Desalination, 63 (1987) 119-133 119

Elsevier Science Publishers B.V., Amsterdam -Printed in The Netherlands

Design of Reverse OsmosisProcess

H. OHYAl ana K. YAJIMA' and R. MIYASHITA*

1
Department of Material Science and Chemical Engineering,Yokohama National Uni-
versity,Yokohama(Japan)
2
The Institute of Japanese Union of Scientists & Engineers,Sendagaya,Shibuyaku,
Tokyo(Japan)

SUMMARY
A generalized approach to reverse osmosis process design is presented for so-
lution-membrane operating systems characterized by the membrane.parameters: hyd-
raulic permeability L_, solute oermeabilitv w 0, reflection coefficient a, solute
induced'compaction-co@fficient B , plasticjzing coefficient of solute permeabil-
ity B ; and mass transfer coeffizient k on the high pressure side of the membrane
and the properties of the solutions. Examples of reverse osmosis process design
are carried out for e-caprolactum concentration and sea-water desalination using
PEC-1000 spiral wound modules and compared with the experimental data reported -
from TORAY and 800 m3/dav reverse osmosis seawater desalination olant at Chiaa-
saki Beach by Water Reuse Promotion Center Japan.

INTRODUCTION
A generaized approach to reverse osmosis process design was presented by Ohya
and Sourirajan(ref. 1) for solution-membrane operating systems characterized by
the three dimensionless parameters y, 6, and XB, defined in terms of two membrane
parameters of transport model proposed by Kimura and Sourirajan(ref. 2), mass
transfer coefficcient k, the properties of the solutions, and the operating con-
ditions. Using this generalized approach, a method for stagewise reverse osmosis
process design was presented for separation of urea from its aqueous solutions
to renovate water in space ships along with a detailed set of illustrative cal-
culations(ref. 3). The application of the same approach for parametric studies
in single stage seawater desalination was illustrated with a set of numerical
calculations using the best cellulose acetate reverse osmosis membrane obtained
at 1968(ref. 4). And the application of the system analysis approach for two-
stage reverse osmosis seawater desalination was discussed in details using cell-
ulose acetate membrane(ref. 5)
Since then, various reverse osmosis membranes of good quality have been devel-
oped and some of them have become commercially available, and more sophisticated
transport models throgh reverse osmosis membrane have been developed. This paper
presents a method to specify reverse osmosis system considering degree of free-
dom and two examples of the applications of the system analysis approach based

OOll-9X4/87/$03.50 0 1987 Elaevier Science Publishers B.V.

120

on one of the sophisticated models(ref. 6) using composite membrane PEC-1000

which has the best quality as far as the rejection and permeation flux concern(
ref. 7) at present.

REVERSE OSMOSIS PROCESS SYSTEM SPECIFICATION

Basic Model
Figure 1 illustrates basic model of reverse osmosis module of any type of
which membrane area is S. Feed stream designated as ST1 enters in the high press
ure side of the module with flow rate FF, concentration of ith component C,(i),

temperature TF, and pressure PF. Flow rate reduces as flowing along the surface
of membrane,through which ith component permeates at flux rate J(i), and brine
or concentrate ST2 leaves the module at FB, CB(i), TB, and PB. Whole permeate
through the membrane ST3 leaves the module at F p, Cp(i), T , and P .
P P

permeate
h?JPwPl~

ST2 brine (concentrate)

k%(i) ,%aPB

Fig. 1. Basic model of reverse osmosis.

Degree of Freedom
(i) Number of variables(N,,!, When number of components is Nc, the total num-
ber of variables NV may be 3N,+lO as shown the follows:

Feed Brine Permeate Sub-total

Flow rate 3
FF FB
Concentration CF(i) CB(i) 3xN,
Temperature TF 3
TB
 121

Pressure P 3
pF pB P
Membrane area S 1

Grand total Nv = 3 x Nc + 10 (1)

(ii) Number of equations of constrain(Nrh Considering total material bal-

ance equation, material balance and flux equations for ith component, and equa-
tions of concentration constrain for feed, brine and permeate, number of equa-
tions of constrain Nr may become 2xN,+3 as shown the following:

FF = FD + F 1
P
FF'xF(i) = FD.xD(i) + Fp*xp(i) NC-l
J(i)= fi(x(i),T,P)
NC
x,(i) = 1'
x,(i) = 1
x,(i) = 1
Grand total Nr=2xNc+3 (2)

(iii) Degree of freedom(Nf& Then, the degree of freedom may be given by the

following equation

Nf = Nv - Nr = (3-N, + 10) - (Z*N, + 3) = NC + 7 (3).

Usually the folTowng 6 parameters are given, pressures of feed PF, brine Pb and
permeate Pp, temperatures of feed, brine and permeate. When the reverse osmosis
system is kept constant temperature as T, we can choose (NC + 1) parameters.
(iv) Specifications for two component system. Figure 2 shows some examles
for two component systems how to choose three of independent variables. For ex-
ample of left top, PF,PB and Pp are already given as stated above and concentra-
tion of component 1 in feed xP(l) and brine xG(1) and flow rate of brine FG are
chosen as independent variables. Then we have-to calculate flow rate of feed FF
and of permeate Fp and membrane area S. Concentration of component 1 in permeate

X,(l) can be obtained by material balance equation.

(a)
122

Fig. 2. How to give specifications in case of two components systems

CALCULATION PROCEDURE
Cross Flow Model
As shown on Figure 3, cross flow model may be assumed as a linear flow re-
verse osmosis module which is devided into many small compartments. Complete mix.
ing occurs and bulk concentration Cl can be assumed constant in each small com-
partment. On the surface of high pressure side of the membrane occurs concentra-
tion polarization of which degree is strongly dependent upon the flow condition
on the membrane or on mass transfer coefficient. The concentration at the inter-
face between the bulk solution and the membrane C2 can be calculated using mass-
transfer coefficient k and fluxes of solvent and solute of which permeation mod-
el should be specified. Calculation of membrane permeation will be continued un-
til the specification which examples are shown on Figure 2, is satisfied as
shown on Figure 4.

FF X i)
4

-, Xpli) membrane permeation

Fe,XB(i)

Fig. 3. Cross flow model

centration polarization.
and con-
Qmem
power
ane area
required

Fig. 4. Flow scheme of

calculation procedure for
computer.
 123

Basic Equations
Basic equations of membrane permeation proposed by Spiegler & Kedem(ref. 8)
are modified according to the recent findings(ref. 9,lO). Pure water permeabili-
ty of hydraulic permeability decreases with the increase of osmotic pressure on
the surface of the high pressure side of membrane as expressed by Equation (4)
in which the exponential term including Bv osmotic pressure induced compaction
coefficient is added. Solute permeabilities with some solutes behave like hydrau-
lic permeability as expressed by Equation (5), but with other solutes, solute
permeabilities increase with the increase of solute concentration on the surface
of the membrane. This means that 6, takes sometime negative value.

J, = LpOeXp(-Bva(C2))(AP-oAr) (4)

where AP = P,-P2 and AT = n(C,) - IT(C,).

J, = woeXp(-E&a(C,)).A,a + (1 - u)csJv (5)

where cs = (C2 + C3)/2 or (C2 - C3)/ln(C2/C3).

The next equation(6) expresses the effect of mass transfer coefficient k on

concentration polarization

(C2 - C )/(C - C ) = exp(J,,/ck) (6)

3 13

And

C3 = J,/J, (7)

Equating Eq.(4) with J,.in Eq.(6) after taking logarithm,

k.c*ln((C2 - C,)/(C, - C,)) = LpOexp(-Qr(C,)).(AP - OAF) ia)

Substitution of Eq.(4) and (5) into Eq.(7) gives the following equation for C3

C3 = (woexp(-Bs~(C2))*Aa)/(Lp0exp(-Bvn(C2))(AP - oAa)) + (1 - u)*c3 (9)

For a given value of Cl, both C2 and C3 can be obtained using Eq.(8) and (9).
Osmotic pressure corresponding given concentration expressed in mole fraction x
may be expressed as the following polynominal expression.
IT = a t b-x t c-x* t d-x3 (10)

For the purpose to evaluate usefulness of this design method, two examples of
calculation were carried out and compared with measured data obtained at large
reverse osmosis plants:(l) to concentrate c-caprolactum from its aqueous solution
and (2) to desalt sea water.

RECOVERY OF E-CAPROLACTUM
Toray Co. Ltd. has constructed a reverse osmosis unit using 8" PEC-1000 spiral
wound modules to recover c-caprolactum from her nylon plant at Nagoya.
124

Process flow sheet and data

The unit is composed of three banks in series, the first bank is made of 11
modules in parallel, the second of 3, and the third of single, as shown on Fig-
ure 5(ref. 11). A typical data obtained with this unit was published as the fol
lowings(ref. 11).

TABLE 1
Example of performance data of reverse osmosis unit for recovery of
e-caprolactum from its dilute aqueous solution. Inlet pressure was 40 kg/c&.

Flow rate Concentration of Amount of

e-caprolactum
Cm3/dayl Cwt% l h/WI
Feed 270 0.081 218.7
Concentrate 4.6 276.0
Permeate 26: 0.0012 3.2

Whole amount of c-caprolactum entering the unit 218.7 kg/day is less than
that leaving 279.2. Usually, accuracy of measurement of large flow rate particu.
larly waste tream is doutful. On the other hand accuracy of measurement of con-
centration is rather good. Therefore flow rate of feed used for design calcula-
tion was assumed 345 m3/day considering material balance of e-caprolactum as
6x0.046/0.00081 = 345.

trated
Lotion

High
Feed Solution Presure
RarP

4
1
Filter \

Feed Pre-
Pwm filter
Feed
Tank +@

Ceding El

Permeate

Fig. 5. Schematic flow diagram of e-caprolactum concentration using 8" PEC-1000

spiral wound modules.
 125

Dimensions of reverse osmosis module

Each R.D. module contains in one pressure vessel 4 of 8" PEC-ID00 spiral
wound element which has the following dimensions: membrane area 30 m3, length of
leaf 83 cm, width of leaf 76 cm, number of leaves 24, depth of channel O.lcm.

Membrane constants and related constants

Membrane constants have been measured with a small pieces of PEC-1000 mem-
branes by one of authors(Ohya) and his coworkers(ref.' 12) and shown as follows:
= 0.0529 [gmol/(m2MPa's)]
LPO
w- = 0.386 x lO-6 [gmol/(m2MPa.s)]
= 0.0201 Ll/MPa]
8:
= 0.0 Cl/Mid
%
0 = 1.0 c- 1
71 = 122.63 xs [Mpa], x,;mole fraction of E-caprolactum
T = 35°C
pressure at inlet = 38.71 atm
pressure drop = 0.005 at.m/m2
pressure at low pressure side = 1.0 attn.

Specification of reverse osmosis design

This case is same as case (d) on Figure 2. That is:inlet pressure PF, feed
flow rate FF, concentration of feed CF , membrane area S, pressure of permeate P
P
and pressure of concentrate P5, are given and flow rate and concentration of
permeate and concentrate Fp, Cp, F8, and CD should be calculated following to
the design procedure mentioned above. Among the four undefined variables three
variables are independent, for material balance of e-caprolactum should be sound.

Calculated results
(i) 1st bank. Total flow rate of 345 m3/day 1s devided by 11 and calculation
is carried out on every module and the results are shown on Figure 6. The con-
centrate from the 1st bank is fed to the second bank.
(ii) 2nd bank. Feed for the 2nd bank 2343.1 kg/h is devided by 3 and the
calculted results are shown on Figure 7. The concentrate from the 2nd bank is
fed to the 3rd bank.
(iii) 3rd bank. The calculated results are shown on Figure 8.

Summary of the results

The sumnary of the calculated results are shown on Figure9. The obsreved
data with the same R.O. unit at' the same operating conditions are reported as
concentrate flow rate 6.0 m3/day and concentration of E-caprolactum 4.6 wt%. The
agreement between the observed and caculted results is very good as shown on
126

6=13068 [kg&r]
CF=01x)081 [W.F]

Ff=38.71 [atmj Y--- I

s= f Fj;=1093.8[laq/hr]
120: -Cp=1866 [ppm]
w1:
I
1
pB=38.11[atm ]

-I-
FB= 21301 [kg/hr]
C8 =000487[W.F]

Fig. 6. Calculated results for one module of 1st bank. FF,CF,PF are defined. PF
is calculated as PF - 120 x 0.005.

b = 781.04 [kg/hr]
+=000487[W.F]
fj+=38.11
[atm] :
I

s=i
120 ’
WI:

&=375lbtm] i

F~=l88.28
[kgihr]
%=(I01998 [WFI

Fig. 7. Calculated results for one module of the 2nd bank. Specifications are
same as on Fig. 6.
 F+=564.84 [kg/hr]
C&O1998[W.F]

I+= 322.32 [ kgihr]

120; ‘G=l66 Ippml
[&I;
b=36.91 [atm 1 ’

t
&j= 24252 [kgk]
Qj=O.O4631[ W.F]

Fig. 8. Calculated results for the 3rd bank. Specifications are same as on Fig.6.

WHOLE PROCESS

14l32.281kglhil

0.004871Wfl O.O1998@NFI 0.04631 CW-FI

P=38.71tatml Pz38.U UrnI P=37.51 CatrriI P~36.91 Ibtml

Fig, 9. Material balance for the whole system. Changes of flow rates, concen-
trations, and pressures are shown. Digits in parentheses are number of modules
in parallel for each bank.
128

TABLE 2
Comparison of calculated results and performance data obtained with reverse os-
mosis unit for recovery of c-caprolactum from its dilute aqueous solution. See
Table 1.

Calculated Performance data

Feed Flow rate[m3/day] 345 345(corrected from
ConcentrationCppm] 810 810 270)
Concentrate Flow rate[m3/day]
Concentration[wt%] ::: i.6
Permeate Flow rate[m3/day] 339.2 339(corrected from
Concentration[ppm] 8.2 12 264)

Table 2.

SEA WATER DESALINATION

Water Reuse Promotion Center(WRPC) has constructed at their Chigasaki Labora-
tory 800 m3/day demonstration plant of reverse osmosis sea water desalination in
September 1979, and been offering this facility for reverse osmosis module manu-
facturers to test their modules. Schematic flow diagram of this plant may be
found elsewhere(ref. 13). Toyobo has been successfully operating their same 8"
cellulose triacetate hollow fiber module since then.
Toray constructed double stage R.O. system using their cellulose acetate spi-
ral wound modules, but in April 1981, has changed single stage system using
their PEC-1000 composite spiral wound module which has been proding desalted wa-
ter of very good quality since then.

Dimensions of spiral wound element for sea water desalination

Each element has the following dimensions: membrane area 32 m2, length of
leaf 79.5 cm, width of leaf 84 cm, number of leaves 24, and depth of channel 0.5
mm. These dimensions are small difference from those of R.O. element for concen-
tration of e-caprolactum. Particularly, depth of channel is halved, because well
pretreated feed is expected to be fed to this element. The length and width are
reversed.

Membrane constants and related constants

Membrane constants were measured with small pieces of PEC-1000 membrane of
which effective area was 12.7 cm2, and are shown as follows:
L 0.1 [gmol/(m2MPa.s)]
po =
w. = 0.75 x 1o-7 [gmol/(m'MPa*s)]

f3" = 0.07 [l/MPa]

8, = 0.0 [l/MPa]
 129

u =l.O [-I
= 0.0245 + 224.48 xs + 764.978 xf + 7621.47 x2, [MPa], xs; mole f';$iOn of
; = 25°C (11)

Caculated results
The high pressure pump of this plant has a capacity about 2000 m3/day at c.a.
6 MPa. The feed flow rate FF for each module is defined, if number of modules is
fixed. Then, design specifications for all cases following is the same as case
(d) of Figure 2.
(i) Control. The following conditions are chosen as a control:(l) one mod-
ule contains 6 elements in a high pressure vessel, (2) feed flow rate to one
module is 69 m3/day, (3) inlet pressure and concentration of feed are 5.46 MPa
and 3.45 wt%,respectively.
(ii) Feed flow rate. Figure 10 shows the effects of feed flow rate to each
module on concentration of permeate, permeation rate and recovery. With the in-
crease of feed flow rate from 35 m3/day to 130 m3/day, concentration of permeate
decreases from 230 mg/l to 70 mg/l, and permeation rate increases from 15 m3/day
to 40 m3/day, but pressure drop also increases. The pressure drop over each mod-
ule should be kept less than 0.03 MPa. Then feed flow rate of 70 m3/day seems a
good compromise.
(iii) Number of elements. Figure 11 shows the effects of number of elements
contained in one module on permeation rate, recovery and concentration of perm-
eate. Permeation rate and recovery increase almost linearly with the number of
elements. But module containing 8 elements does not shows the same tendency.
Flowing along a high pressure vessel , water permeates throgh the membrane and
flow velocity on the surface of membrane on the high pressure side decreases.
Therefore, concentration polarization increases and concentration of the bulk
sea water also increases, resulting decrease of permeation velocity at the last
two or three elements. Six elements in one module might be recomnended from this
point of view.
(iv) Pressure. Figure 12 shows the effects of average operating pressure on
permeation rate, recovery and concentration of permeate. Increasing the operat-
ing pressure, permeation rate and recovery increase almost linearly upto 5.5 MPa
but concentration of penneate decreases in shape of hyperbole
(v) Concentration of feed. Figure 13 shows the effects of salt concentration
of feed sea water on permeation rate, reaovery, and concentration of permeate.
With the increase of salt concentration of feed sea water, its osmotic pressure
increases as expressed by Equation (11) and hydraulic permeability decreases as
Equation (4),resulting decrease of effective pressure difference over membrane.
Hence, permeation rate and recovery decrease linearly witb the increase of con-
centration of feed sea water and concentration of permeate increases. At higher
130

concentration of 4.5 wtf, the increase of operating pressure by 0.6 MPa from
5.4 to 6.0 MPa results in small increase of recovery by 6% and in small decrease
of concentration of permeate by 18 mg/l from 183 mg/l.

Comparison with observed data

The calculated results at the control conditions are compared on the Table 3
with the observed data which were obtained at July lo,1981 208 hours after start
up of the operation when rather stable operation was attained. The agreement
between both data is quite satisfactory.

TABLE 3
Comparison of data calculated and observed. 29 modules which contained 6 elem-
ents were used in parallel.

Data observed of Run 1 at Caculated data at the

July 10,1981(208 hs after control conditions.
s art-up of PEC-1000, 800
m 5/day sea water desalina-
tion plant)

Feed
Brine Feed Brine Permeate
Temperature ["Cl 23.6 25.4 24.1 25.0
Pressure EMPal 5.46 5.32 0.1 5.46 5.33
Flow rat Lm3/day] 2001.6 1193.5 808.1 2001.6 1194.0 80%
Recovery
Copcentratioks% ’ 40.4 40:4

%a1 Cppml 33,500

solids[ppm] 18,490 $,:;i
, 108
61.5 34,500 106

ekmenk
06 C+ 3&5v,W.

Fig. 10. Effects of feed flow rate

With the increase of feed flow
rate, permeation rate increases,
and recovery and concentration of
permeate decrease.

I I
50 20 -lo
50 loo
FeeciRateperk&Module [rns/*]
 131

-4073
67
,E
a#

-302
E
._
5
pi
-202

-10

Fig. 11. Permeation rate, recovery and concentration of permeate increase with
the increase of elements.

I ’
z200
!?
d

ii
h 150t

4.5 5.0 5.5 60

P tMk1

3g. 12. With the increase of average operating pressure, permeation rate and
pecovery increase, and concentration of permeate decreases.
132

50
*? t =25”c ?=5.4 MPh

410 0

:
I -

-2

501 I L
JlO
3.0 35 4.0 4.5 5.0
+Iwt %I

Fig. 13. With the increase of salts concentration of feed sea water, concentra-
tion of permeate increases, and permeation rate and recovery decrease. The aver-
age operating pressure was 5.4 MPa.

t=2!YC,b.O~
F~69ni%kiy,elem&s=6
EC-lOOO60 -50

Fig, 14. With the increase of

salts concentration of feed sea
water, concentration of permeate
increase, and permeation rate and
recovery decrease. The average op.
erating pressure was 6.0 MPa.
 133

CONCLUSION
(I) It is shown how to choose independent variables when specifying a re-
verse osmosis system.
(2) Calculation procedure to design a reverse osmosis system of cross-flow
model is shown based on more general equations of permeations of solutes and
solvent.
(3) Calculations were carried out for E-caprolactum concentration and sea
water desalination, and comparison between the calculated results and observed
data is shown. The agreement between the both data is satisfactory.

REFERSNCES
H. Ohya and S. Sourirajan, Some general equations for reverse osmosis process
design, AIChE J.,15(6) (1969) 829-836.
S. Kimura and S. surirajan, Analysis of data in reverse osmosis with porous
cellulose acetate membrane used, ibid, 13(3) (1967) 297-503.
H. Ohya and S. Sourirajan, Reverse osmoss separation of urea in aqueous sol-
utions using porous cellulose acetate membranes, I&EC Process Design & Devel.
g(l) (1969) 131-142.
4 Idem, Some parametric studies in sea water desalination by reverse osmosis
using porous cellulose acetate membranes, Desalination, 6(2) (1969) 153-178.
5 H. Ohya, S. Kasahara and S. Sourirajan, Application of system analysis in two
stage reverse osmosis process design for sea water desalination, ibid, -16(4)
(1975) 375-393.
6 H. Ohya, K. Matsumoto, Y. Negishi, T. Osada, Y. Baba and A. Komura, Reverse
osmosis concentration of several aqueous solutions of low molecular weight
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September 21-25, 1986 Vol.111, pp. 247-250.
7 K. Kamiyam, N. Yoshioka, K. Matsui, I. Kawada and K. Nakagome, Low pressure
type composite reverse osmosis membrane module NTR-2750, Nitto Technical Re-
port, 23(l) (1885) 53-65.
8 K.S. S$egler and 0. Kedem, Thermodynamics of hyperfiltration(reverse osmosis
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), Kagaku Kogaku Ronbunshu, 8(2) (1982) 144-149.
10 H. Ohya, M. Okada, K. Okuno and Y. Negishi, Reverse osmotic concentration of
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