 250 mm from the
basis; the melting coil (M) was placed at
a distance of 100 mm from the top. During
the transient period, the filling of the tower
is carried out until an ice bed of 1300 mm
is formed, without extraction of fresh
water. In this way the effect of washing is
intensified and steady conditions are rapidly
attained.
The quantity of ice melted is measured
by the discharge of water flowing in the
coil and the value of the thermal difference
between water inlet and outlet.
It is possible in this way to calculate the
heat subtracted from the coil and, knowing
the outlet temperature of fresh water, it is
possible to calculate the mass of melted ice.
The ratio between such a mass and the
mass of water extracted by the dosing
pump supplies the numerical value of y1.
The determination of numerical value of
a was determined by measuring the rising
speed of the ice bed, easily estimated
thiough the transparent wall. A value of
0.3 was found and this figure was nearly
constant in several experiments. The salt
during the experimental tests by a register
ing salinometer with platinum electrodes.
Salt content was also controlled by chlorine
titration with AgNO,. The original saline
water used in experimental work was always
a solution of NaCl in water (c„ = 33%) .
The time employed to complete the test
varied between 24 and 70 hours.
As we have explained before, the prelimi
nary experiments were carried out by
changing the extraction ratio y and the
value of mass ice discharge G. During ex
perimental tests the concentration of fresh
water at the tower's outlet and the concen
tration of the original water to be treated
759
 were determined at the same time.
Using the experimental data and Equa
tion (9) , we calculated the values of ka:
they agree quite well. As a matter of fact,
a number of experiments was carried out,
during which y was changed between the
value 0.417 and 0.858, G was changed be
tween the value 1.47 • 10"* and 2.53 • 10"*
g/s cm" and с./с", between 15 and 30. The
resulting values of ka were comprised in
the span between 1.98 • 10"* and 2.32 • 10"*
Г*. These data are satisfactory if we cqn-
sider the effective operational conditions.
The most important difficulty we experi
enced during the tests was that of obtaining
a steady-state in the wash tower. This diffi
culty is a consequence of the smallness of
the plant—the greatly reduced flows which
resulted were not easy to control. In order
to permit visual inspection of the phenom
ena, the tower was built of a transparent
material (lucite) , without thermal insula
tion. This caused a partial melting of the
ice on the external wall of the cylinder and
thereby induced a different operational con
dition from the theoretical one. From this
particular point of view, a difference of
± 7.5 per cent from the average value of ka
can be accepted.
The determination of a more exact value
of ka is not very difficult, because it is only
connected with the experimental methods.
On the contrary, the greatest uncertainty
is whether the value practically determined
in a small tower can reasonably be em
ployed for the design of a larger one.
On that point, we can determine that the
ka constancy depends on the diffusion coeffi
cient of saline solution, on granulometry of
ice, and on the rate of thickening of ice
bed. These factors seem to depend on the
freezing conditions, i.e., temperature, freez
ing ratio, concentration, and quality of salts
LIST OF SYMBOLS
a volumetric fraction of ice in the y
slurry
1 — о volumetric fraction of brine
G mass ice discharge for unity of tower H
area h vertical coordinate of simplified
ß„ density of ice
v. absolute rising speed of ice X horizontal coordinate of simplified
2s width between ice vertical lamellae
(elementary channel) (L brine viscosity
ßi water density C„ concentration of saline water at
W fresh water extracted from tower
top (for unity of time and unity of c„
tower area)
760
in the solution, rather than on the size of
the tower. For these reasons, it seems that
the ka value, even if deduced through an
integral relationship, could be used as a
constant coefficient in a tower of different
size than the one employed by us. Only
tests carried out on a pilot plant with a
wash tower of larger dimensions can con
firm what we have asserted above. Steps
are now being taken to build a pilot plant
for an output of about 24 ra* pd.
Using the data we have obtained here
and specifically the average value of ka of
2.14 • 10"' г*, it is very interesting to pre
dict the indicative figure of specific produc
tion of fresh water (mass of fresh water
converted for unity volume of tower and
unity time) with a fixed concentration ratio
c„/c", and a fixed extraction ratio or y.
For instance, the specific production of a
plant to extract potable water with 500
ppm from sea water with 30,000 ppm can
be calculated with Equations (1) , (2) . and
(9) . The figures we must insert are the
following:
c„/c", = 60 /3, = 1 g/cm» ß0 - 0.91 g/cm1
For the extraction ratio we have fixed
the reasonable value of 0.8, for a the value
of 0.3, in the hypothesis of a rate of thick
ening identical to that of experimental
plant, and a freezing ratio J equal to zero
With the above-mentioned values, we ob
tained a specific production of ice (G/H).
equal to 0.675 • 10"* g/scm*, equivalent to
24.4 kg/h m". The corresponding specific
value of fresh water produced is 195 kg/m"
h. With this specific production data, the
construction cost and the size of wash tower
of an industrial plant seems to be accept
able. For instance, the above-mentioned
pilot plant of 24 m* pd requires a tower
having a volume of 50 m*.
extraction ratio or yield ratio (ratio
between mass of water extracted
and mass of ice melted)
height of tower
model
model
tower inlet (bottom)
concentration of (original) saline
water
 brine charged at bottom (volume
for unity of time and tower area)
Q". volume of brine discharged at tower
bottom
с» concentration of brine at tower
bottom
с" average concentration in the up
ward flow of brine
average concentration in the down
с
ward flow of brine
b index: indicates flows between the
tower and the bottom section
SUMMARY OF DISCUSSION
There was no discussion.
Le Procede de Congelation
G. Bozza, С. Dassù, G. Giambelli
Italie
Le procédé de congélation pour le des
salement de l'eau salée ou des eaux
saumâtres est bien connu dans ses caracté
ristiques principales et possède certains
avantages inéluctables, à la fois des points
de vue thermodynamiques et technologiques.
II n'a pas encore dépassé le stade de l'expé
rimentation pilote pour atteindre celui du
développement industriel, sauf en ce qui
concerne certaines variantes du procédé qui
sont exploitées sur une grande échelle dans
divers pays (comme le procédé Zarkin) .
Il existe encore plusieurs points à étudier
avant qu'il soit possible de rationaliser et
d'optimiser la conception des installations
et, par conséquent, le procédé dans son
ensemble.
Nous ne discuterons pas des avantages et
des désavantages de la méthode directe de
congélation par rapport à la méthode in
directe, ni des caractéristiques de construc
tion des machines effectuant le cycle de
réfrigération par lequel les différences entre
les sources chaudes et froides doivent être
maintenues aussi faibles que possible pour
arriver à une bonne efficacité thermo
dynamique; nous ne discuterons pas non
plus de la construction et du rendement des
dispositifs ayant pour but de laver les
cristaux de glace, de la bonne construction
index: indicates flows between the
tower and the top section
freezing ratio (ratio between mass
quantity of ice and mass quantity
of original saline water entering
the plant)
discharges of the upward and down
ward flows of water (volume for
unity of time and tower area)
к exchange coefficient
a total exchange area for unitary
volume
mécanique pour un ensemble à toute
épreuve, de l'optimisation relative des dif
férentes parties, ni des dimensions d'instal
lation, etc.
L'objectif de cet exposé n'est pas d'étu
dier ces points ni d'explorer les résultats
d'autres chercheurs ou les rendements
pratiques de toutes installations pilotes
existantes. Nous espérons, cependant, que la
partie que nous avons développée, le rende
ment d'une colonne de lavage pour les
cristaux de glace, sera utile à une bonne
compréhension de la totalité du procédé.
Nous avons commencé par une série d'ex
périences sur la formation de la glace à
partir de solutions salines sur des surfaces
froides, dans le but d'obtenir la glace en
paillettes claires, d'une bonne épaisseur,
sans la présence de liqueur mère. Cepen
dant, nous n'avons pu obtenir la glace
compacte que nous voulions, soit dans des
solutions calmes soit dans des solutions
agitées, sur des surfaces statiques ou des
surfaces mobiles, avec la solution l'écoulant
en une couche fine ou vaporisée sur les
surfaces de refroidissement ou avec une
différence faible ou élevée de température
entre la surface et la saumure. Ainsi, la
glace obtenue de concentrations salées
(NaCl) correspondant à de l'eau saline ou
761
 de l'eau saumâtre, bien que parfois trans de glace, en supposant que le réseau
parente, comprenait toujours certaines des granules se forme de lui-même, sous
quantités de liqueur mère concentrée; donc, forme d'un jeu parallèle de canaux verti
l'eau obtenue après fonte n'était pas puri caux, chacun avec des parois se déplaçant
fiée de façon satisfaisante. vers le haut avec une vélocité égale à la
D'autre part, il est très facile d'obtenir vélocité de montée de la glace dans la tour.
la glace sous forme de masse poreuse de Dans un but de simplicité, on a effectué;
cristaux, avec une fraction élevée de vide un calcul en supposant des canaux entre
à l'intérieur, entièrement imprégnée de les lamelles parallèles de glace. Cependant,
saumure, de drainer la masse aussi com en décrivant la tendance du phénomène,
plètement que possible en laissant un temps les résultats ne sont pas différents de сеиж
suffisant d'infiltration, de détacher les obtenus avec d'autres formes de canaux. On
cristaux dans une boue et de filtrer la suppose que les écoulements sont lami
masse par application de succion ou de naires. Les variantes à considérer sont:
force centrifuge. Mais il reste toujours une 1) la fraction de vide a dans la masse
couche de solution adhérant aux granules poreuse de glace; 2) la décharge de glace,
de glace. Des expériences montrent que le alimentée à la tour, P; 3) la fraction ex
pourcentage de cette solution par rapport traite à la partie supérieure sous forme
л la glace est d'environ 1:1. L'efficacité du d'eau douce, y, et 4) les décharges d'eau
lavage dans le filtre et le centrifuge n'est I Qi I du courant vers le haut et | Q, | du
pas grande. Ainsi, la quantité d'eau douce, courant vers le bas, pour la section unitaire
nécessaire au fonctionnement adéquat de de la tour.
ce procédé, est si élevée qu'elle rend la Les principaux résultats sont les suivants:
productivité du système non économique. Si il est possible d'écrire le rapport entre
nous voulons utiliser seulement une quan I Q, I et |Q»|, dont la différence devrait
tité limitée d'eau douce sur un dispositif être le courant net de lavage, c'est-à-dire
continu, systématique, à contre-courant, (1 — y) P; ils dépendent strictement de la
c'est-à-dire une colonne de lavage, nous fraction de vide a et du rapport d'extrac
croyons qu'il est absolument nécessaire de tion y.
compter sur l'échange de diffusion du sel En appliquant ces résultats au rendement
dissous depuis la couche adhérente plus d'une tour, nous pouvons écrire l'équation
concentrée vers les couches moins concen de la ligne de fonct ionnement, en reliant
trées de la solution de lavage. les concentrations moyennes des deux
Lors de l'étude des expériences effectuées écoulements à contre-courant dans toute
dans notre laboratoire, nous avons essayé section de la tour.
de mettre sur pied une théorie du rende En supposant que nous puissions décrire
ment d'une telle colonne de lavage. Nous l'échange de sel entre les courants comme
avons ici le fait particulier que la masse étant dépendant d'une façon linéaire de la
montante de glace entraîne avec elle, vers différence entre les concentrations moyennes
le haut, une fraction définie de la liqueur avec un coefficient d'échange k, combiné
mère. Ainsi, nous pouvons considérer le avec une zone d'échange totale nominale a,
phénomène de lavage comme la diffusion dans le volume unitaire de la tour
de liquide entre deux courants, l'un en (ka = s-1) , il est possible d'écrire l'équation
traîné vers le haut par la glace, l'autre suivante:
forcé vers le bas dans les canaux entre les
granules de glace. Nous supposons qu'une I Q. I ft 10,1 ft
bouc de glace est alimentée de façon con —P ka pâi — — G ka Pla, =
tinue à la partie inférieure de la tour et 1=7
est mélangée dans la section inférieure avec a- о-?) ) 0-у)
le courant de lavage. La glace dans la boue In ft 10=1
se dépose sous forme de couche de cristaux 1-yS
détachés et s'élève lentement, remplissant Г (1 - ») , С 1
la hauteur de fonctionnement de la colonne. L 1-7 + c", J
A la partie supérieure, la glace est retirée où G est la décharge de glace pour la
par un dispositif approprié et est fondue, section unitaire de la tour, V est le volume
transférant la chaleur de fusion. Une partie de fonctionnement de la tour, H est la
de l'eau douce en résultant est l'eau pro hauteur opérative de la tour, S un rapport
duite; l'autre partie est renvoyée à la partie de congélation ou fraction de l'eau originale
supérieure de la tour pour le lavage. transformée en cristaux de glace, ß, la den
Nous pouvons faire un modèle simplifié sité de la saumure, c„ la concentration du
du mode compliqué des courants dans la sel dans l'eau saline originale, c", sel de

762
 correspondant à l'épaississement spontané
l'eau douce extraite. Le paramètre -g- de la boue.
ka Ces résultats provisoires ont besoin d'être
(égal à —— ka /3,) est mis sous forme confirmés avec une installation plus impor
de tableau et certains diagrammes sont tante. En fait, il était très difficile, en raison
donnes. de la petitesse de l'installation de labora
Les résultats expérimentaux d'une petite toire, de contrôler le fonctionnement de la
installation de laboratoire (hauteur de tour et, en outre, les effets thermiques
fonctionnement de la tour 150 m, diamètre secondaires sont un inconvénient inévitable
039 m) , sous une variété de conditions, de la dimension réduite. Mais la valeur
confirment l'ensemble de l'hypothèse qu'il provisoire de ka et les éléments d'une
est possible de calculer une valeur provi théorie peuvent nous permettre de créer,
soire de ka, oscillant dans une gamme entre avec assez de confiance, une installation
environ 1,98 x 10" et 2,32 x 10 V1; avec pilote appropriée pour essayer les autres
une valeur moyenne de 2,14 x 10-V1. Le conditions technologiques et de fonctionne
paramètre a avait été pris comme étant 0,3, ment.

О Процессе Вымораживания

Г. Бозза, Г. Дассу, Г. Джиамбелли

Италия

Процесс вымораживания для опресне В рамки этого доклада не входит

ния соленой и солоноватой воды в об
щих чертах хорошо известен и несом
ненно имеет некоторые преимущества,
как с термодинамической, так и с тех
нологической точки зрения. Он еще не
вышел из стадии опытного изучения и
не достиг промышленного развития, за
возможным исключением некоторых
вариантов процесса, проводимых в ши
роком масштабе в некоторых странах
(как например, процесс Заркина).
До достижения возможности рацио
нализировать и оптимизировать кон
струкцию установки необходимо иссле
довать несколько пунктов, а потому и
процесс в целом.
Мы не будем обсуждать: преимуще
ства и недостатки прямого метода вы
мораживания по сравнению с косвен
ным; условия проектирования машин,
работающих на цикле вымораживания,
при котором различие между теплыми
и холодными источниками должно
быть, как можно ниже, чтобы достичь
хорошей термодинамической эффектив
ности; конструкцию и производитель
ность устройств, запланированных для
промывки ледяных кристаллов; механи
чески прочную конструкцию, удобную
для сборки; относительную оптимиза
цию различных частей; размеры уста
новки и т.д.
изучение этих пунктов, описание ре
зультатов, достигнутых другими иссле
дователями и практической производи
тельности какой-либо существующей
установки. Но мы надеемся, что та
часть которую мы разработали — про
изводительность промывной колонны
для ледяных кристаллов — окажется
полезной для ясного понимания всего
процесса.
Мы начали с ряда опытов, связан
ных с образованием льда из соленых
растворов на холодных поверхностях,
имея намерение получить подходящей
толщины прозрачные чешуйки льда без
маточного раствора. Однако, получить
нами желаемый плотный лед оказалось
невозможным ни в неподвижных, ни в
перемешиваемых растворах, ни на ста
ционарных, ни на движущихся поверх
ностях с раствором, протекающим в
виде тонкого слоя или разбрызгивае
мым по холодным поверхностям, ни при
низком, ни при высоком перепаде тем
ператур между поверхностью и рас
солом. Лед, таким образом полученный
из концентраций соли (хлористого на
трия), соответствовавших соленой или
солоноватой воде, хоть иногда и бывал
прозрачным, но всегда включал неко
торое количество маточного раствора;
поэтому полученная после растаплива

763
 ния вода не была достаточно хорошо
очищена.
С другой стороны очень легко: полу
чить лед в виде пористой массы, со
стоящей из кристаллов и содержащей
в значительной своей части пустые
пространства, целиком пропитанные
рассолом; как можно осторожнее осу
шить массу, дав достаточно времени
на перколирование; освободить во
взвеси кристаллы и профильтровать
массу, применив к ней отсасывание или
центробежную силу. Но там всегда
остается слой раствора, пристающий к
гранулам льда. Опыты показывают, что
соотношение этого раствора ко льду
примерно составляет 1 : 1. Эффектив
ность промывки в фильтре и в центри
фуге не высока. Следовательно коли
чество потребной пресной воды для
соответственного проведения процесса
настолько велико, что оно делает про
дуктивность системы неэкономичной.
Если мы хотим затратить только огра
ниченное количество пресной воды —
пользуясь систематическим, непрерыв
ным, противоточным устройством, т.е.
промывной колонной — нам кажется,
что абсолютно необходимо полагаться
на диффузионный обмен растворенной
соли от более концентрированного при
легающего слоя к менее концентриро
ванным слоям промывного раствора.
При планировании опытов для про
ведения в нашей лаборатории мы пы
тались создать теорию поведения та
кой промывной колонны. Мы здесь
имеем своеобразный факт, что поды
мающаяся масса льда тянет вверх опре
деленную фракцию маточного раство
ра. Поэтому мы можем рассматривать
явление промывки, как диффузию жид
кости между двумя потоками, из кото
рых один тянется со льдом вверх, а
другой форсируется через каналы меж
ду гранулами льда. Мы предполагаем,
что ледяной шламм непрерывно подво
дится ко дну колонны и смешивается
в нижней секции с промывным пото
ком. Лед в шламме осаждается в виде
свободных кристаллов и медленно по
дымается, заполняя рабочую высоту
колонны. С помощью подходящего
устройства лед в верхней секции уда
ляется и расплавляется, отдавая тепло
ту плавления. Часть получаемой прес
ной воды является водой-продуктом;
другая часть возвращается в верхнюю
секцию колонны для целей промывки.
Сложный характер потоков в массе
льда может быть изображен в виде
упрощенной модели, предполагая, что
764
в сети из гранулей образуется ряд па
раллельных вертикальных каналов,
стенки которых движутся вверх со ско
ростью равной скорости подымающе
гося в колонне льда. С целью упроще
ния рассчет был произведен на осно
вании гипотезы о каналах между па
раллельными пластинками льда. Одна
ко, при описании характера явления по
лучаются одинаковые результаты и при
других формах каналов. Принимается,
что потоки имеют ламинарное течение.
В число переменных величин входят:
1) фракция пустот в пористой массе
льда; 2) выпуск Р льда, поступающего
в колонну; 3) его фракция, извлечен
ная сверху в виде пресной воды и 4)
выпуски (Qj) идущих вверх и (Q2)
идущих вниз потоков воды на единицу
секции колонны.
Главные результаты состоят в сле
дующем: является возможным устано
вить зависимость между (Qj) и (Q2),
разность которых должна равняться
промывному потоку нетто, т. е.
(1 -у) Р; они целиком зависят от фрак
ции пустот а и коэффициента извлече
ния у.
Применив эти результаты к произ
водительности колонны, мы можем на
писать уравнение рабочей линии, свя
зывающей средние концентрации двух
противоточных потоков в любой сек
ции колонны.
В предположении, что обмен соли
между потоками находится в линейной
зависимости от разности между двумя
средними концентрациями с коэффи
циентом обмена к, связанным с общей
номинальной площадью обмена а в
единичном объеме колонны (ка = S-1),
можно написать следующее уравнение:
I Q. I fr IQ. [ft
v H G ' G
р ßi — £ ka —
Г=у
(1 — (I — у ) П.- у)
ft IQ.
• In-
1 — yí
где G является выпуском льда на еди
ницу секции колонны; V — рабочий
объем колонны; H — рабочая высота
колонны; 5 — т.н. соотношение вымо
раживания или фракция первоначаль
ной воды, превратившейся в кри
сталлы льда, ßj — плотность рассола;
с„- концентрация соли в первоначаль-
ной соленой воде; с',' — концентрация
соли в извлеченной пресной воде. Па-
H V
раметр-^-ка р1 (равный-р-ка
приведен в таблице и даны некоторые
диаграммы.
Экспериментальные результаты, по
лученные на небольшой лабораторной
установке (рабочая высота колонны
1,50 м., диаметр 0,29 и.) при различных
условиях, подтверждают общую гипо
тезу, что можно рассчитать опытную
величину ка, колеблющуюся в преде
лах 1,98» 10-8 и 2,32« ÎO-SS-1; средняя
величина достигает 2,14 • ННЧЭ-1. Пара
метр а был принят равным 0,3, соот
El Proceso de Congelación
G. Bozza, G. Dassù, G. Giambelli
Italia
El proceso de congelamiento para desali-
nización de aguas saladas o salobres es bien
conocido en sus lineamientos generales y
tiene algunas ventajas incuestionables desde
el punto de vista termodinámico y tecno
lógico. Aún no ha sobrepasado la etapa
de experimentación a escala piloto y alcan
zado el nivel de desarrollo industrial, -con
la posible excepción del proceso que se
conduce a gran escala en algunos países
(por ejemplo el proceso Zarkin) .
Existen varios puntos que deben ser estu
diados antes de que sea posible racionalizar
y optimizar el diseño de plantas y, por lo
tanto, el proceso en conjunto.
No discutiremos las ventajas y desventajas
del método de congelamiento directo com
parado con el congelamiento indirecto, ni
el requisito de diseño de la maquinaria
que cumple el ciclo de congelamiento con
forme al cual la diferencia de temperatura,
entre la fuente caliente y la fría, debe ser
tan pequeña como sea posible a fin de
lograr una buena eficiencia termodinámica;
ni el diseño y eficiencia de los aparatos
planeados para el lavado de los cristales de
hielo; o la construcción mecánicamente
sólida para un ensamble seguro; o la opti
mización relativa de las distintas partes; ni
las dimensiones de la planta, etc.
No es el propósito de este trabajo inves
tigar estos puntos ni exponer los resultados
ветствуя самопроизвольному сгущению
шламма.
Эти предварительные результаты
требуют подтверждения на крупной
установке. Вследствие малой величины
лабораторной установки было весьма
трудно регулировать производитель
ность колонны, а кроме того, вторич
ные термические эффекты являются
неизбежным недостатком уменьшенно
го размера. Но опытная величина ка
и теоретическая схема дают нам воз
можность достаточно уверенно спро
ектировать подходящую опытную уста
новку для испытания других техноло
гических и рабочих условий.
de otros investigadores o la eficiencia prác
tica de las plantas piloto existentes. Con
fiamos, sin embargo, que el aspecto que
hemos desarrollado—la eficiencia de la
columna de lavado de los cristales de hielo
—será de utilidad para una clara compren
sión de todo el proceso.
Nosotros comenzamos con una serie de
experimentos sobre la formación de hielo
a partir de soluciones salinas sobre super
ficies frías, con el propósito de obtener
hielo, en laminillas claras, de suficiente
grosor sin la presencia de las aguas madres.
Sin embargo, no fue posible obtener el
hielo compacto que se deseaba, tanto en
soluciones en reposo o con agitación, sobre
superficies estáticas o con movimiento, con
soluciones fluyendo en delgadas capas o
pulverizadas sobre superficies enfriadas, o
con diferencias de temperaturas altas o
bajas entre la superficie y la salmuera. El
hielo obtenido de soluciones salinas de
cloruro de sodio, de concentraciones equi
valentes a las de las aguas salinas o salobres,
aunque algunas veces transparentes, siempre
incluían alguna cantidad de aguas madres
concentradas; por lo tanto, el agua obte
nida de la fusión de los cristales no era
purificada satisfactoriamente.
Por otra parte, es muy fácil obtener hielo
como masa porosa de cristales, con una alta
proporción de aire encerrado, embebido en
 salmuera; escurrir la masa tan completa
mente como sea posible, permitiendo un
tiempo de escurrido suficiente; aflojar los
cristales en un mortero y filtrar la masa
aplicando succión o hierra centrifuga. Pero
siempre se queda una película de solución
adherida a los cristales o gránulos de hielo.
Experimentalmente se comprueba que la
proporción de esa solución a hiela es 1:1
aproximadamente. La eficiencia del lavado
en el filtro y en la centrífuga no es alta.
Por lo tanto, la cantidad de agua pura
requerida para una operación adecuada
del proceso es tan grande que rebajando
la productividad del mismo lo hace anti
económico. Si deseamos usar solamente una
cantidad limitada de agua fresca—en un
aparato que utilice sistemáticamente una
contracorriente continua, por ejemplo una
columna de lavado—consideramos que es
absolutamente necesario basarse en la difu
sión de la sal disuelta de la película más
concentrada que rodea los cristales a las
capas menos concentradas de las soluciones
de lavado.
Al proyectar los experimentos a ser lleva
dos a cabo en nuestro laboratorio, tratamos
de definir una teoría de la operación de
tal columna de lavado. Tenemos aquf el
hecho peculiar de que la masa de cristales
de hielo en su movimiento ascendente lleva
consigo una definida cantidad de las aguas
madres. Por lo tanto, podemos pensar en el
fenómeno de lavado como la difusión de
liquido entre dos corrientes, la ascendente
con los cristales y la otra forzada hacia
abajo por los canales existentes entre los
cristales de hielo. Suponemos que un mor
tero de hielo se alimenta continuamente
en la base de la columna y es mezclado en
la sección inferior, con la corriente de
lavado. El hielo en el mortero queda como
una capa de cristales sueltos y se eleva
lentamente llenando la altura útil de la
columna. En la parte superior de la co
lumna el hielo se extrae mediante un dis
positivo adecuado y se funde transfiriendo
el calor de fusión. Parte del agua dulce
obtenida constituye el producto final agua,
la otra parte se envia a la parte superior
de la columna para ser utilizada en la
operación de lavado.
Podemos hacer un modelo simplificado del
complicado conjunto de flujos en la masa de
hielo, asumiendo que la red de granos y
cristales se agrupa de tal manera de formar
un conjunto de canales paralelos verticales,
cada uno de ellos con las paredes movién
dose hacia arriba con una velocidad igual
a la velocidad de ascenso del hielo en la
columna. En aras de la simplicidad, el
cálculo fue realizado sobre la hipótesis de
766
canales entre láminas paralelas de hielo.
Sin embargo, al describir la tendencia dc-I
fenómeno, los resultados no difieren con
otros tipos de canales. Los flujos se suponen
laminares. Las variables a ser consideradas
son: 1) la fracción de poros en la nu-j
de hielo porosa a: 2) el hielo descargado,
introducido en las torres, P; 3) la fracción
del mismo que es extraído como agua pura.
7; y 4) las descargas 1 Q, 1 del flujo de agua
hacia arriba y | Q, | del flujo de agua hacia
abajo, por unidad de sección de la torre.
Los resultados más importantes son los
siguientes: Es posible establecer la relación
entre I Q, I y | Q, |, cuya diferencia debería
ser el flujo neto de lavado, es decir.
(1 — 7) P; son estrictamente dependientes
de la fracción de poros a y del porcentaje
de extracción 7.
Cuando se aplican estos resultados a la
operación de una torre, podemos escribir
la ecuación de la línea de operación, ligan
do las concentraciones promedio de los dos
flujos de las contracorrientes en cualquier
sección de la torre.
Suponiendo que podemos describir el
intercambio de sales entre los flujos como
dependencia lineal de la diferencia entre
las concentraciones promedios, con un co
eficiente de intercambio k, ligado a un área
nominal de intercambio a en la unidad de
volumen de la torre (ka = s">) , es posible
escribir la siguiente ecuación.
I Q. I ft I Q. I ft
V ,ka /5, = H ka ft = -
—
1—
) (i - y)
ft 10»
In_
1-yS
donde G es la descarga de hielo por unidad
de sección de la torre, V es el volumen útil
de la torre, H es la altura útil de la torre.
S es la llamada razón de congelamiento o
la fracción del agua original transformada
en cristales de hielo, ft la densidad de la
salmuera, ç, la concentración de la sal en
el agua salobre original, c", la del agua pura
extraída. El parámetro H/G • ka • ft (igual a
V/P • ka • ft) se consigna en forma tabular v
se ofrecen algunos diagramas.
Los resultados experimentales de una
pequeña planta de laboratorio (diámetro
0,29 m; altura útil 1,50 m) , bajo condicio
nes variadas, confirman en conjunto la
hipótesis de que es posible calcular un
valor tentativo para ka. oscilando entre
1,98 • 10" y 2.32 • lO-'s1: con un valor medio
de 2,14 • ÎO'V1. El parámetro fue tomado
como 0,3 correspondiendo al grosor espon
táneo del mortero.
Estos resultados provisionales requieren
confirmación en una planta de mayor ta
maño. Fue muy difícil, debido a la peque-
ñez de la instalación de laboratorio,
controlar la operación de la torre y,
además, los efectos térmicos secundarios
constituyen una desventaja inevitable del
tamaño reducido. £1 valor tentativo de ka
y los lincamientos de una teoría puede
permitirnos diseñar, con suficiente con
fianza, una planta piloto conveniente para
comprobar otras condiciones de operación
y tecnológicas.
767
 The Koppers Hydrate Process

Peter van der Heem

United States of America

INTRODUCTION
The Koppers Hydrate Process is a chemi
cal process for the removal of pure water
from salt solutions. It uses gas hydrates,
which are solid materials containing a high
percentage of water. Hydrates are formed
spontaneously when a hydrating agent, such
as propane, refrigerant-12 (CF,C1,) , or
chlorine, is contacted by liquid water at
proper temperature and pressure. The Kop
pers process is based on the property of gas
hydrates to exclude salts from their crystals
when formed in salt water. When hydrate
crystals are separated from the brine in
which they were formed and subsequently
decomposed, salt-free water and the hydrat
ing agent are obtained. The agent is
recycled.
Koppers Company, Inc., holds the basic
patent for this process01. Its principle of
operation is illustrated by Figure 290.
Hydrate formation takes place in a reactor
vessel which contains boiling, liquid hydrat
ing agent and salt water. Control of pressure
(i) u.s. Passat 2.»04,6ii atw.
in the reactor fixes the boiling temperature
of the agent and, consequently, the reactor
temperature. The reactor produces a
hydrate slurry which contains approximately
10 per cent solid material. This slurry is
pumped into a filter compartment or into
a continuous filter with a moving hydrate
bed. A solid hvdrate cake is formed, which
contains too much salt to be suitable for
immediate decomposition. The cake is first
washed with pure water, then decomposed.
Decomposition produces a mixture of
pure water and liquid agent, which are
separated by decantation. Less than 10 per
cent of the net production of potable water
is used for washing. The liquid hydrating
agent goes back to the reactor. It is reused
in the formation of new hydrate, but a
large part evaporates due to the heat of
hydrate formation. The amount of agent
generated is approximately proportional to
the amount of hydrate formed. The vapor
is compressed, and its temperature rises
sufficiently to make it usable for decomposi
tion of pure hydrate.

FIGURE 290. OPERATIONAL PRINCIPLE OF THE KOPPERS

HYDRATE PROCESS.
 In most applications of the Koppers
Hydrate Process, there is an optimum sea
water conversion percentage at which the
conversion is lowest in cost. This figure is
often higher than 10 per cent. If it is as
high as SO or 40 per cent, sea water must
be treated several times with hydrating agent
before it can be discarded. A sea water
conversion of considerably more than 10
per cent per pass through the reactor would
THE NATURE OF GAS HYDRATES
A gas hydrate is a solid chemical com
pound formed of water and one or more
hydrating agents. It is a hydrate of the
clathrate type. This means that no chemical
bonds exist between agent and water mole
cules. The water molecules are attached to
each other with hydrogen bonds formed by
interactions of electrical dipoles. The same
type of bond exists in ice and, to a lesser
degree, in liquid water. The most signifi
cant structural difference between ice and
hydrate is that the hydrate structure is
more open. Its structure contains cavities
which can be filled with a molecule of
hydrating agent. The open structure can
exist only when a certain minimum fraction
of the cavities are filled.
There are several different gas hydrate
structures. Each has a different formula.
The formula determines the amount of
water which would be transported by the
hydrating agent used in this process. This
is important in selecting a hydrating agent
for the Koppers Hydrate Process. The three
most important formulas were first described
by von Stackelberg<e. Their structures can
be represented by the following theoretical
formulas: A • 17 H.O; В • 7.67 H.O; and
С • 5.75 H.O. А, В and С represent the
hydrating agents. The formulas are valid
only when each suitable cavity is filled with
HYDRATE FORMATION
When a gas hydrate is formed, it gener
ally has a higher thermal stability than ice.
Its melting point (or temperature of de
composition) depends on the hydrating
agent. Propane hydrate decomposes at 6°C;
refrigerant-12 (CF,C1,) forms a hydrate
which decomposes at 12°C; refrigerant-31
(2) See for example: Jeffrey, G. A., Dechema
Monograph, no. i7 (1962) 849.
(8) Sugden, S., Parachor and Valmcy (Rout-
ledge and Sons, Ltd., London, 1980).
(4) van der Heem, P., Parachor and Gaa Hy
drate Structure, to be published in "Science".
(6) See for example: H. GUman, Organic
Chemistry (Wiley, N. Y., 1949) p. 968, 1746.
770
make the hydrate slurry too viscous for
convenient handling. The higher conversion
is obtained by recycling part of the residual
brine to the reactor. It is also possible to
put a number of hydrate reactors, each
with its own filtration equipment, in series.
Residual brine from one reactor would be
feed for the next. The use of reactors in
series would be advantageous only in very
large conversion plants.
a molecule of hydrating agent. When
hydrates are prepared on a large scale, a
small fraction of the cavities remains empty.
Under such conditions, hydrates would be
better characterized by formulas with
slightly higher coefficients.
The size of the hydrating agent molecule
has some influence on the type of hydrate
the agent will form, but it is not the only
factor. A molecule with a maximum dimen
sion of 5.5 Angstrom units can form a
hydrate with a theoretical formula with 17
molecules of water (which happens in the
case of CH,I) , as well as one with 5.75
molecules of water (in the case of dH,)"1.
Recently it has been found that the para-
chor, as defined by Sugden™, can be used
as a more reliable criterion to predict a
hydrate formula'". If the parachor of the
hydrating agent is larger than approxi
mately 1S2, a hydrate with 17 molecules of
water is obtained. A parachor smaller than
110 results in a hydrate with the formula
С • 5.75 H.O. Between these values the
third formula is obtained. Sugden and many
others'" give simple rules for calculating
the parachor of most chemical compounds.
The prediction of the hydrate formula by
using the parachor is valid only for simple
gas hydrates, not for hydrates containing
more than one hydrating agent.
(CHjFCl) has a hydrate which is stable up
to 18°C. A hydrate is formed only above a
minimum pressure characteristic for the
hydrating agent that is used.
The conditions for hydrate formation can
be explained with the phase diagram shown
in Figure 291. Each point in the diagram
represents a temperature and a pressure
within a hypothetical hydrate reactor which
contains only hydrating agent and pure or
salt water. The diagram shows the line S'Q
which is the vapor pressure line of the
hydrating agent. Gaseous hydrating agent
will condense at any point above the line;
below this line, liquid agent will evaporate.
Hydrate cannot exist at temperatures higher
Chan Te- At lower temperatures, a hydrate
is stable when the pressure is higher than
indicated by lines QR and RD. If water
and hydrating agent are in contact under
conditions at point A, hydrate formation
•will occur. If conditions are as indicated by
point B, no hydrate can be formed.
Hydrates are less stable in salt water than
in pure water. This shows in the phase
diagram as a shift of the line QR to the
left; i.e., to Q'R'. Hydrates would be stable
at lower temperatures and, in some cases, at
the same temperatures but at higher
pressures.
If a reactor must produce hydrate in
large quantities, it is not sufficient to have
operating conditions above and to the left
of Q'R' in the phase diagram. Koppers re
search has shown that the reaction rate
between ice and hydrating is unsatisfactory.
"The rate between water and liquid agent
without a gas phase is also unsatisfactory.
"The reactions are very slow and the hydrate
crystals very small. The conditions available
FIGURE 291. PHASE DIAGRAM OF GAS HYDRATES.
for large-scale hydrate production are en
closed by the triangle Q'R'S'. The exact
location of the triangle depends on salt
concentration, and it moves downward ap
proximately 0.5°C for every per cent of salt
in the aqueous phase.
The Koppers hydrate reactor works best
when boiling liquid agent forms a separate
liquid phase. Its operating point is slightly
below the vapor pressure line. The distance
from the line Q'S' is controlled by heat
transfer to this liquid phase. The heat
necessary for evaporation is supplied by the
heat of hydrate formation supplemented by
other small heat inputs. The distance of
the operating point from the line Q'R' is
the driving force for hydrate formation. As
the distance increases, hydrate formation
becomes faster and hydrate crystals become
smaller. The Koppers hydrate reactor works
with a driving force of the order of magni
tude of one degree centigrade, which gives
satisfactory results. Crystal concentration in
the reaction mixture and residence time of
crystals in the reactor are among the many
factors that influence crystal size and
hydrate formation rate.
WATER +
 THE RECOVERY OF WATER AND AGENT FROM HYDRATE
Hydrate slurry produced by the reactor
will be filtered in a filtration compartment
or by equipment in which a moving and
continuously growing hydrate bed is formed.
The filtered hydrate cake always contains
some free hydrating agent, hence its condi
tion can be characterized by Q' in Figure
291. When the cake has been washed in the
same equipment, its temperature will have
increased to T,.
The large-scale decomposition of pure
hvdrate always occurs at temperature Tc.
If heat is supplied to a hydrate cake or
slurry at a constant pressure lower than P„
the temperature rise is not interrupted at
the level where the corresponding point on
QR is reached but proceeds to T„. The
aqueous liquid which surrounds each hy
SOME CHARACTERISTICS OF THE KOPPERS HYDRATE PROCESS
An important factor in the conversion
costs of sea water is the temperature differ
ence between sea water and the hydrate
reactor. Lower reactor temperatures will
result in higher conversion costs. If a freez
ing process would operate with freezer cool
ing and ice melting, similar to the energy
cycle described for the Hydrate Process, the
latter would have the advantage of a smaller
temperature difference between reactor
(freezer) and sea water.
In filtration, washing, and decomposition,
ice and hydrate behave differently. Ice
crystals melt under pressure when the tem
perature is close to their atmospheric melt
ing point. Hydrate does not decompose at
moderately high pressures. An ice filtercake
formed under pressure consists of adhering
particles; in a hydrate filtercake, the par
ticles exhibit very little attachment to each
other and none to equipment walls. The
latter fact explains why a hydrate cake in
a filler compartment can be decomposed
easily by the introduction of gas: a hydrate
slurry is easily obtained. Heat transfer from
the condensing gas to the aqueous slurry
is high. If the filter compartment does not
contain large dead corners, decomposition
will be fast and complete.
The specific gravity of a hydrate depends
on the agent. While the empty structure
(if it could exist) is lighter than ice, some
hydrates are in fact heavier than water.
Others are lighter. Some agents form the
bottom layer during décantation, while
others float on water. Development work
on the Hydrate Process at the Koppers labo
ratories did not show any particular prob
drate particle is supersaturated with hydrat
ing agent, so the crystal behaves as if the
pressure in the system was P, or higher.
In the basic Hoppers Hydrate Process,
hydrate is decomposed with vapor gener
ated by the reactor. If the reactor works
under conditions described by point A
(Fig. 291) , the generated vapor will have
corresponding pressure and temperature. If
this vapor is adiabatically compressed to
conditions at point C. it can be used to
decompose hydrate. Pure hydrate cake is
at the lower temperature Tc. Hence, heat
transfer will take place to condense the
vapor and decompose the hydrate into a
mixture of liquid agent and liquid water
to be separated by décantation.
lem or advantage with either kind.
A controlling factor for the growth of a
hydrate crystal from the solution of a rather
insoluble hydrating agent is the diffusion
of agent through the liquid toward the
crystal surface. Because of this phenomenon,
hydrate growth is generally slower than
the growth of ice crystals. However, re
search at Koppers has proved that suffi
ciently high growth rates can be obtained,
resulting in crystals large enough to guar
antee satisfactory filtration and washing of
hydrate cake. Conclusions are based on in
vestigations in a 10-gallon reactor.
The most important difference between
the Koppers Hydrate Process and most other
sea water conversion systems is the chemical
nature of the former. The phase change,
in which pure water is separated from sea
water, takes place under the influence of
another substance. It creates an extra de
gree of freedom. The use of the hydrating
agent contributes to the sea water conver
sion costs, hence circulation losses must
remain low. Recovery of traces of agent
dissolved in discarded brine and in potable
water must be as complete as possible.
Engineering and pilot plant studies at Kop
pers have shown that the incremental cost
derived from losses and recovery of hydrat
ing agent contributes only a minor amount
to the total sea water conversion costs.
Different hydrating agents can be used
in the Hydrate Process. Thus, it can oper
ate at different pressures and temperatures.
For very large installations, low-pressure
agents can be particularly useful. For parts
of such systems, brine-resistant concrete
could be considered as a construction ma-
terial. This would lead to installation costs
lower than those if conventional materials
PROCESS DESCRIPTION
The basic process is illustrated in Figure
292. The refrigeration circuit contains a re
actor, primary and secondary compressors,
a condenser cooled with sea water, and a
hydrate decomposition vessel. The second
ary compressor is necessary because the
primary unit produces more compressed
vapor than can be condensed on the de
composing hydrate. This excess is due to
the heat leak through the walls of the
reactor and other equipment, the incom
plete heat exchange which causes incoming
sea water to be at a higher temperature
than the reactor, and the energy input with
the primary compressor. The excess is re-
compressed in the secondary compressor.
The resulting pressure is sufficiently high
to permit the use of sea water in the com
pressor discharge condenser. While sea
water used for conversion is deaerated be
fore it is cooled in the heat exchangers,
traces on noncondensables collect in the
condenser of the secondary compressor and
are bled off.
The hydrate slurry which leaves the
reactor is introduced in the lower part of
the continuous filter-washer. The upper
half of this apparatus is used for washing
FIGURE 292. KOPPERS HYDRATE PROCESS.
were used. Temperature variations can have
other important consequences, which will
be described later.
the hydrate cake. The midsection wall is
replaced by a filter screen. In this region
and at lower levels, a hydrate cake forms
continuously. Filtrate is removed through
the screen, and a pressure drop over the
lower part of the apparatus produces a
continuous upward vertical motion of the
hydrate bed. Wash water is introduced at
the highest point of the apparatus. A
scraper continuously removes the top of the
washed hydrate cake. This hydrate, mixed
with an excess of pure water, is transported
to the decomposer. Decomposition is effected
by the introduction of vapor from the pri
mary compressor.
Koppers has also developed a filter-
washer-decomposer for batch operation. It
utilizes filter compartments which are
larger than, but similar in design to, the
frames of a filter press. In this type of
operation, a compartment (A) is filled with
solids by filtering slurry from the reactor
until the pressure drop across the compart
ment has increased to a predetermined
value. The washing of compartment A starts
by connecting it with another compartment
(B) which already is being washed. Com
partment A reuses the washwater from B.
773
 As soon as В is sufficiently free of salt,
washwater is introduced directly into A.
Another compartment (C) , newly filled
with hydrate, is put in series with A. Vapor
from the primary compressor is introduced
in В until the clean hydrate cake is com
pletely converted into a mixture of potable
water and liquid hydrating agent. A small
gas stream is bled off and sent to the second
ary compressor to avoid accumulation of
noncondensable gases in the filter compart
ments. The hydrate bed in A is decomposed
after its washing has been completed.
The results with both systems of washing
are satisfactory. Experiments on a larger
scale will show which system requires lower
investment and operating costs.
The load on the secondary compressor
will vary with the sea water temperature.
If this temperature is relatively low, less
excess vapor is available for this compressor.
When the sea water temperature is the
same as the reactor temperature, the second
ary compressor compresses an amount of
vapor only slightly higher than the amount
needed to compensate for the energy input
by the primary compressor.
Lower sea water temperatures will com
pletely eliminate the need for a secondary
compressor.
At these low sea water temperatures, the
Koppers Hydrate Process can he modified as
illustrated in Figure 293. Sea water is de-
«la-^ _ ^ tlCA«T«ne« I
«щит, mu
FIGURE 293. SIMPLIFIED KOPPERS HYDRATE PROCESS WITH
COLD SEA WATER.
774
aerated before being introduced into the
reactor. The temperature of this water in
creases and soon reaches the temperature
of the rest of the reactor contents. In this
way it contributes to the reactor cooling.
Vapor generated by the reactor is not com
pressed but condensed in a cooler which
uses sea water as a cooling medium. A
small stream of noncondensables is bled off.
Liquid hydrating agent is returned to the
reactor.
The hydrate slurry produced by the re
actor is filtered and washed in the same
way described for the basic process. It is
necessary to use an external energy source
for hydrate decomposition. When hydrate
is brought into direct contact with water
which is a few degrees warmer than the
decomposing hydrate, decomposition will
be rapid. Circulating water can be reheated
by a low temperature heat source.
In the Koppers Hydrate Process, as illus
trated in Figure 292, electric power is the
main energy source. This electricity usually
contributes considerably to total sea water
conversion costs. In the simplified Hydrate
Process (Fig. 293) wilh cold sea water, elec
tricity consumption is nearly eliminated.
Costs of the low level heat will varv accord
ing to local circumstances. If cooling water
from other industrial installations could be
reused as the heat source, these costs would
be quite low.
UWII ЛИНТ
nam UÜStf-
JF—
 A hydrating agent which might prove
useful for the cold water Hydrate Process
is refrigerant-22 (CHF.C1) , which forms a
hydrate stable up to 17°C. It could be used
for conversion of sea water with a tempera
ture of 7°C or lower.
If hydrating agents which could form
hydrates with higher thermal stabilities
were made available, the range of appli
FUTURE PILOT PLANT STUDIES
A pilot plant is being built on the test
site of the Office of Saline Water, at Wrights-
ville Beach, N. C. The installation is ex
pected ultimately to produce 10,000 gpd
of potable water. A large part of the re
search program will be devoted to studying
and optimizing the various operations in
the Koppers Hydrate Process. Optimum re
action conditions will be determined. Con
tinuous and batch filtration and washing
(6) McMullan, Richard and Jeffrey, G. A.,
"Hydrates of tetra n-butyl and tetra i-amyl
quaternary ammonium salts", Journ. Chem. Phy§.
no. SI, (1953) pp. 1231-4.
SUMMARY OF DISCUSSION
An explanation of the relationship of
crystal habit to the hydrating agent was
requested. The reply stated that the more
Procede Koppers a L'Hydrate
Peter van der Heem
Etats-Unis d'Amérique
Le procédé Koppers à l'hydrate est un
procédé chimique pour l'extraction d'eau
pure de solutions salines. Il provoque la
formation d'hydrates solides de gaz dans
l'eau salée. Le procédé est basé sur la
propriété qu'ont les hydrates de gaz d'ex
clure les sels de leurs cristaux lorsqu'ils
se forment dans l'eau salée. Koppers Com
pany, Inc., détient le brevet fondamental
pour ce procédé.
Son fonctionnement est essentiellement
celui-ci: la formation de l'hydrate a lieu
dans un réservoir de réaction qui contient
un agent liquide d'hydratation en ébullition
et de l'eau salée. Le réacteur produit une
cability of the cold water Hydrate Process
could be broadened. It is encouraging that
Jeffrey et al'" have discovered hydrates
with higher thermal stabilities and low
formation pressures. While their hydrating
agents would be unsuitable for use in saline
water conversion, their discovery indicates
that the search for new agents has not
ended.
will be compared. Circulation losses of
hydrating agent will be studied. Refrig-
erant-12 (CF,C1.) will be used initially.
All data will be compared with pilot
plant studies which were completed pre
viously by Koppers and published by the
Office of Saline Water, Department of the
Interior, Washington. D.C., in two reports,
PB 166,397 and PB 181577.
After the pilot study at Wrightsville
Beach has been completed, a full evaluation
of the Hydrate Process will be made, in
cluding detailed operating costs.
soluble type hydrating agents give the best
crystals,
boue d'hydrate d'environ 10% d'hydrate.
Cette boue est filtrée et l'accumulation
d'hydrate restant est lavée. Ensuite, l'hydrate
propre est décomposé. Le mélange en résul
tant contient l'agent d'hydratation liquide
et de l'eau pure. L'agent est ré utilisé; une
petite quantité de l'eau de production est
utilisée comme eau de lavage.
Les hydrates utilisés dans ce procédé sont
des cristaux lacunaires. Les molécules d'eau
sont attachées les unes aux autres avec des
liens hydrogènes seulement, non pas aux mo
lécules de l'agent. Chacune de ces dernières
trouve un emplacement dans une des cavités
formées par la structure de l'eau. Ce
 phénomène peut je produire dans l'un quel
conque des différents types d'hydrates. La
dimension de la molécule de l'agent a une
influence sur le type qui est formé. Un
diagramme de phase pour l'eau et l'agent
d'hydratation peut illustrer les conditions
de fonctionnement dans lesquelles les
hydrates peuvent être fabriqués. Des tra
vaux de recherche effectués dans les labo
ratoires de la Société Koppers ont démontré
que les conditions favorables de réaction
sont: la présence d'un agent d'hydratation
liquide et une force d'entraînement de la
réaction pour la formation de l'hydrate
d'environ 1°C.
La Société Koppers a mis au point un
procédé continu de filtration et de lavage
ainsi qu'un système de filtration et de
lavage qui fonctionne en discontinu en uti
lisant des compartiments filtres. La con
sommation d'eau de lavage semble être
inférieure à 10% dans l'un ou l'autre des
types de fonctionnement.
Le procédé à l'hydrate fonctionne à une
température qui est d'environ 10°C supé
rieure à la température de congélation de
l'eau de mer, facteur favorable du point
de vue des frais de conversion. Les pro
priétés des cristaux d'hydrate, qui sont
souvent différentes de celles de la glace,
rendent la conception de nombreuses parties
d'une installation utilisant le procédé à
l'hydrate différente des parties correspon
dantes d'une installation employant des
procédés de congélation. La possibilité
Гидратационный Процесс Копперса
Питер ван дер Хим
Соединенные Штаты Америки
Гидратационный процесс Копперса
является химическим процессом для вы
деления чистой воды из соленых раст
воров. Он образует в соленой воде
твердые гидраты газов. Процесс осно
ван на способности гидратов выделять
соли из своих кристаллов, когда они
образованы в соленой воде. На этот
процесс Копперс Компани, Инк. имеет
основной патент.
Работа по существу состоит в сле
дующем: в реактивном сосуде, в ко
тором находятся кипящий, жидкий гид
ратационный агент и соленая вода, про-
776
d'utiliser différents agents d'hydratation
rend la flexibilité du procédé à l'hydrate
particulièrement importante. L'augmenta
tion des frais de conversion, provoquée
par les pertes et la récupération de l'agent
d'hydratation, ne représente qu'un mon
tant très minime du coût total de conver
sion de l'eau de mer.
Le cycle de réfrigération, qui fournit
la chaleur nécessaire pour la décomposition
de l'hydrate, contient le compresseur pri
maire et le réservoir de décomposition
d'hydrate. Les inefficacités du procédé
rendent nécessaires la compression d'un
excès de l'agent d'hydratation vaporisé a
une pression suffisamment élevée pour qu'il
puisse être condensé avec l'eau de mer. Si la
température de l'eau de mer est suffisam
ment base, ce cycle de réfrigération peut
être remplacé par un système dans lequel
l'agent d'hydratation est condensé avec l'eau
de mer et l'hydrate est décomposé par une
source extérieure de chaleur de basse tem
pérature (environ 40"C) . Lorsque dis
ponible, cette source de chaleur constitu
erait une fourniture d'énergie principale à
bon marché pour l'installation. CHF,C1 est
un agent d'hydratation prometteur роит
ce procédé modifié.
Une installation pilote d'une capacité de
400 m" d'eau potable est en construction
sur l'emplacement de Wrightsville Beach
(Caroline du Nord) . Au début, le CF.Cl,
sera utilisé comme agent d'hydratation.
исходит образование гидратов. В ре
акторе возникает гидратный шламм с
приблизительным 10-процентным со
держанием гидратов. Этот шламм филь
труется и остающаяся лепешка из гид
рата промывается. Затем чистый гидрат
подвергается разложению. Получающа
яся смесь состоит из жидкого гидра-
тационного агента и чистой воды. Агент
рециркулируется; небольшая часть про
дукта используется в качестве воды
для промывки.
Применяемые в этом процессе гидра
ты имеют решетчатую структуру. Mo-
лекулы воды соединены водородными
связями между собой, но не с молеку
лярными агентами. Каждый из послед
них находит себе место в одной из
пустот, находящихся в структуре воды.
Это явление может происходить в лю
бом из нескольких типов гидратов.
Размер молекулярного агента имеет
влияние на образуемый тип. Диаграм
ма фаз для воды и гидратационного
агента может служить иллюстрацией
эксплуатационных условий, при кото
рых возможно производство гидратов.
На основании исследований в лабора
ториях Копперса было выяснено, что
благоприятными условиями для реак
ций являются: присутствие жидкого
гидратационного агента и движущая
сила для образования гидратов поряд
ка одного градуса Цельзия.
Копперс разработал непрерывный
процесс фильтрации и промывки, а так
же систему фильтрации и промывки,
функционирующей периодически и при
меняющей фильтрующие отделения.
Потребление промывочной воды быва
ет ниже 10% при обоих типах работы.
Гидратационный процесс протекает
при температуре примерно на 10°С вы
ше температуры замерзания морской
воды, что является благоприятным фак
тором с точки зрения стоимости опре
снения. Из за свойств кристаллов гид
рата, которые зачастую сильно отли
чаются от кристаллов льда, конструк
ции многих частей установки, работа
ющей с помощью гидратационного про
цесса, соответственно отличаются от
применяемых при процессах вымора
живания. Возможность пользования
El Proceso de Hidrato Koppers
Peter van der Heem
Estados Unidos de Norteamérica
El proceso de hidrato Koppers es un
proceso químico para la extracción de agua
pura de soluciones salinas. Durante el
mismo, se forman en el agua salada hidra
tos sólidos de gas. El proceso se basa en
la propiedad de los hidratos de gas de
excluir sales de sus cristales cuando se
forman en agua salada. Koppers Com
pany, Inc. retiene la patente básica de este
различными гидратационными агентами
делает гидратационный процесс осо
бенно гибким. Увеличение расходов по
опреснению в связи с потерями и ре
куперацией гидратационного агента
является незначительным по сравнению
с полной стоимостью опреснения мор
ской воды.
В рефрижерационный цикл, который
доставляет необходимое тепло для раз
ложения гидрата, входят гидратацион
ный реактор, первичный компрессор и
сосуд для разложения гидрата. Вслед
ствие недостаточностей процесса при
ходится сжимать излишек гидратацион
ного агента, находящийся в газовой фа
зе, до достаточно высокого давления,
чтобы его можно было конденсировать
вместе с морской водой. Если темпера
тура морской воды достаточна низка,
этот рефрижирационный цикл можно
заменить системой, при которой гидра
тационный агент конденсируется вме
сте с морской водой, а гидрат подвер
гается разложению с помощью внеш
него источника тепла низкой темпера
туры (приблизительно 40вС). Им, если
он имеется, обыкновенно служит глав
ный источник дешевой энергии, потреб
ляемой установкой. CHF2C1 является
многообещающим гидратационным а-
гентом для этого модифицированного
процесса.
В Райтсвилл Бич, шт. Северная Каро
лина на месте для испытаний строится
опытная установка с производитель
ностью 10.000 галлонов питьевой воды
в сутки. Вначале в качестве гидрата
ционного агента будут пользоваться
CF2C12.
proceso.
Su operación es básicamente la siguiente:
la formación de hidratos se produce en un
recipiente de reacción que contiene, en
ebullición, el agente hidratante líquido y
agua salada. En el recipiente de reacción se
produce una mezcla que contiene aprox
imadamente un 10% de hidrato. Esta mezcla
se filtra y la torta de hidrato resultante
777
 es lavada. Luego el hidrato limpio se
descompone. La mezcla resultante contiene
el líquido hidratante y agua pura. El
agente es reciclado; una pequeña cantidad
de la producción es usada como agua de
lavado.
Los hidratos usados en este proceso son
reticulados. Las moléculas de agua sólo
están unidas entre si con enlaces de hidró
geno; no están unidas a las moléculas del
agente. Cada una de estas últimas, encuen
tra ubicación en cada una de las cavidades
formadas por la estructura del agua. Este
fenómeno puede ocurrir con cualquiera de
los distintos tipos de hidratos. El tamaño
de la molécula del agente tiene influencia
sobre el tipo de hidrato que se forma. Un
diagrama de fase para el agua y el agente
hidratante puede ilustrar las condiciones
de operación bajo las que pueden fabri
carse los hidratos. Las investigaciones reali
zadas en los laboratorios de Koppers han
demostrado que las condiciones favorables
de reacción, son: la presencia del agente
hidratante liquido y una fuerza promotora
de la formación de hidrato de, aproximada
mente, un grado centígrado.
Koppers desarrolló un proceso continuo
de ñltración y lavado así como un sistema
de filtración y lavado que opera sobre la
base de lotes usando compartimentos de
filtro. El consumo de agua de lavado apa
rentemente es de menos del 10% en
cualquiera de los dos procesos.
El proceso de hidrato opera a una tem
peratura que es aproximadamente 10°C
más elevada que la temperatura de conge
lamiento del agua de mar, lo cual es un
factor favorable desde el punto de vista de
los costos de conversión. Las propiedades
de los cristales de hidrato, que con fre
778
cuencia son claramente diferentes de los
de hielo, son motivo de que el diseña de
muchas partes de una planta, usando el
proceso de hidrato, difiera del diseño de las
correspondientes a una planta con proceso
de congelamiento. La posibilidad de usar
diferentes agentes hidratantes da lugar a
que la flexibilidad del proceso de hidrato
sea particularmente amplia. El incremento
en los costos de conversión, causado por las
pérdidas y la recuperación del agente hidra
tante contribuyen sólo en grado reducido
al costo total de conversión de agua de
mar.
El ciclo de refrigeración, que proporciona
el calor necesario para la descomposición
del hidrato, contiene el reactor de hidrato,
el compresor primario y el recipiente de
descomposición del hidrato. Insuficiencias
del proceso hacen necesario la compresión
de un exceso del agente hidratante vapori
zado a una presión suficientemente alta
que permita condensarlo con agua de
mar. Si la temperatura del agua de mar es
suficientemente baja, este ciclo de refrigera
ción puede seT reemplazado por un sistema
en el que el agente hidratante es conden-
sado con agua de mar y el hidrato es
descompuesto por una fuente externa de
calor a baja temperatura (aproximadamen
te 40°C) . Cuando se dispone de ella, esta
fuente de calor sería una fuente básica de
energía de bajo costo para la planta. El
CHF,C1 es un agente hidratante que ofrece
buenas posibilidades para este proceso
modificado.
En Wrightsville Beach, Carolina del
Norte, se halla bajo construcción una
planta piloto de una capacidad de 10.000
gpd de agua potable. Inicialmente se usará
el CFjCl, como agente hidratante.
 Multieffect Multistage Flash

Distillation

W. R. Williamson, F. W. Gilbert and T. R. Scanlan ¿

United States of America

INTRODUCTION TO THE MULTIEFFECT MULTISTAGE FLASH CYCLE

The conventional flash distilling plant is
usually arranged as shown in Figure 294 and
designated SEMS for a Single-Effect Multi
stage plant. Operating with this cycle ar
rangement, the maximum operating tem
perature with acid injection is limited to
250°F with brine, concentrated one and
one-half times, recirculating through the
one effect. The number of stages is usually
limited to a 4°F flashdown per stage because
of the low pressure differential available at
the deep vacuum conditions prevalent in
the last stages. Costly arrangements employ
ing gravity assist, or logarithmic increase in
heat exchanger surface can alleviate this
problem. However, determining the maxi
mum number of stages poses an upper limit
on the design thermal economy, and con
centration considerations limit the top cycle
temperature.
In order to circumvent these two limita
tions of SEMS, increase the number of
stages in a plant, minimize the amount of
heat transfer surface required, and minimize
the brine concentration at the head end of
the plant, several recirculation SEMS plants
were piped in series. The feed was ducted
through a separate feed heating compart
ment in the heat exchangers and introduced
at 1.0 sea water concentrations into the
evaporation cycle at the hot end of the
plant. Each of the SEMS plants in this ar
rangement is an effect and the entire con
figuration as shown in Figure 295 is called
a Multieffect Multistage plant or MEMS.
Another way to overcome the two limita
tions of the SEMS process would be to vary
the interstage temperature decrement so
that a large number of relatively short
length stages are crowded in the top of the
plant and a lesser number of longer stages
are introduced in the low-temperature end
of the plant. Since it probably would
not be practical to design a plant with a

DEAE4AT0R àj—i
SC* WATER
COOLAMT
I I I M
I I I I I I I I I ~3r

FIGURE 294. SINGLE-EFFECT MULTISTAGE FLASH PLANT

(SEMS).
 different temperature decrement and heat
exchanger length for each stage, the same
results could be approximated by designing
the plant with groups of stages having the
same temperature decrement and heat ex
changer length in each group, but varying
from group to group.
In attempting to improve the cycle char
acteristics of SEMS, this variable heat ex
changer approach was considered. While
this is an improvement over conventional
SEMS, the MEMS approach incorporates
even further advantages. The following four
examples illustrate the relative merits of
each system.
Figure 296 shows a conventional SEMS
operating at a top temperature of 250'' F.
15 concentrations, and 80°F sea water sup
ply with 40 stages operating at an average
of 4°F per stage. The thermal economy or
gained output ratio is 16 to 1 and the
surface effectiveness (pounds per hour of
product yield per square foot of heat trans
fer surface installed) is 4.0 at an average
design heat transfer rate of 500 Btu/hr/
ftVF.
RECYCLE BRINE
BRINE HEATER
I I I I I I Í I
I I I I I I I I I I
JJJ.
I I I LI JJJJ Hi,
Li. I I I
TD
1С EFFECT
FIGURE 295. MULTIEFFECT MULTISTAGE FLASH PLANT
(MEMS).
40 STAGES
MAXIMUM CONCENTRATION - с ■ 1.5
TOTAL ECONOMY - E » * DIST /1000 BTU - 16
TOTAL SURFACE EFFECTIVENESS -D - * DIST /FTf-4
FIGURE 296. TYPICAL SEMS HEAT BALANCE @ 250<>F.
780
Figure 297 shows the variable area SEMS
mentioned above. For the same design con
ditions of 250°F top cycle temperature, 80°F
ambient sea water temperature, and 1-5 sea
water concentrations, some 60 stages can be
installed from 250° to 190°F, SO from 190*
to 1S0"F. and 10 from ISO" to 90°F. The
thermal economy is 16 to 1 and the surface
effectiveness is 4.4 using an average design
heat transfer rate of 500. Thus some 10 per
cent saving of heat transfer surface can be
realized over a standard SEMS.
Figure 298 shows a 100-stage MEMS plant
operating at the same conditions as in
Figure 297. The thermal economy is 16 to 1,
the surface effectiveness is 4.0 and the de
sign heat transfer rate is 500. Thus MEMS
in this heat envelope is as good as con
ventional SEMS, but not as good as the
variable area SEMS. However, the assumed
conditions do not present MEMS in its most
favorable light. One of the unique features
of MEMS is that the acidified and deaerated
feed is ducted to the top temperature or first
effect and then mixed with the first effect
brine recycle stream. Thus by properly
SUPPI
8 от
DIST
BRINE
90*
designing the plant it is possible to operate
the first effect at a top temperature of
275°F and 1.15 concentrations, a gain in
operating temperature range of 25°F.
Figure 299 shows the addition of a fourth
effect to the MEMS plant accomplishing
this increase in top temperature. With this
arrangement it is possible to have 125 stages
from 275 °F to 100°F brine temperature at
the same thermal economy of 16 to I. The
new surface effectiveness is 5.0, based on the
same design U value of 500. A net savings
of 20 per cent in heat transfer surface is
achieved over the SEMS arrangement.
There is still a further saving in heat
transfer surface not yet accounted. MEMS
makes most of its distillate at the higher
temperatures where the heat transfer rate
is correspondingly higher. Rates have been
measured well in excess of 900 at 200°F and
above. SEMS in any arrangement has a
constant distillate production per unit AT.
MEMS has a higher distillate production
per unit AT at the high-temperature end
and thus there would be an even greater
saving of heat transfer surface than indi
cated above.
By suitable design, it is possible to oper
ate at 3.0 concentration in the low-
temperature effect while operating at 1.15
concentrations in the top-temperature effect.
This reduces by 50 per cent the amount of
feed to be treated, the amount of acid
required, and the size of the deaerator, air
ejector, feed pump and acid pump. In the
case of more exotic feed treatments for
operation, >275°F, there would be still
greater potential gain for MEMS systems
over SEMS.

m \80'F „ I20°F SW SUPPLY

♦ 240PF 6*0 STAGES IS STAGES k/ stages^ 80°F
C* 1.5 C' 1.5 C-15 DIST
V) E- 6
V E- 6 E« 4
1 25CfF . A« 126 FT I90°F r A* 133 FT8 I30°F A- I.OOFT2 BRINE
90*F

MAXIMUM CONCENTRATION* c -L5

TOTAL ECONOMY* E«#DIST/lOOO BTU = I6
TOTAL SURFACE EFFECTIVENESS • D ■#DIST/FTZ« 4.4

FIGURE 297. VARIABLE AREA SEMS HEAT BALANCE @ 250°F.

iooV,

MAXIMUM CONCENTRATION- c- 3.0

TOTAL ECONOMY* E •# D IST/lOOO BTU- 16 2
TOTAL SURFACE EFFECTIVENESS - D=ttOIST/FT -40
FIGURE 298. MEMS @ 250°F TRIPLE EFFECT- 100 STAGES.

781

MAXIMUM CONCENTRATION • c- 3.0
TOTAL ECONOMY • E-8 DIST/IOOO BTU ■ 16
TOTAL SURFACE EFFECTIVENESS • D-ttDIST/FT ■ 5
FIGURE 299. MEMS @ 275°F QUADRUPLE EFFECT-125 STAGES.
Thus the gains for MEMS over SEMS
for a given thermal economy are:
(1) Reduction by at least 20 per cent
of heat transfer surface.
(2) Reduction by 50 per cent in the
amount of acid required.
(3) Reduction by 50 per cent in de-
aerator and feed system size.
(4) Gain of at least 25°F additional
operating temperature range.
The MEMS system permits large дТ'в
per stage at the low-temperature end of
the plant and small ДТ'5 per stage at the
high-temperature end of the plant. This is
extremely advantageous as the ДР per unit
ДТ is low at the low temperatures and
relatively speaking much greater at the high-
temperature end of the plant. Thus the
ДР per stage can be kept more nearly con
stant in MEMS than SEMS. This is accom
plished by using higher circulation rates
in the high-temperature effects of the plant
than in the low-temperature effects. In
order to keep reasonable terminal tempera
ture differences at the hot end of the plant
with the high circulation rates, the number
of stages per unit ДТ must be high. This
maximizes the terminal temperature differ
ence and logarithmic mean temperature
difference and minimizes thé surface re
quirements where the circulation rates are
high. At the low-temperature end, where
the ДР per unit ДТ is small, reducing the
circulation rate for the same heat input
together with the requirement for larger
ДТ'5 per stage results in fewer stages and
larger terminal temperature differences and
logarithmic mean temperature differences.
This has the effect of tending to minimize
782
9£fF
*
the heat transfer surface required at the
low temperature end of the plant. Thus,
MEMS lends itself to the criterion that the
surface requirements be minimized through
out the entire temperature range of oper
ation.
A better understanding of MEMS is ob
tained by following the flow of the heat
from its entrance into the MEMS plant at
the high-temperature end until its rejec
tion to the environmental surroundings at
the low-temperature end. Reiterating once
more, MEMS is several recirculation SEMS
plants connected in series with each SEMS
considered as a separate effect. Each effect
is composed of two sections, a heat rejection
section and a heat recovery or reheat sec
tion. A thermal envelope drawn around
each effect reveals that the heat input to
the brine heater of any effect is rejected
from the effect by two means: (1) the
difference in heat content between the feed
entering the effect and the brine and dis
tillate streams leaving the effect: and (2)
the heat added to the brine recirculating
stream from the next lower effect. This is
true for each effect and thus the heat input
to the brine heater is eventually rejected to
the surroundings from the lowest tempera
ture effect.
A thermal envelope for the first effect
drawn so as to include the heat entering
the plant through the brine heater but to
exclude the condensers in the heat rejection
part of the effect reveals that the heat
absorbed in the heat rejection condensers
is equal to the heat input to the effect as
long as the final brine temperature of the
effect is made equal to the temperature of
the feed stream and recirculating brine
stream leaving the heat rejection section of
the effect. This holds true for any of the
effects. Thus, the heat transferred to the
heat rejection condensers has two functions:
heating the feed and heating the recircula
tion stream of the next lower effect. Due to
temperature continuity requirements and
the lowering of the circulation rate from
the hot to the cold effects with subsequent
larger iT's in each heat rejection section,
the amount of heat for feed heating in
FLASH DEVICES
To date, practically no information has
been published by any investigator on the
design of the flash device used to pass the
brine from stage to stage. The outcome of
experimental investigations conducted has
apparently been considered proprietory and
the results unpublished. However, the flash
device is the heart of any flash evaporator
and can be the key to successful operation.
A properly designed flash device should
yield stable, self-regulating operation in a
minimum chamber volume, possess a mini
mum of system losses, and yet pass a maxi-
of fluid per unit AP and
FIGURE 300. TWO-STAGE FLASH CHAMBER TEST MODULE.
creases slightly with a corresponding re
duction in heat for the recirculation stream
of the next lower effect.
In summary then, MEMS offers the fol
lowing advantages:
(1) Higher AT for plant operation.
(2) Reduced feed treatment require
ments.
(5) More stages at hot end and fewer
at the cold end.
(4) Minimized heat transfer surface
requirements.
flow area.
The flash device used in American Ma
chine 8c Foundry Company evaporators con
sists of a nozzle and a deflector. The flashing
of liquid into vapor is confined to a small
critical flashing zone near the throat of the
flash nozzle. This zone shifts within_ the
flash nozzle to compensate for the varying
pressure differences between stages as oper
ating conditions vary. The flash zone is
shown on Fgure 300 in a typical two-stage
flash chamber test module. The "instant
vapor" created by the small flash zone elimi
nates the need to provide for brine
 retention in the flash chamber to reach
equilibrium thus reducing the size and com
plexity of the chamber. In this flash nozzle,
the unflashed brine is discharged as ap
proximately horizontal, high-velocity, thin
sheets of liquid. This simplifies the liquid-
vapor separation, minimizes the reheat
problem commonly associated with flooded
flash chambers, and provides for efficient
scrubbing of the vapor by the thin liquid
sheets.
Experience has shown that efficient flash
devices are also extremely effective deaera-
tors. A flash deaerator, called "Flashaera-
tor", is incorporated in the evaporator plant
to remove dissolved and entrained gases
from the feed stream. This is accomplished
without supplying external steam and yet
yields additional potable distillate. It util
izes the same compact highly efficient flash
device installed in each flash evaporator
stage. A typical Flashaerator is shown in
operation in Figure SOI. FIGURE 301. FLASHAERATOR.

SURFSIDE MEMS PLANT FOR RIVERHEAD, NEW YORK

One of the first large plant applications
of the new MEMS technology will be the
New York State Atomic and Space Develop
ment Authority's SURFSIDE project at
Riverhead, New York. SURFSIDE, which
stands for Small Unified Reactor Facility
with Systems for Isotopes, Desalination, and
Electricity, will use a nuclear reactor with
a thermal power rating of approximately
33 megawatts and a radioactive isotope
production capacity of 400,000 Cobalt equiv
alent curies per year, a 1.000,000 US gpd
MEMS Reboiler, and a 3500 kw gross to
2.500 kw net turbine generator.
Although the concept of integrating a
reactor, turbine generator, and distilling
plant is relatively new, the variation in the
orientation of the components with respect
to each other has been limited by the con
ventional practice of connecting the turbine
to the heat source and exhausting to the
distiller. In reality, however, as shown in
Figure 302, there are at least four basic ways
in which these components can be grouped.

CASE С
I 80,000 FT -SEMS REBOILER
1 or
j^50,000 FT - MEMS REBOILER

95.0QO*/hr 2Q.0QQ*/HR
\ 10° 20 peg CASE В ч
JÊ
MEMS 63STG *73-
jzacfc steam
REACTOR. Л' \У9 ] - — . — — - ■— —[ •
ПУТ
rrr-N ISEMS GASEA
IQ 5TG' РГЗ*

260 F

FIGURE 302. COMPARATIVE ARRANGEMENT OF DISTILLING

PLANTS FOR SURFSIDE.
784
all of which were investigated for the
SURFSIDE project.
Case A: In this, the classical approach,
high grade energy obtained from the re
actor is used to drive a back pressure tur
bine exhausting to the brine heater of a
distilling plant. Due to the low exhaust
temperatures (1S0°F) required to produce
the necessary power, the distilling plant
must produce one mgd while operating
over a small flashdown range. This would
require 150,000 square feet of heat ex-
changer surface. The use of the classical
approach is neither practical nor economical
for the SURFSIDE conditions.
Case B: In an alternate arrangement, the
distilling plant and turbine generator set
are installed in parallel. In this case a three-
effect MEMS plant would operate at a top
temperature of 250°F using 90 stages to
produce the 1,000,000 gpd capacity due to
the small quantity of heat available. Ap
proximately 125,000 square feet of heat
transfer surface would be needed and the

SOLUBILITY LIMIT OF
2nd EFFECT Ca SOv^HgO FROM
O.S.W 1961 ANNUAL
MEMS <B
REPORT
2.0 CONG

O
csi

SEMS@
1-5 CONC

i
1st EFFECT MEMS
0 13 CONC

TOPPING EFFECT
<3 1.15 CONC

in
200 223 &0 275 300 325 350
TEMPERATURE — F
FIGURE 303. CONCENTRATION VS TEMPERATURE FOR
SURFSIDE MEMS AND SEMS.
 capital cost would be rather high.
Case C: A more novel arrangement is to
install the evaporator between the reactor
and the turbine. In order to generate steam
for the turbine, the last stage of the evapo
rator heat rejection section must be a re-
boiler. A 1 3-stage SF.MS designed to operate
at 1.5 concentrations in the temperature
interval of 260°F to 225°F would require a
total installed surface of 80,000 square feet.
A 1 3-stage SEMS designed to operate from
245" to 225°F with 2.0 concentrations
would require approximately 100,000 square
feet of heating surface. A double-effect 14-
stage MEMS Reboiler designed to operate
from 260°F to 225°F with a final brine
concentration of 2.0 and a concentration of
1.3 in the first effect required only 50,000
square feet of heating surface. The two-
effect MEMS Reboiler shown in Figure 302
was selected for SURFSIDE as it had the
lowest capital cost and produced the re
quired amounts of isotopes, water, and
power.
The significant advantage to feed heating
requirements when operating the MEMS
Reboiler at this temperature and concen
tration range compared to a SEMS boiler
in the same range can readily be seen in
Figure 303. The operation of a SEMS plant
at 260°F and 1.5 concentrations is shown
by the dash line. The solid lines show
where the first and second MEMS effects
would operate. A third solid line shows
where a future topping effect installed
from 280" to 260°F would operate.
The unique cycle arrangement selected
allows a conventional MEMS plant having
an economy of 3.33 to perform at an ap
parent overall economy of 24.8. This cal
culation is as follows:
Total Heat ffom Reactor
(10"Btu/hr) 105
Less Heat to Turbine
Generator 80
Less Condensate Reheat for
Turbine Generator 11
Heat Chargeable to Evaporator
(10e Btu/hr) 14
An added advantage of this approach is
the high surface effectiveness possible (7
pounds of distillate per square foot of heat
exchanger surface) because of the increased
number of stages and higher heat transfer
rates at these high temperatures. Further,
recent research and development in high
temperature flash distillation have resulted
in important reductions in flash evaporator
release areas. Findings verify that the re
786
lease area can be reduced by 75 per cent
at the high temperatures selected for the
SURFSIDE MEMS Reboiler operation (Fig.
304).
The MEMS Reboiler also has the capa
bility of future expansion as shown in
Figure 305. The first expansion step, phase
B, would add 350,000 gpd water capacity
by installing an additional "topping" effect
at the high-temperature end of the plant.
The maximum temperature of this effect
would be between 280° and 290°F. The
evaporator plant is capable of operation up
to 290°F. If the reactor exhibits normal
"stretch" characteristics, that is, the ability
to operate at temperature levels above the
design point, the 290°F maximum tempera
ture will be used. The 280°F temperature
level shown for phase В can be reached
without exceeding the reactor design con
ditions. The gross power produced would
be 3300 kilowatts with a net salable power
production of 2,300 kilowatts. The economy
or gained output ratio of the phase В
1,350,000 gpd plant integrated into the
power plant cycle would be greater than
30 to 1.
The next step in the planned expansion
program, phase C, would be the installation
of several effects on the low-temperature
end of one half of the basic plant expand
ing the temperature range from 225°F to
a temperature of 100°F or less, and would
add 1,825,000 gpd to the installed capacity-
raising the total plant output to 3,175.000
gpd. The gross power produced would be
2.100 kilowatts which is the amount required
to operate the plant. Thus, no excess power
would be produced for sale. This 3.175.000
gpd plant, part of which would be in
tegrated and part of which would be inde
pendent of the power plant cycle, has an
overall economy or gained output ratio of
27 to 1.
The final expansion step, phase D. would
add 1,825,000 gpd additional capacity rais
ing the total plant output to 5,000.000 gpd
by installing several effects similar to phase
С on the low-temperature end of the other
half of the basic plant. This would expand
that half of the plant to operate in the
full low-temperature range from 225"^
down to 100°F or less. The power required
to operate the plant would be 3.000 kilo
watts. No power would be produced by the
plant. The economy or gained output ratio
of this 5,000,000 gpd plant operating across
the full temperature range of 280°F down
to 100°F or less would be 16.5 to 1.
788
 ADVANTAGES OF MEMS REBOILER SYSTEM IN LARGE PLANTS
Because of the numerous advances in
technology exhibited in the MEMS Reboiler
application at SURFSIDE, an investigation
was made into the integration of a similar
system in large combined power and water
plants.
Other desalination systems (long tube
vertical, vapor-compression, etc.) as well as
multistage flash were studied. These pre
liminary investigations indicate that a
MEMS Reboiler integrated into a large
power plant cycle at the crossover point
between the high-pressure turbine and the
low-pressure turbine will produce more
vapor for a given amount of cycle heat
degradation than a multistage flash plant
installed anywhere else in the power plant
heat cycle.
The advantages of the MEMS Reboiler
cycle are effectively demonstrated by a
FIGURE 306. INTEGRATED POWER WATER CYCLE.
CONCLUSION
The salient features of MEMS compared
to SEMS were shown to be:
(a) Reduced total feed treatment cost
by 50 per cent.
(b) Reduces heat transfer surface by
at least 20 per cent.
(c) Allows for more stages at the hot
end of the plant and fewer stages
at the cold end of the plant.
A practical application of MEMS tech
nology at the SURFSIDE nuclear power and
comparison with a conventional nuclear
dual-purpose plant designed to produce
150,000,000 gpd of water and 1,800 mega
watts of electricity. The cycles selected for
comparison were single-effect multistage
flash evaporators using either acid or poly
phosphate feed treatment and turbine bleed
steam. Calculations indicate that a MEMS
Reboiler installed as shown in Figure S06
at the turbine crossover in the same plant
would produce approximately 13 per cent
more water for the same reactor heat out
put and electric power production. In ad
dition, compared to the conventional SEMS
plants, the MEMS Reboiler would be about
one-fourth the physical size and would re
quire approximately one-half the heat
transfer surface, which should reduce the
cost of water.
LP TURBINE
170x10 GPD
DIST
water plant led to the introduction of the
MEMS Reboiler concept which shows prom
ise of lowering potable water cost on large
dual-purpose power and water plants.
Compared to large dual-purpose power
and water plants of the conventional SEMS
design, a MEMS Reboiler installed in the
crossover line between the high-pressure
turbine and low-pressure turbine would
require only one-quarter of the land area
and one-half the heat transfer surface.
789
 SUMMARY OF DISCUSSION
It was pointed out that economic infor
mation is not given in this paper, and the
author was asked what amount of savings
is achieved in water and power. The author
stated that the engineering department re
ported savings of about 20 per cent in the
capital cost of the plant with a 2 to 3 per
cent increase in piping costs. The overall
economics is about 8 per cent savings. When
asked about problems in operation and
maintenance costs or complexities, the
author replied that there had been no in
crease in complexities of operation and that
no problems had arisen in any of these
areas. It was asked if use of an extraction
Distillation Instantanée en Etages
Multiples a Effets Multiples
W. R. Williamson, F. W. Gilbert et T. R. Scanlan
Etats-Unis d'Amérique
CYCLE DE DISTILLATION INSTANTANÉE EN
ÉTAGES MULTIPLES A EFFETS MULTIPLES
Les caractéristiques de construction et de
fonctionnement des évaporateurs instan
tanés, y compris ceux installés à Aruba,
Curaçao, Koweït, Point Loma et en d'autres
lieux du monde sont bien connus de tous.
Ce type d'évaporateur est un évaporatcur
en étages multiples à un seul effet ou
évaporateur SEMS. L'économie maximale
thermique d'une installation SEMS pour
toute efficacité de surface prédéterminée
(livres d'eau produites par pied carré de
surface d'échange de chaleur) est limitée
par deux considérations:
(1) Des considérations de concentration
limitent la température supérieure
du cycle.
(2) Le petit Д P par unité Д T à l'ex
trémité basse température limite le
nombre maximal d'étages permis.
En essayant de porter au maximum l'éco
nomie thermique pour toute efficacité de
surface, plusieurs dispositions différentes de
tuyauterie ont été étudiées. On en discute
deux ici:
(1) L'installation à vaporisation instanta
née en étages multiples à un seul effect
à surface variable.
turbine had been considered. The reply
stated that this was investigated and found
not to be economical.
It was asked if any optimization tech
niques had been applied. The reply was
affirmative and further stated that circula
tion rates and concentration in each effect
had been varied. The author stated that
the maximum concentration was 5.0 and
that any higher concentration would cause
the calcium sulphate to drop out. The
author also stated that pressure vs tempera
ture limitations and minimum surface re
quirements had been studied.
(2) L'installation à vaporisation instanta
née en étages multiples à effets mul
tiples ou MEMS.
Le système SEMS à surface variable
diffère du système SEMS normal en ce qu'il
possède un coefficient d'amortissement dé
croissant de la température au fur et a
mesure que la température de fonctionne
ment augmente. D'autre part, le système
MEMS non seulement possède cette carac
téristique, mais en plus le circuit unique
principal d'écoulement du système SEMS
est hydrauliquement divisé si bien que l'in
stallation d'évaporateur est disposée en de
nombreux effets ou installations SEMS à
recirculation en séries. Chaque effet possède
sa propre section de récupération de
chaleur et de réjection de chaleur simi
laire au système SEMS à recirculation
rendant l'économie thermique ou le rapport
de rendement acquis de chaque effet supé
rieur à un. L'économie thermique totale
du système est égale à la somme des
économies thermiques de chaque effet.
Pour un traitement particulier d'alimen
tation, on obtient un gain considérable
dans la température supérieure permise du
cycle en canalisant l'alimentation à travers
un compartiment séparé d'échange de
chaleur jusqu'au premier effet ou effet à
haute température. II est maintenant pos rateur à turbine de 3.500 kW bruts—2.500
sible, pour la première fois, de donner à kW nets.
un évaporateur instantané les mêmes gra Quatre méthodes différentes ont été
dients favorables de concentration employés étudiées. La première méthode consistait à
par les évaporateurs à tubes submergés à étudier l'utilisation de l'échappement de la
effets multiples. turbine pour l'évaporateur SEMS et de
Comme l'entrée de chaleur à chaque mandait 150.000 pieds carrés (14.000 m") .
effet est constante et égale à l'entrée de Ceci a été considéré non économique. La
chaleur au réchauffeur de saumure, il est seconde méthode portait sur l'étude d'une
possible, en raison d'isolement hydraulique installation MEMS fonctionnant en paral
de chaque effet, de modifier le taux de lèle avec la turbine et nécessitant 125.000
recirculation dans chaque effet. La varia pieds carrés (11.600 m*) . La troisième avait
tion de Д P par Д T unitaire avec la trait à l'étude d'un distillateur SEMS
température de l'eau saturée est telle qu'il fonctionnant entre le réacteur et la turbine.
est permis de concevoir des taux de circula Il nécessitait 80.000 pieds carrés (7.400 m1) ,
tion importants et un certain nombre car des considérations de concentration de
d'étages à l'extrémité haute température de mandaient d'importants taux d'alimentation
l'installation et de petits taux de circulation
et par conséquent d'importants réchauffeurs
et nombres d'étages au côté froid de l'instald'alimentation. Enfin, on a étudié un dis
lation. Comme on le montre dans le tableau tillateur MEMS à double effet installé entre
suivant, une économie dans la surface le réacteur et la turbine. Des considérations
d'échange de chaleur d'au moins 20% est de concentration ont permis d'abaisser les
possible avec le système MEMS. taux d'alimentation de 35% et de réduire
la surface totale d'échange de chaleur à
SEMS SEMS à MEMS 50.000 pieds carrés (4.600 mr) , représentant
type sur'ace
variable une efficacité de surface de 7,0. L'économie
Economie thermique 16 thermique du cycle est calculée à 24,8. Cet
16 i6 évaporateur MEMS à 14 étages à double
Température supé
rieure du cycle 250 250 effect fonctionnant entre 260°F et 225°F
275 (126° et 107°C) avec une concentration
Concentration
maximum 13 1,5 3,0 de premier effet de 1,3 et une concentra
Nombre d'étages 40 100 125 tion de deuxième effet de 2,0 a été sélec
Efficacité surface 4,0 4,4 5,0 tionné pour l'installation de Surfside. L'éco
nomie thermique est calculée comme suit:
On peut résumer comme suit les avantages Chaleur totale pro
du système MEMS par rapport au système venant du réacteur
SEMS pour la même économie thermique. (10" BTU/h) 105 (26 Kcal/h
(1) Réduction d'au moins 20% de la X 10")
surface d'échange chaleur. moins chaleur
(2) Réduction de 50% de la quantité au générateur
d'acide nécessaire. à turbine 80 (20)
(3) Réduction dè 50% dans la dimension moins réchauffage
du système dégazeur et d'alimenta du condensât
tion. pour générateur
(4) Gain d'une variation de température à turbine 11 (2,75)
de fonctionnement supplémentaire Chaleur ajoutable
d'au moins 25°F (14"C) . à l'évaporateur
(10« BTU/h) 14 (3,25 Kcal/h
INSTALLATIONS MEMS SURFSIDE X 10")
POUR RIVERHEAD, NEW YORK Un avantage supplémentaire de cette
Une des premières applications d'installa méthode est la haute efficacité de surface
tions à grande échelle de la nouvelle tech possible (7 livres de condensât par pied
nologie MEMS sera le projet Surfside à carré (34 kg/m2) de surface d'échangeur de
Riverhead, New York, pour la New York chaleur) a cause du nombre accru d'étages
State Atomic and Space Development Au et des taux de transfert de chaleur plus
thority, projet qui utilisera un réacteur élevés à ces températures élevées. En outre,
nucléaire avec une puissance thermique des travaux de recherche récents et de mise
d'environ 33 MW et une capacité de pro au point dans la distillation instantanée a
duction d'isotopes radioactifs de 400.000 haute température ont eu pour résultat de
curies équivalents de cobalt par année, un réduire considérablement la surface de
distillateur MEMS d'un million de gallons détente de l'évaporateur instantané. On a
américains (3.750 m") par jour et un géné trouvé que la surface de détente pouvait

791
 être réduite de 75% aux temperatures éle
vées sélectionnées pour le fonctionnement
de l'évaporateur MEMS de Surfside.
AVANTAGES DU SYSTÈME A ÉVAPORATEUR
MEMS DANS LES GRANDES INSTALLATIONS
Etant donné les nombreux avantages
de technologie présentés par l'application
de l'évaporateur MEMS à Surfside, on a
effectué une enquête concernant l'intégration
d'un système similaire dans de grandes
installations combinées de production
d'énergie et d'eau.
D'autres systèmes de dessalement (à longs
tubes verticaux, par compression de vapeur,
etc.) ainsi que l'évaporation en étages
multiples ont été étudiés. Ces enquêtes
préliminaires indiquent qu'un évaporateur
MEMS intégré dans le cycle d'une grande
centrale électrique, au point de croisement
entre la turbine à haute pression et la tur
bine à basse pression, peut produire plus
de vapeur pour une quantité donnée de
dégradation du cycle de chaleur qu'une
installation à évaporation instantanée à
étages multiples installée à n'importe quel
Многоступенчатая Многостадиальная
Дистилляция с Мгновенным Вскипанием
У. Р. Уильямсон, Ф. У. Гильберт и Т. Р. Сканлан
Соединенные Штаты Америки
Цикл многоступенчатой многостадиаль
ной дистилляции с мгновенным вски
панием
Всем известны проекционные и экс
плуатационные характеристики испари
телей с мгновенным вскипанием, кото
рые были установлены в Арубе, Кюра
сао, Кувейте, Пойнт Лома и в других
местах земного шара. Они принадлежат
к типу одноступенчатого многостади
ального испарителя, сокращенно назы
ваемого SEMS. Максимальная терми
ческая экономия установки SEMS при
любой заранее установленной поверх
ностной эффективности (фунтов опре
сненной воды на квадратный фут тепло-
обменной поверхности) ограничена
двумя соображениями:
(1) Соображения концентрации огра
ничивают максимальную темпе
ратуру цикла.
792
autre endroit dans le cycle de chaleur de
la centrale.
Les avantages du cycle de l'évaporateur
MEMS sont démontrés de façon effective
par une comparaison avec une installation
nucléaire classique à double usage conçue
pour produire 150 millions de gallons
(565.000 m") d'eau par jour et 1.800 MW
d'électricité. Les cycles sélectionnés pour la
comparaison ont été des évaporateurs a
étages multiples à un seul effet utilisant
soit un traitement de l'alimentation à
l'acide, soit au polyphosphate, et employant
la vapeur d'échappement des turbines. Les
calculs indiquent qu'un évaporateur MEMS
installé au point de croisement des turbines
sur la même installation produirait approxi
mativement 13% plus d'eau pour le même
rendement thermique du réacteur et la
même production d'électricité. En outre,
par comparaison avec les installations
normales SEMS, l'évaporateur MEMS serait
d'environ 14 de la dimension et exigerait
environ la moitié de la surface d'échange
de chaleur, ce qui réduirait le prix de
revient de l'eau.
(2) Малая величина ДР на единицу
ДТ на конце с низкой температу
рой ограничивает максимально
допустимое число стадий.
При попытке увеличения до предела
термической экономии, было исследо
вано несколько систем трубопроводов.
Две из них обсуждаются здесь:
(1) Установка мгновенного вскипа
ния SEMS с переменной пло
щадью.
(2) MEMS или многоступенчатая
многостадиальная установка
мгновенного вскипания.
SEMS с переменной площадью от
личается от обыкновенной в том от
ношении, что имеет декремент пони
жающейся температуры по мере того,
как рабочая температура повышается.
MEMS с другой стороны не только об
ладает этой особенностью, но кроме
того цикл главного одиночного потока
SEMS гидравлически отделяется, так
что испарительная установка устроена
в виде многих ступеней или последо
вательно включенных рециркуляцион
ных установок SEMS. Подобно рецир
куляции SEMS-a, каждая ступень име
ет свою собственную секцию регене
рации тепла и секцию теплового сбро
са, делая величину термической эконо
мии или коэффициента повышенной
выработки равной более единицы. Тер
мическая экономия всей системы соот
ветствует сумме термических экономий
всех отдельных ступеней.
Благодаря специальной манипуляции
с исходной водой, достигается значи
тельное увеличение допустимой макси
мальной температуры цикла посред
ством проведения питания через осо
бое теплообменное отделение в первую
или высокотемпературную ступень. Те
перь впервые испаритель с мгновенным
вскипанием получает возможность ра
ботать при благоприятных градиентах
концентрации многоступенчатых испа
рителей с трубками погруженного типа.
Так как подача тепла в каждую сту
пень постоянна и равна подаче тепла
в подогреватель рассола, становится,
благодаря гидравлической изолирован
ности каждой ступени возможным, ва-
риировать в ней скорость рециркуля
ции. Колебание дР на единицу ДТ с
температурой насыщенной воды тако
во, что оно позволяет применять боль
шие скорости циркуляции и большое
число стадий на конце высоких темпе
ратур установки, и ряд стадий на ее
холодном конце. Как видно из ниже
следующей таблицы, в MEMS-e можно
уменьшить по крайней мере на 20%
поверхность теплопередачи.
gif § трации позволили снизить скорость пи
Термическая
экономия 16 16 16
Максимальная
температура
цикла 250 250 275
Максимальная
концентрация 1,5 1,5 3,0
Число стадий 40 100 125
Эффективность
поверхности 4,0 4.4 5,0
Резюмируя преимущества MEMS-a
по сравнению с SEMS-ом, получается:
(1) Уменьшение по крайней мере на
20% теплопередаточной поверх
ности.
(2) Уменьшение на 50% потребного
количества кислоты
(3) Уменьшение на 50% деаэратора
и размеров системы питания.
(4) Повышение по крайней мере на
25°F рабочей температуры.
Установка «СЕРФСАИД» типа MEMS
для Риверхед, шт. Нью-Йорк
В проект «СЕРФСАЙД» Управления
по атомному и космическому развитию
Штата Нью-Йорк, который находится
в Риверхед, шт. Нью-Йорк, входит од
на из первых крупных установок, при
меняющих новую технологию MEMS.
Она будет пользоваться ядерным ре
актором с номинальной мощностью
термической энергии около 33 мегаватт
и выработкой радиоактивных изотоп в
количестве 400.000 кобальт-эквивален
тов кюри в год; в ее оборудование
войдет кипятильник MEMS на 1 мил
лион американских галлонов в день и
турбогенератор мощностью 3.500 кило
ватт брутто и 2.500 киловатт нетто.
При первом подходе исследовался
выхлоп турбины в испаритель SEMS,
при чем требовалось 150.000 кв. фут.
Это было признано неэкономичным.
При втором подходе изучалась уста
новка MEMS, параллельно работавшая
с турбиной и требовавшая 125.000 кв.
футов. При третьем, рассматривался
кипятильник SEMS, работавший меж
ду реактором и турбиной. Для него
требовалось 80.000 кв. фут., так
как по соображениям концентрации
были нужны большая скорость пита
ния и в связи с этим большие подогре
ватели исходной воды. Наконец, был
изучен двухступенчатый кипятильник
MEMS, установленный между реакто
ром и турбиной. Соображения концен
тания на 35% и уменьшить общую по
верхность теплообмена до 50.000 кв.
фут, при чем поверхностная эффектив
ность соответствовала 7,00. Термиче
ская экономия цикла по рассчету рав
на 24,8. Этот двухступенчатый 14-ста-
диальный кипятильник MEMS, рабо
тающий при температурах между 260° F
и 225°F с концентрацией 1,3 в первой
ступени и с концентрацией 2,0 во вто
рой, был выбран для установки «СЕРФ
САИД». Подсчет термической экономии
состоит в следующем:
Общее тепло от реактора
(10« Б.Т.Е./час) 105
793
 минус Тепло для турбоге нием были изучены и другие (верти
нератора 80 кальные длиннотрубные, со сжатием
минус Подогрев конденса пара и т.д.). Эти предварительные ис
та для турбогенератора 11 следования указали, что кипятильник
Тепло передаваемое в испа MEMS, включенный в точке перехода,
ритель (10* Б.Т.Е./час) 14 между турбиной высокого давления н
турбиной низкого давления, в цикл
Дополнительным преимуществом это большой энергетической установки,
го подхода является возможность вы при заданном количестве рассеяния те
сокой поверхностной производительно пла в цикле выработает больше пара,
сти (7 фунтов дистиллята на квадрат чем многостадиальный агрегат с мгно
ный фут поверхности теплообменника) венным вскипанием, включенный в те
вследствие большего числа стадий и пловой цикл энергетической установки
большей скорости теплопередачи при в каком-либо другом месте.
этих высоких температурах. Кроме то Преимущества цикла кипятильника
го, современные исследования и усо MEMS ясно видны при сравнении с
вершенствования в области дистилля обыкновенной ядерной установкой
ции с мгновенным вскипанием при вы двойного назначения, спроектирован
сокой температуре привели к значи ной для производства 150 миллионов
тельному уменьшению выпускных про галлонов опресненной воды в сутки и
странств испарителя этого типа. Было 1.800 мегаватт электричества. Циклами,
установлено, что при высоких темпе выбранными для сравнения, были од
ратурах, выбранных для работы кипя ноступенчатые многостадиальные испа
тильника MEMS на проекте «СЕРФ- рители с кислотной или полифосфатной
САИД>, удастся уменьшить выпускные обработкой питания, потреблявшие
пространства на 75%. спускной пар из турбины. Подсчеты
Преимущества системы кипятильника указывают, что кипятильник MEMS,
MEMS для крупных установок включенный в ту же самую установку
в точке перехода у турбины, сможет
Вследствие многих технологических дать примерно на 13% больше опрес
улучшений, обнаруженных в кипятиль ненной воды при той же самой выра
нике MEMS, примененном в <СЕРФ- ботке реактором тепловой и электри
САИД», было произведено исследова ческой энергии. Кроме того, по срав
ние о включении подобной системы в нению с обыкновенными установками
крупные комбинированные системы, SEMS, кипятильник MEMS при при
производящие электрическую энергию мерно половинной площади теплопере-
и опресненную воду. даточной поверхности будет почти в
Кроме многостадиальной опресни четыре раза меньше по объему, что
тельной системы с мгновенным вскипа уменьшит стоимость воды.

Destilación Instantánea Con Etapas

Multiples en Multiple Efecto

W. R. Williamson, F. W. Gilbert y T. R. Scanlan

Estados Unidos de Norteamérica

CICLO DE DESTILACIÓN INSTANTANEA DE o evaporador SEMS. La economía térmica

MÚLTIPLES ETAPAS EN MÚLTIPLE EFECTO
Son para todos familiares las caracterís
ticas de diseño y operación de los evapora-
dores instantáneos instalados en Aruba,
Curaçao, Kuwait, Point Loma y otros sitios
en el mundo. Este tipo de evaporador es
un evaporador de etapas múltiples de
simple efecto (Single Effect Multistage
794
máxima de una planta SEMS para cual
quier efectividad de superficie predetermi
nada (libras del agua producto por pie
cuadrado de superficie de intercambio
térmico) está limitada por dos considera
ciones:
1) Consideraciones de concentración li
mitan la temperatura tope del ciclo.
 2) El pequeño AP por unidad de AT
en la zona de baja temperatura limita
el número de etapas posibles.
En un intento de maximizar la economía
térmica, para cualquier efectividad de su
perficie, fueron investigados diferentes
arreglos de colocación de la tubería. Se dis
cuten aquí dos de ellos:
1) Plantas instantáneas SEMS de área
variable.
2) Plantas instantáneas con etapas múl
tiples de múltiple efecto (Multieffect
Multistage) o MEMS.
El SEMS de área variable difiere del
SEMS convencional en que tiene un decre
mento de temperatura decreciente a medida
que la temperatura de operación aumenta.
MEMS por otra parte, no sólo posee esta
característica sino que además, el circuito
de flujo mayor único de SEMS está hidráu
licamente dividido de tal manera que la
planta del evaporador se encuentra arregla
da con muchos efectos o plantas SEMS de
recirculación en serie. Cada efecto tiene su
propia sección de recuperación y rechazo
de calor, similar a la recirculación SEMS
haciendo la economía térmica o razón de
producción ganada de cada efecto mayor
que uno. La economía térmica total del
sistema es igual a la suma de las econo
mías térmicas de cada efecto.
Para un sistema particular de trata
miento de alimentación, se logra una con
siderable ganancia, en la temperatura tope
posible del ciclo, mediante la canalización
del agua de alimentación a través de un
compartimiento separado de intercambio
de calor al efecto primero o de temperatura
más alta. Ahora es posible, por primera
vez, que el evaporador instantáneo tenga
las ventajas de gradientes de concentración
favorables empleados por los evaporadores
de múltiple efecto de tubos sumergidos.
Dado que el calor de alimentación de
cada efecto es constante e igual a la
alimentación de calor del calentador de
salmuera, es posible, debido a la aislación
hidráulica de cada efecto, variar la velo
cidad de recirculación en cada efecto. La
variación de AP por unidad de AT con la
temperatura de agua saturada es tal, que
permite el diseño con grandes velocidades
de circulación y número de etapas en la
zona de alta temperatura de operación y
con pequeñas velocidades de circulación y
número de etapas en la zona de baja tem
peratura de operación de la planta. Como
se muestra en la siguiente tabulación, es
posible un ahorro en la superficie de trans
ferencia de calor de por lo menos 20%
con MEMS:
SEMS SEMS, MEMS
típico Area
variable
Economía térmica 16 16 16
Temperatura
máxima del ciclo 250 250 275
Concentración
máxima 1,5 13 3,0
Número de etapas 40 100 115
Efectividad de
superficie 4,0 4,4 5,0
Resumiendo, las ventajas de MEMS sobre
SEMS a igualdad de economía térmica son:
1) Reducción de por lo menos 20% de la
superficie de transferencia de calor.
2) Reducción en 50% de la cantidad de
ácido requerido.
S) Reducción en 50% en el tamaño del
desaireador y sistema de alimentación.
4) Ampliación en, por lo menos, 25°F
en la escala de temperaturas de ope
ración.
PLANTA MEMS SURFSIDE PARA
RIVERHEAD, NEW YORK
Una de las primeras aplicaciones de la
nueva tecnología MEMS se hará en el pro
yecto SURFSIDE de la Autoridad para el
Desarrollo Atómico y Espacial del Estado
de New York (New York State Atomic and
Space Development Authority) en River-
head, en el que se usará un reactor nuclear
con un poder térmico evaluado en 33 me-
gavatios aproximadamente y una capacidad
de producción de isótopo radioactivo de
40.000 curios por año equivalentes de co
balto, una columna de destilación continua
MEMS de un millón de galones americanos
por día y una turbina generadora de 3.500
Kv brutos, 2500 Kv netos.
Cuatro enfoques diferentes fueron estu
diados. El primer enfoque investigó el va
ciamiento de la turbina en un evaporador
SEMS y requirió 150.000 pies cuadrados.
Esto fue considerado antieconómico. El
segundo enfoque estudió una planta MEMS
operando en paralelo con la turbina y
requirió 125.000 pies cuadrados. La tercera
posibilidad investigada fue una columna
de destilación continua SEMS operando
entre el reactor y la turbina. Se requerían
80.000 pies cuadrados dado que las conside
raciones de concentración demandaban
grandes velocidades de alimentación y por
tanto grandes calentadores del agua de
alimentación. Finalmente se estudió una
columna de destilación continua MEMS de
doble efecto instalada entre el reactor y la
turbina. Consideraciones sobre concentra
ción permitieron una reducción de 35% en
las velocidades de alimentación y reducción
795
 de la superficie total de intercambio de SURFSIDE, se llevó a cabo una investiga
calor a 50.000 pies cuadrados, lo que re ción de la integración de un sistema similar
presenta una eficiencia de superficie de 7,0. en plantas combinadas, de energía y agua,
La economía térmica del ciclo se calcula de gran tamaño.
en 24,8. Esta columna de destilación con Fueron estudiados otros sistemas de desa-
tinua MEMS de dos efectos y 14 etapas linización (tubos verticales largos, compre
operando entre 260'F y 225° F con una sión de vapor, etc.) conjuntamente con la
concentración en el primer efecto de 1,3 y destilación instantánea de etapas múltiples.
una concentración en el segundo efecto de Estas investigaciones preliminares indican
2,0 fue la seleccionada para la planta que una columna de destilación MEMS
SURFSIDE. La economía térmica se calcula integrada con el ciclo de una gran planta
como sigue: de energía en el punto de cruzamiento
Calor total producido por entre la turbina de alta presión y la tur
el reactor (10« BTU/h) bina
105 para un de baja presión, producirá más vapor
Menos calor a la turbina volumen dado del ciclo de degra
generadora 80 dación térmica que una planta instantánea
Menos recalentamiento del de múltiple etapas instalada en cualquier
condensado para la otro punto del ciclo térmico de la planta
turbina generadora 11 de energía.
Calor asignable al Las ventajas del rielo de la columna de
evaporador (10* BTU/h) 14 destilación continua MEMS se demuestran
efectivamente mediante una comparación
Una ventaja adicional de este enfoque con una planta nuclear, de doble finalidad,
es la alta efectividad de superficie posible convencional diseñada para producir 150
(7 libras de destilado por pie cuadrado de millones de galones de agua por día y 1800
superficie de intercambio de calor) debida megavatios de electricidad. Los ciclos selec
a un número mayor de etapas y más altas cionados para fines comparativos fueron
velocidades de transferencia de calor a estas evaporadores instantáneos de múltiple
temperaturas más altas. Adicionalmente, in etapas con simple efecto, usando para tra
vestigaciones y desarrollos recientes en la tamiento del agua de alimentación tanto
destilación instantánea a alta temperatura ácido como polifosfatos y usando vapor de
han significado importantes reducciones en escape de la turbina. Los cálculos indican
las áreas de descarga del evaporador instan que una columna de destilación continua
táneo. Experiencias prácticas verifican que MEMS instalada, en el cruce de tubos de
el área de descarga puede ser reducida en la turbina, sobre la misma planta, produ
75% a las altas temperaturas seleccionadas cirla aproximadamente 13% más agua con
para la columna de destilación continua del igual producción de calor del reactor e
SURFSIDE MEMS. igual producción de energía eléctrica.
Además, comparada con las plantas SEMS
VENTAJAS DEL SISTEMA DE COLUMNA DE convencionales, la columna de destilación
DESTILACION CONTINUA MEMS EN PLANTAS MEMS sería de un tamaño físico de aprox
DE ORAN TAMAÑO imadamente la cuarta parte y requerirla
Debido a los numerosos avances de tecno aproximadamente la mitad de la superficie
logía que representa la aplicación de la de transferencia térmica, lo que deberá
columna de destilación continua MEMS en significar una reducción del costo del agua.

796
 Desalination in Spain
Jorge Suarez and Jose M. Pliego
Spain
INTRODUCTION
The scarcity of water in many parts of
the globe, due mainly to the extraordinary
increase in consumption which is caused by
the improvement of hygiene, industrializa
tion and the irrigation of extensive areas,
has revived in nearly all nations the ancient
interest of humanity in the conversion of
salt water or brackish water into fresh water.
The countries with limited water re
sources hope to remedy their water short
age by desalination, while the countries
which are more developed industrially in
tend to open new avenues for their ex
ported equipment; we can therefore say
that all countries, for one purpose or an
other, are following the day-by-day progress
of the technique in the various processes.
Conscious of this, the Government of the
United States, which with the creation of
the Office of Saline Water can proudly
consider itself at the head of the research
in this field, has convoked this international
symposium to explain the latest scientific
and technical advances in the world, pre
senting a panoramic view of the conversion
of salt water or brackish water into fresh
water and its practical applications.
INTEREST OF DESALINATION IN SPAIN
Spain is a semiarid country, with partial
water shortage in some of its regions. These
are precisely the most privileged in their
temperate sunny climate which makes them
attractive from the point of view of inter
national tourism, new export industry and
source of currency.
For this reason, the possibilities for appli
cation of desalination techniques are of great
interest to official circles of the country. An
Interministerial Desalination Commission,
in which are represented the various gov
ernmental departments having any connec
tion with water, has recently been created.
There is also a working group on the same
matter which depends on the Institute of
Hydrology, which is represented in the
Working Group on "Fresh water from sea
water" of the European Federation of
Chemical Industries. The purpose of this
Commission and Working Group is to main
tain up to date the technical and scientific
information regarding the various processes
which are being planned or tested with,
and their economic possibilities.
The national budget has not yet per
mitted the investment of substantial sums
in research, and we can cite only the tests
on solar distillers and foajn distillation.
On the other hand, the desirability of build
ing commercial conversion plants to supply
water to some cities has been considered.
These plants will also permit us to obtain
experience regarding exploitation condi
tions and production costs, which will un
doubtedly be of value for new studies and
projects.
Although the planning and construction
of the first plants has been entrusted to
foreign firms, it is hoped that the in
creasing industrial development in Spain
will shortly permit the construction of new
plants in the country. In fact, a high per
centage of the components of the plants
now under construction has been manu
factured by Spanish firms.
As is well-known, the problem of the con
verting salt water into fresh water is a
technicoeconomic problem which depends
principally on the local conditions. The
technique is at the present time fairly rent
able, but the desirability of a conversion
plant depends on the price which can be
paid for the water obtained. Thus, fol
lowing a selective criterion, plants have
797
 been built in the whole world under the
cosi profit relationship; this relationship in
cludes the considerations of direct and
indirect rentability, so that indirect rent-
ability may refer to factors such as strategic
benefit, oil interests, etc.. which are not
directly related to the normal conditions of
use of the water for domestic purposes.
The present prices for obtaining fresh
water from the sea are not rentable for
irrigation, but they meet industrial or popu
lation water needs, especially in areas of
tourism. The Spanish Interministerial Com
mission estimated the following price limits
for a first estimate of the desirability of
desalination:
Agricultural uses 0.05 $/m'
Water supply for city or
village 0.17 "
Tourist or industrial supply 0.40 "
These prices may be varied, depending,
as mentioned above, on the specific local
conditions.
GRAPH
ICpHm3
300
FIGURE 307. TOTAL EVOLUTION OF RAIN IN SPAIN
(YEARS 1947-64).
798
As we can see, taking as a basis the price
of 0.25 $/m*. obtained in some pilot plants
of the Office of Saline Water, desalination
may be acceptable as a means of supplying
tourist or industrial water needs, but not
for regular city or village needs, except in
special cases, and much less for agricultural
use. However, by combining the production
of potable water with the production of
electric power, a method which has already
been considered in many countries, better
prices can be obtained, on the order of
0.10 $/m* for plants larger than 50,000
m"/day. Extrapolating the results, it is esti
mated that with the installation of large
thermal or nuclear plants the price could
go below 0.05 $/m*, which would permit
use of this water in agriculture. In any case,
the technical problems anticipated in the
planning and construction of such gigantic
plants, will no doubt be considerable.
HYDRAULIC AND POWER RESOURCES
Hydrology in Spain is extremely irregular.
Average annual precipitation is 350.000
mm
I 0 00
900
Hm*, distributed irregularly over a surface
of 500,000 km', which supposes an average
of 700 mm. The extreme values observed in
the past few years have been 500 mm in
1950 and 1954 and 960 mm in I960 (Fig.
307).
In the north of the country, precipitation
is abundant, with over 1,000 mm per year,
while in the plateaus and central valleys
the average varies from 300 to 600 mm. In
the southeast, the most arid area of the
counrty, but also the one with the most
temperate climate precipitation is less than
300 mm. There is little snow; there is
some snow in the Pyrenees and a few
mountain ranges of the interior (Fig. 308).
This natural irregularity has been par
tially corrected by numerous regulating
works. Over 300 dams were built for vari
ous purposes, for irrigation, production of
electric energy and domestic needs. The
average annual contribution of the Spanish
rivers is 93.000 Hm'; the present dam capac
ity is 25,000 Hm*, which permits regulating
45 per cent of this water. In the next 20
years, this capacity will be increased to the
limit of 60,000 Hm', which will permit
regulating 70 per cent of the water.
In addition to this surface water, there
are many sources of underground water,
mainly on the eastern and southern coasts
of Spain, in the Baleares and Canary Is
lands, and in a few regions of the interior
of the peninsula. This water is used for
irrigation and water needs; a rational ex
ploitation of all underground resources has
not yet been reached. Studies have been
recently undertaken in the south and south-
cast on the rational exploitation of this
water. However the basic research and study
of water use require great caution; in some
cases water salinity increased with ex
ploitation, until it reached such a degree
that the water was no longer acceptable
for drinking or for agriculture.
In 1964 30,000 million kwh/year was pro
duced, providing approximately 1,000 kwh/
year for each of the 30 million inhabitants,
a figure which is lower than that of other
more developed European countries, but
which represents a 600 per cent increase
since 1944. Of this energy 70 per cent is
of hydraulic origin and the remaining 30
per cent of thermal origin, produced in
power plants fed mainly by fossil fuels,
coal, or fuel-oil (Fig. 309) .
The total power potency in December,
1964 was 7 million kw in hydraulic power
plants and 2.7 million kw in thermal power
plants, that is to say 9.7 million kw total,
showing an average of 3,100 hours of utili
sation. The thermal power plants work on
a seasonal basis in the peninsula to cover
the period of low water and also the dry
years, thus supplementing the hydraulic
production.
However, within the next few years, in
view of the anticipated increase in con
sumption by industrial as well as domestic
users, we hope to increase the thermal pro
duction considerably; the hydraulic possi
bilities will be exhausted. The thermal
power plants will therefore have to work
on the basis of the load curve of the coun
try, hydraulic energy covering the peak
periods, in the margin of the exceptional
cases of very humid years.
The above considerations mean that with
in the next few years, many thermal power
plants will be built in Spain, operating
generally at full load, specially during the
low water season during which the water
consumption naturally increases. In fact,
this demand for water as well as electric
energy offers interesting perspectives for
simultaneous production by dual-purpose
plants powered by fuel-oil or nuclear
energy. The chance of location for these
power plants, from an electricity point of
view, does not present any difficulty since
the whole country is practically inter
connected by big transmission lines. Some
of these power plants could be located in
regions of water scarcity, such as the south
east of the peninsula.
The Spanish city of Ceuta, in the north
of Africa, and the cities of Arrecife, Lan-
zarote, and las Palmas in Grand Canary,
in the Canary Archipelago, are special cases;
their water needs had to be met inde
pendently by the construction of dual-pur
pose conversion plants to meet their water
and energy requirements, since their hy
draulic resources were practically exhausted.
Other examples of special cases are the
many coastal settlements which are in
habited by a few families of humble con
dition who live mainly on fishing and who
lack the water necessary for their hygienic
needs. It is difficult to provide these small
villages with costly collecting and conduct
ing plants or with small-sized conversion
plants, of the naval type for example.
Therefore the possibility of providing them
with the means to build small solar dis
tillers of familiar or common type was con
sidered and some research and tests have
been conducted in this matter.
EXPERIENCE WITH SOUR DISTILLERS
These tests and experiments on solar stills
were conducted by the National Commis
sion of Special Energies, member of the
799
800
Mediterranean Cooperation for Solar Energy
(COLMES) and the Society of Solar Energy
(SES) .
Studies on insolation and solar energy
were made in various parts of the country;
the results obtained showed an average of
over 3,000 hours of insolation in the south
of the peninsula and north of Africa, and
a solar energy averaging 375 calories per
cm* per day, reaching over 400 in Almeria
(Figs. 310 and 311).
opment (OCDE) , several solar distillation
pilot plants are to be built shortly in the
southeast of the country. The first one,
which is already planned and ready to be
built, will occupy a surface of 900 m" and
will supply drinking water to a small agri
cultural community, Las Marinas (Almeria) ,
with about 50 families; their underground
water, which is used for the cultivation of
the land, is brackish, and although it serves
for tomato and alfalfa crops, is not potable.

OF KWH 25,750
(J HYDRAULIC PRODUCTION MILLIONS
OF KWH
29000 О THERMAL PRODUCTION
0 TOTAL PRODUCTION
DUPLICATION EVERY TEN
YEARS 21,330
MILLIONS
20000

ISOCO

10000

5000 4y420
MILLIONS

60 '' 19«

FIGURE 309. ENERGY PRODUCTION IN SPAIN (1944-63).

In view of this data, which strengthened DISTILLATION TESTS WITH

the general impression regarding the Utili
zation of this natural source of energy,
experiments were made with 10 common
types of small size solar distillers built from
easily available materials. The process
proved economically acceptable. Thus, for
example, about 1500 liters of fresh water
per year may be obtained for an investment
of S50 in one of these distillers.
Recently, continuing in this line of appli
cation for domestic uses, multistage solar
distillers were tested; these are composed
of adjacent chambers separated by parallel
plates. The results were encouraging (Fig.
312) .
Finally, through an agreement between
the Spanish Government and the Organiza
tion for Cooperation and Economic Devel-
FOAMING AGENTS
The Center of Technical Study of Special
Materials, of the National Institute of In
dustry, has conducted experiments on a new
distillation process which promises interest
ing results for small domestic, marine, and
military installations.
The basic idea of this process is to in
crease the evaporating surface area of salt
water by converting it into foam by means
of the addition of a foaming agent (sodium
alkylbenzene sulfonate) . The foam is ob
tained by the injection of air in sea water
with a small amount of the foaming agent
which gives great stability to the foam and
an electric resistivity much higher than that
of sea water (Fig. 313) .

801
802
 700 700

000 000

r
000 J 000
/ 100

too /
000
/
too 1 100

0
I II III IV V VI VII VW IX X XI xu X XI XII
MONTHS MONTHS
LAS ROZAS (MADRID) SEVILLA

roe

wo ■00

400 400

100

too A

1 00
<4
3 0
1 n hi IV V VI VN VMIX X » Xlt I II ID IV V VI VI va IX X M XH
MONTHS MONTHS
ALMERIA BADAJOZ

FIGURE 311. SOLAR ENERGY IN SOME SPANISH STATIONS

803
FIGURE 312. MULTISTAGE SOLAR DISTILLER BEING TESTED.
FIGURE 313. DISTILLATION WITH ADDITION OF FOAMING
AGENT.
An electric alternating current passing
through the foam breaks it up through the
heat produced by joule effect, and causes
the practically instantaneous evaporation of
fresh water. This vapor passes through a
back flow column to avoid dragging any
particles of detergent and permit recovery
of the agent. The vapor is converted into
fresh water in the condenser. The heat of
condensation is used to heat the input sea
water, thus making the process more
efficient.
THE LANZAROTE PLANT
The city of Arrecife, in Lanzarote, one
of the Canary Islands, suffers the conse
quences of the water shortage which
characterizes all the islands. To remedy this
situation, the municipal government of ihc
city called for bids to increase its supply,
which was adjudicated to the private firm
TERMOLANSA.
Their solution consisted of a dual-purpose
plant for conversion of sea water and pro
duction of electric energy for a maximum
capacity of 2,000 m'/day and 1.500 kw of
power, using the flash evaporation system.
The plant was financed and designed by-
Burns and Roe of New York, and built by
this same firm in collaboration with
805
 Dragados and Construcciones. The principal
components of the installation were manu
factured by Westinghouse and Foster
Whyler.
The evaporators consist of three stages in
primary circuit and fourteen in closed
circuit. The working pressure of the vapor
is 50 kg/cm* and the maximum tempera
ture of the brine 110°C. The plant started
operating in the spring of 1965, and the
anticipated price of the water is about
055 $/m'.
THE CEUTA PLANT
The Spanish city of Ceuta, in the north
of Africa, is located in the Straits of Gibral
tar. It is a commercial city with a port
which supplies fuel to many merchant
ships; it is also an important point of
communication between Europe and Africa.
The population of Ceuta is about 80,000,
and its water endowment is meager: some
100 liters per inhabitant and per day in
winter and 50 liters in summer. Natural
resources are practically exhausted and all
the sources of fresh water available in the
territory are being used.
The municipal government of the city
requested the assistance of the government,
which through the Ministry of Public
Works conducted a study of several works
for the purpose of improving the water
supply situation. Among these was a plant
for the desalination of sea water which
would increase the quantity of water avail
able by 50 liters per inhabitant and per day.
An international call for bids was made,
under the condition that the conversion sys
tem would remain open, and six firms
answered, all of them offering solutions
through the flash evaporation system. The
installation was adjudicated to the firm of
Atlas Werke of Bremen, Germany, who had
offered a dual-purpose plant producing
4,000 m' of water per day and 3,500 kw of
power. The plant was designed by this same
firm, who built the evaporators in Bremen;
nearly all the other components were manu
factured in Spain.
The installation consists of a boiler for
the production of vapor at a maximum
pressure of 40 at, two turbines with a
pressure of 35 at and back pressure of 1.5
at, two electric generators of 1,750 kw each,
and two flash evaporators for 2,000 m"/day
each with 4 stages in open circuit and 20
in closed circuit, planned for operating at
a maximum temperature of 83.5°C. The
concentration of the residual brine is
70,000 ppm.
The cost of the plant was $1,600,000. The
806
anticipated price of water is about 0.17
$/m", without counting amortization of the
plant, the latter depending upon the num
ber of hours of utilization in accordance
with the natural resources available and
the increasing consumption of the city.
All types of connections between dupli
cate elements of the installation were
planned to achieve better elasticity in the
production of fresh water or electric energy,
according to the market demand, and also
to obtain experience regarding the opera
tion and operating costs under different
load conditions. The plant will operate at
first on the basis of the load curve during
the major part of the day, the peak hours
being covered by the present thermal power
plant.
The various elements of the installation
are now being tested and it is hoped that
the plant will start operating normally in
November, 1965.
LAS PALMAS FUTURE PLANT
The Canary Archipelago is composed of
seven islands of volcanic origin. Over one
million inhabitants live on these islands,
distributed half and half in two provinces:
Tenerife, which comprises four islands, and
Las Palmas, which comprises three islands.
Eighty per cent of the population of the
archipelago lives on two islands, Tenerife
and Grand Canaryé in both islands, half of
the population is concentrated in the capi
tal cities of Santa Cruz and Las Palmas
respectively, the latter having somewhat
over 200,000 inhabitants.
The Las Palmas plant was built in part
to supply water to the capital but to under
stand the reason for the project, it is neces
sary to consider the total resources of the
Grand Canary Island.
This island is nearly circular with a
diameter of 50 km. It is formed bv a
volcanic cone 2,000 meters above sea level,
strongly eroded by twelve very rugged
radial gorges. The main resources of the
island are its location and its climate.
Because of its location, the port of Las
Palmas is one of the principal Spanish
ports. Because of its climate a subtropical
agriculture is possible, providing seasonal
opportunities on the European market. The
location and climate are the two reasons
for the growth of Las Palmas; they make
possible easy commercialization of its prod
ucts and the development of tourism.
The hydrologie panoramic view of the
island is disappointing. Precipitation falls
with a marked concentric character indicated

FIGURE 314. AVERAGE ISOHYETS, PERIOD 1949-58.
by differences of 200 to 1,300 mm, but
unfortunately with an average of only
400 mm. There are no permanent natural
streams because of the irregularity of the
precipitation, and the great permeability of
the ground (Fig. 314) .
On the other hand, the exploitation of
these scarce resources is developed to the
utmost, as indicated by the fact that out of
the 300 big Spanish dams recorded by
ICOLD, 35 of them are located in the small
island of Grand Canary (1300 km1), and
there are over one thousand wells for the
exploitation of underground water of an
average depth of over 100 m with an intri
cate distribution network that reaches a
total length of 150 km.
Of the 600 million m* of water, which is
the estimated annual precipitation on the
island, it is calculated that 420 million are
lost by evaporation etc., with 100 million
of surface water and 80 million of under
ground water being used.
THE GRAND CANARY ISLAND
With this exhaustive use of water in
Grand Canary, it is not surprising that any
development is checked or curbed by the
problem of the scarce resources. Thus the
present water supply of the city of Las
Palmas hardly reaches the amount of 60
liters per inhabitant per day, which is
insufficient for a city which benefits from
marked touristic preferences.
To meet the most elementary needs of
the city, the municipal government was
forced to purchase water on the insular
market under variable economic conditions,
depending upon periodic circumstances, but
at an average price of approximately
0.10 $/m«.
In agreement with the Spanish legis
lation, the municipal government requested
the assistance of the Ministry of Public
Works for the study, planning, and con
struction of the appropriate works to
increase their water supply. For this pur
pose, a "Plan 1964" was prepared which
807
 includes, among other projects, the finishing
of some collecting and conducting plants
which were already started, a salt water
desalination plant, and a purifying station
for residual water.
The object of the purifying station for
residual water, apart from the prevention
of natural contamination of the sea on the
beaches near the city, is to obtain potable
water at a very economical price. This
water will not be used as water supply for
obvious psychological reasons but will
permit trading with the possessors of„ water
presently intended for irrigation. The an
ticipated 50 per cent yield in water recov
ery in this installation will assume the
doubling of the water available from other
sources, including that of the desalting
plant. The price anticipated for the water
recovered in this plant, including operating
costs, amortization and exchange, will not
reach 0.04 $/m*. a substantial reduction of
the price for obtaining fresh water from
sea water.
The case of the Las Palmas water supply-
therefore constitutes an appropriate field
for salt water conversion, not only because
of the lack of any other alternative, but
also because of the inclusion of an eco
nomic advantage, somewhat bold, but
reasonable.
After a survey by various foreign firms
specializing in desalination techniques, the
municipal government of Las Palmas re
ceived some proposals to supply the water
needs of the city by means of dual-purpose
plants for conversion of salt water and
production of energy.
The electric power capacity of the island
is 30,000 kw, distributed mainly among
groups powered by fuel-oil or Diesel groups.
FUTURE POSSIBILITIES
As we have said above, the driest area of
the peninsula is the southeastern region
which includes the provinces of Almeria,
Murcia and Alicante. The city of Cartagena
is located on the coast of the province of
Murcia, with its port and naval base, and it
has always suffered from the water shortage
which is a characteristic of the whole
region.
Surface or underground water in Carta
gena is of poor quality and low in volume.
Early studies on methods of obtaining
drinking water fell back on the project of
tapping the Taibilla river, a tributary of
the Segura, and transporting the water over
a length of more than 200 km in order to
supply water to nearby population centers.
808
The present load curve has a night valley
in the order of 9,000 kw, while a dual plant
with an available capacity of 10,000 kw
could operate practically with full load
during the whole year.
Based on the necessity of increasing the
installed electric power capacity, which was
estimated at 10,000 kw for the next four
years, and of increasing the water supply
by 10,000 m"/day, these figures were used
in the study of a dual plant which, together
with the other projects, would permit
reaching a desirable allocation of 150 liters
per inhabitant and per day.
For this purpose, the corresponding
economic study and feasibility report was
prepared, after approval by the government
of an international call for bids for the
construction of this plant. As has been
explained above, this installation represents
the minimum necessary to cover the present
deficit situation, and it must be realized
that, after a period of three or four years,
it will be necessary to double the installa
tion. It is difficult to establish the dates
and consumptions very precisely, in view of
the fact that since the city has always had
an inadequate water supply, it is not pos
sible to estimate in any way a future
situation which will depend on the thirst
of the consumers in relation to the logical
price increase.
The project contemplates the installation
of the plant on the "El Cernícalo" beach,
about 6 km south of the city. The flash
evaporation process will be used in the
plant, since it is the most commercially
tested process to date. It is hoped that this
plant will be built and will start operating
during the first months of 1968.
The Union of the Taibilla Canals was
created for the preparation of the projects
and execution of the work; it is also in
charge of water administration. The main
canal has been supplying water regularly
to the villages and cities of this region
(Fig. 315) .
The increasing tourism in the southeast,
which offers a temperate climate with very
little rain and beautiful coastal scenery,
has been curbed by the lack of water. For
this reason, the various ministries tackled
the problem of supplying water to these
coasts, and in view of the possibilities
offered by desalination, were forced to con
sider the feasibility of a solution of this
type.
STHE
EOXHUPOF
IN MAP
YTS15.
LFIGURE
OHDIERTASTUILO.NISC
 One of the major thermal power plants
of the country, which will need to be
expanded very shortly within the next few
years, along the lines explained above, is
located at Escombreras, near Cartagena.
This has suggested the possibility of study
ing the installation of a desalting plant in
combination with the new groups which are
being built.
The first estimates lead us to assume that
a plant of 50,000 or 100,000 m'/day could
PINAL CONSIDERATION
In this report, we have only presented a
general outline of the present situation and
desalination possibilities in Spain. Our
country does not yet have sufficient experi
ence in this field to offer results of interest;
this is why this report was limited to a
quick examination of the hydrological pos
sibilities of some regions and the benefit to
be derived in applying these techniques for
the improvement of the water supply situa
tion. Within the next few years, with the
experience gained in the plants which are
being built, we hope to be able to offer
results that may be of benefit to other
countries which see in desalination a means
810
offer reasonable prices to supply water to a
great part of the touristic centers and coastal
settlements, thus alleviating the present
situation of the Taibilla Canal, and releas
ing it of obligations which could be turned
over to other villages of the interior.
The first studies have been initiated for
this purpose, and it is hoped that in the
future this project will be the principal
project to be considered.
for solving or minimizing the problem of
water shortages; however, apart from the
newly-born activity which has recently been
noted in Spain in the field of basic research,
and the particular attention paid to the
manufacturing problems of desalination
plant components by the Spanish industries,
the present so-called Spanish program (Fig.
316) may be summarized as follows:
Capacity
Plant ш'/day Prêtent ttaUa
Laniarote 2.0O0 In service
CeuU 4,000 Beine tested
Lu Palma* 10,000 Awaiting offers
Escombreras 100,000 Preliminary pla
 FIGURE 316. LOCATION OF DESALTING PLANTS
CONSTRUCTED OR IN PROJECT.

SUMMARY OF DISCUSSION
There was no discussion.

811
 Le Dessalement en Espagne
Jorge Suarez et Jose M. Pliego
La pénurie d'eau dans de nombreuses
parties du monde, due principalement à
l'augmentation extraordinaire de consom
mation, elle-mime résultant de l'améliora
tion des conditions hygiéniques, de l'indus
trialisation et de l'irrigation de grandes
superficies, a éveillé, dans presque tous les
pays, l'intérêt manifesté depuis les temps
anciens par l'humanité en ce qui concerne
la conversion de l'eau de mer en eau douce.
On peut classer l'Espagne parmi les pays
semi-arides souffrant d'une pénurie partielle
d'eau dans certaines de ses régions. Celles-ci
sont précisément celles les plus favorisées
par un climat tempéré avec un nombre
élevé d'heures solaires ce qui les rend
attrayantes au tourisme international,
source récente de devises étrangères.
Jusqu'à maintenant, le budget espagnol
n'a pas autorisé de crédits tris importants
pour les travaux de recherche, et seuls des
essais portant sur les alambics solaires et
la distillation par formation de mousse ont
été effectués. D'autre part, on a considéré
l'avantage de construire des installations
commerciales de conversion de l'eau de mer
pour l'alimentation en eau de certaines
villes. Ces installations permettront en
même temps d'acquérir une certaine expé
rience en ce qui concerne les conditions de
fonctionnement et les coûts de production,
ce qui, sans aucun doute, sera très utile
pour de nouvelles études et de nouveaux
projets.
La pluviosité en Espagne est très inégale.
La moyenne annuelle des chutes de pluie
est de 350.000 Hm" tombant de façon irré
gulière sur une surface de 500.000 Km*, ce
qui donne une moyenne de 700 mm. Les
valeurs extrêmes enregistrées au cours des
récentes années ont été de 500 mm en 1954
et 960 mm en 1960.
Cette irrégularité naturelle a été partielle
ment corrigée par des travaux de régula
tion. Plus de 300 réservoirs ont été con
struits avec des objectifs différents dont les
principaux sont: l'irrigation, l'énergie
hydro-électrique et l'approvisionnement en
eau des villes. En dehors de l'utilisation de
l'eau de surface, il existe de nombreux cas
d'utilisation d'eau souterraine principale
ment sur les côtes orientale et méridionale
de l'Espagne, dans les lies Baléares et aux
Canaries, et dans certaines régions de l'in
térieur de la péninsule.
En 1964, la production d'énergie élec
trique était de 30.000 millions de kWh ce
qui, divisé entre les 30 millions d'habitants
de l'Espagne donne une production, par
habitant, de 1.000 kWh par an. Ce chiffre
est plus faible que dans les pays plus dé
veloppés, mais il représente une augmenta
tion de 600% par rapport à 1944. Soixante-
dix pour cent de cette énergie est hydro
électrique et les 30% restant sont produit
dans des centrales thermiques utilisant le
charbon ou le fuel oil.
Néanmoins, dans le proche avenir, en
raison de l'augmentation prévue dans la
consommation d'énergie par les utilisations
industrielles et domestiques, on s'attend à
ce qu'il y ait une augmentation considé
rable dans la production thermique coïnci
dant avec la diminution de l'énergie hydro
électrique. Les centrales thermiques devront
fonctionner à une charge de base, utilisant
l'énergie hydro-électrique pour les pointes
sauf si l'année est très humide.
Les considérations ci-dessus signifient que,
dans le proche avenir, beaucoup plus de
centrales thermiques seront construites en
Espagne et seront utilisées à pleine charge
particulièrement au cours de la saison
sèche lorsque la consommation d'eau aug
mente également. Le fait qu'il existera une
demande pour l'énergie et poifr l'eau offre
des possibilités intéressantes pour la pro
duction simultanée des deux au moyen
d'installations doubles utilisant du fuel oil
ou de l'énergie nucléaire. Du point de vue
électrique, il n'y a aucun problème quant
à l'emplacement de ces centrales, car toutes
les régions du pays sont reliées entre elles
par de grandes lignes de transport. En con
séquence, on peut les établir dans les régions
qui manquent chroniquement d'eau, telles
que le sud-est de la péninsule.
Des cas spéciaux dans la situation géné
rale mentionnée ci-dessus sont constitués
par la ville espagnole de Ceuta en Afrique
du Nord, les villes d'Arrecife de Lanrarote
et Las Palmas de Gran Canaria dans les
Canaries. A ces endroits, des installations à
double usage ont dû être construites pour
la fourniture de l'eau comme de l'énergie
car les ressources hydrologiques sont
pratiquement épuisées.
D'autres cas spéciaux sont constitués par
les nombreux petits villages cAtiers ha
bités par quelques familles, généralement
d'origine humble, qui dépendent principale
ment de la pèche et qui manquent de l'eau
nécessaire pour leurs besoins hygiéniques.
C'est pourquoi on a considéré de leur
donner des moyens de pouvoir construire
de petits alambics solaires familiaux ou
communaux et un certain nombre d'essais
et d'études sont en cours avec cet objectif
en vue.
Dans quelques années, avec l'expérience
acquise dans les installations qui sont en
voie de construction, nous espérons pouvoir
offrir des résultats qui pourront être utiles
Опреснение Воды в Испании
Хорге Суарес и Хозэ М. Плиего
Испания
Недостаток воды во многих частях
земного шара, главным образом выз
ванный чрезвычайным увеличением по
требления вследствие улучшения гигие
нических условий, индустриализации
и орошения больших районов, пробу
дил почти во всех странах древний ин
терес человечества к обращению соле
ной воды в пресную.
Испания может быть причислена к
полу-засушливым областям с частичной
в некоторых ее районах нехваткой во
ды. Как-раз этим районам особенно
благоприятствует умеренный климат с
большим числом часов солнечного сия
ния, что делает их привлекательными
для международного туризма, совре
менного источника иностранной валю
ты.
Пока-что на производство исследова
ний в Испанский бюджет не были
включены заслуживающие внимания
суммы и были проведены только пробы
выпарных, работающих с помощью
солнечной энергии, аппаратов и элек
тродиализной дистилляции. С другой
à d'autres pays qui considèrent le dessale
ment comme un moyen de résoudre ou de
diminuer leur problème de pénurie d'eau.
De plus, en dehors de la fusion des acti
vités constatée dans les recherches fonda
mentales et de l'attention consacrée par
l'industrie espagnole à la fabrication de
l'équipement de dessalement d'eau, ce qu'on
pourrait appeler le programme espagnol
sur la conversion de l'eau de mer se résume
à ce qui suit:
Installation Capacité Etat de l'ex
m* par jour ploitation
Lanzarote 2.000 en service
Ceuta 4.000 en essai
Las Palmas 10.000 en attente de la
réception des
soumissions
pour la
construction
Escombreras 100.000 en avant-projet
стороны, была принята во внимание
желательность сооружения опресни
тельных установок коммерческого на
значения для снабжения водой некото
рых городов. В то же самое время эти
установки дадут возможность приоб
рести опыт, касающийся рабочих усло
вий и стоимости продукции, что, не
сомненно, будет ценным для новых
изысканий и проектов.
Выпадение осадков в Испании отли
чается большой неравномерностью. В
среднем оно составляет в год 350.000
куб. гм., неравномерно выпадающих на
площади 500.000 кв. километров, что
дает в среднем 700 мм. Крайними вели
чинами за последние годы являлись 500
мм в 1954 г. и 960 мм в 1960 г.
Эти нерегулярные явления природы
были частично исправлены регуляци
онными работами. Было построено бо
лее 300 резервуаров различных назна
чений, среди которых самыми важными
были ирригация, гидроэлектрическая
сила и городское водоснабжение. Кро
ме использования поверхностных вод
 выло много случаев каптажа грунто
вых вод, главным образом на восточ
ном и южном побережья Испании, на
Балеарских и Канарских островах и в
некоторых районах метрополии, нахо
дящихся вдали от прибрежной полосы.
Выработка в 1964 г. электрической
энергии составила 30 миллиардов кило
ватт-часов, что при 30-миллионном на
селении Испании соответствует средней
продукции на человека 1.000 киловатт-
часов в год. Эта цифра ниже, чем в
странах, достигших очень высокого
развития, но представляет собой 600%
увеличение по сравнению с 1944 г. На
гидроэлектрическую энергию приходят
ся 70%, а остальные 30% термически
генерируются на электростанциях, сжи
гающих уголь или нефтяное топливо.
Однако, вследствие ожидаемого в
близком будущем расширения потреб
ления энергии на покрытие нужд про
мышленности и населения, предвидится
значительный рост термической выра
ботки при относительном понижении
использования гидросилы. Тогда тер
мическим электроцентралям придется
нести основную нагрузку, пользуясь
гндросилой только в периоды макси
мального спроса, если не будет весьма
дождливой погоды.
Из вышеуказанных соображений сле
дует, что в скором времени в Испании
будет построено много новых терми
ческих электростанций для их исполь
зования при полной нагрузке особенно
в сухие периоды, когда тоже увеличи
вается потребление воды. Самый факт
спроса на энергию и воду открывает
интересные возможности их одновре
менного производства с помощью уста
новок двойного назначения, питаемых
нефтяным топливом или ядерной энер
гией. Выбор мест постройки этих уста
новок с точки зрения производства
электричества не создает никаких про
блем, так как вся страна соединена
большими линиями передачи. Потому
их можно будет соорудить в районах,
хронически нуждающихся в воде, как*
например юго-восток Полуострова.
На фоне общего вышеописанного
положения, испанские города Цеута в
Северной Африке и Арресифе де Лан-
814
сароте и Лас Пальмас де Гран-Канариа
на Канарских островах являются осо
быми случаями. Там пришлось постро
ить установки двойного назначения для
снабжения водой и электроэнергией,
так как местные гидрологические за
пасы были фактически исчерпаны.
К другим специальным случаям от
носятся многочисленные маленькие
прибрежные деревушки, населенные
несколькими семьями, обычно скромно
го происхождения, которые главным
образом живут рыболовством и не
имеют необходимой воды для своих
гигиенических потребностей. Поэтому
имелось в виду снабдить их средствами
для постройки небольших семейных
или общинных выпарных агрегатов, ра
ботающих с помощью солнечного из
лучения, и были проведены некоторые
опыты и исследования, относящиеся к
делу.
Приобретя опыт на строющихся уста
новках, мы надеемся через несколько
лет быть в состоянии представить ре
зультаты, которые смогут оказаться
полезными тем странам, которые видят
в опреснении способ разрешения или
уменьшения проблем, связанных с не
хваткой воды. Фактически, кроме раз
вивающейся научно-исследовательской
деятельности и последних попыток ис
панской промышленности в области
производства опреснительного обору
дования, то, что можно назвать Испан
ской Программой опреснения морской
воды, в настоящее время сводится к
следующему:
Установка Производи Стадия работы
тсяьность
Кубометров
в день
ЛАНСАРОТЕ 2.000 В эксплуата
ции
ЦЕУТА 4.000 В стадии ис
пытаний
ЛАС ПАЛЬМАС 10.000 Постройка
сдается с
торгов
ЭСКОМБРЕРАС 100.000 В стадии изу-
чения
 La Desalación en Espana
Jorge Suarez & Jose M. Pliego
España
La escasez de agua en muchas regiones
del globo debida principalmente al extraor
dinario incremento del consumo que han
ocasionado la mejoría de las condiciones
de higiene, la industrialización y la puesta
en regadía de extensas zonas, ha despertado
en casi todas las naciones el antiguo interés
de la humanidad por la conversión del
agua de mar o salobre en agua dulce.
España se puede considerar entre los
países semiáridos con escasez parcial de
agua en algunas de sus regiones, precisa
mente las más favorecidas por un clima
templado, con un número elevado de horas
de sol, que las hace apetecibles para el
turismo internacional, reciente industria de
exportación y fuente de divisas.
Los presupuestos del pafs no han permi
tido hasta la fecha invertir cantidades
apreciables en investigación, pudiéndose
citar solamente los ensayos realizados sobre
destiladores solares y destilación con espu
mantes. Por el contrario, si se ha conside
rado la conveniencia de construir plantas
convertidoras del tipo comercial para el
abastecimiento de algunas poblaciones.
Estas plantas permitirán, al mismo tiempo,
obtener experiencia sobre las condiciones
de explotación y costes de producción, que
serán de indudable valor para nuevos estu
dios y proyectos.
La hidrología en España es sumamente
irregular. La precipitación media anual es
de 350.000 Hm* distribuidos también irre
gularmente sobre una superficie de 500.000
km* lo que supone una media de 700 mm.
Los valores extremos observados en los
últimos años han side 500 mm. en 1950 y
1954 y 960 mm. en 1960.
Esta irregularidad natural ha sido en
parte corregida con numerosas obras de
regulación. Se han construido más de 300
embalses con fines diversos entre los que
destacan los regadíos, producción de energía
eléctrica y abastecimiento de poblaciones.
Aparte de esta utilización de aguas super
ficiales existen numerosos aprovechamien
tos de aguas subterráneas principalmente
en las costas del E. y S. de España, en las
Islas Baleares y Canarias, y en algunas
regiones interiores de la península.
La producción de energía eléctrica en
1964 ha sido de 30.000 millones de kwh/año,
que repartidos entre 30 millones de habi
tantes suponen una producción per cápita
de 1.000 kwh/año, cifra interior a otros
países europeos más desarrollados pero que
en el nuestro supone un 600% de incre
mento con relación a 1944. El 70% de esta
energía es de origen hidráulico y el 30%
restante de origen térmico, en centrales
alimentadas principalmente con combusti
bles fósiles, carbón o fuel-oil.
En los próximos años, debido al aumento
previsto del consumo, tanto por la indus
tria como por los usuarios domésticos, se
espera un incremento notable en la pro
ducción térmica, a medida que se irán
agotando simultáneamente las posibilidades
hidráulicas. Las centrales térmicas habrán
de trabajar entonces en la base de la curva
de carga del país cubriéndose las puntas
con energía hidráulica, - al margen de los
casos excepcionales de años muy húmedos.
Las consideraciones anteriores significan
que se construirán en España muchas más
centrales térmicas que operarán general
mente a plena carga, especialmente durante
el estiaje en que, por otra parte, aumenta
naturalmente el consumo de agua. De
hecho, esta situación de demanda tanto de
agua como de energía eléctrica ofrece pers
pectivas interesantes para la producción
simultánea mediante la instalación de plan
tas duales alimentadas por fuel-oil or ener
gía nuclear. La selección del emplazamiento
de estas centrales, desde el punto de vista
eléctrico, no ofrece ninguna dificultad al
estar prácticamente interconectado todo el
país con grandes líneas de transporte. Se
puede, por tanto, situar alguna de estas
centrales en las regiones escasas de agua
como el S.E. de la península.
Casos especiales en la situación general
esbozada lo constituyen la ciudad española
de Ceuta, en el N. de Africa y las ciudades
de Arrecife de Lanzarote y Las Palmas de
Gran Canaria, en el Archipiélago Canario,
cuyos abastecimientos han tenido que
ser resueltos independientemente con la
81.5
 construcción de plantas convertidoras duales que se están construyendo, esperamos poder
para atender a sus necesidades de agua y ofrecer resultados en los próximos años
energía, al estar prácticamente agotados sus que puedan ser de utilidad para otros
recursos hidráulicos. países que vean en la desalación un medio
Otros casos particulares lo constituyen de resolver o aminorar los problemas de
también numerosos núcleos de poblaciones su escasez de agua, toda vez que, aparte la
costeras habitados por unas pocas familias naciente actividad que últimamente se
de condición humilde que viven principal viene notanto en España en el campo de
mente de la pesca y que carecen del agua la investigación básica y la atención por
precisa para cubrir sus necesidades higié el problema de la fabricación de elementos
nicas. Es difícil abastecer a estos pueblos de plantas de desalación que demuestra la
minúsculos con obras costosas de captación industria española, lo que podríamos llamar
y conducción o con la instalación de plan programa español actual puede resumirse
tas convertidoras de pequeño tamaño, tipo así:
naval por ejemplo, por lo que se ha pen
sado en la posibilidad de facilitarles los Planta Capacidad Estado de
medios para que puedan construirse pe m'/dia realización
queños destiladores solares de tipo familiar Lanzarote 2.000 en servido
o comunal, y hacia ellos se han dirigido Ceuta 4.000 en pruebas
algunos ensayos e investigaciones. Las Palmas 10.000 en espera de ofertas
Con la experiencia ganada en las plantas Escombreras 100.000 en anteproyecto

816
 "Las Marinas"
Pilot Plant
P. Blanco, C. Gomella, and J. A. Barasoain
Spain, France, Spain
INTRODUCTION
INITIATIVE AND PURPOSE
The construction of pilot plants for the
solar conversion of salt water was initiated
in the agreement of December 30, 1964
between the Organization for Economic
Cooperation and Development (O.C.D.E.)
and the Spanish Government, to establish
in Spain an International Solar Distillation
Investigation Center; point (II) of Article
2 of the above-mentioned agreement indi
cates that the second portion of the pro
gram consists of "the building of and
experimenting with solar distillation pilot
plants".
The purpose of these pilot plants is to
investigate the behavior of solar distillers
serving a small community, carry out the
studies and experiments necessary to reduce
their manufacturing and operating costs,
and thus meet the water requirements of
certain regions whose expansion is limited
at the present time by the scarcity of
potable water.
SELECTION OF THE SITE
Las Marinas (Almeria) was selected as
the site of the first plant proposed in the
above-mentioned agreement after a visit
made in November, 1963, to the south
eastern area of the Iberian Peninsula by a
committee composed of engineers from the
National Special Energy Commission, of
Spain, and Dr. Lof, whom the O.C.D.E.
had put in charge of an investigation on
the potable water requirements of said
region.
Las Marinas, located 20 km west of Al
meria and 4 km south southwest of Roquetas
(Fig. 317) , is a small village recently built
Solar Conversion
(Spain)
by the National Colonization Institute in
an area reclaimed for cultivation which
does not have potable water. The village
has a population of about 300 people, and
is relatively near the sea in an area of
abundant brackish water. All of these cir
cumstances had an influence on its selection
as the site of the pilot plant, since this
plant would not need to be very large, and
the location would present the advantage
of possible experimentation with sea water
as well as with brackish water similar to
the water in many desert areas.
DESIGN OF THE PLANT
The execution of the agreement men
tioned above between the O.C.D.E. and the
Spanish Government was entrusted to the
National Special Energy Commission, which
was in charge of establishing the Interna
tional Solar Distillation Investigation Center.
To carry out the corresponding work, it
was deemed practical to form an Interna
tional Investigating Group comprised of a
director, two investigators and two assist
ants, who are respectively:
Professor P. Blanco, Spanish
Eng. C. Gomella, French
Dr. J. A. Barasoain, Spanish
Dr. T. Perez Santos, Spanish
Eng. B. Nowacki, French
Professor P. Blanco was named director of
the Investigating Group and of the project;
Eng. C. Gomella was named Scientific
director.
The plans for the "Las Marinas" solar
conversion pilot plant were made by this
817
 FIGURE 317. ZONE, LOCALITY, AND LOCATION OF THE
PILOT PLANT.

818
group with the cooperation of the National
Special Energy Commission, of Spain. The
land was donated by the National Coloniza
tion Institute (INC) . The plans have been
prepared and the site has been levelled.
Construction of the plant is about to begin.
TYPE OF DISTILLER ADOPTED
The problems raised by the construction
of large-size solar distillers were discussed
at the United Nations Conference on New
Sources of Energy held in Rome in August
1961. Messrs. Blanco and Barasoain took an
active part in this conference; in particular,
these problems were analyzed by the General
Chairman on solar distillation, Mr. Gomella.
After studying the literature on solar
distillation, including the documents of the
above mentioned Rome conference, the group
rejected the distillers which anticipated
energy recovery, such as multistage distillers
and separate heating and condensing
distillers.
Their reason was that the complications
and increase in the manufacturing cost in
volved in the introduction of the improve
ments, permitting certain energy recovery,
are not yet compensated by a sufficient
increase in the specific yield. In fact, how
ever interesting these improvements are
from a scientific and technical point of
view, their impact on the cost of the
potable water produced is still unfavorable.
However, even though these solutions have
been rejected in the case of the Las Ma
rinas Solar Conversion Pilot Plant, they
could be studied within the framework of
the working program of the group.
With respect to the solar distillers of the
"hothouse" type, the group was faced with
the following possibilities:
GENERAL
PRINCIPAL CHARACTERISTICS
OF THE PILOT PLANT
To provide potable water for the more
essential domestic uses of the 300 inhabit
ants of the village of Las Marinas, we
assumed an average consumption of 10
liters per capita per day, i.e., a total con
sumption of some 3 cubic meters per day.
The information available to the National
Special Energy Commission and the mem
bers of the working party, as well as their
own experience, led to the adoption of an
average daily production of 3 to 4 liters
(a) Build it with a single pond, or by
juxtaposing small prefabricated elements.
(b) Select the transparent cover, either
of plastic or of glass.
In selecting the type of still, the follow
ing goals were considered:
(1) Greatest possible use of unskilled local
labor for construction and subsequent
maintenance operations.
(2) Reduction of construction and main
tenance costs by building a single-purpose
still of the necessary size, rather than ob
taining the total surface through the joining
of small elements.
(3) Elimination of vapor formation in
the plastic a few hours after application of
any of the conventional antivapor liquids.
This vapor causes a subsequent decrease in
the output; attempts to eliminate it from
the plastic by successive applications of
the anti-fume liquid increase the main
tenance costs considerably. Condensation on
glass offers less difficulties and the water
slides rapidly toward the collecting ducts.
(4) Reduction of the canalization costs
by using the canal of Union Salinera S.A.
which connects two neighboring salt-works
(the distance from the still to the coast is
1.5 km) . During the cleaning periods, this
canal is dry, and it will then be necessary to
use brackish well water or, in case of emer
gency, the INC irrigation canal; these
abnormal cases lead us to think that the
cleaning and renewal of the pond water
should require the least possible water,
which brings us to the solution of a shallow
depth pond, which favors distillation (Saline
Water Conversion Report, 1962, Department
of Interior, U.S.A., January 1963.)
For the above reasons, it was decided to
adopt a still with a single pond of little
depth and a glass cover.
per rn! of free water surface for the present-
day distillers of the roofed or hothouse
type, in the case of simple solar distillation.
The figure of 3.5 l/m* was taken, and an
evaporating surface of 3,000 1/35 l/m" =
857.1 m! was obtained for the still, but a
surface of JO ra x M m - 900 m* was
adopted. However, the irregularity of the
parcel of land that had to be used for the
construction of the still did not permit us
to give it the form of a square plant with
thirty meters sides (Fig. 318) .
819
 NOTE ROWS OF 15 HIGH SUPPORTS AND B LOW SUPPORTS ARE
PLACED ALTERNATIVES ON THE AXES SHOWN.
THERE IS A TOTAL OF 10 ROWS OF LOW SUPPORTS AND II ROWS OF HUH SUPPORS

FIGURE 318. PLAN VIEW AND SECTIONAL VIEW OF THE

SOLAR DISTILLER.

820
 ASPHAOX SEALING JOINT

jm^*" |цгч||' lir^- p^'viii1' ЩИ* ^ Z SEALING JOINT

SECTION A - A

" BMI " TYPE SOLUTIONS

PLASTIC JOINT WfTH ASBESTOS FIBER FOR WATERPROOFING

ALUMINUM FLUME Ф TROUGH

SECTION B-B
"CINIDES" TYPE SOLUTIONS

FIGURE 319. TYPES OF FLUMES AND SEALS.

The pilot plant in question is composed ment, and electric system,

of a shallow distilling pdnd, double feed
and drain system for salt water and brack-
ish water, collectors and canalization for
distilled water and rain water, sterilization,
mineralization, reservoirs, pumping equip-
We must point out that is was deemed
expedient to simplify the construction so as
to reduce the cost by incorporating the
distilled water collecting flume into the
lower supporting beam for the glass cover,

821
instead of using an independent collecting
flume, as had been done previously (Lof,
Eibling, Edlin, Gomella, etc.) . The con
tinuity of the joints and the tightness of
this whole new system of flumes will be
obtained by putty which will also serve as
expansion joint between each two elements
of the beam, and with special white paint
which covers the bed bottom over which
the distilled water will flow; however, in
this first real application of our innovation,
it did not seem prudent to us to apply it to
all the flumes, eliminating the internal
lining of aluminium sheeting; it \will be
applied only to some of them to check on
the behavior of various types of putty and
paint. We wish to point out that this novel
method differs from the solution which is
usual in conventional solar distillers, details
of which are found in Figure 319. If it
proves to be acceptable, it could represent
an interesting simplification in construction.
With respect to the salt water feed and
draining, the dual solution indicated below
was adopted:
(1) Feeding in salt water from the sea
by the canal of Union Salinera S.A. and
draining the concentrated brine through
the canal.
(2) Feeding in brackish water originat
ing from well and draining the brine on
the parcel of land, the filtering being facil
itated by a blind well.
Emergency feeding was also planned with
DESCRIPTION OF THE ELEMENTS AND FACILITIES OF THE PLANT
SITE PREPARATION
The portion of land of parcel No. 52 of
the Fresh Water Development Zone, where
the distiller of the pilot plant was to be
built, was levelled at an elevation of 9.75 m.
It was placed at the disposal of the Na
tional Special Energy Commission of the
Supreme Counsel of Scientific Investigations,
with all foreign elements removed, by the
National Colonization Institute. The north
(Canal side) and west side of the land
were provided, in the levelled off portion,
with a draining canal having vertical walls
of 0.20 m deep by 0.40 m wide, located at
approximately 1 meter from the natural
boundaries of the land. The rest of the
levelled land, which surrounds a platform
of about 29 X 32 square meters which will
be occupied by the distiller, will comprise
a free circulation zone.
The purpose of this drainage is to rid the
distiller and circulation zone of any accu
mulation of storm water during hurricanes
or storms.
water originating from the irrigation canal
of the I.N.C., which flows along the North
boundary of the parcel of land, to prevent
lack of water from destroying the water
proof bottom of the still basin.
The reasons for adopting this solution
are as follows:
(1) The canal which connects the neigh
boring salt-works has water only during
the period March to October, which is the
production period for the salt-works; this
prevents using the canal, whose distance
from the plant is about a fourth of its
distance to the sea, as the sole feed source.
This forces us to provide a feed system for
well water, which will be brackish as is the
water of all the wells of the area.
(2) Because of the distance between the
plant and the coast (1,600 meters) and its
altitude above sea level (10 meters) , it
would be more costly to feed from and
drain off into this source than to use the
solution adopted.
It is interesting to observe that the
adopted solution, in addition to being more
economical than feeding from the coast and
draining into the sea, offers the additional
advantage of enabling us to experiment
with brackish water, which is encountered
in most arid zones, and to check the results
obtained with the use of this type of
distiller in these portions of the arid zones
which are at some distance from the coast.
FEEDING OF SALT WATER AND
BRACKISH WATER
A well will be built near the solar still
and the extraction of brackish water will
be effected by means of an electric pumping
system. The water will be sent to a tank
from which it will flow into the still bv
gravity.
Piping to the feed canal of a salt -work at
the portion which is the nearest to the solar
still will be installed. The salt water will
be extracted from the canal by an electric
pumping system and will be sent to the
tank from which it will flow into the dis
tiller by gravity.
SOLAR STILL
(a) Waterproof pond or reservoir: A layer
of sand of varied granule sizes, having a
thickness of 0.15 m. will be placed on the
previously levelled land, inside a rectangle
of about 900 ma delineated by a low wall
made of concrete blocks. This will be the
surface occupied by the pond of the still.
Side slopes having a slope of 1/1 cover the
outside of said wall. All these surfaces will
be covered by a waterproof layer formed by
a single sheet of a bituminous material
reinforced with glass fibers, forming the
interior portion of the 900 ms rectangle
which is the bottom of the still pond. The
single sheet is made by hot welding of
small sheets.
(b) Glass cover at 10°: The waterproof
pond will be covered by a glass cover form
ing the roof with an angle of inclination of
10° over the horizontal on both sides.
The glass panels are supported at their
upper and lower ends by small beams of
reinforced concrete, although at their lower
ends cross-beams resting on the above-
mentioned beams support these glass panels.
The other two sides of each glass panel will
be in contact with the same sides of the
contiguous panels, in such a manner that
one glass sheet in every consecutive three
rides over the two contiguous sheets and
overlaps each of said panels by some two
centimeters. The whole glass cover will be
calked with a heat-resistant seal, to make
it water-tight and prevent the escape of
the vapor produced.
For the waterproof joints of the lower
sides of the glass cover, we have adopted
the Cinides-type solution (Fig. 319) , instead
of the BMI-type solution adopted by the
Rattelle Memorial Institute (Special report
on "Design of a Basin-Type Solar Still",
May 19. 1964, by J. W. Bloemer, J. R.
Irwin and J. A. Eibling) , so as to prevent
the condensed water which slides over the
internal face of the glass from flowing by
capillarity over the waterproof joint or seal.
We have also adopted the CINIDES-type
solution for the waterproof seals of the
oblique sides of the glass cover, to avoid
the heat slackening of the joint and flow
by gravity between two contiguous glass
panels toward the inside of the still, leaving
a passage for the vapor toward the outside.
Although the overlap of each two consecu
tive glass panels requires a large amount of
glass, the placing of the joint is easier and
faster with this system.
The precast concrete beams which support
the glass cover rest upon supports formed
by concrete blocks placed directly over the
waterproof lining.
The beam-flumes will be covered with
a continuous sheeting of aluminium strips,
over the area to be used as flume, and their
inclination will insure the draining of the
fresh water produced toward a general
collector.
POTABLE WATER COLLECTOR
The purpose of the collector is to effect,
outside of the still, the draining by gravity
of the potable water produced. It will con
sist of a rigid piping or tube of polyvinyl
chloride having a diameter of 45 x 50 mm,
provided with the necessary ramifications
to connect the various flumes coming from
the distiller.
This connection will be effected by means
of flexible plastic tubes affixed by metallic
brackets or clamps.
The canalization, placed near one of the
longitudinal walls of the drainage canal
for rain water, will flow into a collecting
reservoir to be pumped to the storage
reservoirs.
DRINKING WATER RESERVOIR
The ideal installation should include a
reservoir for the storage of 200 ma of pota
ble water so as to insure interannual regu
lation of the distilled water and rain water
collected over the cover of the still. How
ever, in view of the high cost of such a
reservoir, together with the fact that it is
not necessary for the initial purpose of this
plant, we did not include its construction
in the plans, even though we take the
liberty of indicating its usefulness to future
users (INC) .
In the present plans, we include only
a small capacity (4 m1) collecting tank for
potable water, from which the water will
be pumped to a feed reservoir of 8 m' (4 of
2 m*) of low height which will feed a
fountain first passing through a mineral
izing tank or reservoir.
The water pumped from the collecting
reservoir to the storage reservoir or tank
will be sterilized by a device actuated by
a pump measuring the sterilizing substance.
RECOVERY OF RAIN WATER
Because of its inclination, the still glass
cover permits the recovery of rain water.
This rain water flows toward the valleys of
the roof sides formed by the glass panels of
the cover, and will be collected by a trans
versal canal which flows into a décantation
well. The canal will be semicircular and
made of asbestos cement, placed directly on
the ground of the east side of the still.
The outlet of the décantation well will
be provided with an overflow system which
will permit partial recovery of the rain
water collected. The excess will be drained
oft through an asbestos cement canalization
having a diameter of 200 mm. toward the
irrigation canal of INC which borders the
823
parcel of land at its cast boundary. If the
above mentioned 200 m* regulating reser
voir were built, this canalization would
flow into it.
STERILIZATION
Sterilization will be effected by a meas
uring pump synchronized with the opera
tion of the pumping system. The sterilizing
substance will be made by the dilution of
a solution of commercial sodium hypo
chlorite.
MINERALIZING RESERVOIR
This container of a capacity of 0.8 m*
will contain half granulated active charcoal
and crushed calcareous gravel. It will be
located at the potable water distribution
outlet of the 8 m* tank.
EMPTYING OF STILL
A single discharge equipment has been
planned, comprising a drain canalization
for concentrated water sent by a retaining
floodgate and an outlet which permits
ECONOMIC ASPECTS
CONSTRUCTION COSTS
Because of its location and other circum
stances, the Las Marinas Solar Conversion
Pilot Plant presents some additional costs
which would not usually be necessary in a
normal service solar distillation plant; these
expenses are caused by the double installa
tion for feeding sea water and brackish water,
the double discharge means for concen
trated water (brine) originating from salted
water or from brackish water, and the
construction of a well to supply the plant
with brackish water.
However, taking into account all the
installations and auxiliary constructions,
including the additional ones which we
have just mentioned and the still itself
but not the price of the land, the cost of
the Las Marinas Pilot Plant, with reference
to the area of the still, is approximately
1.000 pts/m'; 61.5 per cent of this is for the
materials and 38.5 per cent for labor includ
ing the builder's profit.
regulation of the water level inside the still.
The concentrated water originating from
sea water (brine) is discharged into the
canal of the salt-works and the brine orig
inating from brackish water is discharged
into a sewer or drain at the lower portion
of the lot.
ELECTRIC NETWORK
The electric energy needs of the plant
and its installations will be served by a
private line from the transformer supplying
the locality. An internal network will sup
ply power for the electric motors, the
exterior lighting of the plant, and the light
ing of the places of work (reservoirs, dis
charge, pump) .
FENCING
To prevent the entrance of animals
which could damage the still or its installa
tions, the lot will be closed by a fence,
which will separate it from the road which
is its eastern limit. The other boundaries
will be protected by the difference of eleva
tion of the contiguous lots.
COST OF THE WATER PRODUCED
In view of the small size of this pilot
plant, the operating and maintenance costs
had to be distributed over the small water
production of the plant. However, taking
into account the above-mentioned costs but
without counting the amortization of the
plant, it is estimated that the cost of the
potable water produced will oscillate be
tween 30 and 35 pesetas per cubic meter.
During the operating period under the
inspection of the Investigating Group, the
data necessary to determine the cost of the
potable water produced by this Pilot Plant
will be gathered, following the "standard
ized procedure for estimating cost of Saline
Water Conversion" established in March,
1956 by the Office of Saline Water of the
Lnited States of America Department of
the Interior.
This paper was submitted for publication
only.
Installation Pilote de Conversion de

L'Eau Salee Par L'Energie Solaire

a Las Marinas (Espagne)

P. Blanco, С. Gomella, et J. A. Barasoain

Espagne, Fiance, Espagne

Cet exposé indique comment l'initiative et ensembles de l'installation pilote de

a été prise et quel est le but de l'installa
tion pilote de conversion de l'eau salée par
l'énergie solaire de Las Marinas, Almería,
dont la construction doit être exécutée aux
termes d'un accord entre l'Organisation
pour la Coopération et le Développement
Economiques et le Gouvernement espagnol.
On donne des détails des solutions adop
tées en ce qui concerne le genre d'appareil
de distillation et de certaines de ses parties,
et on présente une description des éléments
900 m3 par jour, qui fournira de l'eau
potable pour utilisation domestique aux
300 habitants de Las Marinas. On fait res
sortir les différences entre cette installation
pilote et les installations normales de dis
tillation solaire, particulièrement en ce qui
concerne les rigoles collectrices et le système
de joints étanches.
Enfin, on fait quelques commentaires très
brefs sur les aspects économiques de l'instal
lation pilote.

Опытная Опреснительная Установка

«Лас Маринас», Работающая с Помощью

Солнечной Энергии (Испания)

П. Бланко, К. Гомелла и X. А. Барасоаин

Испания, Франция, Испания

Этот доклад описывает, как была за ки площадью 900 квадратных метров,

хвачена инициатива и в чем состоит
цель постройки Опытной опреснитель
ной, работающей с помощью солнеч
ной энергии, установки Лас Маринас
в Альмерии, которая будет сооружена
согласно договору между Организацией
для экономического сотрудничества и
развития и Испанским правительством.
Приведены подробности относитель
но принятых решений о типе перегон
ного аппарата и некоторых его частей,
а также дано описание составных ча
стей и оборудования Опытной установ
которая будет поставлять питьевую
воду для домашнего потребления 300
жителей Лас Маринас. Специально
подчеркнуты различия между этой
Опытной установкой и обыкновенными
дистилляционными агрегатами, работа
ющими с помощью солнечной энергии,
особенно касающиеся устройства лот
ков и изолирующих слоев.
Наконец, коротко комментируются
некоторые экономические стороны
Опытной установки.

825
 Planta Piloto de Potabilizacion Solar
de "Las Marinas"
P. Blanco, C. Cornelia y J. A. Barasoain
En el presente trabajo se indica a quien
se debe la iniciativa y cual es la finalidad
de la construcción de la Planta Piloto de
Potabilización Solar de Las Marinas (Alme
ría) que se llevara a cabo al amparo de
un acuerdo entre la Organización de
Cooperación y Desarrollo Económico y el
Gobierno español.
Se razonan las soluciones adoptadas tanto
para el tipo de destilador como para algu
nas de sus partes y se describen las carac
terísticas de los elementos e instalaciones
826
(España)
de la Planta Piloto de 900 metros cuadra
dos para facilitar agua potable para usos
domésticos a los 300 habitantes de Las
Marinas. De modo especial se ponen de
manifiesto las diferencias existentes entre
esta Planta Piloto y los destiladores solares
clásicos, principalmente en lo que se refiere
a las canaletas y al sistema de juntas de
estanqueidad.
Finalmente se hacen unas breves consi
deraciones de carácter económico en rela
ción con la Planta Piloto.
 INDEX

Page Page

A conversion processes, distillation type 275

A New Ion-Exchange Technique 69 Cooke, B. A. 219
A Pilot Plant Design Based upon a Direct Corrosion Resistance of Materials in Sea Water 549
Contact Flash Distillation Process with
Liquid-Liquid Heat Exchange 717 D
A Simple Calculation Method for the Vapor Dassu, G. 753
Reheat Process 415 Datar, D. S 193
A Survey of Electrodialysis Developments Datta, R. L 193
in the United States 389 DeHaven, C. G. 367
achievements in desalination, British 407 Delyannis. A. 627
Ahmed, S. Y 193 demoralization process, "Sirotherm" 103
Akimoto, Shinkitchi 25 desalinated water, utilization of in Japan .... 475
Aleksenko, Yu. N 499 Desalination by Liquid-Liquid Extraction 239
An Appraisal of Scale Control Methods at Desalination in Spain 799
the O.S.W. Flash Evaporator Plant in Desalination of Saline Water by
San Diego, California 139 Electrodialysis 511
An Engineering Evaluation of the Vertical desalination
Tube Falling-Film Distillation Process 337 British achievements in 407
Appraisal of Scale Control Methods at the by electrodialysis 511
O.S.W. Flash Evaporator Plant in by ion-exchange method 575
San Diego, California, An 139 by liquid-liquid extraction 239
Aspects of Two-Phase Flow and Heat Transfer development of evaporation in solar
in Distillation Type Conversion Processes 275 stills for 193
distillation
B multiple-phase ejector as a vapor
Barasoain, J. A. 819 compressor in 735
Barduhn, Allen J 641 prevention of scale formation in by
Battel le experience in solar distillation, means of seeding 539
review of 609 in Israel, a survey of 87
Batov, V. V 499 in Spain 799
Beckmann, R. B 239 membranes, for reverse osmosis 159
Blanco, P 819 plants
Bloemer, J. W. 609 low capacity nuclear 499
Bolotov, A. A. 523 reverse osmosis, design criteria for 367
Bolto, B. A 103 use of ion-exchange membranes for 561
Bona, G. 753 desalination plants, low capacity nuclear 499
Brehm, Arthur 415 Design Criteria for Reverse Osmosis
Britain, see United Kingdom Desalination Plants 367
byproduct recovery, removal of scale direct contact flash distillation process
formers with 697 with liquid-liquid heat exchange 717
C direct contact heat transfer, vapor-
compression evaporation with 181
calculation method for the vapor reheat distillation
process 415 conversion processes, aspects of two-
Carnavos, T. C 205 phase flow and heat transfer in 275
Chadov, V. N 523 desalination systems
Chemezov, V. A. 523 multiple-phase ejector as a
Chernozubov, V. B 523,539,549 vapor compressor in 735
chloride solutions, slit and point corrosion prevention of scale formation
(pitting) of stainless steel in 531 in by means of seeding 539
Cohan, Howard J 389 direct contact flash with liquid-liquid heat
concentration polarization in electrodialysis, exchange 717
some phenomena associated with 219 falling-film, vertical tube 337
condensation, dropwise 589 flash
conversion direct contact, with liquid-liquid
laboratory of the University of California 301 heat exchange 717
of sea water by evaporation 481
of water, use of freezing processes for heat and mass transfer in without
in the United States 641 metallic interfaces 57
processes, aspects of two-phase flow and multieffect/multistage flash 781
heat transfer in distillation type .... 275 multistage flash, some problems and
solar, "Las Marinas" pilot plant (Spain). 819 research in 1
Conversion of Sea Water by Evaporation 481 of sea water, scale control in 25
827
 H
, i review of . . . 609 Harper, George F. 747
in Greece 7. 627 Hashizume, Masao 475
vapor compression, operational Heat and Mass Transfer in Flash Distillation
and future aspects of 659 without Metallic Interfaces 57
vertical tube falling-film, heat exchange
engineering evaluation of 33/ intensification of in evaporator
distillation desalination plants, prevention of installations 523
scale formation in by means of seeding .... 539 liquid-liquid 717
distillation, thin film 205 heat transfer and two-phase flow in distillation
distillation type conversion processes, aspects type conversion processes, aspects of 275
of two-phase flow and heat transfer in 275 heat transfer, direct contact 181
Dropwise Condensation 589 Herbert, L S 39
Dukler. A. L 275 Hodges, Carl N 429
Dyakov, A. A. 549 Howe, Everett D 301
humidification cycle desalination,
E solar powered 429
Eibling, J. A. 609 hydrate process, Koppers 771
electrodialysis
desalination of saline water by 511 I
developments in the United States 389 Improvement in Fabrication Techniques for
operation, influence of membrane Reverse Osmosis Desalination Membranes . . 159
phenomena on 13 Influence of Membrane Phenomena on
phenomena associated with concentration Electrodialysis Operation 13
polarization in 219 Intensification of Heat Exchange in Evaporator
electrodialytic Installations 523
equipment, requirements for 461 interlaces, see metallic interfaces
water desalting, limitations of with ion-exchange
permselective membranes 461 membranes, use of 561
Elliott, LC 275 method, water desalination by 575
Ellis, W. B 239 Ion-Exchange Pretreatment 251
Engineering Evaluation of the Vertical Tube Ion-Exchange Technique, A New 69
Falling-Film Distillation Process, An 337 Irwin, J. R 609
Erb, Robert A. 589 Israel, survey of water desalination in 87
evaporation, conversion of sea water by 481
Evaporation of Sea Water in Solar Stills and J
Its Development for Desalination 193 Japan, utilization of desalinated water in 475
evaporator installations, intensification of
heat exchange in 523 K
F Keilin, B 367
Kemper, Clarence A 735
fabrication techniques for reverse osmosis Kennedy, Roger W. 389
desalination membranes, improvement in . . 159 Khoroshavin, V. D 499
falling-film distillation process, vertical tube . 337 Klimova, Z. V 561
flash distillation Klyachko, V. A. 511
direct contact with liquid-liquid Kogan, Abraham 57
heat exchange 717 Konstantinova, E. V 549
multistage/multieffect 781 Koppers Hydrate Process, The 771
without metallic interfaces, heat Koryakin, Yu. 1 499
and mass transfer in 57 Kronberger, H 493
flash evaporator plant (O.S.W.) in San Diego, Kunin, Robert 69
California, an appraisal of scale control Kurtepov, M. M 531
methods at 139 Kuznetsov, S. P 499
flash systems, methods for scale control in . . 317
Fokin, M. N 531 L
Freezing Process, On the 753 "Las Marinas" Solar Conversion Pilot Plant
Freezing Processes for Water Conversion (Spain) 819
in the United States, The 641 Laskorin, B. N 561
G Leigh, John, Jr 735
Limitations of Electrodialytic Water Desalting
Gasnikov, P. E. 499 with Permselective Membranes and the Re
Geiringer, Paul L 659 quirements for Electrodialytic Equipment,
General Review of the Work of the Sea Water The 461
Conversion Laboratory of the University liquid-liquid
of California 301 extraction, desalination by 239
Giambelli, G 753 heat exchange, direct flash distillation
Gilbert, F. W. 781 with 717
Glater, Julius 139 Loeb, S 159
Golub, S. 1 523,539 Lof, G. 0. G. 609
Gomella, C 819 Loginov, A. A. 499
Gomkale, S. D 193 Low Capacity Nuclear Desalination Plants . . . 499
Gousse, S. William, Jr 735
Greece, solar distillation in 627 M
Groh,
" J Johnv, I. E.1 429
499 McCutchan, J. W. 139,159
Mcllhenny, W. F. 251
828
 Page Page

McNeill, R 103 resistance, see corrosion resistance

Macpherson, A. S 103 reverse osmosis desalination
Mandersloot, W. G. В 461 membranes, improvement in fabrication
Manjikian, S 159 techniques for 159
Matsuda, Toshihiko ■•• 25 plants, design criteria for 367
membrane phenomena, influence of on elec- Rolfe, P. F 39
trodialysis operation 13
Messina, Phil •• 697 S
metallic interfaces, heat and mass transfer in saline water desalination by electrodialysis . . 511
flash distillation without 57 Saline Water Distillation—Scale Prevention by
Methods for Scale Control in Flash Systems . . 317 Polymer Additives 39
Minukhin, LA 523 Salutsky, Murrell L 697
Mrezhin, LS 523 Savenko, 0. D 561
Mulford, Stewart 139 Scale Control in Sea Water Distillation 25
Multieffect/Multistage Flash Distillation 781 scale control methods
Multiple-Phase Ejector as a Vapor Compressor at the 0. S. W. flash evaporator plant in
In Distillation Systems, The 735 San Diego, California 139
multistage flash distillation process, some in flash systems 317
problems and research in 1 scale formation in distillation desalination
plants, prevention of by seeding 539
N scale formers, removal of (with byproduct
Nakayama, Michio 481 recovery) 697
New Ion-Exchange Technique, A 69 scale prevention by polymer additives 39
Novikov, E. P 539 Scanlon.T. R 781
nuclear desalination plants, low capacity 499 sea water, corrosion resistance of materials in 549
sea water conversion
by evaporation 481
0 Laboratory of the University of California,
Objectives of the United Kingdom Research general review of the work of 301
and Development Program 493 sea water distillation, scale control in 25
On the Freezing Process 753 seeding, prevention of scale formation by
Operational and Future Aspects of Vapor- means of 539
Compression Distillation 659 Semenova, LS 549,561
Oreshkin, V. 1 531 Serenkov, V. 1 561
O.S.W. flash evaporator plant In San Diego, Serikbaeva, S. M 561
California, an appraisal of scale control Shatsillo, V. G 539
methods at 139 Shostak, F. T 561
Silver, R. S 1
Simple Calculation Method for the Vapor Re
P heat Process, A : 415
Pashkov, А. В 561 "Sirotherm" Demineralization Process, The . . 103
permselective membranes, limitations of elec- Sirotkin, A. P 499
trodialytic desalting with 461 Siudak, R 103
Pervov, G. G. 511 Slit and Point Corrosion (Pitting) of Stainless
phenomena Steel in Chloride Solutions at Temperatures
associated with concentration polariza up to 100°C 531
tion in electrodlalysis 219 Smagin, V. N 575
membrane, influence of on electrodialysis Smirnova, N. M 575
operation 13 Smith, Andrew С 407
Pilot Plant Design Based upon a Direct Con solar conversion
tact Flash Distillation Process with Liquid- "Las Marinas" pilot plant (Spain) 819
Liquid Heat Exchange, A 717 solar distillation
Pinder, K. L 181 Battelle experience in 609
Piperoglou, E. 627 In Greece 627
pitting, of stainless steel in chloride solutions 531 Solar Distillation—A Review of the Battelle
Pliego, José M 799 Experience 609
polarizaton, see concentration polarization Solar Distillation in Greece 627
Polushkin, К. К 499 Solar Powered Humidification Cycle Desal
polymer additives, scale prevention by 39 ination 429
Preddy, D. L 337 solar stills, evaporation of sea water in 193
pretreatment, ion-exchange 251 Soit, G. S 13
Prevention of Scale Formation in Distillation Some British Achievements in Desalination . . 407
Desalination Plants by Means of Seeding . . 539 Some Phenomena Associated with Concentra
problems and research In the multistage flash tion Polarization in Electrodialysis 219
distillation process 1 Some Problems and Research in the Multistage
Flash Distillation Process 1
Spain
R desalination in 799
Removal of Scale Formers with Byproduct "Las Marinas" pilot plant 819
Recovery 697 stainless steel, slit and point corrosion
research (pitting) of 531
and development programs of the United Sterns, U. J 39
Kingdom, objectives of 493 Suarez, Jorge 799
and problems in the multistage flash dis Survey of Electrodialysis Developments in the
tillation process 1 United States, A 389
 Page

Survey of Water Desalination In Israel 87 V, L D 511

Swinton, E. A. 103 Utilization of Desalinated Water in Japan .... 475
T V
Taniguchi, Yoshio 25 van der Heem, Peter 771
The Freezing Processes for Water Conversion vapor-compression distillation, operational
in the United States 641 and future aspects of 659
The Koppers Hydrate Process 771 Vapor-Compression Evaporation with Direct
The Limitations of Electrodialytic Water Desalt Contact Heat Transfer 181
ing with Permselective Membranes and the vapor compressor, multiple-phase ejector as 735
Requirements for Electrodialytic Equipment 461 vapor reheat process, a simple calculation
The Multiple-Phase Ejector as a Vapor Com method for 415
pressor in Distillation Systems 735 vertical tube falling-film distillation process,
The "Slrotherm" Déminéralisation Process ... 103 an engineering evaluation of 337
Thelen, Edmund 589 Vilentchuk, 1 87
Thin Film Distillation 205
Thompson, T. Lewis 429 W
Tldball, R. A 317 water conversion, use of freezing processes for 641
Tikhomlrova, N. S 561 Water Desalination by the Ion-Exchange Method 575
Tlsov, Yu. 1 561 water desalination
Ttiach, V. 1 539 in Israel 87
Two-Phase Flow and Heat Transfer in Distilla use of ion-exchange membranes for .... 561
tion Type Conversion Processes, Aspects of 275 water desalting, limitations of electrodialytic
U with permselective membranes 461
Watson, Clyde Don 717
United Kingdom, objectives of research and Weiss, D. E 103
development programs of 493 Williamson, W. R 781
United States Willis, D 103
freezing processes for water conversion in 641 Woodbury, R. E. 317
survey of electrodialysis developments in 389
University of California, general review of the Z
sea water conversion laboratory of 301 Zaostrovsky, F. P 523.539
Use of Ion-Exchange Membranes for Water De Zhukov, M. A 561
salination 561 Zhuravlev, V. К 531

ft u.s. eo ICE: 1987—0 219-432

830
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