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C, the surface of
BPH particles have been covered with a CaO layer in aqueous media having a higher melting point than pure BPH. To investigate the effect
of this CaO layer on the calcination of BPH, the samples were fed into the batch calcinator. During the calcination process, quantities such as
the bulk density value, particle size distribution, sodium borate and calcium content of anhydrous borax have been determined as a function
of temperature. It was found that the anhydrous borax can be obtained by calcination of BPH particles covered with CaO in 50, 20 and 5 min
time intervals at a temperature range of 300, 400 and 500
C, respectively. As a result, puffed anhydrous borax of 99% purity with bulk density
of 0.082 g cm
3
and containing 0.670% Ca
2+
has been produced by this method in 5 min interval at 500
C.
2004 Elsevier B.V. All rights reserved.
Keywords: Borax pentahydrate; Anhydrous borax; Calcium oxide; Coating
1. Introduction
Borax pentahydrate (BPH) is one of the most important
commercial boron compounds containing water of crystal-
lization. The structure formula of BPH can be best repre-
sented as Na
2
B
4
O
5
(OH)
4
2.67H
2
O which means that there
are 2 mol of water in the molecular structure, remaining be-
ing real crystal water [1]. BPH is used in many areas, such as
perborate and boric acid production and detergent formula-
tions. However, its water content is not appropriate in some
applications such as the manufacture of high quality glass,
frit production ceramic and the renement of precious met-
als. Thus, BPH should be dehydrated to anhydrous borax
(BA) state.
The production methods of BA from BPH or borax dec-
ahydrate may be categorized into three main groups. These
are: (a) azeotropic distillation, (b) melting and (c) dehydra-
tion in uidized bed.
The method of azeotropic distillation is not yet suitable
for industrial purposes because of low yield and high heat
input needed. In addition, BPH cannot be converted by BA
using this method [2].
C at different parts
of rebox. The high temperature decreases the viscosity of
the molten mass, in order to produce proper uidization
conditions for ow out from the rebox. The molten borax
is highly corrosive which can only be prevented by forming
a layer of solid calcined borax on the refractory material of
the furnace, thus the melting of borax is the most critical
an the most expensive step, which cause some difculties in
operation and results in somewhat contaminated products.
Slow cooling gives crystal formation but immediate cooling
gives an amorphous glass [3]. By using this process, high
density of BA is produced, but there are many technical
difculties in the process, such as corrosion and handling
problems. The other disadvantage of this method is that the
product needs crushing, grinding and homogenization before
being used.
Production of BA without fusion is very attractive with
respect to energy consumption and corrosion. Thus, the at-
tempts have mostly been in dehydration borax pentahydrate
in a uidized bed via a stage-wise calcination [4,5]. The
main disadvantage of this process is the pufng of the par-
0255-2701/$ see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.cep.2004.03.004
2 . Sahin et al. / Chemical Engineering and Processing 44 (2005) 16
ticles during removal of water. In a uidized bed, the calci-
nation of BPH cannot exceed 300
C in
uidized bed. At temperatures higher than 300
C, the amor-
phous BA particles which soften readily adhere strongly to
each other since BPH dissolves in their water. This prob-
lem has been solved in our system by covering the particles
with a material that has a higher melting point than the -
nal agglomeration temperature. For this propose, the surface
of BPH was covered with Ca(OH)
2
layer in aqueous me-
dia. The presence of Ca(OH)
2
prevents the agglomeration of
BPH particles up to 500
C.
The degree of pufng is very high, thus the calcination was
carried out in an oven.
The only disadvantage of this method is that the ob-
tained product (BA) has a lower bulk density. Such a puffed
product, with large quantities of liquids and gas, can be
loaded onto the expanded borax. For example, organic such
as trichloroethylene, cyclohexanone and pentachlorophenol
can be loaded at very high percentages onto the puffed bo-
rax, as can non-ionic and anionic surfactants, with the prod-
uct retaining its free-owing characteristics. This renders
the puffed borax very useful in such diverse compositions
as dairy cleaners, fabric softeners and bath additives [8].
In addition, this puffed BA having large surface area can
be used for solidgas reactions. Recently, one popular appli-
Fig. 1. Schematic diagram of the experimental procedure.
cation of this BA reaction has been the production of sodium
borohydride. Sodium borohydride which is used as a hydro-
gen storage medium can also be synthesized by the reaction
of BA, with MgH
2
through ball milling at room temperature
as shown the following reaction [9]:
8MgH
2
+Na
2
B
4
O
7
+Na
2
CO
3
4NaBH
4
+ 8MgO + CO
2
The obtained anhydrous borax is very fragile, thus it can be
easily converted to powder form by grinding. This operation
increases the bulk density of BA.
2. Experiments
The calcination of BPH to BA was carried out in a batch
calcinator (thermolyne 6000 furnace) which is heated to a
predetermined calcination temperature (Fig. 1). During con-
stant temperature experiments, particles were fed into the
calcinator, which was in thermal equilibrium at the experi-
mental temperature. At a predetermined time interval, sam-
ples were withdrawn using a vacuum sampling tube. Titri-
metric method was used to determine the Na
2
B
4
O
7
content
of sample [10]. The Ca
2+
content of samples was determined
by Jenway PFP 7 model ame photometer. Bulk density of
BA was measured by a standard method [11].
The particle size of BPH used in the experiments was
chosen in the range 630 + 450 m and bulk density was
determined as 0.91 g cm
3
. Technical grade BPH obtained
from ETIHOLDING (Kirka, Turkey) was used in the ex-
periments. Original Na
2
B
4
O
7
content of samples was deter-
mined as 69.95% by titrimetric method [10].
Each series of experiments carried out with 10 g of BPH
washing 20 ml Ca(OH)
2
solution with predetermined con-
centration during 1 min. This washed BPH particles were
then dried at 65
C for 10 min.
The other series of experiments, particles covering with
different Ca(OH)
2
fed into the calcinator to investigate the
thermal decomposition behavior in the calcinator at 300,
. Sahin et al. / Chemical Engineering and Processing 44 (2005) 16 3
400, 500
C. At the end
of this kind of calcination, the conversion of BPH to BA is
found as about 99.6%. But, the BPH samples containing 2
and 4 wt.% CaO agglomerated slightly. However, agglomer-
ation was not observed at the concentration of CaO higher
than 5 wt.%. Table 1 shows the values found at the end of
this group. As can be seen from this table, the maximum
content of Ca
2+
in BA particle was found in the particle size
smaller than 315 m. The particle size of BA is expanded
about twice higher than used for BPH particles at the begin-
ning of experiment by thermal shock. The result obtained
at the end of this step shows that the agglomeration can be
prevented in presence of CaO. However, the obtained prod-
uct (BA) at the end of this kind of operation contains high
4 . Sahin et al. / Chemical Engineering and Processing 44 (2005) 16
70
75
80
85
90
95
100
0 10 20 30 40
time(min.)
%
N
a
2
B
4
O
7
50
300 C
400 C
500 C
Fig. 3. Changes of calcination time with temperature for the BPH samples containing about 2.5 wt.% Ca
2+
.
Table 2
Properties of dehydrated BPH covering with 2.5 wt.% Ca
2+
layer
Particle size (m) 300
C 400
C 500
C
% fraction Ca
2+
% (g cm
3
) % fraction Ca
2+
% (g cm
3
) % fraction Ca
2+
% (g cm
3
)
+1250 96.407 1.01 0.0552 90.998 1.00 0.0312 81.344 1.00 0.0589
+1000 8.927
+800 0.638
+630
+560
+450
+315
315 3.593 1.88 9.002 1.361 9.009 1.50
values of CaO which is not suitable for industrial applica-
tions.
In the second group of experiment, the surface of BPH
particle were covered with Ca(OH)
2
in aqueous solution.
TG analysis of the BPH both in pure state and covered with
2.46 wt.% Ca
2+
were performed under nitrogen atmosphere
at 10
C, all
Table 3
Properties of dehydrated BPH particles containing about 0.670 wt.% Ca
2+
Particle size (m) 300
C 400
C 500
C
% fraction Ca
2+
% (g cm
3
) % fraction Ca
2+
% (g cm
3
) % fraction Ca
2+
% (g cm
3
)
+1250 33.463 0.201 0.0727 61.318 0.170 0.044 28.940 0.210 0.0824
+1000 39.779 26.689 38.607
+800 18.739 5.574 22.708
+630 4.013 3.482
+560
+450
+315
315 4.006 0.467 6.419 0.498 6.263 0.471
crystal water and some structure water dehydrated quickly
caused agglomeration. Thus, the mass transfer in this step
looked as the constant rate period where moisture movement
within the solid is sufciently rapid to maintain a saturated
condition at the surface. In the case of dehydration of BPH
particles covered with Ca(OH)
2
layer to increase the mass
transfer resistance between the particles and hot carrier gas,
the calcination is mainly controlled by the Ca(OH)
2
layer.
Fig. 3 illustrates the Na
2
B
4
O
7
content of the samples
containing about 2.50 wt.% Ca
2+
taken from the batch cal-
cinator at different stages during isothermal decomposition
conducted at various temperatures. The total Na
2
B
4
O
7
con-
tent of samples increased with increasing calcination tem-
. Sahin et al. / Chemical Engineering and Processing 44 (2005) 16 5
peratures. The BA contains some CaO, hence the conver-
sion percentages of BA never attained 100% as seen from
Fig. 3. The conversion of BPH to BA takes place in two
stages namely dehydration and calcination [7]. But dehy-
dration stage cannot be observed in Fig. 3 because of rapid
dehydration of BPH. Fig. 3 illustrates that the calcination
of BPH to BA at 300
C. The Ca
2+
content, bulk density and sieve
analysis of BA obtained at the end of this group of exper-
iments are illustrated in Table 2. As can be seen from this
table, the Ca
2+
content of calcination realized at 300, 400
and 500
C is about 2.5 Ca
2+
wt.%. The chosen particle size
range of BPH before calcination was 630 + 450 m and
the particle size of almost nine to ten part of calcines was
increased to +1210 m shown in Table 2. Thus, it can be
said that pufng is more effective in cause size increment
with respect to shrinking and fragmentation of puffed parti-
cles. The operation of covering BPH particles with Ca(OH)
2
can not be attained at the temperature higher than 500
C
because of agglomeration. It is interesting to see that the
bulk density increased from 0.0317 to 0.0599 g cm
3
with
increasing the temperature from 400 to 500
C. This behav-
ior of BPH can be easily explained by increasing sintering
effect which depends on the increasing temperature. In the
light of above results, it can also be concluded that better
operation could be possible from the second group of ex-
periment by decreasing the Ca
2+
layer on the surface of
BPH particles. Thus, a third group of experiments were car-
ried out using very low Ca(OH)
2
aqueous solution to cover
the BPH particles surface. The changes of Na
2
B
4
O
7
con-
tent of samples containing about 0.60 wt.% Ca
2+
with time
in this group are given in Fig. 4 at various constant temper-
atures. The Na
2
B
4
O
7
content of the samples increases with
increasing calcination temperature. The calcination rate of
this group is higher than the previous group given in Fig. 3.
This behavior may be attributed to the fact that increas-
ing the percentages of additive caused the formation of a
70
75
80
85
90
95
100
0 10 20 30 40
time (min.)
%
N
a
2
B
4
O
7
50
300 C
400 C
500 C
Fig. 4. Effect of temperature on the calcination of BPH samples containing
about 0.67 wt.% Ca
2+
.
thick and homogenous cover on the surface of the anhy-
drous borax. The thickness of CaO layer controls the trans-
fer rate of liberated water from borax pentahydrate to air.
The sieve analysis, bulk density and Ca
2+
content of BA
obtained at the end of operation having different tempera-
Fig. 5. Microscopic photographs of borax pentahydrate: (a) pure, (b)
containing 0.67 wt.% Ca
2+
and (c) containing 2.5 wt.% Ca
2+
.
6 . Sahin et al. / Chemical Engineering and Processing 44 (2005) 16
tures are given in Table 3. As can be seen in this table, parti-
cle size shows a distribution which is attributed to the Ca
2+
content and temperature. In addition, the particles smaller
than 315 m contain twice higher Ca
2+
than all other parti-
cle sizes contained. Microscopic photographs of borax pen-
tahydrate in pure, containing 0.67 wt. and 2.5 wt.% Ca
2+
are given in Fig. 5, respectively. In pure state, the surface
of BPH particles are smooth whereas the quality of par-
ticles are decreased with increasing Ca
2+
quantity on the
surface.
4. Conclusion
In order to obtain anhydrous borax with low bulk den-
sity by calcination in batch calcinator, particular attention is
paid to cover BPH surface with Ca(OH)
2
layer. The follow-
ing conclusion can be withdrawn from the results obtained
during the calcination of covered BPH particles in a batch
calcinator:
(a) The calcination of BPH with single stage cannot be
carried out at the temperature higher than 300
C since
agglomeration is started. The calcination of BPH to BA
also takes longer at around 300
C.
(b) BPH can be transformed to BA without agglomeration
by mixing CaO with BPH in solid state at temperature
range 300500
g
v
2
i
2
(1)
In the Shepherd and Lapple [11] model, is obtained by
assuming static pressure drop given as
= 16
ab
D
2
e
(2)
In Casal and Martinez [3], is derived from the statistical
analysis on experimental data given as
= 11.3
ab
D
2
e
2
+3.33 (3)
In Dirgo [5] model, is a function of cyclone dimension
given as
= 20
ab
D
2
e
S/D
(H/D)(h/D)(B/D)
1/3
(4)
In Coker [4], is given as
= 9.47
ab
D
2
e
(5)
5. Result and discussion
5.1. Pressure drop prediction under different inlet velocity
Measurement of the cyclone pressure drop was carried out
for inlet velocity ranging from 4.62 to 14.16 m/s by Bohnet
[2], and from 5.1 to 25 m/s by Grifths and Boysan [8].
The numerical calculation was made with a ne numerical
Fig. 2. CFD surface mesh for (A) Stairmand high efciency, and (B)
Bohnet [2] cyclone.
grid as shown in Fig. 2. Several empirical correlation from
literature, Shepherd and Lapple [11], Casal and Martinez [3],
Dirgo [5] and Coker [4], were also considered to compared
experimental data and numerical solution from Fluent code.
Figs. 3 and 5 present the comparison. The three-dimension
map of static pressure of Bohnet and Stairmand cyclones is
shown in Figs. 4 and 6, respectively.
5.2. Pressure drop prediction under different
operating temperature
Measurement of the cyclone pressure drop of different op-
erating temperature was carried out for temperature ranging
from 293 to 1123 K by Bohnet [2]. The comparison between
the Bohnet experiment, empirical model and CFD prediction
is shown in Figs. 7 and 8. Fig. 9 shows the three-dimension
map of static pressure for operating temperature of 950 K.
The calculated static pressure drop of cyclone between
inlet and outlet for the different numerical model is shown
in Figs. 3, 5, 7 and 8. It is shown that good agreement of
0
500
1000
1500
2000
2500
4 6 8 10 12 14
Inlet gasvelocity (m/s)
P
r
e
s
s
u
r
e
D
r
o
p
(
P
a
)
16
Dirgo
Shepherd & Lapple
Coker
Casal & Martinez
CFD RSM
CFD RNGk-
Fig. 3. Evolution of pressure drop with inlet velocity. Comparison between
data presented by Bohnet [2], the predictions of CFD and four empirical
models (P = 1 bar, T = 293 K, D = 150 mm, geometry Bohnet [2]).
10 J. Gimbun et al. / Chemical Engineering and Processing 44 (2005) 712
Fig. 4. Evolution of pressure drop with inlet velocity. Comparison between
data presented by Grafths and Boysan [8], the predictions of CFD and
four empirical models (P = 1 bar, T = 293 K, D = 0.305 m, geometry
Stairmand high efciency.
0
500
1000
1500
2000
2500
5 10 15 20
Velocity (m/s)
P
r
e
s
s
u
r
e
D
r
o
p
(
P
a
)
25
Shepherd & Lapple
Dirgo
Coker
Casal & Martinez
CFD RSM
CFD RNG k-
Fig. 5. 2D and 3D map of static pressure of Bohnet [2] cyclone for inlet
velocity of 4.62 m/s and temperature 293 K.
Fig. 6. 3D map of static pressure of Stairmand cyclone for inlet velocity
of 20 m/s and temperature 293 K.
0
500
1000
1500
2000
2500
0 200 400 600 800 1000 1200
Temperature (K)
P
r
e
s
s
u
r
e
D
r
o
p
(
P
a
)
Dirgo
Coker
Casal & Martinez
CFD RSM
Shepherd & Lapple
CFD RNGk-
Fig. 7. Evolution of pressure drop with operating temperature. Compar-
ison between data presented by Bohnet [2], the predictions of CFD and
four empirical models (Q = 100 m
3
/h, T = 2931123 K, D = 150 mm,
geometry Bohnet [2].
0
200
400
600
800
1000
1200
1400
1600
0 200 400 600 800 1000 1200
Temperature (K)
P
r
e
s
s
u
r
e
D
r
o
p
(
P
a
)
Dirgo
Coker
Casal & Martinez
CFD RSM
Shepherd & Lapple
CFD RNGk-
Fig. 8. Evolution of pressure drop with operating temperature. Compar-
ison between data presented by Bohnet [2], the predictions of CFD and
four empirical models (Q = 80 m
3
/h, T = 2931123 K, D = 150 mm,
geometry Bohnet [2].
Fig. 9. 3D Map of static pressure of Bohnet [2] cyclone for inlet velocity
of 11.48 m/s and temperature 850 K.
J. Gimbun et al. / Chemical Engineering and Processing 44 (2005) 712 11
the CFD numerical calculation when compared with experi-
mental data, and predictions from empirical correlation. The
results show that the CFD prediction by using the Fluent
code can be used for pressure drop evaluation in cyclone
design. This low-pressure centre can be responsible for the
ow reversion and deviation of the axial velocity peak to
the wall of the vortex nder pipe as showed in Figs. 4, 6
and 9.
The Fluent code with the RSM turbulence model, predict
very well the pressure drop in cyclones and can be used in
cyclone design for any operational conditions (Figs. 3, 5,
7 and 8). In the CFD numerical calculations a very small
pressure drop deviation were observed, with less than 3%
of deviation at different inlet velocity which probably in
the same magnitude of the experimental error. The CFD
simulations with RNG k turbulence model still yield a
reasonably good prediction (Figs. 3, 5, 7 and 8) with the
deviation about 1420% of an experimental data. It consid-
erably tolerable since the RNG k model is much less on
computational time required compared to the complicated
RSM turbulence model. In all cases of the simulation the
RNG k model considerably underestimates the cyclone
pressure drop as revealed by Grifths and Boysan [8].
However under extreme temperature (>850 K) there is no
signicant difference between RNG k and RSM model
prediction.
The cyclone pressure drop can be rewritten as a func-
tion of inlet velocity head. The empirical model used for
the prediction of pressure drop is much depends on the cy-
clone operating condition. Shepheard and Lapple [11] and
Dirgo (1990) model show a good prediction on cyclone pres-
sure drop under different operational inlet velocity (Figs. 3
and 4), the prediction within 620% of the measured value.
However, Dirgos model does not take into account temper-
ature in its model: its predictions are, therefore, not reliable
under different operating temperature (Figs. 7 and 8). Under
high temperature Dirgos model considerably overestimates
the cyclone pressure drop with relative error of more than
90%.
The pressure drop decreases signicantly with rising
temperature. This effect is mainly due to the decrease of the
density and the increase of the viscosity of the gas. Accord-
ing to Figs. 7 and 8, the models of Shepheard and Lapple
give quite a good approximation of the pressure drop with
an error in the prediction of about 37%. The model of Casal
and Martinez, and Coker were under predicts the cyclone
pressure drop under different operating temperature with
relative error of 72 and 52%, respectively. Since Casal and
Martinez, and Coker models consistently underestimate the
cyclone pressure drop in all the conditions studied, they are
therefore not particularly useful for design purposes. It is
always more practical to design for a larger pressure drop
than for a smaller one. In overall, the cyclone pressure drop
is somewhat closer to Coker model for the operating tem-
perature more than 500 K and close to Shepherd and Lapple
model for the operating temperature lower than 500 K.
6. Conclusions
The CFD code FLUENT with the RSM turbulence model,
predict very well the pressure drop in cyclones and can be
used in cyclone design for any operating conditions. In the
CFD numerical calculations a very small pressure drop de-
viation were observed, with about 3% of deviation, probably
in the same magnitude of the experimental error. However
behind the accuracy of the complicated RSM model it does
require much expensive computational effort compared to
the RNG k model. CFD with RNG k turbulence model
still yield a reasonably good prediction on cyclone pressure
drop with deviation of 1418% on measured value.
The cyclone pressure drop can be rewritten as a function
of inlet velocity head. The model used for the prediction of
pressure drop depends on the cyclone operating condition.
Both Shepherd and Lapple, and Dirgo models show a good
prediction on cyclone pressure drop under different opera-
tional inlet velocity. However, Dirgos model is unable to
predict accurately the pressure drop under different oper-
ating temperature. For the various temperature conditions,
Shepherd and Lapples pressure drop model prediction is
the best. We therefore, conclude that the Shepherd and Lap-
ple model should be used for estimation of pressure drop
in cyclone design.
Acknowledgements
The authors would like to thank Dr. Tom Fraser, Fluent
India and Fluent Europe UK for their guidance and support.
The authors are grateful to the referees for their useful com-
ments.
Appendix A. Nomenclature
a cyclone inlet height (m)
b cyclone inlet width (m)
B cyclone dust outlet diameter (m)
D cyclone body diameter (m)
D
e
cyclone gas outlet diameter (m)
h cyclone cylinder height (m)
H cyclone height (m)
P cyclone pressure drop (Pa)
S cyclone gas outlet duct length (m)
v
i
inlet velocity (m/s)
Greek letters
velocity head, pressure drop coefcient (m)
g
gas density (kg/m
3
)
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Chemical Engineering and Processing 44 (2005) 1321
A pollution reduction methodology in reactor design
Qishi Chen, Xiao Feng
Department of Chemical Engineering, State Key Laboratory of Multi-Phase Flow in Power Engineering, Xian Jiaotong University, Xian 710049, China
Received 20 January 2003; received in revised form 18 March 2004; accepted 26 March 2004
Available online 18 May 2004
Abstract
An algorithm for waste and pollutants reduction in reactor design is presented in this paper. This algorithm use potential environmental
impact balance (PEI) and PEI rate-law expression to track the generated PEI throughout reaction process within a reactor; and study how
reaction conditions (temperature, pressure, concentration, etc.) and various engineering factors (heat and mass transfer, and back-mixing and
so on) affect process environmental performance. The form of PEI rate-law expression should be consistent with the method for calculating
the overall PEI of mixtures of chemicals inside reactors. The algorithm can be used as a tool to aid in designing chemical reactors with
environmentally friendliness processes. The use of the methodology is illustrated with the reaction system of allyl chloride production.
2004 Elsevier B.V. All rights reserved.
Keywords: Reactor design; Potential environmental impact; Chemical reaction engineering; Impact analysis
1. Introduction
There is currently a great deal of interest in the devel-
opment of methods that can be used to prevent or at least
reduce the generation of pollution, because it may result in
lower operating costs due to better utilization of raw mate-
rials and energy and reduced waste treatment and disposal
costs. Researches have shown that the most opportunities
of environmental impact minimization exist in the process
research and development and design stage of chemical pro-
cesses [1,2]. Waste and pollutant generation in many chemi-
cal manufacturing process can be traced back to the reaction
system, where reaction pathways that produce high yields
may also generate toxic byproducts or use environmentally
unfriendly raw materials, solvents, and catalystswhich
must be dealt with downstream at a signicant cost [3];
and the size, conguration, and composition of the reactor
are very important factors controlling the greenness of a
process [4]. Therefore, the design of new reactor is a very
important element in preventing pollution at the source.
Abbreviations: CSTR, continuous stirred-tank reactor; EIM, environ-
mental impact minimization; NP, non-products; PEI, potential environ-
mental impact; PFR, plug-ow reactor
I
in
I
out
+
I
gen
= 0 (1)
where
I
in
and
I
out
are the input and output rates of PEI,
respectively, and
I
gen
denotes the PEI generation rate inside
the processes.
I
in
=
j
m
(in)
j
k
x
kj
k
+ (2)
I
out
=
j
m
(out)
j
k
x
kj
k
+ (3)
where m
(in)
j
is the mass ow rate of input stream j, m
(out)
j
the mass ow rate of output stream j, x
kj
the mass fraction
of chemical k in stream j, and
k
the overall potential envi-
ronmental impact (PEI) of chemical k.
k
=
s
kl
(4)
where
s
kl
is the specic potential environmental impact of
chemical k for environmental impact category l, in units of
PEI/kg of chemical k. Details of the method for calculat-
ing
s
kl
appeared in reference [7]. The impact categories in-
volved in this theory fall into two general area concerning
with four categories in each area:
(1) The global atmospheric categories:
Global warming potential (GWP).
Ozone depletion potential (ODP).
Acidication and acid-rain potential (AP).
Photochemical oxidation or smog formation potential
(PCOP).
(2) The local toxicological impact categories:
Human toxicity potential by ingestion (HTPI).
Human toxicity potential by either inhalation or der-
mal exposure (HTPE).
Aquatic toxicity potential (ATP).
Terrestrial toxicity potential (TTP).
In Eq. (4),
l
is a relative weighting factor for impact type
l independent of chemical k, and represent the value that
society places on particular types of environmental impact
[8]. This factor allows Eq. (4) to be customized to specic
or local conditions. The suggested procedure is to initially
set all
l
to a value of one, and allow users to vary indi-
vidual
l
from 1 to 10 according to local needs and polices
[5,8].
3. The algorithm
In order to perform waste reduction and pollution pre-
vention in reactor design, studying the effects of reaction
conditions and engineering factors and the like on the gen-
eration of waste or pollutant is very important. However,
studying each of wastes and pollutants within reactor is
time-consuming and cost-consuming and the results may be
conicting or competing, that is to say that reducing one pol-
lutant or waste may increasing the others. In addition, this
research method does not address the impact of the pollu-
tion generated within a reactor. For example, reactor A may
produce 50 kg/h of pollutants while reactor B may produce
100 kg/h. However, the pollutants generated within reactor
A may be much more environmentally unfriendly than those
generated within reactor B. Thus, the strategies for reduc-
ing pollutants and wastes generated from reaction process
should be studied through their PEI rather than their mass
or concentrate, the results would be, then, scientic and be-
yond conicting.
Traditionally, the foundation of reactor design is the equa-
tions such as reaction rate equation, mass, energy and mo-
mentum balances as well as the model describing the uid
ow within reactors. With these equations, reactor designers
can track compositions of chemicals, pressure and tempera-
ture throughout reaction process and discover the effects of
reaction conditions as well as engineering factors on these
parameters, and then, an appropriate reactor with protable
processes can be designed. Nevertheless, this kind of design
method does not consider environmental perspective of pro-
cesses effectively.
If the PEI generated within reactors could be tracked
throughout the process, the inuence of reaction conditions
and engineering factors on the generated PEI could also
be claried, and then reactors that generate the minimum
amount of PEI would be easily obtained. The above thinking
can be implemented by using the PEI balance and the PEI
rate-law expression in reactor design. In this way, the design
method is similar to the traditional reactor design method
based on balance equation and reaction rate equation.
3.1. PEI rate-law expression
The PEI transformation rate of chemical k can be dened
as:
r
PEI,k
=
dI
k
V dt
(5)
where I
k
represents PEI of chemical k, I
k
= m
k
k
, m
k
is the mass of substance k,
k
the overall PEI per unit
mass of chemical k in units of PEI/kg, and V the reaction
volume. According to Eq. (2), the PEI transformation rate
of a reaction system r
PEI
, in units of PEI/(Ls), is:
r
PEI
=
k
r
PEI,k
=
k
r
k
k
M
k
10
3
(6)
where M
k
denotes molecular weight of chemical k in units
of g/mol, and r
k
the rate of appearance of chemical k in units
of mol/(Ls).
Q. Chen, X. Feng / Chemical Engineering and Processing 44 (2005) 1321 15
Such an expression, which shows how the rate depends on
the concentrations of reactants, is called PEI rate-lawexpres-
sion. Note, PEI rate-lawexpression should be consistent with
the method for calculating the overall PEI in Eqs. (2) and
(3), which ignore the combinational impacts that could be
associate with mixtures of chemicals which accounts for the
additional terms not included into those equations. It should
be realized that if the method for calculating the overall PEI
of mixtures in reactors improve or adopt other method, the
form of the PEI rate-law expression should be adjusted ac-
cordingly.
Obviously, r
PEI
can be expressed in terms of reaction tem-
perature and concentration or partial pressure of chemicals
and so on. Therefore, the PEI rate-law expression can be
helpful to analyze the effect of concentrations and temper-
ature on the PEI transformation rate, r
PEI
, and to study the
inuence of back-mixing on process environmental perfor-
mance. At least, the PEI rate-law expression can reveal the
factors that control the transformation rate of PEI, so as to
provide guidance for the selection of reactor type and opera-
tion conditions, and the inner structure of the reactor, which
produce desired products while creating minimum undesired
potential environmental impact.
3.2. PEI balance
Since desired products are the substance we desire and the
objective of this paper is to present a methodology of waste
reduction, that is the primary concern is reducing the impact
and the amount of the non-products, the
k
of the desired
products is not considered in PEI balance. This insures that
the user or producer is not directly penalized for producing
a chemical that has a high PEI value. Auxiliary materials
(catalyst, solvent and so on) used in reaction processes must
leave the production process completely as waste or emis-
sion [10], so the PEI of the auxiliary materials should be
considered. Raw materials that if possible shall be entirely
processed into the desired product are not as a rule com-
pletely converted into the product. The losses that arise are
the cause of generated waste and emission [10], thus their
potential environmental impact should be taken into account.
To sum up, the PEI balance of reaction system under steady
state is:
I
NP
gen
=
I
NP
out
I
NP
in
(7)
where the superscript NP represents materials except de-
sired products, that is, non-products.
I
NP
out
and
I
NP
in
are input
and output rates of PEI caused by non-products, and
I
NP
gen
the rate at which impact is generated in a reactor.
For a differential ow reactor, dV, we write a PEI balance
equation over the reactor:
d
I
gen
= r
PEI
dV (8)
With PEI balance Eq. (7), combining with other equations,
designers can reveal how PEI change with reaction time or
axial and radial direction inside reactors, i.e. can track the
changing of PEI throughout reactors; using Eq. (8) combin-
ing with other rate equations, the inuence of operation pa-
rameters such as temperature, concentration, pressure and
reaction time, etc. on environmental metrics of a chemical
process could be analyzed facilely, and then, reactors gen-
erating a minimum of PEI could be designed easily.
4. Case study
In this case study, we use the environmental impact indices
below, which can be derived from Eq. (1), to characterize
environmental performance of reaction processes [7,8]:
(1) Potential environmental impact generation rate by non-
products
I
NP
gen
.
(2) Specic potential environmental impact due to non-
products
PEI
.
PEI
=
I
NP
gen
p
p
p
(9)
where p
p
is the mass ow rate of product p, and
PEI
has
units of potential environmental impact per mass of prod-
ucts. Obviously, the smaller the values of
I
NP
gen
and
PEI
,
the more environmental friendly the process, and all others
factors such as economics being equal, the more desirable.
I
NP
gen
would be useful in comparing different designs on an
absolute basis, while
PEI
would be useful in comparing
different designs independently of plant size [8].
These indices characterize some aspects of the genera-
tion of PEI within a reaction process. They are very useful
in addressing questions related to the ability of the reactor
to produce desired products while creating a minimum of
undesired potential environmental impact.
To illustrate the use of the algorithm, a case of allyl chlo-
ride manufacturing was used. Allyl chloride is manufactured
by means of non-catalytic chlorination of propylene. Con-
sider the following reaction system.
The principle reaction is:
Cl
2
+ CH
2
=CHCH
3
CH
2
=CHCH
2
Cl + HCl (10)
The main secondary reaction is further chlorination of allyl
chloride to 1,3-dichloropropene:
Cl
2
+CH
2
=CHCH
2
Cl ClCH=CHCH
2
Cl +HCl (11)
Another important side-reaction is the additive chlorination
of propene to 1,2-dichloropropane:
Cl
2
+ CH
2
=CHCH
3
CH
2
ClCHClCH
3
(12)
This reaction system is a kind of complex van de vusse
reaction, a typical reaction process involving consecutive
and parallel reactions. It is, therefore, sufciently complex
to illustrate the algorithm. Due to the limit to the space of
the article, we only select temperature, concentration and
back-mixing to be the object of research to illustrate the use
of the algorithm.
16 Q. Chen, X. Feng / Chemical Engineering and Processing 44 (2005) 1321
The following calculations and curves drawing can be ac-
complished by mathematical software such as Mathcad2000
or Matlab.
4.1. Preconditions
The kinetics of the reaction system [11] are:
r
1
= k
1
C
A
C
B
(13)
r
2
= k
2
C
A
C
C
(14)
r
3
= k
3
C
A
C
B
(15)
where r
1
, r
2
, and r
3
represent the rates of the reactions
in reaction Eqs. (10)(12), respectively, expressed in
terms of mol/(Ls), and k
1
= 1.5 10
6
e
66271/RT
, k
2
=
4.4 10
8
e
99410/RT
and k
3
= 100 e
33140/RT
. Letters AF
represent Cl
2
, propylene, allyl chloride, hydrogen chloride,
1,3-dichloropropene and 1,2-dichloropropane, respectively.
Since the purpose of this case study is only to illustrate
the use of PEI balance and PEI rate-law expression, not
a practical reactor design, we might as well suppose the
reaction process is isovolumetric.
For all cases in this case study, the inlet concentrations
of all chemicals are C
A,0
= C
B,0
= 0.024 mol/L, C
C,0
=
C
D,0
= C
E,0
= C
F,0
= 0 mol/L. The volumetric ow rate
of the reaction feed at the reactor inlet is v
0
= 325 L/s.
The specic potential environmental impact values for
each impact category for the chemicals involved in the pro-
cess are shown in Table 1. Details of the method for calcu-
lating these data appear in reference [7]. Using these data,
the overall PEI of each chemical can be obtained according
to Eq. (4).
4.2. Mathematical models of ideal reactors
4.2.1. Plug-ow reactors (PFR)
The differential mass balances of PFR reactors are:
v
0
dC
A
= r
A
dV (16)
v
0
dC
B
= r
B
dV (17)
v
0
dC
C
= r
C
dV (18)
where r
A
= r
1
+r
2
+r
3
, r
B
= r
1
+r
3
, and r
C
= r
1
r
2
.
r
A
, r
B
and r
C
are the rate of appearance of A, B and C,
Table 1
The specic potential environmental impact values for each category for the chemicals used in this case study [9]
Compound HTPI HTPE ATP TTP GWP PCOP AP
A 0 5.4 10
4
22 0 0 0 0
B 0 0 3.1 10
2
0 0 2.1 0
C 0.51 5.4 10
4
0.10 0.51 0 0 0
D 0.78 2.3 10
4
4.6 10
4
0.78 0 0 0.86
E 1.1 0 0.014 1.1 0 0 0
F 0.61 0 0.0059 0.61 0 0 0
Values are in PEI/kg.
respectively.The differential PEI balance of PFR reactors
is:
d
I
gen
= r
PEI
dV (19)
Dividing Eq. (18) by Eq. (17), then integrate, we obtain:
(C
C
)
PFR
=
b
a 1
(C
B
C
1a
B,0
C
a
B
),
a =
k
2
k
1
+ k
3
, b =
k
1
k
1
+ k
3
(20)
Dividing Eq. (19) by Eq. (17), and then integrate this, we
obtain:
(
I
gen
)
PFR
= v
0
C
B
C
B,0
r
PEI
r
B
dC
B
(21)
4.2.2. Continuous stirred-tank reactors (CSTR)
For CSTR reactors, the mass and PEI balances are:
v
0
C
C
= r
C
V (22)
v
0
(C
B,0
C
B
) = r
B
V (23)
I
gen
= r
PEI
V (24)
From Eqs. (23) and (24), we obtain:
I
gen
=
r
PEI
r
B
(C
B
C
B,0
)v
0
(25)
From Eqs. (22) and (23), we obtain:
r
C
r
B
CSTR
=
C
C
C
B
C
B,0
= a
C
C
C
B
b
Solving this equation, we can get:
(C
C
)
CSTR
=
bC
B
(C
B,0
C
B
)
a(C
B,0
C
B
) + C
B
(26)
4.3. The effect of back-mixing on environmental
performance
It is well known that PFR represents reactors without
back-mixing, CSTR represents reactors with the maximum
back-mixing, we can therefore study effect of back-mixing
on process environmental aspect by studying these two kinds
of reactor.
Q. Chen, X. Feng / Chemical Engineering and Processing 44 (2005) 1321 17
4.3.1. The effect on
I
gen
4.3.1.1.
l
= 1. When
l
= 1, namely, the importance of
the above eight environmental impact categories is deemed
the same, and the PEI of each non-product is considered,
the PEI rate-law expression due to non-products is:
r
PEI
= 1.6k
1
C
A
C
B
1.5k
3
C
A
C
B
1.2k
2
C
A
C
C
(27)
r
PEI
has units of PEI/(Ls). The value of r
PEI
is negative be-
cause the overall PEI of the reactant A is far greater than that
of each reaction products, in addition, the PEI of product C
is not considered. Suppose reaction temperature T = 530 K,
and at the outlet of reactor, C
B,out
= 0.007 mol/L. Substi-
tute Eqs. (20) and (26) into r
PEI
/r
B
, respectively, and then
graph them in Fig. 1, respectively.
r
PEI
r
B
=
1.6k
1
+ 1.5k
3
+ 1.2k
2
(C
C
/C
B
)
k
1
+ k
3
(28)
According to Eq. (25),
I
gen
of CSTR is:
I
gen
= [A
ABCD
+ 1.5(0.024 0.007)]v
0
where A
ABCD
is the area of rectangle ABCD in Fig. 1. Ac-
cording to Eq. (21),
I
gen
of PFR is:
I
gen
=
A
A
BCD
+ 1.5(0.024 0.007)
v
0
where A
A
BCD
is the area of curved trapezoid A
BCD
(the
shaded region) in Fig. 1. Obviously, when the outlet concen-
tration C
B,out
is identical for both reactors, A
ABCD
is greater
than A
A
BCD
, thus, lower
I
gen
will be achieved by using
CSTR. The calculation results show that, when C
B,out
=
0.007 mol/L, and v
0
= 325 L/s,
I
gen
of CSTR is 3.7
10
4
PEI/h, and
I
gen
of PFR is 3.310
4
PEI/h. Apparently,
I
gen
of CSTR is about 12% lower than that of PFR.
Fig. 2. Curves of r
PEI
/r
B
vs. C
B
of PFR ignoring the overall PEI of A. r
PEI
/r
B
in units of PEI/mol. The numbers 17 denote the reaction temperatures
of 450, 470, 490, 500, 510, 520 and 530 K, respectively.
Fig. 1. Curves of r
PEI
/r
B
vs. C
B
, r
PEI
/r
B
in units of PEI/mol. The solid
curve is for PFR, the dashed for CSTR.
4.3.1.2. Not considering PEI of A. To illustrate the use of
the algorithm effectively, suppose
A
= 0 PEI/kg, and the
weighting factor for each impact type is likewise 1, and the
PEI of each non-product except Cl
2
is also considered. Note
that this case is probably impractical in real manufacturing
processes. The PEI rate-law expression, r
PEI
, in units of
PEI/(Ls), is:
r
PEI
=1.1 10
3
k
1
C
A
C
B
+ 0.049k
3
C
A
C
B
+0.33k
2
C
A
C
C
(29)
r
PEI
r
B
=
1.1 10
3
k
1
0.049k
3
0.33k
2
(C
C
/C
B
)
k
1
+ k
3
(30)
Using the same method as mentioned previously, we can
obtain the curves describing the changing of r
PEI
/r
B
of
PFR and CSTR with C
B
at various reaction temperature, as
shown in Figs. 2 and 3, respectively.
According to Eq. (21), if the inlet and outlet concentration
of B are 0.024 and 0.007 mol/L, respectively,
I
gen
of PFR
equals the area of the region below the curves in the range
of C
B
= 0.0070.024 mol/L in Fig. 2 multiplied by v
0
. For
example, when reaction temperature T = 450 K,
I
gen
of
18 Q. Chen, X. Feng / Chemical Engineering and Processing 44 (2005) 1321
Fig. 3. Curves of r
PEI
/r
B
vs. C
B
of CSTR ignoring the overall PEI of A. r
PEI
/r
B
in units of PEI/mol. The numbers 17 denote the reaction temperatures
of 450, 470, 490, 500, 510, 520 and 530 K, respectively.
PFR equals the area of the shaded region multiplied by v
0
.
From Eq. (25),
I
gen
of CSTR is the product of v
0
and the
area of the corresponding rectangle in Fig. 3. For example,
when reaction temperature is 450 K,
I
gen
of CSTR equals
the area of the rectangle in Fig. 3 multiplied by v
0
. In such
case, the value of
I
gen
is positive number. Comparing Fig. 2
with Fig. 3, it can be found that lower
I
gen
will be obtained if
we adopt PFR and lower reaction temperature. For example,
when reaction temperature is 500 K, and v
0
is 325 L/s,
I
gen
of PFR is 4.8 10
1
PEI/h, while for CSTR,
I
gen
= 1.1
10
3
PEI/h, which is 2.3 times that of PFR.
4.3.2. The effect on
PEI
From Eqs. (9), (21) and (25), we obtain the formulas for
calculating
PEI
. Suppose v
0
is 325 L/s, then for PFR:
PEI
=
I
gen
v
0
C
C,out
M
C
10
3
=
13.0
C
C,out
C
B
C
B,0
r
PEI
r
B
dC
B
(31)
for CSTR:
PEI
=
I
gen
v
0
C
C,out
M
C
10
3
=
13.0
C
C,out
r
PEI
r
B
(C
B
C
B,0
)
(32)
where C
C,out
is the outlet concentration of C.
According to Eqs. (31) and (32), using the curves about
r
PEI
/r
B
versus C
B
and corresponding area, the superior-
ity in environmental index
PEI
about PFR and CSTR
can be discovered. When
l
= 1, the outlet concentration
C
C,out
= 0.011 mol/L and reaction temperature T = 500 K,
using CSTR will obtain lower
PEI
than using PFR. In
this case, for CSTR,
PEI
= 31 PEI/kg; for PFR,
PEI
=
26 PEI/kg. Nevertheless, if not considering
A
, for the
same C
C,out
and T, using PFR will obtain lower
PEI
than using CSTR, for PFR,
PEI
= 0.30 PEI/kg, while for
CSTR,
PEI
= 0.80 PEI/kg, which is 2.6 times that of PFR.
4.4. The effect of temperature on environmental
performance
4.4.1. The effect on
I
gen
When
l
= 1, from Eq. (27), it can be seen easily that the
value of r
PEI
decreases (its absolute value increase) as the
reaction temperature rises, that is,
I
gen
can be lowered by
increasing reaction temperature. For example, when reaction
temperature increases from 500 to 600 K, and the outlet
concentration C
B,out
= 0.007 mol/K, and v
0
is also 325 L/s,
I
gen
of PFR and CSTR would decrease from 3.210
4
and
3.510
4
to 3.710
4
and 4.210
4
PEI/h, respectively.
The effect of reaction temperature on
I
gen
can also be found
from Figs. 2 and 3.
When not considering the PEI of Cl
2
, from the PEI
rate-law expression, expressed in Eq. (29), we can nd that
in the initial stage of the reaction, the determining part
in the right side of Eq. (29) is 1.1 10
3
k
1
C
A
C
B
+
0.049k
3
C
A
C
B
, due to the concentration of C is very low
while the concentrations of A and B are relatively high.
Comparing the magnitudes of the two activation energies
in the two terms, we conclude that the value of this part
decreases as the reaction temperature increases. Thus, in
the early stage of this reaction process, to lower the value
of r
PEI
, the reactor should operate at relatively high tem-
perature. As the reaction proceeds, the concentration of C
is increasing while C
A
and C
B
is decreasing, so that the
inuences of the third term, 0.33k
2
C
A
C
C
, is becoming sig-
nicant. Since the magnitude of activation energy in this
term is the maximum, operating at relatively low temper-
ature would result in a relatively low value of r
PEI
in this
stage. Accordingly, for the reaction system in this case, a
PFR operating at higher temperature rst and then lower
temperature must generate lower value of
I
gen
than that sim-
ply operating at a corresponding uniform temperature. The
Q. Chen, X. Feng / Chemical Engineering and Processing 44 (2005) 1321 19
curves in different temperature in Fig. 2 intersect each other,
this fact also indicate this result. For example, when the inlet
and outlet concentrations of B are 0.024 and 0.007 mol/L,
respectively, and v
0
is 325 L/s, for PFR operating at reaction
temperature of 450K,
I
gen
= 3.9 10
1
PEI/h, and for PFR
at 530 K,
I
gen
= 6.7 10
1
PEI/h. While for a two-stage
PFR, in which the rst stage operates at 530 K, and the
second stage operates at 450 K, the inlet concentration of B
of the second stage is 0.018 mol/L,
I
gen
= 3.4 10
1
PEI/h.
Obviously, it is 13% lower than that of the PFR simply
operating at reaction temperature of 450 K, and 49% lower
than that of the PFR simply operating at 530 K.
4.4.2. The effect on
PEI
Known from Eqs. (31) and (32), r
PEI
/r
B
can be used to
study the effect of the reaction temperature. When
l
= 1,
it is not difcult to nd that increasing reaction temperature
would decrease the values of r
PEI
/r
B
, accordingly the value
of
PEI
also decreases. For example, for CSTR operating at
500 K, if its outlet concentration C
C,out
= 0.011 mol/L, and
v
0
is 325 L/s, the value of
PEI
is 31 PEI/kg, while for
CSTR operating at 530 K and with the same C
C,out
, the value
of
PEI
is 36 PEI/kg, that is, this CSTR reduced the value
of
PEI
by 16%. Similar to this example, for the case of not
considering the potential environmental impact of Cl
2
, one
can also conclude the effect of temperature on
PEI
.
4.5. The effect of concentration on environmental
performance
We here only study the effect of concentration on
PEI
.
Similar to previous method in Section 4.4.2, one can also use
r
PEI
/r
B
to study the effect of concentration. From Eqs. (31)
and (32), it can be found that for a particular outlet concen-
tration of C the value of
PEI
would be decreased by in-
creasing the value of r
PEI
/r
B
. When
l
= 1, from Eq. (28),
the value of r
PEI
/r
B
can be increased by augmenting C
C
and
decreasing C
B
within a reactor. Since C is a product whereas
B is a reactant, using CSTR will lead to higher C
C
and lower
C
B
within a reactor than using PFR. Therefore, in this case,
using CSTR would result in lower value of
PEI
than using
PFR operating at the same reaction conditions. When not
considering the potential environmental impact of Cl
2
, from
Eq. (30), decreasing C
C
and increasing C
B
within a reactor
will increase the value of r
PEI
/r
B
, accordingly, using PFR
would result in lower
PEI
than using CSTR. These results
are also concluded in Section 4.3.2.
5. Discussion
In the case study, the indexes involved are
I
gen
and
PEI
.
However, these two indexes only express the situation of
PEI generation within processes. The environmental perfor-
mance of a process also relates to its emission of PEI. There-
fore, in the WAR algorithm, the output rate of PEI,
I
out
, and
the total PEI per mass of product streams leaving the system,
I
out
, are another category of indices to characterize some
aspects of emission of PEI from a manufacturing process.
According to Eq. (1):
I
out
=
I
in
+
I
gen
(33)
I
out
is obtained by dividing
I
out
by the output of products to
give:
I
out
=
I
out
p
p
=
I
in
+
I
gen
p
p
(34)
Substituting Eq. (9) into Eq. (34), we obtain:
I
out
=
I
in
p
p
+
PEI
(35)
For the case study, it is not difcult to obtain that
I
in
=
4.6 10
4
PEI/h, i.e.
I
in
is a constant. Therefore, when the
feed condition of a reaction process is xed, back-mixing
and reaction temperature affect
I
gen
and
I
out
in the same
way. Since
p
p = v
0
C
C,out
M
C
10
3
, it is not difcult
to nd that, when the feed condition and C
C,out
are spec-
ied, back-mixing and reaction temperature inuence
I
out
and
PEI
in the same way, too.
Thus, in Section 4.3, when
l
= 1 and the reaction pro-
cess is operated in the specied conditions, the results that
I
gen
and
PEI
of CSTR are less than those of PFR indicate
that using CSTR can obtain lower
I
out
and
I
out
than us-
ing PFR. That means at the given conditions, back-mixing
make the emission of potential environmental impact de-
crease. By contrast, when not considering the PEI of A, the
results are converse, i.e. using PFR would gain lower PEI
generation rate than using CSTR; and the value of
PEI
of
CSTR that operate at reaction temperature 500 K and out-
let concentration C
C,out
= 0.011 mol/L is 2.6 times that of
PFR. The results indicate that at the given reaction condi-
tions, back-mixing will increase the emission of potential
environmental impact of the reaction processes, accordingly,
reactor designers should try to avoid it in such case.
In Section 4.4, when
l
= 1, the results show that a higher
reaction temperature is favorable for the decrease of
I
gen
and
PEI
in the giving conditions. Therefore, increasing the
reaction temperature will lead to the decrease of
I
out
and
I
out
. When not considering the PEI of Cl
2
, PFR operating
at a high temperature in the rst section and low tempera-
ture in the remainder section can result in lower generation
and emission of PEI than that operating at a corresponding
uniform temperature.
To study the effects of concentration on environmental
performance of reaction processes, two analyses are intro-
duced in Section 4.5. The results show that when
l
= 1,
operating at relatively low concentration of B and high
concentration of C is favorable for decreasing the poten-
tial environmental impact created in manufacturing a unit
mass of the product C. This also is true for total PEI leav-
ing the system per mass of product streams according to
20 Q. Chen, X. Feng / Chemical Engineering and Processing 44 (2005) 1321
the relations about these two categories of indexes. By
contrast, when neglecting the PEI of Cl
2
, the results are
converse.
In the cases study, we have only studied the effects of
back-mixing on the environmental performance. Whereas
the phenomena of back-mixing is only one of engineering
factors, which still involve pre-mixing, heat and mass trans-
fer, thermostability and so on. However, the effects of those
engineering factors not involved in the case study on envi-
ronmental performance can also be simulated and therefore
well studied through a combination of reactor mathematical
model, which relates to corresponding engineering factors,
with PEI balances. As for the effects of other reaction con-
ditions not involved in the case study, such as space time,
pressure, compositions of feeds and so on, which may af-
fect the environmental performance of reaction processes
signicantly in some cases, can also be studied with the
help of corresponding PEI balances and the PEI rate-law
expressions, because we can ultimately simulate the change
of the environmental indexes with these reaction conditions
through PEI balance and PEI rate-law expression.
The reaction system involved in the case studied is a kind
of relatively complex van de vusse reaction, nevertheless the
reaction system in real manufacturing process may involve
more reaction types and, therefore, is more complex than
that one. One can, however, simulate the change of envi-
ronmental indexes within a reactor by combining traditional
reactor mathematical model with the PEI balance, and may
also discover the effects of reaction conditions and engineer-
ing factors on environmental performance by PEI rate-law
expression and/or combinations it with other reaction rate
equations as well as other related equations in reactor math-
ematical models.
Note that assuming
l
= 1 and not considering the PEI of
Cl
2
are just for illustrating the algorithm, these assumptions
may be inappropriate for a real reactor design. Other users of
this methodology may choose to weight effects differently
to reect local needs and polices where the plants locate [8].
In the case study, the quantitative environmental impact
assessment and the PEI indexes are cited from the WAR al-
gorithm, it is worth noting that, however, quantitative impact
assessment and environmental indexes are likely to improve
with time, and that these improvements can be incorporate
Appendix A. Nomenclature
AF chlorine, propylene, allyl chloride, hydrogen chloride, 1,3-dichloropropene and
1,2-dichloropropane, respectively
C
A
, C
B
, etc. concentration of chemicals A, B, etc. (mol/L)
C
A,0
, C
B,0
, etc. initial concentration of chemicals A, B, etc. (mol/L)
C
B,out
, C
C,out
, etc. outlet concentration of chemicals B and C, etc. (mol/L)
dV, dC, d
I
gen
differential V, C and
I
gen
I
gen
potential environmental impact generation rate (PEI/h)
I
NP
gen
potential environmental impact generation rate of non-products (PEI/h)
into this methodology as they become available. It is suggest
that either the WAR algorithms assessment method and the
PEI indexes, another similar method and indexes, or even a
more sophisticated and comprehensive method and indexes
be used to this pollution reduction methodology.
In the case study, the calculations of the impact indexes
should be accurate to no more than one signicant gure
[12]. But two signicant gures are used in order to allow
readers to reproduce the calculations if necessary. It is also
worth noting that, even being accurate to one signicant
gure, one can still discern signicant differences in the
index between different cases.
6. Conclusions
To perform pollution prevention in the process of reac-
tor design, studying the effects of reaction conditions such
as temperature, pressure and concentration as well as vari-
ous engineering factors on environmental performance of a
reaction process is very important. In this paper, potential
environmental impact balance and PEI rate-law expression
are proposed as a tool to be used to carry out this work. The
form of PEI rate-law expression should be consistent with
the method for calculating the overall PEI of mixtures of
chemicals inside reactors. The effectiveness of the method
has been demonstrated through the reaction of allyl chlo-
ride production. From the processes of the analyses in the
case study, analyzing with PEI balance and PEI rate-law ex-
pression combining with other corresponding equations and
some mathematic knowledge can give important insights
into how reaction conditions as well as engineering factors
affect the environmental performance of reaction processes.
This kind of study is one of the bases for developing chem-
ical reactors with environmental benign processes.
Acknowledgements
Financial support provided by the National Natural Sci-
ence Foundation of China under Grant No. 20176405 and
the Major State Basic Research Development Program un-
der Grant No. G2000026307 is gratefully acknowledged.
Q. Chen, X. Feng / Chemical Engineering and Processing 44 (2005) 1321 21
I
in
potential environmental impact input rate (PEI/h)
I
NP
in
potential environmental impact input rate of non-products (PEI/h)
I
k
potential environmental impact of chemical k (PEI)
I
out
potential environmental impact output rate (PEI/h)
I
NP
out
potential environmental impact output rate of non-products (PEI/h)
m
(in)
j
mass ow rate of stream j into a process (kg/h)
m
(out)
j
mass ow rate of stream j out of a process (kg/h)
m
k
mass of chemical k
m
k,0
mass of chemical k at initial state of reaction
m
k, out
mass of chemical k at reactor exit or at the moment of reaction termination
m
p
mass ow rate of desired product p (kg/h)
M
k
molecular weight of chemical k (g/mol)
r
A
, r
B
, etc. the rate of appearance of chemicals A, B, etc. (mol/(Ls))
r
PEI
total PEI transformation rate (PEI/(Ls))
r
PEI,k
PEI transformation rate of chemical k (PEI/(Ls))
S area of a certain gure
T reaction temperature (K)
v
0
volume ow rate entering a reactor (L/s)
x
kj
mass fraction of chemical k in stream j
Greek letters
l
weighting factor for impact category l
PEI
generated PEI per unit mass of all desired products (PEI/kg)
s
kl
the specic PEI of chemical k for environmental impact category l (PEI/kg of chemical k)
k
overall PEI of chemical k (PEI/kg of chemical k)
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Chemical Engineering and Processing 44 (2005) 2332
Effects of hydraulic residence time on metal uptake by activated sludge
Tlay A. zbelge
Cand 70.01,
respectively, by electronic controllers. A synthetic wastew-
ater with known inlet substrate concentration (in terms of
Table 1
Composition of synthetic wastewater
Constituents (mg/L)
Proteose-peptone 1221.7
NaCl 407.4
Na
2
SO
4
44.6
K
2
HPO
4
44.6
MgCl
2
.6H
2
O 3.7
FeCl
2
.2H
2
O 3.7
CaCl
2
.2H
2
O 3.7
MnSO
4
0.057
H
2
MoO
4
0.031
NaOH 0.008
ZnSO
4
0.046
CoSO
4
0.049
CuSO
4
0.076
chemical oxygen demand) of a COD of S
o
= 1300 mg/L
was fed, in which Proteose-peptone (1221.7 mg/L) was the
sole carbon and nitrogen source. Other minor nutrients were
also added in sufcient quantities to make carbon the limit-
ing nutrient (Table 1). Solutions of CuSO
4
and ZnSO
4
were
added to the wastewater to provide Cu
2+
and Zn
2+
ions at
the desired concentrations. Further details are given else-
where [17,2123].
2.2. Experimental method
Biomass obtained from the wastewater treatment plant
of Middle East Technical University (METU) was used as
seed in the experiments. In the acclimation of MOs to HMs,
maximum concentrations of Cu
2+
and Zn
2+
reached dur-
ing acclimation were decided from previous work [17,21].
The literature showed that when these metals were present
individually in the system, ASP failed to operate at steady
state values of 15 mg/L for Cu
2+
and 90 mg/L for Zn
2+
, re-
spectively [5]. Therefore, one-third of threshold concentra-
tions of these metals (that is, 5 mg/L for Cu
2+
, and 30 mg/L
for Zn
2+
) were used to constitute the combined threshold
concentration for mixtures of copper and zinc ions. Accli-
mation experiments were performed by gradually increasing
the concentrations of Cu
2+
and Zn
2+
to two, three and four
times their combined threshold concentration. The optimum
condition for a successful acclimation providing the growth
of healthy MOs, as observed from the increase in turbidity
values, was obtained at the concentrations corresponding to
twice their combined threshold concentration [21].
Experiments without HMs were conducted using syn-
thetic WW inoculated with 10% (v/v) acclimated seed MOs
to twice their combined threshold concentration (that is,
10 mg/L Cu
2+
, and 60 mg/L Zn
2+
). The reactor was op-
erated as a batch system for 48 h with the growth of new
biomass. Then, continuous feeding of synthetic WW to the
reactor at a desired volumetric ow rate (or desired resi-
dence time) was started. The system reaches steady state
in about 1244 days depending on the inuent metal con-
centrations and the hydraulic residence time (HRT); efuent
T.A. zbelge et al. / Chemical Engineering and Processing 44 (2005) 2332 25
samples from the reactor were analyzed for substrate, S, and
biomass, X, concentrations. MLSS concentration was used
as the primary indicator for steady state conditions. At each
residence time, steady state was reached when the efuent
S (COD) and X (MLSS) concentrations remained constant
with respect to time.
Experiments with HMs were performed at two concentra-
tion levels of each metal (low levels: (Cu
2+
) = 1.5 mg/L
and (Zn
2+
) = 9 mg/L; high levels: (Cu
2+
) = 4.5 mg/L
and (Zn
2+
) = 27 mg/L, for different values of HRT in the
range of 240 h using the same synthetic WW having the
composition given in Table 1. In these experiments, 1.8 L
of synthetic WW was inoculated with 0.2 L of acclimated
seed MOs in the activated sludge reactor, and the system
was operated in batch mode for almost 72 h to ensure the
growth of biomass by observing the increase in measured
turbidities of the samples from the reactor. Then, the con-
tinuous operation was started by feeding the reactor with
synthetic WW containing copper and zinc ions at the de-
sired inlet concentrations. Inuent ow rate was adjusted
in order to provide a required HRT. Samples were taken
from the efuent stream at different times in order to deter-
mine the efuent S and X concentrations until steady state
was reached. Then, a sample of 1.5 L from efuent stream
was collected for the metal analyses, and the operation was
stopped.
2.3. Analytical methods
Substrate concentrations were determined in centrifuged
sample aliquots by standard COD analysis, and gravimet-
ric method was used to measure the biomass concentrations
[24]. Analyses were repeated at least twice with the sam-
ples under the same experimental conditions and the average
values were obtained.
2.3.1. Distribution of metals among the constituents of
activated sludge mixed liquor
Since metals were distributed between the two phases of
mixed liquor in the reactor, namely solution and biomass, the
amounts of copper and zinc associated with these phases and
the forms of these metals in the biomass were determined
at steady state condition for each HRT.
Firstly, the concentrations of HMs in efuent were de-
termined. At least three samples of 40 mL were acidied
with 10 mL of concentrated HNO
3
to decompose MOs.
These samples were diluted to the sensitivity range of the
atomic absorption spectrophotometer (AAS) (Model: Philips
9200X-AAS) (diluted 5 times for Cu
2+
analysis, and 25
times for Zn
2+
analysis) and then analyzed. The average of
these measurements yielded the total HM concentration in
the efuent, C
T
(mg/L), for that specic experimental run.
To convert (mg metal/L) to (mg metal/kg sludge), the mea-
sured metal concentration (as, mg metal/L) at each HRT
was divided by the steady state MLSS concentration (as, kg
TSS/L).
Secondly, concentrations of the HMs associated with the
solution, and solid phases of the efuent were determined.
Two of 50 mL aliquots were collected from the efuent of
the reactor, centrifuged at 1300 rpm for 15 min, by using
a RC5C type Dupont centrifuge, to separate the solution
and solid phases, and the supernatants transferred to sam-
ple tubes. Then, supernatants and the residual solid phase
were acidied by adding 10 mL concentrated HNO
3
to each
sample tube. Samples were then analyzed by AAS after per-
forming the necessary dilutions to the sensitivity range of
the instrument as explained above. The average of the results
from the two samples were recorded as C
S
(metal concen-
tration in the solution phase), and C
A
(metal concentration
in the solid phase) values for each HM.
The distribution of different metal forms in the sludge
was determined by using the sequential extraction pro-
cedure [25]. Activated sludge mixed liquor of 1.5 L,
corresponding to 0.2500.100 g of sludge, was collected
from the outlet of the reactor at the steady state. In order
to separate the sludge and supernatant, centrifugation at
1300 rpm for 15 min was carried out using a RC5C type
Dupont centrifuge. Then the extraction process was started
by adding the reagents of KNO
3
, KF, Na
4
P
2
O
7
, EDTA
(ethylene-diamine-tetraacetic-acid) and HNO
3
on the con-
centrated sludge (order of addition given in Table 2), which
are capable of extracting exchangeable, adsorbed, organi-
cally bound, carbonates, and suldes forms of the metals
in the sludge sample, respectively. To provide complete
extraction, samples were shaken on a platform shaker, then
centrifuged at 1300 rpm for 15 min, and supernatants were
decanted into separate tubes. Between each extraction, the
sludge residue was washed with 50 mL of de-ionized water
by shaking for 30 min, and the samples centrifuged again
under the same conditions. Both supernatants from the ex-
traction and washing were combined and acidied with two
drops of 5 M HNO
3
before metal analysis, in order to pre-
serve the solutions. All metal concentrations were measured
as before and conversions were made to obtain the concen-
trations of each form of each metal as mg metal/ kg sludge,
for which the metal concentration as mg/L was divided by
the dried MLSS concentration (kg TSS/L), determined at
the steady state. The same procedure was followed for the
other reagents, the only exception being that double extrac-
tion was performed with EDTA and supernatants pooled
before the metal analyses. The remaining solid residue in
Table 2
Details about sequential extraction process parameters [25]
Reagents Molarity
(M)
pH Extraction
time (h)
(Solution/solids)
ratio
KNO
3
1 24 50/1
KF 0.5 6.5 24 80/1
Na
4
P
2
O
7
0.1 24 80/1
EDTA 0.1 6.5 224 80/1
HNO
3
1 24 50/1
26 T.A. zbelge et al. / Chemical Engineering and Processing 44 (2005) 2332
the sample tube, at the end of the extraction procedure, was
decomposed with 5 mL of concentrated HNO
3
in order to
determine the levels of metals not extracted by the protocol.
3. Results and discussion
Two phases exist in the activated sludge reactor; the liq-
uid phase consists of water, soluble ions and soluble sub-
strate while the solid phase (biomass or sludge) has settleable
waste materials, dead and alive MOs in it. Metals associated
with these phases were investigated in this study. The ma-
terial balance for the metals at the steady state is dened as
follows:
C
T
= C
A
+C
S
(1)
where C
T
is the total HM concentration in efuent (mg/L),
C
A
is the HM concentration taken up by the sludge (mg/L)
and C
S
is the heavy metal concentration in the solution
(mg/L). This balance was applied to each run using HMs. In
Tables 36, material balance results for copper and zinc are
presented for two sets of experiments (in the rst set, inu-
ent HM concentrations being (Cu
2+
) = 1.5 mg/L, (Zn
2+
)
= 9 mg/L, and in the second set, inuent HM concentrations
Table 3
Material balance on copper at the inuent concentration of (Cu
2+
)
= 1.5 mg/L
h
(h) C
T
C
S
C
A
[(C
S
+ C
A
) C
T
]
100/C
T
17.18 1.47 1.38 0.15 +1.04
14.68 1.61 1.42 0.12 4.35
9.22 1.63 1.60 0.09 +3.68
5.12 1.63 1.58 0.06 +0.61
3.75 1.43 1.43 0.02 +1.40
Table 4
Material balance on zinc at the inuent concentration of (Zn
2+
) = 9 mg/L
h
(h) C
T
C
S
C
A
[(C
S
+ C
A
) C
T
]
100/C
T
17.18 11.13 10.32 0.54 2.43
14.68 10.57 10.70 0.55 +6.43
9.22 10.68 10.70 0.44 +4.31
5.12 9.88 9.09 0.39 4.05
3.75 9.79 9.83 0.29 +3.37
Table 5
Material balance on copper at the inuent concentration of (Cu
2+
)
= 4.5 mg/L
h
(h) C
T
C
S
C
A
[(C
S
+ C
A
) C
T
]
100/C
T
40 5.24 4.88 0.22 2.67
20 4.68 4.53 0.18 +0.64
10 4.27 4.23 0.13 +1.02
5 4.20 4.19 0.08 +1.67
2.5 4.58 4.57 0.04 +0.66
Table 6
Material balance on zinc at the inuent concentration of (Zn
2+
)
= 27 mg/L
h
(h) C
T
C
S
C
A
[(C
S
+ C
A
) C
T
]
100/C
T
40 29.20 29.14 0.72 +2.26
20 27.13 26.23 0.65 0.92
10 29.69 28.75 0.63 +1.04
5 28.38 27.68 0.52 0.63
2.5 28.88 28.52 0.44 +0.28
being (Cu
2+
) = 4.5 mg/L, (Zn
2+
) = 27 mg/L. It is seen
in these tables that the total metal concentration in the ef-
uent is greater than that in the inuent to the reactor at the
steady state due to the experimental error occurred in the
determination of these concentrations in very small amounts
of sludges produced. In spite of this, the obtained results are
consistent as indicated by the small differences between the
two sides of the material balance at each run, the maximum
percent experimental error being within 5%.
Fig. 1 shows the percent metal removals. Small percentage
removals (up to 10%) are because only small amounts of
biomass were produced in the systemunder the experimental
conditions used. This is expected in a system where toxic
0
2
4
6
8
10
12
0 10 20 30 40
residence time (h)
p
e
r
c
e
n
t
m
e
t
a
l
r
e
m
o
v
a
l
Cu: 1.5 mg/L
Cu: 4.5 mg/L
Zn: 9 mg/L
Zn: 27 mg/L
Fig. 1. Percent removal of each metal [(C
A
/C
T
) 100] in the ex-
periments of Set-1 (inuent concentrations: (Cu
2+
) = 1.5 mg/L,
(Zn
2+
) = 9 mg/L) and Set-2 (inuent concentrations:
(Cu
2+
) = 4.5 mg/L, (Zn
2+
) = 27 mg/L).
T.A. zbelge et al. / Chemical Engineering and Processing 44 (2005) 2332 27
metals inhibit the microbial community to yield low MLSS
values at the steady state and thus low removals of HMs
[9,1215]. Since the highest value of HRT is 40 h (less than
2 days) in this work, which is equal to the sludge age in
the present OTASP, therefore, the biomass concentrations
in the efuent stream were low as expected. However, in
an ASP with recycle, it may be possible to obtain higher
percent removals of copper and zinc by increasing the sludge
age up to 812 days [1216] due to the higher biomass
concentrations in the reactor. As seen in Fig. 1, the percent
copper and zinc removals by biomass increased with the
increasing HRT or the decreasing dilution rate (D = 1/
h
),
keeping the inlet HM concentrations constant. At the low
level of inuent HM concentrations ((Cu
2+
) = 1.5 mg/L,
(Zn
2+
) = 9 mg/L), the percent metal uptakes were higher
than those at the higher level, ((Cu
2+
) = 4.5 mg/L, (Zn
2+
)
= 27 mg/L), for both of the metals at each residence time,
due to the lower HM toxicities to biomass at the low level
of the HM concentrations. The higher percent removals of
zinc compared to those of copper at the short residence
times of
h
<5 h can be attributed to the lower toxicity of
zinc in spite of the lower biomass concentrations at these
residence times. Although the toxicity of copper is greater
than that of zinc at the same level of concentration, the
percent copper removals exceeded those of zinc at the longer
residence times of
h
>5 h; the reasons for this nding is
because of the lower inuent copper concentrations studied
in this experimental work compared to those of zinc, and the
occurrence of higher biomass concentrations at the longer
residence times which has an effect in decreasing the HM
toxicities. This may also be due to the greater contribution
of the precipitated form of copper to the sludge produced,
as reported by Vian et al. [16].
When the amount of HM removed per kg of activated
sludge produced (mg metal/kg sludge) for each metal is ob-
served in Fig. 2 that these values are higher for Zn
2+
be-
cause of the higher inuent concentrations of Zn
2+
in the
experiments; (mg metal/kg sludge) values for zinc decrease
with the increasing residence time due to the increase in the
amount of sludge produced at the higher HRTs. This de-
creasing effect on the ratio of masses will be more signi-
cant for zinc than that of copper, since the percent removals
are lower for zinc than those of copper as seen in Fig. 1; but,
still these values are above those of copper due to the higher
inuent concentrations of zinc ions studied at both the low
and high concentration levels of the HMs in the experiments
compared to those of copper.
The increase in the amount of copper and decrease in the
amount of zinc removed by activated sludge, as the residence
time is increased, can be explained by transport processes,
adsorption onto surfaces or the possible competition between
copper and zinc ions in binding to available sites on the
enzymes. It may be that the interaction between copper and
biomass increases as the residence time increases eventually
leading to an increase in the amount of copper taken up
by activated sludge. As a result, the afnity of zinc for the
0
1000
2000
3000
4000
5000
6000
7000
0 10 20 30 40 50
residence time (h)
a
m
o
u
n
t
o
f
m
e
t
a
l
r
e
m
o
v
e
d
(
m
g
m
e
t
a
l
/
k
g
s
l
u
d
g
e
)
Cu: 1.5 mg/L
Cu: 4.5 mg/L
Zn: 9 mg/L
Zn: 27 mg/L
Fig. 2. Amount of metal bound to the sludge as (mg metal bound/kg
sludge produced) for the experiments of Set-1 and Set-2.
sludge decreases, since the available sites on the enzymes
to be occupied by the metals are limited. It was reported
earlier that both nickel and zinc uptakes decreased when the
inlet concentration of copper in the mixture was increased, at
constant inlet concentrations of nickel and zinc [16]. It was
also reported by Vian et al. [16] that the percentage of zinc
removal was higher than that of copper due to the increasing
percentage of zinc removed by precipitation although the
percent of zinc uptaken by sludge was lower than that of
copper for the higher toxicity effect of zinc at its higher
concentrations. Although these data [16] seem to support
the above hypothesis, they did not discuss the effect of HRT
on metal uptake by activated sludge in an ASP with recycle
where the sludge age was kept almost constant. Therefore,
it is necessary to investigate this hypothesis further.
3.1. Distributions of different metal forms in the sludge
According to the sequential extraction procedure [25] out-
lined earlier, the forms of HMs in the sludge are dened as
exchangeable (extracted by KNO
3
), adsorbed (by KF), or-
ganically bound (by Na
4
P
2
O
7
), carbonates (by EDTA), and
suldes (by HNO
3
). The results of these experiments are
given in Figs. 36. Rankings of the different forms of copper
and zinc in the sludge for the two sets of experiments (rst
set: inuent (Cu
2+
) = 1.5 mg/L, (Zn
2+
) = 9 mg/L; sec-
ond set: inuent (Cu
2+
) = 4.5 mg/L, (Zn
2+
) = 27 mg/L
suggest that,
28 T.A. zbelge et al. / Chemical Engineering and Processing 44 (2005) 2332
0
100
200
300
400
500
600
700
800
2 4 6 8 10 12 14 16 18
residence time (h)
m
g
m
e
t
a
l
r
e
m
o
v
e
d
/
k
g
s
l
u
d
g
e
Exchangeable
Adsorbed
Organically bound
Carbonates
Sulfides
Fig. 3. Distribution of Zn
2+
among its forms in the sludge using the data
of Set-1 experiments.
0
1000
2000
3000
4000
0 10 20 30 40
residence time (h)
m
g
m
e
t
a
l
r
e
m
o
v
e
d
/
k
g
s
l
u
d
g
e
Exchangeable
Adsorbed
Organically bound
Carbonates
Sulfides
Fig. 4. Distribution of Zn
2+
among its forms in the sludge using the data
of Set-2 experiments.
0
20
40
60
80
100
120
140
160
180
2 4 6 8 10 12 14 16 18
residence time (h)
m
g
m
e
t
a
l
r
e
m
o
v
e
d
/
k
g
s
l
u
d
g
e
Exchangeable
Adsorbed
Organically bound
Carbonates
Sulfides
Fig. 5. Distribution of Cu
2+
among its forms in the sludge using the data
of Set-1 experiments.
in Fig. 3, for (Zn
2+
) = 9 mg/L: organically bound >
carbonates > exchangeable > adsorbed > suldes,
in Fig. 4, for (Zn
2+
) = 27 mg/L: organically bound
= exchangeable = adsorbed > carbonates > suldes,
in Fig. 5, for (Cu
2+
) = 1.5 mg/L: carbonates > organi-
cally bound > exchangeable > adsorbed > suldes,
in Fig. 6, for (Cu
2+
) = 4.5 mg/L: organically bound >
exchangeable > carbonates > adsorbed > suldes.
As shown in Figs. 36, at low concentration levels of both
metals, namely for (Cu
2+
) = 1.5 mg/L and for (Zn
2+
)
= 9 mg/L, the rankings of metal forms remained unchanged
as the HRT increased. On the other hand, at the high
concentration levels of these metals, namely for (Cu
2+
)
= 4.5 mg/L and for (Zn
2+
) = 27 mg/L, the rankings of
the different forms of these metals changed with the HRT;
the least represented forms for both are the suldes, and the
dominant metal forms are the organically bound forms for
both zinc and copper.
The rankings of the different forms are more marked at
lowinuent metal concentrations than those at the high level.
However, the dominant and the least represented forms are
the same. It has been reported that the dominant forms of
HMs could vary for different sludges [25]. Therefore, the
rankings of the metal forms for copper and zinc, should not
be assumed to be the same for all kinds of sludges.
To determine the efciency of the metal extraction pro-
cedure, the sample remaining at the end of the extraction
was acidied with HNO
3
to determine the amounts of resid-
ual metals not extracted by the reagents. Ideally, the total
T.A. zbelge et al. / Chemical Engineering and Processing 44 (2005) 2332 29
0
100
200
300
400
0 10 20 30
residence time (h)
m
g
m
e
t
a
l
r
e
m
o
v
e
d
/
k
g
s
l
u
d
g
e
40
Exchangeable
Adsorbed
Organically bound
Carbonates
Sulfides
Fig. 6. Distribution of Cu
2+
among its forms in the sludge using the data
of Set-2 experiments.
amount of the metals determined by the extraction proce-
dure should be equal to the amount of metal bound to the
sludge, the discrepancy between the two being denoted by
C
H
. Thus, the material balance for extraction can be shown
as:
C
A
= C
E
+C
H
(2)
where C
A
is the concentration of metal bound to the sludge
(mg/L, or mg metal/kg sludge), C
E
is the concentration
of metal extracted in the analysis (mg/L or mg metal/kg
sludge) and C
H
is the concentration of metal not extracted
by the used reagents in the extraction (mg/L or mg metal/kg
sludge). Thus, the extraction procedure used is capable of
extracting most of the metals bound to the biomass, varying
between 93.85 and 98.98% of the total amount of the HMs
in the sludge. Also, the total concentrations of the metals
extracted are mostly consistent with the C
A
values. The ex-
perimental error in the sequential extraction analysis falls
within 10%.
It should be noted that these data were obtained by ex-
tracting the relatively small amounts of biomass, which can
exagerate the experimental error. The reasons for working
with small amounts of biomass are two-fold; rstly, the sam-
ples were collected here at the steady state directly from the
efuent of the system at one day intervals. Samples can de-
generate due to the continuing interaction between metals
and biomass before the analysis, which can cause changes
in the relative amounts of the metal forms in sludge over
the time. Secondly, biomass concentrations in the efuent of
the reactor are quite low anyhow due to metal inhibition ef-
fects, a problem which can be overcome if a recycle is used
in the system. Therefore, further studies are planned to be
performed in an ASP with recycle.
In the literature, equilibrium biosorption of Zn
2+
and
Cu
2+
by nonviable activated sludge was investigated in a
packed column adsorber [26], where metabolically induced
interactions between HMs and MOs were eliminated; thus,
the problems, such as toxicity of metals to MOs, mainte-
nance requirements of MOs in controlling the pH within a
range suitable for the MOs were avoided. It was observed
by Utgikar et al. [26] that equilibrium metal uptakes from
solutions containing single metal ion were 2.5 and 3.4 mg/g
dried biomass for Zn
2+
, and 1.9 and 5.9 mg/g dried biomass
for Cu
2+
at pH of 3.0 and 3.8, respectively. Equilibrium up-
take of metals was modeled using the Langmuir adsorption
isotherm. Equilibrium uptakes from binary mixtures were
30% lower than single component solution uptakes for both
metals, indicating some competition between the two metals.
No hysteresis was detected between adsorption and desorp-
tion equilibria. The simultaneous sorption of metal cation
and sulfate anion was probably occurring at pH of 3.0, while
proton exchange predominated at pH of 3.8. They pointed
out the usefulness of non-viable activated sludge as a biosor-
bent for removing metal ions from WWs.
On the other hand, the removal of metal ions in an ASP
was affected adversely due to the toxicity of HMs to MOs.
It was reported that the presence of Cu
2+
ions in wastewater
inhibited the net specic growth rate of autotrophic biomass
to a larger extent than Zn
2+
ions [27]. Therefore, in an ASP
treating such a WW, it is expected that the concentration
and the composition of EPS (consisting of protein, polysac-
charide and DNA) produced by microbial cells will vary
[28], since it is known that the EPS formation rate is pro-
portional to the rate of substrate utilization, thus to the rate
of biomass production [29]. When EPS are not involved in
the process, MOs may not easily display high occulation
and metal uptake capacity, as the oc forming bacteria can
interact with each other [30]. However, the precise role of
EPS in biosolidliquid separation is not well understood al-
though EPS are thought to be of considerable importance in
bioocculation and settling of activated sludge [28]. For ex-
ample, the EPS content has been shown to be directly [31],
or conversely [32] related to sludge volume index (SVI).
Besides, the low protein levels were obtained at high car-
bohydrate concentrations depending on microbial consortia
due to the intracellular storage of excess carbon substrate and
lower sludge retention time, particularly, in the pulppaper
and textile industries lab-scale activated sludge systems.
The low protein content was probably due to the inhibition
of EPS production in the aforementioned industies as re-
ported by Dignac et al. [33]. It was noted that the wastewater
composition rather than operating conditions had a strong
inuence on EPS composition and the physicochemical
properties of ocs in an ASP. For example, if the ASP was
operated at high F/M ratios, both carbohydrate and DNA
content of EPS increased as the protein content decreased;
30 T.A. zbelge et al. / Chemical Engineering and Processing 44 (2005) 2332
as a result of this, a more hydrophobic (larger contact angle)
and less negatively charged oc surface was observed [28].
The present OTASP was operated at high F/M ratios [23];
although no data were obtained about the concentration and
the composition of EPS produced in this work, it might be
predicted from the available literature that the protein con-
tent of the produced EPS in the ocs was low; thus the set-
tling ability of the resulting sludge, most probably with a
high value of SVI was not good. Actually, low settlability of
the produced sludge was observed in the experiments. The
effect of operational conditions on EPS composition will be
the subject of a future study in which it will be investigated
in an ASP with recycle to compare the effects of sludge
residence time (SRT), HRT, EPS and F/M ratio on the set-
tlability of produced sludge and metal uptake. In this study,
the change in bacterial prole of the MLSS with metal con-
centration was not followed, but it was reported in the lit-
erature [34] that many different species of bacteria isolated
from activated sludge were shown to produce EPS. These
polymers might be in the form of loose slime or capsules
adhered to the cell wall. In activated sludge, slime polymers
remained in the dissolved and colloidal phases of an efu-
ent, while capsular polymers remained attached to the ocs
and hence settled with the sludges. Some activated sludge
bacteria did not produce capsules or extracellular material.
In these bacteria, metals might be accumulated either in the
cytoplasm or by adsorption on to the cell wall. Some re-
searchers [35] concluded that only the half of the observed
metal uptake could be attributed to EPS and that cell itself
played a role in accumulating metals. In another work [36],
EPS were extracted, cells were broken up using ultrasound
and cell envelopes were sedimented by centrifugation. Only
small quantities of copper were found in the cytoplasm, but
substantial amounts of copper were bound to cell envelopes
and EPS. The metabolism of elements occurred in many
species of bacteria. It was also reported that four major types
of metal transformation in organisms occurred [37], these
being chelate formation by the binding of metals to organic
ligands, shifts in metal valencies, substitution of one metal
for another and biomethylation of metals to microorganisms.
When metals were chelated to substrate molecules, the ad-
sorption of these molecules might represent a means of accu-
mulating metals within a cell. These metabolic transforma-
tions of metal ions by bacteria were different for each metal
and for different combinations of metals in the medium.
Therefore, in such a dynamic system as is ASP, it is not
plausible to use metal uptake as a measure of EPS content.
As it is seen in Fig. 2, the copper uptake increases with the
HRT up to 20 h then it shows a slight decrease between 20
and 40 h. This can be explained with the change in the given
ranking in Fig. 6. The chemical speciation and distribution
of copper in an activated sludge slurry can be quantied
using an equlibrium constant approach including complex-
ation with inorganic and organic ligands and adsorption by
activated sludge solids [38]. It can be observed in Fig. 6 that
the amount of copper carbonate per kg of sludge is higher
than the amount of organically removed copper at a HRT of
40 h, while it was lower than that of organically bound cop-
per at a HRT of 20 h. Therefore, it is shown in Fig. 2 that
the copper uptake at a HRT of 40 h is less than that at 20 h.
The copper uptake is probably less at a HRT of 40 h due to
the effect of changing metabolic activity of microbial ocs
and the solubility constant of copper carbonate complex in
the medium at the prevailing conditions. The desorption of
copper into the solution might have occurred due to the sol-
ubility constant of this complex.
4. Conclusions
The effect of hydraulic residence time (in the range of
2.540 h) on the removal of Zn
2+
and Cu
2+
ions by acti-
vated sludge was investigated in a once-thro activated sludge
process (OTASP) at a constant pH of 7 and temperature of
25
h
hydraulic residence time (h or days)
c
mean cell residence time or sludge age (days)
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Chemical Engineering and Processing 44 (2005) 3339
Porous catalyst intraparticle status of parallel,
equilibrium-restrained reactions
Guangsuo Yu
Corresponding author.
E-mail address: gsyu@ecust.edu.cn (G. Yu).
Several quantitative analyses of the effect of intraparticle
heat and mass transport have been carried out for parallel, ir-
reversible reactions [1]. Roberts and Lamb [2] have worked
on the effect of reversibility on the selectivity of parallel
reactions in a porous catalyst. The reaction selectivity of a
kinetic model of two parallel, rst order, irreversible reac-
tions with a second order inhibition kinetic term in one of
them has also been investigated [3].
The reaction-diffusion model inside a catalyst pellet is
a differential equations set of boundary-value problem, the
standard solving methods for which are nite difference,
numerical integration shooting, weighting residual, singular
perturbation [4], Green function [5], false transient [6], or-
thogonal collocation [7], moving grid nite element [8], etc.
Based on the investigation of reaction, heat transfer and
mass transfer of the KD306-type sulfur-resisting methana-
tion catalyst [911], the non-isothermal one-dimensional
and two-dimensional reaction-diffusion models for the key
components have been established, and solved using an or-
thogonal collocation method in this paper. The scope is to
study the catalyst intraparticle reaction-diffusion processes
that involve parallel, non-rst order, equilibrium-restrained
reactions.
0255-2701/$ see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.cep.2004.04.003
34 G. Yu et al. / Chemical Engineering and Processing 44 (2005) 3339
2. Reaction system and fundamental data
With the reducing supply of low sulfur petroleum, the
demand for residual oil and coal with high-sulfur con-
tent is increasing. The development and application of
sulfur-resisting catalysts have received great attention. The
KD306-type sulfur-resisting methanation catalyst, a sulde
catalyst such as Mo and W of group VIB as the primary
species and Fe, Co, Ni of group VIII as the indispens-
able promoters, can be used in methanation reaction with
sulfur-containing syngas as the reactants at high reactivity
and selectivity. The cylindrical catalyst pellets (diameter
= 5.422 mm, length = 4.327 mm) were prepared by com-
pressing particles.
Methanation reaction and watergas shift reaction
(WGSR), which are chosen as the examples for presenta-
tion, are expressed as follows:
CO +3H
2
= CH
4
+H
2
O, H
298
= 206 kJ/mol
CO +H
2
O = CO
2
+H
2
, H
298
= 41 kJ/mol
The former is a volume-decreasing reaction, while the
latter is not. Both reactions are exothermic. Methanation
is a deep hydrogenation reaction for carbon monoxide and
WGSR is a complete oxidation reaction in which carbon
monoxide is oxidized into carbon dioxide and water is re-
duced with the formation of hydrogen. As in the preparation
of methane, other hydrocarbons, low alcohols and particu-
larly, carbon dioxide and water are formed. Because of the
presence of water, WGSR always occurs in the methana-
tion process, which reduces the selectivity and yield of the
desired product.
Fig. 1 shows reaction equilibrium constants of the metha-
nation reaction and the WGSR [12]. The mole composition
of town gas is: CO 20%, H
2
40%, CO
2
10%, H
2
O
0%, N
2
the rest. Methanation reaction is almost irreversible
673 723 773 823 873
1
10
100
1000
10000
0
4
8
12
16
K
p
,
s
h
i
f
t
K
p
,
m
e
t
h
a
n
a
n
t
i
o
n
,
a
t
m
-
2
T, K
Fig. 1. Reaction equilibrium constants of methanation reaction and shift
reaction.
under the reaction conditions at 400600
C. The equilib-
rium constant of the WGSR is small and varies insignif-
icantly with temperature. Due to the water formation and
the concentration variations in carbon monoxide and hydro-
gen, which are consequences of the methanation reaction,
the overall WGSR occurs both as the direct and reverse re-
action at internal surface of the catalyst. So, the fundamental
features of this reaction system are equilibrium-restrained,
namely reversible, parallel reactions.
2.1. Reaction kinetics [9]
The intrinsic kinetics was measured in an isothermal in-
tegrated reactor and the reaction rate equations in terms of
power function have been established
(r
CH
4
)
w
= 3.8333 10
6
exp
46 944
RT
P
0.58
CO
P
0.52
H
2
mol s
1
kg
1
(r
CO
2
)
w
= 4.1089 10
5
exp
58 349
RT
P
0.58
CO
P
0.98
H
2
O
(1 ) mol s
1
kg
1
where = J
P
/K
P
.
The macrokinetics were measured in a gradientless reac-
tor.
2.2. Effective diffusivity D
effA
[10]
Mass transport inside the catalyst has been usually de-
scribed by applying the Fick equation, by means of an effec-
tive diffusivity D
effA
. Based on properties of the interface
and neglecting the composition effect, composite diffusivity
of the multi-component gas mixture is calculated through
the simplied Wilke model [13]. The effect of pore-radius
distribution on Knudsen diffusivity is taken into account.
The effective diffusivity D
effA
is given by
D
effA
=
r
max
r
min
1
1 y
A
N
j=A
y
j
D
Aj
+
1
D
Ak
(r)
1
f(r) dr
where is the tortuosity factor of the KD306 catalyst, which
was measured using single pellet string reactor technique.
2.3. Thermal conductivity
eff
[11,14]
Based on the Woodside stochastic model, thermal con-
ductivity
eff
can be calculated from gas composition and
temperature of the catalyst exterior surface by
eff
s
=
fm
where
s
is given by
s
=19.90005 +0.12333T 2.38169(
1
100
T)
2
+0.151983(
1
100
T)
3
G. Yu et al. / Chemical Engineering and Processing 44 (2005) 3339 35
3. Theory [15,16]
The assumptions made for the reaction-diffusion models
are as follows:
(1) parallel, equilibrium-restrained reactions occur (namely,
methanation reaction is irreversible, while WGSR is re-
versible);
(2) non-rst order reactions;
(3) non-isothermal;
(4) quasi-homogeneous;
(5) only key components are considered (methane and car-
bon dioxide).
3.1. One-dimensional model
Commonly [17], when the length-to-diameter ratio of a
cylindrical catalyst is close to 1, the cylindrical catalyst can
be simplied as a sphere, the radius of which, R
p
, is calcu-
lated by 3V
p
/S
p
. The one-dimensional, key-component based
reaction-diffusion models of methanation system are as fol-
lows:
d
2
C
CH
4
dx
2
+
2
x
dC
CH
4
dx
=
R
2
p
D
eff,CH
4
(r
CH
4
)
w
p
d
2
C
CO
2
dx
2
+
2
x
dC
CO
2
dx
=
R
2
p
D
eff,CO
2
(r
CO
2
)
w
p
d
2
T
dx
2
+
2
x
dT
dx
=
R
2
p
eff
p
[(r
CH
4
)
w
(H
CH
4
)
+(r
CO
2
)
w
(H
CO
2
)]
Boundary conditions
x =
r
R
p
= 1, C
CH
4
= (C
CH
4
)
s
, C
CO
2
= (C
CO
2
)
s
,
T = T
s
x = 0,
dC
CH
4
dx
= 0,
dC
CO
2
dx
= 0,
dT
dx
= 0
Applying orthogonal collocation method, the above equa-
tions become
N+1
k=1
B
jk
+
2
x
A
jk
C
CH
4
,k
=
R
2
p
D
eff,CH
4
(r
CH
4
)
w,j
p
N+1
k=1
B
jk
+
2
x
A
jk
C
CO
2
,k
=
R
2
p
D
eff,CO
2
(r
CO
2
)
w,j
p
N+1
k=1
B
jk
+
2
x
A
jk
T
k
=
R
2
p
eff
p
[(r
CH
4
)
w,j
(H
CH
4
)
+(r
CO
2
)
w,j
(H
CO
2
)]
The solutions of the above non-linear equations can be ob-
tained using the Broyden quasi-Newton method [18]. Based
on the mass balance, the concentrations of other component,
such as CO, H
2
, H
2
O and so on, can be calculated from the
key components [9].
According to the denitions
CO
2
=
4R
2
p
D
eff,CO
2
(dC
CO
2
/dR)
s
(4/3)R
3
p
p
(r
CO
2
)
w,s
the effectiveness factors for the catalyst pellet can be calcu-
lated from
CO
2
=
3
N+1
j=1
A
N+1,j
C
CO
2
,j
(R
2
p
/D
eff,CO
2
)
p
(r
CO
2
)
w,s
,
CH
4
=
3
N+1
j=1
A
N+1,j
C
CH
4
,j
(R
2
p
/D
eff,CH
4
)
p
(r
CH
4
)
w,s
3.2. Two-dimensional model
R
P
and H
P
are the radius and semi-length of cylindri-
cal catalyst, respectively. Assume a cylindrical ring element
with the length dH and the radial thickness dR at the axial
position H and the radial position R in the 2D cylindrical
system. Introducing the dimensionless variables
x =
R
R
p
, z =
H
H
p
The species (methane and carbon dioxide) mass balance
and energy conservation in the cylindrical ring element at
steady state lead to the following 2Dpartial differential equa-
tions:
2
C
CH
4
x
2
+
1
x
C
CH
4
x
+
R
p
H
p
2
C
CH
4
z
2
=
R
2
p
D
eff,CH
4
p
(r
CH
4
)
w
2
C
CO
2
x
2
+
1
x
C
CO
2
x
+
R
p
H
p
2
C
CO
2
z
2
=
R
2
p
D
eff,CO
2
p
(r
CO
2
)
w
2
T
x
2
+
1
x
T
x
+
R
p
H
p
2
T
z
2
=
R
2
p
eff
p
[(H
CH
4
)(r
CH
4
)
w
+(H
CO
2
)(r
CO
2
)
w
]
with the associated boundary conditions
x = 0,
C
CO
2
x
=
C
CH
4
x
=
T
x
= 0
z = 0,
C
CO
2
z
=
C
CH
4
z
=
T
z
= 0
x = 1 or z = 1, C
CO
2
= C
CO
2
,s
, C
CH
4
= C
CH
4
,s
, T = T
s
Each item of the model at collocation point (I, J) may be
expressed as
36 G. Yu et al. / Chemical Engineering and Processing 44 (2005) 3339
F = C
CO
2
F = C
CH
4
F = T
(F)
I,J
N+1
j=1
N+1
i=1
a
ij
x
2i2
I
z
2j2
J
N+1
j=1
N+1
i=1
b
ij
x
2i2
I
z
2j2
J
N+1
j=1
N+1
i=1
c
ij
x
2i2
I
z
2j2
J
F
x
I,J
N+1
j=1
N+1
i=1
(2i 2)a
ij
x
2i3
I
z
2j2
J
N+1
j=1
N+1
i=1
(2i 2)b
ij
x
2i3
I
z
2j2
J
N+1
j=1
N+1
i=1
(2i 2)c
ij
x
2i3
I
z
2j2
J
2
F
x
2
I,J
N+1
j=1
N+1
i=1
(2i 2)(2i 3)a
ij
x
2i4
I
z
2j2
J
N+1
j=1
N+1
i=1
(2i 2)(2i 3)b
ij
x
2i4
I
z
2j2
J
N+1
j=1
N+1
i=1
(2i 2)(2i 3)c
ij
x
2i4
I
z
2j2
J
2
F
z
2
I,J
N+1
j=1
N+1
i=1
(2j 2)(2j 3)a
ij
x
2i2
I
z
2j4
J
N+1
j=1
N+1
i=1
(2j 2)(2j 3)b
ij
x
2i2
I
z
2j4
J
N+1
j=1
N+1
i=1
(2j 2)(2j 3)c
ij
x
2i2
I
z
2j4
J
where, I = 1, 2, . . . , N
R
+1, J = 1, 2, . . . , N
A
+1.
We obtain
N
X
+1
k=1
BX
Ik
C
CH
4
,kJ
+
1
x
I
N
X
+1
k=1
AX
Ik
C
CH
4
,kJ
+
R
p
H
p
2
N
Z
+1
k=1
BZ
Jk
C
CH
4
,kI
=
R
2
p
p
D
eff,CH
4
(r
CH
4
)
w,IJ
N
X
+1
k=1
BX
Ik
C
CO
2
,kJ
+
1
x
I
N
X
+1
k=1
AX
Ik
C
CO
2
,kJ
+
R
p
H
p
2
N
Z
+1
k=1
BZ
Jk
C
CO
2
,kI
=
R
2
p
p
D
eff,CO
2
(r
CO
2
)
w,IJ
N
X
+1
k=1
BX
Ik
T
kJ
+
1
x
I
N
X
+1
k=1
AX
Ik
T
kJ
+
R
p
H
p
2
N
Z
+1
k=1
BZ
Jk
T
kI
=
R
2
p
eff
[(H
CH
4
)
IJ
(r
CH
4
)
w,IJ
+(H
CO
2
)
IJ
(r
CO
2
)
w,IJ
]
The concentration and temperature proles are calculated
from the above non-linear equations using the Broyden
quasi-Newton method. The effectiveness factors for the
catalyst pellet may be expressed as
CO
2
=
N
R
+1
I=1
N
A
+1
J=1
(r
CO
2
,w
)
I,J
W
R,I
W
A,J
(r
CO
2
,w
)
s
N
R
+1
I=1
W
R,I
N
A
+1
J=1
W
A,J
,
CH
4
=
N
R
+1
I=1
N
A
+1
J=1
(r
CH
4
,w
)
I,J
W
R,I
W
A,J
(r
CH
4
,w
)
s
N
R
+1
I=1
W
R,I
N
A
+1
J=1
W
A,J
where W
R
, W
A
are weight coefcients of the Gauss integral
formulae, dened as
1
0
x
2i2
x
1
dx =
N+1
j=1
W
j
x
2i2
j
=
1
2i 2 +
,
i = 1, 2, . . . , N
4. Results and discussion
4.1. Model testing
The experimentally-determined effectiveness factor is
determined as the ratio of the experimental macro reaction
rate to the intrinsic reaction rate under the same interface
(bulk) composition and temperature. Based on the ex-
perimental conditions of the macrokinetics, the predicted
effectiveness factors of the methanation reaction and the
WGSR are obtained by solving the above non-isothermal
one-dimensional and two-dimensional reaction-diffusion
models for the key components. Table 1 shows the calcu-
lated effectiveness factors and the experimental values. By
taking into account the fact that there are errors in measuring
intrinsic kinetics, macrokinetics, effective diffusivity, and
thermal conductivity, the calculated effectiveness factors
are in reasonable agreement with the experimental values.
From Table 1, it can be concluded that the simulation results
of the one-dimensional model are close to the results of the
two-dimensional model; also, the methanation reaction ef-
fectiveness factors of the two-dimensional model are closer
to the experimental data than those of the one-dimensional
model. With these models, the concentration proles and
temperature prole in the catalyst pellet can be predicted.
4.2. Results
Predicted parameter distributions within catalyst pellet for
some experimental conditions are presented in Tables 25.
As shown in Tables 2 and 3, the deeper inside the pellet,
the higher the concentration of carbon dioxide and methane
are, and the lower the concentration of carbon monoxide is.
The effectiveness factor
CH
4
of the methanation reaction
is large, while the effectiveness factor
CO
2
of the WGSR
is very low and nearly equal to zero. Because the equilib-
rium constant of WGSR is small and varies only slightly
with temperature, and the methanation reaction changes the
gas composition, there are zones where the direct reaction
and the reverse reaction of WGSR dominate at internal sur-
face of catalyst, which is shown in Tables 2 and 4. The
low mole-fraction of water results in the reverse reaction of
WGSRwithin the region beneath the exterior surface. Due to
reaction consumption of carbon monoxide, the mole-fraction
of carbon monoxide within the core region is low, which
leads to the reverse WGSR. The reaction rate of reverse
WGSR is large, especially at the exterior surface and the
G. Yu et al. / Chemical Engineering and Processing 44 (2005) 3339 37
Table 1
Simulation results of one-dimensional and two-dimensional models by orthogonal collocation method
Number T (K) P (atm) Interface composition
CH
4
,e
CO
2
,e
CH
4
,cone
CO
2
,cone
CH
4
,ctwo
CO
2
,ctwo
y
CH
4
y
CO
1 703.45 7.91 0.1774 0.1773 0.9277 0.0440 0.6699 0.0090 0.7192 0.0699
2 702.65 14.22 0.2508 0.1672 0.6992 0.0084 0.6128 0.0098 0.6696 0.0926
3 704.35 10.28 0.2739 0.1499 0.6679 0.0255 0.6490 0.0183 0.7022 0.0824
4 703.15 11.86 0.2816 0.1446 0.8273 0.0198 0.6351 0.0163 0.6901 0.0816
5 738.35 12.05 0.2836 0.1560 0.5774 0.0151 0.5558 0.0085 0.5832 0.0428
6 738.55 8.30 0.2330 0.1730 0.6665 0.0082 0.6081 0.0134 0.6513 0.0727
Table 2
One-dimensional parameter distribution within catalyst pellet for Number 1 (T = 703.45 K, P = 7.91 atm)
x y
CO
2
y
CH
4
y
CO
T (K) r
CH
4
10
3
mol s
1
kg
1
r
CO
2
10
3
mol s
1
kg
1
0.0000 0.1944 0.3443 0.0427 703.79 0.2620 5.4989
0.2154 0.1902 0.3392 0.0486 703.78 0.2862 0.1375
0.4206 0.1846 0.3236 0.0590 703.74 0.3391 0.1907
0.6063 0.1736 0.2977 0.0781 703.69 0.4319 0.3417
0.7635 0.1558 0.2634 0.1066 703.62 0.5625 0.4908
0.8851 0.1330 0.2256 0.1411 703.55 0.7124 0.7889
0.9653 0.1137 0.1935 0.1704 703.48 0.8398 2.3307
1.0000 0.1118 0.1774 0.1773 703.45 0.8905 18.9060
core center. The direct WGSR dominates between the men-
tioned above regions but its rate is low. The region of direct
reaction is big, while the region of reverse reaction is small.
Internal diffusion is not the major factor leading to low
CO
2
.
The existence of regions of the direct and reverse WGSR
contributes to a greater extent to low
CO
2
, which in turn
causes the low net reaction rate. This low reaction rate does
Table 3
Two-dimensional parameter distribution within catalyst pellet for No.
3-y
CH
4
(T = 704.35 K, P = 10.28 atm)
z x
0.0000 0.2390 0.5262 0.7639 0.9275 1.0000
0.0000 0.4220 0.4183 0.4002 0.3615 0.3085 0.2739
0.2390 0.4175 0.4141 0.3969 0.3597 0.3081 0.2739
0.5262 0.3967 0.3942 0.3809 0.3504 0.3053 0.2739
0.7639 0.3561 0.3548 0.3474 0.3289 0.2981 0.2739
0.9275 0.3052 0.3051 0.3027 0.2966 0.2852 0.2739
1.0000 0.2739 0.2739 0.2739 0.2739 0.2739 0.2739
Table 4
Two-dimensional parameter distribution within catalyst pellet for No.
3-r
CO
2
10
3
(T = 704.35 K, P = 10.28 atm)
z x
0.0000 0.2390 0.5262 0.7639 0.9275 1.0000
0.0000 18.909 9.619 8.904 8.136 9.467 52.009
0.2390 10.049 0.155 0.206 0.557 0.812 52.009
0.5262 9.140 0.306 0.333 0.641 0.767 52.009
0.7639 8.375 0.687 0.678 0.905 0.604 52.009
0.9275 10.533 16.161 1.648 1.513 3.006 52.009
1.0000 52.009 52.009 52.009 52.009 52.009 52.009
not imply that WGSR hardly occurs in the catalyst pellet due
to internal diffusion. WGSR occurs remarkably at all sites of
catalyst pellet, and the reaction rate of each site is not equal
to zero. As a result of the existence of direct and reverse
reaction of WGSR, and also the volume-decreasing metha-
nation reaction, there is small variation of carbon dioxide
concentration due to the site change in the pellet.
It is shown in Tables 2 and 5 that the methanation reac-
tion takes place as a direct reaction throughout the whole
internal-surface of the pellet. Carbon monoxide, which is
the product of the reverse WGSR, promotes the methanation
reaction. The interaction between the methanation reaction
and the WGSR enhances the methanation reaction and also
improves
CH
4
. Internal diffusion also affects the methana-
tion reaction.
To put it briey, the effectiveness factors for parallel
equilibrium-restrained reactions cannot describe the utiliza-
tion degree of catalyst internal-surface accurately. Therefore,
the intraparticle distributions of the temperature, the concen-
trations of species and so on should be taken into account.
Table 5
Two-dimensional parameter distribution within catalyst pellet for No.
3-r
CH
4
10
3
(T = 704.35 K, P = 10.28 atm)
z x
0.0000 0.2390 0.5262 0.7639 0.9275 1.0000
0.0000 0.1672 0.1891 0.2690 0.4486 0.7055 0.8575
0.2390 0.1922 0.2129 0.2889 0.4617 0.7112 0.8575
0.5262 0.2844 0.3015 0.3621 0.5058 0.7256 0.8575
0.7639 0.4739 0.4849 0.5206 0.6098 0.7616 0.8575
0.9275 0.7212 0.7260 0.7378 0.7682 0.8251 0.8575
1.0000 0.8575 0.8575 0.8575 0.8575 0.8575 0.8575
38 G. Yu et al. / Chemical Engineering and Processing 44 (2005) 3339
5. Conclusions
Based on the studies on the KD306-type sulfur-resisting
methanation catalyst, the non-isothermal one-dimensional
and two-dimensional reaction-diffusion models for the
key-components have been established, which were solved
using an orthogonal collocation method. The simulation val-
ues of the effectiveness factors for the methanation reaction
CH
4
and the shift reaction
CO
2
are in fair agreement with
the experimental values, which indicates that both mod-
els are able to predict intraparticle transport and reaction
processes within catalyst pellets.
The effectiveness factor
CH
4
of the methanation reac-
tion is large, while the effectiveness factor
CO
2
of the
WGSR is very small and nearly equal to zero. The inter-
action between the methanation reaction and the WGSR
leads to the existence of the direct and reverse WGSR
in catalyst pellet, which is called equilibrium-restrained
WGSR.
The effectiveness factors calculated for the parallel,
equilibrium-restrained reaction systems are not able to
predict the catalyst internal-surface utilization accurately.
Therefore, the intraparticle distributions of the temperature,
the concentrations of species and so on should be taken into
account.
Appendix A. Notations
A, B, AX, transition matrices
BX, BZ
C
i
concentration of component i (mol/m
3
)
C
is
interface concentration of component
i (mol/m
3
)
D
Aj
binary diffusion coefcient of a mixture A
and j (m
2
/s)
D
Ak
Knudsen diffusion coefcient of
component A (m
2
/s)
D
effA
effective diffusivity of component A (m
2
/s)
f(r) aperture distribution function
H
CH
4
heat of methanation reaction (J/mol)
H
CO
2
heat of WGSR (J/mol)
H
p
semi-length of pellet (m)
J
P
, K
P
partial pressure ratio and equilibrium
constant of WGSR, respectively
N
R
, N
A
numbers of radial and longitudinal
collocation point, respectively
R
p
radius of pellet (m)
(r
CH
4
)
w
, methanation reaction rate and WGSR rate,
(r
CO
2
)
w
respectively (mol s
1
kg
1
)
T
s
interface temperature (K)
T temperature (K)
x dimensionless coordinate along radial
distance
y
i
mole-fraction of component i
z dimensionless coordinate along
longitudinal distance
Greek letters
tortuosity
CO
2
,cone
predicted effectiveness factor of WGSR of
one-dimensional model
CO
2
,ctwo
predicted effectiveness factor of WGSR of
two-dimensional model
CO
2
,e
experimental effectiveness factor of WGSR
CH
4
,cone
predicted effectiveness factor of methanation
of one-dimensional model
CH
4
,ctwo
predicted effectiveness factor of methanation
of two-dimensional model
CH
4
,e
experimental effectiveness factor of
methanation
porosity
fm
gas heat conductivity in the pore (W/(mK))
s
heat conductivity of solid (W/(mK))
eff
thermal conductivity (W/(mK))
p
grain density (kg/m
3
)
References
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Chemical Engineering and Processing 44 (2005) 4149
PID controller tuning using mathematical programming
George Syrcos
a
, Ioannis K. Kookos
b,
a
Controls Department, TEI Pireaus, 250 Petrou Ralli & Thivon Ave, 12244 Athens, Greece
b
Department of Chemical Engineering, UMIST, PO Box 88, Manchester M60 1QD, UK
Received 19 December 2003; received in revised form 18 February 2004; accepted 1 April 2004
Available online 18 May 2004
Abstract
Proportional integral derivative (PID) controllers are extensively used in the process industry. As a result a large number of general purpose
tuning methodologies are available. These tuning methodologies can offer initial estimates of the parameters of the PID controllers. However,
the design objectives used for the development of these tuning methods can be quite different from the performance objectives specic to a
process under investigation. As a result, the control engineer often needs customized tuning methods in order to speed up or even eliminate the
retuning procedure, and thus, minimize the time and effort needed to design a satisfactory closed loop system. This paper presents a general
mathematical programming formulation for the development of customized PID controller tunings. A reformulation of the mathematical
formulation is proposed that transforms the initially nonlinear formulation to a linear one that can be solved to global optimality. A number
of case studies are presented to clarify the proposed methodology.
2004 Elsevier B.V. All rights reserved.
Keywords: PID-controller tuning; Mathematical programming
1. Introduction
Proportional integral derivative (PID) controllers are ex-
tensively used in the process industry. It was recently esti-
mated that more than 90% of all control loops involve PID
controllers [1]. The simplicity and transparency of PID con-
trol mechanism, the availability of a large number of highly
efcient, reliable, and cost-effective commercial PID con-
trol modules and their acceptance from the operators are
among the reasons for their success [2]. Tuning of the PID
controllers is achieved in two steps. In the rst step a simpli-
ed model of the process is obtained and initial tunings are
calculated using well-known tuning rules (such as the mod-
ied Ziegler-Nichols [2] or IMC-based [3]). In the second
step, the performance of the loop is assessed and the initial
tunings are modied in order to take into account the oper-
ating specications of the process. The success or failure of
this procedure strongly depends on the judicious choice of
initial tunings. However, all available tuning methods have
been developed to satisfy specic design objectives that, in
most cases, cannot be translated into the design objectives of
k=1
J[x
k
, u
k
], s.t.
_
_
x
k+1
= Ax
k
+bu
k
+Ev
k
y
k
= Cx
k
+du
k
+Fv
k
e
k
= r
k
y
k
u
k
= u
k1
+u
k
u
k
= k
C
e
k
y
L
k
y
k
y
U
k
u
L
k
u
k
u
U
k
u
L
u
k
u
U
(4)
Problem (4) is a nonconvex, nonlinear programming prob-
lem. The nonconvexities are due to the bilinear form of the
control law. This term can be linearized at the expense of
optimizing over a discrete (rather than continuous) set of
controller gains.
First, we assume that an initial controller gain k
C,0
is
available and calculated using classical control techniques.
Then we consider a discrete set of q tuning factors
that
lie in the interval [
L
,
U
] and dened as follows:
=
L
+
_
1
q 1
_
(
U
L
), = 1, 2, . . . , q (5)
Furthermore, we dene q binary variables
{0, 1} to
denote the selection of tuning factor
= 1) or not (
=
0). Then, the control gain can be expressed as follows:
k
C
=
q
=1
(6)
q
=1
= 1 (7)
where
= k
C,0
=1
_
e
k
, k (8)
Finally, we dene the variable E
,k
to be equal to the product
of the binary variable
e
k
, , k (9)
and Eq. (8) can be written in the following linear form
u
k
=
q
=1
E
,k
, k (10)
Then, the nonconvex Eq. (9) can be replaced by the fol-
lowing set of equivalent linear inequalities [4,5]
e
L
E
,k
e
U
(11a)
e
k
e
U
(1
) E
,k
e
k
e
L
(1
) (11b)
It should be noted that when
= 0 then E
,k
= 0, k,
while when
= 1 E
,k
= e
k
, k. As a result, the equiva-
lence of Eqs. (9), (11a), and (11b) can be established easily.
In summary, the nonconvex formulation given by Eq. (4)
can be replaced by the following linearly constrained for-
mulation
min
=
N
k=0
J[x
k
, u
k
],
s.t.
_
_
x
k+1
= Ax
k
+bu
k
+Ev
k
y
k
= Cx
k
+du
k
+Fv
k
e
k
= r
k
y
k
u
k
= u
k1
+u
k
u
k
=
q
=1
E
,k
e
L
E
,k
e
U
,
e
k
e
U
(1
) E
,k
e
k
e
L
(1
),
q
=1
= 1
y
L
k
y
k
y
U
k
u
L
k
u
k
u
U
k
u
L
u
k
u
U
{0, 1} ,
(12)
Depending on the form of the objective function, formu-
lation (12) corresponds to a mixed integer, nonlinear pro-
gramming (MINLP) problem if the objective is nonlinear,
to a mixed integer quadratic programming (MIQP) problem
if the objective is quadratic or to a mixed integer linear pro-
gramming (MILP) problem if the objective is linear. In this
paper consideration is restricted to the case of convex objec-
tive functions for which the global optimum solutions can
be found using available algorithms [4].
G. Syrcos, I.K. Kookos / Chemical Engineering and Processing 44 (2005) 4149 43
2.2. Tuning of proportional-integral (PID) controllers
The PID control law considered here contains the P, PI,
PD, and PID control laws as special cases. The velocity form
of the discrete approximation of an ideal PID controller is
given by [2]
u
k
=k
C
__
1 +
S
I
+
D
S
_
e
k
_
1 +
2
D
S
_
e
k1
+
D
S
e
k2
_
(13)
where
S
is the sampling time, k
C
the controller gain,
I
the
integral time, and
D
is the derivative time. We dene the
following variables:
P
k
= e
k
e
k1
(14)
I
k
=
S
e
k
(15)
D
k
=
1
S
(e
k
2e
k1
+e
k2
) (16)
and Eq. (13) can be written as
u
k
= K
P
P
k
+K
I
I
k
+K
D
D
k
(17)
K
P
= k
C
, K
I
=
k
C
I
, K
D
= k
C
D
(18)
The complete formulation of the closed loop system op-
timization using a PID controller is as follows
min
K
P
,K
I
,K
D
=
N
k=0
J[x
k
, u
k
],
s.t.
_
_
x
k+1
= Ax
k
+bu
k
+Ev
k
y
k
= Cx
k
+du
k
+Fv
k
e
k
= r
k
y
k
u
k
= u
k1
+u
k
u
k
= K
P
P
k
+K
I
I
k
+K
D
D
k
P
k
= e
k
e
k1
I
k
=
S
e
k
S
D
k
= e
k
2e
k1
+e
k2
y
L
k
y
k
y
U
k
u
L
k
u
k
u
U
k
u
L
u
k
u
U
K
P,L
K
P
K
P,U
K
I,L
K
I
K
I,U
K
D,L
K
D
K
D,U
(19)
This is a nonlinear formulation due to the bilinear terms
involved in Eq. (17) and the (possibly) nonlinear objective.
Following the same procedure as in the previous subsection
we can replace Eq. (17) by a set of linear inequalities.
We rst assume that initial values of the controller param-
eters have been obtained using any classical control tech-
nique. We then introduce tuning factors
P
,
I
and
D
as
well as the binary variables
P
,
I
, and
D
=1
, m (20)
q
m
=1
= 1, m (21)
= k
m
C,0
, , m (22)
,k
=
P
P
k
, , k (23)
O
,k
=
I
I
k
, , k (24)
,k
=
D
D
k
, , k (25)
where m {P, I, D}. Eq. (17) can then be written in the
following linear form:
u
k
=
q
P
=1
,k
+
q
I
=1
O
,k
+
q
D
=1
,k
, k (26)
P
L
,k
P
U
P
k
P
U
(1
P
) E
,k
P
k
P
L
(1
P
)
_
, , k
(27)
I
L
O
,k
I
U
I
k
I
U
(1
I
) O
,k
I
k
I
L
(1
I
)
_
, , k
(28)
D
L
,k
D
U
D
k
D
U
(1
D
)
,k
D
k
D
L
(1
D
)
_
, , k
(29)
Depending on the form of the objective function, the nal
formulation obtained by replacing the nonlinear Eq. (17) by
the set of linear inequalities corresponds to a MINLP (non-
linear objective), to a MIQP (quadratic objective) or to a
MILP (linear objective). For the cases where the objective
function is linear, solution to global optimal solution is guar-
anteed using currently available software. The same holds
true for the more general case where the objective function
is a convex function.
The proposed formulation addresses the problem of PID
controller design solely in the time domain. It is important to
44 G. Syrcos, I.K. Kookos / Chemical Engineering and Processing 44 (2005) 4149
emphasize that no approximations have been introduced in
the proposed formulation. This is not the case, for instance,
when the design is based on the frequency domain where
conservative (in most cases) approximations are introduced
in order to translate constraints fromthe time domain into the
frequency domain [6,7]. A further advantage of the proposed
formulation is the fact that the problem can be solved to
global optimality using direct optimization. Classical control
design techniques do not share these desirable characteristics
[6].
3. Case studies
In order to apply the proposed methodology the control
engineer needs to supply the model of the process under
investigation in discrete form (see Eq. (1)), an initial con-
troller tuning (that can be obtained using any classical tech-
nique) and a performance criterion. Then, the optimization
problem can be solved using any commercial optimization
software. In this work GAMS [8] interface to CPLEX and
MINOS solvers was used to solve the proposed formulation.
All results were obtained on an Intel P4 2.66 GHz/512 Mb
computer and the computational time was of the order of
few seconds.
3.1. Control of integrating processes with time delay
(IPTD)
Integrating processes with time delay are among the most
commonly encountered processes. Liquid levels, for in-
stance, exhibit integrating behavior. A typical plant involves
a large number of liquid level loops whose performance
affects strongly the overall performance of the regulatory
control systems. The transfer function of an integrating
process with time delay is the following:
g(s) =
k
P
s
e
ds
(30)
PID controller tunings for this model have been given
by a number of researchers [913]. Chen and Fruehauf
[9] have given an industrial example of the level control
in a distillation column where the open loop dynamics
follows the IPTD model with parameters k
P
= 0.2 and
d = 7.4 min.
The proposed methodology has been applied using the
following objective function:
min
K
P
,K
I
=
S
N
k=0
(|e
k
| + |u
k
|) (31)
where N
S
=
f
= 300 min. A unit step disturbance at t =
0 min was assumed followed be a unit step change in the set
point at t = 150 min. The optimization problem was solved
with = 1/
S
and
S
= 0.2 min giving
K
P
= 0.553, K
I
= 0.0178 (32)
Time (min)
-1
-1.5
0
-2
3
2
1
0
150 100 50 0
-1
y(t)
0
-0.5
u(t)
50 100 150
Time (min)
Fig. 1. Load response of the closed loop IPDT system (proposed: con-
tinuous line, Luyben [10]: dotted line).
Figs. 1 and 2 compare the closed loop behavior obtained
using the tuning proposed in this work and the tunings
proposed by Tyreus and Luyben [10]. Fig. 1 shows that a
signicant improvement in the closed loop load response is
obtained when the proposed methodology is used. The value
of the objective function (Eq. (31)) is = 59.4 for the pro-
posed and = 197.7 for the Luybens tunings. Fig. 2 com-
pares the two methodologies for a unit step set point change.
The responses are comparable and the proposed method
results in = 28.6 while for Luybens tunings = 29.7.
3.2. Systems with inverse response and time delay
Luyben [14] has recently investigated a class of mod-
els that involve both inverse response and time delay. More
specically he has considered the following type of pro-
cesses:
g(s) = k
P
1
z
s
(1 +
P
s)
2
e
ds
(33)
that have a positive zero at s = +1/
z
as well as time a
delay d. Using the objective function given by Eq. (31) with
= 1/
S
and
S
= 0.1 we obtained
K
P
= 0.356, K
I
= 0.154 (34)
for a hypothetical system with
z
= d = 1.6, k
P
= 1 and
P
= 1. A unit step disturbance at t = 0 min was assumed
followed be a unit step change in the set point at t = 50 min.
Fig. 3 compares the closed loop response obtained using the
proposed tunings with the tunings given by Luyben [14].
Luybens tunings correspond to = 19.5 while the ones
proposed in this work to = 16.7. It is interesting to note
that the proposed tunings result in improved load as well as
set point response.
G. Syrcos, I.K. Kookos / Chemical Engineering and Processing 44 (2005) 4149 45
Time (min)
1
0
-0.5
150 100 50 0
2
1.5
1
0.5
0
150 100 50 0
y(t)
0.5
u(t)
Time (min)
Fig. 2. Unit step set point response for IPDT system (proposed: continuous line, Luyben [10]: dotted line).
3.3. Control of integrating processes with time delay and
inverse response (IPTD&IV)
The open loop transfer function of an IPDT&IV process
is the following:
g(s) = k
P
1
z
s
s(1 +
P
s)
e
ds
(35)
and combines the adverse effects associated with having a
right half plane zero at 1/
z
, a pole at zero and a time delay
d. Recently, Luyben [15] proposed a successful and simple
enough tuning techniques for PID controllers and IPDT&IV
systems.
0 10 20 30 40 50 60 70 80 90 100
0
0.5
1
0 10 20 30 40 50 60 70 80 90 100
-1.5
-1
-0.5
0
0.5
y(t)
Time
u(t)
Time
Fig. 3. Closed loop responsecase study 2 (proposed: continuous line, Luyben [14]: dotted line).
In Figs. 4 and 5 the closed loop response obtained using
the tunings proposed by Luyben (PI controller with k
C
=
0.854 and
I
= 23) is compared with the one obtained using
the criterion given by Eq. (31) (k
C
= 1.117 and
I
= 6.32)
with = 1/
S
and
S
= 0.025 for the system:
g(s) = 0.457
1 0.418s
s(1 +1.06s)
e
0.1s
(36)
It is clear that for the set point change the two method-
ologies offer comparable performance ( = 7.4 for the
proposed and = 6.6 for Luybens method). However, as it
becomes clear from inspecting Fig. 4, the proposed method-
ology offers massive improvement for the load response
46 G. Syrcos, I.K. Kookos / Chemical Engineering and Processing 44 (2005) 4149
0 10 20 30 40 50 60 70 80 90 100
-0.5
0
0.5
1
1.5
0 10 20 30 40 50 60 70 80 90 100
-2
-1.5
-1
-0.5
0
0.5
Time (min)
Time (min)
y(t)
u(t)
Fig. 4. Load response of the closed loop IPDT&IV system (proposed:
continuous line, Luyben [15]: dotted line).
case. The value of the objective function for the Luybens
method ( = 28.2) is 3.5 times the value of the objective
function obtained using the proposed method ( = 8.1).
3.4. Control of an unstable process
Most chemical processes exhibit stable open-loop behav-
ior. However, there are some important processes, such as
chemical and biological reactors, that might be operated
around an unstable steady state. The tuning of PID controller
for unstable systems has recently attracted attention [1619].
Lee et al. [18] have presented a powerful IMC-based tun-
ing methodology that appears to surpass most of available
tuning techniques for unstable systems with low order dy-
0 2 4 6 8 10 12 14 16 18 20
-0.05
0
0.05
0.1
0.15
0.2
0 2 4 6 8 10 12 14 16 18 20
-2
-1.5
-1
-0.5
0
Time
Time
y(t)
u(t)
Fig. 6. Load response of the open-loop unstable system (proposed: continuous line, Lee et al. [18]: dotted line).
0 5 10 15 20 25 30 35 40 45 50
0
0.5
1
1.5
0 5 10 15 20 25 30 35 40 45 50
-0.5
0
0.5
1
Time (min)
Time (min)
y(t)
u(t)
Fig. 5. Unit step set point response for IPDT&IV system (proposed:
continuous line, Luyben [15]: dotted line).
namics. They have, among other case studies, considered
the following system:
g(s) =
e
0.5s
(5s 1)(2s +1)(0.5s +1)
(37)
and have demonstrated clearly the superiority of their
method over most of the available tuning techniques. The
same process was considered here with the objective func-
tion given by Eq. (31) ( = 0.1 and
S
= 0.01) and the
proposed method gave the following tunings:
K
P
= 6.905, K = 1.707, K
D
= 11.824 (38)
which are very close to the result reported by Lee et al.
[18]. In Fig. 6, the closed loop response obtained using the
G. Syrcos, I.K. Kookos / Chemical Engineering and Processing 44 (2005) 4149 47
0 10 20 30 40 50
0
0.2
0.4
0.6
0.8
1
0 10 20 30 40 50
-1
-0.8
-0.6
-0.4
-0.2
0
Time
Time
y(t)
u(t)
Fig. 7. Load response of the FOPTD/PI system (proposed: continuous line, Tang et al. [20]: dotted line).
proposed methodology is compared to that obtained using
the PID controller parameters reported in [18]. The improve-
ment obtained using the proposed methodology is again
clear.
3.5. Control of rst order processes with large time delay
(FOPTD)
The transfer function of a rst order plus time delay pro-
cess is given by
0 5 10 15 20 25 30
0
0.2
0.4
0.6
0.8
1
0 5 10 15 20 25 30
-1
-0.8
-0.6
-0.4
-0.2
0
Time
Time
y(t)
u(t)
Fig. 8. Load response of the FOPTD/PID system (proposed: continuous line, Tang et al. [20]: dotted line).
g(s) =
k
P
P
s +1
e
ds
(39)
By dening the dimensionless parameter = d/
P
Eq. (39) can be written in the following form:
g(s) =
k
P
s
+1
e
s
(40)
where s
_
(42)
P
= 0.777 +0.45 (43)
P
= 0.44 0.56
_
1
_
2.2
(44)
In Fig. 9 a number of responses to a unit step load dis-
turbances are shown. The performance of the closed loop
system is acceptable since the controller eliminates quickly
the deviation with a reasonable amount of oscillation.
Based on the success of the proposed tuning formulas
(Eqs. (42)(44)) within the limits of for which they were
derived an extreme test was used to investigate its applicabil-
ity by selecting a process with = 10. Luyben [21] has also
applied different PID controller forms and tuning techniques
such as the IMC method [7] and a method reported by Mar-
lin [22] (CianconeMarlin or CM method) to this process
and the reader is referred to [21] for an interesting discus-
sion on the subject. The different closed loop responses to a
unit step load disturbance are compared in Fig. 10. For the
CM method the PID2 from [21] was used to derive the sim-
ulation results (k
C
= 0.3,
I
= 5,
D
= 2.7, a = 0.1). For
the IMC method the PID3 from [21] was used to derive the
simulation results (k
C
= 0.48,
I
= 6,
D
= 0.83,
F
= 1).
The proposed tuning formulas offer, to our surprise, an im-
proved closed loop response despite the fact that they were
applied to a case which is well outside the limits for which
they were derived.
4. Conclusions
This paper presents a general mathematical programming
formulation the can be used to obtain customized tuning for
PID controllers. A reformulation of the initial NLP prob-
lem is presented that transforms the nonlinear formulation
to a linear one. In the cases where the objective function is
convex then the resulting formulation can be solved easily
to global optimality. The usefulness of the proposed formu-
lation is demonstrated in ve case studies where some of
the most commonly used models in the process industry are
employed. It was shown that the proposed methodology of-
fers closed loop performance that is comparable to the one
achieved by using the best available tunings for a number
of simplied but yet challenging process models.
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Chemical Engineering and Processing 44 (2005) 5158
Separation of acetic acidwater mixtures through acrylonitrile
grafted poly(vinyl alcohol) membranes by pervaporation
N. Alghezawi
a
, O. Sanl
a,
, L. Aras
b
, G. Asman
a
a
Gazi Universitesi Fen-Edebiyat Fakltesi Kimya Blm 06500 Teknik Okullar Ankara, Turkey
b
Orta Do gu Teknik Universitesi Fen-Edebiyat Fakltesi Kimya Blm, Ankara, Turkey
Received 19 May 2003; received in revised form 29 March 2004; accepted 30 March 2004
Available online 15 June 2004
Abstract
The pervaporation separation of acetic acidwater mixtures was performed over a range of 1090 wt.%acetic acid in the feed at temperatures
ranging 2550
C using acrylonitrile (AN) grafted poly(vinyl alcohol) (PVA) membranes. The permeation and separation characteristics of
PVA-g-AN membranes were studied as a function of membrane thickness, feed composition, operating temperature and pressure. When the
downstream pressure increased permeation rate increased with decreasing separation factor and at high acetic acid concentrations PVA-g-AN
membranes shows grater tendency for the separation of acetic acidwater mixtures. Depending on the membrane thickness, feed composition
and temperature PVA-g-AN membranes gave separation factors 2.314 and permeation rates 0.181.17 kg/m
2
h. It was also determined that
PVA-g-AN membranes were found to have lower permeation rate and grater separation factors than PVA membranes.
2004 Elsevier B.V. All rights reserved.
Keywords: Membranes; Selectivity; Separations; Transport processes; Pervaporation; Acetic acidwater mixtures; Poly(vinyl alcohol) membranes; Graft
copolymerization
1. Introduction
Pervaporation is a membrane separation process where
the liquid feed mixture is in contact with the membrane in
the upstream under atmospheric pressure and permeate is re-
moved from the downstream as vapor by vacuum or a swept
inert gas. Most of the research efforts of the pervaporation
have concentrated on the separation of alcoholwater sys-
tem [120] but the separation of acetic acidwater mixtures
has received relatively little attention [2134]. Acetic acid is
an important basic chemical in the industry ranking among
the top 20 organic intermediates. Because of the small dif-
ferences in the volatilitys of water and acetic acid in dilute
aqueous solutions, azeotropic distillation is used instead of
normal binary distillation so that the process is an energy
intensive process. From this point of view, the pervapora-
tion separation of acetic acidwater mixtures can be one of
the alternate processes for saving energy.
C then with
DMF at 55
C [5,38].
The proposed grafting mechanism between PVA and AN is
given in Fig. 1.
2.3. Preparation of membranes
1.2% (w/v) solution of PVA-g-AN in DMSO were
prepared. The solutions of 2030 mL were poured on to
petri-dishes (9.2 cm in diameter) and the solvent was evap-
orated at 80
C.
3.2. Effect of membrane thickness
Membranes with varying thickness (1540 m) were pre-
pared from the copolymer by casting method. The perme-
ation rate and separation factor as a function of membrane
thickness was studied for 20 wt.% acetic acid solutions at
30
C) Q (kg/m
2
h)
PVA PVA-g-AN PVA PVA-g-AN
25 0.95 0.18 1.76 2.58
45 4.47 1.10 1.23 3.03
50 5.70 1.17 1.05 3.03
20 wt.% CH
3
COOH; P = 23 Pa, t = 1.5 h.
54 N. Alghezawi et al. / Chemical Engineering and Processing 44 (2005) 5158
0
0.1
0.2
0.
0.4
0.5
0 10 30 50 70 90 100
CH
3
COOH (wt %)
Q
(
k
g
/
m
2
h
)
0.0
2.0
4.0
6.0
8.0
10. 0
12. 0
14. 0
16. 0
C) Q (kg/m
2
h)
25 0.18 2.60
30 0.66 3.00
40 1.07 3.00
50 1.17 3.00
20 wt.% CH
3
COOH; P = 23 Pa, t = 1.5 h.
3.3. Effect of AN grafting on the performance of the PVA
membranes
In order to understand the effect of grafting on the perfor-
mance of PVA membranes, PVA-g-AN (PVA-2) membranes
were compared with the heat treated PVA membranes that
were prepared by casting method from 7% (w/v) PVA solu-
tion (Table 3).
As it is reected fromthe table that the presence of ANde-
creases the permeation rate while increasing the separation
factor. Increase in the separation factor is caused from the
0. 0
0. 1
0. 2
0. 3
0. 4
0. 5
0 10 30 50 70 90 100
CH
3
COOH (wt %)
0. 0
2. 0
4. 0
6. 0
8. 0
10 .0
12 .0
14 .0
16 .0
Q
(
k
g
/
m
2
h
)
Fig. 5. Change of total permeation rate and separation factor with feed composition: () Q (30
C); () Q (40
C); () (30
C); () (40
C).
hydrogen bonding between acetic acid and CN groups of
AN; so it becomes difcult for acetic acid molecules to dif-
fuse through the membrane and separation factor toward wa-
ter increases. Decrease in permeation rate can be explained
by the dense structure of the grafted membrane. In Fig. 4
permeation rate of grafted membranes at different grafting
ratio with respect to the feed composition was given. As it
seen from the graph although permeation rate decreases with
the amount of AN separation factors were almost the same.
3.4. Effect of temperature on pervaporation
The effect of temperature on the separation performance
of PVA-g-AN (PVA-2) membranes was studied in the tem-
perature range of 2550
C.
Aminabhavi and Naik [37] obtained similar results in the
pervaporation of acetic acidwater mixtures by using PVA
membranes. They reported that for 20 wt.% acetic acid so-
lutions separation factor stayed constant at 35 and 45
C al-
though permeation rate increased with temperature.
The permeation at various operating temperatures is
thought to be governed by three factors [7,23].
1. Change in the free volume of the polymer membrane
swollen by pure components, which affects mainly per-
meation rates.
2. Change in the free volume due to the plasticizing effect.
3. Change in the interaction between permeants in the mem-
brane.
According to the free volume theory as the temperature
increase the frequency and amplitude of chain jumping (i.e.
thermal agitation) increase and the resulting free volumes
become larger. Increase in temperature also decreases the
interaction between acetic acid and water molecules so it
will be easy for both acetic acid and water molecules to
N. Alghezawi et al. / Chemical Engineering and Processing 44 (2005) 5158 55
0
0.1
0.2
0.3
0.4
10 30 50 70 90
CH
3
COOH (wt %)
Q
(
H
2
O
)
(
k
g
/
m
2
h
)
0.0
1.0
2.0
3.0
4.0
5.0
Q
(
C
H
3
C
O
O
H
)
(
k
g
/
m
2
h
)
x
1
0
2
Fig. 6. Effect of feed composition on permeation rate of water and acetic acid: () Q (H
2
O) (30
C); () Q (H
2
O) (40
C); () Q (CH
3
COOH) (30
C);
() Q (CH
3
COOH) (40
C).
diffuse through the free volumes resulted by the increase
in temperature. This situation leads to constant separation
factors.
3.5. Effect of feed composition
At 30 and 40
C).
crease steadily with the increase in acetic acid content of
feed.
Similar results were obtained in the pervaporation separa-
tion of acetic acidwater mixtures using blended polyacrylic
acidnylon 6 membranes [22], poly(4-vinylpyridine-co-
acrylonitrile) membranes [11] and in the permeation and
separation of aqueous alcohol solutions through PVA-AN-
HEMA latex membranes [5].
However, in the studies of Huang and Yeom [23,24] using
chemically crosslinked PVA membranes, maximum perme-
ation rates were reported at low acetic acid concentrations
(10 wt.%).
Looking at the permeation rate of individual components
(Fig. 6), the permeation rate of water component decreases
with the decrease in the water content of the feed solution
56 N. Alghezawi et al. / Chemical Engineering and Processing 44 (2005) 5158
Table 5
Comparison of the performance of the membranes based on pva for the pervaporation separation of acetic acidwater mixtures
Polymer Temperature (
C) Mass % of acetic
acid in the feed
Permeation rate
(kg/m
2
h)
Separation factor () Ref. no.
PVA-g-PAAm 35 80 0.056 3.90 [45]
PVA/PAA (Blend membranes) 25 90 0.300 6.60 [46]
PVA/PHC 25 90 0.140 7.90 [46]
PVA/PVP 25 90 0.800 2.40 [46]
PVA 35 80 0.056 6.71 [37]
PVA 45 80 0.124 6.39 [37]
PVA-g-AAm (48%) 35 80 0.086 5.38 [37]
PVA-g-AAm (93%) 35 80 0.094 3.81 [37]
PVA-g-AN (52%) (PVA-2) 30 90 0.090 14.60 This study
PAAm, poly(acryl amide); PAA, poly(acrylic acid); PHC, poly(hydroxycarboxylic acid); PVP, poly(N-vinyl-2-pyrolidone); PVA, poly(vinyl alcohol); Aam,
acryl amide; AN, acrylonitrile.
and the permeation rate of water is higher than that of acetic
acid regardless of feed composition. These phenomena can
be explained in terms of plasticizing effect of water. As the
water concentration in the feed is increased, the amorphous
regions of the membrane becomes more swollen; hence the
exibility of polymer chains increases the energy required
for diffusive transport through the membrane decreases. This
could be the reason why low separation factors were ob-
tained at low acetic acid concentrations.
Additionally in pervaporation separation follows the
solution-diffusion mechanism. Therefore the molecular size
of the permeating molecules becomes very important to
characterize the permeation behavior [43]. It is known that
acetic acid has larger molecular size (0.40 nm) than water
molecules (0.28 nm). As the amount of acetic acid increases
in the feed mixture it becomes difcult for acetic acid
molecules to diffuse through the less swollen membrane, so
separation factor increases at high acid concentrations.
Pervaporation separation index values were calculated us-
ing Eq. (3) and presented in Fig. 7. As it is reected from
0.0
0.2
0.4
0.6
2 4 6 8
P (Pa x 10
-3
)
Q
(
k
g
/
m
2
h
)
0.0
1.0
2.0
3.0
4.0
Fig. 8. Effect of down stream pressure on the total permeation rate and separation factor (20 wt.% CH
3
COOH; T = 30
C): () Q () .
the gure that PSI values of the membranes increases with
the acetic acid concentration which shows that the perfor-
mance of PVA-g-AN (PVA-2) membranes are good at high
acetic acid concentrations
For comparison purposes several results regarding
the separation of acetic acidwater mixtures obtained
by various authors with different type of membranes
listed in Table 5. One can see that PVA-g-AN mem-
branes have high selectivity although they have almost the
same permeation rate depending on the feed composition
and temperature than the membranes studied up in the
table.
3.6. Effect of pressure on pervaporation
Effect of the down stream pressure on the permeation rate
and the separation factor was shown in Fig. 8 for 20 wt.%
acetic acid solution at 30
Corresponding author. Tel.: +1 314 935 7187; fax: +1 314 935 7211.
E-mail address: muthanna@che.wustl.edu (M.H. Al-Dahhan).
(CT) scanner with -ray source at the Chemical Reaction
Engineering Laboratory (CREL), Washington University [5]
has been used successfully in the past to characterize ow
distribution of liquid and gas over non-structured packing
[6]. Hence, it is the tool of choice for studies on structured
packing.
Many studies on the ow distribution in random packed
beds have been reported in the literature. Mercandelli et al.
[8] published a short review of the ow distribution work in
random packed trickle bed, which includes the list of various
techniques used to determine and quantify the ow distri-
bution. Conventional methods include, for example, collect-
ing liquid at the bottom of the column from different zones
while advanced methods include tomographic techniques.
Mercandelli et al. [8] used several techniques to quantify
liquid distribution in columns of diameters up to 30 cm with
three different distributor designs. They used global pres-
sure drop measurements, global residence time distribution
(RTD) of the liquid, local heat transfer probes, capacitance
tomography and a collector at the bottom of the column.
Boyer and Fanget [7] used computed tomography to
quantify liquid distribution in a 60-cm-diameter trickle bed
0255-2701/$ see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.cep.2004.03.010
60 S. Roy et al. / Chemical Engineering and Processing 44 (2004) 5969
reactor (downow of gas and liquid over randomly packed
particles). The apparatus was very similar to that being used
in the Chemical Reaction Engineering Laboratory (CREL)
at Washington University in St Louis, albeit, with a higher
number of detectors (32 of 1.27-cm-diameter BGO detectors
as against 9 of 5-cm-diameter Nal detectors) and increased
radioactive source strength (300 mCi as against 85 mCi).
A comprehensive study was performed to quantify the error
associated with the measurements and the authors were able
to detect solids holdup within 3% accuracy. The authors
also proposed a correlation to predict liquid holdup based
on a force balance on liquid lm and showed that tomog-
raphy can reproduce the liquid holdup as predicted by the
model for liquid ow rates up to 1.7 cm/s (no gas owing).
Yin et al. [15] investigated liquid distribution in a col-
umn of 60 cm in diameter containing pall rings. The authors
found that the distributor type had a signicant effect on the
distribution, which was veried using computational uid
dynamics (CFD).
Examples of the use of tomographic techniques to deter-
mine gas/liquid distribution in structured packing is limited
in the open literature. Mewes et al. [9] studied ow distribu-
tion in monoliths using capacitance tomography. A spatial
Fig. 1. Schematic diagram of the experimental setup: (a) Process diagram (all dimensions in centimeter); (b) packing element; (c) liquid distributor. DP,
differential pressure transmitter; FI, ow indicator; TI, temperature indicator.
resolution of about 510% of the column diameter in the
measurement plane was claimed [912]. Mewes et al. [9]
used water which was introduced through a large number of
injection nozzles into a 120 mm diameter reactor containing
monolith. With increasing liquid velocity, the liquid distri-
bution improved. The authors did not demonstrate the effect
of gas velocity on the liquid distribution.
Toya et al. [13] used X-ray tomography to scan gas/liquid
ow in a corrugated structured packing known as Sulzer
Mellapak 250 Y. The solids prole of the dry structured
packing was reproduced with fair accuracy. The scan was
performed in a 60-cm-diameter column. Very thin liquid lm
owing past the structure at 0.006 m/s was also detected by
the tomography unit.
Iluita and Larachi [4] developed a hydraulic mechanistic
model for prediction of the irrigated pressure drop, liquid
holdup and the effective interfacial area in the preloading
zone of structured packing operated in countercurrent ow
of gas and liquid under partial wetting condition. The model
mimics the two phase ow situation by a network of double
slits consisting of dry and wet slits. The model was success-
ful in predicting the irrigated pressure drop, liquid holdup
and effective interfacial area under various conditions.
S. Roy et al. / Chemical Engineering and Processing 44 (2004) 5969 61
This work focuses on investigating the ow distribution in
a structured packed bed using gamma ray computed tomog-
raphy. Gas and liquid ow in a countercurrent mode over
a bed packed with corrugated structured packing is usually
used in reactive and catalytic distillation columns. This in-
vestigation includes determining the liquid holdup and its
distribution in the cross-section of the reactor at a range of
gas and liquid velocities.
2. Experimental work
2.1. Experimental setup and operating conditions
The experimental setup, schematically shown in Fig. 1a,
was developed to measure gasliquid ow distribution in
countercurrent ow structured packed bed. It consists of a
packing section, distributor and liquid and gas delivery sys-
tems. The Plexiglas column is 152.4 cm high and 30.48 cm
in diameter and holds four packing elements each 27.3 cm
in diameter and height. The packing is of corrugated type
made of stainless steel and frequently used in modern re-
active distillation columns, commercially known as Norton
packing (Fig. 1b). The corrugations are at a 45
angle to the
vertical axis. The packing elements are held in position us-
ing a donut ring at the bottom of the Plexiglas column. The
liquid is recirculated and introduced at the top through a dis-
tributor having seven holes of 2.5-cm-diameter; the middle
one is covered with a mesh (Fig. 1c).
Water was used as the liquid phase. The liquid delivery
system consists of a feed tank, pump, and a ow indicator.
Water is recycled, as well as added if necessary, to maintain
a constant suction head at the pump. The in-house air system
was used as the gas delivery system through a rotameter.
Air enters the setup at a point below the packing. Two taps
are mounted at the inlet and outlet of the packed column for
pressure drop measurement.
Flow scans were performed at three axial levels (1.5, 2.5
and 3.5D) from the top packing surface (D being the diam-
eter of the packing), for various ow conditions. Supercial
liquid and gas velocities used, denoted as U
L
and U
g
, re-
spectively, are listed in Table 1.
2.2. The newly developed gamma ray computed
tomography (CT) scanner design
A newly installed computed tomography (CT) scan-
ner was used in this study. This is a modied unit of the
third-generation fan-beam conguration originally devel-
Table 1
Range of operating conditions available for the experimental setup used.
U
G
0 to 10 cm/s
U
L
0.63 to 2.17 cm/s
Scan Levels: 1.5D, 2.5D, 3.5D from the top, D 27.3 cm.
Fig. 2. Schematic diagram of the newly developed CREL computed
tomography.
oped by Kumar et al. [5] at CREL. The key system elements
are illustrated in Fig. 2. The CT scanner consists of an ar-
ray of Nal (TI) detectors with a diameter of 5 cm as well
as an encapsulated 70 mCi Cs
137
source located opposite
to the center of the array of detectors. Nine detectors are
used in the present study to cover the cross-section of the
30.48-cm-diameter column. The detectors and the source
are mounted on a plate, which can be rotated around the
axis of the column by a stepping motor that is controlled
through a microprocessor. Moreover, the whole assembly
can be moved in the axial direction along the column to
perform a scan at different axial levels of the column. The
source collimator provides a collimated fan beam of 40
around the
column using a total scanning time of about ve hours and
collecting numerous beam path attenuations (approximately
2500 projections). The nal holdup distribution images are
obtained from the attenuation data using the relationships
and the procedure developed by Chen et al. (2000) [6] for
packed bed.
2.3. CT scan evaluation
Since this was a new CT scanner developed to be used
for the rst time, it was imperative to evaluate the perfor-
mance of the unit in terms of spatial and density resolution.
Two CT scans were performed to evaluate the system. In the
rst case, a 5.08 cm jar was lled with water and scanned
(Fig. 4). In the second case, a hollow ball dipped in water
was scanned and gas holdup was evaluated (Fig. 5). Further,
a third validation, which will be discussed in the following
section of the Results and discussion, was also performed
by determining the solids fraction of the packing using com-
puted tomography, which was compared to the one measured
by water displacement method.
For the rst case of a jar lled with water, the results are
as follows.
The collimator used in the present CT has an aperture of
2 mm and therefore, theoretically, spatial resolution should
be around 2 mm. In this test case, a 70 mm domain con-
taining 5.1 cm outer diameter glass jar lled with water was
reproduced (as shown in Fig. 4b). The diameter of the ob-
ject obtained from CT was 5.3 cm, which indicates that we
have a spatial resolution of 2 mm in this case. The attenua-
tion in the water region should be uniform. In this case, the
scan gives a slightly non-uniform attenuation as shown in
Fig. 4c. The calculated error in the attenuation coefcient
was found to be within 6.5%.
For the second case, a hollow ball was dipped inside a
jar lled with water and scanned. The diameters of the ball
and jar were 6.98 and 18.95 cm, respectively, as shown in
Fig. 5a. A scan area of 27 cm in diameter was reproduced
using the reconstruction algorithm. The dimensions of the
objects as reproduced by the scan were 6.97 and 19.20 cm,
respectively, as shown in Fig. 5b, which give a maximum
spatial error of about 2.5 mm. This is good enough to re-
solve relatively small maldistribution, if it exists, inside the
30.48-cm-diameter column used in this study. The gure
shows that the overall error in the estimated total holdup is
within 12.8%.
It must be noted that the resolution changes with the size
of the object being scanned due to different attenuation of
the gamma rays. However, the obtained resolutions should
be adequate for a column of 30.5-cm-diameter.
64 S. Roy et al. / Chemical Engineering and Processing 44 (2004) 5969
Fig. 5. CT validation using: (a) hollow ball in water Jar; (b) density distribution of the object; (c) gas holdup prole of the system.
3. Results and discussion
3.1. Solids fraction of the packing
Solids fraction of the packing was rst evaluated using CT
at the same axial levels used for the actual ow scans, i.e.,
at 1.5, 2.5 and 3.5D, from the top packing surface, where
D denote the diameter of the packing (30.48 cm). Fig. 6a
shows the solids distribution at those three axial positions.
The azimuthally averaged solids fraction is shown in Fig. 6b
and is approximately equal to 2.5%. The solid fraction was
also measured experimentally by immersing the packing el-
ement in water-lled bath and measuring the volume of wa-
ter displaced, which was found to be approximately 3%.
This overall average value is close to the values obtained
by CT scanning. Considering the error associated with the
measurement of small amount of the displaced water, this
indicates that CT provides adequate measurements of the
solids distribution in the bed despite its small values.
3.2. Liquid distribution in the bed of corrugated structured
packing
Fig. 7ac shows the time-averaged cross-sectional liquid
saturation distribution in the column at supercial gas ve-
locities of 0, 5 and 10 cm/s, respectively. For each gas veloc-
ity, the liquid saturation distribution is shown at three axial
positions and three liquid velocities. Also provided are the
S. Roy et al. / Chemical Engineering and Processing 44 (2004) 5969 65
Fig. 6. Determination of solid distribution at three axial positions: (a) cross-sectional distribution; (b) azimuthally averaged solids holdup and (c) overall
solids holdup. The horizontal line indicates experimentally determined solids fraction.
time and cross-sectionally averaged liquid saturation values,
L
, as well as the uniformity factor expressed as percentage
f
(discussed later). Liquid saturation is the ratio of liquid
volume to the bed void volume. It can be seen that, for the
ow conditions used, as supercial liquid velocity increases,
the cross-sectional averaged liquid saturation increases. For
all the supercial gas and liquid velocities used, the liquid
saturation varies between 6 to 15%.
Fig. 7ac also illustrates the liquid saturation distribution
along the length of the column. In general, it is observed
that as the liquid moves downward, liquid saturation in-
creases. At all conditions studied, the uniformity factor
shows that the liquid distribution improves at the bottom
section of the bed (i.e. 3.5D). This could be due to the
liquid distributor design, which produces seven liquid jets
at the top of the bed. These jets disperse while moving
downward. At high liquid supercial velocity (2.17 cm/s),
the uniformity factors are smaller than those obtained at
lower liquid supercial velocities, since, at this high liquid
velocity, the jets require longer bed length to disperse and
distribute.
Fig. 8 shows the time and azimuthally averaged radial
liquid saturation proles at varying supercial gas and liq-
uid velocities at the middle axial position (2.5D). The gure
shows that liquid saturation is nearly at, which suggests
a fair uniformity of liquid distribution. Moreover, with in-
creasing liquid velocities, liquid saturation increases. Simi-
lar trends were obtained at all scan heights.
66 S. Roy et al. / Chemical Engineering and Processing 44 (2004) 5969
Fig. 7. Time averaged cross-sectional liquid saturation distribution in structured bed at (a) Ug: 0 cm/s; (b) Ug: 5 cm/s; (c) Ug: 10 cm/s. In the table,
L
shows the liquid saturation and
f
% show uniformity factor percentage.
S. Roy et al. / Chemical Engineering and Processing 44 (2004) 5969 67
Fig. 7. (Continued ).
Fig. 8. Effect of supercial gas and liquid velocities on the liquid saturation
radial prole at axial position of 2.5D.
Fig. 9 illustrates the effect of supercial gas and liquid ve-
locities on the cross-sectionally averaged liquid saturation at
the middle of the column (2.5D axial position). It is obvious
that the effect of gas velocity on the liquid saturation is not
signicant within the range of ows studied. This could be
due to the fact that solid and liquid holdups are very small,
leaving enough space for the gas to ow upwards without
signicant interactions with the liquid phase owing down-
ward.
The measured cross-sectionally averaged liquid holdup
(i.e. measured liquid saturation times the bed voidage) are
consistent with previously reported results [4]. For a sim-
ilar packing structure, Illiuta and Larachi [4] found liquid
holdups, as calculated by their mechanistic model and com-
pared with the reported experimental results, slightly lower
than the values obtained in this study. However, there are
some differences between the two studies: this work was
performed in a smaller diameter column (30 cm versus
Fig. 9. Effects of gas and liquid supercial velocities on the cross-
sectionally averaged liquid saturation.
68 S. Roy et al. / Chemical Engineering and Processing 44 (2004) 5969
100 cm), and higher supercial gas velocity was used. Il-
liuta and Larachi [4] mentioned that gas ow rate had a
marginal effect on liquid holdup, a fact reected in this work
as well.
Experiments were also performed to compare the holdup
and ow distribution in a bed, randomly packed with 3 mm
spherical alumina particle, under the same ow conditions
as was done for structured packing. However, it was evident
that the successful operating conditions for structured pack-
ing were too severe for random packed bed, due to very high
pressure drop. For very low liquid velocity (1 mm/s) and
no gas ow, when the experiment was possible, the liquid
distribution was poor as indicated by a low uniformity factor
(40%). However, this information is insufcient to com-
pare the distribution characteristics of structured and random
packings.
3.3. Uniformity factor (
f
)
The uniformity of the liquid ow distribution across the
column cross-section was quantied in this work. This is
presented in Fig. 7ac in a tabular form along with time and
cross-sectionally averaged liquid saturation values. Various
methods have been used in the literature to quantify the ow
uniformity across a column cross-section. Mercandelli et al.
[8] used a maldistribution factor, which was a variation of
the standard deviation among nine sectors that the ow do-
main was divided into. The factor varied between 0 and 1.
This method is suitable for ow domains, which are divided
into small number of sectors. For cases where large num-
ber of sectors are used (e.g. holdup obtained by tomography
where large number of pixels are used), the maldistribution
values invariably give small values, thus making it impos-
sible to ascertain the quality of distribution. Jiang proposed
the relative standard deviation to quantify the uniformity of
ow [1]. However, since standard deviation can take values
up to innity, this quantity will also not provide a proper
feel for the uniformity.
In the present work, the degree of uniformity is cal-
culated based on the t-test method. The circular domain
representing the reactor is divided into several sub-domains,
each having a xed number of pixels. In this work, 10 pix-
els were arbitrarily taken. This constitutes several groups
of data points for liquid saturation; t-test was then carried
out between the group representing the overall averaged
cross-sectional distribution of liquid saturation and the av-
erage of one sub-domain group. If the group passes the
t-test, this indicates that the null hypothesis is satised and
the two groups are statistically the same. Then 1 is assigned
to that pair. If the two groups are statistically not simi-
lar, then 0 is assigned. Uniformity factor is then dened
as the percentage number of groups that are statistically
similar (i.e. passes the t-test) to the group representing the
whole cross-sectional distribution of liquid saturation and
its average. In this method, a uniform distribution yields
a uniformity factor of 100%, and a completely maldis-
tributed domain would give a uniformity factor very close
to 0%.
The domain consisted of 60 by 60 pixels (3600) out of
which 2936 pixels represent the actual cross-section of the
column, and these are the pixels which represent the liquid
saturation distribution. Fig. 7ac show the uniformity factor
in percentage (
f
%) for different liquid and gas supercial
velocities for the scans performed in this work. In most of the
cases, the uniformity factor is large (above 70%), suggesting
a fairly uniform distribution of liquid achieved in the studied
setup.
3.4. Pressure drop in corrugated structured packing
The pressure drop across the length of the packing was
extremely small and was beyond the detectable limit of the
available pressure gauges. The full scale of the available
transducer (validyne differential transducer) was 200 units,
which correspond to a pressure drop of 1 cm of water. In
our study, it was observed that the maximum pressure drop
within the gas and liquid ow rates studied was about 1 mm
of water (20 calibration units). A trend was seen wherein
the pressure drop increases with increasing gas and liquid
velocities.
4. Final remarks
It was established that the newly developed CT unit has
a spatial resolution of about 2 2.5 mm. This is quite ac-
ceptable given the size of the column used in this study. The
solid fraction as determined by CT scan was about 2.5%,
which was close to the value of 3% as determined by water
displacement method.
The liquid saturation increases with increasing supercial
liquid velocity. Moreover, the liquid saturation increases as
the liquid phase moves downward. The liquid distribution
was found to be fairly uniform in general as expressed by the
uniformity factor which was relatively large, between 70 to
95%. Liquid distribution was better at the bottom of the bed,
compared to the upper section. The effect of gas velocity,
was in general, found to be very small at the conditions used
in this study.
Acknowledgements
The nancial support provided by ABB Lummus Global,
Inc. is acknowledged which made this work possible.
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Chemical Engineering and Processing 44 (2005) 7179
Effect of cycling operations on an adsorbed natural gas storage
O. Pupier, V. Goetz
, R. Fiscal
IMP-CNRS UPR 8521, Institut de Science et Gnie des Matriaux et Procds, Rambla de la Thermodynamique, 66100 Perpignan, France
Received 18 February 2004; received in revised form 7 May 2004; accepted 7 May 2004
Available online 1 July 2004
Abstract
Adsorbed natural gas (ANG) is an interesting opportunity for developing natural gas vehicles technology. In this case, adsorbents such as
activated carbons are used to store natural gas at moderate pressure, 3.5 MPa, compared to the high-pressure (20 MPa) required for current
compressed natural gas technology. Many studies are devoted to the elaboration of suitable adsorbent materials to optimise the methane storage
capacity. Nevertheless, since natural gas (NG) is composed of about 95%of methane mixed with other components, an important deterioration
of the storage performance is observed after successive cycles of an ANG system (lling and delivery). It is the result of adsorption of the
other components present in NG that are mainly higher molecular-weight hydrocarbons, carbon dioxide and nitrogen. In the present study,
the evolution of the storage capacity of a 2 l vessel cycled with NG is experimentally measured. As a function of the cycle number, the gas
composition at the outlet of the ANG system is determined using gas chromatography analysis.
2004 Elsevier B.V. All rights reserved.
Keywords: Activated carbon; Adsorption; Storage; Natural gas; Cycling operation
1. Introduction
Natural gas is a possible alternative as a transportation
fuel. Moreover, natural gas vehicles (NVGs) provide bene-
ts as cleanliness and safety [1,2]. However, the disadvan-
tage of NG is its low volumetric energy density compared to
that of conventional liquid fuels. Current gas vehicles em-
ploy storage vessels at high pressure (20 MPa). This implies
high manufacturing and lling costs. Adsorbed natural gas
(ANG) on a suitable microporous adsorbent offers an inter-
esting opportunity of developing NGVs technology. ANG
technology can provide adequate energy density at a low
pressure, that is, 3.5 MPa and at room temperature. Natural
gas storage capacity of an adsorbent is currently expressed
in terms of the delivered volume of natural gas per unit of
volume containing the adsorbent, measured at standard con-
ditions (P = 0.101 MPa, T = 273 K). To be a commercially
attractive system, the nal objective is to reach a delivered
quantity equal to 150 (v/v) under real operating conditions
[3]. Numerous aspects occur in ANG storage that affect its
performance, and hence, its viability. The rst one is the
AC
(kg m
3
)
ENG
(kg m
3
) (Wm
1
K
1
) k 10
12
(m
2
)
720 90 2.4 0.023
298 K measured with a high-pressure volumetric device [19]
under pressure up to 5 MPa.
From this raw material, a consolidated adsorbent com-
posite block was prepared following a procedure previously
detailed [10] in the case of Maxsorb
. Each bafe is 30 mm in
width and 1 mm in thickness. There are some semicircular
holes on the plate and each hole has a tongue-like plate fac-
ing the upstream to break bubbles. Because of the returning
Fig. 1. Schematic of the experimental equipment.
ow of the downcomer, the ow near the sparger is not axial
symmetry. But the unsymmetry will disappear about 130 cm
above the sparger. So the internal is installed 165 cm above
the sparger.
Fig. 2. Photo of the internal used in this work.
T. Zhang et al. / Chemical Engineering and Processing 44 (2005) 8187 83
The local gas holdup and bubble behavior were measured
by a reective optic ber probe developed by Wang and
co-workers [21,22]. It can be known whether the probe is im-
merging in the gas. The rate of the time that probe immerg-
ing in the gas and the total sample time is gas holdup. Gas
velocity can be got by the time difference that one bub-
ble touch two probes and the distance between two probes.
Chord length can be obtained from one bubble velocity and
the time that the probe stays in the bubble. Bubble size dis-
tribution is got from the probability density of the chord
length based on some numerical method. The local liquid
velocity in the riser was measured by a backward scattering
LDA system (system 9100-8, model TSI). Details have been
given by Lin et al. [23].
3. Results and discussion
3.1. Gas holdup
The upper surface of the internal is dened as the zero
of the axial position. Axial positions are positive above this
and negative below this. The radial proles of the gas holdup
at ve axial positions were measured, as shown in Fig. 3.
The radial prole of the gas holdup becomes much atter
after owing through the internal, with an increase in the
gas holdup near the wall and a decrease in the center region
as compared with the gas holdup below the internal. As
the distance above and away from the internal increases,
the prole becomes more and more similar to that before
contact with the internal. The local radial proles of the gas
holdup at axial positions 144 and 209 cm show almost no
difference. This shows that the inuence of the internal on
the radial prole of the gas holdup becomes weaker and
weaker with increasing distance away from the internal and
is no longer felt beyond a certain distance. The analysis of
the local gas holdup proles shows that the inuence of
the internal persists to a distance of about 1.4 m. In order
to show the effect of the internal on the radial prole of
Fig. 3. Radial prole of the gas holdup at different axial positions.
Fig. 4. Radial maldistribution index of the local gas holdup at different
axial positions.
the gas holdup clearly, a radial maldistribution index, , is
introduced, dened as:
=
1
n 1
n
i=1
(y
i
y)
2
(1)
where y can be gas holdup, bubble velocity, bubble diameter
or liquid velocity. Fig. 4 shows the change in maldistribu-
tion index
R
0
g
(r)u
b
(r)rdr
A
g
(2)
where A is the cross-sectional area.
Fig. 8 shows the average bubble velocity as a function
of the axial distance at different supercial gas velocities.
The average bubble velocity decreases after contact with the
internal to a minimum, then it increases gradually to the
original velocity above the position of 144 cm. Fig. 9 shows
u
b
as a function of the axial distance at different supercial
gas velocities. It decreases notably after contact with the
internal to a minimum at 39 cm above the internal, then
increases gradually. According to the analysis of Figs. 79,
the radial prole of the bubble rise velocity above the internal
are much atter than that below, and the average bubble rise
velocity increases after the bubble had passed through the
internal. The change caused by the internal gets smaller and
T. Zhang et al. / Chemical Engineering and Processing 44 (2005) 8187 85
Fig. 8. Average bubble rise velocity as a function of the axial position.
then vanishes gradually with increasing distance from the
internal.
3.3. Bubble Sauter diameter
Precise knowledge of the bubble size is important for a
better understanding of the hydrodynamics, mass transfer,
and reactor design. Zun [27] concluded that small bubbles
tend to have uniform radial proles while large bubbles tend
to rise in the central region. Smaller bubbles and a uniform
radial prole lead to a larger interfacial area and a lower rise
velocity, which increases mass transfer.
The Sauter bubble diameter, d
32
, is commonly used to
show the statistic size distribution of the bubbles [28].
d
32
=
n
i
d
3
i
n
i
d
2
i
(3)
Fig. 10 shows the radial prole of the bubble Sauter di-
ameter at ve axial positions. The bubble size is very much
decreased after owing through the internal and then in-
creases with an increase of the distance from the internal.
The difference between the values at the positions of 144
and 209 cm above the internal is negligible and their radial
Fig. 9. Axial change in the radial maldistribution index of the bubble rise
velocities.
Fig. 10. Bubble Sauter diameter radial prole at different axial positions.
prole is similar to that below the internal. According to
the analysis of bubble diameter, it can be concluded that the
effective distance of the internal is about 140 cm.
While owing through the internal, bubbles rise along the
undersurface of the bafes and collide with the tongue-like
bars, and are broken up into smaller bubbles as shown in
Fig. 10. The difference in the direction of adjacent bafes
increases the liquid turbulent intensity, which is benecial
to the breakup of large bubbles. With increasing distance
from the internal, the turbulent intensity decreases and coa-
lescence becomes dominant until a new equilibrium between
the breakup and coalescence of bubbles is reached.
3.4. Bubble size distribution
The bubble size detected by the probe is subject to a
probability distribution [28,29] and only the mean statistical
value of the bubbles is given by d
32
. The analysis of the
bubble size distribution helps us understand the uniformity
of the bubble sizes and its axial evolution. Fig. 11 shows
the axial change of the bubble size distribution at r/R = 0
and r/R = 0.97, respectively. Below the internal, the peak
Fig. 11. Bubble size distribution at different axial positions.
86 T. Zhang et al. / Chemical Engineering and Processing 44 (2005) 8187
of the distribution at r/R = 0.97 is to the left of that at r/R
= 0. Due of bubble breakup by the internal, the bubble size
distributions at the center and near the wall are narrower than
that obtained below the internal and the peaks are shifted to
the left after passing through the internal. This means that the
bubble size decreases and the bubble size distribution is more
uniform above as compared with that below. With increasing
distance from the internal, the effect of the internal vanishes
gradually and the bubble size distributions become wider and
the peaks shift to the right. There is no difference between
the size distributions obtained at the position of 144 and
209 cm above the internal, which means that the region of
the inuence of the internal on bubble size distribution is
about 1.4 m.
3.5. Liquid velocity
Fig. 12 shows the radial prole of the liquid velocity at
different axial positions. Due of the bafes, the liquid is re-
distributed in the radial direction and the turbulent intensity
is increased. The radial prole of the liquid velocity is al-
most uniform after passing the internal. Liquid velocity is
lower at the center and higher near the wall as compared
with that below the internal. With increasing distance from
the internal, the turbulence intensity diminishes and the wall
effect becomes more apparent, that is, the liquid velocity in-
creases at the center and decreases near the wall. The radial
prole obtained at the position of 114 cm from the internal
is similar to that obtained below the internal and is the same
as that at the position of 144 cm.
The radial maldistribution index of the liquid velocity,
u
l
, is dened according to Eq. (1). Fig. 13 shows the ax-
ial changes in
u
l
at different supercial gas velocities.
u
l
is much decreased after passing through the internal and
reaches a minimum at 5 cm above the internal, then it in-
creases gradually with increasing axial height. According to
the analysis of the radial prole of the liquid velocities, it
can be concluded that the region in which the internal inu-
ences the liquid velocity is only within 110 cm.
Fig. 12. Radial prole of the liquid velocity.
Fig. 13. Axial change of the radial maldistribution index of liquid veloc-
ities.
4. Conclusions
Mass transfer is essential in EL-ALRs. Smaller bubbles
and a uniform gas holdup radial distribution increase the in-
terfacial area and improve mass transfer. Intensied turbu-
lence increases the surface renewal frequency and decreases
bubble size. A novel internal to improve mass transfer and
the hydrodynamic behavior in a gasliquid system is re-
ported. Experiments were carried out to study the effect of
the internal on the bubble behavior and liquid velocity in an
EL-ALR.
The radial proles of the gas holdup and bubble rise veloc-
ity become more uniform after passing through the inter-
nal. With increasing distance from the internal, the radial
proles of the gas holdup and bubble rise velocity change
back to be similar to that below the internal. At 144 cm
above the internal, the radial proles of the gas holdup
and the bubble rise velocity are the same as those below,
while
and
u
b
reach their minimum 39 cm above the
internal.
The bubble Sauter diameter very much decreases after
passing the internal, then increases with increasing dis-
tance from it. The bubble size distribution becomes nar-
rower after the internal and its peak is shifted to the left.
The bubble size at 144 cm above the internal has increased
back to be the same as that below.
Turbulence is intensied after passing through the inter-
nal. The radial prole of the liquid velocity becomes at-
ter.
u
l
reaches a minimum 5 cm above the internal. The
liquid velocity 114 cm above the internal is the same as
that below, that is, the internal affects the liquid velocity
up to about 110 cm above the internal.
The internal used in this work has good performance in
intensication of gasliquid mass transfer and in improv-
ing the ow distribution, and has a good perspective in
application in airlift reactors. Meanwhile, further study on
the internal should be carried out.
T. Zhang et al. / Chemical Engineering and Processing 44 (2005) 8187 87
Acknowledgements
The authors gratefully acknowledge nancial support by
the National Natural Science Foundation of China (No.
20276035) and by the Ministry of Education Ph.D. Fellow-
ship Program (No. 20020003060).
Appendix A. Notations
A cross-section of the reactor (m
2
)
d
32
Sauter bubble diameter (mm)
H axial distance from the upper surface of
the internal (m)
r radial position in the reactor (m)
R radius of the riser (m)
u local velocity (m/s)
U supercial velocity (m/s)
local gas holdup
radial maldistribution index
Subscriptions
b bubble
g gas phase
l liquid phase
u velocity
gas holdup
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Chemical Engineering and Processing 44 (2005) 89100
Multicriteria synthesis of exible heat-exchanger networks
with uncertain source-stream temperatures
Cheng-Liang Chen
, Ping-Sung Hung
Department of Chemical Engineering, National Taiwan University, Taipei 10617, Taiwan, ROC
Received 23 May 2003; received in revised form 28 July 2003; accepted 31 March 2004
Available online 2 July 2004
Abstract
A multi-criteria synthesis strategy for heat-exchanger networks (HENs) simultaneously considering minimum utility consumption, max-
imum source-stream temperature exibility, and even minimum number of matches is proposed. The exible HEN synthesis problem is
formulated as a multi-objective mixed-integer linear programming (MO-MILP). For handling the multiple conict design targets, a two-phase
fuzzy multi-criteria decision-making method is presented to attain a best compromised solution. Two numerical examples with exibility pref-
erences in source-stream temperatures are supplied, demonstrating that the proposed strategy can provide denite and feasible compensatory
solutions for multi-criteria HEN synthesis problems.
2004 Elsevier B.V. All rights reserved.
Keywords: Heat-exchanger network; Synthesis; Flexibility; Superstructure; MILP; Multi-criteria decision-making; Fuzzy optimization
1. Introduction
A heat exchanger network (HEN) synthesis problem can
be described as the one that synthesize a HEN congura-
tion to reach some assigned targets such as minimum util-
ity consumption, minimum total number of heat exchangers,
etc., with given heating/cooling utilities and hot/cold process
streams be cooled/heated from nominal inlet temperatures
to specied target temperatures [1].
Most of the existing HEN synthesis methods rely on ei-
ther heuristic rules (for example, pinch analysis method [2])
or mathematical programming (for example, simultaneous
optimization approach [36]). And further, to some typical
objectives considered in the HEN synthesis such as utility
consumption, total number of matches, and total exchanger
area, the exibility of the HENs for feasible operation un-
der possible variation of source-stream temperatures and/or
heat-capacity ow rates has been emphasized in some re-
cent articles [610]. For HEN synthesis, the analysis of this
exibility, dened as the size of the region of feasible oper-
ation in the space of desired or undesired deviations of pa-
iHP
qcu
(0)
i
+
jCP
qhu
(0)
j
(1)
x
_
_
_
z
ijk
, zcu
i
, zhu
j
; t
ik
, t
jk
; dt
ijk
, dtcu
i
, dthu
j
;
q
ijk
, qcu
i
, qhu
j
;
i HP, j CP, k ST
_
_
_
(2)
C.-L. Chen, P.-S. Hung / Chemical Engineering and Processing 44 (2005) 89100 91
=
_
_
x
(T
in
i
T
out
i
)FCp
i
=
kST
jCP
q
ijk
+qcu
i
(T
out
j
T
in
j
)FCp
j
=
kST
iHP
q
ijk
+qhu
j
_
_
overall heat balances
(t
ik
t
i,k+1
)FCp
i
=
jCP
q
ijk
(t
jk
t
j,k+1
)FCp
j
=
iHP
q
ijk
_
_
stage heat balances
t
i,1
= T
in
i
{T
in(0)
i
, T
in(0)
i
+}
t
j,N
T
+1
= T
in
j
{T
in(0)
j
, T
in(0)
j
+}
_
_
_
uncertain inlet temperatures
t
ik
t
i,k+1
t
jk
t
j,k+1
T
out
i
t
i,N
T
+1
T
out
j
t
j,1
_
_
feasibility of temperatures
(t
i,N
T
+1
T
out
i
)FCp
i
= qcu
i
(T
out
j
t
j,1
)FCp
j
= qhu
j
_
_
_
utility loads
q
ijk
z
ijk
0
qcu
i
zcu
i
0
qhu
j
zhu
j
0
_
_
logical constraints
dt
ijk
t
ik
t
jk
+(1 z
ijk
)
dt
ij,k+1
t
i,k+1
t
j,k+1
+(1 z
ijk
)
dtcu
i
t
i,N
T
+1
T
out
CU
+(1 zcu
i
)
dthu
j
T
out
HU
t
j,1
+(1 zhu
j
)
_
_
approach temperatures
dt
(0)
ijk
T
min
dtcu
(0)
i
T
min
dthu
(0)
j
T
min
_
_
nominal approach temp. bounds
iHP,jCP,kST
z
ijk
+
iHP
zcu
i
+
jCP
zhu
j
MEU
max
_
_
_
maximumexchanger units
z
ijk
, zcu
i
, zhu
j
{0, 1}
t
ik
, t
jk
, dt
ijk
, dtcu
i
, dthu
j
, q
ijk
, qcu
i
, qhu
j
; 0
i HP, j CP, k ST
_
_
(3)
where x and denote variables for design and the feasible
searching space, respectively; is the targeted exibility for
source-stream temperatures [10]; the superscript
(0)
denotes
the nominal condition; and the upper bound for unit num-
bers is MEU
max
. The searching space is comprised of all
heat balances constraints and relevant logical constraints. As
pointed out in [610], this problem is difcult to solve di-
rectly since it involves a max-min-max constraint that leads
to a non-differentiable global optimization problem. For the
HEN synthesis problem with uncertain source-stream tem-
peratures, the feasible region dened by the reduced inequal-
ity constraints is convex [6], so the critical point that limits
the solution lies at a vertex of the polyhedral region of un-
certainty. For the problem of Eq. (7) with N ( N
H
+N
C
)
uncertain source-stream temperatures, the vertex-based for-
mulation is given as follows [10]:
min
x
V
V
J
(0)
=
iHP
qcu
(0)
i
+
jCP
qhu
(0)
j
(4)
92 C.-L. Chen, P.-S. Hung / Chemical Engineering and Processing 44 (2005) 89100
or
min
x
V
V
J
(ave)
=
1
N
V
+1
n{0}VT
_
_
iHP
qcu
(n)
i
+
jCP
qhu
(n)
j
_
_
(5)
x
V
=
_
_
z
ijk
, zcu
i
, zhu
j
; dt
(n)
ijk
, dtcu
(n)
i
, dthu
(n)
j
;
t
(n)
ik
, t
(n)
jk
; q
(n)
ijk
, qcu
(n)
i
, qhu
(n)
j
;
i HP, j CP, k ST, n {0} VT
_
_
(6)
V
=
_
_
x
V
(T
in(n)
i
T
out
i
)FCp
i
=
kST
jCP
q
(n)
ijk
+qcu
(n)
i
(T
out
j
T
in(n)
j
)FCp
j
=
kST
iHP
q
(n)
ijk
+qhu
(n)
j
(t
(n)
ik
t
(n)
i,k+1
)FCp
i
=
jCP
q
(n)
ijk
(t
(n)
jk
t
(n)
j,k+1
)FCp
j
=
iHP
q
(n)
ijk
T
in(n)
i
= (T
in(0)
i
+r
(n)
i
) = t
(n)
i,1
T
in(n)
j
= (T
in(0)
j
+r
(n)
j
) = t
(n)
j,N
T
+1
t
(n)
ik
t
(n)
i,k+1
t
(n)
jk
t
(n)
j,k+1
T
out
i
t
(n)
i,N
T
+1
T
out
j
t
(n)
j,1
(t
(n)
i,N
T
+1
T
out
i
)FCp
i
= qcu
(n)
i
(T
out(n)
j
t
(n)
j,1
)FCp
j
= qhu
(n)
j
q
(n)
ijk
z
ijk
0
qcu
(n)
i
zcu
i
0
qhu
(n)
j
zhu
j
0
dt
(n)
ijk
t
(n)
ik
t
(n)
jk
+(1 z
ijk
)
dt
(n)
ij,k+1
t
(n)
i,k+1
t
(n)
j,k+1
+(1 z
ijk
)
dtcu
(n)
i
t
(n)
i,N
T
+1
T
out
CU
+(1 zcu
i
)
dthu
(n)
j
T
out
HU
t
(n)
j,1
+(1 zhu
j
)
dt
(0)
ijk
T
min
dtcu
(0)
i
T
min
dthu
(0)
j
T
min
iHP,jCP,kST
z
ijk
+
iHP
zcu
i
+
jCP
zhu
j
MEU
max
z
ijk
, zcu
i
, zhu
j
{0, 1}
t
(n)
ik
, t
(n)
jk
, dt
(n)
ijk
, dtcu
(n)
i
, dthu
(n)
j
, q
(n)
ijk
, qcu
(n)
i
, qhu
(n)
j
0
i HP, j CP, k ST, n {0} VT
_
_
(7)
Here, r
(n)
i
and r
(n)
j
are the vertex identiers which take val-
ues of N
V
= 2
(N
H
+N
C
)
combinations of +1 and 1, see
Table 1 in [10]. Therein, Eq. (4) considers nominal utilities
and Eq. (5) takes into account the average of all vertical op-
erating points.
For the benchmark example mentioned in [10], a
2-hot/2-cold streams problem along with heating steam and
cooling water, the maximal allowable variation of various
possible minimum-utility HEN structures is examined by
C.-L. Chen, P.-S. Hung / Chemical Engineering and Processing 44 (2005) 89100 93
Table 1
Problem data of example 1
Process streams and utilities Heat-capacity ow rate FCp (kW/K) Input temperature T
in
(K) Output temperature T
out
(K)
Hot stream 1 (H1) 10 650 370
Hot stream 2 (H2) 20 590 370
Cold stream 1 (C1) 15 410 650
Cold stream 2 (C) 13 350 500
Hot utility (HU) 680 680
Cold utility (CU) 300 320
T
min
= 10 K.
Table 2
The resulting HEN structure of example 1 with increasing exibility target
( 0, see Table 2 of [10] for labeling HEN structures)
Specied value Resulting HEN structure Maximum exibility
0 36.95 A 36.95
36.95 + B1
a
70.63
40 B7
a
90.00
50 B6 90.00
60 B1
a
70.63
70 B7
a
90.00
80 B7
a
90.00
90 B7
a
90.00
90 + C2 120.0
120150 D 150.0
increasing the value over [0, 150] and solving Eq. (4)
or Eq. (5). There are 18 sets of structure-determining bi-
nary variables and 11 of them possess unique structures
(see Table 2 of [10]). However, we found that the resulting
HEN structures with increasing exibility targets are prone
to variation, and the true maximal exibilities of these HEN
structures are usually greater than the required targets, as
illustrated in Table 2. Similar results can also be found
should restricted heat-load constraints on vertices, as shown
in Eqs. (8) and (9), be taken into consideration in the HEN
synthesis.
min
x
V
load
J
(0)
=
iHP
qcu
(0)
i
+
jCP
qhu
(0)
j
(8)
or
min
x
V
load
J
(ave)
=
1
N
V
+1
n{0}VT
_
_
iHP
qcu
(n)
i
+
jCP
qhu
(n)
j
_
_
(9)
load
=
_
_
q
(n)
ijk
, qcu
(n)
i
, qhu
(n)
j
q
(0)
ijk
(1 ) q
(n)
ijk
q
(0)
ijk
(1 +)
qcu
(0)
i
(1 ) qcu
(n)
i
qcu
(0)
i
(1 +)
qhu
(0)
j
(1 ) qhu
(n)
j
qhu
(0)
j
(1 +)
i HP, j CP, k ST, n VT
_
_
(10)
In this paper, the targeted source-stream temperatures
are directly treated as individual design objective, and the
multi-criteria optimization approach is adopted for HEN
synthesis. The minimizing utility and the maximizing oper-
ational exibility can be simultaneously considered as two
conict objectives for synthesis of the network structure.
Furthermore, other targets such as minimizing number of
matches can also be considered, such as,
min
x
V
V
J
(0)
1
=
iHP
qcu
(0)
i
+
jCP
qhu
(0)
j
or
min
x
V
V
J
(ave)
1
=
1
N
V
+1
n{0}VT
_
_
iHP
qcu
(n)
i
+
jCP
qhu
(n)
j
_
_
and
max
x
V
V
J
2
= and
min
x
V
V
J
3
=
iHP
jCP
kST
z
ijk
+
iHP
zcu
i
+
jCP
zhu
j
(11)
In such a case, a unique HEN structure with satisfactory
levels in nominal or average utility consumption and opera-
tional exibility as well as unit numbers will be obtained. A
two-phase fuzzy optimization method is proposed to nd a
best compromised solution for the multi-criteria HEN syn-
thesis problem, as discussed in the next section. The basic
number of constraints and variables for the multi-objective
MILP formulation are summarized in the following.
1. The number of constraints:
(a) for linear equality constraints: (N
V
+ 1)[N
T
(N
H
+
N
C
) +4(N
H
+N
C
)];
94 C.-L. Chen, P.-S. Hung / Chemical Engineering and Processing 44 (2005) 89100
(b) for linear inequality constraints: (N
V
+ 1)[(N
H
+
N
C
)(N
T
+3) +3N
T
N
H
N
C
] +N
T
N
H
N
C
+N
H
+N
C
.
2. The number of variables:
(a) binary variables: N
H
N
C
N
T
+N
H
+N
C
;
(b) positive continuous variables: (N
V
+1)[N
T
(2N
H
N
C
+
N
H
+N
C
) +2(N
H
+N
C
)] +1.
3. Fuzzy multi-criteria optimization
Consider the multi-criteria optimization problem de-
ned in Eq. (11). Because of the fact that these objective
functions usually conict with each other in practice, the
optimization of one objective implies the sacrice of other
targets; it is thus impossible to attain their own optima, J
s
,
s S = [1, . . . , S], simultaneously. Therefore, the decision
maker (DM) must make some compromise among these
goals. In contrast to the optimality used in single objec-
tive optimization problems, Pareto optimality characterizes
the solutions in a multi-objective optimization problem
[13].
The weighting-sum method, among methods found in lit-
eratures for solving multi-objective optimization problems,
is the one that is used most often. Basing on the subjective
comprehension for each objective, the DM of this method
can weigh and sum up these objectives into a scalar form,
and then nd the solution by any existing single-objective
optimization method. However, as the situation of combin-
ing weighting factors becomes more complex, this method
becomes more tedious and the solution could be still in-
valid. Moreover, it is difcult for the DM to attribute a set
of incompatible objectives, such as utility consumption,
operational exibility, or number of matches in a heat ex-
changer network, without knowledge of the possible level
of attainment for these objectives. The physical mean-
ing of the nal scalar objective function is thus usually
vague.
In this work, we adopt the fuzzy set theory [14] to deal
with the multi-objective optimization problem. By consid-
ering the uncertain property of human thinking, it is quite
natural to assume that the DM has a fuzzy goal, J
s
, to
describe the objective J
s
with an interval [J
1
s
, J
0
s
]. For the
sth objective to be minimized, it is quite satised as the
objective value J
s
J
1
s
, and is unacceptable as J
s
J
0
s
.
The degree of satisfaction decreases as the objective value
increases from J
1
s
to J
0
s
. A strictly monotonic decreas-
ing membership function,
J
s
(J
s
(x
V
)) [0, 1], can be
used to characterize such a transition from the objective
value to the degree of satisfaction, therein value of 1 de-
notes absolutely satisfactory, and 0 means unacceptable.
Notably, an interval of [J
0
s
, J
1
s
] and a monotonic increas-
ing membership function should be used for dening a
fuzzy objective to be maximized. Without loss of gener-
ality, we will adopt linear membership functions in the
following.
J
s
(J
s
(x
V
))
=
_
_
1; for J
1
s
J
s
J
0
s
J
s
J
0
s
J
1
s
for J
1
s
J
s
J
0
s
0; for J
s
J
0
s
for J
s
to be minimized
(12)
J
s
(J
s
(x
V
))
=
_
_
1; for J
s
J
1
s
J
1
s
J
s
J
1
s
J
0
s
for J
0
s
J
s
J
1
s
0; for J
0
s
J
s
for J
s
to be maximized
(13)
The original multi-criteria optimization problem is now con-
verted to the one that looks for a suitable decision variable
vector that can provide the maximal degree-of-satisfaction
for the multiple fuzzy objectives.
max
x
V
V
(
J
1
(x
V
), . . . ,
J
S
(x
V
)) (14)
Under incompatible objective circumstances, a DM must
make a compromise decision that provides a maximal
degree-of-satisfaction for all these conict objectives. The
new optimization problem, Eq. (14), can be interpreted as
the synthetic notation of a conjunction statement (maximize
jointly all objectives). The result of this aggregation can be
viewed as a fuzzy intersection of all fuzzy goals, J
s
, s S,
and is still a fuzzy set, D.
D = J
1
. . . J
S
(15)
The nal degree-of-satisfaction resulting from certain vari-
able set,
D
(x
V
) can be determined by aggregating the
degree-of-satisfaction for all objectives,
J
s
(x
V
), s S, via
specic fuzzy intersection operator, T.
D
(x
V
) = T
_
J
1
(x
V
), . . . ,
J
S
(x
V
)
_
(16)
The fundamental properties for a fuzzy set and the related
operators can be found in [15]. As the ring level for each
policy is determined by the above procedure, the best so-
lution, x
V
, with the maximal ring level,
D
(x
V
), can be
selected.
max
x
V
D
(x
V
) = max
x
V
V
T(
J
1
(x
V
), . . . ,
J
S
(x
V
)) (17)
Using the fuzzy intersection operator, the original multi-
objective optimization problem, Eq. (11), is converted into a
single objective problem, Eq. (17). Several operators for im-
plementing fuzzy intersection can be selected for T, therein
two most popular ones are shown below.
T(
J
1
, . . . ,
J
S
)
=
_
min(
J
1
, . . . ,
J
S
) T = minimum
(
J
1
+. . . +
J
S
)
S
T = average
(18)
The average operator simultaneously takes all membership
values into account. But, no guarantee can be made for any
C.-L. Chen, P.-S. Hung / Chemical Engineering and Processing 44 (2005) 89100 95
single objective. The minimum operator concentrates on im-
proving the worst scenario. However, the minimum operator
may result in multiple solutions since contribution of those
objectives with membership values greater than the mini-
mum one would not be cared. We thus combine these two
fuzzy intersection operators to take advantages of both and
propose a two-phase optimization procedure [11,12]. The
minimum operator is rst used in phase I to nd the least
degree of satisfaction for the worst objective, then the aver-
age operator is applied in phase II to promote satisfaction
levels of all objectives with guaranteed least membership
value. The merit of this method is that we can not only ob-
tain the unique optimal solution by using average operator
but also guarantee each objective to go after their own max-
imum on the basis of taking the least degree of satisfaction
as the lower-bound constraint. So, now we can summarize
the procedure of the two-phase fuzzy satisfying approach
for the multi-criteria optimization problem.
Step 1. For a function to be minimized, determine its ideal
solution and anti-ideal solutions by directly mini-
mizing and maximizing the objective function.
min
x
V
V
J
s
= J
1
s
(ideal solution ofJ
s
, totally acceptable
value) (19)
max
x
V
V
J
s
=
J
0
s
(anti ideal solution ofJ
s
,
unacceptable value) (20)
Notably, direct maximization and minimization
should be taken for a maximizing objective to
obtain the ideal and anti-ideal solutions.
Step 2. Based on the importance of different objective func-
tions and the acceptable ranges for objective val-
ues, subjectively select suitable lower/upper bounds,
J
1
s
J
1
s
J
0
s
J
0
s
for minimizing objective and
J
0
s
J
0
s
J
1
s
J
1
s
for maximizing objective. De-
ne membership functions for multiple fuzzy ob-
jectives as given in Eqs. (12) and (13).
Step 3. (Phase I). Use the minimum operator to nd the
maximal degree of satisfaction for the worst objec-
tive,
min
.
max
x
V
D
= max
x
V
V
min(
J
1
, . . . ,
J
S
) =
min
(21)
Step 4. (Phase II). Use the average operator to simultane-
ously promote satisfaction levels of all objectives
with new constraints of guaranteed minimal degree
of satisfaction.
max
x
V
+
V
D
= max
x
V
+
V
J
1
+ +
J
S
S
(22)
where
+
V
=
V
{
J
s
min
, s S} (23)
The new feasible space guarantees the least degree
of satisfaction for each fuzzy objective.
4. Numerical example
Two numerical examples adapted from [4,10] are supplied
to demonstrate the efcacy of proposed HEN synthesis strat-
egy. To solve this MO-MILP for the HEN model, GAMS
[16] and CPLEX are used as the modeling environment and
the MIP solver, respectively. The computing machine is a
personal computer with an Intel Pentium IV 2.26 GHz CPU.
Example 1. The 2-hot/2-cold streams example studied by
[10], with problem data presented in Table 1, is illustrated.
With these parameters, the multi-objective MILP formula-
tion has 408 linear equality constraints, 760 linear inequal-
ity constraints, 12 binary variables, and 545 positive con-
tinuous variables. Notably, the restriction of MEU
max
= 6
in Eq. (7) will be removed should the minimum number of
matches be simultaneously taken into account as one of the
design objectives.
According to the model formulation and the problem data,
we solve the multi-criteria MILP synthesis problem by us-
ing the fuzzy optimization procedure discussed in Section
3. The ideal and anti-ideal solutions, obtained by sequen-
tially minimizing and maximizing each objective function,
are shown in Table 3. Within these lower/upper limiting val-
ues, several preference intervals are subjectively selected to
establish linear membership functions for the fuzzy objec-
tives. In implementing the two-phase fuzzy optimization, we
rstly use the minimum operator to maximize the degree of
satisfaction for the worst target,
min
. The average operator
is then applied to optimize the aggregated objectives with
guaranteed level of satisfaction.
At rst, only two conict objectives are considered: the
minimal utility consumption and the maximal exibility to
all source-stream temperatures. And then the third objective,
the minimal number of matches, would be appended. Results
of two-phase fuzzy optimization with preference intervals of
[2550, 12750] or [2550, 8850] for utility, [0, 150], [40, 90]
or [40, 70] for exibility, and [4, 7] for unit numbers, along
with either or not considering restrictions on heat loads at
extreme operating points, are listed in Table 4. The resulting
HEN structures are also depicted in Fig. 2. Notably, the re-
duced range of exibility, [40, 90], implies that the required
minimum tolerance for temperature deviation is at least 40 K
and a tolerance of maximum temperature deviation for 90 K
Table 3
The ideal/anti-ideal solutions of various objectives of example 1
Objective function Ideal solution J
1
i
Anti-ideal solution
J
0
i
J
(0)
1
utility (kW) 2550 12750
J
2
exibility (K) 150 0
J
3
units 4 12
96 C.-L. Chen, P.-S. Hung / Chemical Engineering and Processing 44 (2005) 89100
Table 4
Results of HEN synthesis for example 1 using two-phase optimization when simultaneously considering minimal utility and maximal exibility (cases
IIV), and additional objective of minimal units (cases V and VI) with different preference intervals, and with or without considering restriction on heat
loads at vertices ( = = 0.6)
Case Preference intervals Heat load Phase Minimum utility Maximum exibility Minimum units
Hot Cold Total Satisfaction Flexibility Satisfaction Units Satisfaction
I [2550, 12750] No I 1300 2950 4250 0.833 120.0 0.800 6
(C2) [0, 150], [, 6] II 1300 2950 4250 0.833 120.0 0.800 6
II [2550, 8850] No I 1050 2700 3750 0.810 80.5 0.810 6
(B7) [40, 90], [, 6] II 1050 2700 3750 0.810 90.0 1.00 6
III [2550, 8850] Yes I 2190 3840 6030 0.448 62.4 0.448 6
[40, 90], [, 6] II 2190 3840 6030 0.448 62.4 0.448 6
IV [2550, 8850] Yes I 1893 3543 5436 0.542 56.3 0.542 6
[40, 70], [, 6] II 1893 3543 5436 0.542 56.3 0.542 6
V [2550, 8850] No I 1300 2950 4250 0.730 73.3 0.667 5 0.667
[40, 90], [4, 7] II 1300 2950 4250 0.730 74.2 0.685 5 0.667
VI [2550, 8850] Yes I 2550 4200 6750 0.333 56.7 0.333 6 0.333
[40, 90], [4, 7] II 2550 4200 6750 0.333 69.8 0.597 6 0.333
Fig. 2. The HEN structures for cases IVI of example 1.
C.-L. Chen, P.-S. Hung / Chemical Engineering and Processing 44 (2005) 89100 97
Table 5
Problem data of example 2
Process streams
and utilities
Heat-capacity
ow rate FCp
(kW/K)
Input
temperature
T
in
(K)
Output
temperature
T
out
(K)
Hot stream 1 (H1) 6 500 320
Hot stream 2 (H2) 4 480 380
Hot stream 3 (H3) 6 460 360
Hot stream 4 (H4) 20 380 360
Hot stream 5 (H5) 12 380 320
Cold stream 1 (C1) 18 290 660
Hot utility (HU) 700 700
Cold utility (CU) 300 320
T
min
= 10 K.
Table 6
The ideal/anti-ideal solutions of various objectives of example 2
Objective function Ideal solution J
1
i
Anti-ideal solution
J
0
i
J
(0)
1
utility (kW) 3780 9860
J
2
exibility (K) 20 0
J
3
units 6 31
is absolutely satised. We choose 90 as the maximum de-
viation for most cases since it is the maximal tolerance for
the HEN with heat load restrictions on vertices.
As shown in Table 4 and Fig. 2, the HEN structure in
case I is the same as C2 of [10], therein the maximum ex-
ibility to temperatures is explicitly given as 120. In case II,
the B7 structure of [10] can be obtained when the tolera-
ble upper bound for utility consumption is decreased from
12750 to 8850, and the preference interval for exibility is
reduced from [0,150] to [40,90]. The resulting utility con-
sumption will be reduced from 4250 (Case I) to 3750 due
Table 7
Results of HEN synthesis for example 2 using two-phase optimization when simultaneously considering minimal utility, maximal exibility and minimal
units with different preference intervals, and with or without considering restriction on heat loads ( = = 0.6)
Case Preference intervals Heat load Phase Minimum utility Maximum exibility Minimum units
Hot Cold Total Satisfaction Flexibility Satisfaction Units Satisfaction
I [3780, 9860] No I 3863 403 4266 0.920 18.4 0.920 8 0.920
[0, 20], [6, 31] II 3793 333 4126 0.943 20.0 1.00 8 0.920
II [3780, 4930] No I 3712 252 3964 0.840 16.8 0.840 10 0.840
[0, 20], [6, 31] II 3660 200 3860 0.930 20.0 1.00 10 0.840
III [3780, 4930] No I 3811 351 4162 0.667 13.3 0.667 8 0.667
[0, 20], [6, 12] II 3793 333 4126 0.699 20.0 1.00 8 0.667
IV [3780, 4930] No I 3811 351 4162 0.667 16.7 0.667 8 0.667
[10, 20], [6, 12] II 3793 333 4126 0.699 20.0 1.00 8 0.667
V [3780, 9860] Yes I 3980 520 4500 0.882 10.6 0.882 8 0.920
[0, 12], [6, 31] II 3980 520 4500 0.882 12.0 1.00 8 0.920
VI [3780, 4930] Yes I 3742 282 4024 0.787 9.4 0.787 11 0.800
[0, 12], [6, 31] II 3742 282 4024 0.787 9.4 0.787 11 0.800
VII [3780, 4930] Yes I 3860 400 4260 0.583 6.99 0.583 8 0.667
[0, 12], [6, 12] II 3860 400 4260 0.583 10.0 0.833 8 0.667
VIII [3780, 4930] Yes I 3860 400 4260 0.583 9.5 0.583 8 0.667
[6, 12], [6, 12] II 3860 400 4260 0.583 10.0 0.667 8 0.667
to the restriction of preference intervals, and the exibility,
90, is equivalent to the maximum of the B7 structure.
All other conditions are equal to those in case II, case
III includes heat-load restrictions ( = = 0.6) on vari-
ous vertical operating points as additional constraints. The
prices of such additional restrictions are increased utility
consumption from 3750 to 6030 and decreased exibility to
temperature deviation from 90 to 62.4, which is still signi-
cantly greater than the minimum targeted value, 40. In case
IV, the preference interval for temperature deviation is fur-
ther reduced to [40, 70]. It is found that the resulting HEN
has smaller utility consumption, 5438, with the expense of
further reduction on exibility, 56.3, since our desideratum
for exibility has been made lower.
Cases V and VI take into account the unit number as
the third design objective, where heat-load restrictions on
vertices are either included or not. In case V, it is found
that the unit number is only ve, exibility to temperature
deviation is 74.2, and the utility consumption is 4250, a little
more than B4 and B5 of [10]. In case VI where heat-load
restrictions on vertices are further included, the total unit
number becomes six, the total utility is increased to 6750
with a reduced maximum temperature exibility of 69.8.
From these results, it is found that the proposed
multi-criteria synthesis strategy can attain a denite and
compromised solution for a problem with assorted conict
objectives. The preference intervals of various objectives
have signicant effects on nal HEN structures. Such ac-
ceptable and/or preference intervals can also reect the
importance of different objective functions. Should one
specic objective is emphasized, a tighter restriction or
shrinking span should be placed on its acceptable ranges.
98 C.-L. Chen, P.-S. Hung / Chemical Engineering and Processing 44 (2005) 89100
Fig. 3. The HEN structures for cases IVIII of example 2.
Observing the results shown in Table 4, we also discover
that the integrated two-phase method can bring the merits of
the minimum and average operators together. The minimum
operator maximize the degree of satisfaction for the worst
objective, and can result in a harmonious solution with
satisfaction levels for objective functions that are equal or
close to each other. The average operator, on the other hand,
can sometimes promote satisfaction levels for other objec-
tives with guaranteed minimum value, such as Cases II, V,
and VI. Owing to these advantages, the two-phase method
can thus provide the best compromised HEN conguration.
Example 2. This problem consists of ve hot streams and
one cold stream, (N
H
= 5, N
C
= 1), along with steam and
cooling water as utilities [3]. The problem data are listed
in Table 5. The number of superstructure stages is set as
N
T
= 5. With these parameters, the MO-MILP formulation
has 3510 linear equality constraints, 8026 linear inequality
constraints, 31 binary variables, and 5981 positive continu-
ous variables. The ideal and anti-ideal solutions are shown
in Table 6. Various preference intervals are sequentially se-
lected for dening the membership functions, as shown in
Table 7.
We directly use the ideal/anti-ideal solutions as the pref-
erence intervals in Case I. The acceptable utility range is
reduced from [3780,9860] to [3780,4930] in Case II. With
such a smaller allowance interval, the resulting utility con-
sumption will be reduced slightly from 3793 to 3660 at the
expense of unit numbers increased from 8 to 10. In Case III,
C.-L. Chen, P.-S. Hung / Chemical Engineering and Processing 44 (2005) 89100 99
the maximum allowable unit number is changed from 31 to
12. The resulting HEN structure is slightly different to that
of Case I, but the required unit numbers, utilities, and exi-
bility are the same as Case I. In Case IV, when the minimum
exibility requirement is upgraded from 0 to 10, the same
HEN structure of Case I results with the same levels of util-
ity, exibility and unit numbers. Cases VVIII give similar
results with additional heat-load restrictions ( = = 0.6)
on various vertical operating points. With such additional
constraints, the HEN structures use similar levels of utilities
and unit numbers, but the exibility levels are dramatically
reduced. The resulting HEN structures are depicted in Fig. 3.
5. Conclusion
In this paper, we use the fuzzy multi-criteria optimization
approach to synthesize the heat-exchanger network where
some conict design objectives such as the total utility
consumption, the exibilities to source-stream temperature
variations, and even the total number of heat exchange units
can be considered simultaneously. Such a exible HEN
synthesis problem can be formulated as a multi-objective
mixed-integer linear programming (MO-MILP). For han-
dling the multiple conict design objectives, a two-phase
fuzzy optimization method is proposed to attain the best
compromised solution. The attractive features of the pro-
posed MO-MILP model are that it not only considers the
trade-off among the utility consumption, the source-stream
temperature exibility, and even the number of matches,
but also avoids the determination of structural boundaries,
as discussed in [10]. Two numerical examples with various
cases are studied, demonstrating that the proposed strat-
egy can provide a feasible compensatory solution for the
multi-criteria HEN synthesis problem.
Acknowledgements
This work is supported by the National Science Council
(ROC) under Contract NSC91-ET-7-002-004-ET. Partial -
nancial support of Ministry of Economic Affairs under grant
92-EC-17-A-09-S1-019 is also acknowledged.
Appendix A. Nomenclature
CP index set of cold process stream
dt
ijk
temperature approach for match i and j in stage k
dtcu
i
temperature approach for match i and cold utility
dthu
j
temperature approach for match j and hot utility
FCp heat capacity owrate
HP index set of hot process stream
J objective function
MEU
max
maximum number of heat-exchange units
N number of uncertain parameters
N
C
number of cold streams
N
H
number of hot streams
N
T
number of superstructure stages
N
V
number of vertices, = 2
N
q
ijk
heat exchanged between stream i and j in stage k
qcu
i
heat exchanged between stream i and cold utility
qhu
j
heat exchanged between stream i and hot utility
r directional identier for vertices
ST index set of superstructure stages
S number of objectives
T
min
minimum approach temperature
t
ik
temperature of stream i at hot end of stage k
t
jk
temperature of stream j at hot end of stage k
T temperature
VT index set of vertices
x, x
V
vector of variables
z
ijk
binary variable for existence of unit for match i
and j in stage k
zcu
i
binary variable for existence of unit for match i
and cold utility in stage k
zhu
i
binary variable for existence of unit for match j
and hot utility in stage k
Greek letters
, parameters used for restriction of heat-load
deviations
exibility index
J
s
membership function for J
s
J
s
a fuzzy goal
S index set of multiple objectives
D a fuzzy set
D
degree of satisfaction
upper bound for temperature difference
upper bound for heat exchange
the feasible searching region
Superscripts
in
inlet
(n)
identier for vertices
out
outlet
(0)
identier for nominal operating condition
Subscripts
CU
cold utility
HU
hot utility
i
index for hot process streams
j
index for cold process streams
k
index for superstructure stages
s
index for objectives
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Chemical Engineering and Processing 44 (2005) 101114
On-line dynamic optimization and control strategy for
improving the performance of batch reactors
A. Arpornwichanop
a
, P. Kittisupakorn
a
, I.M. Mujtaba
b,
a
Department of Chemical Engineering, Chulalongkorn University, Bangkok 10330, Thailand
b
School of Engineering, Design & Technology (EDT 3), University of Bradford, Bradford, West Yorkshire BD7 1DP, UK
Received 23 December 2002; received in revised form 25 August 2003; accepted 28 April 2004
Available online 2 July 2004
Abstract
Since batch reactors are generally applied to produce a wide variety of specialty products, there is a great deal of interest to enhance batch
operation to achieve high quality and purity product while minimizing the conversion of undesired by-product. The use of process optimization
in the control of batch reactors presents a useful tool for operating batch reactors efciently and optimally. In this work, we develop an approach,
based on an on-line dynamic optimization strategy, to modify optimal temperature set point prole for batch reactors. Two different optimization
problems concerning batch operation: maximization of product concentration and minimization of batch time, are formulated and solved using
a sequential optimization approach. An Extended Kalman Filter (EKF) is incorporated into the proposed approach in order to update current
states from their delayed measurement and to estimate unmeasurable state variables. A nonlinear model-based controller: generic model
control algorithm (GMC) is applied to drive the temperature of the batch reactor to follow the desired prole. A batch reactor with complex
exothermic reaction scheme is used to demonstrate the effectiveness of the proposed approach. The simulation results indicate that with the
proposed strategy, large improvement in batch reactor performance, in term of the amount of a desired product and batch operation time, can
be achieved compared to the method where the optimal temperature set point is pre-determined.
This paper gathers and integrates efcient well-known methodologies such as EKF, GMC and on-line optimization together, resulting in
an applicable, reliable and robust control technique for batch reactors.
2004 Elsevier B.V. All rights reserved.
1. Introduction
In many chemical industries, there is an increasing trend to
place a consideration on the production of high value prod-
ucts (e.g. polymers, pharmaceuticals, and specialty chemi-
cals) in batch processes. As an important main unit in such
processes, a batch reactor is generally involved in manufac-
turing of these products. The use of batch reactors offers
many advantages. Firstly, a batch reactor is quite exible, it
can adapt to small volume production of various products,
which are greatly submitted to the rapid changes in market
conditions and the advent of new technology. Secondly, a
batch reactor provides the natural way to scale-up processes
from laboratory experiment where complex chemical syn-
thesis is studied, to industrial manufacturing. Finally, it is
j
Cp
j
(T
jsp
T
j
) Q
j
V
j
j
Cp
j
(6)
Tr
Tj
TRC
Heat exchanger Batch reactor
Heating fluid
Cooling fluid
TJC
Fig. 1. Batch reactor system.
with
k
1
= exp
k
1
1
k
2
1
T
r
+ 273.15
k
2
= exp
k
1
2
k
2
2
T
r
+ 273.15
W = MW
A
M
A
+ MW
B
M
B
+ MW
C
M
C
+ MW
D
M
D
M
r
= M
A
+ M
B
+ M
C
+ M
D
Cp
r
=
(Cp
A
M
A
+ Cp
B
M
B
+ Cp
C
M
C
+ Cp
D
M
D
)
M
r
Q
r
= H
1
(k
1
M
A
M
B
) H
2
(k
2
M
A
M
C
)
Q
j
= UA(T
j
T
r
)
A =
2W
r
where M
i
is the amount of mole of component i, T
r
is the
reactor temperature, T
j
is the jacket temperature, and T
jsp
is
a set point value of the jacket temperature control system.
The meaning of other variables and parameters are explained
in the nomenclature.
The dynamic behavior of the reactor can be simulated
by solving Eqs. (1)(6). The differential-algebraic solver
DASSL [14] is used to give the solution of these equations.
The initial conditions for M
A
, M
B
, M
C
, M
D
used in all
simulation studies are 12, 12, 0, and 0 kmol, respectively.
The initial values of both reactor and jacket temperature are
set to 20
C)
Cp
B
= 167.36 kJ/(kmol
C)
Cp
C
= 217.57 kJ/(kmol
C)
Cp
D
= 334.73 kJ/(kmol
C)
H
1
= 41840 kJ/kmol
H
2
= 25105 kJ/kmol
= 1000 kg/m
3
j
= 1000 kg/m
3
Cp
j
= 1.8828 kJ/(kg
C)
V
j
= 0.6912 m
3
104 A. Arpornwichanop et al. / Chemical Engineering and Processing 44 (2005) 101114
0.2 min is used for temperature measurements. It is noted
that measurement noise is also included in the temperature
sensors having Gaussian noise with zero mean and 1
Cstan-
dard deviation. In addition, it was assumed that the concen-
tration (amount of mol) of reactants in the reactor is mea-
sured infrequently and has a sampling time and measure-
ment delay of 10 min.
3. On-line dynamic optimization strategy
The aim of a dynamic optimization problem is to deter-
mine a control prole minimizing (or maximizing) a given
objective function subject to process constraints. With the
optimal control policy, the controlled system is driven from
the initial state to a nal desired state in an optimal way.
However, in the presence of modeling error, the pre-specied
control prole may lose its optimal character [2]. For this
reason, an on-line optimization strategy through a receding
horizon scheme is employed in this work to compensate
such an error. The basic concept is to compute the optimal
control prole based on current feedback information. How-
ever, only the initial value of the optimal trajectory is sent
to the system as a set point for the controller. After new
information of states is available from either measurement
or estimation, the optimization is repeated again to generate
updated optimal set point prole at the next time interval.
The method proposed for improving the batch operation
can be divided into two phases: on-line modication of the
reactor temperature trajectory and on-line tracking of the de-
sired temperature trajectory. The rst phase involves deter-
mining an optimal temperature set point prole by solving
the on-line dynamic optimization problem and will be de-
scribed in this section. The other phase involves designing a
nonlinear model-based controller to track the obtained tem-
perature set point and will be presented in the next section.
Since both the on-line dynamic optimization and the
model-based control strategy rely on process models, the
knowledge of current states and/or model parameters is
required. However, in most industrial processes, state vari-
ables are not all measurable and some parameters are not
known exactly. As a consequence, there is a need for es-
timating these states and parameters. In this work, two
Extended Kalman Filters (EKF) are implemented. The rst
one is applied to predict the reactant concentration, which
will be used for on-line dynamic optimization, from its
delayed measurement. The other one is applied to esti-
mate the unknown heat of reaction, which will be used
for model-based controller, from the frequently available
measurements of temperature.
3.1. Problem statements
As a batch reactor is utilized for the production of a wide
variety of high value products, an optimization of batch op-
erating conditions, e.g. temperature, operating time, etc. is
the more efcient approach to obtain a maximum yield in a
minimum time or minimum cost and also to reach the spe-
cic nal conditions of the products in terms of quality and
quantity.
In general, an objective function in the optimization prob-
lem can be chosen, depending on the nature of the problem.
Here, two practical optimization problems related to batch
operation: maximization of product concentration in a xed
batch time and minimization of batch operation time given
amount of desired product, are considered to determine an
optimal reactor temperature prole. The rst problem for-
mulation is applied to a situation where we need to increase
the amount of desired product while batch operation time is
xed. This is due to the limitation of complete production
line in a sequential processing. However, in some circum-
stances, we need to reduce the duration of batch run to allow
the operation of more runs per day. This requirement leads
to the minimum time optimization problem. These problems
can be described in details as follows.
3.1.1. Maximum product concentration problem (P1)
In this type of problem, the objective is to compute the
optimal temperature policy maximizing the amount of a de-
sired product concentration for a given xed batch time sub-
ject to bounds on the reactor temperature. The problem can
be written mathematically as
max
T(t)
J = X(t
f
)
subject to
x = f(x(t), T, p, t) process model
x(t
0
) = x(0) initial conditions
T
L
T T
U
t
f
= t
f
where X is the amount of the desired product at a given nal
batch time, x is the vector of state variables, x is the derivative
of x with respect to time (t), T is the reactor temperature, p
are process parameters, t
f
is the xed batch time, and T
L
and
T
U
are lower and upper bounds of the reactor temperature.
3.1.2. Minimum batch time problem (P2)
The purpose of this optimization problem is to determine
the optimal temperature proles to achieve the desired -
nal product concentration in minimum batch time, thus the
performance index is the nal time whereas the desired pro-
duction concentration is dened as a terminal constraints.
The formulation of the minimum batch time problem can be
shown as
min
T(t)
J = t
f
subject to
x = f(x(t), T, p, t) process model
A. Arpornwichanop et al. / Chemical Engineering and Processing 44 (2005) 101114 105
x(t
0
) = x(0) initial conditions
T
L
T T
U
X(t
f
) = X
where X
t
f
0
(y
sp
y) dt (16)
The GMC control response can be designed via the tuning
parameters K
1
and K
2
based on the tuning curve given by
[24]. It should be noted that the GMC approach is a special
case of the global input output linearizing control technique
in which a transformed control action is chosen properly
with the external PI controller. The use of Eq. (16) forces y
toward its set point, y
sp
, with zero offset. If Eq. (15) is dif-
ferentiated, and the Eq. (16) is substituted into the resulting
equation, the GMC control law is
u =
[K
1
(y
sp
y) + K
2
(y
sp
y) dt (dh/dx)f(x, d, t)]
(dh/dx)g(x, t)
(17)
4.2. Application of GMC controller to the batch reactor
To implement the GMC, an energy balance around the
reactor is required; it gives the relation between the reactor
temperature (controlled variable) and the jacket temperature
(manipulated variable). Based on the assumption that the
amount of the heat accumulated in the walls of the reactor
is negligible compared to the heat transferred in the reactor,
the energy balance equation becomes
dT
r
dt
=
Q
r
+ U
r
A
r
(T
j
T
r
)
W
r
Cp
r
(18)
where U
r
is the heat transfer coefcient, A
r
is the heat trans-
fer area, W
r
is the mass of the reactor contents, Cp
r
is the
mass heat capacity of the reactor content, and Q
r
is the heat
released by the reactions.
Rearranging the Eq. (18) as in the form of GMC algo-
rithm, the following functions, f, g, and h can be dened
f(x, p, t) =
Q
r
U
r
A
r
T
r
W
r
Cp
r
(19)
g(x, t) =
U
r
A
r
W
r
Cp
r
(20)
h(x) = T
r
(21)
Replacing these equations in Eq. (17), we have
T
j
=T
r
+
W
r
Cp
r
U
r
A
r
K
1
(T
rsp
T
r
)
+K
2
t
0
(T
rsp
T
r
) dt
Q
r
U
r
A
r
(22)
In order to make the GMC control law available for an
on-line control implementation, the integral term in Eq. (22)
is approximated by numerical integration. This leads to the
discrete-time form of the GMC algorithm as given in the
following equation.
T
j
(k) =T
r
(k) +
W
r
Cp
r
U
r
A
r
K
1
(T
rsp
T
r
(k))
+K
2
k
0
(T
rsp
T
r
(k)) t
Q
r
(k)
U
r
A
r
(23)
where t is the sampling time chosen to be equal to the
frequency of the temperature measurement. It is sufciently
small to approximate the continuous-time form without re-
quiring a large number of sampled values.
However, Eq. (23) gives the actual jacket temperature
(T
j
(k)) required at the next sampling time to control the re-
actor temperature (T
r
(k)) at the desired trajectory (T
rsp
). As
in usual practice, the reactor temperature control is cascaded
with the jacket temperature control (heating and cooling sys-
tem); the output of reactor temperature controller (master
loop) is the set point of the jacket temperature controller
(slave loop), as demonstrated in Fig. 3. In addition, as the
model of the heat exchanger system for heating and cooling
is not included in Eq. (18), if T
j
(k) is applied directly as the
set point for jacket temperature control system without con-
sidering on its dynamic, the resulting control response would
be sluggish. To accommodate such an effect, it is reason-
able to assume that the dynamic of the jacket control system
108 A. Arpornwichanop et al. / Chemical Engineering and Processing 44 (2005) 101114
REACTOR
Dynamic
compensation
GMC
EKF
with simplified
reactor model
Tr(k) Tj(k)
Mi (K-1)
EKF
On-line dynamic
optimization problem
Updated Mi (K)
Initial
setpoint
New reactor
temperature setpoint
Trsp (K)
Tj Tjsp
Qr(k)
Fig. 3. The proposed strategy for on-line update and control of reactor temperature prole.
can be approximated by a rst order model with time con-
stant (
j
) [25]. Consequently, the T
jsp
(k) can be computed
by
T
jsp
(k) = T
j
(k 1) +
j
T
j
(k) T
j
(k 1)
t
(24)
With this jacket temperature set point, a jacket temper-
ature controller (setting as a PI controller) through a heat
exchanger system opens or closes control valve reecting to
the owrate of heating and cooling uid. However, in real-
ity the ability of the heat exchanger in adjusting the jacket
temperature is always limited, thus, in this work the jacket
temperature is bounded between 0
C and 120
C. The tun-
ing parameters of GMC are given in Table 2.
As shown in Eq. (23), the heat released (Q
r
(k)), which
cannot be measured, is needed in the GMC algorithm. Here,
the EKF algorithm, as used in on-line optimization strategy,
coupled with the simplied reactor model, given by [26],
is also applied to estimate the heat released (Q
r
(k)). The
reason of using the simplied model, not the exact model
of the plant, is because if the exact model were used, too
many uncertain/unknown parameters as well as too many
unmeasurable states would be involved. That may lead to
poor performance of the EKF. Hence, the simplied model
with less uncertain/unknown parameters and unmeasurable
Table 2
Parameters in GMC algorithm
W
r
= 1560 kg
Cp
r
= 1.8828 kJ/(kg
C)
U
r
= 40.842 kJ/(min m
2
C)
A
r
= 6.24 m
2
j
= 2 min
K
1
= 2.4
K
2
= 10
4
states as shown below is used instead.
dT
r
dt
=
Q
r
+ U
r
A
r
(T
j
T
r
)
W
r
Cp
r
(25)
dT
j
dt
=
F
j
j
Cp
j
(T
jsp
T
j
) U
r
A
r
(T
j
T
r
)
V
j
j
Cp
j
(26)
dN
dt
= bNT
r
(27)
dQ
r
dt
= N
dT
r
dt
+ T
r
dN
dt
(28)
db
dt
= 0 (29)
where N = bM
r
(H), b is a pseudo reaction rate constant,
M
r
is the total reactant concentration, and His heat of reac-
tion. It should be noted that the variable N representing two
unknown parameters (M
r
and H) can be estimated instead
of these parameters so that the number of state equations for
estimation decrease and an error of estimation correspond-
ing to the uncertainty of each parameters can be reduced.
Eqs. (25)(29) correspond to Eq. (A.1) in the EKF algo-
rithm. Once the reactor and jacket temperature measurement
are available, the EKF with simplied model estimates the
heat release of reactions (Q
r
(k)). Table 3 summarizes the
initial conditions and tuning parameters of the EKF used in
this simulation work.
5. Simulation results
5.1. Maximum conversion problem (P1)
All simulation results given here are based on the opti-
mization problem P1. The objective in the problem formu-
lation is to nd the optimal reactor temperature prole, such
A. Arpornwichanop et al. / Chemical Engineering and Processing 44 (2005) 101114 109
Table 3
Parameters and initial conditions in EKF
Estimate M
i
, k
1
2
and k
2
2
M
A
(0) = 12 kmol P = diag[100 10 100 100 100 2000]
M
B
(0) = 12 kmol Q = diag[100 1 100 1 500 5000]
M
C
(0) = 0 kmol R = diag[10 10 10 10]
M
D
(0) = 0 kmol
k
1
2
(0) = 38.9057
k
2
2
(0) = 17000
Estimate Q
r
T
r
(0) = 20
C) 120.
5.1.1. Temperature set point prole determined off-line
with perfect tracking
First, simulation studies have investigated the case where
the optimal temperature prole is determined by off-line
computation and perfect tracking of such a prole is as-
sumed. This results in the maximum amount of product C
(maximum conversion) that can be achieved at the end of
batch run and is served as a reference to be compared with
results obtained from the proposed strategy. The optimal
control problems have been solved using time interval with
equal length varied from one to 40 intervals to discretize the
prole. The switching time is xed and the length of each
interval is specied by dividing the batch operation time (t
f
)
by a number of time intervals (P). Thus, the problem is to
seek an optimal temperature value (decision variables) in
each subinterval.
Simulation results with different time interval (P) are re-
ported in Table 4. Optimal control policy in reactor tem-
perature for each case is shown in Fig. 4. As shown in
Table 4, when one time interval (P = 1) is used, the amount
of product C obtained at the nal time (t
f
= 200 min) is
7.0171 kmol and the optimal temperature (isothermal opera-
tion) set point is 88.01
(s)
1 7.0171 1.3464 0.1591
5 7.0281 1.3605 1.2600
10 7.0339 1.3594 1.9778
20 7.0379 1.3585 2.8066
40 7.0402 1.3579 5.0519
C
which is below the optimal temperature set point, the GMC
controller attempts to drive the reactor temperature from this
condition to the specied set point. However, due to the dy-
namics of the reactor temperature, the reactor temperature
differs from the optimal set point during the rst 20 min,
causing that the amount of the product C obtained from the
on-line strategy with the GMC controller (C = 6.9584) is
less than that obtained from the off-line strategy with perfect
tracking (see Table 4 for P = 20, C = 7.0379)
For the mismatch in k
1
2
, the value of the desired prod-
uct C = 7.8851 can be achieved at the end of batch for the
on-line optimization strategy which is higher than that ob-
tained from off-line strategy where the mismatch is not no-
ticed (C = 7.6751). Similar results can be observed under
the case of plant model mismatch in k
2
2
as shown in Table 5.
These results indicate clearly that the performance of batch
reactor operation is improved via the proposed strategy. Due
to similarity in their control responses, only the result for
change in k
1
2
is shown in Fig. 7.
Finally, with a change in both k
1
2
(50% k
0
) and k
2
2
(+20% Ea) in plant model, the results using the on-line opti-
mization strategy show that the GMC controller is able to ac-
commodate this change very well as can be seen in Fig. 8(a).
Fig. 8(b) presents the performance of the EKF for estima-
tion of k
1
2
and k
2
2
. Since the EKF estimates these parameters
close to the true values, the mismatch is eliminated. That
leads to high product C obtained at the nal batch time (C
= 10.2137) compared to the value of C = 8.5827 obtained
from the off-line optimization strategy.
A. Arpornwichanop et al. / Chemical Engineering and Processing 44 (2005) 101114 111
Fig. 6. (a) Product prole (on-line, nominal case): actual (solid), estimated (). (b) Control response (on-line, nominal case): T
rsp
(dash), T
r
(solid), T
j
(dot). (c) Estimate of k
1
2
and k
2
2
(on-line, nominal case): actual (solid), estimated ().
Fig. 7. Control response (on-line, mismatch in k
1
2
): T
rsp
(dash), T
r
(solid),
T
j
(dot).
5.2. Minimum time problem (P2)
The results presented here correspond to the case where
the objective is to minimize the batch time of operation
subject to the terminal constraints on the desired amount
of mole of product C (M
C
(t
f
) = 6.00 kmol). The reactor
temperature constraints are same as in problem P1.
Several simulations have been carried out under process
parameter uncertainties e.g. in pre-exponential rate constant
(k
0
) and activation energy (Ea). In all case studies we consid-
ered 10 time intervals when reactor temperature and switch-
ing time are optimized while minimizing the nal batch op-
eration time. Results, reported in the value of minimumbatch
time to obtain the desired product C and the amount of the
desired product C at the end of batch operation, from on-line
dynamic optimization strategy are also compared with those
from the off-line strategy.
With an 20% increase of parameter k
1
2
in plant model, it
can be seen from Table 6 that the nal batch time needed
to achieve the desired product C from the proposed on-line
112 A. Arpornwichanop et al. / Chemical Engineering and Processing 44 (2005) 101114
Fig. 8. (a) Control response (on-line, mismatch in k
1
2
and k
2
2
): T
rsp
(dash),
T
r
(solid), T
j
(dot). (b) Estimate of k
1
2
and k
2
2
(on-line, mismatch in k
1
2
and k
2
2
): actual (solid), estimated ().
modication of temperature set point prole (t
f
= 49.4 min)
is shorter compared to the result with the off-line strategy (t
f
= 64.8 min). This is because the EKF can acknowledge this
parameter uncertainty, so that the temperature set point pro-
le is updated corresponding to a modied parameter value
close to the actual value. Fig. 9 shows, for this mismatch,
the control response of GMC controller to deliver the reac-
tor temperature from initial condition to the temperature set
point determined off-line. For the on-line temperature set
Table 6
Comparisons of the results obtained from off-line and on-line optimization strategy with GMC controller (problem P2)
Case studies Final time (min)/product C (kmol)
Off-line On-line
(1) 50% k
0
of reaction 2 in plant model (k
1
2
= 38.2125) 64.8/6.0049 49.4/6.0089
(1) +20% Ea of reaction 2 in plant model (k
2
2
= 20400) 56.4/6.0147 44.6/6.0104
(1) 50% k
0
and + 20% Ea of reaction 2 in plant model 56.7/6.0144 45.2/6.0121
Fig. 9. Control response (off-line, mismatch in k
1
2
, problem P2): T
rsp
(dash), T
r
(solid), T
j
(dot).
Fig. 10. Control response (on-line, mismatch in k
1
2
, problem P2): T
rsp
(dash), T
r
(solid), T
j
(dot).
point modication, as expected, GMC controller can also
control the reactor corresponding to the changes in temper-
ature set point as can be seen in Fig. 10
The results for the remaining case studies are summa-
rized in Table 6. An important aspect obtained from these
results is that in all cases, the minimum batch time to obtain
the desired product concentration in the on-line set point
A. Arpornwichanop et al. / Chemical Engineering and Processing 44 (2005) 101114 113
modication strategy decreases. This points out the effec-
tiveness of the proposed method to improve the operation
of batch reactor.
6. Conclusions
In this work, the method using an on-line dynamic opti-
mization and control strategy to enhance batch reactor oper-
ation has been proposed. The on-line dynamic optimization
by the idea of receding horizon scheme is performed. The ap-
proach is based on the updated current information of states
of the system which are estimated from the delayed mea-
surement of the amount of reactants in the reactor using an
Extended Kalman Filter (EKF) technique, at specied time
interval to provide a new updated optimal reactor temper-
ature set point prole. Two types of optimization formula-
tion related to batch operation (maximum concentration and
minimum time problem) were considered in the proposed
on-line set point modication strategy. The obtained reac-
tor temperature set point was implemented using a generic
model control (GMC). The EKF was also incorporated into
the GMC algorithm in order to estimate the heat released by
reactions using the direct measurement of reactor and jacket
temperature. A batch reactor with highly exothermic reac-
tions was used as a simulation case study to demonstrate the
effectiveness of the proposed approach. Simulation studies
have been carried out in both nominal case and plant/model
mismatch case and the results show that the performance of
the batch reactor in terms of the amount of a desired prod-
uct and batch operation time can be improved signicantly
by the proposed strategy. In addition, they also clearly in-
dicate the capability of the GMC controller to control the
reactor temperature along the specied trajectory and that
of the EKF to estimate the states and parameters of the
system.
Acknowledgements
The nancial support to A. Arpornwichanop through local
graduate scholarship from the national science and technol-
ogy development agency (NSTDA) is gratefully acknowl-
edged. A. Arpornwichanop also acknowledges the support
of the Department of Chemical Engineering, University of
Bradford, UK during his stay as a visiting researcher at the
University in 2000.
Appendix A. The EKF algorithm
Since in this work the process models used are in time
continuous form and measurements are in discrete form, the
EKF in discrete/continuous formulation [27] is used. The
basic algorithm of the EKF can be summarized as follows:
For nonlinear systems, the process model can be described
by differential equations
x = F(x(t), u(t), t) + (t) (A.1)
y = G(x(t)) + (t) (A.2)
where F is a vector of system function, G is a vector of
measurement function, is a zero mean Gaussian process
noise with covariance Q, and is a zero mean Gaussian
measurement noise with covariance R.
The equations for the EKF are given by a set of correction
and prediction equations as shown in the following:
Correction phase: Correct the prior estimates of state at
k 1 and update the weighting matrix
K
k1
= P
k1/k2
C
k1
T
[C
k1
P
k1/k2
C
k1
T
+ R]
1
(A.3)
x
k1/k1
= x
k1/k2
+ K
k1
[y
k1
C
k1
x
k1/k2
]
(A.4)
P
k1/k1
=[I K
k1
C
k1
]
P
k1/k2
[I K
k1
C
k1
]
T
+K
k1
RK
T
k1
(A.5)
Prediction phase: Integrate the nonlinear state and co-
variance equations from time k 1 to k in order to acquire
estimate x
k/k1
and
P
k/k1
x = F(x, u) (A.6)
P = A
k1
P +
PA
T
k1
+ Q (A.7)
where x
k/k1
denotes the estimate of state x at t = k from
information at t = k 1, K is Kalman gain matrix, P is
covariance matrix, and matrices
A
k1
=
F
x
x
k1|k1
and C
=
G
x
x
k1|k2
C))
Cp
i
molar heat capacity of component i (kJ/(kmol
C))
114 A. Arpornwichanop et al. / Chemical Engineering and Processing 44 (2005) 101114
F owrate (m
3
/min)
H
i
heat of reaction of reaction i (kJ/kmol)
K
1
, K
2
GMC controller parameters
M
i
number of moles of component i (kmol)
MW
i
molecular weight of component i (kg/kmol)
P covariance matrix
Q covariance matrix of process noise
Q
r
heat released from reactions (kJ/min)
R covariance matrix of measurement noise
R
i
rate of reaction i (kmol/min)
T reactor temperature (
C)
U heat transfer coefcient (kJ/(min m
2
C))
V reactor volume (m
3
)
W Reactor content (kg)
density (kg/m
3
)
Subscripts
f lter
j jacket
r reactor
sp set point
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Chemical Engineering and Processing 44 (2005) 115119
Synthesis of nano-sized particles from metal carbonates
by the method of reversed mycelles
Christo Karagiozov, Dana Momchilova
Departement of Chemical Engineering, Faculty of Technical Sciences, University Prof. Dr. Assen Zlatarov Bourgas,
Bul: Prof. Iakimov 1, 8010 Bourgas, Bulgaria
Received 2 December 2003; received in revised form 30 April 2004; accepted 5 May 2004
Available online 25 August 2004
Abstract
The nano-sized particles of calcium carbonate and barium carbonate have specic characteristics. They are important materials for the
industry. The main object of this investigation is to obtain nanoparticles of calcium carbonate and barium carbonate by chemical reaction
carried out in microemulsion of water in oil. The nanoparticles obtained are spherical. Their sizes vary from 20 to 30 nm. The shape and size
of particles are determinated by electron microscopy.
2004 Elsevier B.V. All rights reserved.
Keywords: Calcium carbonate; Barium carbonate; Nanoparticles; Microemulsion; Surface tension
1. Introduction
The concepts of the nano-world suggested recently re-
vealed new elds of scientic research. The number of the
publications, patents, projects, implementations and compa-
nies involved with nano-technology has been exponentially
increasing during the last 10 years. Nano-technology is a
transition eld between the concepts of the classic quantum
mechanics and physical chemistry of solid state [1].
The investigations of materials obtained from nano-sized
particles showed that they have unknown properties or
enhanced characteristics compared to common materials.
Many alkaline carbonates have take in especially application
in practice. Calcium carbonate is widely used for production
of toothpaste, binding agents, etc. [12,13]. Barium carbon-
ate is used mainly in glass production industries, as well as
water softening agent, etc. Both substances are crystalline,
with rhombic lattice and practically insoluble in water [12].
Many methods have been used for synthesis of nano-sized
particles: vapour transport [2], precipitation of homogeneous
solution [3], synthesis by sol-gel process [4], freeze-drying
C.
3. Results and discussion
Solid nano-sized particles of CaCO
3
and BaCO
3
were ob-
tained from the experiments carried out using chemical re-
Table 1
Ratio of volumes of organic and inorganic phases
Experiment
no.
Inorganic
phase
Organic
phase
Volume of inorganic
phase V
1
(ml)
Volume of organic
phase V
2
(ml)
V
1
/V
2
1 2 3 4 5 6
1 Ca(OH)
2
n-C
6
H
14
5 45 0.111
2 Ca(OH)
2
n-C
6
H
14
10 40 0.250
3 Ca(OH)
2
n-C
6
H
14
15 35 0.429
4 Ca(OH)
2
n-C
6
H
14
20 30 0.667
1 Ba(OH)
2
n-C
6
H
14
30 20 1.5
2 Ba(OH)
2
n-C
6
H
14
25 25 1
3 Ba(OH)
2
n-C
6
H
14
20 30 0.667
4 Ba(OH)
2
n-C
6
H
14
15 35 0.429
5 Ba(OH)
2
n-C
6
H
14
35 15 2.333
7 Ba(OH)
2
n-C
6
H
14
40 10 4
Note: 1. All the experiments were carried out under stirring for 60 min at 400 rpm, 2. CO
2
bubbling time was 60 min.
action in a microemulsion of type water in oil. The qual-
itative analyses of the organic and inorganic phases for all
the experiments showed the presence of calcium or barium
carbonate. The shape and size of the particles were deter-
mined by electron microscopy. Photographs of nano-sized
particles of BaCO
3
are presented in Fig. 2.
The nano-particles synthesized were with spherical shape
and almost equal sizes varying from 20 to 30 nm.
The electron-microscopy analysis (Fig. 2) revealed that
processes of particles agglomeration took place. Since the
opalescence observed with the organic phase from the ex-
periments was not very good, the agglomeration was sup-
posed to occur during the electron microscopy analysis it-
self. It may result from the irradiation of the samples by the
high-energy electron beam used for the analysis. Photograph
A was taken from samples obtained from the experiment
carried out at a ratio of inorganic phase Ba(OH)
2
to organic
phase n-C
6
H
14
15/35 ml. Photograph B was taken at phase
ratio Ba(OH)
2
/n-C
6
H
14
= 40/10 ml.
The results sustained the opinion that the synthesis of
nano-particles in microemulsion (w/o) is to be preferred.
In common emulsions, both phases spontaneously separate
from each other while microemulsions are thermodynami-
cally stable, do not segregate and appear to be transparent.
This can be explained with the size of the water droplets
[14,11]. Microemulsions are also characterized by the so
called dynamic exchange process. The emulsion droplets
in such emulsions constantly integrate and disintegrate, thus
exchanging substance between each other.
The substance dissolved in the emulsion droplets was
quite small amount, i.e. the reagent concentration in the
droplet was low so it could be expected to obtain small par-
ticles with almost equal sizes.
In the case studied, the following physical model was sug-
gested. The microemulsion water solution/organic phase was
formed preliminarily. It contained only one of the reagents
(in this case solution of Ca(OH)
2
or Ba(OH)
2
). The sec-
ond reagent was added in the form of a gas (CO
2
). The
gas passed through the organic liquid, diffused through the
C. Karagiozov, D. Momchilova / Chemical Engineering and Processing 44 (2005) 115119 117
Fig. 2. Electron microscopy photographs of nano-sized particles of BaCO
3
.
interphase surface oil/water solution in the drops and then
interacts with the inorganic phase present in them. Thus,
a chemical reaction was initiated which gave slightly solu-
ble products (CaCO
3
and BaCO
3
). This hypothesis can be
schematically represented as follows (Fig. 3).
The summarized equation of the chemical reaction pro-
ceeding between the corresponding hydroxide and CO
2
is
Me(OH)
2
+CO
2
MeCO
3
+H
2
O (1)
The chemistry of the separate stages of the process within a
droplet can be described by the following reactions:
Me(OH)
2
Me
2+
+2OH (2)
CO
2
+H
2
O H
2
CO
3
(3)
H
2
CO
3
HCO
3
+H
+
(4)
CO
2
+OH
HCO
3
(5)
HCO
3
H
+
+CO
2
3
(6)
Me
2+
+CO
2
3
MeCO
3
(7)
where Me = Ca, Ba.
The basic parameter characterizing nano-particles is their
specic area, which can be determined by the formula [15]
A = 4r
2
N(m
2
/kg) (8)
where A: specic area (m
2
/kg), r: particles radius (m), N:
number of particles per unit of weight.
The number of particles can be calculated from
N =
1
(4/3)r
3
(9)
Substituting Eq. (11) into Eq. (10) gives the following ex-
pression for calculation of the specic area:
A =
3
r
(m
2
/kg) (10)
The size of the nanoparticles of BaCO
3
obtained was
about 2030 nm. Their specic area was calculated to be
from 6.82 10
7
to 4.55 10
7
m
2
/kg. The particles with
20 nm sizes have specic area of 6.82 10
7
m
2
/kg while
particles with 30 nm size 4.55 10
7
m
2
/kg. Therefore, the
specic area decreased with the increase of particle radius
(Fig. 3).
For the microemulsion system inorganic solution/
n-C
6
H
14
, it is important to prove that the inorganic so-
lution was dispersed in the organic phase in the form of
microdrops. To determine the distribution of the phases in
the microemulsion, the forces of surface tension for each
microdrop should be estimated, as well as the forces acting
at the interphase surface.
Forces of surface tension act on the surface of the parti-
cles in the liquid phase. It can be expressed as the work for
the formation of a unit of interphase surface under constant
thermodynamic parameters of the state (temperature, pres-
sure, chemical potentials of the components). This process
is reversible and isothermal. The surface tension forces can
be regarded also as free energy per unit area, i.e. specic
free energy (G
S
). Then, the free energy per unit weight of
particles would be
G
S
= G
S
A (11)
Fig. 3. Probable mechanism of contact between the reagents.
118 C. Karagiozov, D. Momchilova / Chemical Engineering and Processing 44 (2005) 115119
Assuming that G
S
is constant value, then free energy
G
S
should increase with the decrease of particle radius A
[16,17].
The surface tension of 0.02 N solution of Ba(OH)
2
was
determined by the formula [18]
Ba(OH)
2
=
0
+0.049(1 a
W
) (12)
where : surface tension of Ba(OH)
2
(dyne/cm),
0
: sur-
face tension of water at 25
C. It is considered to be
71.97 dyne/cm [18], a
w
: activity of water in the solution.
The water activity in the solution was determined by the
well-known equation [18]
ln a
W
=
tm
Ba(OH)
2
M
Ba(OH)
2
55510RT
B
1
+at +bt
2
+
B
2
1000 +M
Ba(OH)
2
m
Ba(OH)
2
m
Ba(OH)
2
M
Ba(OH)
2
+
1
E
(13)
where R: universal gas constant = 8.314441 J/mol, T: tem-
perature (K), m
i
: solution molality (g/l), M
i
: mole weight
(g/mol), B
1
, a, b, B
2
, E: coefcients calculated by mathe-
matical treatment of the experimental data for heat capacity.
Value of the surface tension of Ba(OH)
2
was calculated to
be 71.88 dyne/cm. Reference data showed that
n-C
6
H
14
=
32.21 [18]. The value of Ba(OH)
2
surface tension was close
to that of water (
0
) since the concentration of Ba(OH)
2
was
low and the solution was very diluted.
Forces of interphase tension
T
1
/T
2
act at the contact sur-
face between the two liquid phases of Ba(OH)
2
(or Ca(OH)
2
)
and n-C
6
H
14
. The thermodynamic condition for a liquid to
spread over the surface of another liquid is [19]
T
2
/
>
T
1
/
+
T
1
/T
2
(14)
where
T
1
/
,
T
2
/
: surface tensions of the liquids related
to their environment (dyne/cm),
T
1
/T
2
: surface tension at
the interphase boundary between the liquids (dyne/cm).
The interphase tension at the phase boundary between an
inorganic solution and oil was assumed to be 50.5 dyne/cm,
according to literary data [19]. The two phases are quite
different by polarity. The basic process taking place at the
contact surface between them is the change of the total con-
tact surface area due to the decrease of the total energy of
the system, i.e. the conditions became suitable for process
of wetting to take place. The coefcient of spreading S can
be calculated from the values of the surface and interphase
tensions according to [20]
S =
T
2
/
T
1
/
T
1
/T
2
, S = 10.853 (15)
At S < 0, the wetting angle can be determined by the equa-
tion [20]
cos
0
=
2
T
2
/
2
T
2
/
2
T
1
/T
2
2
T
1
/
T
2
/
(16)
i.e. cos
0
= 0.3717
Its value was calculated to be
0
= 68.18
. At
0
< 90
T
1
/T
2
= S
k
= 50.5 > 0. It means that the surface tension of
n-C
6
H
14
remained lower than that of the inorganic solution,
i.e. n-C
6
H
14
wetted the polar phase of aqueous solution of
Me(OH)
2
.
4. Conclusions
The following conclusions can be formulated on the basis
of the results obtained
1. A technique and process for preparation of nano-sized
particles from alkali carbonates was developed on the
basis of the method of reversed micelles and a probable
mechanism was suggested.
2. Nano-sized particles of barium and calcium carbonate
were obtained by a chemical reaction in a microemulsion.
The particles were studied by electron microscopy and
were found to possess spherical shape and diameters from
20 to 30 nm.
3. The nano-sized particles were obtained at various ratios
of the phases forming the microemulsion. They were
about the same size, which conrmed the advantage of
the method selected.
4. The particles synthesized were observed to agglomer-
ate, probably due to effects induced by the electron mi-
croscopy analysis.
5. The values of the surface tensions of the individual phases
were calculated, as well as the value of the interphase
tension. The results conrmed that the inorganic phase
was dispersed in the organic phase.
Appendix A. Nomenclature
a
w
activity of water in the solution
m
i
solution molality (g/l)
r particles radius (m)
o oil
w water
A specic area (m
2
/kg)
B
1
, a, b, B
2
, E coefcients calculated by mathematical
treatment of the experimental data for
heat capacity
G change of the free energy per unit area
C. Karagiozov, D. Momchilova / Chemical Engineering and Processing 44 (2005) 115119 119
G
S
specic free energy
M
i
mole weight (g/mol)
N number of particles per unit of
weight
R Universal gas constant (J/mol)
T temperature (K)
S coefcient of spreading
surface tension of Ba(OH)
2
(dyne/cm)
0
surface tension of water at 25
C (dyne/cm)
T
1
/T
2
surface tension at the interphase boundary
between the liquids (dyne/cm)
T
1/
,
T
2
/
surface tensions of the liquids related
to their environment (dyne/cm)
References
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Ti
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12
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Chemical Engineering and Processing 44 (2005) 121130
Mechanism of mass transfer from bubbles in dispersions
Part II: Mass transfer coefcients in stirred gasliquid reactor
and bubble column
V. Linek
, M. Korda c, T. Moucha
Department of Chemical Engineering, Prague Institute of Chemical Technology, Technick 5, 166 28 Prague 6, Czech Republic
Received 15 December 2003; accepted 14 May 2004
Available online 2 July 2004
Abstract
Experimental data on the average mass transfer liquid lm coefcient (k
L
) in an aerated tank stirred by Rushton turbine and in bubble
column are presented. Liquid media were used as 0.8 M sodium sulphite solution, pure or with the addition of Sokrat 44 (copolymer of
acrylonitrile and acrylic acid) or short-ber carboxymethylcellulose (CMC) for the Newtonian and long-ber CMC for the non-Newtonian
viscosity enhancement and ocenol (cis-9-octadecen-1-ol) or polyethylenglycol (PEG) 1000 for surface tension change. Volumetric mass
transfer coefcient (k
L
a) and specic interfacial area (a) were measured by the Danckwerts plot method. Coefcients k
L
measured by pure
oxygen absorption in pure sulphite solution and Newtonian viscous liquids are well tted by the eddy model in the form of k
L
= 0.448
(ev/)
0.25
(D/v)
0.5
with a mean deviation of 20%. Surface-active agents (ocenol and PEG) and non-Newtonian additive (long-ber CMC)
reduced k
L
value signicantly but their effect was not described satisfactorily neither by surface tension nor by surface pressure. It is shown
that the decisive quantity to correlate k
L
in the stirred tank and bubble column is power dissipated in the liquid phase rather than the bubble
diameter and the slip velocity. Absorption of air did not yield correct k
L
data, which did not depend on or slightly decreased with increasing
power. This is due to the application of an improper gas phase mixing model for absorption data evaluation.
2004 Elsevier B.V. All rights reserved.
Keywords: Gasliquid contactor; Bubble column; Agitated vessel; Mass transfer coefcient; Viscosity; Surfactants
1. Introduction
Mass transfer from swarm of bubbles into turbulent liq-
uid controls the rate of many chemical and biochemical pro-
cesses. It is assumed that the mechanism of mass transport
in liquid phase is due to a renewal of the liquid at the bub-
ble surface. Models of the process differ in the scale of ow,
which is responsible for the renewal.
The rst group of models (eddy models) assumes that
the liquid renewal is due to small-scale eddies of the turbu-
lent eld. These models are based on idealized eddy struc-
tures of turbulence in the bubble vicinity. Lamont and Scott
[1] have assumed that the small scales of turbulent motion,
which extend from the smallest viscous motions to the iner-
ev
0.25
D
v
0.5
(1)
Different authors predict different values of the constant c
1
:
0.301 [2], 0.4 [1], 0.531 [3], 0.592 [4] and 1.13 [5].
The second group of models (slip velocity models) as-
sumes a gross mean ow of uid relative to the bubble (slip
velocity) and a bubble surface mobility control of this re-
newal rather than the small-scale eddies of the turbulent
eld. The model proposed by Calderbank and Moo-Young
[6] belongs to this group. They [6] have divided bubbles by
size into two categories: the small bubbles (d < 1 mm),
which behave always as a rigid sphere, and the large
ones (d > 2.5 mm), which always have a completely mobile
0255-2701/$ see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.cep.2004.05.009
122 V. Linek et al. / Chemical Engineering and Processing 44 (2005) 121130
surface. An expression for the calculation of k
L
for the
large bubbles has been deduced fromdimensionless analy-
sis of mass transfer from rising particle in gravitational eld.
k
L
= 0.42
1/3
D
v
1/2
(2)
For the small bubbles, an expression for the calculation of
k
L
has been obtained by the equation proposed by Frssling
[7] for dissolution of a rigid sphere.
k
L
= 0.31
1/3
2/3
(3)
The transition between these two bubble categories was
unclear and strongly dependent on the presence of surfac-
tants. An expression for calculation of the mass transfer
coefcients in this transition region was not given.
Recently, Vasconcelos et al. [8] and Alves et al. [9] pro-
posed another variant of the slip velocity model. Their
model is based on experimentally observed phenomena of
an abrupt change of the dissolution rate of free-oating bub-
bles held stationary in a downward water ow. Starting from
these experiments, they have interpreted the mass transport
from bubbles in terms of bubble contamination kinetics, us-
ing a stagnant cap model, according to which bubbles sud-
denly change from a mobile interface to a rigid condition
when surface tension gradients, caused by surfactant accu-
mulation, balance out shear stress. The fresh bubble entering
the dispersion has clean, completely mobile interface. For
the bubbles with completely mobile surface, k
L
is given by
the equation, which follows from the well-known penetra-
tion model with exposition time equal to d/v
sl
:
k
mobil
L
= 1.13
v
sl
d
D
1/2
(4)
After some time (
mobile
), enough contaminant for transition
to rigidity is accumulated on the surface. For the rigid bub-
bles, an expression for the calculation of k
L
follows from
Frssling [7] equation.
k
rigid
L
= 0.6
v
sl
d
D
2/3
v
1/6
(5)
Gasliquid slip velocities v
sl
are assumed to be close to
single-bubble terminal velocities in still water, v
t
, on which a
correction for turbulence is introduced, v
sl
= 0.65v
t
[9]. As-
suming monosized bubble dispersion and considering only
two possible values of k
L
(k
mobil
L
and k
rigid
L
, depending on
surface mobility), they deduced the following relation for
the average mass transfer coefcient:
k
L
=
k
mobil
L
mobile
+k
rigid
L
(
R
mobile
)
R
(6)
where
R
is the average bubble residence time.
R
=
V
L
q(1 )
(7)
The time
mobile
depends on bubble diameter and surfactant
concentration.
mobile
= k
d
1/2
ln (d/h
trans
)
c
surf
(8)
where d is an average bubble diameter, k is an empirical con-
stant related with surfactant properties, c
surf
is the concen-
tration of surfactant and h
trans
is the bubble clean segment
height at the transition point from mobile to rigid.
The main difference between the eddy and the slip
velocity models is in the inuence of turbulence inten-
sity on mass transfer coefcient: the eddy models predict
an increase while the slip velocity models a decrease of
k
L
with increasing turbulence intensity, i.e. with increasing
power dissipated in the liquid. This is due to the fact that
k
L
from rigid bubbles is cca four times lower than from the
ones with a mobile surface. The small bubbles, which ei-
ther have lower k
L
(according to Calderbanks conception)
or become rigid more quickly (according to Alves concep-
tion,
mobile
diminishes with diminishing bubble diameter
d, see Eq. (8)), are generated in large amount just at higher
turbulence intensities. As a result, this leads to the decrease
of average mass transfer coefcient with increasing power
dissipated in the liquid. Literature data on k
L
in stirred tanks
supporting both these models can be found.
In dispersions with no mechanical agitation (bubble
columns, air-lifts), the only source of energy is the expansion
of the entering gas which gives the relation e = gv
s
. Reith
[10], Dillon and Harris [11], Kawase et al. [5] and Vzquez
et al. [12] revealed strong dependence of liquid-side mass
transfer coefcient on gas ow rate in bubble columns:
k
L
v
s
0.25/0.5
. Slight dependence or independence of k
L
on v
s
was found by Schumpe and Deckwer [13], Bouai
et al. [14], Wongsuchoto et al. [15] and Vasconcelos et
al. [8]. The values of k
L
corresponded to values predicted
by Calderbanks model for large bubbles. Values which
correspond also to small bubbles were found by Vzquez
et al. [12] and Vasconcelos et al. [8] only, who worked with
solutions of surfactants. Vasconcelos et al. [8] interpreted
their results in terms of bubble contamination kinetics.
In dispersions with mechanical agitation, following au-
thors found an increase of k
L
with increasing energy dissi-
pation e: Prasher and Wills [4] (k
L
e
0.25
); Figueiredo and
Calderbank [16] (k
L
e
0.33
); Bouai and Roustan [17] (k
L
e
0.22
); Panja and Rao [18] (k
L
e
0.15
); and Linek et al.
[19] (k
L
e
0.14
). Power dissipated in the liquid by an agi-
tator is proportional to the third power of impeller rate (e
f
3
). Thus, we can add the results of authors that presented k
L
as a function of impeller rate f: Koetsier and Thoenes [20]
(k
L
f
0.9
e
0.3
) and Yoshida and Miura [21] (k
L
f
0.6
e
0.2
). Robinson and Wilke [22] measured k
L
that did not
depend on power dissipated and Hassan and Robinson [23]
obtained coefcients that decreased with increasing power
dissipated. It was shown [32] that the reported independence
on or the decrease of k
L
with increasing power dissipated
was a result of misinterpretation of k
L
a data.
V. Linek et al. / Chemical Engineering and Processing 44 (2005) 121130 123
Figueiredo and Calderbank [16] have analysed the suit-
ability of Calderbanks model [6] for small and large
bubbles to the interpretation of mass transfer coefcients in
stirred vessels. They analysed an effect of the gas phase mix-
ing model used for k
L
a evaluation by the dynamic method
based on the inlet gas exchange N
2
/air. In their original
work [6], the k
L
a evaluation assumed that the interchange
of the gases in gas hold-up is immediate (steady-state model
of the gas phase). Corresponding k
L
values were indepen-
dent of power dissipated in the liquid by the agitator and
matched the constant value of 4.03.10
4
ms
1
as predicted
by Calderbanks model [6] for large bubbles (Eq. (2)).
When the gas phase dynamics was taken into account (the
ushing out of an old gas by a new one), the correspond-
ing values of k
L
were higher and well tted by the eddy
model (Eq. (1)) with c
1
= 0.5, see Fig. 1. (It was shown
by Linek et al. [24] that faulty sampling of liquid used by
Figueiredo and Calderbank [16] leads to considerably over-
estimated k
L
a values for k
L
a > 0.1 s
1
. Therefore, k
L
values
corresponding to this range are not included in the gure.)
They concluded [16] (in difference with the original work
[6]) that k
L
is dependent on the turbulent intensity expressed
as a function of the power dissipated per unit volume and
that the coefcient is considerably higher than would be
found for bubbles in free rise under gravitational force as
given by the model of small and large bubbles.
Vasconcelos variant of the slip velocity model based
on bubble contamination kinetics, Eqs. (4)(8), was used
by Alves et al. [9] to interpret k
L
data in a double Rush-
ton turbine-stirred tank. The application of Vasconcelos
model to the interpretation of unreliable mass transfer co-
Fig. 1. Effect of gas phase mixing model used for k
L
a evaluation; k
L
values calculated from k
L
a and a presented by Figueiredo and Calderbank [16].
efcients in the stirred vessel has been analysed by Linek
et al. [3]. Alves et al. [9] measured the overall volumetric
mass transfer coefcients k
L
a by the peroxide decomposi-
tion steady-state technique with air as a gas phase, show-
ing that k
L
decreased slightly with power dissipated. Linek
et al. [25] showed, however, that the steady-state methods
with air absorption/desorption give substantially lower k
L
a
values at high mixing intensities as compared to pure oxy-
gen absorption. If the coefcients k
L
a were measured by the
non-problematic pressure dynamic method [26] with pure
oxygen absorption in the same apparatus as in Alves et al.
[9], the relevant k
L
data were well interpreted in terms of the
eddy model (Eq. (1)) with c
1
= 0.531 [3]. The corrected
data have shown that the decisive quantity to correlate k
L
in
stirred tanks is power dissipated in the liquid phase rather
than the bubble diameter and their rigidity and that k
L
in-
creases with increasing turbulence intensity.
It seems from the literature survey that in mechanically
agitated dispersions, the intensity of energy dissipation plays
a dominant role in the value of the mass transfer coefcient
and that the successful applications of the slip velocity
models in stirred tanks are probably only a result of errors
in evaluation of k
L
a. On the contrary, in dispersions with no
mechanical agitation, both conceptions (eddy and slip
velocity) are equally successful. This may indicate that the
mechanism of mass transfer without mechanical agitation
differs from that in the presence of agitation, as was sug-
gested by Bouai et al. [14]. The same indicate the results by
Lamont and Scott [1]. They compared rates of mass trans-
fer from turbulent liquid into bubbles owing in vertical
and horizontal tube where the bubbles can and cannot rise
124 V. Linek et al. / Chemical Engineering and Processing 44 (2005) 121130
freely through the turbulent liquid, respectively. If the bub-
bles could rise freely through the liquid, the mass transfer
coefcient did not depend on intensity of turbulence at low
Reynolds number. With increasing Re number, the role of
the intensity increased and at high Re number, the dependen-
cies for both arrangements (with and without the free rise of
bubbles) coincided. It means that both mechanisms operate
simultaneously but they apply at different extent, depending
on intensity of turbulence.
Surface-active substances reduce the mass transfer coef-
cient markedly in gasliquid dispersions. Although a con-
siderable effort was made to identify the mechanism of mass
transfer in the presence of surfactants, no consistent conclu-
sion had been drawn. Two possibilities were offered [27]:
surfactant molecules affect mass transfer via hydrodynam-
ics effects or via the formation of an interfacial barrier layer.
The barrier effect is due to a monolayer of the surfactants
formed at the interface, which can offer a resistance to be
crossed by the gas molecule. The resistance exerted by the
monolayer is a complex phenomenon, possibly depending on
the effects of absorbing gassurfactantwater interactions,
which are related to the molecular structure of the surfac-
tant: the polarity of the hydrophilic group, the molecular
weight of the hydrophilic group, the hydrophilic chain length
and the orientation of the molecules at interface. Hydrody-
namics effects are induced by the difference in composition
and physical properties of the liquid at the interface and in
the bulk of liquid. Surfactants (but also electrolytes [28,29])
tend to create different spatially oriented structures in close
proximity of the interface and in bulk liquid and thus, their
presence causes an energetic barrier for the surface renewal
due to additional requirements of reordering the liquid en-
tering or leaving the interface. For example, if the liquid
turbulent eddies penetrate to the interface, they would bring
about an increase in the free energy per unit area of inter-
face due to the replacement of the interfacial liquid layer
by inner liquid of higher surface tension. This dampens the
rejuvenation of the interfacial liquid by fresh bulk liquid,
renders mass transfer more difcult and lowers the value
of mass transfer coefcient. Llorens et al. [27] decided the
hydrodynamic effect to be the principal. They offered the
surface pressure (i.e. the difference in surface tension of
the solution without and with
s
, the surfactant) to rep-
resent a measure of the additional work needed to replace
a surface element: (k
L
)
s
/k
L
= 1/(1.25 + 0.073 ) for 0.4 <
< 16 mNm
1
and (k
L
)
s
/k
L
= 0.41 for > 16 mNm
1
.
The form of the correlation did not depend on the type of
surfactant. Zieminsky and Whittemore [28] offered the ionic
strength and Machon and Linek [29] the electrical surface
potential to correlate the reduction of k
L
in electrolyte solu-
tions as measures of the additional work needed to replace a
surface element in these solutions. Vzquez et al. [12] used
a simple correlation between the mass transfer coefcient
and surface tension of solution under the form k
L
1.35
.
Vasconcelos et al. [8] interpreted mass transfer coefcients
in air-lift and bubble columns with solution of surfactants by
the model of gradual surface contamination (Eqs. (4)(8))
using three empirical parameters: h
trans
, k/c
surf
and v
t
/v
sl
.
The aim of this paper is to make measurements with liq-
uids of various physical properties in order to dene the
effect of the liquid properties and operating conditions on
the parameter k
L
and the limits of validity of the literature
models for the interpretation of mass transfer coefcients in
bubble dispersions. The method, which is used for the mea-
surements, was veried in Part I to minimize misinterpreta-
tions.
2. Experimental
The experiments were performed in a at-bottomed
cylindrical vessel with internal diameter 0.19 m, equipped
with standard Rushton turbine of 0.075 m in diameter lo-
cated 0.08 m above the bottom. Four bafes (1/10 of the
vessel diameter width) were symmetrically mounted. A
membrane-covered polarographic oxygen probe was sit-
uated in the bottom to measure the equilibrium partial
pressure of oxygen in the bulk of liquid. Gas (pure oxygen
or air) was taken from a pressure ask and introduced 2 cm
under the impeller through a tube of i.d. 4 mm. The bubble
column was realized by keeping zero rotational frequency of
the agitator. The experiments were performed with the same
solutions as those used in the kinetics measurement: 0.8 M
sodium sulphite solution, pure or with the addition of vis-
cosity or surface tension-changing additives (see Table 1).
Physical properties of the solutions are given in Part I of
this work. The vessel was lled with liquid to the height of
226 mm, which amounts to 5.9 l. Supercial velocities of
aeration gas were 1.8, 3.6 or 5.4 mms
1
, which correspond
to volumetric ow rates 5.1 10
5
, 10.2 10
5
and 15.3
10
5
m
3
s
1
, respectively. The impeller rotational speeds
were 0, 5.5, 10, 14.33 and 18.83 l/s. Temperature was kept
at 30 1
C by a cooling coil.
The specic power dissipated by agitators in the liquid,
e
agit
, was measured by a strain gauge mounted on the im-
peller shaft. The total specic power e dissipated in the liq-
uid by the agitator and the rising bubbles was calculated as
e = e
agit
+ gv
s
. The volumetric mass transfer coefcient
and interfacial area were measured by the Danckwerts plot
method described in detail in Part I.
3. Results
3.1. Volumetric mass transfer coefcient
The overall volumetric mass transfer coefcients mea-
sured by pure oxygen absorption were expressed as a func-
tion of the total specic power dissipated in the liquid as
follows:
k
L
a =
1
e
2
(9)
V. Linek et al. / Chemical Engineering and Processing 44 (2005) 121130 125
Table 1
Solutions used in this work and pertinent symbols and lines used in gures and parameters , and in correlations (9), (10) and (11) obtained by
regression of the experimental data
Solution Symbol Lines Parameter i = 1 i = 2 Mean
deviation (%)
Mean
deviation
a
0.8 kmol m
3
Na
2
SO
3
i
3.35 10
5
1.18 34 21
i
0.523 0.863 36 36
i
1.06 10
4
0.238 19 20
0.8 kmol m
3
Na
2
SO
3
+ Sokrat 44 (3 vol.%)
i
3.26 10
5
1.16 44 43
i
0.507 0.913 40 43
i
6.70 10
5
0.243 11 11
0.8 kmol m
3
Na
2
SO
3
+ CMC TS.5 (0.2 wt.%)
i
3.65 10
5
1.08 30 29
i
1.21 0.632 33 49
i
1.04 10
4
0.276 25 26
0.8 kmol m
3
Na
2
SO
3
+ CMC TS.20 (0.6 wt.%)
i
2.21 10
4
0.771 14 14
i
1.80 0.689 13 14
i
1.15 10
4
0.090 5 5
0.8 kmol m
3
Na
2
SO
3
+ ocenol (3 ppm by volume) +
i
1.27 10
4
0.732 27 14
i
2.35 0.492 12 9
i
7.97 10
5
0.188 17 13
0.8 kmol m
3
Na
2
SO
3
+ PEG 1000 (100 ppm by mass)
i
2.65 10
5
1.15 1
i
1.14 0.903 2
i
0.237 0.246 1
a
Mean deviation when the gas ow rate v
s
is taken into account as an additional parameter (e.g., k
L
a =
1
e
2
v
3
s
).
1, 2
values together with mean deviations of the data are
given for all batches in Table 1. Taking into account gas
ow rate v
s
as additional independent parameter has not
improved delity of the correlation as follows from a com-
parison of the mean deviations of the relation (9) with and
without taking into account v
s
(see Table 1). Fig. 2 clearly
shows that k
L
a data for pure sulphite solution agree well
with a recommended correlation for non-coalescent batches
Fig. 2. k
L
a/(v
s
)
0.4
measured by pure oxygen absorption as a function of total power dissipated in the liquid, e. Symbols and lines (see Table 1).
of electrolyte solutions [24]. Marked reductions of k
L
a
are observed with ocenol (up to 10 times) and long-ber
carboxymethylcellulose (CMC) TS.20 (up to four times).
The ocenol has a strong antifoaming effect that enhances
the coalescence rate of bubbles in dispersion. The resulting
coefcients are even lower than those predicted by a corre-
lation suggested for coalescent batches like pure water [24].
The reduction of k
L
a due to CMC TS.20 cannot be ascribed
126 V. Linek et al. / Chemical Engineering and Processing 44 (2005) 121130
Fig. 3. Interfacial area a measured by pure oxygen absorption as a function of total power dissipated in the liquid, e. Symbols and lines (see Table 1).
unequivocally to higher viscosity of the batch as the addi-
tion of Sokrat 44 (which increased the viscosity to the same
extent as CMC) made no reduction in k
L
a.
3.2. Specic interfacial area
The specic interfacial areas measured by pure oxygen
absorption were expressed as a function of the total specic
power dissipated in the liquid as follows:
a =
1
e
2
(10)
1, 2
values together with mean deviations of the data are
given for all batches in Table 1. Taking into account gas
ow rate v
s
as an additional independent parameter has not
improved delity of the correlation as follows from a com-
parison of the mean deviations of the relation (10) with and
without taking into account v
s
(see Table 1). This agrees
with the nding of Westersterp et al. [30], who stated that
the interfacial area is independent of gas ow rate at im-
peller speeds higher than a critical one. The critical im-
peller speed for Rushton turbine and sulphite solution equals
9.4 s
1
[29]. All but one of the impeller speeds used in this
work were higher than this critical value. The results given
in Fig. 3 show that ocenol and short-ber CMC TS.5 pro-
duce a marked decrease of the interfacial area (up to ve and
three times, respectively), and that a marked increase is pro-
duced by polyethylenglycol (PEG) (up to three times) and
a smaller one by the addition of Sokrat (up to two times).
3.3. Mass transfer coefcient
Mass transfer coefcients were calculated by the ratio
k
L
a/a. The coefcients evaluated from the data measured by
pure oxygen absorption were expressed as a function of the
total specic power dissipated in the liquid as follows:
k
L
=
1
e
2
(11)
1, 2
values together with mean deviations of the data are
given for all batches in Table 1. The results show clearly that
k
L
increases with increasing power dssipated in the liq-
uid with exponent
2
equal approximately to 0.25 in agree-
ment with the eddy model (1) (see Fig. 4). Exceptions
are the solutions with the addition of long-ber CMC TS.20
and ocenol. In these solutions, the coefcients increase with
power but the exponent
2
is lower than 0.25 (
2
= 0.09
and 0.188, respectively). The correlation (11) also ts well
the data measured in the bubble column, which are repre-
sented by the points for e < 100 Wm
3
in Fig. 4. k
L
data
for all Newtonian batches without surface-active agents (i.e.
pure sulphite solution and with the addition of Sokrat and
short-ber CMC) are well tted by the equation
k
L
= 0.915
ev
0.243
D
v
0.623 (12)
with a mean deviation of 19%. If the theoretical value 0.25 of
the power exponent and 0.5 of Schmidt number exponent
are used, the equation changes to
k
L
= 0.448
ev
0.25
D
v
0.5
(13)
with a mean deviation of 20%. Since the deviation is prac-
tically the same as the deviations of correlation (11), cor-
relations (12) and (13) describe the effects of viscosity and
diffusivity satisfactorily. Experimental and calculated values
from Eq. (13) of k
L
are compared in Fig. 5.
V. Linek et al. / Chemical Engineering and Processing 44 (2005) 121130 127
Fig. 4. Liquid lm mass transfer coefcient measured by pure oxygen absorption vs. total power dissipated in the liquid, e. Symbols and lines (see Table 1).
Literature data for Newtonian batches (water [3,4,16,17]
and for sodium sulphite solutions [3,19]) together with
our Newtonian data were also evaluated according to
relation
k
L
= c
1
ev
c
2
D
v
c
3
(14)
yielding the regression constants c
1
, c
2
and c
3
given in
Table 2. Correlation (14) with the theoretical exponents c
2
= 0.25 and c
3
= 0.5 ts our and literature data on Newto-
nian batches with a mean deviation of 20%. Experimental
and calculated values of k
L
from Eq. (14) are compared in
Fig. 6.
Fig. 5. Comparison of experimental and calculated values of mass transfer
coefcient k
L
from Eq. (13). Symbols (see Table 1).
Table 2
Parameters c
1
, c
2
and c
3
in correlation (14) obtained by regression of
literature and our data for Newtonian batches
k
L
= c
1
(ev/)
c
2
(D/v)
c
3
c
1
c
2
c
3
Mean deviation (%)
0.363 0.213 0.542 19
0.265 0.210 0.500 19
0.463 0.250 0.500 22
3.4. Effect of surfactants
Additions of substances for surface tension depression
(ocenol, PEG, CMC TS.20, see Table 1 of Part I) induced
a signicant reduction of the mass transfer coefcient (by
Fig. 6. Comparison of our and literature experimental data for Newtonian
batches with those calculated from Eq. (14) with c
1
= 0.463, c
2
= 0.25
and c
3
= 0.5. Hollow symbols (see Table 1) [31].
128 V. Linek et al. / Chemical Engineering and Processing 44 (2005) 121130
Fig. 7. Relative decrease of mass transfer coefcient in the presence of
surfactant (in comparison to its value in pure sulphite solution) as a
function of surface pressure . Comparison with literature data measured
in bubble columns [12,8] and in wetted-wall column [27].
40 up to 80%). The results are given in Fig. 7 together with
literature data measured in bubble columns [12,8] and in
wetted-wall column [27]. In the gure, the relative decrease
of k
L
(in comparison to its value in pure sulphite solution,
(k
L
)
s
/k
L
) is plotted as a function of surface pressure . It is
apparent that neither the surface pressure nor surface tension
alone (cf. the values of given in Table 1 of Part I) is
Fig. 8. Comparison of k
L
a, a and k
L
data measured by pure oxygen and air absorption in pure sulphite solution and with addition of ocenol. Air
absorption, lled symbols; oxygen absorption, hollow symbols; see Table 1.
the proper parameter to correlate the effect of surfactants
on k
L
.
3.5. Effect of diluted gas (air) absorption
Experiments with air were performed in pure sulphite so-
lution (non-coalescent batch) and with the addition of ocenol
(coalescent). The results are plotted in Fig. 8 together with
those measured by pure oxygen absorption. While the mass
transfer coefcients measured with oxygen increase with in-
creasing dissipated power, the k
L
values determined with air
either do not depend (in pure sulphite solution) or slightly
decrease with increasing power (in sulphite with ocenol).
The coefcients roughly coincide at the lowest stirring
intensity (330 rpm). With increasing stirring intensity, the
difference between them increases up to 70% at the highest
stirring intensity (1130 rpm). The differences can be caused
by application of an improper gas phase mixing model of the
dispersion, leading to an incorrect value of the driving force
for absorption, which proliferates to k
L
values. Application
of pure oxygen absorption avoids the problem as the oxygen
concentration and, therefore, the absorption efciency are
the same for all bubbles. Thus, k
L
data used in this work are
measured by pure oxygen. The absorption of air has only
been used to demonstrate the possible reason of discrepancy
in the literature data. Fig. 9 shows that k
L
data measured
with air can be interpreted in terms of Calderbanks model:
data measured in pure sulphite solution are independent
of bubble diameter and correspond to Eq. (2) for large
V. Linek et al. / Chemical Engineering and Processing 44 (2005) 121130 129
Fig. 9. Comparison of mass transfer coefcients measured by air absorption in pure sulphite solution and in the solution with addition of ocenol with
Calderbanks model.
bubbles. (The average bubble diameter was calculated from
gas hold-up and interfacial area as d = 6/[(1)a].) The
data measured in solution with ocenol fall between the
values for large and small bubbles. This is usually
interpreted by partial contamination of bubble surface by
surfactant, which shifts the transition between large and
small bubbles to higher bubble diameters. The decrease
of k
L
values with increasing stirring intensity (see Fig. 8 for
ocenol) can be explained by an increasing amount of small
bubbles. Such interpretation is frequently used in literature
for the data measured by absorption of diluted gas.
4. Conclusions
Mass transfer coefcients measured by absorption of pure
oxygen increased in all batches with increasing power dis-
sipated in the liquid raised approximately to 0.25. An ex-
ception was the addition of long-ber CMC for which the
exponent is only 0.09. k
L
data for all Newtonian batches
without surface-active agents (i.e. pure sulphite solution and
with addition of Sokrat and short-ber CMC) are well t-
ted by the eddy model of Lamont and Scott [4], Eq. (13).
Substances that depress the surface tension of the absorp-
tion solution (ocenol, PEG, CMC TS.20) induced a signif-
icant reduction of the mass transfer coefcient (by 40 up
to 80%). Absorption of air (diluted gas) did not yield cor-
rect k
L
data, not depending on or slightly decreasing with
increasing power. This is due to the application of an im-
proper model of gas ow pattern in the dispersion (i.e. per-
fect mixing of gas phase), which leads to an incorrect value
of the driving force for absorption that proliferates to k
L
values. Since this data are well interpreted by Calderbanks
model of small and large bubbles, this model seems to
be the result of interpretation of physically inconsistent k
L
data.
Acknowledgements
This work was supported by the Grant agency of Czech
Republic through the project no. 104/98/1126 and by Czech
Ministry of Education through the scientic project no.
223400007.
Appendix A. Nomenclature
a specic interfacial area based on the liquid
volume, m
1
c
1, 2, 3
constants in correlation (14)
d bubble diameter, m
D gas diffusivity in the liquid, m
2
s
1
e total specic power dissipated in the liquid
volume, Wm
3
e
agit
specic power dissipated by agitators in the
liquid volume, Wm
3
f impeller rate, s
1
g gravitational constant, ms
2
k
L
liquid-side mass transfer coefcient measured by
oxygen absorption, ms
1
(k
L
)
s
liquid-side mass transfer coefcient in the
presence of surfactant, ms
1
(k
L
)
air
liquid-side mass transfer coefcient measured by
air absorption, ms
1
k
L
a volumetric mass transfer coefcient referred to
the liquid volume, s
1
k empirical constant of the model of bubble
contamination kinetics, mol m
7/2
s
130 V. Linek et al. / Chemical Engineering and Processing 44 (2005) 121130
q volumetric gas ow rate, m
3
s
1
v
s
supercial velocity, ms
1
v
t
single bubble terminal velocity in still water, ms
1
v
sl
slip velocity, ms
1
Greek symbols
, , constants in correlations (9), (10) and (11)
gas hold-up
kinematics viscosity of the liquid phase, m
2
s
1
=(
s
), surface pressure, Nm
1
density of the liquid phase, kg m
3
=(
liquid
gas
), kg m
3
s
, surface tension of solution with or without
surfactant, Nm
1
mobile
time for transition of bubble surface to rigidity, s
R
average bubble residence time, s
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[32] V. Linek, P. Bene, V. Vacek, F. Hovorka, Analysis of differences
in k
L
a values determined by steady-state and dynamic methods in
stirred tanks, Chem. Eng. J. 25 (1982) 7788.
Chemical Engineering and Processing 44 (2005) 131137
Separation of n-hexaneethyl acetate mixtures by azeotropic batch
distillation with heterogeneous entrainers
I. Rodriguez-Donis
a
, J. Acosta-Esquijarosa
a
, V. Gerbaud
b,
,
E. Pardillo-Fondevila
a
, X. Joulia
b
a
Centro de Quimica Farmaceutica, Ave. 200 y 21 Atabey Apdo. 16042, Playa, C. Habana, Cuba
b
Laboratoire de Gnie Chimique UMR CNRS 5503, ENSIACETUPSCNRS, BP1301, 5 rue Paulin Talabot, 31106 Toulouse Cedex 1, France
Received 26 February 2004; received in revised form 4 May 2004; accepted 14 May 2004
Available online 2 July 2004
Abstract
In this article, a systematic study of the separation of the n-hexaneethyl acetate mixture with an entrainer by heterogeneous azeotropic
batch distillation is performed. Based upon the thermodynamic behaviour of the ternary mixtures, potential entrainers partially miscible with
one or two original azeotropic components are chosen. In all cases, the entrainer adds a heterogeneous binary or ternary azeotrope that is the
lowest boiling point in the ternary diagram. Therefore, it leaves the column by the overhead streamwhich is subcooled to get two liquid phases
in the decanter. The phase with the highest amount of the original component is removed as distillate product whereas the entrainer-rich phase
is continuously reuxed to the column. Considering methanol, acetonitrile, water and nitromethane as heterogeneous entrainers, screening was
performed based on the composition of the unstable heteroazeotropic mixture, the ratio of both liquid phases in the condensed top vapour and the
purity of the distillate product determined by the liquidliquid envelope at the decanter temperature. The process feasibility analysis is validated
by using rigorous simulation with the batch process simulator ProSimBatch. Simulation results are then corroborated in a bench experimental
column for the selected entrainer, showing several advantages of heterogeneous batch distillation (HBD) compared to homogeneous systems.
2004 Elsevier B.V. All rights reserved.
Keywords: Batch distillation; Heterogeneous entrainer; Azeotropic distillation
1. Introduction
Batch processes are again becoming important because
of recent expansion of the pharmaceutical and speciality
chemical industries in many developing countries. Besides,
recycling of liquid waste streams is becoming a key issue in
all processing plants to meet stricter environmental regula-
tions. Batch distillation is a widely used separation method
in batch processes because of its inherent operational ex-
ibility due to some extent to its time dependent operation.
The separation of azeotropic mixtures or close boiling com-
ponents is a challenging task in many chemical processes
as it is impossible using a single conventional column or
as a pressure swing distillation is an uneconomical process.
Alternative techniques based on the addition of an auxiliary
C)
Binary azeotrope with
ethyl acetate (77.1
C)
Ternary azeotrope
(
C) x
molar
a
T (
C) x
molar
a
T (
C) x
molar
a
T (
C)
Methanol 64.7 0.5100
b
50.6 0.708 62.05
Acetonitrile 81.5 0.5755
b
54.4 0.6730 76.1
Water 100.0 0.7860
b
61.8 0.7000
b
70.5 0.5764
b
60.7
0.2558
Nitromethane 101.2 0.7271
b
62.0 Zeotropic
a
The mole fraction indicated is that of the lightest component in the mixture.
b
Heteroazeotrope.
ponents are selected. From the analysis of residue curve map
features, in particular the decanter phases composition and
the distillation region separatrices curvature, the sequence of
products to be drawn from the rectier column can be pre-
dicted. The number of distillation tasks in the whole process
is set by the products targeted purity.
2. Selection of a suitable entrainer for the separation
of n-hexaneethyl acetate mixtures by heterogeneous
azeotropic batch distillation
Liquidvapour equilibrium data for the binary mixture
n-hexaneethyl acetate have been scarcely reported in the
scientic literature [8]. Those authors reported a mini-
mum boiling temperature azeotrope with an average mole
fraction of n-hexane equal to 0.6565 and a temperature
of 65.15
C
Entrainer Binary azeotrope with
n-hexane
Ternary azeotrope
x
I
nhexane
x
II
nhexane
x
I
x
II
C) 25
Distillation time (h) 4.8
0.3991
1.01
0.7
I. Rodriguez-Donis et al. / Chemical Engineering and Processing 44 (2005) 131137 135
Fig. 2. Simulation and experimental results of the separation of n-hexane
ethyl acetate by using batch distillation with acetonitrile as a heavy
heterogeneous entrainer.
an innite reux step and a distillate removal step described
in detail below are simulated.
The amount of heterogeneous entrainer to be added to
the original binary mixture is established from material bal-
ances considering that the entrainer composition in the still
should be less than 0.01 at the end of innite reux batch
step 1. Simulation shows that this composition is reached
after two hours, which is the end of batch step 1. It should
be noted that the initial ternary composition F is placed in
distillation region I that is not limited by the vertex of ethyl
acetate (see Fig. 2). Therefore, in order to reach the vertex
of ethyl acetate located in region II at the end of the distil-
lation process, the still path must cross the unstable separa-
trix connecting the heteroazeotrope with the homoazeotrope
n-hexaneethyl acetate. As established by Rodriguez-Donis
et al. [6], such a crossing is possible with different reux
policies, either the reux of entrainer-rich phase or a com-
Table 5
Simulation and experimental results (x
1
: n-hexane; x
2
: ethyl acetate; x
3
: acetonitrile)
Simulation results Experimental results
Quantity (mol) Molar fraction Quantity (mol) Molar fraction
Initial mixture 12.2 x
1
0.705 12.2 x
1
0.705
x
2
0.173 x
2
0.173
x
3
0.122 x
3
0.122
n-Hexane-rich phase (distillate + decanter) 8.6 x
1
0.951 8.4 x
1
0.968
x
2
0.002 x
2
0.001
x
3
0.047 x
3
0.031
Acetonitrile-rich phase (decanter) 1.1 x
1
0.107 0.99 x
1
0.082
x
2
0.157 x
2
0.190
x
3
0.736 x
3
0.728
Final still content (ethyl acetate) 1.7 x
1
0.001 1.6 x
1
0.001
x
2
0.992 x
2
0.991
x
3
0.007 x
3
0.008
Ethyl acetate recovery yield 81.04% 75.1%
n-Hexane recovery yield 95.1% 94.5%
Acetonitrile recovery yield 54.5% 48.4%
bination of both decanted liquid phases. In this example, the
distillate removal step (batch step 2) is performed reuxing
a combination of entrainer-rich L
R
and entrainer-weak L
W
phases coming from the decanter, the reux policy 2.3 of
Rodriguez-Donis et al. [6]. As in Rodriguez-Donis et al. [6]
the acetonitrile-rich phase L
R
C and
total liquid reux is provided at the top of the column by a
solenoid valve. The open/close time of the solenoid valve is
dened considering that 70% of the condensed vapour is re-
turned to the column. The 30% remaining condensed vapour
is collected into the decanter (70 ml) where the light phase
is drawn as distillate (n-hexane-rich phase) whereas a por-
tion of the heavy entrainer-rich phase is recycled to the top
of the column with a peristaltic pump.
Experiments taking into account these operating condi-
tions (Table 4) are carried out in the bench distillation col-
umn and the results are presented in Fig. 2 and Table 5.
Analysis of the still composition is performed every 0.5 h.
The analysis of purity of the light and heavy phases in the
decanter and of the distillate product is made at the end of
the process (4.8 h). The acetonitrile, n-hexane and ethyl ac-
etate compositions are determined using a FISONS HRGC
chromatograph with a FID detector and with a column HP
INNOWax (30 m 0.53 mm, 0.25 m lm). The injector
and detector temperature are held at 180
C. Prior calibration is
done using internal standards; the samples were prepared by
weighing on a SARTORIUS BP 211D balance with a pre-
cision of 10 mg. The standard accuracy and reproducibility
in the composition for all components are found to be 0.1
and 0.3%, respectively.
As shown in Fig. 2, the still path obtained experimentally
(circles) is in excellent agreement with the still trajectory
calculated by simulation. The selected reux policy permits
the still path to cross the separatrix into another distillation
region than the initial feed region. Hence, the still path is
able to reach the ethyl acetate vertex and this component re-
mains pure into the still at the end of the distillate removal
step. Such a behavior is not possible with a homogeneous
entrainer that gives rise to a similar residue curve map be-
cause the distillation process is restricted to the distillation
region where the initial composition of the mixture is lo-
cated. In this case, ethyl acetate could not be obtained as an
isolated product.
Table 5 displays the quantity and composition of the main
streams of the process. n-Hexane is drawn of as distillate
product with a molar purity of 96.8%. Another binary batch
distillation step is required to obtain n-hexane with a high-
est purity. Ethyl acetate with 99.6% of purity is recovered in
the still at the end of the process, while the acetonitrilerich
phase obtained from decanter can be reused in the next batch
distillation process. The make-up of fresh entrainer for the
next cycle of n-hexaneethyl acetate separation is approxi-
mately 52%.
5. Conclusions
Acetonitrile was chosen as a suitable heterogeneous
entrainer for the separation of the azeotropic mixture
n-hexaneethyl acetate by heteroazeotropic batch distil-
lation from the comparison of the residue curve maps of
several candidate entrainers. We have conrmed the feasi-
bility of the heteroazeotropic batch distillation via simula-
tion and by experimentation in a bench batch distillation
column. Good agreement was obtained between simulation
and experimental results. The novel process with a single
heterogeneous distillation column shows a great potential
over a reported hybrid process with a homogeneous distilla-
tion column and a liquidliquid extraction column. Indeed,
the consumption of entrainer is low and the separation of
all three components can be performed in a single batch
distillation step using the dened reux policy. The ethyl
acetate purity is high enough to enable its recycling in a
chromatography process whereas the n-hexane-rich phase
must be puried in a simple non azeotropic batch distillation
process.
References
[1] I. Rodriguez-Donis, V. Gerbaud, X. Joulia, Entrainer selection rules
for the separation of azeotropic and close boiling temperature mix-
tures by homogeneous batch distillation, Ind. Eng. Chem. Res 40
(2001) 27292741.
I. Rodriguez-Donis et al. / Chemical Engineering and Processing 44 (2005) 131137 137
[2] R. Dssel, J. Stichlmair, Separation of azeotropic mixtures by batch
distillation using an entrainer, Comp. Chem. Eng. 19 (1995) s113
s118.
[3] J. Khler, H. Haverkamp, N. Schadler, Zur diskontinuierlichen Rekti-
kation azeotroper Gemische mit Hilfsstoffeinsatz, Chem. Ing. Tech.
67 (1995) 967971.
[4] S. Skouras, S. Skogestad, Separation of ternary heteroazeotropic
mixtures in a closed multivessel batch distillation-decanter hybrid,
Chem. Eng. Proc. 43 (2004) 291304.
[5] I. Rodriguez-Donis, V. Gerbaud, X. Joulia, Heterogeneous entrainer
selection rules for the separation of azeotropic and close boiling
temperature mixtures by heterogeneous batch distillation, Ind. Eng.
Chem. Res. 40 (2001) 49354950.
[6] I. Rodrguez-Donis, V. Gerbaud, X. Joulia, Feasibility of heteroge-
neous batch distillation, AIChE J. 48 (2002) 11681178.
[7] I. Rodriguez-Donis, U. Juregui-Haza, E. Pardillo-Fondevila, Sepa-
ration of n-hexane-ethyl acetate mixtures by azeotropic distillation,
Latin Am. Appl. Res. 29 (1999) 119127.
[8] J. Gmehling, J. Menke, J. Krafczyk, K. Fischer, Azeotropic Data,
Verlag Chemie, Weinheim, 1994.
[9] J. Acosta, A. Arce, J. Martnez-Ageitos, E. Rodil, A. Soto, Vapour
liquid equilibrium of the ternary system ethyl acetate + hexane
+ acetona at 101.32 kPa, J. Chem. Eng. Data 47 (2002) 849
854.
[10] S.A. ProSim, 2000, http://www.prosim.net, Reference Manual.
[11] J. Gmehling, U. Onken, VapourLiquid Equilibrium Data Collection,
DECHEMA Chemistry Data Series, vol. 1, 12 parts, DECHEMA,
Frankfurt am Main, 1982.
| |
| |
CHEMICAL ENGINEERING AND PROCESSING
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Chemical Engineering and Processing 44 (2005) 139140
Editorial
Special issue on conveying and handling
of particulate solids
Dear reader,
Already almost 1 year has own away since the Fourth
International Conference on Pneumatic Conveying and Han-
dling of Particulate Solids took place in Budapest, Hungary,
2730 May 2003. This was the very rst event that took
place in Europe followed by previous meetings held in Israel
(Herzilya 1995, Jerusalem 1997, Dead Sea 2000). In
addition to the habitually pleasant and friendly atmosphere
of these conferences, this latter was even greater from pro-
fessional point of view. During this 4 full days meeting,
more than 200 presentations were delivered by excellent sci-
entists. Among them, 20 plenary or keynote lectures, 120
oral presentations in four parallel streams of sessions, as
well as 60 posters gave detailed information on the research
and industrial practice carried out and applied recently in the
eld. In addition, the marvelous conference center of Ho-
tel Inter-Continental Budapest and its surroundings with the
historical district of the Hungarian capital, one of the most
beautiful part of the worlds heritage, offered more than suit-
able milieu for the meeting and satellite workshops.
The objective of the event was to bring together re-
searchers, practicing engineers, industrialist and students
from all over the world. The rich scientic and technical
program have attracted great attention: more than 220 par-
ticipants joined to the conference from 28 countries, most
of them from Germany, Israel, United Kingdom, Poland,
USA, Hungary, Australia, Japan, Norway and France.
Full text papers have been published in two thick vol-
umes of conference proceedings, having altogether more
than thousand pages. However, to ensure broader publicity,
the International Scientic Council (ISC) and the Interna-
tional Organizing Committee (IOC) have decided to select
the most suitable papers for publication in several interna-
tionally respected periodicals, too.
Chemical Engineering & Processing was among the jour-
nals best suited to the topics of the majority of papers sub-
mitted to the conference. Selection of papers was the task
of ISC and invited guest editors on basis of quality and con-
tent. All papers submitted for publication in this special is-
sue were peer-reviewed by two independent referees. After
reviewing and nal revisions, 27 papers were accepted for
publication. These papers give representative sample on the
conference topics, especially from respect to the scope of
this journal.
The rst, memorial paper written by Prof. David Mills
gives honour to the oeuvre of Prof. Predrag Marjanovic, one
of the most distinguished personalities in particle technol-
ogy, late member of ISC, who left us tragically not long ago.
The next three papers by M.J. San Jos et al., I. Descamps
et al., as well as J. Li et al. deal with gassolids systems and
disperse particle ow. Gas ow pattern in spouted bed, mod-
eling of particle take-off in turbulent ow, as well as solids
deposition during pneumatic conveying were discussed, re-
spectively. During pneumatic conveying various transforma-
tions of particles can also take place, as is shown in two
next papers: L. Frye and W. Peukert describe specic attri-
tion mechanism in dilute phase process, while I. Skuratovsky
et al. show the results of a numerical simulation study on
drying process during pneumatic conveying.
Particle production is an important process of particle
technology. The paper of J. Tth et al. discusses the results
of investigation on salting-out precipitation of glycine and
sodium chloride. In another paper, production of micronized
cocoa butter particles by supercritical process was reported
by J.-J. Letourneau et al.
Relatively big number of contributions has been selected
for this special issue dealing with processing particulate
materials. J. Fitzpatrick and L. Ahrn gave comprehensive
summary on food powder handling and processing. Microen-
capsulation of heat sensitive ne particles was reported by
H. Krber and U. Teipel in a novel uidized-bed process
using supercritical carbon dioxide as solvent for coating ma-
terial. Plasma spheroidization of ceramic particles was de-
scribed by Z. Karoly and J. Szpvlgyi, while thermal plasma
processing was applied by I. Mohai and J. Szpvlgyi for
treatment of particulate metallurgical wastes. M.J.R. Aguado
et al. studied conical spouted bed reactor for pyrolysis of
plastic wastes using sand particles as uidizing packing to
avoid agglomeration.
Energy demand of granulation process was studied by T.
Gluba, described in the next paper. Elimination of particle
aggregation during nanomilling was realized and described
by W. Peukert et al. Four more papers are dealing with size
reduction processes: milling, grinding, attrition and particle
0255-2701/$ see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.cep.2004.05.001
140 Editorial / Chemical Engineering and Processing 44 (2005) 139140
degradation (R.K. Sahoo and D. Roach, A. Heim et al., V.
Mizonov et al., and P.B. Kis et al.). Separation and classi-
cation are inevitable processes in particle technology. M.
Shapiro and V. Galperin gave a review on various techniques
of separation of particles. The paper of W. McBride and S.
Keys have applied vertical Venturi separator to improve re-
cycling of automotive tyres.
A worldwide revival of research activities nowadays on
mixing, blending, homogenization processes of particulate
solids is evidenced by three papers. A new pulsated bottom
mixer and its investigation were described by M. Nemenyi
and A.J. Kovacs. Process dynamics and homogenization ef-
ciency of mammoth silos were studied by D.L. Schott et
al. Assessment of homogeneity in powder mixtures by elec-
trical capacitance measurement was proposed N. Ehrhardt
et al., as a good tool to examine segregation during particle
ow or the efciency of a mixer.
As a special topic, solids transport in a pilot-scale rotary
kiln was studied and outlined in a paper of N. Descoins et al.
Finally, two papers give examples on environmental aspects
of this eld. A nice overview on dust control and explosions
in solids handling plants are given P. Wypych et al. with
description of some own experimental results. Application
of uidized bed process for photo-catalytic degradation of
harmful gas components are described by T.H. Lim and S.D.
Kim.
We hope that this special volume offers a good cross-
section on the professional work of the conference for the
readers, giving useful information on the results achieved
recently in the eld, and will also stimulate the participation
at the next event to be held in 2006 in Rome.
April 2004.
Janos Gyenis
Research Institute of Chemical and Process Engineering
University of Veszprem, P.O. Box 158
Veszprem 8201, Hungary
Corresponding author. Tel.: +36 88 425 206
fax: +36 88 424 424
E-mail address: gyenis@mukki.richem.hu
(J. Gyenis)
Avi Levy
Ben-Gurion University of the Negev
Beer-Sheva, Israel
Available online 19 June 2004
Chemical Engineering and Processing 44 (2005) 141151
A review of the research work of Professor Predrag Marjanovi c
David Mills
to
+90
bends.
A sketch of the test facility and pipeline is given in Fig. 21.
A number of sets of test results obtained for different back
pressures and line pressure drops are presented in Fig. 22.
Minimumconveying air velocity was also determined dur-
ing the test programme. It was found that this velocity is in-
uenced by system pressure, with its value decreasing from
10.5 m/s at atmospheric pressure to 6 m/s at a pressure of
20 bar gauge. This effect was expected due to a signicant
increase of gas density at higher pressures.
Fig. 22. Conveying characteristics for coal at different back pressures.
D. Mills / Chemical Engineering and Processing 44 (2005) 141151 149
12. What could have come
We are naturally left wondering what might have been
achieved with so many more years that should have been his,
to spend on the loves of his life: his family and his research
work, and not forgetting the golf that he discovered in his
new home in Scotland. Thank you for being such a valued
colleague and friend. You will be long remembered by us
all.
Further reading
References and publications
[1] P. Marjanovi c, M. Sasic, Hydraulic transport of ash in thermo-
power stations, Proceedings of the 4th Yugoslav Thermal Symposium,
Belgrade, Yugoslavia, 1975 (in Serbian).
[2] M. Sasic, P. Marjanovi c, On the methods for calculation of hydraulic
transport and their reliability in practice. Part 1, Proceedings of the
5th International Conference on Hydraulic Transport of Solids in
Pipes, vol. 1, Hanover, Germany, 1978, pp. A5:61A5:76.
[3] M. Sasic, P. Marjanovi c, On the methods for calculation of hy-
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[5] M. Sasic, P. Marjanovi c, Hydromechanics of gassolid systems, Jnl
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[6] P. Marjanovi c, J. Jovanovic, R. Askovic, Sur lecoulement dun
liquide conducteur dans la region dentree un tube circulaire en
presence dun champ magnetique. Publ. of Mathematical Institute
SANU, new series, vol. 3, no. 11, Belgrade, Yugoslavia, pp. 7580.
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[8] M. Sasic, P. Marjanovi c, Non-isothermal compressible ow in pipes,
ZAMM 62 (1982) 226228.
[9] P. Marjanovi c, A comparative study of performance characteristics for
horizontal and vertical pneumatic conveying in pipelines, Proceedings
of the Pneumatech 1. PAC Conference Stratford-upon-Avon, UK,
1982.
[10] D. Mills, J.S. Mason, P. Marjanovi c, Pneumatic conveying vertically
down. Proceedings of the 8th Powder and Bulk Solids Conference,
Atlanta, USA, May 1983, pp. 546557.
[11] D. Mills, J.S. Mason, P. Marjanovi c, An analysis of the dense phase
pneumatic conveying of cement in vertical pipelines. Proceedings of
the 9th Powder and Bulk Solids Conference, Chicago, USA, May
1984, pp. 125147.
[12] D. Mills, J.S. Mason, P. Marjanovi c, The inuence of pipeline
bore on dense phase pneumatic conveying in vertical pipelines.
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[13] P. Marjanovi c, An investigation of the behaviour of gassolids mix-
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CNAA, Thames Polytechnic, London, UK, 1984.
[14] D. Mills, J.S. Mason, P. Marjanovi c, The inuence of product type
on dense phase pneumatic conveying in vertical pipelines, Proceed-
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Canterbury, UK, September 1984, pp. 193210.
[15] D. Mills, J.S. Mason, P. Marjanovi c, A comparison of pressure drops
in horizontal and vertical dense phase pneumatic conveying, Proceed-
ings of the 3rd International Conference on Pneumatic Conveying,
Pecs, Hungary, March 1985.
[16] D. Mills, P. Marjanovi c, J.S. Mason, An analysis of line pressure
gradient for dense phase vertical gassolids ow, Proceedings of the
GAMM Congress, Dubrovnik, Yugoslavia, April 1985.
[17] P. Marjanovi c, D. Mills, J.S. Mason, An investigation of high con-
centration vertical pneumatic conveying, J. Procesna Tehnika, vol. 1,
no. 2, Belgrade, Yugoslavia, December 1985, pp. 3949 (in Serbian).
[18] P. Marjanovi c, On the choking velocity for vertical pneumatic con-
veying, Proceedings of the 17th Yugoslav Congress of Theoretical
and Applied Mechanics, Zadar, Yugoslavia, 1986 (in Serbian).
[19] P. Marjanovi c, The design of vertical pneumatic conveying using
high-pressure blow tank system, Proceedings of the International
Colloquium on Modern Trends in the Development of Pneumatic
Conveying, Sarajevo, Yugoslavia, June 1986, pp. 4564.
[20] P. Marjanovi c, D. Mills, J.S. Mason, A method of calculating
ow parameters for pneumatic conveying in pipelines, Proceedings
of the Pneumatech 3, PAC Conference, Jersey, UK, March 1987,
pp. 143167.
[21] P. Marjanovi c, I. Vuskovic, L. Bodiroga, Hydraulic Transport of
granular activated carbon in water renery plant, Symposium on
Water Supply, Belgrade, Yugoslavia, 1987 (in Serbian).
[22] P. Marjanovi c. Bends in gassolids mixture ow in pipes a view to
the prediction of pressure loss, GAMM Congress, Vienna, Austria,
1988.
[23] P. Marjanovi c, Analysis of the change of ow parameters in dis-
continuous pneumatic conveying systems, Proceedings of the 18th
Yugoslav Congress of Theoretical and Applied Mechanics, Vrnjacka
Banja, Yugoslavia, 1988, pp. 8992 (in Serbian).
[24] P. Marjanovi c, Determination of performance characteristics of dilute
phase pneumatic conveying system, Proceedings of the 3rd Sympo-
sium of Process Industry Applications, Belgrade, Yugoslavia, 1988,
pp. 215223 (in Serbian).
[25] P. Marjanovi c, A comparison between pneumatic and hydraulic con-
veying, Proceedings of the 19th Yugoslav Congress of Theoretical
and Applied Mechanics, Ohrid, Yugoslavia, 1990, pp. 6166 (in Ser-
bian).
[26] P. Marjanovi c, D. Mills, J.S. Mason, The inuence of bends on the
performance of a pneumatic conveying system, Proceedings of the
15th Powder and Bulk Solids Conference, Chicago, USA, June 1990,
pp. 391399.
[27] P. Marjanovi c, D. Mills, J.S. Mason, The inuence of pipeline ma-
terial on the performance of pneumatic conveying systems, Proceed-
ings of the Pneumatech 4, Glasgow, UK, June 1990, pp. 453464.
[28] N. Barbalic, P. Marjanovi c, E. Dzaferovic, Z. Mujcinovic, A. Cam-
para, Measurement of P.F. ash pneumatic conveying system parame-
ters in thermo-power station Ugljevik-1, J. Procesna Tehnika, vol.
7, no. 1, Belgrade, Yugoslavia, 1991, pp. 2326 (in Serbian).
[29] P. Marjanovi c, M. Stanojevic, B. Todorovic, A. Vlajcic, The inu-
ence of variable operating conditions on the design and exploitation
of air-slide systems in thermo-power stations, Proceedings of the
RelPowFlo 2, EFChE Publication Series no. 96, Oslo, Norway, 1993,
pp. 659671.
[30] P. Marjanovi c, Modelling the transient behaviour of blow tank pneu-
matic conveying system. Powder handling and processing, Trans.
Tech. Pub. 5 (3) (1993) 219226.
[31] P. Marjanovi c, Pneumatic conveying in an inclined pipeline: inappro-
priate, unfortunate or wrong concept? Proceedings of the 19th Powder
& Bulk Solids Conference, Chicago, USA, May 1994, pp. 235251.
[32] P. Marjanovi c, D.J. Mason, Gassolid ows in an inclined pipeline,
Proceedings of the 1st International Particle Technology Forum, vol.
3, Denver, USA, August 1994, pp. 466471.
[33] P. Marjanovi c, Assessing the ow properties of powdered materials,
IMechE Seminar on Hoppers and Silos, London, UK, 1994.
150 D. Mills / Chemical Engineering and Processing 44 (2005) 141151
[34] P. Marjanovi c, V. Djordjevic, On the compressible ow losses through
abrupt enlargements and contractions, J. Fluids Eng. Trans ASME
116 (1994) 756762.
[35] P. Marjanovi c, D. Geldart, J.L.R. Orband, T. Mooney, A comparative
analysis of two hopper design methods, Proceedings of the Interna-
tional Congress for Particle Technology PARTEC 95, Nrnberg,
Germany, March 1995, pp. 6978.
[36] B. Armstrong, M.G. Jones, P. Marjanovi c, G. Welford, P.J. Blenkin,
R.G. Holder, An evaluation of the effects of high system pressure
on the performance of pneumatic coal conveyors, Proceedings of the
20th International Conference on Coal Utilization & Fuel Systems,
Clearwater, USA, 1995, pp. 393403.
[37] T. Mooney, P. Marjanovi c, Bend pressure loss in a pneumatic con-
veying system, Proceedings of the 20th Powder & Bulk Solids Con-
ference, Chicago, USA, May 1995, pp. 6173.
[38] P. Marjanovi c, G. Welford, M.G. Jones, Pneumatic conveying of coal
against high back pressures, Proceedings of the 12th International
Pittsburgh Coal Conference, Pittsburgh, USA, September 1995.
[39] M.G. Jones, P. Marjanovi c, G. Welford, The prediction of pneumatic
conveying performance when conveying into back pressures up to
20 bar, Proceedings of the 1st International Conference BULK ASIA,
Singapore, 1995, pp. 107115.
[40] R.J. Hitt, P. Marjanovi c, A computer technique to develop a model
of vertical dense phase gassolids ow from experimental data.
Proceedings of the 1st International Symposium on Two-Phase Flow
Modelling and Experimentation, vol. 1, Rome Italy, October 1995,
pp. 6774.
[41] P. Marjanovi c, M.G. Jones, Assessment of a new technique for
measuring ow properties of powdered materials stored in hoppers,
IMechE J. Process. Mech. Eng. 210 (1996) 18.
[42] P. Marjanovi c, Theoretical and practical silo design, Seminar on
Storage and Transportation of Bulk Solids, Moreton-in-Marsh, UK,
March 1996.
[43] M.G. Jones, P. Marjanovi c, Maintaining product quality in pneumatic
conveying, Proceedings of the Conveyorex 96 Seminar, Harrogate,
UK, April 1996.
[44] P. Marjanovi c, G. Welford, M.G. Jones, Pneumatic conveying of
solids at high system pressures, Proceedings of the 21st Powder &
Bulk Solids Conference, Chicago, USA, May 1996, pp. 9198.
[45] M.G. Jones, P. Marjanovi c, The modication of material properties
for improved ow characteristics, Proceedings of the Seminar on
Solving Problems in Hopper and Silo Systems, IMechE, London,
UK, June 1996.
[46] P. Marjanovi c, D.J. Mason, T. Mooney, The Performance of a pneu-
matic conveying system which incorporates an inclined pipeline sec-
tion, Proceedings of the 1st International Conference on Pneumatic
and Hydraulic Conveying Systems, Florida, USA, 1996.
[47] D.J. Mason, P. Marjanovi c, A. Levy, A simulation system for pneu-
matic conveying systems, Proceedings of the 1st International Con-
ference on Pneumatic and Hydraulic Conveying Systems, UEF Con-
ference, Florida, USA, 1996.
[48] P. Marjanovi c, D.J. Mason, The transient ow conditions during
feeding pneumatic conveying system using high-pressure blow tank,
Proceedings of the 12th International Congress of Chemical and
Process Engineering. Prague, Czech Republic, August 1996.
[49] D.J. Mason, A. Levy, P. Marjanovi c, Modelling the inuence of bends
on the ow of gas-solids mixture through pipelines, Proceedings of
the 12th International Congress of Chemical and Process Engineering,
Prague, Czech Republic, August 1996.
[50] A. Levy, P. Marjanovi c, D.J. Mason, A Comparison of analytical
and numerical models for gas-solid ow through straight pipe of
different inclinations with experimental data, Proceedings of the 12th
International Congress of Chemical and Process Engineering, Prague,
Czech Republic, August 1996.
[51] P. Marjanovi c, Determination of bulk solids indices using the Johan-
son indicizer system, Proceedings of the Bulk 96 Design Seminar,
Manchester, UK, December 1996, pp. 233238.
[52] T. Mooney, A. Levy, P. Marjanovi c, D.J. Mason, An investigation
of gassolids ow through inclined pipes, Proceedings of the 1997
Jubilee Research Event, vol. 1, Nottingham, UK, 1997, pp. 425428.
[53] P. Marjanovi c, M.G. Jones, G. Welford, Pneumatic conveying of
solids at high system pressures, J. Powder/Bulk Solids Technol. 1 (1)
(1997) 37.
[54] P. Marjanovi c, M. McGarvey, R.B. McKay, Development of lab-
oratory methodology to determine ow properties of organic pig-
ment powders, Proceedings of the 2nd Israel Conference for Con-
veying and Handling of Particulate Solids, Jerusalem, Israel, 1997,
pp. 2.282.33.
[55] A. Levy, T. Mooney, P. Marjanovi c, D.J. Mason, Analytical, Nu-
merical and experimental investigations for gassolid ow through
straight pipe of different inclinations, Proceedings of the 2nd Is-
rael Conference for Conveying and Handling of Particulate Solids,
Jerusalem, Israel, 1997, pp. 4.304.35.
[56] D.J. Mason, A. Levy, P. Marjanovi c, The inuence of bends on the
ow of gas-solids mixtures through pipelines, Proceedings of the
2nd Israel Conference for Conveying and Handling of Particulate
Solids, Jerusalem, Israel, 1997, pp. 4.364.41.
[57] P. Marjanovi c, D.J. Mason, Gas solids ow in an inclined pipeline.
Powder handling and processing, Trans. Tech. Pub. 9 (3) (1997)
217220.
[58] A. Levy, T. Mooney, P. Marjanovi c, D.J. Mason, A comparison of
analytical and numerical models with experimental data for gassolid
ow through a straight pipe at different inclinations, Powder Technol.
93 (1997) 253260.
[59] D.J. Mason, P. Marjanovi c, A. Levy, A simulation system for pneu-
matic conveying systems, Powder Technol. 95 (1998) 714.
[60] D.J. Mason, A. Levy, P. Marjanovi c, The inuence of bends on the
performance of pneumatic conveying systems, Adv. Powder Technol.
9 (3) (1998) 197206.
[61] D.J. Mason, P. Marjanovi c, Re-Visit of the fundamental denitions
of uid-solids ow properties in freight pipelines, Proceedings of
the 9th International Symposium on Freight Pipelines, Monterrey,
Mexico, April 1998.
[62] P. Marjanovi c, A. Levy, D.J. Mason, An investigation of the ow
structure through abrupt enlargement of circular pipe, Proceedings
of the 9th International Symposium on Freight Pipelines, Monterrey,
Mexico, April 1998.
[63] P. Marjanovi c, M. McGarvey, R.B. McKay, Development of labora-
tory methodology to determine ow properties of organic pigment
powders. Powder handling and processing, Trans. Tech. Pub. 10 (2)
(1998) 151154.
[64] M.G. Jones, P. Marjanovi c, The inuence of rotary valve air leakage
on pneumatic conveying system performance, Proceedings of the
23rd Powder & Bulk Solids Conference, Chicago, USA, May 1998,
pp. 231239.
[65] M.G. Jones, P. Marjanovi c, The inuence of rotary valve air leakage
on pneumatic conveying system performance, J. Powder/Bulk Solids
Tech. 2 (2) (1998) 310.
[66] M.G. Jones, P. Marjanovi c, The optimisation of an existing pneumatic
conveying system, J. Powder/Bulk Solids Technol. 2 (2) (1998) 12
16.
[67] P. Marjanovi c, D. Geldart, J.L.R. Orband, Techniques for assess-
ing powder owability a comparison, Proceedings of the World
Congress on Particle Technology 3, Brighton, UK, July 1998.
[68] D.J. Mason, A. Levy, P. Marjanovi c, The inuence of bends on
the ow of gas-solids mixture trough pipelines, Proceedings of the
World Congress on Particle Techn 3, Brighton, UK, July 1998.
[69] M.G. Jones, P. Marjanovi c, D. McGlinchey, R. McLaren, Segregation
in handling processes of blended industrial coal, Proceedings of the
6th International Conference on Bulk Material Storage, Handling
and Transportation, Wollongong, Australia, September 1998.
[70] P. Marjanovi c, M. McGarvey, R.B. McKay, Development of labora-
tory methodology to determine ow properties of organic pigment
D. Mills / Chemical Engineering and Processing 44 (2005) 141151 151
powders, Hopper & Silo Discharge: Successful Solutions. IMechE,
London, UK, November 1998.
[71] E.A. Knight, M.G. Jones, P. Marjanovi c, On-site measurement for
troubleshooting pneumatic conveying systems, Proceedings of the
Bulk Design Seminar, Sutton Coldeld, UK, December 1998.
[72] D.J. Mason, P. Marjanovi c, Re-visit to the fundamental denitions
of uid-solids ow properties in conveying pipelines, Proceedings
of the 2nd International Conference on Pneumatic and Hydraulic
Conveying Systems. UEF Conf. Davos, Switzerland, June 1999.
[73] P. Marjanovi c, E. McGee, Determination of powder ow properties
using different shear cells, Proceedings of the RelPowFlo 3, Pors-
grunn, Norway, August 1999, pp. 151158.
[74] M.G. Jones, P. Marjanovi c, D. McGlinchey, D. Morrison, Investiga-
tion of the discharge pattern of industrial coals from wedge shaped
hoppers, Proceedings of the RelPowFlo 3, Porsgrunn, Norway, Au-
gust 1999, pp. 543550.
[75] P. Marjanovi c, A. Levy, D.J. Mason, An investigation of the ow
structure through abrupt enlargement of circular pipe, Powder Tech-
nol. 104 (1999) 296303.
[76] P. Marjanovi c, M. McGarvey, R.B. McKay, Determination of the
inuence of surface coating and particle size on ow properties of
organic pigment powders, Proceedings of the 3rd Israel Conference
for Conveying and Handling of Particulate Solids, Dead Sea, Israel,
vol. 1, May 2000, pp. 3.393.44.
[77] M.G. Jones, P. Marjanovi c, D. McGlinchey, An investigation of
degradation and segregation in typical coal handling processes, Pro-
ceedings of the 3rd Israel Conference for Conveying and Handling
of Particulate Solids, vol. 1, The Dead Sea, Israel, May 2000, pp
8.558.60.
[78] D.J. Mason, J. Li, P. Marjanovi c, Numerical simulation of solids
feeding in a gas-solids pneumatic transport system, Proceedings of
the 3rd Israel Conference for Conveying and Handling of Particulate
Solids, vol. 2, The Dead Sea, Israel, May 2000, pp. 10.9310.101.
[79] D. McGlinchey, P. Marjanovi c, M. G. Jones, S. Cook, Particle seg-
regation in pneumatic conveying lines, IMechE Conference Trans-
actions, June 2000, pp. 331340.
[80] M.G. Jones, A.G. Mason, P. Marjanovi c, E. A. Knight, Bend Ef-
fects in Pneumatic conveying, IMechE Conference Transactions, June
2000, pp. 351361.
[81] R.O. Ansell, P. Marjanovi c, Hazardous substances COSHH revis-
ited, Powder Rep. 3 (4) (2000) 1314.
[82] P. Marjanovi c, E.A. Knight, J.R. Pugh, On-site measurement of
pneumatic conveying system performance: why, when, what and how,
Proceedings of the 16th International Conference on Material Flow,
Machines and Devices in Industry, Belgrade, Yugoslavia, December
2000, pp. 2025.
[83] J.S. Xiang, P. Marjanovi c, Modelling and simulation for pyroow
type circulating uidised bed boiler, Proceedings of the Interna-
tional Congress for Particle Tech PARTEC 2001, Nrnberg, Ger-
many, March 2001.
[84] P. Marjanovi c, Technology transfer between academia and industry
two-way street leading to mutual benet and success, MHEA
Bulk 2001 Technical Awareness Seminar, Manchester, UK, April
2001.
[85] P. Marjanovi c, E.A. Knight, J.R. Pugh, Benchmarking, optimising
and uprating of discontinuous pneumatic conveying system perfor-
mance through on-site measurement, Proceedings of the 6th World
Congress of Chemical Engineering, Melbourne, Australia, September
2001.
[86] J. Li, P. Marjanovi c, J.S. Xiang, E.A. Knight, An experimental tech-
nique for the analysis of plugs travelling through pneumatic pipelines
using pressure measurements, Proceeding of the 7th International
Conference on Bulk Materials Storage, Handling and Transportation,
Newcastle, Australia, October 2001, pp. 5367.
[87] E. McGee, P. Marjanovi c, L. Bates, Modifying ow behaviour in
hoppers using inserts and novel wall proles, Proceedings of the 7th
International Conference on Bulk Materials Storage, Handling and
Transportation, Newcastle, Australia, October 2001.
[88] J.S. Xiang, P. Marjanovi c, Hydrodynamic model of gas-solid ow
in circulating uidised bed, Proceedings of the 7th International
Conference on Bulk Materials Storage, Handling and Transportation,
Newcastle, Australia, October 2001, pp. 825832.
Chemical Engineering and Processing 44 (2005) 153157
Inuence of the particle diameter and density in the
gas velocity in jet spouted beds
Mara J. San Jos
, has a
similar tracing for all the systems, the velocity decreases as
the longitudinal position at the axis increases, Fig. 4. These
velocity proles are more pronounced than those of conical
spouted beds [24].
The maximum velocity at the axis of the contactor, u
j
(0),
is a function of the geometric factors and operating condi-
tions. The experimental results have been tted to an em-
pirical equation for calculation of the interstitial velocity
at the contactor axis in jet spouted beds. The tting has a
Fig. 4. Evolution with the dimensionless position in the bed, *, of the
vertical component of the gas interstitial velocity at the axis, u
j
(0), in jet
spouting regime. = 36
, D
o
= 0.04 m, H
o
= 0.23 m for the different
materials of particle diameter d
p
= 3.5 mm.
regression coefcient of r
2
= 0.97 and the standard devia-
tion of 3%.
u
j
(0) =2.14 10
5
2.78 10
2
D
2
o
+H
8
o
d
p
0.17
K
1 +K
(3)
K=H
0.81
o
0.1
(
0.85
0.22D
0.5
o
+0.75d
0.5
p
+0.21
0.5
0.248 1.17 10
6
s
)
(4)
The expression proposed for the vertical component of
velocity near the wall, u
W
, which has been chosen taking
into account simplicity and because it gives a satisfactory
tting for all the experimental data is only function of the
dimensionless spherical radius,
:
u
W
= 20
2
exp(1.4
2
) (5)
From the vertical components of points velocity in the
contactor and by using the continuity equation, the radial
component, u
r
, and consequently, the modulus and direction
of velocity vector at each point in the contactor are calcu-
lated.
The continuity equation applied to differential volume el-
ement in cylindrical coordinates is:
1
r
r
(ru
r
) +
u
z
= 0 (6)
In Fig. 5, the map of velocities and of uid direction is
shown as an example, which corresponds to the system =
156 M.J. San Jos e et al. / Chemical Engineering and Processing 44 (2005) 153157
Fig. 5. Map of gas interstitial velocity vector in jet spouting regime.
= 36
, D
o
= 0.04 m, H
o
= 0.23 m and extruded polystyrene of particle
diameter d
p
= 3.5 mm.
36
, D
o
= 0.04 m, H
o
= 0.23 m and extruded polystyrene
d
p
= 3.5 mm. The length of the arrows is proportional to
the value of the corresponding velocity vector modulus.
From the results it has been proven for all the experimen-
tal systems studied that the ow rate is constant along the
streamtubes dened in the annular zone, such as has been
proposed in the model.
In order to solve the model conservation equations, only
the knowledge of the average interstitial velocity in the
spout zone at each level, u
s
, is required. This is calculated
as:
u
s
=
1
A
s
u dA
s
=
1
A
s
D
o
/2
0
2u
r
dr (7)
The values of u
s
calculated using Eq. (7) are very similar
(differ in less than 3%) to the values of velocity at the axis
u
j
(0) for beds of sawdust and expanded polystyrene. Conse-
quently, the velocity prole in the spout zone is almost at
in beds of these solids. Nevertheless, for beds of glass beads
and extruded polystyrene the velocity proles in the spout
zone are more pronounced.
4. Conclusions
In jet spouted bed regime in conical spouted bed, the gas
interstitial velocity at the axis, u
j
(0), decreases as the dimen-
sionless longitudinal position at the axis,
, increases; be-
ing this decreasing more pronounced as the solid density in-
creases. Besides these velocity proles are more pronounced
than those of conical spouted bed regime.
Empirical correlations proposed in this paper have been
proven to be valid for calculating the interstitial velocity
at any position of the contactor. These equations takes into
account, as well as the geometric factors of the contactor
the operating variables such as particle size, particle density
and particle shape.
The calculated average velocity in the spout at each level
are very similar to the velocity at the axis for beds of low
density solids. Nevertheless, for beds of solids of higher
density, the velocity proles in the spout zone are more
pronounced.
Acknowledgements
This work was carried out with the nancial sup-
port of the University of the Basque Country (Project
9/UPV00069.310-13607/2001).
Appendix A. Nomenclature
A
r
Archimedes number gd
3
p
g
(
s
g
)/
2
A
s
cross-sectional area of the spout (m
2
)
d
p
particle diameter (m)
D
b
, D
c
, D
i
, D
o
diameter of the upper level of the
stagnant bed, of the column, of the bed
base and of the inlet, respectively (m)
g gravity constant (ms
2
)
H
c
, H
o
height of the the conical section of the
contactor, and of the stagnant bed,
respectively (m)
r, z radial and longitudinal coordinates (m)
R contactor radius at z height (m)
(Re
o
)
mj
Reynolds modulus of minimum jet
spouting referred to D
o
u, u
j
(0), u
j
, u
w
vertical component of interstitial velocity,
maximum velocity at the axis, at any
position and at the contactor wall (ms
1
)
u
r
, u
s
radial component of interstitial velocity
and vertical component of the average
interstitial velocity in the spout at z level,
respectively (ms
1
)
u
o
bed voidage of the static bed,
dimensionless
particle shape factor
contactor angle (deg)
viscosity (kg m
1
s
1
)
M.J. San Jos e et al. / Chemical Engineering and Processing 44 (2005) 153157 157
,
N
,
o
longitudinal spherical coordinates,
maximum and minimum longitudinal
spherical coordinates (m)
g
,
s
,
v
density of the gas, of the solid and of
the glass beads, respectively (kg m
3
)
, Bernard Baudoin
Dpartement Energtique Industrielle, Ecole des Mines de Douai, 941 rue Bourseul, B.P. 838, 59508 Douai, France
Received 23 June 2003; received in revised form 4 April 2004; accepted 15 April 2004
Available online 2 July 2004
Abstract
The aim of this work is to estimate more accurately fugitive dust emissions due to wind erosion of exposed aggregate storage piles. The
model constructed allows to quantify the temporal evolution in the mass ux when a bed of materials is exposed to a turbulent ow. It is based
on the interaction between particles take-off and wall turbulence. The model allows as well to take into account materials having a wide size
distribution, which is typical of materials such as coal or ore. Some experimental studies have shown a temporal decrease in the mass ux as
the bed contains a wide range of particle sizes. This decrease, due to large particles, is predicted by the model. The rate depends on the ow
velocity and the characteristics of the particles.
2004 Elsevier B.V. All rights reserved.
Keywords: Fugitive dust emissions; Wind erosion; Particle take-off; Mass ux
1. Introduction
Atmospheric diffuse dust emissions constitute a pollution
source, which is difcult to be quantied. In fact, a diffuse
emission is dened as a polluting atmospheric ux which
is spread out over a large area or which is not concentrated
[1]. In the case of steelwork sites, diffuse dust emissions can
represent many as 20% of airborne particle pollution, they
result from conveyances and handling of materials and from
wind erosion of exposed aggregate storage piles. This latter
category of emission source is widely predominant.
The aims of the investigations presented in this paper are
to estimate accurately fugitive dust emissions resulting from
wind erosion. Thus, a model which allows to quantify emis-
sions resulting from an exposed particle bed to a turbulent
ow has been developed. Its originality is to take into ac-
count the wide particle size distribution of materials used,
as example, at steelwork sites. Typically, the ner particles
can have a size of about 10 m and the larger running to
centimetres. This characteristic is very important. In fact,
Meunier [2] observed for various experimental tests carried
Corresponding author. Tel.: +33 3 2771 2379; fax: +33 3 2771 2915.
E-mail address: harion@ensm-douai.fr (J.-L. Harion).
out in a wind tunnel with coal and ore, that the emitted mass
ux of particles decreases with time. He remarked the very
fast take-off of ne particles staying at the bed surface, then
the increasingly difcult take-off of the particles being be-
low. This can be explained by the presence of coarse par-
ticles close to the surface, which dont take-off because of
their inertia. These large particles constitute a cover and this
phenomenon is called the pavement. The pavement of the
bed, which is inherent to the wide size distribution of parti-
cles (especially to the presence of non-erodible particles at
the bed surface), generates a temporal decrease in emitted
mass ux.
The temporal decrease in emitted mass ux in the case of
particles with a wide size distribution has been shown by a
few experimental studies [35]. These authors assume that
the temporal decrease in emitted ux is due to modica-
tion of soil surface during wind erosion. These experimen-
tal studies underline the importance to consider the tempo-
ral evolution of the emitted mass ux in order to accurately
estimate particles emissions with a wide size distribution.
The rst part of the present work describes the wind ero-
sion model of a horizontal particle bed. A simple test of the
model is presented in the second part, which reports the in-
uence of a wide size distribution on the emitted mass ux
of particles.
0255-2701/$ see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.cep.2004.04.007
160 I. Descamps et al. / Chemical Engineering and Processing 44 (2005) 159166
2. Wind erosion model of a particle bed
2.1. Aerodynamic entrainment modelling
The modelling of aerodynamic entrainment is based on
the close link between particles take-off and turbulent co-
herent structures above the surface. In fact, some authors
[6,7] have experimentally observed that a particle take-off
can be associated to the ejection of uid from the wall re-
gion due to the presence of streamwise counter rotating vor-
tices. If it is assumed that the presence of two streamwise
counter rotating vortices produces only one ejection, each
pair of streamwise vortices is considered as a possibility that
a particle takes-off. Thus, for each of these possibilities, a
take-off criterion is tested.
The vortex structures appear with statistical spatial peri-
odicities, whose values are dependent on the ow properties
and velocity, and on the presence or not of particles. Jimenez
and Moin [8] have obtained, by numerical simulations, the
values of average spatial periodicities of appearing in the
spanwise and streamwise directions of the ow which are
respectively,
z
+
100 and
x
+
250300.
The periodicities are adimensionalized with the two scale
parameters of the inner layer of the turbulent boundary, the
kinematic viscosity and the friction velocity u
, by the
equation:
+
=
u
(1)
Although, these values are established in the case of a
smooth wall, they will be considered in the rst approxima-
tion like the spanwise and streamwise spatial periodicities
of the coherent structures over the particle bed. The parti-
cle bed is thus subdivided into boxes having spanwise and
streamwise sizes given by average spatial periodicities of
the turbulent coherent structures.
Fig. 1 shows the number of taking-off possibilities over
the bed surface if it is assumed that each box, which contains
an ejection, is associated with a possibility of taking-off. The
numbers of possibilities of taking-off along the spanwise
and streamwise directions of the bed are equal respectively
to l/
z
and L/
x
. Consequently, they depend on the ow
velocity.
The frequency of the take-off criterion, which is tested for
each box, is supposed to be equal to the burst frequency in
Fig. 1. Number of taking-off possibilities at the bed surface.
the wall region of the turbulent boundary layer. Blackwelder
and Haritonidis [9] have shown that the average periodicity
of occurence is given by T
B
+
250 whose expression is:
T
+
B
=
T
B
u
2
(2)
So the time step of the model is equal to T
B
.
2.2. The take-off criterion
Before the take-off criterion, a size range of representa-
tive diameter D
p
is selected randomly from the total number
of size ranges of the particle size distribution. The take-off
criterion, which is established from the balance of forces
exerted on a particle lying at a at surface, requires the
lift force from the ow to exceed the forces holding the
particle down, namely the adhesive forces and the particle
weight. The expression of the lift force used in the model
is given by the experimental expression of Mollinger and
Nieuwstadt [10]. They have developed a new technique for
measuring the lift force and its uctuations. Consequently,
the instantaneous lift force value is equal to the sum of the
average lift force F
aero
and the uctuating lift force F
aero
,
which is selected randomly fromits probability density func-
tion which has been measured by Mollinger and Nieuwstadt
[10]. In the same way, the adhesive force is selected ran-
domly from its probability density function given by Zimon
[11].
The aerodynamic entrainment model is based on the com-
parison between the distributions of forces holding the par-
ticles on the bed and of the lift force exerted on the particles
by the ow. The expression of the take-off criterion is given
for each size range by:
F
aero
(D
p
) +F
aero
(D
p
) P(D
p
) +F
ad
(D
p
) +F
ad
(D)
Particle take-off
The take-off test of the model developed in the present
study allows to simulate the stochastic nature of the phe-
nomenon. The establishment of the take-off criterion is de-
tailed more precisely in the thesis of Descamps [12].
One of the characteristic parameters of particle take-off
is the threshold ow velocity, at which particles start to take
off. The threshold ow velocity can be dened from the
take-off criterion.
I. Descamps et al. / Chemical Engineering and Processing 44 (2005) 159166 161
Fig. 2. Take-off curve [13].
Fig. 2 shows the take-off curve obtained by Foucaut [13].
It traces out the adimensionalized threshold friction velocity
u
D
p
=
D
p
D
p
ref
u
=
u
ref
(3)
Fig. 3. Integration of the effect of the pavement by diminishing by graduated steps the lift force exerted on a particle.
Fig. 4. Principle of the model of simulation of the emitted mass ux.
The values of D
p
ref
and U
ref
are, respectively, (
2
/
p
g)
1/3
and (
p
g)
1/3
, where
p
= (
p
)/ [13]. The take-off
curve allows to estimate by knowing the adimensional-
ized friction ow velocity the granulometric slice liable to
take-off. In fact, the diameter noted
D
pcrit1
is the diameter
from which the particles take-off and the diameter
D
pcrit2
162 I. Descamps et al. / Chemical Engineering and Processing 44 (2005) 159166
is the diameter from which the particles dont take-off be-
cause of their inertia. Thus, if the value of
D
pcrit2
is known,
the proportion of non-erodible particles can be determinate.
2.3. Modelling of the pavement
The temporal decrease in emitted mass ux can be ex-
plained by the phenomenon of pavement, which is linked to
the strong inertia particles, which cannot take-off and which
form a protection, called cover. It is supposed that these
non-erodible particles remain at the bed surface, and conse-
quently, overlay it completely from a certain depth, which
is called erosion depth, E
erosion
. From this depth, the vortex
structures bump only particles which they are not able to
entrain. No more take-off is possible.
In order to determinate the erosion depth, we assume that
the particles have a spatial uniform distribution along the
height Hof the bed. For each size range, the number of layers
N
c
(D
p
) including into the height of the bed is calculated by
dividing the height of the bed by the particle diameter. The
number of particles N
part
(D
p
) of each size range, given by
the size distribution of beds particles, is distributed equally
on each layer of the bed:
N
p
(D
p
) =
N
part
(D
p
)
N
c
(D
p
)
(4)
Now, the depth from which all the non-erodible particles
cover the bed surface has to be determined. Kurose and
Komori [14] dene the rate of cover like the ratio between
the surface equal to the projected area of particles on the wall
and the total area of the considered surface. Consequently,
the rate of cover is determined for each size range by:
T
C
(D
p
) =
N
p
(D
p
) D
2
p
/4
L l
(5)
Thus, the bed surface covered by the non-erodible parti-
cles is calculated by successive summation on all the size
ranges of the non-erodible particles in the increasing order
of diameters. For a y depth of the bed given, the surface
covered by the non-erodible particles can be determinate
since the number of layers, included by y, is known for
each size range. The evolution of the surface, covered by the
non-erodible particles, according to the depth can be estab-
lished. The depth from which the covered surface is equal
to the bed surface, namely the value of the erosion depth
E
erosion
, is deduced from this evolution. We suppose that, if
there are not non-erodible particles in the bed, the erosion
depth is equal to innity. The erosion depth is then divided
by the diameter D
p
of each size range. The number of layers
likely to be affected by erosion is given by:
N
erosion
(D
p
) =
E
erosion
D
p
(6)
For each size range, the value of the lift force is then de-
creased as soon as all the particles of a layer have taken-off.
The increment is given by:
F
aero
(D
p
) =
Max pdf(F
aero
initial
) Min pdf(P +F
ad
)
N
erosion
(D
p
)
(7)
Fig. 3 shows schematically the modelling of the bed pave-
ment.
This formulation allows to include in the model the lift
force inuence decrease for particles which are in a deeper
position in the bed. When the erosion depth is attained, the
take-off criterion can no more be respected. Indeed, the val-
ues of the probability density functions of the instantaneous
Fig. 5. Algorithm of the model.
I. Descamps et al. / Chemical Engineering and Processing 44 (2005) 159166 163
lift force are always smaller than the sum of the adhesion
and weight forces. In fact, the maximum of the probability
density function of the lift force is lower than the minimum
of the sum of the probability density function of the adhe-
sion force and the weight force.
2.4. Synthesis and algorithm of the model
This part describes concisely the model presented in this
paper. The modelling is constituted of three parts (Fig. 4):
the aerodynamic entrainment of particles, which is based
on the interaction between the coherent structures appear-
ing at the bed surface and the particles take-off;
the denition of the take-off criterion which depends on
the particles diameters and density for a given ow veloc-
ity;
the pavement modelling as a result of the presence of
coarser particles at the bed surface.
The principle of the model is to scan the bed surface,
which is subdivided into boxes whose the width and the
length are equal respectively to the spanwise and streamwise
statistical periodicities of appearing of the coherent struc-
tures. In fact, some authors have shown that the phenomenon
of ejection in a turbulent boundary layer could be connected
with the particles take-off.
For each box, namely for each ejection, the criterion for
taking-off is tested. Previously, it is necessary to determine
which particle, that is to say, which size range will be tested.
The size range of representative diameter D
p
of the particle
likely to be carried away by the ow is selected randomly
fromthe size distribution. If all the particles of this size range
have taken-off, then an other size range is randomly selected.
For each take-off, a particle is substracted from its size
range then it is counted in the emitted mass ux. Propor-
tionately to these takes-off, the ow has more and more dif-
culty to carry away particles, this difculty is taken into
account by the modelling of the bed pavement.
The model algorithm is showed on Fig. 5.
Fig. 6. Size distributions tested by the model.
The input variables are:
the exposition time to the turbulent ow, d
expo
;
the ow velocity, U
;
the particles density, the representative diameters of the
size distribution and their mass percentages, the number
of size ranges and the value of their depth;
the adimensionnalized values of the streamwise, spanwise
and temporal appearing periodicities of coherent struc-
tures;
the sizes of the bed (height, width and length);
the kinematic viscosity and the density of the ow.
Afterwards, the modelling is divided into various parts:
the calculation of N
part
(D
p
), N
c
(D
p
) and N
p
(D
p
);
the establishment of E
erosion
and N
erosion
(D
p
),
the calculation of F
aero
(D
p
) and of the average lift force,
the standard deviation of the probability density function
of the lift force, the average adhesion force, the standard
deviation of the probability density function of the adhe-
sion force, the weight force,
the bed is scanned along width and length. The iterations
number is equal to the number of coherent structures ap-
pearing along the width multiplied by the number of co-
herent structures appearing along the length multiplied by
the ratio between the exposition period and the occurence
period of the vortex structures. The take-off criterion is
tested for each iteration and the modelling of the pave-
ment is taken into account.
The results obtained by the model are the temporal varia-
tion of the emitted mass and of the mass ux as well as the
temporal evolution of the surface size distribution and the
size distribution of eroded particles.
3. Numerical results
This part aims at showing that the model allows to
estimate the temporal decrease of the emitted mass ux
164 I. Descamps et al. / Chemical Engineering and Processing 44 (2005) 159166
observed in presence of non-erodible (relatively coarse)
particles.
A test has been investigated with a simple size distri-
bution constituted by a blend of erodible (60160 m)
and non-erodible sand particles (540640 m). The rate of
non-erodible particles, which is the cover rate noted tdc,
varies from 0 to 80%. Fig. 6 shows the size distributions
which are tested by the model.
The input variables are:
the exposition time to the turbulent ow, d
expo
= 60 s,
the ow velocity, U
= 10 m/s,
the particles density,
p
= 2500 kg/m
3
, the representative
diameters of each size range, D
p
, and the mass percentages
corresponding, P
mass
, which are given by Fig. 6,
the statistical spatial and temporal periodicities of appear-
ing of ejections
x
+
=300,
z
+
=100 and T
B
+
= 250,
the sizes of the bed H = 2.5 cm, L = 48.5 cm and l = 8.7
cm.
Fig. 7 shows the results obtained by the model. The gure
traces out the evolutions of the mass ux in kg/m
2
s according
to the time in s for a velocity of the ow equal to 10 m/s
and for various cover rates, tdc = 0, 20, 40, 60 and 80%.
Several remarks can be made from the numerical results.
If the particles bed does not contain any non-erodible parti-
cles, then the emitted mass ux is constant with time. When
the particles bed contains non-erodible particles, the emitted
mass ux decreases with time.
Fig. 7 shows that the rate of the temporal decrease is
higher when the initial percentage of large particles in-
creases, which corresponds to experimental observations.
Moreover, the initial ux of particles decreases with the
presence of non-erodible particles.
Other tests, which are not represented in this paper, have
shown that, when the velocity is higher, the rate of the tem-
Fig. 7. First results obtained by the model in the case of a wide size distribution: U
=10 m/s;
p
=2500 kg/m
3
; tdc = 0, 20, 40, 60 and 80%.
poral decrease and the initial percentage of the emitted mass
ux increase.
All these results can be deduced from the modelling of
the wind erosion of the bed. The decrease rate goes higher,
when the cover rate, noted tdc, increases. This can be ex-
plained by the modelling of the pavement, described in part
2.3. The reduction increment of the lift force is inversely
proportional to the erosion depth (Eq. (6)). According to the
denition of the erosion depth, the higher is the proportion
of non-erodible particles, the smallest is the erosion depth.
Consequently, when the proportion of non-erodible particles
is increased, the reduction increment becomes greater and
the temporal decrease is faster.
When the mass percentage of non-erodible particles
is greater, the emitted mass ux is lower. In fact, be-
fore the take-off criterion, a size range is randomly se-
lected from the size distribution. So, the proportion of
non-erodible particles is taken into account. When cover
rate is increased the chances that the particle is erodible are
weaker.
As ow velocity is increased, the emitted mass ux in-
creases. In fact, the number of taking-off possibilities equals
the number of boxes at the bed surface times the number
of time step of the model. Moreover, the number of boxes
at the bed surface multiplied by the number of time step is
proportional to U
4
.
When the takes-off are more numerous, the layers of par-
ticles are blown off faster. Consequently, the decrease of
emitted mass ux is greater.
Fig. 7 also shows a temporal decrease in mass ux in
graduated steps. The bound from one step to another is due
to the passage of one layer to another in the numerical model
and consequently to the decrement of the probability density
function of the lift force. This is not directly representative of
the reality. However, a general trend of the temporal decrease
I. Descamps et al. / Chemical Engineering and Processing 44 (2005) 159166 165
Fig. 8. Interpolation of the temporal decrease in emitted mass ux obtained by the model: U
=10 m/s;
p
=2500 kg/m
3
; tdc= 20, 40, 60 and 80%.
in the mass ux can be obtained by interpolating the data
by a negative exponential function.
In Fig. 8 it is observed that the temporal decrease of emit-
ted mass ux can be interpolated by an exponential negative
function:
ux(t) = ux(t
initial
)exp(k
d
t) (8)
k
d
is the decrease rate and ux(t
initial
) is the emitted mass
ux at t
initial
0 s.
4. Conclusions
The pavement modelling allows to introduce into the
model the temporal evolution of the size distribution of
materials at the bed surface. By a progressive decrease of
the probability density function of the lift force, this model
successfully predicts the temporal decrease in mass ux
that occurs with the presence of coarse particles at the sur-
face. The rate of this decrease depends on the ow velocity
and the characteristics of the particles. In order to improve
the accuracy of the estimation of fugitive particle emissions
with a wide size distribution, it is necessary to take into
account this temporal decrease.
An experimental study, whose aim is to measure the tem-
poral decrease in mass ux, is on running and will allow to
compare the results obtained by the model with the measure-
ments. Thus, it will allow to adjust the numerical results.
Various improvements could be brought to the model.
Another study, whose objective is to measure the statistical
periodicities of the coherent structures on a rough wall, will
allow to adjust the results obtained by the model with the
experimental results.
This study constitutes a rst step on studying the mod-
elling of wind erosion of multiple size grains bed.
Acknowledgements
This work was carried out with the nancial support
of ADEME (the French Agency for Environment and
Energy Management), ARCELOR Dunkerque and Fos-
sur-Mer (steelworks in France) and European Community
(FEDER).
Appendix A. Nomenclature
D
p
particle diameter (m)
E
erosion
erosion depth (m)
F
ad
adhesion force (N)
F
aeroinitial
initial instantaneous lift force (N)
F
aero
mean lift force (N)
F
aero
uctuating lift force (N)
H bed height (m)
l bed width (m)
L bed length (m)
P particle weight (N)
P
mass
mass percentage (%)
t time (s)
T
B
average periodicity of burst
occurence (s)
tdc cover rate: mass percentage of non-erodible
particles (%)
T
C
size range cover rate (%)
u
friction velocity (m s
1
)
U
ow velocity (m s
1
)
166 I. Descamps et al. / Chemical Engineering and Processing 44 (2005) 159166
Greek letters
x
+
adimensionalized average streamwise
periodicity of appearing of vortex structure
z
+
adimensionalized average spanwise
periodicity of appearing of vortex structure
kinematic viscosity (m
2
s
1
)
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[2] M.A. Meunier, Envol et transport de particules en couche limite
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France, 1999.
[3] L. Li, L.W. Martz, Aerodynamic dislodgement of multiple size grains
over time, Sedimentology 42 (1995) 683694.
[4] M.V. Lpez, Wind erosion in agricultural soils: an example of limited
supply of particles available for erosion, Catena 33 (1998) 1728.
[5] L.Y. Liu, P.J. Shi, X.Y. Zou, S.Y. Gao, H. Erdon, P. Yan, X.Y. Li,
Z.B. Dong, J.H. Wang, Short terms dynamics of wind erosion of
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[6] Schet, P., Contribution ltude des structures cohrentes en tur-
bulence de paroi, De leur inuence sur le transport des sdiments
dans le cas du charriage, Ph.D. Thesis, INPT, France,. 2000.
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in the near-wall region of an open channel ow: Implications for
sediment transport, J. Fluid Mech. 326 (1996) 285319.
[8] J. Jimenez, P. Moin, The minimal ow unit in near wall turbulence,
J. Fluid. Mech. 225 (1991) 213240.
[9] R.F. Blackwelder, J.H. Haritonidis, Scaling of the bursting frequency
in turbulent boundary layers, J. Fluid. Mech. 316 (1983) 285
306.
[10] A.M. Mollinger, F.T.M. Nieuwstadt, Measurement of the lift force
on a particle xed to the wall in the sublayer of a fully devel-
oped turbulent boundary layer, J. Fluid. Mech. 316 (1996) 285
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ration, 1982.
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granulomtrique, Ph.D. Thesis, University of Valenciennes France,
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[13] J.M. Foucaut, M. Stanislas, Take-off threshold friction velocity of
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Chemical Engineering and Processing 44 (2005) 167173
Solids deposition in low-velocity slug ow pneumatic conveying
J. Li
a,
, C. Webb
a
, S.S. Pandiella
a
, G.M. Campbell
a
,
T. Dyakowski
a
, A. Cowell
b
, D. McGlinchey
b
a
Department of Chemical Engineering, Satake Centre for Grain Process Engineering, UMIST, P.O. Box 88, Manchester M60 1QD, UK
b
Centre for Industrial Bulk Solids Handling, School of Engineering, Science and Design, Glasgow Caledonian University, Glasgow G4 0BA, UK
Received 26 August 2003; received in revised form 4 December 2003; accepted 11 February 2004
Available online 25 September 2004
Abstract
Solids deposition in the horizontal pipeline of a pneumatic conveying system was studied both mathematically and experimentally. Math-
ematically modelled results using the coupled discrete element method (DEM) and computational uid dynamics (CFD) approach have
demonstrated an intensive exchange of particles between the stationary layer (deposited particles) and the moving slug and a variation of
solids concentration and pressure and velocity distributions across the slug. Slug ows were also visualised experimentally through a glass
section and analysed by a high-speed video camera. The amount of particle deposition in the pipeline after a conveying was calculated
by controlling the solids feeding rate using a rotary valve and by monitoring the solids ow out of the system using dynamic load cells.
Experimentally generated data have quantitatively shown a tendency of more solids deposition with lower gas mass ow rate in slug ows
except that, below a certain amount of solids mass ow rate, the deposition becomes independent of gas ow rate.
2004 Published by Elsevier B.V.
Keywords: Pneumatic conveying; Slug ow; Solids deposition; CFD model; DEM simulation
1. Introduction
Low-velocity slug ow pneumatic conveying has become
more and more common in many industrial sectors ranging
across chemical, pharmaceutical and food industries, due to
its advantages over conventional high-velocity suspension
ow in preventing product degradation and plant wear and
in delivering high throughput and efcient power utilisation
[1]. One of the distinguishing characteristics in such an op-
eration is the gravitational deposition of solid particles in
pipelines, which is due to the low gas velocity used, usu-
ally below the solids saltation velocity. A layer of particles
at the bottom of the horizontal conveying line is commonly
seen in these systems and this solids deposition signicantly
affects the transition and ow of slugs along the pipeline.
This paper presents mathematical and experimental stud-
ies of solids deposition characteristics in the horizontal
pipeline of a dense phase slug ow pneumatic conveying
1
7
3
1
6
9
Fig. 2. Solids slug ow and deposition DEM/CFD simulation (time interval between each picture 0.2 s and total time 1.0 s).
170 J. Li et al. / Chemical Engineering and Processing 44 (2005) 167173
Fig. 3. Snapshots of slug ow from video footages recorded in experi-
ments.
an instantaneous time of 0.4 s. A clear response of pressure
build-up at the back of and across the slug is shown and
a pressure difference between top and bottom of the pipe
cross-section at the back of the slug is observed, both of
which have been conrmed by experiments using accurate
pressure measurement [17]. Obviously the pressure build-up
Fig. 4. Pressure drop along the pipeline DEM/CFD simulation (at 0.4 s).
Fig. 5. Gas velocity prole along the pipe DEM/CFD simulation (at 0.4 s).
is due to the blockage of gas passage by particles in the pipe
cross-section and the gas retention characteristics in front
of the slug plays an important role in determining solids
slugging behaviours. The presence of particles has severely
altered the gas ow eld in the vicinity of the slug. Figs. 5
and 6 show the simulated gas velocity proles horizontally
along the pipeline and vertically in the pipe cross-section
at different locations, respectively. In general the axial gas
velocity is much higher at the top of the pipe cross section
than at the bottom and the highest occurs at the back of the
slug (around 0.4 m), which follows the prole of the solids
assembly at the back of the slug. However, gas velocity pro-
les become much atter in the middle of the slug as shown
in Fig. 5 at 0.5 m. It is also interesting to see the change
of gas ow direction in the pipe cross-section as shown in
Fig. 6 (positive value indicating an up-ow and negative a
down-ow). An up-ow of gas is observed at the front of
the slug (0.6 and 0.7 m) and the far back of the slug (0.3 m)
and a down-ow at the back of the slug (0.4 m) but a com-
plex picture in the middle of the slug (at 0.5 m). In general,
these cross section velocity proles comply with the axial
velocity proles in terms of mass balance in the gas phase.
J. Li et al. / Chemical Engineering and Processing 44 (2005) 167173 171
Fig. 6. Gas velocity prole in pipe cross section DEM/CFD simulation (at 0.4 s).
The gas velocity proles may explain why a loose slug
front is generated. That is particles in the front of the slug
wave are pushed by the slug body and dragged ahead of
the slug by the high local gas velocity at the top pipe cross
section while being agitated through severe interactions in-
curred by the rising particles from the stationary layer be-
neath the slug front and oating over them. The agitated
particle layer underneath the slug front is actually acting as
multiple uidised rolling wheels for the slug, which greatly
reduces the frictional forces comparing with a direct inter-
action with the pipe bottom wall. In some cases, even an
air pocket or a particle swirling ow is created between the
suspended loose slug front and the bottom particle layer, of
which the resulting mechanisms and its consequence on slug
ow need further studies.
3. Experimental analysis
Experiments were conducted to determine quantitatively
the amount of particle deposition in the pipeline of a spe-
cially designed pneumatic conveying system [17,18]. A
schematic layout of the rig is shown in Fig. 7. Briey
Table 1
Solids deposition in a pneumatic conveying system
U
g
(ca.)
(m/s)
M
g
(kg/s) M
s1
M
s2
M
s3
M
s4
Fixed
(kg/s)
Deposition
(kg)
Fixed
(kg/s)
Deposition
(kg)
Fixed SLR5
(kg/s)
Deposition
(kg)
Fixed SLR10
(kg/s)
Deposition
(kg)
25 0.1534 1.2270 0.00 0.6135 0.00 0.7669 0.00 1.5337 0.00
8 0.0491 1.2270 3.94 0.6135 9.35
a
0.2454 11.35
a
0.4908 9.51
6 0.0368 1.2270 6.28 0.6135 7.29 0.1840 9.18
a
0.3681 5.43
4 0.0245 1.2270 6.05 0.6135 8.03 0.1227 8.33
a
0.2454 8.05
2.6 0.0160 1.2270 9.79 0.6135 8.92 0.0798 11.70 0.1595 12.88
a
a
Large difference ( > 2 kg) of load cell readings occurred between repeated runs, which may be due to the unstable ow of slugs in these ow
conditions.
it comprises of a feed vessel, a receiving vessel, a 13 m
long conveying pipeline with interchangeable 5.1, 7.6 and
10.2 cm (i.e. 2, 3 and 4 in.) nominal bore pipes, a bank of air
supply nozzles, a variable speed rotary valve with dropout
box, an air lter unit, and connecting pipes and control
valves. In the system, both gas and solids mass feeding
rates are closely controlled through the choked nozzle bank
and the variable speed rotary valve. A set of three load cells
is mounted underneath the receiving vessel to monitor the
weight of solids conveyed. This particular design allows the
desired solids mass ow rate to be selected by adjusting
the rotary valve speed while the actual conveying rate is
calculated simultaneously from the load cell readings. Fig.
8 shows a typical diagram of a non-suspension wave-like
ow. Each step in the mass collected history is caused by
the arrival of a slug of solids. It is noticed that there is a
difference between the mass of solids owing into and out
of the system and the difference in the nal masses is the
deposition of solids in the system, which usually forms a
particle layer in the pipeline at the end of conveying.
Different combinations of gas and solids ow rates were
tested in a 7.6 cm bore pipe with a common industrial gran-
ular material - polyethylene pellets. The pellets were spher-
172 J. Li et al. / Chemical Engineering and Processing 44 (2005) 167173
Fig. 7. Schematic layout of the pneumatic conveying rig.
ical in shape with an average diameter of 3 mm, a particle
density of 880 kg/m
3
and an approximate bulk density of
550 kg/m
3
. The experiments were started initially with high
supercial gas velocity at 25 m/s, in which very little particle
deposition occurred (This was conrmed with visualisation
via a 3 m glass section in the conveying line). When using
Fig. 8. Mass trace and solids deposition in slug ows.
low gas velocity (< 10 m/s), a particle layer was built at the
bottom of the pipeline after a slug passing and at the end of
each test case. This solids deposition was assumed equiva-
lent to the difference of the nal load cell readings between
the tested cases and that obtained using a high gas velocity
(25 m/s).
J. Li et al. / Chemical Engineering and Processing 44 (2005) 167173 173
Table 1 summarises solids depositions in the four groups
of tests conducted: M
s1
- xed mass ow rate of solids
with a higher rate at 1.2270 kg/s, M
s2
- xed mass ow
rate with a lower rate at 0.6135 kg/s, M
s3
- xed solids
loading ratio (ratio between solids and gas ow rates) SLR
= 5, and M
s4
- xed SLR = 10, totalling 20 experimen-
tal cases. From M
s1
, a strong tendency for more solids de-
position with a lower gas mass ow rate is shown. How-
ever, this effect does not appear to be true for either the
lower solids mass ow rate M
s2
, or the two groups with
xed SLR, M
s3
and M
s4
(also with lower mass ow rate
< 0.5 kg/s). It shows that below a certain amount of solids
mass ow rate the deposition of solids becomes independent
of gas ow rate, which can be explained by the uidised
motion of particles before a full slug moves and the grad-
ual build-up of long slugs in the down stream pipeline as
discussed previously in Li et al. [18]. Further experiments
with a wider range of ow conditions using advanced mea-
suring tools such as tomographic image analysis [19] are
required to validate the model and to build up a quantita-
tive description of solids deposition for different particulate
materials.
4. Conclusions
Gravitational solids deposition in a horizontal pipeline
of a pneumatic conveying system was studied both math-
ematically and experimentally. Mathematically modelled
results using the DEM/CFD simulation have demonstrated
an intensive exchange of particles between the slug body
and the stationary layer as slugs move along the pipeline,
and a large variation of solids concentration and pres-
sure and velocity distributions across the slug. A slug
wave actually compresses the particle layer just ahead of
it, pushing some of the particles up from the layer into
the wave. On the other hand, particles at the tail of the
slug fall into the bottom part of the pipeline and form a
stationary particle layer behind the slug. These phenom-
ena have been conrmed by analysing recorded video
footages.
Experimentally generated data have quantitatively shown
a tendency of increased solids deposition at lower gas mass
ow rate in slug ows except that, below a certain amount of
solids mass ow rate, the deposition becomes independent
of the gas ow rate, which is due to particle uidised motion
before a slug ow commences. Further work will focus on
experiments with a wider range of ow conditions using
sophisticated measuring tools to validate the model and to
build up a quantitative protocol for the description of solids
deposition in conveying pipes.
Acknowledgements
Funding for this project was provided in part by the Satake
Corporation of Japan.
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Chemical Engineering and Processing 44 (2005) 175185
Identication of material specic attrition mechanisms
for polymers in dilute phase pneumatic conveying
Lars Frye
a,
, Wolfgang Peukert
b
a
Technische Universitt Muenchen, Lehrstuhl fr Feststoff und Grenzchenverfahrenstechnik (LFG),
Boltzmannstr. 15, 85748 Garching, Germany
b
Institute of Particle Technology, Friedrich-Alexander-Universitt Erlangen-Nrnberg, Cauerstr. 4, 91058 Erlangen, Germany
Received 22 July 2003; received in revised form 25 February 2004; accepted 19 March 2004
Available online 27 August 2004
Abstract
In the approach presented, attrition of bulk solids in pneumatic conveying is regarded as a result of a process function (stress conditions)
and a material function (inuence of material properties). For dilute phase conveying the process function was determined by employing
computational uid dynamics (CFD). Opposed to what was expected initially, the numerical simulations indicate that sliding friction apparently
is of importance in dilute phase conveying. This conclusion can be drawn from the low calculated impact angles in a pipe bend (r
B
/D
n
= 5;
D
n
= 80 mm) whichlie between5and35
the
calculated angles are comparatively small. This results in
low normal (525 m/s) and high tangential (3344 m/s) im-
pact velocity components which leads to the conclusion that
not only impact stresses contribute to attrition in dilute phase
conveying but that sliding friction stresses might play an im-
portant role as well. The differences in the distributions of
the tangential velocity component can be mainly attributed
to the already mentioned slight variations in the initial par-
ticle velocities.
Since the results were unexpected, the particle wall im-
pact locations were plotted from the data generated in the
simulations for a total of 2000 individual particles. They are
shown in Fig. 3 from two different angles. Due to the large
particle diameters resulting in high inertia forces the parti-
cles do not follow the gas stream in the pipe bend, but pro-
ceed directly to the outer bend wall. Only a slight sinking
caused by the gravity force can be observed. Since this be-
havior can be attributed to the high initial particle velocities,
simulations varying these have been carried out. They lead
to changes in the respective number distributions of impact
angle and velocity components, but did not have any effect
on the maximum angle. It can thus be concluded that not
only the bend geometry is of inuence as simulations with
varying r
B
/D
n
ratio have shown but that the curvature of
the pipe plays an important role for the impact conditions
as well. Although Fig. 3 clearly shows that the results are
reasonable an experimental validation of the simulations is
nevertheless still necessary.
For reasons of completeness, results for the determina-
tion of the process function for plug ow conveying shall
be stated briey as well. Since in this case a two phase ow
with high particle concentrations is regarded the options to
178 L. Frye, W. Peukert / Chemical Engineering and Processing 44 (2005) 175185
Fig. 3. Visualization of particle wall impact locations for 2000 particles of PP 1040 N with a diameter x
p
= 4 mm and initial gas and particle velocities
v
x,i
41 m/s.
simulate this ow are very limited. Therefore, experimental
results obtained by Mi and Wypych [13,14] were used to
obtain at least a rough estimate of the stress conditions the
particles are subjected to. If it is assumed that the particles
in a plug are at least for short times xed relative to each
other, the highest relative velocities will occur between the
particles forming the outer layer of the plug and the pipe
wall. The stress mode in this case is sliding friction. From
measurements of the pressure exerted by a plug on the pipe
wall and by applying the Hertzian equations for elastic con-
tact, a contact pressure between a single particle and the
pipe wall of roughly 4 MPa is obtained.
4. The material function
4.1. Concept for determination
It is generally known that different bulk solids might ex-
hibit widely varying attrition rates even if conveyed in the
Fig. 4. General concept and experimental devices to determine the material function for attrition processes.
same mode, q.v. [3]. Since under these circumstances the
stress conditions are almost identical the signicance of the
material function becomes obvious. Unfortunately it is still
unknown which material properties determine the attrition
behavior. In the case of polymers the identication is dif-
cult due to their viscoelastic nature. Thus the concept for
the determination of the material function shown in Fig. 4
was developed.
The crucial point is to simulate the previously identied
basic stress modes impact and friction under well dened
stress conditions. This way, material properties can be re-
lated to attrition caused by these stress modes and the re-
spective attrition mechanisms in effect. For this purpose it
was chosen to perform single particle experiments in simple
experimental setups to realize the dened stress conditions.
Details on these setups are given in the next section.
Ideally, the stress conditions obtained from the process
function are used as input parameters for the single particle
experiments. But due to practical reasons this is not always
possible, since a compromise between stress conditions
L. Frye, W. Peukert / Chemical Engineering and Processing 44 (2005) 175185 179
closely related to the conveying process and conditions
where the attrition rates can be measured reliably has to
be found. The knowledge gathered from the single particle
experiments will be broadened by and compared to results
of the dened stressing of a particle ensemble. For this
purpose, experiments in a pipe bend are carried out to in-
vestigate the polymers under conditions closely related to
those in the conveying pipelines.
The results of the attrition experiments are compared to
various material properties in order to identify those rele-
vant for attrition. The long term goal is to develop a phys-
ical model of the attrition process which makes it possible
to predict the amount of attrition that will be encountered
in a pneumatic conveying installation by knowledge of the
process and material functions.
4.2. Experimental setup and parameters
The experimental setups of two out of the three installa-
tions used to date are shown in Fig. 4. The installation on the
left-hand side is used to stress single particles under normal
impact loads. It was originally developed by Schnert and is
described in Marktscheffel and Schnert [15]. The particles
are fed one by one into the center of a rotor (2) by means
of vibration (1). In the rotor, the particles are accelerated in
radial channels and nally hit the impact ring (3) under an
impact angle of 90
(, T)| =
A
A
(2)
The viscoelastic behavior of the polymers is reected in
the phase lag between the deformation signal and the cor-
Fig. 8. Setup of a DMA-experiment in the single cantilever conguration.
responding stress signal. For a fully elastic material, would
be zero whereas it would be 90
.
E
(, T) = |E
| cos (3)
E
(, T) = |E
| sin (4)
The storage modulus is proportional to the amount of
energy which is stored in the material elastically, whereas
the loss modulus corresponds to the energy that is dissipated
during one load cycle. Both quantities are combined in the
damping factor tan which is dened as
tan =
E
(5)
After checking the inuence of various experimental pa-
rameters as well as the reproducibility of the measurements,
a standard procedure was developed. The polymer samples
are cooled quickly with liquid nitrogen to a temperature of
140
) and loss (E
) and loss (E
) T
g
(E
)
T
g
(DSC) holds. The materials where a second temperature
value is given in italics do not only possess a glass transi-
tion but also show a second order transition. For PP 2500 H,
PMMA G7 and G55 these second order transitions which
are most likely caused by increased mobility of side-chains
L. Frye, W. Peukert / Chemical Engineering and Processing 44 (2005) 175185 183
Fig. 11. Comparison of the attrition rates obtained from sliding friction experiments for 6 m/s, 0.61 MPa and 200 m against St-bend with storage (E
) and
loss modulus (E
C.
or chain segments lie below their glass transition tempera-
tures. PE 2420 H and PE 5031 L on the other hand show
their respective second order transitions above their glass
transition temperatures (see Fig. 10). Here it is not quite
clear what causes them.
If the ambient temperature at which the single particle ex-
periments were carried out is regarded as the macroscopic
stress temperature, it can be observed with respect to the
experimentally obtained attrition rates, that the polypropy-
lenes which are attrited by sliding friction are stressed in
their glass transition regimes whereas the glass transition
temperature of PMMA and PS lies well above the stress
temperature. Obviously, the relation between the values of
the macroscopic stress temperature and the glass transi-
tion temperature can be used to evaluate which material
specic attrition mechanism impact or sliding friction
is dominating in attrition formation. This conclusion is
also valid for PE 5031 L, while PE 2420 H which is a
very soft material (see Youngs modulus in Table 1 or stor-
age modulus in Fig. 10) does not t. In this case, addi-
tional effects like adhesion are likely to play an important
role.
For PP it was furthermore found that the attrition rates
observed in the sliding friction experiments decrease with
decreasing values of both storage and loss modulus. A
Table 2
Glass transition temperatures as obtained from DMA measurements ( =
10 Hz)
Name T
g
(E
) (
C) T
g
(E
) (
C)
PP 1040 N 17.54 15.08
PP 1100 RC 15.04 15.10
PP 1148 RC 15.16 15.08
PP 2500 H 37.33/12.43 34.88/9.99
PE 2420 H 122.32/12.02 114.82/9.62
PE 5031 L 107.31/45.03 109.81/55.12
PMMA G7 45.07/107.69 29.90/110.20
PMMA G55 90.12 25.05/95.12
PS 144 C 92.13 95.17
PS 158 K 107.84 110.20
possible explanation for this behavior can be found in
the microscopic attrition mechanisms known from tribol-
ogy and was briey discussed in [17]. As Fig. 11 shows,
PE 5031 L ts well into this tendency while PE 2420 H
again does not. From the materials which are attrited by
an impact mechanism, PMMA G7 and G55 also follow
the above trend while the two polystyrenes do not. It is
currently under investigation how this observation can be
explained.
If the above comparison is made for the attrition results
from the pipe bend installation, again a decrease in attrition
rate for the polypropylenes corresponds to decreasing E
and
E
Q heat ux (W/s)
r radius (m)
s sliding distance (m)
t time (s)
T temperature (
C)
v velocity (m/s)
x
p
particle diameter (m)
x, y, z cartesian coordinates (m)
Greek symbols
angle (
)
phase lag ()
deformation (m)
frequency (Hz)
density (kg/m
3
)
stress (Pa)
Subscripts
a after attrition
A amplitude
B bend
c critical, contact
e entrance
f lter, uid
g glass transition
i initial
p particle
s sliding
V Vickers
x, i initial component in x-direction
y yield
L. Frye, W. Peukert / Chemical Engineering and Processing 44 (2005) 175185 185
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Chemical Engineering and Processing 44 (2005) 187192
Two-dimensional numerical simulations of the
pneumatic drying in vertical pipes
I. Skuratovsky, A. Levy
, I. Borde
Department of Mechanical Engineering, Ben-Gurion University of the Negev, Beer-Sheva 84105, Israel
Received 5 August 2003; received in revised form 16 December 2003; accepted 11 February 2004
Available online 25 June 2004
Abstract
The Two-Fluid model has been used for modeling the ow of particulate materials through pneumatic dryer. The model was solved for
a two-dimensional steady-state condition and considering axial and radial proles for the ow variables. A two-stage drying process was
implemented. In the rst drying stage, heat transfer controls evaporation from the saturated outer surface of the particle to the surrounding
gas. At the second stage, the particles were assumed to have a wet core and a dry outer crust; the evaporation process of the liquid from a
particle assumed to be governed by diffusion through the particle crust and by convection into the gas medium. As evaporation proceeds, the
wet core shrinks while the particle dries.
Our developed model was applied to simulate drying process of wet sand in a pneumatic dryer. The numerical solutions were compared
with the results of independent numerical and experimental investigations. These comparisons are quite encouraging.
2004 Published by Elsevier B.V.
Keywords: Pneumatic drying; Two-uid model
1. Introduction
Pneumatic drying is a widely used process in chemical
industries and includes simultaneous conveying, and heat
and mass transfer between the particles and the hot gas.
The large surface area for heat and mass transfer and the
high convective heat and mass transfer coefcients, which
appear in these units, are leading to high drying rates and
as a consequence to high drying capacity. The increase in
the use of this unit operation requires reliable mathematical
models to predict processes in the industrial facilities.
Three types of theoretical approaches can be used for
modeling the gas-particles ows in the pneumatic dry-
ers, namely: Two-Fluid Theory [1], Eulerian-Granular [2]
and the Discrete Element Method [3]. Traditionally the
Two-Fluid Theory was used to model dilute phase ow.
In this theory, the solid phase is being considering as a
pseudo-uid. It is assumed that both phases are occupy-
ing every point of the computational domain with its own
volume fraction. Thus, macroscopic balance equations of
mass, momentum and energy for both the gas and the solid
Corresponding author.
E-mail address: avi@bgumail.bgu.ac.il (A. Levy).
phases are formulated. Often the ow in a pneumatic dryer
can be classied as dilute.
One-dimensional mathematical models are widely applied
to calculate drying processes, which can predict average
values of different properties of the phases in cross-sections
of the dryer [49].
Rocha and Paixo [10] presented a pseudo two-dimensional
mathematical model for a vertical pneumatic dryer that
was based on the two-uid approach. Axial and radial
proles for gas and solid velocity, water content, porosity,
temperatures and pressure were considered. Their predic-
tions were not validated with experimental results. Another
two-dimensional numerical investigation was conducted by
Silva and Nebra [11] for drying of particulate material in
cyclone. They used the two-uid approach and presented
steady-state drying model that considered incompressible,
axi-symmetric, turbulent gassolids ow, slip condition
of particles on the wall, particleswall heat transfer and
particles shrinkage. Gravity force effect on the spherical
particle was neglected. The predictions of their numerical
simulations were compared with experimental results and
it was claimed that the parameters most inuencing the
predictions are the particles slip conditions on the walls and
material shrinkage during the drying process.
0255-2701/$ see front matter 2004 Published by Elsevier B.V.
doi:10.1016/j.cep.2004.02.012
188 I. Skuratovsky et al. / Chemical Engineering and Processing 44 (2005) 187192
Blasco et al. [12] proposed two-dimensional mathemati-
cal model for the drying process of dense phase pneumatic
conveying. However, heat and mass transfer were not consid-
ered and therefore their model may be used for dense phase
pneumatic transport only. In their paper, both experimental
and numerical predictions for axial and radial proles for
gas and solid velocity, axial proles for solid concentration
and pressure drop were presented.
Contrary to traditional one-dimensional models, two-
dimensional models are required for taking into consid-
eration the effects of the radial distribution of the most
inuential thermophysical properties. As can be seen from
the above literature survey, not many studies have adopted
the two-dimensional approach for simulation the drying
process in a vertical tube. In addition, their predictions were
not validated with experimental data and in some cases only
the momentum transfer was taken into account.
In the present study, two-dimensional Two-Fluid Eulerian
model was used to describe the steady state, dilute phase ow
of a wet dispersed phase (wet solid particles) in a continuous
gas phase through a pneumatic dryer. The predictions of
the numerical solutions were compared successfully with
the results of other one-dimensional numerical solutions and
experimental data of Baeyens et al. [5] and Rocha [13]. Axial
and the radial distributions of the characteristic properties
were examined.
2. Theoretical model
A two-dimensional, Two-Fluid model has been developed
for modeling the steady-state ow of particulate materi-
als through vertical pneumatic dryer. Two-dimensional ow
eld interpretations provide information about properties of
the continuous and dispersed phases at every point of the
ow eld. Axial and radial proles were obtained for the
ow variables.
The gas phase was treated as a mixture of gas and liquid
vapor. The wet particle is made of porous solid structure
that contains saturated liquid. The drying model considered
a two-stage drying process. In the rst drying stage, heat
transfer controls evaporation fromthe saturated outer surface
of the particle to the surrounding gas. In the second stage,
the particles are assumed to have a wet core and a dry outer
crust. The evaporation of the liquid from a particle assumed
to be governed by diffusion through the particle crust and by
convection into the gas medium. As evaporation proceeds,
the wet core shrinks as the particle dries.
The developed model was solved numerically and applied
to simulate drying of wet sand in a laboratory-scale pneu-
matic dryer.
The drying model is based on the following assumptions:
Steady-state ow.
The ow in the dryer is vertical, two-dimensional,
non-rotational and axi-symmetrical.
Non-slip and non-penetrating wall conditions.
Dispersed phase behavior like continuous phase.
The particles are made from a substance containing solid
porous matrix and liquid or gas with liquid vapor.
The specic densities of the liquid and the solid, which
compose the particle, are constants.
Mass, momentum and heat transfer occur only between
the two phases and not between the particles themselves.
The gas phase is a mixture of water vapor with air.
The gas behaves as ideal gas.
Inuence of gravity on gas phase is neglected.
Heat transfer can occur between the pipe wall and the
continuous gas phase.
The acting forces per unit volume between the phases are
due to drag and virtual-mass.
At the rst drying stage, the particle is isothermal and at
the second drying stage the particle wet core temperature
is different from that of dry crust.
The inuence of the pressure gradient on the inertia of the
solid particles is negligible in comparison to that of the
drag force.
Electrical and surface tension forces are neglected.
Based on the above-mentioned assumptions, the mass,
momentum and energy balance equations for the gas and the
dispersed phases in two-dimensional, two-phase ow were
developed [14]. In order to solve the mass, momentum and
energy balance equations, several complimentary equations,
denitions and empirical correlations were required. These
were presented by [14]. In order to obtain the water vapor
distribution the gas phase the water vapor diffusion equa-
tion was added. During the second drying period, the model
assumed that the particle consists of a dry crust surround-
ing a wet core. Hence, the particle is characterized by two
temperatures i.e., the particles crust and core temperatures.
Furthermore, it was assumed that the heat transfer from the
particles crust to the gas phase is equal to that transferred
from the wet core to the gas phase i.e., heat and mass cannot
be accumulated in the particle crust, since all the heat and
the mass is transferred by diffusion through the crust from
the wet core to the surrounding gas. Based on this assump-
tion, additional heat balance equation was written.
The mass transfer source term was obtained by multiply-
ing the evaporation rate from a single particle by the total
number of particles per unit volume. Two-stage drying pro-
cess was applied for calculating the mass transfer from a wet
particle to the gas phase [6]. In the rst drying period, the
gas phase resistance controls the evaporation rate. When the
liquid evaporated from the particle surface and lls all the
voids inside the porous particle, the second drying period
starts. During this drying period, the dry crust causes addi-
tional resistance to heat and mass transfer. This resistance,
which occurs between the outside diameter of the particle
and the diameter of the wet core is governed by a diffu-
sion process. The evaporation rate from a particle with a dry
crust was expressed by Stephan-type diffusion rule [15]. The
I. Skuratovsky et al. / Chemical Engineering and Processing 44 (2005) 187192 189
Fig. 1. Comparison between the predictions of the present pneumatic drying model, DryPak model, Rocha in [20] and Levy and Borde [8] models and
the experimental data for (a) gas temperature, (b) solid temperature, (c) gas humidity and (d) particles moisture content along the dryer length.
mass transfer coefcient was calculated in analogy to the
heat transfer coefcient from the Sherwood number, which
is equivalent to the Nusselt number. It should also be noted
that both the gas and the dispersed phases are mixtures, and
hence all their thermodynamic properties were calculated
using the mixture theory.
3. Numerical simulations
The pneumatic drying model was solved numerically for
the drying processes of sand particles. The numerical proce-
dure includes discretization of the calculation domain into
torus-shaped nal volumes, and solving the model equa-
tions by implementation of the semi-implicit method for
pressure-linked equations (SIMPLE) algorithm[16]. The nu-
merical procedure also implemented the Interphase Slip Al-
gorithm (IPSA) of [17] in order to account the various cou-
pling between the phases. The simulation stopped when the
moisture content of a particle falls to a predened value or
when the ow reaches the exit of the pneumatic dryer.
In order to validate the theoretical model, the predic-
tions of the numerical simulations were compared with
experimental data. Comparison between the results of the
present two-dimensional model and the results of experi-
mental data and one-dimensional models requires a repre-
sentation model for presenting the two-dimensional data in
one-dimensional terms. Thus, an averaging technique was
used to obtain the average values of the various solution
properties at the dryer cross-section. The average value of
a property, , at the dryer cross-sectional area was obtained
by mass weighted method and an average temperature of
a phase was evaluated by the mean bulk temperature across
the tube.
=
2
R
0
urdr
2
R
0
urdr
; T
ave
=
2
R
0
uc
p
Trdr
2
R
0
uc
p
rdr
(1)
4. Numerical results and discussion
The predictions of the numerical simulations with
Baeyens et al.s [5] correlation for heat transfer were also
compared with the experimental results of Rocha [13] (pre-
sented by Silva and Correa [18]) that were obtained in a
4-m high pneumatic dryer with diameter of 5.25 cm. In this
study, 380-m sand particles having density of 2622 kg/m
3
and solid mass ow rate of 4.74 10
3
kg/s were dried
190 I. Skuratovsky et al. / Chemical Engineering and Processing 44 (2005) 187192
Fig. 2. The predictions of the pneumatic drying model for (a) gas phase velocity, (b) dispersed phase velocity, (c) gas phase temperature, (d) dispersed
phase temperature, (e) gas humidity, (f) particles moisture content and (g) particles diameter along stream lines and the dryer length.
I. Skuratovsky et al. / Chemical Engineering and Processing 44 (2005) 187192 191
with 3.947 10
2
kg/s air mass ow rate. Comparison
between the predictions of the numerical simulations and
the experimental data for changes of gas temperature, solid
temperature, gas humidity and particles moisture content
with length under known wall temperature operating condi-
tions is presented in Fig. 1ad, respectively. When known
wall temperature operating conditions were simulated, it
was assumed that in average the pipe wall temperature is
just about the outlet air temperature and it is falling linearly
from 360 K at the inlet to 354 K at the outlet. In this way,
heat losses from the dryer walls are considered indirectly.
In these gures, the star symbols represent the experimen-
tal data of Rocha [13] that were published by Silva and
Correa [18] and the other curves and symbols represent the
predictions of various models and numerical simulations.
Form these gures, it can be seen that the predictions of the
two-dimensional numerical simulations t fairly well with
the experimental data and both one-dimensional DryPak
[19] and Levy and Borde [8] models. Detailed comparison
between the various one-dimensional models can be found
at Levy and Borde [20]. Since the theoretical pneumatic
drying model and the numerical simulations done in the
course of this study predicted successfully the most impor-
tant ow parameters (gas temperature, solid temperature,
gas humidity and particles moisture content) of the drying
process, it was concluded that the presented model could
be used for further investigations. The distributions of the
various ow properties along the dryer length for various
stream lines (i.e., xed r/R) are presented in Fig. 2.
Form these gures, it can be seen that a fully developed
ow was obtained after about 3 m from the dryer inlet. In
addition, various thicknesses of boundary layers were ob-
tained for the various phases properties. This may inuence
the nal product properties.
5. Conclusions
Two-Fluid, two-dimensional model was developed for
modeling the dilute ow of particulate materials through
pneumatic dryer. The model was solved for a steady-state
condition. Axial and radial proles for the ow variables
were obtained. The developed model was applied to sim-
ulate the drying process of wet sand in a laboratory-scale
pneumatic dryer. The numerical solutions were compared
with the results of other numerical and experimental in-
vestigations. The successful comparisons validate the theo-
retical and the numerical models. As demonstrated by the
two-dimensional numerical simulations, the radial distribu-
tion of the ow characteristics causes an uneven product
quality. Thus in order to improve the drying process, a re-
liable two-dimensional model is required. Further investi-
gations are needed in order to validate the two-dimensional
distribution of the ow characteristic and to improve the
model to account for particle circulation in the investigated
domain. The present investigation signicantly extends the
ability to simulate and to predict drying processes in pneu-
matic dryer.
Appendix A. Nomenclature
c
p
(J/kg K) specic heat of the gas
R (m) radius of the pipe
T
ave
(K) average temperature
T (K) temperature
u (m/s) velocity
Greek symbols
density
dummy property
References
[1] R.M. Bowen, in: A.C. Eringen (Ed.), Theory of Mixtures in Con-
tinuum Physics, Academic Press, NY, USA, 1976.
[2] D. Gidaspow, Multiphase Flow and Fluidization, Academic Press,
Boston, USA, 1994.
[3] P.A. Cundall, O.D. Strack, A discrete numerical model for granular
assemblies, Geotechnique 29 (1979) 4765.
[4] J. Andrieu, R. Bressat, Experimental, experimental & theoretical
study of a pneumatic dryer, Proc. 3rd Int. Drying Symp. 2 (1982)
1019.
[5] J. Baeyens, D. van Gauwbergen, I. Vinckier, Pneumatic drying: the
use of large-scale experimental data in a design procedure, Powder
Technol. 83 (1995) 139148.
[6] D. Levi-Hevroni, A. Levy, I. Borde, Mathematical modelling of
drying of liquid/solid slurries in steady sate one-dimensional ow,
Drying Technol. 13 (5-7) (1995) 11871201.
[7] A. Levy, D.J. Mason, I. Borde, D. Levi-Hevroni, Drying of wet solids
particles in a steady-state one-dimensional ow, Powder Technol. 85
(1988) 1523.
[8] A. Levy, I. Borde, Steady-state one-dimensional ow for a pneumatic
dryer, Chem. Eng. Proc. 38 (1999) 121130.
[9] Z. Mindziul, A. Kmiec, Modeling gas-solid ow in a pneumatic-ash
dryer, Drying96 Proc. 10th Int. Drying Symp. A (1996) 275
282.
[10] S.C.S. Rocha, A.E.A. Paixo, Pseudo two-dimensional model for a
pneumatic dryer, Drying96 Proc. 10th Int. Drying Symp. A (1996)
340348.
[11] M.A. Silva, S.A. Nebra, Numerical simulation of drying in a cyclone,
Drying Technol. 15 (6-8) (1997) 17311741.
[12] R. Blasco, R. Vega, P.I. Alvarez, Pneumatic drying with superheated
steam: bi-dimensional model for high solid concentration, Drying
Technol. 19 (8) (2001) 20472061.
[13] S.C.S. Rocha, Contribution to the study of pneumatic drying: simula-
tion and inuence of the gas-particle heat transfer coefcient, Ph.D.
Thesis, So Paulo University, So Paulo, Brazil, (in Portuguese),
1988.
[14] I. Skuratovsky, A. Levy, I. Borde, Two-uid, two-dimensional model
for pneumatic drying, Drying Technol. 21 (9) (2003) 16491672.
[15] N. Abuaf, F.W. Staub, Drying of liquidsolid slurry droplets, Drying
86 Proc. 5th Int. Drying Symp. 1 (1987) 227248.
[16] S.V. Patankar, Numerical Heat Transfer and Fluid Flow, Hemisphere
Publishing Corporation, New York, USA, 1980.
[17] D.B. Spalding, Developments in the IPSA procedure for numeri-
cal computation of multiphase-ow phenomena with interphase slip,
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unequal temperatures, etc. in: Numerical Properties and Method-
ologies in Heat Transfer, Hemisphere, Washington, DC, 1983,
pp. 421476.
[18] M.A. Silva, J.L.G. Correa, Using DryPak to simulate drying process,
in: Proceedings of 11th International Drying Symposium Drying98,
vol. A, 1998, pp. 303310.
[19] Z. Pakowski, DryPak v.3, Program for psychometric and drying
computation, 1996.
[20] A. Levy, I. Borde, Two-uid model for pneumatic drying of
particulate materials, Drying Technol. 19 (8) (2001) 1773
1788.
Chemical Engineering and Processing 44 (2005) 193200
The formation of ne particles by salting-out precipitation
Judit Tth
Corresponding author. Tel.: +36 88 405 265; fax: +36 88 424 424.
E-mail address: toth@mukki.richem.hu (J. T oth).
mental ndings [3], it is possible to reduce or even elim-
inate the agglomeration in the presence of protective col-
loids or surfactants and/or by controlling the precipitation
kinetics.
In this work, batch salting-out experiments were per-
formed with the objective to know more about the limits and
possibilities on the formation of ne particles. As model ma-
terial the zwitterionic glycine was investigated within a wide
range of initial supersaturations. Considering the polymor-
phic nature of glycine, the non-polymorphic, ionic sodium
chloride was also investigated as reference system.
2. The precipitation theory
Not long ago, the main crystallization trend was to pro-
duce well-developed, bigger crystals in proper size and habit.
Accordingly, the research activities focused on the growth
process and the role of habit modifying additives. Nowa-
days, when extra ne particles are claimed by several in-
dustrial areas, increased attention has been paid to the early
stages of nucleation by applying even extreme conditions
for the particle formation. This area is the typical eld of
the colloidal state which is not yet enough utilized for the
industrial practice but it is getting more and more impor-
tant due to the increasing demands on the production of
nes.
0255-2701/$ see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.cep.2004.02.013
194 J. T oth et al. / Chemical Engineering and Processing 44 (2005) 193200
In the colloid chemistry practice the antisolvent precip-
itation is called Weimarns method. Weimarn published
his famous work The precipitation laws early in the past
century [4] but his statements seem to be still valid and
useful for reconsidering. His main conception was that the
mean size of precipitates may change with the supersatura-
tion through a maximum. The maximum shifts up and left
with increasing time until the system reaches its stable state
where the precipitation process is completed. The principle
of the Weimarn laws on precipitation is schematically shown
in Fig. 1. According to the Weimarn laws, ne particles can
be produced both at low and high supersaturation depending
on the time of crystallization and the solubility of the pre-
cipitate. Weimarn based his statements on his chemical pre-
cipitation experiences. What is the situation for salting-out
precipitation? It is not necessarily the same because there
is a fundamental difference between the chemical- and salt-
ing out precipitation. In the rst case the supersaturation
changes with the concentration of the reaction partners while
the equilibrium concentration (solubility) remains constant,
but at salting-out processes both the supersaturation and the
equilibrium solubility change with the solution/antisolvent
ratios, therefore, both can inuence the particle size.
The relationship between particle size, solubility
and supersaturation is expressed by the well-known
GibbsThomson equation [5a]:
ln
c(r)
c
= ln S =
2V
kTr
, (1)
where c(r) is the solubility of the particles of size (radius)
r, c* is the normal equilibrium solubility of the substance,
S is the supersaturation ratio, is the surface energy, V is
the molecular volume, k is the Boltzmann constant, T is the
absolute temperature. Eq. (1) does not consider the growth
process which follows the nucleation step. At precipitation,
in most cases, the growth process is rather an aggregation
step. When aiming ne crystals, the growth subprocess has to
be retarded, consequently, the precipitation has to be stopped
Supersaturation, S
M
e
a
n
s
i
z
e
o
f
c
r
y
s
t
a
l
l
i
n
e
i
n
d
i
v
i
d
u
a
l
s
stable state
time
u
n
s
t
a
b
l
e
s
t
a
t
e
s
Fig. 1. The Weimarn laws on precipitation (via [4]).
(quenching) before the particles could grow up their nal,
stable size.
3. Experimental
In the experiments analytical grade chemicals: glycine
(purity 98.5%) or sodium chloride (99.5%), ethanol (99.8%)
and deionized water were used. The precipitation mode
was one-shot: at high supersaturations various amount (V
0
= 0.00412 cm
3
) of saturated or undersaturated aqueous so-
lutions of glycine (c
0
= 20.000.50 g/100 g solution) were
added in one portion to 12 cm
3
ethanol at ambient temper-
ature. At low supersaturations 12 cm
3
saturated solutions of
glycine were added to various amount (V
e
= 0.112 cm
3
) of
ethanol. Depending on the solution/antisolvent ratios, series
of initial supersaturations were created. In each case con-
centrated ethanol, saturated at 298 K (0.0037 g glycine/100 g
solvent) was used. In the most cases the crystals appeared
at once after the shots but 10 min stirring was applied ad-
ditionally. No longer stirring time was allowed not to leave
time for the polymorphic change. Some precipitation runs,
together with the in-line particle size measurements, were
carried out directly in the 15 cm
3
volume MALVERN cu-
vette. When the suspension densities were higher than al-
lowed in direct CSD measurements by MALVERN 2600
the samples were precipitated in an Erlenmeyer ask under
stirring. In these cases the CSD measurements were possi-
ble after the appropriate dilution of the slurry. The diluting
agent was the actual mother liquid or concentrated and satu-
rated ethanol. For characterizing the particle size the volume
mean diameter was used:
d =
nd
4
nd
3
, (2)
where n is the number of particles of equivalent diameter d.
For characterizing the particle size distribution the so called
span was used:
span =
D
90
D
10
D
50
, (3)
where D
10
, D
50
, and D
90
is the diameter below which 10,
50 and 90% of the volume of the particles lies.
The precipitates were separated by glass bre lter,
washed by ethanol and air-dried. In some cases X-ray
diffraction (by Philips 3710) for polymorphism and SEM
analysis (by Philips XL 30 ESEM) for habit determination
were made.
The runs with sodium chloride were carried out by
the same techniques as detailed above but the operational
concentrations were different: c
0
was changed between
26.55 and 7.40 g/100 g solution. A characteristic difference
between the two systems was their solubility in ethanol
(0.0037 g glycine/100 g solvent and 0.0649 NaCl g/100 g
solvent) at 298 K. Because of the slower precipitation abil-
J. T oth et al. / Chemical Engineering and Processing 44 (2005) 193200 195
ity of sodium chloride, longer (60 min) additional stirring
was allowed.
4. Experimental results and discussion
The main driving force of a salting-out precipitation pro-
cess is the supersaturation generated by the different solubil-
ities of the solute in the solvent and antisolvent. The one-shot
mode generally means that the necessary amount of the an-
tisolvent is added in one portion to the initial solution (either
saturated or undersaturated) as it is schematically shown in
Fig. 2. In our cases the aqueous solution was added to the
antisolvent. As a result of the antisolvent addition the orig-
inal solubility of the substance will change until the new
equilibrium solubility, c
eq
has been reached. To characterize
the supersaturation driving force in a precipitation system
the so called initial supersaturation, S
i
is used:
S
i
=
c
0
c
eq
, (4)
i.e. it is a ratio between the initial concentration of the
solution to be crystallized (in this case the aqueous solu-
tion) and the equilibrium concentration (solubility) in the
solute-solvent-antisolvent system. In this way different val-
ues of S
i
can be chosen as experimental parameter by chang-
ing the concentration of the aqueous solution or the ratio of
the aqueous solution and the antisolvent. Although S
i
means
a certain simplication but it is still acceptable, because the
actual operational concentrations are very uncertain accord-
ing to the micromixing insufciencies. The highest applied
initial supersaturations were S
i
5000 for glycine and S
i
C) to give
this feeling [1].
The most abundant are monounsaturated TAGs, the un-
saturated fatty acid (very often oleic acid) being in the
2-position. 1-Palmitoyl-2-oleyl-3-stearoylglycerol (P-O-S),
P-O-P and S-O-S account for 3638, 1416 and 2328%,
respectively of the total TAGs. It is these TAGs which are
mainly responsible for the behaviour of chocolate when un-
dergoing crystallisation [2].
There are six different ways for these TAGs to arrange
themselves when they crystallise. Six different polymorphs
noted Ithe less stable with the lowest melting point 290 K
(17
Corresponding author. Tel.: +33 563 493088; fax: +33 563 493025.
E-mail address: letourne@enstimac.fr (J.-J. Letourneau).
URL: http://wwww.enstimac.fr.
end product. If the wrong type of fat is present the chocolate
may exhibit a white powdery surface called fat bloom which
is to be avoided because of its unpleasant appearance. The
most desirable form is known as form V (or
2
) having a
melting temperature of 305307 K (3234
C) a succession
of cooling to 300 K (27
C higher
than common seeding and several degrees higher than most
industrial tempering step. Therefore, the chocolate is very
much thinner.
The powder samples described in series E-I and E-IV
(obtained with the smallest nozzle) gave the best results. The
seeding was carried out at 305 K(32
, U. Teipel
Fraunhofer Institute for Chemical Technology, Joseph-von-Fraunhofer-Str. 7, D-76327 Pnztal, Germany
Received 1 August 2003; received in revised form 25 December 2003; accepted 11 February 2004
Available online 19 June 2004
Abstract
In this contribution a novel uidized-bed coating process is introduced to encapsulate heat-sensitive materials with particle sizes below
100 m. Supercritical carbon dioxide is used as solvent for the coating material as well as carrier uid for the core material. The behaviour
of the high pressure uidized-bed was investigated for different process parameters and materials. It is shown that the uidization starts at
lower uid velocities if the pressure is increased and it was possible to uidized particles with a mean size below 10 m. The coating of glass
beads with stearyl alcohol was carried out and layers with a thickness of 18 m were achieved.
2004 Elsevier B.V. All rights reserved.
Keywords: Microencapsulation; Fluidized-bed; Supercritical; Fluids; RESS process
1. Introduction
Solid particles are encapsulated for use in various prod-
ucts, including pharmaceuticals, processed food and fer-
tilizers, and energetic materials. To encapsulate particles,
a uidized-bed coater equipped with a spray nozzle such
as a Wurster Coater is commonly used [1]. Conventional
coating processes involve layering a liquid coating mate-
rial usually in the form of atomized droplets through the
nozzle onto a uidized-bed of particles. After the atomized
droplets of coating material come into contact with the
core particles, the solvent must evaporate quickly. If excess
droplets are present in the bed, agglomeration takes place,
leading to particle growth and deuidization. Therefore,
proper droplet atomization and drying are essential to avoid
unplanned agglomeration of solid particles. In case of ne
particles (<100 m), however, agglomeration becomes a
serious problem because of their strong cohesive forces.
The feed liquid acts as a binder for the ne particles.
A novel uidized-bed coating process using the rapid ex-
pansion of supercritical solutions (RESS) is described for
the encapsulation of ne particles [2,3]. This process ex-
ploits the capability of supercritical uids to act as a selec-
tive solvent. Supercritical uids are noteworthy in that their
1 +
P
w
m
t
w
m
P,0
1
(1)
where
P
and
w
are the density of the encapsulated par-
ticles and the density of the coating material, respectively,
r
P,0
the radius of the core particles and m
P,0
the total mass
of the uidized-bed material [4]. The total mass m
w
of the
deposited encapsulation substance can be calculated as func-
tion of the collection efciency E
g
of the uidized-bed and
as a function of time:
m
t
w
= E
g
t
0
m
w
dt (2)
H. Krber, U. Teipel / Chemical Engineering and Processing 44 (2005) 215219 217
Assuming homogenous expansion of the uidized-bed the
collection efciency E
g
may be calculated as a function of
process parameters, for example the size of the collector
particle d
P
or the height of the uidized-bed z as well as
the effective single particle collection efciency and the
porosity of the uidized-bed :
E
g
=
m
dep
m
in
=
m
in
m
out
m
in
= 1 exp
3
2
1
d
P
z
(3)
The collection efciency E
g
can be determined by mea-
suring the total mass of the coating deposited on the core
particles (m
dep
) by thermal gravimetric analysis (TGA) and
calculating the total mass of the coating reaching the reactor
(m
in
) fromthe phase equilibriumin the extractor (p
extr
,
extr
)
and from the mass ow of CO
2
through the nozzle. This
mass ow rate can be calculated [7] and depends strongly
on the conditions before the nozzle (p
N
,
N
) and the nozzle
diameter (d
N
).
A successful coating process requires that the encapsu-
lation substance adheres sufciently to the surface of the
uidized-bed material. Of course, the adhesion also affects
the collection efciency. In literature [4,8,9], the impact of
adhesion to the coating process is taken into consideration
by introduction of the adhesion coefcient . Thus effective
single particle collection efciency may be formulated:
= (4)
Herein, is the single particle collection efciency. Ac-
cording to literature [9] for liquids or very soft substances
the adhesion coefcient has a value near to one. Another
study indicates that for solid aerosols having a diameter in
the range of 0.7 m the adhesion coefcient may vary from
0.001 to 0.01 [4].
There have been extensive studies focusing on the cal-
culation of the single particle collection efciency [10,11].
Generally, the calculation of the single particle collection
efciency requires the calculation of the aerosol stream line
around the particle. Therefore transport mechanisms like dif-
fusion and inertia as well as deposition mechanisms like in-
terception have to be taken into account. For example, the
stochastic random motion of aerosol particles is likely to in-
crease the probability of aerosol deposition on the collector.
According to the literature [12] diffusion is the dominating
deposition mechanism for aerosols having diameters below
0.1 m at a ow velocity below 0.1 m/s. Studies indicate
that in most cases the different deposition mechanism are
independent of each other [13,14]. Hence, the single particle
collection efciency may be calculated by adding the sin-
gle particle collection efciency maintained for the different
transport and deposition mechanisms.
=
D
+
R
+
T
+
E
(5)
where the indices D, R, T and E indicate diffusion, inertia
as well as interception and electrostatic forces. Correlation
for the calculation of the single particle collection efciency
may be found in literature [4,15,16].
4. Results
4.1. Fluidization
Before starting with the microencapsulation the uid dy-
namic of the high pressure uidized-bed was investigated.
Fig. 3 shows the porosity (bed voidage; = V
space
/V
total
= 1V
particle
/V
total
) of the uidized-bed (glass beads 3 are
used) at different pressures (corresponding to different uid
densities). As expected the porosity increases if the uid ve-
Fig. 3. Bed voidage of glass beads (mean particle size: 124.6 m) vs.
uid velocity at different operating pressures (
R
= 328 K).
Fig. 4. Inuence of pressure on uidization velocity for different glass
beads (
R
= 328 K).
Fig. 5. Thickness of the coating in dependency of coating time for different
pre-expansion pressures (d
50
= 70 m, p
R
= 8 MPa,
R
= 328 K,
N
= 353 K, d
N
= 100 m).
218 H. Krber, U. Teipel / Chemical Engineering and Processing 44 (2005) 215219
Fig. 6. SEM pictures of untreated glass beads (left) and with stearyl alcohol coated particles (right).
locity is increased. At low velocities a sharp increase of the
porosity is seen. This point represents the transition between
the xed-bed and uidized-bed regime. The minimum ve-
locity which is necessary to uidize the particles decreases
if the pressure is risen. At 2 and 8 MPa this velocity is 8 and
2.9 cm/s, respectively.
The uidization of smaller particles started at lower
velocities and the inuence of the pressure on the min-
imum velocity was reduced. Using the glass beads 1
this velocity was 0.95 cm/s at 2 MPa and 0.67 cm/s at
6 MPa. Fig. 4 shows the inuence of pressure on the
minimum uidization velocity for the glass beads 1
and 2.
4.2. Microencapsulation
In rst coating experiments glass beads with a mean par-
ticle size of 70 m were encapsulated with stearyl alcohol.
The layer thickness was measured at different coating times
by thermal gravimetric analysis. Fig. 5 presents these re-
sults for different pressures before the nozzle. The condi-
tion inside of the uidized-bed reactor were constant (
R
= 328 K, p
R
= 8 MPa). As nozzle we used a 100 m Laval
nozzle which was heated up to 353 K. The extraction condi-
tions were equal to them at the nozzle (353 K; 1619 MPa).
The velocity of the carrier uid (carbon dioxide) through the
uidized-bed was twice of the minimum uidization veloc-
ity. The coating thickness varies from 1 to 8 m, depend-
ing on the coating time, and that, at long times, the thick-
ness approaches a constant value. It is seen that at higher
pre-expansion pressure the layer thickness increases. One
reason for that is the higher solubility of stearyl alcohol
if extraction pressure increases so that more coating mate-
rial reaches the reactor. This tendency is supported by an
increase of the mass ow rate of carbon dioxide through
the nozzle at elevated pressures. Furthermore, Krber et al.
showed that the droplet size of the aerosol of stearyl alcohol
behind the nozzle is independent of the pressure before the
nozzle [7].
SEM pictures of the encapsulated particles show that the
coating layer is uniform and smooth. In Fig. 6 coated glass
particle is presented and compared to untreated material.
5. Conclusions
A new uidized-bed coating process (particle encapsula-
tion with supercritical uids; PESF process) was introduced
to encapsulate ne and heat-sensitive particles. It was shown
that the uidization of particles under sub- or supercritical
conditions is different from that under atmospheric pressure.
With increasing pressure the minimum uid velocity which
is necessary to start the uidization decreases. It was possible
to uidize glass beads with a mean particle size of 7.4 m.
Stearyl alcohol was used for rst coating experiments with
glass particles of a mean particle size of 70 m. Complete
coatings with a layer thickness between 1 and 8 m can be
achieved depending on the coating time and process condi-
tions.
Further investigations of the particle coating in a high
pressure uidized-bed will be carried out. Especially, vari-
ations of the particle and coating material as well as coat-
ing conditions like pressure and temperature will be per-
formed. The encapsulation of particles smaller than 10 m
with very thin layers without agglomeration is a challenge of
this project. Therefore, the hydrodynamic of the high pres-
sure uidized-bed has to be characterized by experiments as
well as calculations.
An estimation of the single particle collection efciency
should be possible by measuring the collection efciency
E
g
and the layer thickness. Using this estimation the time
which is necessary to obtain a particular layer thickness can
be predicted.
H. Krber, U. Teipel / Chemical Engineering and Processing 44 (2005) 215219 219
References
[1] D. Wurster, Air-suspension technique of coating drug particles, J.
Am. Pharm. Assoc. 48 (1959) 451454.
[2] D.W. Matson, J.L. Fulton, R.C. Petersen, R.D. Smith, Rapid expan-
sion of supercritical uid solutions: solute formation of powders,
thin lms and bers, Ind. Eng. Chem. Res. 26 (1987) 22982306.
[3] H. Krber, U. Teipel, H. Krause, Manufacture of submicron particles
via expansion of supercritical uids, Chem. Eng. Technol. 23 (2000)
763765.
[4] M. Niehaus, Mikroverkapselung von Partikeln in einer Wirbelschicht
unter Verwendung von verdichtetem Kohlendioxid, Ph.D.-Thesis,
University Karlsruhe, 1999, Wissenschaftliche Schriftenreihe des
Fraunhofer ICT, Band 23.
[5] A. Tsutsumi, S. Nakamoto, T. Mineo, K. Yoshida, A novel
uidized-bed coating of ne particles by rapid expansion of super-
critical uid solutions, Powder Technol. 85 (1995) 275278.
[6] U. Teipel, P. Gerber, H. Krause, Characterization of the phase equi-
librium of the system trinitrotoluene/carbon dioxide, Propellants Ex-
plosives Pyrotechnics 23 (1998) 8285.
[7] H. Krber, U. Teipel, Mikroverkapselung feiner Partikel in einer
berkritischen Wirbelschicht, Chem. Ing. Technol. 74 (2002) 1715
1717.
[8] E. Schweers, Einu der Filterstruktur auf das Filtrationsverhal-
ten von Tiefenltern, PhD-Thesis, University Karlsruhe, Germany,
1993.
[9] K.V. Thambimuthu, Gas ltration in xed and uidized beds,
PhD-Thesis, University Cambridge, UK, 1980.
[10] F. Hhner, Trgheitsbedingte Abscheidung von Aerosolpartikeln an
Einzelkugeln und Kugelverbnden Ph.D.-Thesis, University Kaiser-
slautern, Germany, 1995.
[11] W.E. Ranz, J.B. Wong, Impaction of dust and smoke particles on
surface and body collectors, Ind. Eng. Chem. 44 (1952) 6.
[12] K. Lee, B. Liu, Theoretical study of aerosol ltration by brous
lters, Aer. Sci. Technol. 12 (1981) 79.
[13] R. Pfeffer, E. Gal, An experimental evaluation of the rotating uidized
bed lter, In: Proceedings of the World Filtration Congress III,
Dowington, PA, USA, 1982.
[14] E. Schmidt, Theoretische und experimentelle Untersuchungen zum
Einu elektro-statischer Effekte auf die Nassentstaubung, J. Air
Pollut. Control Assoc. 28 (1978) 2, 143.
[15] F. Lfer, Staubabscheiden, Georg Thieme Verl., Stuttgart, rst ed.,
1988.
[16] M.M. El Halwagi, Mathematical modeling of aerosol collection in
uidized bed lters, Aer. Sci. Technol. 13 (1990) 102.
Chemical Engineering and Processing 44 (2005) 221224
Plasma spheroidization of ceramic particles
Z. Kroly
, J. Szpvlgyi
Institute of Materials and Environmental Chemistry, Chemical Research Center,
HAS, P.O. Box 17, Budapest 1525, Hungary
Received 30 August 2003; received in revised form 18 December 2003; accepted 11 February 2004
Available online 19 June 2004
Abstract
Formation of spherical, micron-sized ceramic particles was investigated in an RF thermal plasma reactor. It has been concluded that a
wide size distribution of feedstock powders gives rise to either excessive evaporation of smaller grains or insufcient melting of bigger ones.
Ceramic spheres with more or less voids inside can also be prepared starting from powders pretreated in special ways.
2004 Elsevier B.V. All rights reserved.
Keywords: Plasma reactor; Ceramic particles
1. Introduction
Spherical particles proved to be superior in several ap-
plications owing to their favorable properties. Thus, they
are used in thermal spraying for their excellent owabil-
ity, in powder metallurgy because of their excellent repro-
ducibility in manufacturing parts with controlled porosity
and as a ller material, as well. Metal microspheres can
be easily produced by melt atomization. Similar method
in the case of ceramics is impractical. Micron-sized ce-
ramic particles, however, can be smelted by thermal plas-
mas that provide exceptional conditions for spheroidization
due to its high temperature. In terms of purity and resi-
dence time of the particles in the hot temperature core, RF
plasmas provide better conditions as compared to arc plas-
mas.
The present report describes the preparation of spherical
ceramic particles of different kind and of different size in an
inductively coupled RF thermal plasma reactor. The effect
of plasma gases and the type of the feedstock materials on
the microstructure of the formed particles was studied in the
experiments.
C.
Both the raw materials and the produced powders were
characterized for density, particle size distribution, specic
0255-2701/$ see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.cep.2004.02.015
222 Z. K aroly, J. Sz epvlgyi / Chemical Engineering and Processing 44 (2005) 221224
surface area, phase composition (XRD) and microstructure
(SEM). Density was determined by means of picnometry.
The particle size distribution by volume of grains was de-
termined by a Malvern Master Particle Sizer. The specic
surface areas were measured with a conventional volumetric
instrument by BET method. A Philips Xpert XRD appara-
tus was used for X-ray diffraction measurements. Standard
X-ray powder techniques were used with Cu K radiations
generated at 40 kV and 30 mA. The microstructural (SEM)
investigations were performed on a JEOL JSN50A appara-
tus. Cross-section images of the particles were made by em-
bedding them into resin that was followed by their cutting
by diamond blade.
3. Results and discussion
According to the scanning images of particles spheroidiza-
tion took place effectively (compare Figs. 1 and 2). A
spheroidization rate as high as 90% could be achieved.
It was previously shown [1] that increasing feed rate en-
tail declining spheroidization efciency. This phenomenon,
however, could not be experienced with increasing mean
Fig. 1. SEM image of alumina feedstock particles.
Fig. 2. SEM image of alumina particles after spheroidization.
particle size of the feedstock powder. Besides spheroidiza-
tion melting usually caused an increase in density that fell
close to the theoretical one ( = 2.32 g cm
3
) at silica pow-
ders. However, the higher was the size of the feedstock par-
ticles, the density of products remained increasingly below
the theoretical one. This can be attributed to the fact, that
above a certain size particles have not got enough time to
be melted on the whole. Thus, the core remains unaffected.
Considerable changes in the size of silica after processing
cannot be observed (Fig. 3), whereas the specic surface
area of products was increased and it was higher with de-
creasing mean particle size of the feedstock. Particles below
the mean size are prone to be evaporated completely to be
condensed again in the nanosize range in the cooler parts
of the plasma reactor. These nano-sized particles usually
cover the surface of bigger ones. Decreasing the power or
reducing the residence times would decrease evaporation
rate, however, it would also jeopardize the spheroidization
of bigger particles.
Spherical alumina can also be formed from commercial,
low cost aluminum-oxides or even from aluminum-hydr-
oxides. In the latter case energy of the plasma should provide
not only the enthalpy of melting but that of dehydration and
subsequent phase transformations of alumina as well. Under
the aforementioned conditions particles below 45 m have a
good chance to be spherodized. Presumably the wide particle
size distribution of starting gibbsite powder accounts for the
less spheroidization rate of 70%.
Application of agglomerated alumina powders as feed-
stock material gives rise to spheroidization too. Density of
product particles falls much below the theoretical one (
th
,
Al
2
O
3
= 3.95 g cm
3
), while signicant increase in the grain
size can be observed in case of alumina (Fig. 4). Scanning
images of these powders, however, show they mainly con-
sist of hollow particles. Formation of hollow particles and
the size enlargement can be attributed to the expansion of
gases located in the interior of melted droplets. The gases
Fig. 3. Main characteristic of silica product powders (S denotes specic
surface area, represents apparent density).
Z. K aroly, J. Sz epvlgyi / Chemical Engineering and Processing 44 (2005) 221224 223
Fig. 4. Comparison of the particle size distribution of feedstock material (straight line) and product (dashed line) ( represents apparent density).
are hindered from leaving after the development of a coher-
ent outer melted layer. The nal size of these cavities are de-
termined by the freezing temperature of the oxide melt that
is approximately T
F
= 0.8T
M
[2,3], where T
M
is the melt-
ing point of particular oxide. The overpressure in the voids
can be calculated by this formula: P = (2/r), where
denotes the surface tension of melt and r denotes the radius
of the hollow. From the above formulas it can be calculated,
that the molar quantity of gas in the resulted voids are in the
same order of magnitude than that of the gas in the porous
structure of the starting grains. It is the case if the raw ma-
terial is made from primary particles of several microns by
spray drying or agglomeration. When the goal is to prepare
hollow spheres some gas-blowing agents can be blended to
the grains in order to provide substantial gas volumes. These
Fig. 5. SEM image of a hollow microsphere.
Fig. 6. SEM image of a hollow microsphere of thick wall.
supplementary materials facilitate bubble generation by re-
leasing gas at a certain temperature by decomposition. This
process was applied to make hollow silica particles in ex-
periment 4 (Fig. 5). Density of particular powder is a mean
value that does not characterize each particle. The wall of
individual particles may differ in considerable extent, as this
can be recognized by comparing Figs. 5 and 6. While the
density of particles having thin shells is less than 1 g cm
3
,
that of the solid particles can reach even the theoretical value.
4. Crystallinity
Freezing of the melted particles takes place rapidly be-
cause of the extremely high temperature gradients being
224 Z. K aroly, J. Sz epvlgyi / Chemical Engineering and Processing 44 (2005) 221224
Fig. 7. XRD pattern of spheroidized alumina powders.
characteristic to thermal plasmas. According to XRD pat-
terns, majority of silica particles were transformed into
amorphous state on plasma treatment, only 12% remained
quartz.
Several papers report [4] that liquid alumina solidies not
in the thermodynamically most stable phase of -Al
2
O
3
,
but rather in the form of -Al
2
O
3
. This is attributed to the
fact that the solidied phase structure is basically deter-
mined by the relative critical free enthalpies of nucleation of
alternative crystal structures. Consequently, not surprising,
that considerable part of spheroidized particles composed
of -Al
2
O
3
and other metastable phases (such as , ) of
alumina (Fig. 7). The latter were formed from the phase
according to the usual route of phase transformation on cal-
cinations, assuming that the temperature history of given
particle makes it possible. For bigger particles (>30 m) the
heat effect of crystallization may promote additional phase
changes.
5. Conclusions
The RF thermal plasmas are suitable tools for making ox-
ide ceramic microspheres, either dense or hollow. The mi-
crostructure of the product can principally be inuenced by
the structure of feedstock materials and to a less extent by
the plasma operating conditions. Highly porous raw materi-
als and/or the presence of blowing agents facilitate formation
of hollow spheres. By varying the process conditions, one
can primarily affect the thermal history of particles, hereby
the degree of evaporation.
References
[1] N.M. Dignard, M.I. Boulos, Sphericity analysis method for the in-
duction plasma processing of powders, in: Proceedings of the ISPC
14, Prague, 1999, pp. 22112217.
[2] R. McPherson, J. Mater. Sci. 8 (1973) 851.
[3] P. Florian, D. Massiot, B. Poe, I. Farnan, J.-P. Coutures, Solid State
Nucl. Mag. 5 (1995) 233.
[4] T. Ishigaki, Y. Bando, Y. Moriyoshi, M.I. Boulos, J. Mater. Sci. 28
(1993) 4223.
Chemical Engineering and Processing 44 (2005) 225229
Treatment of particulate metallurgical wastes in thermal plasmas
I. Mohai
, J. Szpvlgyi
Institute of Materials and Environmental Chemistry, Chemical Research Center, Hungarian Academy of Sciences,
P.O. Box 17, Budapest H-1525, Hungary
Received 27 August 2003; received in revised form 25 March 2004; accepted 15 April 2004
Available online 19 June 2004
Abstract
Steelmaking and plating industry generates large quantities of dusts and sludge. They are regarded as hazardous wastes because of the
leachingout of their toxic components. Therefore, particular wastes are stockpiledat highcost. Our workaimedat RFthermal plasma processing
of a steelmaking ue dust and sludge fromthe hot plating of steel products. Waste samples were treated in reducing atmosphere, respectively, to
produce ne metallic powders and in neutral/oxidizing atmosphere to synthesize zinc ferrite nanopowders. Starting powders and products were
characterized by their chemical (ICP-AES) and phase (X-ray diffraction, XRD) composition, particle size and morphology (scanning electron
microscopy, SEM). It was found that iron and zinc content of the particular wastes can be reduced to metals in the presence of hydrogen. In
neutral/oxidizing conditions spinel ferrites of variable composition were formed even during the very short residence time in the reactor.
2004 Elsevier B.V. All rights reserved.
Keywords: Metallurgical wastes; Thermal plasmas; Reduction; Ferrites
1. Introduction
Aplasma, considered as the fourth state of matter, consists
of a mixture of electrons, ions and neutral species, although
overall it is electrically neutral. Hot or equilibrium plas-
mas can be characterized by the approximate equality be-
tween heavy particle and electron temperature. Such plas-
mas are known as thermal plasmas. During the last decades
much work has been done to develop new processes based
on plasma technology. One option is to recycle metallurgical
wastes of valuable metal content by thermal plasma treat-
ment. PLASMADUST technology of SKF, which combines
a plasma gas heater with a coke-lled shaft furnace, pro-
duces alloyed molten iron, and metallic zinc and lead vapour
from steelmaking dusts [1]. More recently, Retech Inc., a
leading company in the application of thermal plasmas for
environmental applications, developed the Plasma Arc Cen-
trifugal Treatment (PACT) technology to process hazardous
metallurgical and military wastes [2]. The PLASMAREC
plant [3], one installation of the PACT technology, can easily
be mobilized and transported to eliminate local contamina-
tions. In the transferred arc plasma developed by Tetronics
Corresponding author. Tel.: +36 1 325 7933; fax: +36 1 325 7892.
E-mail address: mohaiti@chemres.hu (I. Mohai).
Co. the carbothermic reduction of steelmaking dusts con-
taining mainly iron and zinc resulted in non-toxic slag and
metallic Zn, as products.
In comparison to the conventional waste destruction pro-
cesses, thermal plasma treatment is inherently more expen-
sive in most cases [4]. Therefore, research activities in this
area have been restricted to special toxic waste destruction
problems, where thermal plasmas offer unique advantages,
such as (i) high temperatures and energy densities allowing
fast and complete decomposition of wastes, (ii) very high
quenching rates allowing the formation of non-equilibrium
compositions and preventing undesirable recombination,
(iii) easy control over the chemistry of processing. Compet-
itive new plasma technologies generate valuable products,
as well.
Contrary to the above mentioned technologies, which are
based on arc plasma furnaces, a radiofrequency (RF) plasma
system can process ne powders without granulation in
a continuous operation. This possibility, together with the
advantageous features of the thermal plasmas mentioned
above, offer great perspectives for the synthesis of special
ceramic powders such as spinel ferrites [5]. The RF plasma
treatment produces nanosized metal and/or oxide powders
depending on the parameters of processing. In this paper
application of an RF thermal plasma system for the treat-
0255-2701/$ see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.cep.2004.04.008
226 I. Mohai, J. Sz epvlgyi / Chemical Engineering and Processing 44 (2005) 225229
ment of wastes from the ferrous metallurgy in reducing and
neutral/oxidative conditions is investigated.
2. Experimental
Two wastes, a converter ue dust (CFD) from the steel-
making process and a sludge from the hot plating of steel
products (hot plating sludge, HPS), were treated in a RF
thermal plasma reactor (35 MHz, max, 35 kW plate power).
Power of the generator was coupled to a TEKNA PL-35
torch which was connected to a water cooled plasma cham-
ber, a cyclone and a lter (Fig. 1). Temperature eld in the
torch and the reactor was calculated by a 2D mathemati-
cal model based on the continuity, momentum, energy and
species conservation equations [6]. The highest gas temper-
ature at the 24 kW plate power case was 11,500 K near to the
coil region [7]. The mean temperature of the plasma ame
was about 5000 K.
Argon was used as the central plasma gas and as the
sheath gas, as well. Reagent (H
2
) or auxiliary (O
2
) gases
were mixed to the sheath gas. Powders were injected axially
into the hottest region of the plasma by a PRAXAIR powder
feeder through a water cooled probe. Both the raw materials
and the products were characterized in terms of particle size,
chemical and phase compositions. In each run products were
collected from the reactor wall (R), from the reactor bottom
(RB) and the cyclone (C).
Particle size distribution was measured by a Particle Size
Analyser (Malvern 2600C). For bulk chemical compositions
samples were digested in diluted HNO
3
solution using a
CEM microwave digestion system. Dissolved samples were
analysed by ICP-AES technique (Labtest PSX7521). Phase
conditions were determined by X-ray diffraction analysis
(XRD, Philips PW 1710). Scanning electron microscopic
Fig. 1. Scheme of the experimental setup.
Table 1
Bulk chemical composition of CFD and HPS samples
Sample Fe Zn Pb Ca Mg Si Cl
Concentration (wt.%)
CFD 65.0 4.22 0.98 1.96 0.15 1.02 0
HPS 17.5 39.5 0.23 2.76 0.29 2.22 6.99
(SEM) analysis was performed by a JEOL JSN50A appara-
tus.
3. Results and discussion
3.1. Reduction of the converter ue dust and the hot
plating sludge
Both CFD and HPS samples had broad particle size dis-
tribution between 1 and 100 m with a mean particle size
of 29.5 and 37.2 m, respectively. The HPS had to be dried
prior to the analysis and the plasma treatment. Its weight
loss on drying at 105
C was 60.8%.
Chemical compositions of the industrial samples are
shown in Table 1. Iron and zinc have the highest concen-
tration in both samples. Chlorine content of HPS (6.99%)
is also worth mentioning. In addition to the data in Table 1
both CFD and HPS samples contained other components,
such as Al, Cr, Ni, Mn, Cu, Cd, P and C in an amount of
less than 1%.
The main crystalline phase of the CFD sample was mag-
netite (FeOFe
2
O
3
) (Fig. 2). Traces of hematite (Fe
2
O
3
)
were also detected. Although carbon content of the sample
was rather low (1.2 wt.%) intense reection of the graphite
could be observed on the diffractogram. This can be ex-
plained by the strong orientation of the graphite particles to
the direction of the X-ray.
Main diffraction peaks of the HPS sample (Fig. 3) can be
20 30 40 50 60
2 ()
I
n
t
e
n
s
i
t
y
(
a
.
u
.
)
G
Fe
M
M
W Sample RB
W W
Fe
M
H
M
M+G Sample CFD
Sample C
Sample R
Fig. 2. X-ray diffractogram of the converter ue dust (CFD) and the
plasma treated samples produced therefrom: sample Rfrom the reactor
wall, sample RBfrom the reactor bottom, sample Cfrom the cyclone.
Assignation of peaks: Fe, metallic iron; M, magnetite; W, wustite; H,
hematite; G, graphite.
I. Mohai, J. Sz epvlgyi / Chemical Engineering and Processing 44 (2005) 225229 227
5 15 25 35 45
2 ()
I
n
t
e
n
s
i
t
y
(
a
.
u
.
)
SI
Sample C
SI
M
ZnO
W
Fe
SI
SI
SI
G ZnO
ZnO
SI
SI
SI
M
ZnO
Zn W
Zn
Fe
SI
SI
SI
SI
SI
Sample RB
Sample R
Sample HPS
Fig. 3. X-ray diffractogram of the hot plating sludge (HPS) and the
plasma treated samples produced therefrom: sample Rfrom the reactor
wall, sample RBfrom the reactor bottom, sample Cfrom the cyclone.
Assignation of peaks: SI, simonkolleite; Fe, metallic iron; M, magnetite;
W, wustite; ZnO, zincite; G, graphite.
assigned as simonkolleite (Zn
5
(OH)
8
Cl
2
H
2
O). Iron com-
pounds are most probably present in the original HPS sam-
ple as amorphous hydroxides.
Typical plasma parameters of the reduction tests with hy-
drogen can be seen in Table 2. Feed rate of the starting
powder was changed by the ow rate of the carrier gas. The
specic energy was calculated as the ratio of plate power re-
lated to the powder feed rate. Hence, this parameter consid-
ers two process variables simultaneously. In each run three
samples were collected from different regions of the plasma
system: (i) from the reactor wall, (ii) from the bottom of
the reactor, and (iii) from the cyclone. Particles deposited to
different places of the plasma reactor and the cyclone were
subjected to different thermal effects, so they probably have
different physical and chemical characteristics, as well.
X-ray diffraction patterns of plasma-treated CFD samples
(Fig. 2) indicated a signicant decrease in the intensity of
the magnetite peaks with a simultaneous increase of metal-
lic Fe peak. Extent of reduction, which is proportional to
the intensity of the Fe100/magnetite100 diffraction lines, is
almost complete in case of sample C. In sample R most of
the magnetite content reacted with hydrogen. However, re-
duction was not complete. Some FeO (wustite) remained in
the product. Powder collected from the reactor bottom (RB)
was hardly reduced: only traces of Fe and some FeO could
be detected by XRD. Explanation of this phenomenon can
be given from scanning electron micrographs of the starting
powder and the products (Fig. 4). Although the primary par-
ticle size of sample CFD is near to the submicron size, these
Table 2
Conditions of reduction tests
Waste powder Flow rate of gases (l/min) Power (kW) Feed rate (g/min) E
spec
(kWh/g)
Plasma Sheath Carrier
CFD 13 (Ar) 45 (Ar) 7.5 (H
2
) 6.3 25.5 4.8 0.09
HPS 15 (Ar) 45 (Ar) 7.0 (H
2
) 5.5 23.4 5.4 0.07
particles are ready to form agglomerates with strong cohe-
sion forces. This is why the mean grain size data obtained
from the laser diffraction method are much bigger. Agglom-
erates above 1015 m cannot warm up to the temperature
where reduction is favoured from thermodynamic point of
view. On the other hand, particles and agglomerates below
this size can evaporate easily with a simultaneous reduction.
Particles and agglomerates of different size pass along tra-
jectories with different residence time in the hot zone of the
plasma ame. Big agglomerates fall through along the axis
of the plasma practically without chemical and morpholog-
ical changes. These agglomerates can be collected from the
reactor bottom. Samples deposited to the reactor wall and
the cyclone, respectively, have much smaller and more uni-
form particle size. This indicates that these products were
formed by melting, evaporation and subsequent condensa-
tion of the starting powder. Extent of agglomeration can be
estimated from the distribution of products on the different
areas of the plasma equipment.
Sample CFD consisted of mostly agglomerated particles,
because about 7075% of the products could be collected
from the reactor bottom. Quantity of C samples is almost
negligible. Agglomeration could be suppressed by the addi-
tion of carbon powder to the sample. Although carbon could
not reduce oxides without hydrogen, in the presence of car-
bon, hydrogen reduction was more effective and the ratio of
nonreacted powder (sample RB) decreased from 7075 to
40%.
XRD measurements of plasma treated HPS samples in
the presence of hydrogen indicated a partial reduction of the
starting material (Fig. 3). Reections of the main crystalline
phase of the starting powder (simonkolleite, SI) could be
observed in all samples. Samples collected from the reac-
tor wall consisted of nonreacted simonkolleite, metallic Fe,
FeO (wustite), magnetite, metallic Zn and ZnO. Diffraction
peak of metallic Zn was quite surprising, because in ther-
modynamic equilibrium Zn vapours are ready to form ox-
ide during condensation in the presence of H
2
O vapours.
This phenomenon can be explained by the high cooling rate
in the plasma reactor which caused a kinetic hindrance of
re-oxidation. Phase compositions of samples C were simi-
lar to those of samples R, but without metallic Zn. In sam-
ples RB extent of reduction was negligible. Heat effect of
the plasma ame could be observed in the formation of
magnetite from the amorphous iron hydroxides and ZnO
from the zinc-hydroxide-chloride (simonkolleite). Relative
amount of RB products was rather small (about 25%). It
228 I. Mohai, J. Sz epvlgyi / Chemical Engineering and Processing 44 (2005) 225229
Fig. 4. Scanning electron micrographs of sample CFD and its reduction products.
indicated a lower agglomeration of the HPS particles com-
paring to the CFD starting material. High extent of the non-
reacted simonkolleite in the plasma treated samples can be
traced back to the volatile content of the HPS sample: due
to thermal effect simonkolleite releases HCl and H
2
O. A
considerable part of the plasma energy may be lost on the
dissociation of these gases.
3.2. Synthesis of zinc ferrites
For the synthesis of zinc ferrite (ZnFe
2
O
4
) of stoichio-
metric composition CFD and HPS samples were mixed
in an appropriate ratio. From the chemical analysis the
Fe/Zn molar ratio of the mixture was 2.18. To override the
problem of the cooling effect of volatiles on the plasma
(mentioned above), prior to mixing HPS sample was pre-
heated at 300
C,
in the RF plasma some milliseconds of residence time was
enough to produce ne ferrite powders from the waste
mixture.
Both powders collected from the reactor wall and from the
reactor bottom showed similar diffraction patterns (Fig. 5.)
indicating the presence of spinel as the dominant phase
(amount of sample C was negligible in these experiments).
Composition of the spinel phase was estimated from the
lattice parameters (a), assuming, that the increase of lat-
tice parameter due to Zn incorporation is proportional to
the Zn concentration. From these calculations the composi-
tions of sample R and sample RB were Zn
0.7
Fe
2.3
O
4
and
Zn
0.4
Fe
2.6
O
4
, respectively. Consequently, some of the Zn
content of the starting mixture could not build into the spinel
structure and left the system through the exhaust in the form
of very ne ZnO powder.
I. Mohai, J. Sz epvlgyi / Chemical Engineering and Processing 44 (2005) 225229 229
20 25 30 35 40 45 50
2 ()
I
n
t
e
n
s
i
t
y
(
a
.
u
.
)
ZF
ZF
ZF
Fig. 5. X-ray diffractogram of the zinc ferrite (ZF) synthetised from the
mixture of CFD and HPS samples.
NiZn ferrites could also be synthesized in RF plasma
reactor from the CFD and HPS powders by admixing
Ni
3
H
4
CO
7
4H
2
O to the waste mixture. Molar ratio of the
metals was set for Ni/Zn/Fe = 0.4/0.6/2. XRD diffrac-
tograms of the products showed the complete transfor-
mation of the starting mixture to spinel phases. However,
in sample R spinel phase consisted of the mixture of
Ni
0.2
Zn
0.5
Fe
2.3
O
4
and Ni
0.6
Zn
0.3
Fe
2.1
O
4
, while in sample
RB for the composition of the spinel (in accordance with the
chemical analysis) Ni
0.2
Zn
0.5
Fe
2.3
O
4
could be estimated
from the lattice parameter.
4. Conclusions
Metallurgical waste powders containing iron and zinc ox-
ides and hydroxides can be reduced to metals in RF thermal
plasma in the presence of hydrogen. However, if the particles
are agglomerated they cannot be reduced due to the short
residence time in the hot plasma region. Thus, to achieve
high reduction non-agglomerated powders with a mean par-
ticle size of less than 20 m should be introduced into the
plasma reactor. Spinel ferrites of variable composition were
formed with actually complete conversion, even during the
very short residence time. This is quite surprising, because
conventional ferrite synthesis needs heat treatment of 46 h
at temperatures above 1000
C.
Acknowledgements
The authors are grateful for the nancial support from the
National Scientic Research Fund OTKA T032272.
References
[1] A.L. Hare, in: J. Feinman (Ed.), Plasma Technology in Metallurgical
Processing, ISS, Warrendale, PA, 1987, pp. 175187.
[2] R.C. Eshenbach, R.E. Haun, in: Proceedings Workshop on Industrial
Application of Plasma Chemistry, Drexel University Press, Minneapo-
lis, MN, 1995, p. 9.
[3] W. Hoffelner, R. Burkhard, V. Haefeli, H. Sun, in: Proceedings of the
13th International Symposium on Plasma Chemistry, Peking University
Press, Beijing, China, 1997, p. 1915.
[4] E. Pfender, Thermal plasma technology: where do we stand and
where are we going, Plasma Chem. Plasma Proc. 19 (1999) 1
31.
[5] I. Mohai, J. Szpvlgyi, I. Bertti, M. Mohai, J. Gubicza, T. Ungr,
Thermal plasma synthesis of zinc ferrite nanopowders, Solid State
Ionics 141-142 (2001) 163168.
[6] A. Gaillat, R.M. Barnes, P. Proulx, M.I. Boulos, Computer modelling
of enclosed inductively coupled plasma discharges, Spectrochim. Acta
B-At. Spectrosc. 50 (10) (1995) 11871205.
[7] Z. Karoly, Project report F 029731 supported by the National Scientic
Research Fund, Hungarian, 2002.
Chemical Engineering and Processing 44 (2005) 231235
Deuidization modelling of pyrolysis of plastics in a conical
spouted bed reactor
Roberto Aguado, Rubn Prieto, Mara J. San Jos
, Sonia Alvarez,
Martn Olazar, Javier Bilbao
Departamento de Ingeniera Qumica, Facultad de Ciencias, Universidad del Pas Vasco, Apartado 644, Bilbao 48080, Spain
Received 3 October 2003; received in revised form 29 January 2004; accepted 11 February 2004
Available online 17 June 2004
Abstract
Thermal pyrolysis for upgrading plastic wastes is one of the better methods for recycling plastics in terms of its perspectives for industrial
implementation. The conical spouted bed reactor proposed in this paper may be a solution to the problems arising in uidized beds handling
sticky solids, as particle agglomeration phenomena, which can cause deuidization. In order to avoid deuidization, experiments have been
carried out in batch mode in the temperature range of 450600
; D
c
= 0.123 m; D
i
= 0.02 m; D
o
= 0.01 m.
When the inert gas ow rate is increased, the gassolid
contact regime evolves from the conventional spouted bed
Fig. 1. Scheme of the reactor.
to a dilute spouted bed (or jet spouted bed, which is char-
acteristic of a conical contactor and in which bed voidage
is uniform and higher than 0.90) [9] and the gas residence
time decreases from a few seconds to approximately 20 ms.
As the plastic material is introduced into the reactor, it
melts onto the sand particles and coats them. The vigorous
cyclic movement of the particles can prevent agglomeration
problems. Temperature is measured by means of three ther-
mocouples placed at different radial positions in the reactor
and provided with free vertical movement. Bed isothermic-
ity is noteworthy, which is attained due to the vigorous par-
ticle circulation.
Reaction temperature is attained by means of two electric
resistances covered with ceramic material. One resistance is
located within the tube for heating the inert gas prior to entry
into the reactor and the second one surrounds the conical
section of the reactor. Temperature in both these positions
is measured by two thermocouples. The two heating zones
are thermically insulated.
The runs have been carried out at 400, 500, 550 and 600
C
by feeding 1 g of plastic material (with a particle size of
approximately 1 mm) and using 30 g of sand (with a size
between 0.63 and 1 mm).
The materials used for pyrolyzing are: low density
polyethylene (LDPE), high density polyethylene (HDPE)
and polypropylene (PP) (supplied by Dow Chemical, Tar-
ragona, Spain). The properties of these materials are set out
in Table 1.
3. Results
3.1. Hydrodynamics and particle velocity
The minimum spouting velocity is determined, as a func-
tion of the geometrical parameters of the particlereactor
system [8]:
(Re)
ms
= 0.126 Ar
0.39
_
D
b
D
o
_
1.68 _
tan
_
2
__
0.57
(1)
where D
b
is the diameter of the upper level of the stagnant
bed:
D
b
= D
i
+2 H
o
tg
_
2
_
(2)
The average cycle time (characteristic to particle trajectories
[10]) is
t
c
=0.85
0.48
_
d
p
D
i
_
0.68
_
D
o
D
i
_
1.31
_
u
u
ms
_
1.14
_
H
o
D
i
_
0.86
_
v
_
0.11
0.51
(3)
The vertical solid velocity in the spout is calculated by the
equation proposed by Epstein and Grace [11] valid at the
R. Aguado et al. / Chemical Engineering and Processing 44 (2005) 231235 233
Table 1
Properties of the materials studied
Material Molecular weight (g/mol) Polydispersity Density
s
(kg/m
3
) Heating value (MJ/kg) Pyrolysis heat (kJ/kg)
LDPE 92200 5.13 923 43 543.6
HDPE 46200 2.89 940 43 429.8
PP 5000090000 2.00 890 44 581.9
minimum spouting velocity and at velocities 20 and 30%
above this value:
z
=
z
(0)
_
1
_
r
r
s
_
2
_
(4)
The calculation of velocity along the axis has been carried
out by solving a force balance for a spherical particle arising
along the spout:
d
z
(0)
dz
z
(0) =
3
4
C
D
g
[u
z
(0)
z
(0)]
s
d
p
(
s
g
)g
s
(5)
The particulate phase in the annular zone of a spouted bed
can be described as an isotropic, incompressible, rigid plas-
tic, non-cohesive Coulomb powder. Assuming that this ma-
terial is in a quasi-static critical condition, the stress eld
can be described by equations developed for a static mate-
rial element.
The solid owis coaxial, so that in cylindrical coordinates,
the following applies:
tan(2) =
z
/r +
r
/z
z
/z
r
/r
(6)
where is the stress angle (the angle between the direction
of the z axis and the direction of the major principal stress
axis).The mass conservation for this zone is
z
[(1 )
s
z
] +
1
r
r
[r(1 )
s
r
] (7)
By solving simultaneously Eqs. (4)(7), the horizontal and
vertical components of particle velocity will be determined.
Fig. 2 shows the results calculated for the experimental sys-
tem used.
3.2. Sand coating with fused plastic
In the deterioration of the particle mixture and evolu-
tion to bed blockage, the mechanism of the initial step of
coating the inert particle (sand) with fused plastic is cru-
cial. Subsequently, the tendency of the particles to agglom-
erate depends on their stickiness, momentum and contact
surface.
Concerning the rst step of coating, when the particles of
polyolen are introduced into the bed, their external surface
becomes softer but their inside is cold, due to their low ther-
mal conductivity. The softened surface is responsible for the
formation of agglomerate made up of a plastic particle sur-
rounded by sand particles. When the whole plastic particle
Fig. 2. Particle velocities.
softens, its material is distributed by coating the surround-
ing sand particles. If the thickness of the layer that coats
the particles is lower than a critical value, the sand particles
do not fuse. This situation corresponds to a low ow rate
of plastic in the feed, and beyond this value, agglomerates
grow irreversibly, and instead of sand coating, total blockage
of the bed or deuidization is the result. This mechanism
of growth depends on the properties of the plastic material
[12].
The good behaviour of the conical spouted bed reactor is
quantied on the basis of the critical thickness of the fused
plastic that may be handled. The critical thickness is the
value above which the particles fuse when they collide and is
a function of the thickness (viscosity) and of the momentum
of the colliding particles. From the hypothesis of the critical
thickness model of Arena and Mastellone [12], the following
expression has been deduced for the critical thickness for
234 R. Aguado et al. / Chemical Engineering and Processing 44 (2005) 231235
which the deuidization of the bed can be avoided:
crit
=
r
2
_
exp
_
m
0
r
2
_
1
_
(8)
Eq. (8) shows the dependency of the critical thickness
with mass m, radius r
p
, and velocity
o
of the inert parti-
cles coated with plastic and with the viscosity of the mate-
rial that coats the sand . For the experimental conditions
(total mass of sand, 30 g; mass of plastic in the feed, 1 g;
sand particle diameter, between 0.6 and 1.2 mm; sand den-
sity 2600 kg m
3
, average velocity of the particles in the an-
nular zones, 0.25 ms
1
[7], the critical thickness predicted
by Eq. (8) is 250 m. In this calculation, the viscosity of the
plastic has been taken at its fusion temperature, 16 poises,
because it is in the initial step of fusion when the stickiness
of the plastic is maximum point.
In the uidized bed, the velocity of the particles is of a
few cms
1
and the critical thickness of the fused plastic is
between 4 and 7 mm. Afact that should be taken into account
is that, although gas velocity is increased, particle velocity
hardly changes because most of the excess gas rises through
the bed in the bubble phase. Nevertheless, in the conical
spouted bed, particle velocity is increased by raising gas
velocity up to the dilute spouted bed, in which bed voidage
is uniform (between 0.9 and 0.99) and the particle descent
velocity is almost equal to the ascent velocity [9].
3.3. Limit operating conditions for the equipment
Eqs. (4)(8) have been used to calculate the maximum
amount of plastic that can be fed (corresponding to the
critical thickness) without bed agglomeration, for different
amounts of sand in the reactor. Fig. 3 shows these results
for different nitrogen ow rates. When the nitrogen ow
rate is increased, the bed is in the regime of spouted bed
(beds made up of high amounts of sand). For intermediate
amounts of sand, the bed is the transition between bed and
Fig. 3. Limit operating conditions.
dilute spouted bed, as velocity is increased from 1.05 to
2.50 u
ms
.
In Fig. 3 it is observed that, for a given amount of sand
in the reactor as gas velocity is increased, the amount of
plastic that may be fed increases almost linearly, which is a
consequence of particle velocity increase. Consequently, the
ratio of plastic/sand in the feed may be as high as 0.03 for
the experimental reactor, which may treat 100 g of sand in a
spouted bed regime and corresponds to 62 mm of stagnant
bed height. Likewise, and taking into account the scaling
capacity of the conical spouted bed, a reactor with a stagnant
bed height of 430 mm (33.3 kg of sand) may treat 1 kg of
plastic in batch operation.
4. Conclusions
The conical spouted bed reactor is especially suitable for
avoiding agglomeration problems in the pyrolysis of poly-
olens, even when the operation is carried out under the
conditions of maximum stickiness. In this reactor, the cyclic
movement of sand particles allows for their uniform coat-
ing with fused plastic. Furthermore, the high velocity of
the particles generates collisions whose energy sufces to
avoid their agglomeration. The critical thickness of the plas-
tic layer is an order of magnitude higher than that corre-
sponding to the uidized bed, which gives way to a higher
yield by reactor volume unit.
Acknowledgements
This work was carried out with the nancial sup-
port of the University of the Basque Country (Project
UPV 069.310-13607/2001) and of the Ministry of Sci-
ence and Technology of the Spanish Government (Project
PPQ2001-0780).
Appendix A. Nomenclature
Ar Archimedes number g d
3
p
g
(
s
g
)
2
D
b
, D
c
, D
i
, D
o
diameter of the upper level of the
stagnant bed, of the column, of the bed
base and of the inlet, respectively (m)
d
p
particle diameter (m)
r
p
particle radius (m)
H
o
height of the stagnant bed (m)
k kinetic constant for pyrolysis of PP (s
1
)
m particle mass (kg)
r
s
spout radius at level z (m)
(Re
o
)ms Reynolds number at the minimum
spouting velocity
t, t
c
time and average cycle time (s)
u, u
ms
gas velocity and gas velocity at the
minimum spouting (ms
1
)
R. Aguado et al. / Chemical Engineering and Processing 44 (2005) 231235 235
u
r
, u
z
, horizontal and vertical components of
gas velocity, respectively (ms
1
)
W
p
plastic mass (kg)
Greek symbols
stress angle
crit
critical thickness of the plastic layer (m)
shape factor
cone angle, radians
viscosity of the melted plastic
(kg m
1
s
1
)
o
average particle velocity in the annulus
(ms
1
)
s
,
v
density of the particle and of glass,
respectively (kg m
3
)
o
,
z
horizontal and vertical components
of particle velocity, respectively (ms
1
)
z
(0) component of particle velocity in the
z direction along the axis of the
contactor (ms
1
)
References
[1] D.S. Scott, S.R. Czernik, J. Piskorz, A.G. Radlein, Fast pyrolysis of
plastic wastes, Energy Fuels 4 (1990) 407411.
[2] J.A. Conesa, R. Font, A. Marcilla, Comparison between the pyrolysis
of types of polyethylenes in a uidized bed reactor, Energy Fuels
11 (1997) 126136.
[3] W. Kaminsky, Possibilities and limits of pyrolysis, Makromol. Chem.
Macromol. Symp. 57 (1992) 145160.
[4] W. Kaminsky, Chemical Recycling of Mixed Plastics by Pyrolysis,
Adv. Polym. Technol. 14 (1995) 337344.
[5] P.T. Williams, E.A. Williams, Fluidised bed pyrolysis of low density
polyethylene to produce petrochemical feedstock, J. Anal. Appl.
Pyrolysis 51 (1999) 107126.
[6] R. Aguado, M. Olazar, B. Gaisn, R. Prieto, J. Bilbao, Kinetic study
of polyolens pyrolysis in a conical spouted bed reactor, Ind. Eng.
Chem. Res. 41 (2002) 45594566.
[7] M. Olazar, M.J. San Jos, S. Alvarez, A. Morales, J. Bilbao, Mea-
surements of particle velocities in conical spouted beds using an
optical bre probe, Ind. Eng. Chem. Res. 37 (1998) 45204527.
[8] M. Olazar, M.J. San Jos, A.T. Aguayo, J.M. Arandes, J. Bilbao,
Stable operation conditions for gas-solid contact regimes in conical
spouted beds, Ind. Eng. Chem. Res. 31 (1992) 17841792.
[9] M.J. San Jos, M. Olazar, S. Alvarez, J. Bilbao, Local bed voidage
in conical spouted beds, Ind. Eng. Chem. Res. 37 (1998) 25532558.
[10] M.J. San Jos, M. Olazar, S. Alvarez, M.A. Izquierdo, J. Bilbao,
Solid cross-ow into the spout and trajectories in conical spouted
beds, Chem. Eng. Sci. 53 (1998) 35613570.
[11] N. Epstein, J.R. Grace, Spouting of particulate solids, In: L. Otten,
M.E. Fayed (Eds.), Handbook of Powder Science and Technology,
2nd ed., Van Nostrand Reinhold, New York, 1997, pp. 532567
(Chapter 10).
[12] U. Arena, M.L. Mastellone, Deuidization phenomena during the
pyrolysis of two plastic wastes, Chem. Eng. Sci. 55 (2000) 2849
2860.
Chemical Engineering and Processing 44 (2005) 237243
The energy of bed processing during drum granulation
Tadeusz Gluba
Faculty of Process and Environmental Engineering, Technical University of Lodz, ul. Wolczanska 213/215, 90-924 Lodz, Poland
Received 30 July 2003; received in revised form 10 December 2003; accepted 11 February 2004
Available online 19 June 2004
Abstract
Results of investigations of the effect of particle size composition of the raw material and the amount of wetting liquid supplied to the
bed on the energy needed for growth and consolidation of granules during wet drum granulation process are presented in the paper. Energy
consumption at subsequent stages of the granulation process was determined on the basis of the instantaneous values of torque recorded every
1 s on the granulator shaft.
2004 Elsevier B.V. All rights reserved.
Keywords: Drum granulation; Agglomeration; Energy consumption; Power demand; Porosity
1. Introduction
An important aspect of each technological process is the
tendency to decrease energy demand necessary to produce a
product of required properties. This can be accomplished by
both a selection of proper processing method and a choice
of appropriate parameters that would ensure correct run of
the process. To achieve advantageous conditions of agglom-
eration in rotary drums, it is necessary to ensure a deter-
mined nature of feed motion that is strictly connected with
its dynamics, and also the conditions for agglomerate forma-
tion and growth, dependent, among the other things, on the
properties of media that participate in the process and their
quantitative interrelations. In horizontal drum granulators
dynamics of the granular bed are main factor contributing
to the torque measured on the granulator shaft, and conse-
quently, on the drive engine power [1,2]. The assessment of
power demand at particular stages of the batch granulation
process and relating it to feed motion and granulated product
properties changing in time is an important problem, both
theoretical and practical. Results of research carried out so
far for model or real materials to some limited extent, only
partly, explain the dependence of torque and power during
granulation on the bed behaviour in the drum [3]. In drum
granulation, there have been only a few attempts to relate
b
=
bl
+
bc
2
(1)
= 1
b
(2)
Table 1
The physical properties of the raw materials
Material
D1 D2 D3 D4 D5
Mean particle size d
m
(m) 10.6 15.8 20.0 28.0 34.9
Bulk density of loose material
bl
[kg/m
3
] 842.5 939.0 891.4 989.6 1031.0
Bulk density of condensed material
bc
[kg/m
3
] 1235.5 1401.6 1348.2 1554.8 1585.0
Mean bulk density
b
[kg/m
3
] 1039.0 1170.3 1119.8 1272.2 1308.0
Mean porosity [] 0.629 0.582 0.600 0.546 0.533
Density (kg/m
3
] 2800
Fig. 1. Comparison of particle size distributions of raw materials.
Physical properties of the materials used in the experi-
ments are shown in Table 1.
3.2. Experimental set-up and methods
The process of granulation was carried out batch-wise
in a drum of diameter 0.5 and 0.4 m long at a constant
rotational speed n = 20 rpm and constant drum lling (
= 10%), for a range of moisture contents w [kg of water/kg
of dry material] selected for each raw material separately. A
schematic diagram of the experimental set-up is shown in
Fig. 2.
Wetting liquid (distilled water) was supplied by two pneu-
matic nozzles to the bed of ne particles tumbling in the
drum (the wetting stage). Operating parameters of the noz-
zles were constant:
water ow rate Q
w
= 3.33 10
6
m
3
/s;
air ow rate Q
a
= 694.44 10
6
m
3
/s; and
air pressure p
a
= 0.3 MPa.
After completing the wetting, the process of granulation
was continued until the moment when the granulated mate-
rial started to stick to the drum walls because water had been
pressed off (granulation stage). During this process, samples
T. Gluba / Chemical Engineering and Processing 44 (2005) 237243 239
Fig. 2. Schematic diagram of the equipment for granulation tests: (1)
granulator drum, (2) pneumatic nozzles, (3) engine, (4) inverter, (5) tripod,
(6) rotameters, (7) water tank, (8) compressor, (9) tachometer, (10) torque
meter, (11) reader, and (12) computer.
representative of the whole feed were taken at determined
time intervals. On this basis, progressions of product prop-
erties (granule size, porosity) were obtained. The rst sam-
ple was taken immediately after wetting (granulation time t
g
= 0) and the last one in the moment when water pressed out
to the granule surface made them stick to the inner surface
of the drum preventing further processing in this way (t
g
= t
gmax
). This limiting (maximum) granulation time t
gmax
depended on the mean particle size of the raw material d
m
and feed moisture content w. For the whole process duration
instantaneous values of torque on the granulator shaft were
recorded every 1 s.
4. Results
The results of investigation show that the particle size
distribution of the raw material and wetting of the bed had
a signicant effect on the granulation process and proper-
ties of the product obtained. Changes in the particle size
distribution of the raw material and feed moisture content
caused changes in dynamic parameters of the bed tumbling
in the drum, and in parallel, affected the rate of changes
in product properties (particle size distribution, porosity
of granules), which nally determined the total energy
demand for processing the raw material into granulated
product of specic characteristics. The energy of bed pro-
cessing was calculated taking instantaneous moments M(t)
measured on the granulator shaft and recorded in time in-
tervals equal to 1 s in the whole wetting and granulation
period.
On the basis of the values of torque M(t), the instantaneous
unit torque M
u
(t) from Eqs. (3) and (4)
for the wetting stage:
M
u
(t) =
M(t) M
i
m
s
+Q
w
w
t
(3)
D2
y = 0.025x + 2.07
Wetting segment 2:
y = 0.0011x + 3.76
Granulation 1:
y = 7E-05x + 4.2
Granulation 2 (w=0.147):
y = -2E-12x
4
+ 2E-08x
3
- 8E-05x
2
+ 0.147x - 96.7
2
3
4
5
0 1000 2000 3000 4000 t [ s ]
0 1000 2000 3000
N
u
[
W
/
k
g
]
Wetting
w=0.147
w=0.155
w=0.160
w=0.165
tg [ s ]
Wetting segment 1:
Fig. 3. Change of power demand during granulation.
for the granulation stage:
M
u
(t) =
M(t) M
i
m
b
(4)
and then unit power demand N
u
(t) from Eq. (5).
N
u
(t) = M
u
(t) (5)
were calculated.
Diagrams representing changes in power demand in time
for the entire cycle of granulated material production (wet-
ting and granulation) are shown in Fig. 3.
The relationships N
u
(t) have a characteristic run. During
feed wetting, a rapid linear increase of power demand in the
initial period and then a slow-down of the growth rate could
be observed. In the initial period of the granulation stage,
this relationship is linear too, while at the end some curving
is clearly visible. In the description of power changes on the
particular stages, linear and polynomial functions were used.
Specic energy values E
u
(t) (i.e. energy per unit mass of
the feed) were calculated by integrating the tted equations
over their respective time intervals (Eq. (6)).
E
u
(t) =
t
1
t
0
N
u
(t) dt (6)
Fig. 4 shows examples (for raw material D2) of the ef-
fect of feed moisture content w on the energy necessary to
produce granulated material of specied mean particle di-
ameter.
It is apparent from Fig. 4 that the energy input required for
agglomerate growth decreases as the amount of liquid sup-
plied to the bed during wetting is increased (in a determined
range). Already a small, below 1%, increase of the liquid
supplied during wetting (particularly in the lower range of
moisture content) leads to a signicant decrease of energy
demand (mainly due to a decrease of the required granula-
tion time).
A signicant effect of the amount of added binding liq-
uid on the process of granulation was also shown by other
240 T. Gluba / Chemical Engineering and Processing 44 (2005) 237243
D2
0
4
8
12
0 4 8 12
E
u
[ kJ / kg ]
d
g
m
[
m
m
]
w=0.147
w=0.155
w=0.160
w=0.165
Fig. 4. Energy input for the granule size growth.
authors [1216]. In the period of granulation after wetting,
Wauters et al. [12,13] distinguished two ranges: induction
stage during which the granules are gradually being com-
pacted and little or no growth occurs, and a stage of rapid
growth of granules that follows afterwards. Results of their
studies proved that the duration of the rst period (induction
stage) is a function of the amount of added wetting liquid.
The higher is duration of this period the smaller is the ex-
cess of added liquid over some value of moisture content
called the critical moisture content. The value of this excess
determines also the granule growth rate in the second stage.
Occurrence of these two granulation periods and the im-
pact of feed moisture content on their duration are conrmed
by the present studies.
During bed wetting, comparable energy inputs were ob-
tained for different particle size distributions of the raw
material and moisture contents of the feed. Also, the mean
particle diameter of the feed after this period is very sim-
ilar and does not depend signicantly on the particle size
distribution of the raw material and bed moisture content.
However, these two parameters have a great inuence on
the proceeding of the second stage, i.e. granulation, and
on the rate of changes in the granulated feed properties.
They affect directly the relationships between individual
feed particles, and also interactions between the bed and
the granulator walls, which determine the nature of motion
of the wetted material tumbling in the drum. This is related
to changing properties of the wetted bed and granulated
product on which the character of bed motion and, con-
sequently, the moment necessary to incline the bed and to
cause its circulation necessary to induce the mechanisms of
agglomerate formation, growth and consolidation depend.
An example of energy input necessary for unit growth
of the mean agglomerate size for different feed moisture
content is shown in Fig. 5.
A comparison of energy input necessary for unit growth
of the mean agglomerate size on the stage of granulation
for subsequent particle size distribution of the raw ma-
terial, depending on the feed moisture content is shown
Fig. 5. Energy input for unit growth of mean granule size.
in Fig. 6. Experimental points for particular raw materi-
als can be approximated by a power function with good
accuracy.
The effect of mean particle size of raw material and feed
moisture content on energy input E
u
related to unit incre-
ment of mean particle size d
gm
on the whole stage of gran-
ulation (from t
g
= 0 to t
g
= t
gmax
) is described with good
accuracy (R = 0.96) by the power function of two variables:
E
u
d
gm
= 1.26 10
7
d
m
6.9
w
18.5
(7)
Exponents in the obtained equation reveal a remarkable
effect of the feed moisture content and mean particle size
diameter of the raw material on energy input for the incre-
ment of granule size.
The advancement of drum granulation, beside the size in-
crement, is measured also by the change of the inner struc-
ture of the agglomerates being formed (thickening of par-
ticles), on which, among the other things, their mechanical
strength depends. The rate of these changes determines a
necessary process time and, as a result, affects the energy
of bed transformation. Results of the research provide ev-
idence on a signicant effect of the two tested parameters
also on the rate of changes in the consolidation of particles
in the granules being formed (porosity of the granules), and
in this connection, on energy consumption.
The method of product porosity measurement depended
on the size of product particles. The porosity of granules for
the size fraction d
g
< 4 mm was determined on the basis of
bulk density measurement. The porosity of granules from a
given size fraction was calculated from the formula
g
= 1
gb
(1
m
)
(8)
where:
m
is intergranular porosity;
gb
, bulk density of
granules (kg/m
3
); and , density of ne-grained material
(kg/m
3
).The intergranular porosity was determined from
T. Gluba / Chemical Engineering and Processing 44 (2005) 237243 241
Fig. 6. Energy input for unit growth of granule size.
the equation
m
= 1
gb0
(1
g0
)
(9)
where:
g0
, porosity of granules at the beginning of gran-
ulation (t
g
= 0); and
gb0
bulk density of granules at the
beginning of granulation (kg/m
3
).
On the basis of the measurements, it was found that inner
porosity of granules obtained after wetting (t
g
= 0) did not
depend on the amount of added wetting liquid and for a
given raw material is similar to mean porosity of initial dry
material (Fig. 7).
This means that the density of particle packing in the
granules that were formed in the wetting period corresponds
to the density of particle packing in the raw material of
Fig. 7. Comparison of porosity of granules formed after wetting
g0
with
mean porosity of raw material .
average bulk density
b
. After the wetting period, the bed
contains, beside granules, non-granulated material particles
whose mass depends on the amount of wetting liquid added.
Hence, spaces between the formed granules can be lled up
partly with non-granulated raw material and partly with air.
The investigations proved that bulk density of the bed after
wetting (in dried state) was often lower than the density of
loose raw material.
It was assumed that intergranular porosity
m
for grain
fraction i with narrow intervals did not change during
granulation and was constant for a given raw material:
mi
= constant (10)
The porosity of granules of size 4 mm was determined
on the basis of mass and volume of a dened number of
granules from a given size fraction from the equation:
g
= 1
m
g
V
g
(11)
where: m
g
, mass of granules taken from a size fraction (kg);
and V
g
= V
gi
, total volume of taken granules (m
3
)
The volume of single granules of shape close to spherical
was calculated on the basis of their dimensions in three main
directions, using the formula for ellipsoid. The volume of
granules of shape different from spherical was determined
by the pycnometric method.
On the basis of porosity determined for the granules from
particular size fractions of product samples taken from the
drum in a specic moment, mean porosity of granules was
calculated from the relation
g
(t) =
i=max
i=1
x
i
gi
(t) (12)
where:
g
, mean porosity of granules at granulation time t
g
;
and
gi
, porosity of granules from size fraction i at time t
g
.
242 T. Gluba / Chemical Engineering and Processing 44 (2005) 237243
Fig. 8. Energy input for granule porosity decrease.
Fig. 8 shows examples of unit energy input for the increase
of particle consolidation in the granules (a decrease of mean
granule porosity) for a selected material (D5), at variable
moisture content of the feed.
In Fig. 8, it is clearly visible that the energy required for
consolidation of particles in the newly formed agglomer-
ates decreases with an increase of the bed moisture content.
Porosity of the granules obtained at the end of the process is
similar for all moisture contents of the feed for a determined
particle size distribution of the raw material. Similar rela-
tionships were obtained for other particle size distributions
of the raw material. Fig. 9 illustrates energy input related
to a unit increment of particle consolidation ( = 1
g
) in
the granules produced from particular raw materials during
granulation (a unit decrease of granule porosity), depending
on the feed moisture content.
The effect of mean particle diameter of the raw material
and feed moisture content on energy input as related to unit
Fig. 9. Energy input for the increase of particle condensation in granules.
decrease of agglomerate porosity during granulation is de-
scribed by the power function of two variables. As a result
of regression, the following equation at correlation coef-
cient R = 0.95 was derived:
E
u
= 5.2 10
5
d
m
3.4
w
15.4
(13)
5. Conclusions
The equations describing the energy input for the incre-
ment of agglomerate size and the rate of particle consolida-
tion in it during granulation prove that the greatest impact
has the amount of wetting liquid supplied to the bed dur-
ing wetting (feed moisture content), and slightly lowerthe
mean particle size of the raw material. Even a slight increase
of the quantity of wetting liquid added (in the range se-
lected for each particle size distribution of the raw material)
causes a signicant decrease of energy input required for
the transformation of wetted powder material into a granu-
lated product. This refers both to the increase of agglomerate
size and the consolidation of its inner structure. These two
phenomena take place in parallel, so the energy inputs can-
not be distributed to each of them. Besides, not whole en-
ergy input is used for the processes of granules growth and
their consolidation. Part of it is used for destructive mech-
anisms occurring in the tumbling bed, and a part is trans-
formed into heat. However, by selecting for a given particle
size distribution of the raw material an adequate quantity
of the wetting liquid, much energy savings can be reached
in the process of transforming the powder into a granulated
product.
The main issue of every technological process is its
optimisation. Also in the process of ne-grained material
granulation, there is a problem of optimisation of outlays
necessary to form a product of dened, most desirable
properties such as granule size, particle composition, homo-
geneity of the composition, porosity, mechanical strength,
binding agent content, solubility, etc. In many cases, it is
related to the selection of appropriate wetting conditions,
in particular the amount of wetting liquid added. This is a
very complex problem, depending on specicity of a given
process and requiring an individual approach. As proven
by results of the presented research, the addition of a larger
amount of wetting liquid to the ne-grained material causes
a decrease of energy input necessary to produce the granu-
lated material. This increase, however, has also an inuence
on changes in product properties that cause formation of
bigger particles with higher moisture content. If such a
product is to be dried, it becomes necessary to provide more
thermal energy. In this case, a reduction of energy input is
not obvious. An increase of the amount of wetting liquid
can also induce some disturbances in the process run re-
lated to feed overwetting (sticking to the drum walls). This
is particularly important for materials whose granulation
proceeds in a very narrow range of moisture content. Addi-
T. Gluba / Chemical Engineering and Processing 44 (2005) 237243 243
tionally, an increase of liquid content in the granulated bed
causes that the increment of granule size at the rapid growth
stage becomes more vehement, which can sometimes make
the process control difcult and consequently result in an
excessive growth of particles. As was shown in the investi-
gations, an important indicator of the granulation process is
the torque measured on the apparatus shaft. The changes of
torque during the granulation can indicate advance of the
process and may facilitate its control.
Acknowledgements
The work was carried out under research project no.
W-10/21/2003/B.W.
Appendix A. Nomenclature
d particle size of raw material (m)
d
g
particle diameter of granulated product (mm)
d
gm
mean particle diameter of granulated product (mm)
d
i
mean particle size of class i (m)
d
m
mean particle size of raw material (m)
E
u
unit energy during granulation (kJ/kg)
m
b
mass of wetted feed in the drum (kg)
M
i
the torque of idle run (at empty granulator) (Nm)
m
s
mass of dry material in the drum (kg)
M
u
unit torque (Nm/kg)
N
u
unit power demand (W/kg)
t time (s)
t
g
granulation time (s)
t
gmax
limiting (maximum) granulation time (s)
x
i
percentage of mass fraction
w moisture content of the feed, kg water/kg
dry material
1
asymmetry coefcient
mean porosity of raw material
g
porosity of granules (intra-granular porosity)
m
intergranular porosity
density of ne-grained material (kg/m
3
)
b
mean bulk density of raw material (kg/m
3
)
bc
bulk density of condensed raw material (kg/m
3
)
bl
bulk density of loose raw material (kg/m
3
)
gb
bulk density of granules (kg/m
3
)
w
density of water (kg/m
3
)
standard deviation
rotational speed of the granulator (1/s)
mean particle consolidation in the granules
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Chemical Engineering and Processing 44 (2005) 245252
Control of aggregation in production and handling of nanoparticles
Wolfgang Peukert
a,
, Hans-Christoph Schwarzer
b
, Frank Stenger
b
a
Institute of Particle Technology, Universitt ErlangenNrnberg, Cauerstr. 4, 91058 Erlangen, Germany
b
Institute of Particle Technology, Technische Universitt Mnchen, Boltzmannstr. 15, 85748 Garching, Germany
Received 22 July 2003; received in revised form 15 December 2003; accepted 11 February 2004
Available online 2 July 2004
Abstract
In product engineering of particulate systems, the property function relates the dispersity to the product properties, whereas the process
function shows how to produce the required dispersity. These principles are applied to the production of nanoparticles. Nanoparticles are
controlled by surface forces. Due to their high mobility nanoparticles are unstable and may coagulate rapidly if the particles are not stabilized.
Stabilization is achieved by tailoring the particulate surfaces, e.g. through repulsive double layer forces. Macroscopic properties are thus
controlled by microscopic control of the interfaces, i.e. we bridge the gap between the molecular level and material properties. These principles
are generally valid and are thus applied to precipitation and to nanomilling in stirred ball mills. The mean particle size in precipitation can be
controlled by either the mixing intensity or the surface charge density of the particles. In stirred media mills oxide particles as small as 10 nm
can be achieved by stabilizing the particles appropriately.
2004 Elsevier B.V. All rights reserved.
Keywords: Nanoparticle; Aggregation; Stabilization; Precipitation; Milling
1. Concept of product engineering
The production of substances with well-dened product
properties under consideration of economical and ecological
boundary conditions is the objective of many processes. For
particulate materials, the product properties depend not only
on the chemical composition but also on the dispersity of the
material. The dispersity is characterized by the particle size
distribution, the particles shape and morphology as well as
their interfacial properties. This relation was called property
function by Rumpf [1]. The control of the property function
is known as product engineering or product design.
Property function :
Product property = f(dispersity, chemical composition)
where dispersity is characterized by particle size and shape
and their respective distribution, particle morphology and
particle surface properties.
The property function relates the particulate structure
(size, shape, morphology, surface) to the product proper-
0
=
2kT
3
(x
1
+x
2
)
_
1
x
1
+
1
x
2
_
(1)
Sedimentation [7]:
0
=g
_
_
x
1
2
_
2
+
_
x
2
2
_
2
__
1
F
P
_
_
x
1
2
_
2
_
x
2
2
_
2
_
2
P
9
_
(2)
Laminar shear [6]:
0
=
4
3
_
x
1
2
+
x
2
2
_
3
(3)
Turbulent shear [8]:
0
=
_
8
15
_
x
1
2
+
x
2
2
_
3
_
_
1/2
(4)
In these equations, x
1
and x
2
denote the particle sizes of the
colliding particles, T the absolute temperature, k the Boltz-
mann constant, the dynamic viscosity of the uid,
F
the
density of the uid,
P
the density of the particle, the lo-
cal shear rate and the local mass-specic power input due
to turbulence.
Fig. 2 compares collision kernels calculated for a 250 nm
particle as function of the collision partner size for Brown-
ian motion, laminar and turbulent shear ows as well as sed-
imentation at 25
P
_
1/D
F
(5)
In this equation m represents the mass of the aggregate and
P
the density of the aggregate material. Recent small angle
neutron scattering (SANS) measurements have shown that
the fractal dimension of aggregates increases from 1.8 for
Brownian diffusion to values in the range of 2.2 when shear
forces prevail [9]. Thus, higher external forces lead to denser
aggregates (e.g. caused by compaction) and the aggregate
structure depends on aggregation mechanism.
In order to take particleparticle interactions into account,
a stability ratio W is included which relates the collision ker-
nel
0
to the aggregation kernel
agg
. The stability ratio W
depends on the interaction potential (r) and is dened as
ratio of the aggregation rate without to the rate with inter-
actions additional to the omnipresent van der Waals forces.
For Brownian motion as dominant reason for collisions, the
stability ratio W can be calculated according to Eq. (6) taken
from Fuchs [10]. In case of shear as aggregation mechanism,
the force d/dr relative to the friction force should rather be
considered instead of the ratio of interaction energy relative
to thermal energy.
agg
=
0
W
=
0
x
_
x
(1/r
2
)exp((r)/kT) dr
(6)
Particles can either be produced by bottom-up pro-
cesses (e.g. precipitation) or topdown approaches (e.g.
wet milling). In these processes particleparticle interac-
tions become relevant when the particle size is below 1 m.
Engineering macroscopic product properties is then only
possible through tailored surface and interfacial properties,
no matter whether a bottomup process like precipitation
[11] or a topdown process such as milling in stirred media
mills [12] is studied. Aggregation is an important aspect in
both processes which are studied in the following.
In precipitation, particle formation is extremely fast due
to high supersaturations which in turn lead to fast nucleation.
At least in the beginning, size distributions are narrow with
particle sizes around one 1 nm. Nanomilling in stirred media
mills is characterized by relatively slow particle formation
kinetics, particle sizes ranging from several microns down
to 10 nm and high solids volume concentrations of up to
40%. Large particles may scavenge the ne fractions. The
evolution of the particle size distribution can be described
for both cases by population balance equations (Eq. (7)),
248 W. Peukert et al. / Chemical Engineering and Processing 44 (2005) 245252
which superposes the terms for nucleation, growth, grinding
and aggregation.
n(x)
t
=B
hom
(x
n
)
. ,, .
nucleation
+ G
dn
dx
. ,, .
growth
+B
agg
(n, x) D
agg
(n, x)
. ,, .
aggregation
S(x)n(x) +
_
x
max
x
S(y)n(y)b(x, y) dy
. ,, .
grinding
(7)
In this equation B
hom
represents the nucleation rate at which
nuclei of size x
n
are formed. G is the linear growth rate and
B
agg
as well as D
agg
are the well-known expressions for the
birth and death rate of aggregation [7], given below. Within
Eq. (7) S(y) is the selection function describing the relative
amount of particles with size y breaking within a time step
dt. The breakage function b(x, y) describes the number of
fragments with size x produced per breaking particle y.
B
agg
(n, x)
=
x
2
2
_
x
0
agg
_
3
x
3
3
,
_
n
_
3
x
3
3
_
n()
(x
3
3
)
2/3
d
(8)
D
agg
(n, x) = n(x)
_
0
agg
(x, )n() d (9)
The kinetics of stabilization must match the kinetics
of aggregation. While ion diffusion and adsorption is fast
(electrostatic stabilization), the diffusion and adsorption of
polymers (steric stabilization) is slow and may be a limit-
ing factor which can only be overcome by applying high
polymer concentrations. The stability of the electrostatic
stabilized suspension in moderately fast processes can for
example be monitored and controlled in-line by modern
electro-acoustic techniques [13].
4. Stabilization during precipitation
In the conducted experiments, barium and sulfate solu-
tions were mixed continuously in a T-mixer resulting in a
supersaturated mixture and consequently the formation of
barium sulfate particles. Apart from educt concentrations it
was found that the intensity of mixing has a strong inu-
ence on the resulting particle size distribution [11,14] in the
nanometer range. The more intense the mixing, the smaller
the particles. The reason for this behavior lies in the differ-
ent dependencies of nucleation and growth rates on super-
saturation, the thermodynamic driving force of solid forma-
tion. With increasing supersaturation, the nucleation rate as
a highly non-linear function increases much stronger than
the growth rate. As a consequence, considerably more parti-
cles are formed at higher supersaturations. The increase is so
strong that even if higher supersaturations were achieved by
higher initial concentrations, smaller particles would result.
While nucleation and growth act as supersaturation sink,
mixing can be considered as supersaturation source. Con-
sequently, the time scale of mixing must t the time scale
of particle formation, i.e. mixing must be at least as fast as
precipitation, and thus highly turbulent mixing is required
for nanoparticle generation.
The precipitation process was simulated based on the
population balance equation (Eq. (7) without the grinding
terms) coupled via mass and species balances with a mixing
model based on the Engulfment model of micromixing by
Baldyga and Bourne [15]. The modications of the mixing
model are described in [14]. The particle formation is mod-
eled through homogeneous nucleation based on the classical
description and diffusion-controlled growth (for details see
[16]). The aggregation of particles is modeled by Eqs. (4), (8)
and (9). As solver for the population balance equation, the
commercial software PARSIVAL by CiT GmbH was used.
The implemented algorithm ts the particle size distribu-
tion by polynomials based on a nite-element type Galerkin
h-p-method optimizing the number of variables (number of
polynomials, order of polynomials) and applies an adaptive
time discretization of Rothes type. Details on the simula-
tion algorithm can be found in [17]. Besides computational
speed, the main advantages of the Galerkin h-p-method are
that no assumptions concerning the shape of the particle
size distribution are necessary and that the overall accuracy
can be estimated quantitatively from the mass defect during
simulation. Simulations of the precipitation process includ-
ing mixing are promising and the number-weighted mean
particle size can be predicted very well by taking into ac-
count mixing, nucleation, particle growth and aggregation.
It is currently worked at an advanced approach that com-
prises computational uid dynamics (CFD) modeling cou-
pled with mixing and the solution of the population balance
accounting for nucleation, growth and aggregation in order
to improve the prediction of the width of the particle size
distribution.
Simulation results of a precipitation process as presented
in Fig. 3 clearly showthe different time scales of mixing, par-
ticle formation and aggregation. Fig. 3 also shows the range
of aggregation for the mentioned conditions and thus the
possible range of particleparticle interactions. Depending
on stabilization conditions, i.e. for stability ratios W ranging
from 1 (no repulsive interaction) to innity, very different
particle sizes (distributions) are obtained even at times in the
range of milliseconds. Thus, the aggregation of nanoparti-
cles is a challenge to be met on time-scales of milliseconds
when controlling or tailoring particle size distributions in
precipitation. This is also depicted in Fig. 4, showing sim-
ulation results of the volume-weighted particle size for dif-
ferent mixing and aggregation conditions. Since fast mixing
requires highly turbulent ows, it comes along with signif-
icant turbulent aggregation. In the presented calculations a
constant stability ration of W = 1 and aggregation only in
the mixer was considered (i.e. during the mean residence
W. Peukert et al. / Chemical Engineering and Processing 44 (2005) 245252 249
precipitation duration in s
10
-6
10
-5
10
-4
10
-3
10
-2
10
-1
s
u
p
e
r
s
a
t
u
r
a
t
i
o
n
S
0
200
400
600
800
1000
1200
m
e
a
n
(
v
o
l
u
m
e
)
p
a
r
t
i
c
l
e
s
i
z
e
i
n
n
m
0
20
40
60
80
100
120
particle size,
no aggregation
(W)
particle size,
aggregation (W=1)
aggregation
particle
formation
mixing &
supersaturation
build-up
r
a
n
g
e
supersaturation
Fig. 3. Time scales in precipitation calculated for BaSO
4
precipitated from
0.5 m BaCl
2
- and 0.33 m H
2
SO
4
-solutions at 25
C. To quantify mixing,
a specic power input typical for the applied T-mixer ( = 10
3
W/kg)
was used.
time), which leads to a residence time effect (the faster the
ow through the mixer, the larger the specic power input
but shorter the residence time). As can be seen, particle sizes
well in the micrometer range can easily be reached within
milliseconds and that the inuence of turbulent aggregation
can be controlled (besides stabilization) by the duration of
aggregation. Latter, however, only applies to turbulent aggre-
gation. Aggregation due to Brownian motion must be con-
trolled by stabilization since the resulting aggregates would
reach the micrometer range within seconds.
Concerning aggregation kinetics and stabilization it was
found in case of barium sulfate that barium ions adsorb more
readily than sulfate ions [11]. Thus, increasing the ratio R of
barium to sulfate ions in the educt composition and thereby
increasing the excess of barium ions after precipitation leads
to high surface potentials and stabilization. Fig. 5 shows
measured particle size distributions of continuously precip-
itated barium sulfate, measured based on quasi-elastic light
scattering (UPA 150 by Microtrac) within 3 min after pre-
particle size in nm
20 100 1000 6000
c
u
m
u
l
a
t
i
v
e
v
o
l
u
m
e
d
i
s
t
r
i
b
u
t
i
o
n
0.0
0.2
0.4
0.6
0.8
1.0
R = 10
R = 3.0
R = 2.0
R = 1.5
R = 1.2
R = 1.1
R = 1.0
excess of
barium ions
out of
measurement
range
Fig. 5. Measured particle size distributions of precipitated barium sulfate showing the inuence of the barium to sulfate initial ratio R on stability and
aggregation, respectively.
residence time in ms
50 20 10 5 2 1 0.5
mean specific power input in W/kg
10
0
10
1
10
2
10
3
10
4
10
5
10
6
10
7
m
e
a
n
(
v
o
l
u
m
e
)
p
a
r
t
i
c
l
e
s
i
z
e
i
n
n
m
0
200
400
600
800
1000
1200
1400
turbulent, W=1
no agglomeration
Brownian, W=1
s
t
a
b
i
l
i
z
a
t
i
o
n
r
a
n
g
e
residence
time
Fig. 4. Simulated inuence of aggregation and stabilization in nanoparticle
precipitation.
cipitation. The theoretically calculated supersaturation (as-
suming ideal mixing) was kept constant in all experiments
while the initial molar ratio R of barium to sulfate ions was
altered. Operating parameters such as ow rate and mixer
geometry were kept constant. Thus, it can be assumed that
mixing, the build-up of supersaturation and solid formation
were similar in all cases and that possible small variations
cannot account for the measured differences. Hence, the sig-
nicant differences in particle size distributions are due to
the altered particleparticle interactions and the resulting al-
tered stabilization. As the barium excess is increased, so
is the stability against aggregation. Thus, particle size and
eventually aggregate structure of a precipitation process can
be adjusted to t needs.
Recent investigations [18] to quantify stabilization were
successful in correlating to observed stability of colloidal
barium sulfate suspensions with the suspension compo-
sition and in particular the concentrations of Ba
2+
- and
250 W. Peukert et al. / Chemical Engineering and Processing 44 (2005) 245252
duration in s
10
0
10
1
10
2
10
3
10
4
10
5
10
6
m
e
a
n
(
v
o
l
u
m
e
)
p
a
r
t
i
c
l
e
s
i
z
e
i
n
n
m
0
100
200
300
400
R = 1.3
D = 1.25
R = 1.5
D = 100
R = 1.5
D = 20
R = 2
D = 80
Fig. 6. Comparison of experimental data and simulation results predicting
the evolution of mean particle size for different suspension compositions
characterized by the initial molar ratio R prior to precipitation and the
dilution ratio D after precipitation.
H
+
-ions. These ions adsorb on barium sulfate and thereby
determine the surface properties, i.e. the surface charge
which is relevant to aggregation kinetics, since the result-
ing repulsive particleparticle interactions lead to increased
stability against aggregation. Fig. 6 shows a comparison
of experimental data and the predicted evolution of the
volume-weighted mean particle size with time for vari-
ous compositions (characterized by the initial molar ratio
R and the dilution ratio D after precipitation), showing
a good agreement. Thus, the general concept presented
in Section 2 is found appropriate to describe, model
and control aggregation and stabilization in nanoparticle
precipitation.
5. Stabilization during wet milling
It has been shown recently in a cooperation with the
Schwedes group [12] that alumina can be ground to 10 nm
particles if particle aggregation is carefully controlled by the
principles discussed in this paper and appropriate milling pa-
rameters. Fig. 7 compares experimental results of milling ex-
periments of -alumina at a concentration of c
m
= 20 wt.%
in a continuously operated 1 l Drais mill with simulation
results. In the experiment -potential was characterized on-
line by electro-acoustic spectroscopy and particle stabil-
ity was controlled through pH-adjustment (10 M HNO
3
).
The simulation results were derived for a combined pop-
ulation balance model for aggregation and breakage based
on Eq. (7).
Within Eq. (7), the selection function S(y) was approx-
imated by S(y) = Ky
c
with adjustable parameters K and c
and the breakage function b(x, y) was simply modeled by
a triangular shaped function between a minimal breaking
particle size of x
0
= 25 nm and x with a modal value at
time in s
10
4
10
5
p
a
r
t
i
c
l
e
s
i
z
e
x
5
0
,
3
i
n
m
0.01
0.1
1
turbulent shear, = 400 W/kg
stability
factor
pure breakage
pH = 5.1
pH = 7.8
simulation
pH = 4.1
Fig. 7. Comparison of mean particle size obtained in a wet milling of
-alumina (c
m
= 0.2) with the results of a population balance model.
x
0
+(y x
0
)/3 full-lling the mass conservation equation.
In a rst simulation step the pure grinding process was
modeled and the parameters of the selection function c and
K were adjusted for particles >1 m (K = 1500 s
1
m
c
,
c = 0.41). With the assumption of a constant grinding
behavior for particles <1 m, the system of differential
equations for grinding and aggregation was solved. Sim-
ulations for grinding and turbulent shear were carried out
to adjust a constant, size-independent stability ratio W to
the experimental data. Again, the system of differential
equations was solved by the above-mentioned software
PARSIVAL.
As can be seen the numerical simulations describe the
observed grinding behavior and the inuence of different
suspension stability conditions reasonably well, although
quite stringent assumptions were made in our model. This
supports the theory that the sub-micron grinding process is
strongly inuenced by suspension stability. In Fig. 8 a com-
parison of the cumulative mass distribution for the grind-
ing experiment conducted at pH 5.1 and the simulation re-
sults are presented. Again a reasonable agreement between
particle size x in m
0.01 0.1 1 10 100
c
u
m
u
l
a
t
i
v
e
m
a
s
s
d
i
s
t
r
i
b
u
t
i
o
n
Q
3
0.0
0.2
0.4
0.6
0.8
1.0
0 min
15 min
20 min
30 min
60 min
120 min
240 min
480 min
1620 min
2280 min
pH = 5.1
W = 2.9
.
10
7
Fig. 8. Comparison of the cumulative mass distribution Q
3
obtained by
wet milling of -alumina (c
m
= 0.2, pH 5.1) at different grinding times
with simulation results.
W. Peukert et al. / Chemical Engineering and Processing 44 (2005) 245252 251
simulation (lines) and experiment (symbols) is achieved es-
pecially for short and very long grinding times. Differences
at the edges of the distributions for intermediate grinding
times can be explained with the fact that the experimen-
tal particle size distributions could not be determined with
one single method over the entire time of the experiment.
While a static light scattering instrument (Malvern Master-
Sizer 2000) was used for particle sizes >1.0 m smaller par-
ticles were analyzed by the method of quasi elastic light
scattering (UPA 150 by Microtrac).
6. Conclusions
Nanoparticles produced by precipitation and by wet
milling must be stabilized against aggregation. This can be
achievedas shown in the presented examples by experi-
ment and simulationby microscopic control of particulate
interfaces, i.e. by the particle surface charge density and
the electrostatic repulsion. Thus, the overall concept of
controlling the microscopic properties in order to tailor the
macroscopic behavior was demonstrated. In this paper, we
show how generally applicable concepts derived from col-
loid and surface science can successfully be applied to a
variety of different unit operations. We thus transcend the
traditional view of the unit operations concept in Chemi-
cal Engineering in two ways: rst, we introduce concepts
which are applicable to various unit operations and thus
open a new engineering point of view for the design of
such systems. Second, we include the material inuence
based on a sound physical understanding of the underlying
molecular phenomena.
Appendix A. Nomenclature
B
agg
birth rate of aggregation (m
4
s
1
)
B
hom
nucleation rate (m
3
s
1
)
b breakage function (m
1
)
c constant in selection function ()
c
m
mass fraction ()
D dilution ratio ()
D
agg
death rate of aggregation (m
4
s
1
)
D
F
fractal dimension of particles (aggregates) ()
G linear growth rate (m/s)
g gravitational constant, g = 9.81 m/s
2
(m/s
2
)
K constant in selection function (s
1
m
c
)
k Boltzmann constant, k = 1.381 10
23
J/K (J/K)
m particle mass (kg)
n number density concentration (m
4
)
pzc point of zero charge
R molar ratio of barium to sulfate ions prior
to precipitation ()
r center-to-center distance of particles (m)
S breakage function (s
1
)
T temperature (K)
t time (s)
W stability ratio ()
x particle size (diameter of volume-equivalent
sphere) (m)
x
0
minimal fracture size (m)
x
n
size of nuclei (m)
x
c
collision diameter of aggregates (m)
x
max
size of largest particles (aggregates) (m)
y particle size (m)
z surface-to-surface distance of particles (m)
Greek symbols
0
collision kernel (m
3
/s)
agg
aggregation kernel (m
3
/s)
shear rate (s
1
)
mass-specic power input (W/kg)
dynamic viscosity (Pa s)
F
uid density (kg/m
3
)
P
density of particle material (kg/m
3
)
particleparticle interaction potential energy (J)
0
surface charge density (C/m
2
)
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Chemical Engineering and Processing 44 (2005) 253261
Effect of different types of impact surface on coal degradation
R.K. Sahoo
, D. Roach
Faculty of Engineering and Physical systems, Central Queensland University, Rockhampton, QLD, Australia
Received 1 August 2003; received in revised form 25 December 2003; accepted 11 February 2004
Available online 25 June 2004
Abstract
Degradation characteristics of South Blackwater and Ensham coal from the stockpiles of Gladstone Port Authority were tested by using
a drop tests apparatus to minimise the nes generation during transport and handling through the Port Authoritys ship loading facilities.
Non-cushioned coal sample of both types of coal dropped on different impact surfaces produced higher percentage of nes than the sample
of cushioned coal, initial 10% nes, initial 30% nes and initial 50% nes. The effect of different types of surfaces onto which the coal was
dropped with initial nes was determined by dropping onto a steel surface, conveyor surface and coal surface (stockpile). The results showed
that the tests with initial 30% nes with lump coal has no signicant difference of nes generation in between the three impact surfaces. Both
types of coal with initial 10%nes dropped on steel surface produced more nes than conveyor and coal surface. The cushioning effect of nes
on coal impact surface was least compare to other two impact surfaces. The degradation model was used satisfactorily for South Blackwater
coal on different impact surfaces.
2004 Elsevier B.V. All rights reserved.
Keywords: Cushioning effects; Degradation; Mean particle size; Types of impact surface
1. Introduction
South Blackwater and Ensham coal are shipped from
Gladstone port in QLD, Australia to the Jindal COREX
plant in India. The COREX process is a unique and modern
process of iron making that has many distinct advantages
over the conventional blast furnace iron making process.
The COREX process does not required coking coal and uses
only thermal coal for generating heat, reduction gas and ade-
quate permeability. The properties of South Blackwater and
Ensham coal used in the Jindal COREX plant are given in
Table 1.
The Mean particle size (MPS) of coal is an important
factor for the COREX Process because a decrease in the
MPS reduces the permeability of the char bed resulting in
gas channelling, which drops the hot metal temperature and
quality. To maintain consistency, the MPS of the coal should
be maintained within 2030 mm, which is a very important
factor for efcient plant operation. The COREX technology
coal should be sized at +16 mm with a top size as high as
7080 mm. Fines coal (16.0 mm) included with the sized
coal is separated at the COREX steel mill and used for either
1/2
i
=
(h h
0
)
g1
s
g2
i
i
(CN)
g3
(1)
where
i
is the mass of size s
i
that is broken when unit mass
of particles of the size s
i
is dropped from a height h.
i
and
CN are the mean tensile strength and mean co-ordination
number for particles of size s
i
respectively, and , h
0
, g1, g2
and g3 are model parameters.
For unit mass of particle of size s
i
, the amount remaining
is (1
i
). The broken mass
i
, appears in smaller sizes and
the distribution of this mass can be described by using an
appropriate breakage distribution function of Austin et al.
[7]:
B
Sj,Si
=
_
s
j
s
i
_
+(1 )
_
s
j
s
i
_
(2)
where , and are parameters and B
Sj,Si
is the mass frac-
tion of material of size s
j
or smaller resulting from breakage
of particles of initial size s
i
.
Their analysis of experimental data shows that tensile
strength was the only parameter that varied as a function
of particle size. Model simulation indicate that larger lumps
were stronger than smaller lumps which is contradictory to
Waters et al. [8], Teo and Waters [9], and Grifth [10] the-
ory of fracture, which implies that larger particle are more
likely to contain larger cracks and hence be more suscepti-
ble to breakage.
Waters et al. [5] stated that the presence of iron ore nes
in the test sample at levels greater than 10% by mass had a
cushioning effect, which reduced lump breakage during drop
tests. They also observed that the amount of degradation
was not signicantly different, when lump iron ore drop on
different impact surface.
3. Experimental procedure
A ve-meter drop tower was used to drop the coal lumps
on different impact surfaces shown in Fig. 1. The differ-
ent impact surfaces are steel plate, conveyor belt and coal
stockpile. The details development of the drop tower was
Polythene envelope
Steel plate (2 m 2 m 3 mm)
1
5
c
m
7
0
c
m
40 cm
2 m
Fig. 1. Line diagram of drop tower.
R.K. Sahoo, D. Roach / Chemical Engineering and Processing 44 (2005) 253261 255
discussed in Sahoo et al. [2]. The drop tower was enclosed
in plastic sheeting to protect the loss of coal nes due to
external winds during drop. The coal was containing in the
released hopper with a bottom release that allowed the coal
to be dropped from various heights.
Samples of South Blackwater and Ensham coal of
+16.0 mm size were collected separately, from the stock-
piles of the Gladstone Port. Before testing, both types of
coals were sieved to obtain a 76.2 + 50.8 mm sized sam-
ples for the drop tests. The sample was placed inside the
released hopper, which was raised by overhead crane. A
sample of 10 kg was dropped each time onto an enclosed
horizontal steel plate, conveyor belt and coal stockpile. The
dropped coal was sieved to remove the nes (16.0 mm
size). In this way the percentage of nes produced at each
drop were determined. The calculation methodology for
nes percentage was given in Sahoo et al. [2].
Experiments were carried out to determine the reduction
of lump coal degradation due to the presence of coal nes
(16.0 mm) with the lumps at the different impact surfaces.
Cushioning effects of nes consists of ve different types
of tests are as follows.
3.1. Non-cushioned coal
Non-cushioned coal is a coal sample having an initial
size range 76.2 + 50.8 mm, which was used for repeated
drops, and has the nes component (16.0 mm size fraction)
removed after each drop.
3.2. Cushioned coal
Cushioned coal is a coal sample having initial size range
76.2 + 50.8 mm, which was used for repeated drops, but
does not remove the nes component after each drop.
3.3. Initial 10% nes
It is a coal sample containing 90% mass of sample to be
dropped of size range 76.2 + 50.8 mm and a 10% mass of
sample of nes of 16.0 mm size fraction.
3.4. Initial 30% nes
It is a coal sample containing 70% mass of sample to be
dropped of size range 76.2 + 50.8 mm and a 30% mass of
sample of nes of 16.0 mm size fraction.
3.5. Initial 50% nes
It is a coal sample containing 50% mass of sample to be
dropped of size range 76.2 + 50.8 mm and a 50% mass of
sample of nes of 16.0 mm size fraction.
South Blackwater Coal, Steel Surface
0
10
20
30
40
50
0 1 2 3 4 5 6
Number of drops
C
u
m
u
l
a
t
i
v
e
P
e
r
c
e
n
t
a
g
e
o
f
f
i
n
e
s
Non-cushioned coal
Cushioned coal
Initial 10% fines
Initial 30% fines
Initial 50% fines
Fig. 2. Cumulative percentage of 16.0 mm nes vs. number of drops of
ve types of cushioning tests of South Blackwater coal on steel surface.
4. Results and discussion
4.1. Cushioning tests of two types of coal on three different
impact surfaces
4.1.1. Steel surface
The cushioning effects of nes of South Blackwater and
Ensham coal tested on steel surface at 5 m drop height
were shown in Figs. 2 and 3. Data for the Fig. 2 are given
in Table 2. The result of these gures shows that, there
was a signicant difference of nes percentage between the
non-cushioned and cushioned coal sample. Non-cushioned
coal sample of South Blackwater coal dropped on steel sur-
face produced 12% more nes than a cushioned coal sam-
ple, 13.3% more nes than a sample of initial 10% nes,
27.5% more nes than a sample of initial 30% nes and
30.9% more nes than a sample of initial 50% nes at 30 m
total drops (six drops at 5 m) shown in Fig. 2.
At 5 m drop height non-cushioned coal sample of Ensham
coal dropped on steel surface produced 11% more nes than
a cushioned coal sample, 15.7% more nes than a sample of
initial 10% nes, 26.3% more nes than a sample of initial
30% nes and 29.8% more nes than a sample of initial
50% nes at 30 m total drops shown in Fig. 3.
Fig. 2 shows that the cushioned coal sample of South
Blackwater coal dropped on steel surface produced 1.3%
Ensham Coal, Steel Surface
0
10
20
30
40
50
0 1 2 3 4 5 6
Number of drops
C
u
m
u
l
a
t
i
v
e
p
e
r
c
e
n
t
a
g
e
o
f
f
i
n
e
s
Non-cushioned coal
cushioned coal
initial 10% fines
initial 30% fines
initital 50% fines
Fig. 3. Cumulative percentage of 16.0 mm nes vs. number of drops of
ve types of cushioning tests of Ensham coal dropped on steel surface.
256 R.K. Sahoo, D. Roach / Chemical Engineering and Processing 44 (2005) 253261
Table 2
Cumulative percentage of 16.0 mm nes of ve types of cushioning tests of South Blackwater coal dropped on steel surface from 5 m height
Number of drops Cumulative percentage of 16.0 mm nes of South Blackwater coal
Non-cushioned coal Cushioned coal Initial 10% nes Initial 30% nes Initial 50% nes
1 7.4 6.2 5.7 2.0 0.9
2 15.0 12.4 11.3 5.1 2.6
3 22.5 18.1 15.9 7.0 4.4
4 29.7 21.7 20.4 10.1 6.7
5 36.0 26.4 25.4 12.1 9.3
6 41.7 29.7 28.4 14.2 10.8
South Blackwater Coal, Conveyor Surface
0
5
10
15
20
25
30
35
0 1 2 3 4 5 6
Number of Drops
C
u
m
u
l
a
t
i
v
e
P
e
r
c
e
n
t
a
g
e
o
f
F
i
n
e
s
Cushioned coal
Initial 10% fines
Initial 30% fines
Fig. 4. Cumulative percentage of 16.0 mm nes vs. number of drops
of three types of cushioning tests of South Blackwater coal dropped on
conveyor surface.
more nes than a sample of initial 10% nes, 15% more
nes than a sample of initial 30% nes and 19% more nes
than a sample of initial 50% nes at 30 m total drops. The
cushioned coal sample of Ensham coal dropped on steel
surface produced 5% more nes than a sample of initial 10%
nes, 16% more nes than a sample of initial 30% nes and
19% more nes than a sample of initial 50% nes at 30 m
total drops shown in Fig. 3.
4.1.2. Conveyor surface
Fig. 4 shows that the cushioned coal sample of South
Blackwater coal dropped on conveyor surface produced
0.5% more nes than a sample of initial 10% nes and
8.3% more nes than a sample of initial 30% nes at 30 m
total drops. At 5 m drop height the cushioned coal sample of
Ensham coal dropped on conveyor surface produced 4.5%
more nes than a sample of initial 10% nes and 12% more
nes than a sample of initial 30% nes at 30 m total drops
Table 3
Cumulative percentage of 16.0 mm nes of three types of cushioning tests of two types of coal on conveyor belt surface from 5 m height
Number of drops Percentage of 16.0 mm nes of South Blackwater coal Percentage of 16.0 mm nes of Ensham coal
Cushioned coal Initial 10% nes Initial 30% nes Cushioned coal Initial 10% nes Initial 30% nes
1 3.4 2.8 1.2 4.1 2.6 1.2
2 7.7 6.9 3.2 8.5 6.1 3.1
3 11.6 10.9 5.5 12.8 10.1 5.3
4 15.1 14.3 8.5 16.6 13.5 8.2
5 17.4 17.1 11.6 19.9 16.2 10.5
6 21.2 20.7 12.9 23.9 19.4 12.2
Ensham Coal, Conveyor Surface
0
5
10
15
20
25
30
35
Number of Drops
C
u
m
u
l
a
t
i
v
e
P
e
r
c
e
n
t
a
g
e
o
f
F
i
n
e
s
Cushioned coal
Initial 10% fines
Initial 30% fines
0 1 2 3 4 5 6
Fig. 5. Cumulative percentage of 16.0 mm nes vs. number of drops
of three types of cushioning tests of Ensham coal dropped on conveyor
surface.
shown in Fig. 5. The data for the Figs. 4 and 5 are given in
Table 3.
4.1.3. Coal surface
Fig. 6 shows that the cushioned coal sample of South
Blackwater coal dropped on coal surface produced 1.3%
more nes than a sample of initial 10% nes and 4.3% more
nes than a sample of initial 30% nes at 30 m total drops.
The cushioned coal sample of Ensham coal dropped on coal
surface produced 2% more nes than a sample of initial
10% nes and 4.5% more nes than a sample of initial 30%
nes at 30 m total drops shown in Fig. 7. The data for the
Figs. 67 are given in Table 4.
The results of cushioning effects of both types of coal in
Figs. 6 and 7 shows that the initial nes with lump coal does
not reduce much nes generation when dropped on coal
R.K. Sahoo, D. Roach / Chemical Engineering and Processing 44 (2005) 253261 257
South Blackwater Coal, Coal Surface
0
5
10
15
20
25
30
35
Number of Drops
C
u
m
u
l
a
t
i
v
e
P
e
r
c
e
n
t
a
g
e
o
f
F
i
n
e
s
Cushioned coal
Initial 10% fines
Initial 30% fines
0 1 2 3 4 5 6
Fig. 6. Cumulative percentage of 16.0 mm nes vs. number of drops
of three types of cushioning tests of South Blackwater coal dropped on
coal surface.
Ensham Coal, Coal Surface
0
5
10
15
20
25
30
35
Number of Drops
C
u
m
u
l
a
t
i
v
e
P
e
r
c
e
n
t
a
g
e
o
f
F
i
n
e
s
Cushioned coal
Initial 10% fines
Initial 30% fines
0 1 2 3 4 5 6
Fig. 7. Cumulative percentage of 16.0 mm nes vs. number of drops of
three types of cushioning tests of Ensham coal dropped on coal surface.
impact surface. Hence, cushioning effects of nes on coal
surface is minimum compare to other two impact surfaces.
4.2. Comparison of three different types of impact surface
tested with three types of cushioning samples (Cushioned
coal, Initial 10% nes and Initial 30% nes)
The comparison of three different impact surfaces tested
with cushioned coal sample, initial 10% nes coal sample
and a sample of initial 30% nes of South Blackwater and
Ensham coal were shown in Figs. 813. The cushioned coal
sample of South Blackwater coal dropped on steel surface
produced 8.5% more nes than the drops onto a conveyor
surface and 13.4% more nes than a coal surface (coal stock-
pile) at 30 m total drops shown in Fig. 8. Similarly, En-
sham coal produced 4.6% more nes on steel surface than
Table 4
Cumulative percentage of 16.0 mm nes of three types of cushioning tests of two types of coal on coal stockpile surface from 5 m height
Number of drops Percentage of 16.0 mm nes of South Blackwater coal Percentage of 16.0 mm nes of Ensham coal
Cushioned coal Initial 10% nes Initial 30% nes Cushioned coal Initial 10% nes Initial 30% nes
1 2.7 2.4 1.0 2.7 2.1 1.0
2 6.2 5.5 2.5 6.2 5.1 2.3
3 9.0 8.1 5.4 8.9 7.7 4.9
4 11.4 10.8 8.0 11.4 10.5 7.8
5 14.1 13.0 10.5 14.0 12.8 10.1
6 16.3 15.0 12.0 16.2 14.6 11.7
South Blackwater Coal, Cushioned Coal
0
10
20
30
40
0 1 2 3 4 5 6
Number of Drops
C
u
m
u
l
a
t
i
v
e
P
e
r
c
e
n
t
a
g
e
o
f
F
i
n
e
s
Steel plate
Conveyor belt
Coal piles
Fig. 8. Comparison of percentage of nes generation of three impact
surfaces of South Blackwater coal tested with cushioned coal sample.
Ensham Coal, Cushioned Coal
0
10
20
30
40
0 1 2 3 4 5 6
Number of Drops
C
u
m
u
l
a
t
i
v
e
P
e
r
c
e
n
t
a
g
e
o
f
F
i
n
e
s
Steel plate
Conveyor belt
Coal piles
Fig. 9. Comparison of percentage of nes generation of three impact
surfaces of Ensham coal tested with cushioned coal sample.
South Blackwater Coal, Initial 10% Fines
0
5
10
15
20
25
30
35
Number of Drops
C
u
m
u
l
a
t
i
v
e
P
e
r
c
e
n
t
a
g
e
o
f
F
i
n
e
s
Steel impact
surface
Conveyor impact
surface
Coal impact
surface
0 1 2 3 4 5 6
Fig. 10. Comparison of percentage of nes generation of three impact
surfaces of South Blackwater coal tested with initial 10% nes coal
sample.
258 R.K. Sahoo, D. Roach / Chemical Engineering and Processing 44 (2005) 253261
Ensham Coal, Initial 10% Fines
0
5
10
15
20
25
30
35
Number of Drops
C
u
m
u
l
a
t
i
v
e
P
e
r
c
e
n
t
a
g
e
o
f
F
i
n
e
s
Steel impact surface
Conveyor impact
surface
Coal impact surface
0 1 2 3 4 5 6
Fig. 11. Comparison of percentage of nes generation of three impact
surfaces of Ensham coal tested with initial 10% nes coal.
South Blackwater Coal, Initial 30% Fines
0
5
10
15
20
25
30
35
0 1 2 3 4 5 6
Number of Drops
C
u
m
u
l
a
t
i
v
e
P
e
r
c
e
n
t
a
g
e
o
f
F
i
n
e
s
Steel impact
surface
Conveyor impact
surface
Coal impact
surface
Fig. 12. Comparison of percentage of nes generation of three impact
surfaces of South Blackwater coal tested with initial 30% nes coal
sample.
Ensham Coal, Initial 30% Fines
0
5
10
15
20
25
30
35
0 1 2 3 4 5 6
Number of drops
C
u
m
u
l
a
t
i
v
e
p
e
r
c
e
n
t
a
g
e
o
f
f
i
n
e
s
Steel impact
surface
Conveyor impact
surface
Coal impact
surface
Fig. 13. Comparison of percentage of nes generation of three impact
surfaces of Ensham coal tested with initial 30% nes coal sample.
conveyor surface and 12.3% more nes than coal surface
shown in Fig. 9.
At initial 10% nes of South Blackwater coal, the steel
surface produced 8% more nes than conveyor surface and
13% more nes than coal surface at 30 m total drops (six
drops at 5 m) shown in Fig. 10. Fig. 11 shows that Ensham
coal with a sample of initial 10% nes, the steel surface pro-
duced 4% more nes than conveyor surface and 9% more
nes than coal surface. The conveyor surface with a sample
of initial 10% nes of both types of coal produced 5% more
Steel Surface
0
10
20
30
0 1 2 3 4 5 6
Number of drops
c
u
m
u
l
a
t
i
v
e
p
e
r
c
e
n
t
a
g
e
o
f
f
i
n
e
s
South B.water
(initial 10% fines)
Ensham (initial 10%
fines)
South B.water
(initial 30% fines)
Ensham (initial 30%
fines)
Fig. 14. Comparison of percentage of nes generation of two types of
coal tested with initial 10% nes and initial 30% nes on steel surface.
nes than coal surface shown in Figs. 10 and 11. The re-
sults of these gures revel that different impact surface has
different degradation characteristics which is opposite to the
results of Waters et al. [5].
Figs. 12 and 13 shows that there were no signicant dif-
ference of nes percentage in between three impact surfaces
tested with sample of initial 30% nes of South Blackwater
and Ensham coal at 30 m total drops. The results of these
gures reveal that at higher percentage of initial nes the
cushioning effects of nes on different impact surfaces are
same.
4.3. Comparison of two types of coal tested on three
surfaces
When two types of coal are compared, the coal sample of
initial 10% nes of south Blackwater coal dropped on steel
surface produced 5% more nes than Ensham coal at 30 m
total drops shown in Fig. 14 and there was no signicant
difference of nes percentage between two types of coal
tested with initial 30% nes sample on steel surface shown
in Fig. 14.
Figs. 15 and 16 shows that, there was no signicant dif-
ference of nes percentage between two types of coal tested
with initial 10% nes and initial 30% nes on conveyor sur-
face and coal surface at 30 m total drops.
Conveyor Surface
0
5
10
15
20
25
30
35
0 1 2 3 4 5 6
Number of Drops
C
u
m
u
l
a
t
i
v
e
P
e
r
c
e
n
t
a
g
e
o
f
F
i
n
e
s
South B.water
initial 10% fines
Ensham initial 10%
fines
South B.water
initial 30% fines
Ensham initial 30%
fines
Fig. 15. Comparison of percentage of nes generation of two types of
coal tested with initial 10% and 30% nes on conveyor surface.
R.K. Sahoo, D. Roach / Chemical Engineering and Processing 44 (2005) 253261 259
Coal Surface
0
5
10
15
20
25
30
35
0 1 2 3 4 5 6
Number of Drops
C
u
m
u
l
a
t
i
v
e
P
e
r
c
e
n
t
a
g
e
o
f
F
i
n
e
s
South B.water
initial 10% fines
Ensham initial
10% fines
South B.water
initial 30% fines
Ensham initial
30% fines
Fig. 16. Comparison of percentage of nes generation of two types of
coal tested with initial 10% nes and 30% nes on coal surface.
4.4. Degradation model of South Blackwater coal on three
impact surfaces
The degradation model of three samples (cushioned coal,
initial 10% nes and initial 30% nes) of South Blackwater
coal is determined on three impact surfaces (steel plate, con-
veyor belt and coal stockpile). Degradation model equation
can be written as follows:
F =
D
j
_
N
i
_
ij
ij
_
m
ij
+h
ij
c
ij
s
ij
__
_
(3)
where, F is the percentage of nes produced as a results of
the drops from different; heights, when dropping the differ-
ent types of coal of various sizes;
ij
, the mass percentage
of each feed size fraction i with each coal type j,
ij
, the
mass percentage of each coal type j with each feed size frac-
tion i; m
ij
, the nes percentage of each feed size fraction i
that would appear at a; particular drop height for coal type
j; h
ij
; the percentage of nes produced during handling of
each feed size fraction i and coal type j; c
ij
, the percentage
of nes reduced due to cushioning effects of each feed size
fraction i and coal type j; s
ij
, the percentage of nes reduced
due to change of impact surfaces of each feed size fraction
i and coal type j; N, number of feed size fractions dropped;
D, number of coal types dropped.
Determination of nes parameter, handling, cushioning
and surface parameters for degradation model of South
Blackwater coal were presented in Sahoo and Roach [11].
The percentage of nes generation varies in different types
and sizes of coal. The number of handling events also in-
creases the nes generation in the handling circuits, which
is varying in coal types and its sizes. Cushioning and surface
parameters are also varies with types and sizes of coal.
In the present research, a single size fraction (76.2
+ 50.8 mm) of one type of coal was dropped on different
impact surfaces from 5 m heights because the Gladstone
Port Authority handles one type of coal at a time from sep-
Table 5
The value of parameters for the degradation model for both types of coal
at 5 m drop heights
Types of coal Drop
height (m)
ij
(%)
ij
(%) m
ij
(%) h
ij
(%)
South Blackwater 5 100 100 7.77 0.27
Steel Surface
0
5
10
15
20
25
30
35
0 1 2 3 4 5 6
Number of Drops
C
u
m
u
l
a
t
i
v
e
P
e
r
c
e
n
t
a
g
e
o
f
F
i
n
e
sRaw data
(Cushioned Coal)
D'Model data
(Cushioned Coal)
Raw data (Initial
10% Fines)
D'Model data
(Initial 10% Fines)
Rawa data (Initial
30% Fines)
D'Model data
(Initial 30% Fines)
Fig. 17. Comparison of raw data and model data of South Blackwater at
5 m drop height. (D
ij
= 100%,
ij
= 100%, N = 1, D = 1 and the value of
other parameters are as indicated in Tables 56. The degra-
dation model data (DModel data) were determined from
above Eq. (3) by Matlab
TM
computer programming.
The results of the degradation model of South Blackwater
coal dropped on steel plate, conveyor belt and coal stock-
pile surfaces from 5 m heights are shown in Figs. 1719
(Table 6). The raw data for the Figs. 1719 are given in
Tables 24 and model data are given in Tables 79. There
was a close agreement between raw data and degradation
model data (DModel data) of both types of coal dropped
on different surfaces. Within the experimental error most of
the raw data of the cushioning tests of the cushioned coal
sample and initial 10% nes sample of South Blackwater
coal dropped from 5 m height on steel surface are same with
the model data shown in Fig. 17. The model data points of
initial 30% nes sample of South Blackwater coal dropped
from 5 m height on steel surface differ from raw data points
by 4% at 30 m total drops shown in Fig. 17.
260 R.K. Sahoo, D. Roach / Chemical Engineering and Processing 44 (2005) 253261
Table 6
The value of parameters for the degradation model for both types of coal at 5 m drop heights
Types of coal Drop height (m) Cushioned parameter = c
ij
(%) Surface parameter = s
ij
(%)
Cushioned coal Initial 10% nes Initial 30% nes Conveyor Coal
South Blackwater 5 2.08 2.26 4.62 1.4 2.2
Coal Stockpile Surface
0
5
10
15
20
25
30
0 1 2 3 4 5 6
Number of Drops
C
u
m
u
l
a
t
i
v
e
P
e
r
c
e
n
t
a
g
e
o
f
F
i
n
e
s
Raw data (cushioned)
D'Model data
(cushioned)
Raw data (initial 10%
fines)
D'Model data (initial
10% fines)
Raw data (initial 30%
fines)
D'Model data (initial
30% fines)
Fig. 19. Comparison of raw data and model data of South Blackwater
coal at 5 m height.
Table 7
Model data of 16.0 mm nes of ve types of cushioning tests of South
Blackwater coal at 5 m height on steel surface
Number of
drops
Model data of 16.0 mm nes of South Blackwater coal
Cushioned
coal
Initial 10%
nes
Initial 30%
nes
1 6.0 5.8 3.4
2 11.6 11.2 6.7
3 16.8 16.4 9.9
4 21.8 21.2 13.0
5 26.5 25.7 16.0
6 30.8 30.0 18.8
Table 8
Model data of 16.0 mm nes of three types of cushioning tests of South
Blackwater coal at 5 m height on conveyor surface
Number of
drops
Model data of 16.0 mm nes of South Blackwater coal
Cushioned
coal
Initial 10%
nes
Initial 30%
nes
1 4.6 4.4 2.0
2 8.9 8.6 4.0
3 13.1 12.6 5.9
4 17.0 16.4 7.8
5 20.8 20.1 9.7
6 24.4 23.6 11.5
Within the experimental error, the raw data points of cush-
ioned and initial 10% nes curves of South Blackwater coal
dropped on conveyor surface differ from model data points
by 3% and the raw data points of initial 30% nes curve dif-
fer from model data points by 1% on 30 m total drops (six
drops at 5 m) shown in Fig. 18.
Raw data points of cushioned and initial 10% nes curve
of South Blackwater coal dropped on coal surface differ
Table 9
Model data of 16.0 mm nes of three types of cushioning tests of South
Blackwater coal at 5 m height on coal surface
Number of
drops
Model data of 16.0 mm nes of South Blackwater coal
Cushioned
coal
Initial 10%
nes
Initial 30%
nes
1 3.8 3.6 1.2
2 7.4 7.0 2.4
3 10.9 10.4 3.6
4 14.2 13.6 4.8
5 17.4 16.7 6.0
6 20.5 19.6 7.1
from the model data points by 4% and the raw data points
of initial 30% nes curve differ from the model data points
by 5% on 30 m total drops (six drops at 5 m) as shown in
Fig. 19.
5. Conclusion
Non-cushioned coal sample of both types of coal dropped
on different impact surfaces produced higher percentage of
nes than the sample of cushioned coal, initial 10% nes,
initial 30% nes and initial 50% nes. The cushioning ef-
fects of South Blackwater and Ensham coal with initial 10%
nes dropped on steel surface produced more nes than
conveyor surface and coal surface. The cushioning effect of
nes on coal surface was least compare to other two impact
surfaces. There was no signicant difference of nes gen-
eration in between the three impact surfaces tested with a
sample of initial 30% nes of both types of coal. The degra-
dation model was used satisfactorily for South Blackwater
coal on different impact surfaces.
Acknowledgements
The authors wish to thanks to the management of Glad-
stone Port Authority for funding and using their coal sam-
ples for this research work. The authors are also grateful to
Queensland Government to arrange this scholarship through
the Port Authority.
References
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Chemical Engineering and Processing 44 (2005) 263266
Using statistical moments to describe grinding in a ball
mill for industrial-scale process
Andrzej Heim, Tomasz P. Olejnik
,1
, Agnieszka Pawlak
1
Faculty of Process and Environmental Engineering, Technical University of Lodz, Wlcza nska 213, 90-924 d z, Poland
Received 4 August 2003; received in revised form 17 December 2003; accepted 11 February 2004
Available online 2 July 2004
Abstract
The aim of the paper was to describe the process of grinding of raw materials used in the industrial-scale production of ceramic tiles, by
applying the theory of statistical moments. Grinding was performed in industrial ball mills in ceramic tile factories Ceramika Parady z Ltd.
and Opoczno S.A. The ball mills operated in a batch mode. A mixture of feldspars and clay was comminuted. Its composition and fractions
depended on the conditions that should be satised by rawmaterials for the production of wall tiles (monoporosis and stoneware) and terracotta.
The ground material was subjected to a particle size analysis. Results of the analysis were used in the calculation of relationships applied in
the theory of statistical moments. The main parameters, i.e. zero moment of the rst order and central moments of the third and fourth order
were determined. The values of central moments were used in the calculation of skewness and atness coefcients. Additionally, changes of
mean particle size in time were determined.
2004 Elsevier B.V. All rights reserved.
Keywords: Ball mill; Industrial-scale; Moment theory; Grinding
1. Introduction
Studies on the application of the theory of statistical mo-
ments in the description of grinding in ball mills have been
carried out in the Department of Process Equipment, d z
Technical University [13]. The research was carried out
in a laboratory scale for selected mineral materials. Results
obtained conrmed applicability of the theory of statistical
moments in the description of particle size distribution dur-
ing grinding.
Modelling of the grinding process covers two problems
[48]. The rst one is a mathematical description of the
particle size distribution of material being ground, i.e. an
equation which describes in the best way the dependence
of particular size fractions on the characteristic dimensions.
The other one includes the equation of grinding kinetics that
describes the rate of changes in the particle size distribution
in time, depending on the properties of material being ground
and process parameters.
i=1
d
i
w
i
(1)
K
1
=
M
3
M
3/2
2
(2)
K
2
=
M
4
M
2
2
3 (3)
where the central moment of the k-th order is
M
k
=
m
i=1
(d
i
m
1
)
k
w
i
(4)
The zero moment of the rst order m
1
is identical to the
mean grain size of the entire set.
A common feature of the classical absolute measures of
skewness and atness is that they do not have a nite numer-
ical interval which theoretically would include all possible
values. In order to interpret the coefcients of atness and
skewness more easily, original modied forms presented by
Eqs. (5) and (6) were proposed.
K
1m
=
M
4
(M
2
)
2
M
4
(5)
K
2m
=
M
3
(M
2
)
3/2
+M
3
(6)
A characteristic feature of these modied coefcients is that
their values are included always in the strictly determined
intervals: the value of modied skewness coefcient K
2m
is
always in the interval 1, 1, while the value of the modied
atness coefcient K
1m
is always in the interval 0, 1.
3. Experimental
Industrial mills in which the experimental grinding was
performed were in two factories. The rst one was in Ce-
ramika Parady z Ltd. at TomaszwMazowiecki, and the other
one in Opoczno S.A., at Opoczno. Selected technical data
are given for each mill in Table 1. Depending on future use,
further in the production, the feed differing in the percent-
age of feldspar, clay and additives was applied. In both fac-
tories, the ground raw materials were a starting material for
wall and oor tile production.
The composition of raw material mixtures used in the pro-
duction of wall tiles (stoneware) and oor tiles (terracotta)
in Opoczno is given in Table 2. Data characterising the feed
in the mill at Parady z are given in Table 3.
Table 1
Selected technical data of the mills
Mill Ceramika Parady z Opoczno S.A.
Inner diameter (m) 2.5 3.1
Water volume (m
3
) 38 38
Frequency of rotations (min
1
) 12.63 13
Table 2
Feed composition for stoneware and terracotta at Opoczno [10]
Stoneware Terracotta
Solid components (kg) 20000 20000
Including feldspar (kg) 6000 10000
Clay (kg) 14000 10000
Liquid components (kg) 1500 1500
Including water (kg) 1422 1422
Flumix (kg) 20 20
Water glass (kg) 68 68
Table 3
Feed composition for monoporosis and terracotta in Parady z [11]
Monoporosis Terracotta
Solid components (kg) 21300 22000
Including feldspar (kg) 3834 11660
Clay (%) 11502 7700
Dolomite (%) 1704 1980
Calcium carbonate (%) 1704
Raw crushed minerals (%) 660
Liquid components (kg) 2100 2600
Including water (kg) 2051 2550
Trisodium polyphosphate (kg) 49 50
Table 4
Ball size and weight in the mills in Ceramika Parady z [11] and Opoczno
S.A. [10]
Ball diameter (m) Weight (kg)
Ceramika Parady z 0.025 4000
0.030 8000
0.040 8000
0.045 6500
Ball diameter (inch) Weight (kg)
Opoczno S.A. 3/4 1700
7/8 2750
1 4150
1(1/4) 8000
1(1/2) 1800
1(3/4) 3050
2 4550
The mills were lled with corundum grinding media. The
nominal packing were the same for both materials ground
at Opoczno and for the mills operating at Parady z (Table 4).
4. Results and discussion
For particle size analysis, around 400 g samples were
taken from the mills at determined time intervals.
The time in which a sample was taken was counted since
the beginning of the grinding cycle for each raw material
and it was, respectively
grinding at Ceramika Parady z: monoporosis 80, 140,
200, 260, 320, 380 and 460 min, terracotta 300,
A. Heim et al. / Chemical Engineering and Processing 44 (2005) 263266 265
Table 5
Comparison of calculated mean particle size m
1
, atness coefcient K
1m
and skewness coefcient K
2m
. Terracotta grinding in the mill at Opoczno S.A.
Grinding time (min)
60 120 180 240 300 360 420 480
m
1
41.07 22.72 23.62 14.59 13.18 11.94 11.30 10.87
K
1m
0.9454 0.9357 0.9612 0.9865 0.9791 0.9854 0.9637 0.9661
K
2m
0.7774 0.731 0.7823 0.7957 0.8056 0.8012 0.8006 0.8105
0
10
20
30
40
50
60
70
0 200 400 600 800 1000
t [min]
m
1
[ m]
Opoczno_terracotta
Parady _terracotta
Opoczno_stoneware
Parady _monoporosis
Fig. 1. Changes in the mean particle size m
1
for raw materials ground at Opoczno and Parady z.
360, 420, 480, 540, 600, 660, 720, 780, 840 and 900
min;
grinding at Opoczno S.A.: stoneware 15, 45, 75, 105,
135 and 175 min, terracotta 60, 120, 180, 240, 300, 360,
420 and 480 min.
The samples were subjected to particle size analysis using
a laser analyser. Results obtained enabled the calculation
0
0,2
0,4
0,6
0,8
1
1,2
0 10 20 30 40 50 60
m
1
[
m]
K
1m
, K
2m
70
K1m (Opoczno - stoneware)
K1m (Paradyz - monoporosis)
K1m (Opoczno - terracotta)
K1m (Parad - terracotta)
K2m (Opoczno - stoneware)
K2m (Parad - monoporosis)
K2m (Opoczno - terracotta)
K2m (Parad - terracotta)
.
yz
.
yz
.
yz
.
Fig. 2. Dependence of the modied atness coefcient K
2m
and skewness coefcient K
1m
on mean particle size m
1
for raw materials being ground.
of a mean particle size (zero moment m
1
) and modied
coefcients of skewness K
2m
and atness K
1m
. Examples of
results obtained for one sample are given in Table 5.
Fig. 1 shows changes in the mean particle size m
1
as a
function of time for raw materials ground in the mills at
Opoczno and Parady z. In all cases, in the initial grinding
period, an intensive change of the mean particle size m
1
takes place. For terracotta and silica ground at Opoczno,
266 A. Heim et al. / Chemical Engineering and Processing 44 (2005) 263266
the technologically required particle size is obtained in a
shorter time (480 and 175 min, respectively) as compared to
the grinding of terracotta and monoporosis at Parady z (900
and 460 min, respectively). The shorter time of grinding at
Opoczno is a result of a different set of grinding balls and
different composition of the feed mixture.
When analysing the dependence of skewness coefcient
K
2m
and atness coefcient K
1m
on the mean particle size,
it is found that coefcients K
1m
and K
2m
are stable in the
tested range of variability of m
1
(Fig. 2).
In the range of mean particle size m
1
(from 10 to 40 m),
almost constant values of the K
1m
(0.98) and K
2m
(0.8)
were observed. The nature of changes, K
1m
and K
2m
, for
the tested grinding process reveals a far reaching similarity
to the changes that are observed in a laboratory-scale grind-
ing. However, in the laboratory-scale experiments, tests were
performed for a bigger range of changes in the mean parti-
cle size m
1
[2,3,1216]. The coefcients K
1m
and K
2m
were
also constant in the range 20 m
1
100 m. For higher
values of m
1
, the coefcient K
1m
decreased approaching a
boundary value 1.
For very small values of m
1
, the coefcient K
1m
reached
values close to 0.9. The atness coefcient was growing up
to the boundary value 0.9, for big mean particle sizes.
To nd analogous tendencies in the change of coef-
cients K
1m
and K
2m
for industrial grinding, it is necessary
to carry out the grinding process, for which the mean par-
ticle size would be in the range above 100 m and below
10 m.
Results obtained in Opoczno and Parady z mills conrmed
applicability of the theory of statistical moments in the de-
scription of particles of the material ground in industrial ball
mills. However, it is necessary to extend the range of vari-
ability of the mean particle size.
Acknowledgements
The work was carried out under research Project no.
3T09C 005 23 nanced by the State Committee for Scien-
tic Research for the years 20022005.
Appendix A. Nomenclature
d
i
mean grain size from size grade i (m)
K
1
atness coefcient
K
1m
modied atness coefcient
K
2
skewness coefcient
K
2m
modied skewness coefcient
m
1
mean grain size (m)
M
2
central moment of the 2nd order
M
3
central moment of the 3rd order
M
4
central moment of the 4th order
t grinding time (s)
w
i
percentage part of mass of grains from size
grade i
References
[1] A. Heim, Determination of particle size distribution of ground ma-
terial, Rudy i Metale 38 (3) (1993) 74.
[2] A. Heim, T.P. Olejnik, Simulation of milling in ball mills, Proceed-
ings of the 2nd Israel Conference for Conveying and Handling of
Particulate Solids, Israel, 1997, p. 813.
[3] A. Heim, T.P. Olejnik., Description of grinding in a ball mill using
statistical moments, Proceedings of the 3rd Israeli Conference for
Conveying and Handling of Particle Solids, Israel, vol. 1, 2000, p.
632.
[4] L.G. Austin, A review introduction to the description of grinding as
a rate process, Power Tech. 5 (1971) 123135.
[5] B. Beke, The Process of Fine grinding, Akademiai Kiado, Budapest,
1981, pp. 2123.
[6] R.P. Gardner, L.G. Austin, J. Inst. Fuel. London 35 (1962) 174.
[7] K. Sedlatschek, L. Bass, Powder Met. Bull. 6 (1953) 148.
[8] E. Verdes, Ph.D. thesis, SZIKKTI, Budapest, 1984.
[9] A. Heim, M. Pietrzykowski, Grinding in a ball mill, Powder Hand.
Process. 5 (4) (1993).
[10] Data from Technological Department, Opoczno S.A.
[11] Data from Technological Department, Ceramika Parady z Sp. z o.o.
[12] A. Heim, T.P. Olejnik, Opis kinetyki procesu rozdrabniania niek-
trych materiaw skalnych za pomoc a teorii momentw, In zynieria
Chemiczna i Procesowa, Zeszyty Naukowe P., vol. 21, 1997,
pp. 101108.
[13] T.P. Olejnik, Zastosowanie teorii momentw do opisu procesu roz-
drabniania w myniekulowym, Ph.D. thesis, Faculty of Process and
Environmental Engineering, Technical University of Lodz, 1999.
[14] A. Heim, T.P. Olejnik., Wpyw cz esto sci obrotowej myna kulowego
na skad granulometryczny produktw rozdrabniania, Proceedings
XXXVI Seminar Fizykochemiczne Problemy Mineralurgii, 1999,
pp. 6373.
[15] A. Heim, T.P. Olejnik, Wpyw masy nadawy oraz kul na kinetyk e
procesu mielenia opisan a teori a momentw, Zeszyty Nauk, Politech-
niki, d z In z. Chemiczna i Procesowa, vol. 838, no. 27, 2000,
pp. 105114.
[16] A. Heim, T.P. Olejnik, A. Pawlak, Z. Korze n, Dobr parametrw
procesu mielenia w mynie kulowym w skali pprzemysowej w
oparciu o teori e momentw statystycznych, Proceedings of the Con-
ference Kruszywa mineralne surowce rynek technologie
jako s c, Polanica Zdrj, 2001, pp. 113122.
Chemical Engineering and Processing 44 (2005) 267272
On possible instability of throughputs in complex milling circuits
V. Mizonov
a
, V. Zhukov
a
, A. Korovkin
a
, H. Berthiaux
b,
a
Department of Applied Mathematics, Ivanovo State Power Engineering University Rabfakovakaya 34, 153003 Ivanovo, Russia
b
Laboratoire de Gnie des Procds des Solides Diviss, Campus Jarlard, Ecole des Mines dAlbi-Carmaux, 81000 Albi, France
Received 15 July 2003; received in revised form 5 January 2004; accepted 11 February 2004
Available online 25 June 2004
Abstract
The objective of the study is to develop an effective and universal approach, based on the theory of Markov chains, to calculate the basic
parameters of the steady state regime of complex technological systems for processing granular materials. In particular, we focus on the
response of a complex milling system to uctuations of the feed rate to the system. It is shown that depending on the characteristics of the
classiers the uctuations can grow unlimitedly, so that the stability of throughputs in the circuit can be lost.
2004 Elsevier B.V. All rights reserved.
Keywords: Throughputs; Milling circuits; Classiers
1. Introduction
Application of complex technological systems in produc-
tion of ne powders is a well known tendency in improve-
ment of the production efciency. In particular, complex
milling circuits allow reducing the specic energy, which is
necessary for grinding. This is due to the correspondence
of the size of grinding bodies and that of current particles,
and also to the evacuation of particles, which are already
ground enough, from the process. Application of networks
of classiers allows obtaining very high sharpness of cut,
even though separate classiers of the network could be
fairly ineffective. A common feature of such circuits is the
use of recycling classier-formed particle ows, formed by
a classier, and directed to further grinding, or to repeated
classication. For instance, in particle size controlled pro-
duction of our, such networks can currently include more
than 50 mills and classiers, while three stages containing
1520 hydrocyclones are needed in the paper pulp process-
ing. However, this feature predetermines some difculties in
the mathematical modelling of the circuits, as well as some
problems in their industrial operation.
P
11
P
12
0
P
21
P
22
0
0 P
31
I
(1)
where P is the block matrix consisting of smaller matrices of
size r r. The matrices on the main diagonal describe transi-
tions among cells (rows) within the corresponding columns,
the matrices on the diagonals neighbouring to the main one
describe forward (upper diagonal) and backward (lower di-
agonal) transitions between elements of the circuit, i.e., be-
tween columns of cells. I is the identity matrix of the same
size as P
ij
, O is the zero matrix of the same size.
An example of the matrix P expressed in numbers is
shown below. The total number of fractions, which are un-
der observation, is taken equal to 3 (r = 3). The transition
V. Mizonov et al. / Chemical Engineering and Processing 44 (2005) 267272 269
probabilities are denoted as p
q
p
where p is the index of the
cell where the material transits to from the cell q.
P =
p
11
11
0 0
p
11
21
p
21
21
0
p
11
31
p
21
31
p
31
31
p
12
11
0 0
0 p
22
21
0
0 0 p
32
31
0 0 0
0 0 0
0 0 0
p
11
12
0 0
0 p
21
22
0
0 0 p
31
32
p
12
12
0 0
0 p
22
22
0
0 0 p
32
32
0 0 0
0 0 0
0 0 0
0 0 0
0 0 0
0 0 0
p
12
13
0 0
0 p
22
23
0
0 0 p
32
33
1 0 0
0 1 0
0 0 1
(1a)
The mass content of fractions in the cells is described by the
state vector F, which is the column block vector consisting
of vectors f
j
related to the jth column of the set of cells
placed one after another:
F =
f
1
f
2
f
3
(2)
where every vector f
j
has the size r 1, and consists of
elements f
ij
, f
2j
, . . . , f
rj
.
The feed vector F
0
is similar to F, and contains mass
fractions, which are added to the circuit after every transi-
tion. In the case shown in Fig. 2a, it contains only the rst
non-zero vector of the three, which is the fraction size dis-
tribution f
0
in the feed to the circuit. The rest two vectors
are the zero vectors of the same size.
If the transition time t is chosen, and matrices P
ij
are
dened, the matrix P can be constructed and successive
evolution of the state vector F can be calculated as:
F
n+1
= P(F
n
+F
n
0
). (3)
The hold-up in the jth element of the circuit and the total
ow rate from it to the pth apparatus of the circuit are:
M
j
=
r
i=1
f
ij
(4)
B
j
p
=
r
i=1
f
ij
p
ij
ip
(5)
where B
j
p
is the mass owrate fromthe jth to the pth element
of the circuit, p
ij
ip
is the probability of transition of the ith
size fraction between these elements.
Under a continuous constant feed to the circuit there exists
a steady-state (asymptotic) regime of the circuit operation.
However, this solution cannot be obtained with the matrix
(1) because it contains the absorbing state, the probability
of which grows unlimitedly. In order to get round the
difculty, the absorbing cell can be presented not like the
end of the chain, but as an intermediate element of the chain
with the probability to stay in it equal to zero, placed just
before the real absorber which is not included in the chain.
In this case, the identity matrix I in (1) is to be replaced by
the zero matrix of the same size, and the matrix P becomes:
P =
P
11
P
12
0
P
21
P
22
0
0 P
31
0
, (6)
and the steady-state (asymptotic) distribution can be calcu-
lated by the formula:
F
= (I P)
1
F
0
, (7)
which follows from the formula for the sum of the innite
geometrical progression written in matrix notation.
After separating the vectors f
i
from F
it becomes pos-
sible to dene fraction size distribution in every element
of the circuit, and then, using (4) and (5)-throughputs and
hold-ups in them.
The algorithm of the circuit matrix construction can be
strongly simplied, if we suppose that, the particle ow in
the mill can be presented as the perfect plug ow, and take
the transition time equal to the particle residence time in
the mill. In this case, the probability to stay within the cell
presenting the mill is equal to zero. Since the residence time
for a mill is normally much longer than it is for a classier,
the same holds true for the probability to stay in the cell
presenting the classier.
In this case, the constructing of the circuit matrix is more
convenient if the axes are directed as it is shown in Fig. 2b.
Under the above assumptions this matrix takes the form:
P =
0 I C 0
G 0 0
0 C 0
, (8)
where G is the matrix of grinding in the mill related to the
transition time t, which is a lower triangle matrix of size r
r (r is the number of fractions under observation) C, the ma-
trix of classication, which is a diagonal matrix of the same
size consisting of discrete values of a grade efciency curve
[8,9,11]. Substitution of the matrix (8) into Eq. (7) gives:
F
= K
1
F
0
(9)
270 V. Mizonov et al. / Chemical Engineering and Processing 44 (2005) 267272
where,
K =
I I C 0
G I 0
0 C I
(10)
is the nal form of the matrix of the circuit, which can be
constructed on the basis of the following rule:
The matrix K of the circuit is the block matrix of size
mx m blocks, i.e., smaller matrices presenting processes
in elements of the circuit, every of which has the size
r r, where m is the number of elements of the circuit
(including the absorber), r is the number of fractions under
observation.
The main diagonal of K contains the identity matrices of
size r r with the sign minus.
Every column of K belongs to an element of the circuit.
The matrix of the element is to be placed in the row of this
column, whose number is equal to the number of element,
where the particle ow is directed.
This rule is universal and can be used for an arbitrary
circuit. The vectors f
i
of the block vector F
is the fraction
size distribution in the particle ow before the ith element.
The matrix K for the network of classiers shown in Fig. 1b
has the following form:
K =
I I C
2
0
C
1
I 0
0 C
2
I
(11)
where, the absorber for the coarse product from the rst
classier is not included into the chain because information
on the state is irrelevant to the objective of this study.
It is necessary to note that the matrix K does not deal with
the hold-ups at all. The same rule for its construction was
suggested in [8,9] on the basis of particle fractions ows bal-
ance only, without referring to Markov chains models. Here
it was obtained as a particular case of the developed model,
which is presented by the matrix P and allows describing
also the evolution of hold-ups in general case provided the
smaller matrices of P are known.
Once the types of equipment a circuit consists of have
been decided upon, we have the preliminary information
on the corresponding matrices, and can calculate the circuit
using the algorithm described above. After calculating the
throughputs, we can select sizes of the equipment chosen.
Thus, we get the complete information on the circuit param-
eters, which are supposed to be reached in the real operation.
If the matrices of the equipment are throughput independent,
small errors in describing them give also a small error in pre-
dicting the circuit parameters. However, if they are through-
put dependent, rst, the error can become much larger, and
second, small variation of operating parameters of the circuit
may cause large variation of throughputs, up to conditions
when the circuit fails to work. Further on, we will try to
express mathematically these ideas and illustrate them with
some simulations.
3. Stability of throughputs in closed circuit systems
3.1. Closed circuit milling system
Let us turn back to the closed circuit milling systemshown
in Fig. 1a. The throughput dependent matrix of grinding was
introduced as follows. For the xed throughput B
s
the ma-
trix P was constructed on the basis of the linear selection
and homogeneous breakage functions [8,10]. It was sup-
posed that the only result of the throughput change was the
variation of the mean residence time. Under the assumption
of a constant hold-up, it gives:
P(B) = P(B
s
)
t
m
/t
ms
= P(B
s
)
(M/B)/(M/B
s
)
= P(B
s
)
Bs/B
(12)
where, t
m
is the mean grinding time, M, the constant is the
hold-up in the mill, and the subscript s indicates the reference
regime of grinding.
The matrix of classication C was introduced on the basis
of the formula by Molerus and Hoffmann [11] for the grade
efciency curve:
q
x
=
1
1 +x/x
c
exp((s/2)(1 x/x
c
))
(13)
where, x and x
c
is the current and cut size respectively, s
is the parameter related to the efciency of classication.
With s Eq. (13) gives the grade efciency curve of
the perfect classier with the cut size x
c
. The elements of
C were calculated as C
jj
= q
x
(x
j
/x
c
) where, x
j
is the mean
size fraction.
When the throughput in a classier is changed, both the
cut size x
c
and the parameter s can be changed. An increase
of the throughput practically always leads to the decrease of
s (the efciency decreases) but the cut size can both increase
and decrease. Both parameters are changing the outows
of ne and coarse material, but it can be shown that the
inuence of the cut size is much stronger. That is why the
assumption that x
c
= x
c
(B), but s = s(B) was introduced.
Despite, the dependence of the cut size on the throughput
can be very complex, as the rst approximation it can be
taken as a linear one around the reference throughput:
x
c
(B) = x
c
(B
s
) k(B B
s
) (14)
where, x
c
(B
s
) is the cut size at the reference throughput,
which was used to choose the classier, k = (x
c
/B)
B=Bs
,
and its positive value is assigned to the decreasing function
x
c
(B), which is being met more often for industrial classi-
ers.
Investigation of transient processes after deviation of the
feed rate was done as a numerical experiment according to
the following procedure. The basic value of the feed rate B
0
V. Mizonov et al. / Chemical Engineering and Processing 44 (2005) 267272 271
Fig. 3. Transient process in the closed milling circuit: (a) k > 0 (1,2:
B
0
= 0.15, 3,4: B
0
= 0.15, 1,3: k = 0.15, 2,4: k = 0.3) and (b) k < 0
(B
0
= 0.15, (1) k = 0.6, (2) k = 0.9).
got a small perturbation B
0
of the impulse kind. Then, the
evolution of perturbations of throughputs and fraction size
distributions in the circuit caused by the impulse was ob-
served. If the perturbations were getting down during itera-
tions, the steady-state regime was considered stable, if they
were growing unlimitedly, or the system was removed to an-
other steady-state regime, the basic steady-state regime was
considered unstable. Fig. 3 shows the evolution of through-
put in the closed milling circuit as the function of itera-
tion number n after introducing the impulse perturbation
to the feed with homogeneous fraction size distribution at
s = 5.
For positive values of k (Fig. 3a), providing the stable op-
eration of the circuit, the perturbation is going down (curves
1,3). If k is larger than the critical value k
0
, and B
0
> 0,
the perturbation is growing unlimitedly and leads to the
mill blockage (curve 2). If B
0
< 0, the throughputs tran-
sit to other steady-state values, which are completely differ-
ent in comparison to preliminary calculated ones (curve 4).
It means that the character of stability loss depends on the
sign of the feed perturbation. The regimes 2 and 4 are ob-
viously unstable and their basic predicted parameters can-
not be realized in practice. At k < 0 the loss of stability is
of oscillating character (Fig. 3b). Fig. 4 generalises the re-
Fig. 4. Areas of stable and unstable operation of the closed milling circuit
(os = 5; s = 15).
Fig. 5. Transient process in the network of classiers at B
0
= 0, 1: (a)
k = l(1), k = 2(2); (b) k = 1(1), k = 2(2).
sults of numerical examples and shows areas in the graph
k
0
= f(B
0
) providing the stable and unstable operation of
the circuit.
3.2. Network of classiers
The general matrix of the network of classiers shown
in Fig. 1b is given by Eq. (11) where, C
1
and C
2
are the
matrices of classication in the rst and the second ap-
paratus, respectively. Investigation of throughputs stability
was carried out according to the procedure described above.
As far as a network normally contains identical classiers,
or at least classiers of the same type, their characteris-
tics were taken identical (x
c1
(B
s
) = x
c2
(B
s
) = 0.5; k
1
= k
2
= k).
The transient process that follows after introducing the im-
pulse perturbation to the feed is shown in Fig. 5. At the stable
conditions stabilization of throughputs can be monotonous
(curve 1 in Fig. 5a) and oscillating (curve 1 in Fig. 5b).
The loss of stability for identical classiers is always of
fast stabilizing oscillation character but the oscillations oc-
curs around the throughput values, which are different in
comparison to the nominal ones. The reason for the appear-
ance of these auto-oscillations is namely the similarity of
Fig. 6. Areas of stable and unstable operation of the network of classiers
(os = 5, s = 15).
272 V. Mizonov et al. / Chemical Engineering and Processing 44 (2005) 267272
the characteristics of the classiers. If the value of k is out
of the stable area, an increase of the feed to the rst clas-
sier leads to the decrease of it to the second one, and, re-
spectively, the decrease of the recycling particle ow. The
classiers work like in opposite phases, and this supports
the auto-oscillations. A generalization of the results of nu-
merical experiments is shown in Fig. 6.
4. Conclusions
In this work, a convenient and effective algorithm for cal-
culation of the steady-state parameters of complex techno-
logical systems for processing granular materials, based on
the theory of Markov chains, has been proposed. It allows
a fast construction of a model representing a circuit of ar-
bitrary complexity and its computational analysis. It is also
shown that, the throughputs in a complex milling circuit
with recycling particle ows calculated for a steady-state
regime can lose the stability and grow unbound, even after
a small perturbation of the feed rate if the characteristics
of the classiers do not satisfy the conditions of stability.
It may cause the blockage of the mill in a closed milling
circuit, and a high deviation of operating parameters from
calculated ones in a network of classiers. This suggests
that a reliable modelling of complex milling systems can-
not be done only on the basis of steady-state parameters of
the equipment employed: it is necessary to analyse the re-
sponse of the system parameters to variation of operating
conditions.
References
[1] R. Nassar, S.T. Chou, L.T. Fan, Modelling and simulation of deep-bed
ltration: a stochastic compartmental model, Chem. Eng. Sci., 1986,
pp. 412017412027.
[2] A. Tamir, Applications of Markov Chains in Chemical Engineering,
Elsevier Publishers, Amsterdam, 1998, p. 604.
[3] H. Berthiaux, J.A. Dodds, Modeling classier network by Markov
chains, Powder Technol. 105 (1999) 266273.
[4] V.E. Mizonov, E.A. Barantseva, K. Marikh, H. Berthiaux, Application
of the theory of Markov chains to model mechanical processes in
chemical engineering. in: the Proceedings of the Fourth International
Conference on Theoretical and Experimental Foundations of Design
of High Effective Processes and Equipment for Chemical Technology,
Ivanovo, 2628 June, 2001, pp. 9294 (Russian).
[5] C. Dechsiri, J.C. Abanades, H.G. Dehling, A.C. Hoffman, P.C.
Wright, A stochastic model for mixing an segregation in slugging
uidised beds, Rcents Progrs en Genie des Procds 14 (2000)
631638.
[6] A.T. Harris, R.B. Thorpe, J.F. Davidson, Stochastic modelling of the
particle residence time distribution in circulating uidised bed risers,
Chem. Eng. Sci. 57 (2002) 47794796.
[7] K.K. Yin, H. Yang, P. Daoutidis, G.G. Yin, Simulation of population
dynamics using continuous-time nite state Markov chains, Compt.
Chem. Eng. 27 (2003) 235249.
[8] V. Mizonov, V. Zhukov, S. Bernotat, Simulation of Grinding: New
Approaches, ISPEU Press, 1997, p. 108.
[9] V.P. Zhukov, V.E. Mizonov, et al., Mathematical modelling and struc-
tural optimisation of complex milling circuits, Theor. Found. Chem.
Eng. 32 (1998) 288293 (Russian).
[10] V.E. Mizonov, H. Berthiaux, et al., On one approach to describe
the kinetics of grinding, Chem. Chem. Technol. 42 (1999) 124126
(Russian).
[11] O. Molerus, H. Hoffmann, Darstellung von Windsichtrtrenn-kurven
durch ein Stochstisches Modell, Chem. Ing. Tech. 41 (1969) 340
344.
Chemical Engineering and Processing 44 (2005) 273277
Optimising design of continuous grinding mill-classier systems
P.B. Kis
a,
, Cs. Mihlyk
b
, B.G. Lakatos
c
a
Institute of Natural Sciences, College of Dunajvros, H-2401 Dunajvros, P.O. Box 152, Hungary
b
Department of Mathematics and Computing, University of Veszprm, H-8201 Veszprm, P.O. Box 158, Hungary
c
Department of Process Engineering, University of Veszprm, H-8201 Veszprm, P.O. Box 158, Hungary
Received 2 September 2003; received in revised form 24 March 2004; accepted 15 April 2004
Available online 26 June 2004
Abstract
An optimising design method is presented for designing closed grinding circuits to meet the requirements for the particulate product
expressed as a combination of the mean value and standard deviation of the particle size. The grinding circuit is modelled by a discrete
mathematical model describing the axial mixing and breakage of particles in the mill and a possible time delay in the recycle line. The design
problemis formulated as a nonlinear programming task in which the convective owvelocity and the axial dispersion coefcient of the ground
material are selected as design variables.
The method proved to be a useful tool for optimising design of grinding systems, and can be applied as a decision aid for process engineers
to improve the efciency of processes and maintaining the quality required for the particular products.
2004 Elsevier B.V. All rights reserved.
Keywords: Continuous grinding; Grinding mill-classier circuit; Optimising design; Nonlinear programming; Simulation
1. Introduction
Grinding is an important operation within the eld of
processing technology. It is aimed to produce particulate
material of a given particle size distribution prepared for
subsequent processing or as an end product. Further, since
grinding is an energy consuming operation, appropriate se-
lection of conguration and design of grinding systems is
of primary importance.
A number of methods have been used for optimisation of
grinding circuits. Espig and Reinsch [1] presented the refer-
ence state method, Gupta et al. [2] applied an enumeration
method based on their expert system, Lestage et al. [3] used
linear programming for real-time optimisation, and Mitra
and Gopinath [4] used a genetic algorithm for multiobjec-
tive optimisation of grinding circuits. Morrell [5] developed
new autogenous and semi-autogenous models for design and
optimisation of grinding.
In most of the previous works dealing with optimisation,
the mills were described as perfectly mixed units. In a num-
ber of grinding systems, however, mixing and breakage of
particles occur simultaneously, so that mixing of the mate-
k=i
p
k,i
(y
1
, x
i
, t
n
)
+a
i
(t
n
) +(V
F
V
B
) (x
i(1/2)
)
(y
J
, x
i
, t
nd
) i = 1, 2, . . . , I. (1)
Internal sections of the mill:
(y
j
, x
i
, t
n+1
) = V
F
(y
j1
, x
i
, t
n
) +(1 V
F
V
B
S(x
i(1/2)
))(y
j
, x
i
, t
n
)
+V
B
(y
j+1
, x
i
, t
n
) +
I
k=i
p
k,i
(y
j
, x
i
, t
n
)
j = 2, . . . , j 1, i = 1, 2, . . . , I. (2)
Last section of the mill:
(y
J
, x
i
, t
n+1
) =V
F
(y
J1
, x
i
, t
n
)
+(1 V
F
S(x
i(1/2)
))(y
J
, x
i
, t
n
)
+
I
k=i
p
k,i
(y
J
, x
i
, t
n
) i = 1, 2, . . . , I.
(3)
Here, parameter V
F
denotes the velocity of forward ow
of particles in the mill in axial direction, while V
B
is the ve-
locity of ow backwards. V
F
and V
B
are intrinsic parameters
of the discrete model [6], while parameters Pe, u and D are
originated in the axial dispersion model. Namely, Pe is the
Peclet number related to the convective ow velocity u and
the axial dispersion coefcient D as Pe = uY/D where Y de-
notes the length of the mill. The Peclet number characterises
the axial mixing of particles in the mill in dimensionless
form, analogously to the dimensional dispersion coefcient
D. It is proved [6] that relations V
F
= (1+Peh
y
)/(Peh
2
y
) and
V
B
= (1/Peh
2
y
) are hold between these parameters where
and h
y
are, in essence, parameters of the numerical scheme.
In Eqs. (1)(3), S() denotes the breakage selection func-
tion by means of which S(x
k
)
S(x
k
) = K
s
x
k
(4)
provides the rate of breakage of particles of size x
k
. The
second function describing the kinetics of breakage is the
breakage distribution function B(,) which usually is used
P.B. Kis et al. / Chemical Engineering and Processing 44 (2005) 273277 275
in the form [8]:
B(x
k
, x
i
) =
_
x
i
x
k
_
+(1 )
_
x
i
x
k
_
,
x
min
x
i
< x
k
x
max
, 0 1. (5)
In expressions (4) and (5), , K
s
, , and are consti-
tutive parameters. Based on these relations, we can precise
also functions p
k,i
in Eqs. (1)(3): p
k,I
= S(x
k
)[B(x
k
,x
i
)
B(x
k
,x
i1
)], I = 1, 2, . . . , I; k = i, . . . , I.
Let us note that in order to have stable numerical scheme
in simulation the condition (Peh
2
y
)/(2 + Peh
y
+
Peh
2
y
S(x
i(1/2)
)) is required to be satised.
The rst term on the right hand side of Eq. (1) gives
the amount of particles of ith size at the moment of time
t
n
which neither moved forwards nor broke during one
time step of simulation. The second term represents those
particles of the same size that moved backwards from the
second section. The third term expresses the amount of
particles that remained in the rst section and have bro-
ken from some size higher than x
i
to that subinterval of
size. Term a
i
(t
n
) denotes the amount of particles of the ith
size that freshly enters the system. Finally, the last term
(V
F
V
B
) (x
i(1/2)
) (y
J
, x
i
, t
nd
) is the fraction of par-
ticles of the ith size that left the mill at the moment of time
t
nd
and was classied by the classier to recycle into the
mill for further grinding. Here, function
i
, 0
i
= (x
i
)
1, describes the operation of the classier, whilst parame-
ter d denotes the discrete time delay in the recirculation line.
The variation of the amounts of particles in the internal
sections of the mill is described by Eq. (2). The rst term on
the right hand side of Eq. (2) represents the fraction of par-
ticles of the ith size that moved forwards from the previous
column, while the third termgives that part of particles of the
same size that moved backwards from the next column. The
second term expresses the amount of particles that have not
changed at all. Finally, the last term describes the amount of
those particles that remained in the section and has broken
from some size larger than x
i
to the ith subinterval.
Finally, the size composition of particles in the last section
of the mill is described via Eq. (3). The rst term on the
right hand side expresses the amount of those particles that
moved forwards from the previous column. The second term
represents particles that have not changed at all, while the
third term gives the amount of particles that remained in the
last column and have broken from some size larger than x
i
to the interval in question.
3. Formulation of the optimisation problem
The particle size distribution of the product is one of the
most important product characteristics of grinding circuits.
Instead of the complete distribution, however, we are limited
mostly to determining a few characteristic parameters of the
product size such as the mean particle size and the variance,
containing information about the average deviation of the
particle size from its mean. Following the model formed by
Eqs (1)(3), the mean particle size and the standard deviation
of size at the outlet are computed as
x(t
n
) =
I
i=1
x
i(1/2)
(y
J
, x
i
, t
n
)
I
i=1
(y
J
, x
i
, t
n
)
(6)
and
s(t
n
) =
_
_
I
i=1
x
2
i(1/2)
(y
J
, x
i
, t
n
)
I
i=1
(y
J
, x
i
, t
n
)
_
x(t
n
)
2
(7)
where x denotes the mean particle size and s stands for
the standard deviation, being the positive square root of the
variance.
Assuming now that the requirements for the quality of
the product are formulated in terms of prescribed mean size
0
and standard deviation
0
, the objective function for
choosing the design variables is formulated as
Q(d) = w
1
( x
s
(d)
0
)
2
+w
2
( s
s
(d)
0
)
2
(8)
where w
1
and w
2
are weighing factors, expressing the
signicance of the mean value and standard deviation terms,
according to the requirements, x
s
(.) and s
s
(.), denote the
steady state values of the mean size and standard deviation,
respectively, computed by solving the set of Eqs. (1)(3),
and d is the vector of the design variables.
Based on these considerations, the purpose of optimisa-
tion is to determine the values of the design variables d of
the grinding circuit to produce such particulate product that
the objective function be minimal.
In this formulation, precising the initial conditions for
Eqs. (1)(3), this set of equations is solved recurrently in
time to generate the steady state values x
s
(.) and s
s
(.), pro-
vided the system parameters and the feed conditions are
given. This means that the set of Eqs. (1)(3) is solved in
each step of searching the optimal solution, monitoring at
the same time if the steady state was reached.
4. Results and discussion
In the simulation runs, the design parameters were chosen
as d = (u,D), i.e. the kinetic parameters of breakage and
the classication function were xed. The size distribution
of particles in the feed stream was constant, selecting 0 for
x = x
max
/2 and 0.05 for x > x
max
/2, while the initial size
distribution of the material in the mill was the same in each
run. The largest particle size was chosen x
max
= 10
3
m,
and the values of the kinetic parameters were K
s
= 10
4
,
= 1.00, = 3.00, = 0.60, = 0.48. The classication
function was a jump function of the form
i
=
_
0, i = 1, . . . , [I/2]
1, i = [I/2] +1, . . . , I
276 P.B. Kis et al. / Chemical Engineering and Processing 44 (2005) 273277
Table 1
Values of the objective function in the environment of local minimum
Convective ow
velocity, u (m/s)
Axial dispersion coefcient, D (m
2
/s)
0.004 0.005 0.006 0.007 0.008 0.009
0.018 40.0625 33.1646 26.9248 21.5284 16.7450 12.6413
0.019 19.6625 14.8512 10.7871 7.4337 4.7141 2.6914
0.020 6.2962 3.7217 1.8271 0.9630 0.0904 0.1579
0.021 0.3416 0.0025 0.3538 1.4282 2.9864 5.1978
0.022 1.8501 3.8073 6.4657 9.7005 13.5153 17.9604
0.023 10.9857 15.3290 20.2159 25.7795 31.7940 38.4365
0.024 27.8646 34.5650 41.8590 49.7104 58.0859 66.9463
The model allows applying more general classication func-
tions, describing non-ideal classication of particles. Since,
however, the parameters of classication were not taken on
as design variables, this ideal classication appeared to be
satisfactory for simulation purposes.
Selecting parameters u and D as design variables for xed
length of the mill, also the mean residence time t = Y/u
and the Peclet number Pe = uY/D become determined.
The intervals of feasible solutions u = [0.018, 0.024] m/s
and D = [0.004, 0.009] m
2
/s, and the value Y = 6.0 m were
selected on the basis of measurement data by Van Nierop
and Moys [9,10]. Finally, the parameters of the numerical
scheme were chosen as d = 10, I = 20, J = 20 and = 0.1.
Based on these considerations, the task of optimising
design was formulated as
min
d
_
Q(d) = ( x
s
(u, D) 56)
2
+0.01 ( s
s
(u, D) 55)
2
_
(9)
{subject to the constraints given by the steady state solutions
of Eqs. (1)(3)}.
The computer program for solving the nonlinear program-
ming problem (9) was developed using Matlab, applying the
simplex method for searching the optimal solution.
The optimal values of the design variables, obtained
as a solution of problem (9), are u
opt
= 0.021 m/s and
D
opt
= 0.005 m
2
/s, and the objective function takes value
Q(0.021,0.005) = 0.0025 here, as it is shown in Table 1.
A number of numerical experiments were carried out to
investigate the sensitivity of the objective function around
the optimal solution. The values of the objective function in
the environment of optimal point are also shown in Table 1,
and these very values are shown graphically in Fig. 3.
Both the data in Table 1 and the surface Q(u,D) in Fig. 3
illustrate well that the sensitivity of the objective function
with respect to the convective ow velocity is signicant.
At the same time, variation of Q as a function of the ax-
ial dispersion coefcient seems to be smaller, which means
that the mean residence time has stronger inuence on the
properties of the particulate product than the axial mixing
of particles.
Fig. 3. Surface of the objective function Q illustrating the sensitivity with
respect to the design variables u and D.
5. Conclusions
An optimising design method was presented for designing
continuous grinding circuits to meet the requirements for the
particulate product expressed as a combination of the mean
value and standard deviation of the particle size. A discrete
mathematical model, describing the axial mixing and break-
age of particles in the mill and some time delay in the recy-
cle line, was applied to describe the behaviour of the closed
circuit. The task was formulated as a nonlinear program-
ming problem in which the convective ow velocity and
the axial dispersion coefcient of the ground material were
selected as design variables. The sensitivity study showed
that the mean residence time has stronger inuence on the
properties of the particulate product than the axial mixing of
particles.
The method proved to be a useful tool for optimising
design of grinding systems, and can be applied as a de-
cision aid for process engineers to improve the efciency
of processes and maintaining the quality required for the
particular products.
P.B. Kis et al. / Chemical Engineering and Processing 44 (2005) 273277 277
Acknowledgements
The work was supported partially by the Hungarian
Research Foundation under Grant T034406. The nancial
support is gratefully acknowledged. Csaba Mihlyk is
grateful for the nancial support of the Jnos Bolyai Re-
search Fellowship of the Hungarian Academy of Science.
Appendix A. Nomenclature
a
i
feed rate of particles of the ith size
B breakage distribution function
d delay in the recycle expressed in time steps
d design vector
D axial dispersion coefcient (m
2
/s)
h
x
length of subinterval of particle size
h
y
length of subinterval of the axial coordinate
K
s
parameter of selection function S
p
k,i
coefcients in Eqs. (1)(3)
Pe Peclet number
Q objective function
s computed standard deviation
s
s
steady state value of s
S selection function
t time (s)
t
n
discrete time
u convective ow velocity (m/s)
V
B
ow velocity forwards in axial direction
V
F
ow velocity backwards in axial direction
x particle size (m)
x
i
discrete particle size (m)
x computed mean particle size (m)
x
s
steady state value of x
y axial coordinate (m)
y
i
discrete axial coordinate (m)
Y length of the mill (m)
w weighing factor of the objective function
Greek letters
parameter of the selection function S
parameter of the breakage function B
parameter of the breakage function B
parameter of the breakage function B
amount of ground material
classication function
discrete time step
References
[1] D. Espig, V. Reinsch, Computer aided grinding circuit optimization
utilizing a new mill efciency curve, Int. J. Miner. Process. 4445
(1996) 249259.
[2] R. Gupta, K.S. Shishodia, G.S. Sekhon, Optimization of grinding
process parameters using enumeration method, J. Mater. Process.
Technol. 112 (2001) 6367.
[3] R. Lestage, A. Pomerleau, D. Hodouin, Constrained real-time opti-
mization of a grinding circuit using steady-state linear programming
supervisory control, Powder Technol. 124 (2002) 254263.
[4] K. Mitra, R. Gopinath, Multiobjective optimization of an industrial
grinding operation using elitist nondominated sorting genetic algo-
rithm, Chem. Eng. Sci. 59 (2004) 385396.
[5] S. Morrell, A new autogenous and semi-autogenous mill model for
scale-up, design and optimisation, Miner. Eng. 17 (2004) 437445.
[6] Cs. Mihlyk, T. Blickle, B.G. Lakatos, A simulation model for
analysis and design of continuous grinding mills, Powder Technol.
97 (1998) 5158.
[7] P.B. Kis, Cs. Mihlyk, B.G. Lakatos, Mathematical models for
simulation of continuous grinding processes with recirculation, Acta
Cybernetica 15 (2002) 529545.
[8] L.G. Austin, A discussion of equations for the analysis of batch
grinding data, Powder Technol. 106 (1999) 7176.
[9] M.A. Van Nierop, M.H. Moys, Premature centrifuging, oscillation
and axial mixing in industrial grinding mill load, Minerals Eng. 11
(1998) 437445.
[10] M.A. Van Nierop, M.H. Moys, Axial mixing of slurry in an auto-
genous grinding mill, Int. J. Mineral Process. 65 (2002) 151164.
Chemical Engineering and Processing 44 (2005) 279285
Air classication of solid particles: a review
M. Shapiro
, V. Galperin
Laboratory of Transport Processes in Porous Materials, Faculty of Mechanical Engineering,
Technion-Israel Institute of Technology, Haifa 3200, Israel
Received 22 June 2003; received in revised form 14 January 2004; accepted 11 February 2004
Available online 1 July 2004
Abstract
An overview is given of modern air classication devices, their operation principles, features and parameters, as cut size, cleanness
and recovery. We outline the separation zones common to existing classiers. In practice, various gravitational and centrifugal classiers
are employed, including those with vertical and horizontal air streams, cascade classiers, uidized bed separators, inertial, vortex, rotor
classiers, etc. Choice of the classier type and designs is dictated by the technological requirements (throughput, cleanness, etc.) and the
properties of materials to be classied. Advantages and limitations of the classiers and basic trends in their development are considered.
2004 Elsevier B.V. All rights reserved.
Keywords: Air classication; Gravitational; Centrifugal; Particles
1. Introduction
Air classication is a technological method of separating
particulates according to their size, as represented by particle
equivalent diameter [1]. The latter may be either geometric
or hydrodynamic/aerodynamic equivalent diameter, depend-
ing on the size-measurement method used. The initial or
original (o) material is divided into two products: coarse (c)
and ne (f). Separation is characterized by a cut size d
50
,
which is a border between these fractions (see below deni-
tion of this quantity in terms of fraction cleanness and recov-
ery). Particles with sizes above d
50
constitute coarse fraction
and those with sizes below d
50
are nes. Due to various
stochastic factors (air turbulence, particle collisions), some
nes get into the coarse product and vice versa. Quality of
particle separation is characterized by mass contents of each
fraction in the suitable product. Denote the mass contents
of the coarse fraction (in per cent) in the feed, coarse and
ne products by C
o
, C
c
and C
f
, respectively. Similarly, F
o
,
F
c
and F
f
are the mass contents of the ne fraction in the
corresponding materials. Fractional cleanness is the mass
content of any useful fraction in the corresponding product,
namely, ne fraction content in the ne product F
f
, and
c
= m
c
C
c
/m
o
C
o
,
f
= m
f
F
f
/m
o
F
o
, respectively. Cleanness
and dirtiness characterize quality of the separated products.
In contrast, fraction recovery characterizes the separation
efciency. In particular if the original product is composed
only of particles having cut size, its fraction recovery is 50%.
In continuous technological processes direct measurement
of products masses is difcult. The recoveries are usually
estimated by determination of the fraction content in sepa-
rated products. This may be done by analyzing their probes,
e.g. by sieving, sedimentation method etc. Using the frac-
tion contents, one can estimate the recoveries of coarse and
ne fractions by the following respective expressions:
c
= C
c
(C
o
C
f
)/[C
o
(C
c
C
f
)],
f
= F
f
(F
o
F
c
)/[F
o
(F
f
F
c
)]. Their average gives total separation efciency:
av
0255-2701/$ see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.cep.2004.02.022
280 M. Shapiro, V. Galperin / Chemical Engineering and Processing 44 (2005) 279285
= 0.5(
c
+
f
). The above denitions of
c
,
f
are suitable
when the cut size is given. Otherwise,
c
,
f
may be esti-
mated by grade efciency curves [1].
2. Particle separation zones
An interior space of a classifying device, where solid
particles interact with air stream, is the separation zone.
Four basic separation zones are known, as described
by Rumpf [2], which include gravitational-counterow,
gravitational-crossow, centrifugal-counterow and centri-
fugal-crossow zone.
2.1. Gravitational-counterow zone
The gravitational-counterowzone exists in air streamris-
ing up with velocity u inside a vertical chamber with parallel
walls (Fig. 1a). Particles experience gravity G and drag F
d
forces acting in opposite directions. Coarse particles, hav-
ing terminal settling velocity V
TS
larger than air ow ve-
locity, move downwards, against the air stream, and nes
rise with the stream. The cut size d
50
is calculated from the
equilibrium G = F
d
combined with zero particles absolute
velocity, i.e. V
TS
= u. Theoretically, the cut size particles
are indenitely suspended in the separation zone. Practi-
Fig. 1. Separation zones: (a) gravitational-counterow zone, (b) gravitational-crossow zone, (c) centrifugal-counterow zone, (d) centrifugal-crossow
zone.
cally all particles are separated due to unavoidable stochastic
factors.
2.2. Gravitational-crossow zone
Ahorizontal air streamentering this zone expands within a
chamber and converges towards the outlet (Fig. 1b). Particles
fed in the chamber with zero velocity accelerate horizontally
by the drag force F
d
and also fall down. At the end of the
acceleration interval the horizontal velocity component v
x
of
all particles almost reaches the are ow velocity u and they
do not separate in this direction. Separation occurs due do
particles vertical motion across the air stream. Each particle
falls at its own terminal settling velocity. Accordingly, due
to the horizontal motion they land on the bottom at different
chamber locations: coarse-close to the inlet, smaller-close
to the outlet. Coarse fraction is gathered on the bottom of
the chamber, nes do not reach the bottom and are carried
away by the air ow through the outlet.
Thus, in the gravitational-crossow zone particle separa-
tion is a two-dimensional process, where their trajectories
are in fact ballistic tracks. Unlike the counterow zone, the
cut size depends not only on the particles terminal velocity,
but mainly on the chamber length and height. These param-
eters are chosen in such a way that particles with the cut
size land at the farthest point A of the bottom (Fig. 1b).
M. Shapiro, V. Galperin / Chemical Engineering and Processing 44 (2005) 279285 281
2.3. Centrifugal-counterow zone
This separation zone is characterized by a at air vortex
prevailing in a cylindrical chamber with tangential inlet and
central outlet (Fig. 1c). In this vortex air rotates and ows
radially towards the chamber centre. The radial air move-
ment (radial sink ow type) serves as the particles separa-
tion track.
Particles fed tangentially with air stream are involved in
rotation. Due to the centrifugal (inertial) force F
c
their tra-
jectories gradually deviate from the air streamlines. Sepa-
ration is governed by the balance between F
c
and the drag
force component F
dr
induced by the radial air movement.
Coarse particles drift towards the chamber walls, where they
fall down to the outlet. Fines move towards the chamber
axis where they are eventually carried out by the air stream.
Particles with cut size theoretically move with zero radial
velocity, but practically go to one of the products. As the
centrifugal force depends on the radial position, so does the
cut size d
50
. This distinguishes the separation process in the
centrifugal-counterow zone from the separation occurring
in the gravitational-counterow zone. To keep the cut size
constant along the radial direction, the classier should be
designed to provide constant tangential air velocity. This
feature is characteristic of the Archimedean spiral or free
vortex ow [2].
2.4. Centrifugal-crossow zone
This zone may be created in an air vortex for example
in a cylindrical chamber with inlet and outlet placed on the
opposite sides of the chamber axis (Fig. 1d). The fed par-
ticles enter with the air stream through whirl blades, which
create a screw-type ow. The blade proles should be de-
signed such that the radial component of the air velocity
everywhere vanishes. Particles rotate while drifting radially
towards the chamber walls with size-dependent velocities.
As they simultaneously proceed along the chamber axis they
reach the wall in different locations. Larger particles arrive
Fig. 2. Cascade classiers: (a) zigzag, (b) shelf classier, (c) with horizontal scavenging.
to the wall faster; smaller ones make it farther along the ax-
ial direction. The chamber is designed in such a way that
the cut size particles reach the periphery at its edge (point
A). The separation process in the centrifugal-crossow zone
is similar to that in cyclones; so these devices have similar
design principles.
3. Air classiers types and designs
Numerous air classier designs are described in the
literature [3,21]. No universal design method can be recom-
mended for separation of different materials, as each device
type has its specic technical requirements and suitable
for specic product. The separation zones described above
serve as a basis for systematizing air classiers, which
may have several zones used in combination in the same
device.
Air classiers may have external or internal aerodynamic
cycles. The former devices are constructed independently
of dust collectors and fans and connected to them via
pipelines. The internal-cycle (recirculating-air) devices
contain these elements in a single unit, and hence need
less production area and normally require lower invest-
ments. They have several technical shortcomings outlined in
subsection 3.5.
Air classiers may also be distinguished by method of
powder feed. Particles may be fed either within air stream, or
separately by freely pouring them within the device. Other
systematizing may be done with respect to the air stream
form, classier design features and operation mode (contin-
uous or batch).
Below we review principal schemes of most commonly
used air classiers to summarize the most important features
of their design and operation. Modern trends of classier
design account for stochastic nature of separation and aero-
dynamic parameters of equipment, creation of precise air
velocity eld, repeated cleaning of both fractions, arrange-
ment of several classifying stages, etc.
282 M. Shapiro, V. Galperin / Chemical Engineering and Processing 44 (2005) 279285
3.1. Gravitational air classiers
3.1.1. Counterow classiers with vertical (rising) ows
Early classiers of such type [3] were constructed as verti-
cal chambers having within a rising air stream (Fig. 1a) with
particles fed fromthe top or fromthe side. Being inexpensive
and simple in construction and maintenance, these devices
have one important shortcoming. Namely, the fed particles
break air ow uniformity and create signicant turbulence.
As such, coarse particles prevent nes from rising with the
air stream. This in combination with the single-stage oper-
ation mode underlies low separation efciency of counter-
ow classiers with rising ows. These classiers are used
only for separation of coarse bulk materials, containing two
types of particles of well differing sizes, e.g. coarse sand or
pebbles of 110 mm mixed with dust 0.10.2 mm.
3.1.2. Crossow classiers with horizontal air stream
Separation in these devices known as winnowing ma-
chines [3], is achieved due to the difference between tra-
jectories of coarse and ne particles in the separation zone
(Fig. 1b). Their operation and efciency are strongly af-
fected by the stochastic factors of the process, in particular
by uncertainties in feeding and particles aerodynamic inter-
actions. In most cases coarse particles prevent proper clas-
sication of nes. Separation efciency of these devices is
usually low. They are normally used for separation of solid
particles according to densities (e.g. grain from peel), rather
than by size. Sometimes crossow separation in horizontal
streams is used in combination with other separation prin-
ciples.
3.2. Cascade air classiers
These devices, known as Zigzag classiers [4], are cas-
cades of several inclined branch pipes of a rectangular cross
section arranged to form a vertical zigzag channel (Fig. 2a).
Air owing from below scavenges the particles fed from
above in cross-current direction. The ow eld within the
chamber has vortexes in the turn points, where the nes are
dragged by the stream, and the coarse particles cross it to-
wards the opposite wall and pour down. Separation occurs in
a cross-ow process. Sequential pipes arrangement enables
multiple scavenging to improve the separation efciency.
Several types of Zigzag classier are produced by Alpine
[5] for separation of ferruginous ore, fertilizers, plastic,
wooden dust, etc. at cut sizes ranging from 0.1 to 10 mm.
The number of parallel chambers varies from one to 16
with output ranging from 1 to 10 t/h.
Although multiple scavenging improves separation,
coarse particles crossing the air stream on each cascade step
collide and mix with nes. This precludes sharp separation
and decreases the efciency. Another disadvantage of the
device is its high aerodynamic resistance (pressure drop of
about 2.53.5 kPa), resulting from the vortexes formed in
cascades turn points.
These shortcomings prevail also in Shelf cascade classi-
er [6], where instead of pipes, inclined shelves are mounted
on the inner walls of a vertical vessel (Fig. 2b). Strong turbu-
lence prevailing under the shelves cause high pressure drops
(of up to 45 kPa) and high energy consumption of these
devices.
Cascade principle was also combined with cross-count
horizontal scavenging [7] in a vertical vessel divided into
separation and precipitation chambers, separated by a per-
meable grid with concave shelves (Fig. 2c). Particles fed
from the top pour onto the upper shelf, glide down and fall
of its edge where they are scavenged by the cross-current
stream. Part of nes is carried into the precipitation chamber
and the rest of the mixture falls onto the next shelf for re-
peated separation. After multiple separations, coarse fraction
exits from the separation chamber and nes leave the pre-
cipitation chamber. The nest fraction exits with the stream
and is collected in cyclones or lters.
This design practically or to a considerable extent elim-
inates particles collisions in the separation zone, which
sharpens separation. As the ow eld in the chamber has no
inherent vortexes the device has lower air resistance and en-
ergy consumption. Several prototypes of this classier were
used in phosphate industry for separation of crushed phos-
phate ore at 1 mm cut size. One such plant with output of 25 t
per hour and pressure drop of 800900 Pa yielded 9698%
cleanness of nes and 7885% of coarse fraction [8].
3.3. Fluidized bed classiers
In these devices classication occurs in the space over
a uidized bed from which ne particles are carried away
with the air stream. The air velocity must essentially ex-
ceed the maximal uidization velocity of ne fraction. These
classiers operate on the gravitational counterow separa-
tion principle with uidized bed used to increase particles
residence time in the separator. Coarse particles can move
horizontally across the bed to the exit, which is another ad-
vantage of this device.
Fluidized bed classiers may have straight or widening
forms. The latter (Fig. 3a) consist of a conical chamber with
a grid permeable for particles fed from below, inlet and
outlet pipes and a branch for coarse product. Air velocity
in the holes is high so that all the particles move far up-
wards into the cone, where the stream expands and the par-
ticles slow down. The coarse part returns to the grid and the
nes are carried away. The cones upper diameter is cho-
sen in such a way that the air velocity does not exceed the
coarse particles terminal velocity. These particles exit from
a pseudo-boiling layer formed above the grid through the
outlet branch. Pass-through grids allow arranging several
cones one over another i.e. to design multi-stage classiers
(Fig. 3b). Each stage has its (coarse) product with size de-
pendent on the chamber diameter.
Classiers with pass-through grids did not nd wide use
in practice mainly because of their big size. For example, a
M. Shapiro, V. Galperin / Chemical Engineering and Processing 44 (2005) 279285 283
Fig. 3. Fluidized bed classiers: (a) single-stage, (b) two-stage, (c) and
(d) continuous operation.
three-stage air classier of 600 kg/h is about 4.5 m tall. Ad-
ditionally, particles crushing resulting from impacts against
the grid, may affect the product quality.
In a later generation of uidized bed classiers the
feed is poured onto the grid from above (Fig. 3c, d), so
crushing is eliminated [9]. Several prototypes of such u-
idized bed classiers with cylindrical or conical chambers
of diameter 3501700 mm and throughput of 0.510 t/h,
were constructed for separation of sand, potassium chlo-
ride and ground phosphate particles with sizes from 50
to 1.5 mm [10]. The recovery of coarse fraction was
7592%.
Fig. 4. (a) Franken/Buell gravitational-inertial classier, (b) Vortex classier, (c) gravitationalcentrifugal classier.
One disadvantage of the uidized bed classiers with
cylindrical chambers of large diameters (above 1 m) is for-
mation of dead zones within the uidized bed far from the
axis, where the particles do not move. These zones are elim-
inated in FB classiers with chambers of oblong (oval) form
(as in Fig. 3d) [11]. Such a device with 40 t/h throughput
and 160 m cut size was built in the Karatau phosphate
works milling plant. It yielded the ne product coarse frac-
tion cleanness of 86% and separation recovery of 78% [10].
Fluidized bed classication plant constructed in the
Technion (Fig. 3d) has 30200 kg/h feeder output, air ow
rate of up to 400 m
3
/h allowing to change the cut from 50
to1000 m [12]. The efciency is about 90% and above,
depending on the material. The grid of changeable slope
allows controlling the rate of discharge of coarse particles
out of the separator. Investigations showed good perfor-
mance stability of the classier in the wide range (up to
four times) of feed rate. These devices have both products
recoveries higher at least by 1520% with respect to other
gravitational classiers.
3.4. Inertial air classiers
These devices are employed for ne powders (40400 m)
and also coarser particles. In the Franken or Vandenhoek in-
ertial separators [13,14] (Fig. 4a) particle-air mixture enters
from the top and falls down in the inlet pipe. The air turns
abruptly to the outlet pipe inclined by about 4550
and
carries the ne particles. Coarse fraction proceeds straight
down because of high inertia towards the discharge pipe.
On its way this material undergoes repeated separation in a
secondary air ow carrying nes into a curvilinear cham-
ber. Then they exit via the outlet pipe with blades mounted
for better air distribution. These classiers, manufactured
by Buell Co., are used for separation of pulverized lime-
stone at cut size of 150 m with feeds from a few pounds
to 600 t/h [15]. In the Buells variant of this device [14]
blades have different angles to increase the efciency. Such
devices were used for separation of 151000 m particles.
In the Buell separators the secondary air stream interferes
with the primary stream causing the ne particles moving
284 M. Shapiro, V. Galperin / Chemical Engineering and Processing 44 (2005) 279285
in the curvilinear chamber to mix with fed material. This
was eliminated by adding a branch pipe in the centre of the
curvilinear chamber to provide a separate exit of nes [16].
One such 20 t/h classier was tested in phosphate works to
separate 50400 m fraction from ground phosphorite. It
had coarse product cleanness of 91% and recovery of 77%.
3.5. Centrifugal air classiers
Two main types of these classiers are known, distin-
guished by method of creating air rotation. In vortex clas-
siers the air is rotated by stationary vanes (or tangential
pipes); in rotor classiers this is done by rotating blades. The
latter devices may have open or closed aerodynamic cycle.
3.5.1. Vortex air classiers
Vortex air classiers have centrifugal-counterow separa-
tion zone. Alpine A-G manufactures several such classiers
on the basis of the Rumpfs developments. One device of
this type (Fig. 4b) is designed as a at horizontal cylinder
containing a vortex chamber. Particle-laden air passes via in-
clined vanes into the chamber, through which the air moves
along a spiral trajectory, carrying the nes out. Coarse parti-
cles are drawn to the wall region and exit via a screw outlet.
These classiers are used for separation of ne powders, e.g.
limestone, quartz, pigments, etc. at cut sizes of 5100 m
[1,17].
3.5.2. Gravitationalcentrifugal air classiers
Gravitationalcentrifugal air classiers are two-stage de-
vices having gravitational and centrifugal separation zones,
with air circulation in most cases induced by orientable
blades. The feed enters the classier in the air stream into
a widening cone (Fig. 4c), where the coarsest fraction is
removed by gravitational separation. The stream with re-
maining material moves up into the centrifugal zone via the
blades having changeable angle to adjust the cut size. Fines
are carried away with the stream, whereas the coarse parti-
cles move to the wall and descend to the exit. These devices
Fig. 5. (a) Rotor classier, (b) classier with proled blades, (c) circulating air classier.
with throughputs of up to about 20 t/h are widely used in
cement and coal milling plants [18].
3.5.3. Rotor classiers
Rotor classiers utilize rotating blades for air circu-
lation. In one such classier [19] (see Fig. 5a) particle
laden air enters from below and rises upward into a con-
ical vessel, containing a drive-activated rotor with a cone
and rotating blades. These blades whirl the air to create a
centrifugal-counterow separation zone in the upper part
of the vessel. The cut size is controlled by adjusting the
drives rotational velocity. These devices with throughputs
of up to 1.5 t/h are used for separation of ne quartz powder,
cement, ground limestone etc. at cut sizes of 20100 m
and coarse product recovery of 7080%. Similar classiers
were developed by Hosokawa Co. [17] for separation of
ground coal, talc, aluminum oxide, etc. A variant of rotor
classiers (Blade Classier) [20] has proled blades similar
to axial compressors (Fig. 5b). The space above the blades
is arranged to form a centrifugal-crossow zone, (rather
than the counterow zone, characteristic of the Hosokawa
classiers). In this zone particle separation occurs as de-
scribed in Section 2.4. Among the various blade proles
tested, the highest efciency was registered for that pro-
viding the solid body air rotation. The blade classiers
allow separation 2060 m powders, e.g. quartz, pigments,
alumina with 7080% both products recovery.
3.5.4. Circulating air classiers
Circulating air classiers are widely used, mainly in ce-
ment industry. One type of such devices produced by Sturte-
vant [22] (Fig. 5c) consists of two coaxial exterior and inte-
rior vessels. Particles entering the device from the top onto
the plate are scattered within the interior vessel by a rotat-
ing plate. There they rotate and move to periphery. The fan
creates a circulating air ow that rises within the interior
vessel and descends within the intermediate space between
the two. The air stream returns into the inner vessel through
the vanes. Coarse particles fall down in the inner vessel be-
M. Shapiro, V. Galperin / Chemical Engineering and Processing 44 (2005) 279285 285
ing separated as in the centrifugal-crossow separation zone
(see Fig. 1d). When the air abruptly turns to the vanes, nes
proceed down to their exit. Air-particle motion within the
intermediate space is similar to that in cyclones.
These classiers may process up to 800 t/h of bulk solids
[22]. They have rather poor dust/air separation in the inter-
mediate zone, resulting in particle accumulation, which re-
duces their efciency. Cut size control in these devices is
difcult.
4. Conclusions
Choice of the classier type is dictated by product re-
quirements, technological and economic factors. Rational
design and improving separation quality is done by creating
a well-dened and stable air ow, reducing turbulence, elim-
inating particles collisions, controlling feed and repeated
cleaning of both fractions. Among gravitational type clas-
siers, uidized-bed based devices provide stable operation
and sharp separation in the cut size range of 501000 m.
Smaller-size particles may be separated by rotor classiers,
enabling easy cut-size control and providing products re-
coveries up to 80%.
References
[1] H. Rumpf, Particle Technology, Chapman and Hall, London, 1990.
[2] H. Rumpf, Fortschritte und Probleme auf dem Gebiete der Wind-
sichtung, Staub, vol. 47, 1956.
[3] A. Taggart, Handbook of Mineral Dressing, John Willey & Sons,
USA, 1950.
[4] F. Kaiser, Der Zickzack-Sichter ein Windsichter nach neuen Prinzip,
Chemie-Ing.-Techn. 35, 1963.
[5] Zerkleinerungsmaschinen, Windsichter, Extruder, Alpine Prospekt
017/2R, 1968.
[6] M. Barsky, Powder Fractionation, Nedra, Moscow, 1980.
[7] V. Galperin, et al., Device for Separating Bulk Materials, USSR
Patent No. 1619535, 1984.
[8] V. Galperin, et al, Dry Classication of Phosphate Ore in Chilisai
Phosphate Field, Chem Industry, 12, Moscow, 1988.
[9] A. Vasilenchuk, et al., Gravitational Air Classier with Fluidized
Bed, USSR Patent 228641, 1968.
[10] V. Galperin, et al., Industrial tests of the Air Classiers with Flu-
idized Bed, Proceedings of Mines and Chemistry Institute for Raw
Materials, issue 57, Moscow, 1985.
[11] V. Galperin, Gravitational Air Classier with Fluidized Bed, USSR
Patent 1619535, 1984.
[12] V. Galperin, M. Shapiro, Separation of Solid Particles in a Fluidized
Bed Air Classier, Powder Handling and Processing, 11, No. 2,
AprilJune 1999.
[13] J.F. Franken, Apparatus for Classifying Particulate Material, USA
Patent 3006470, 1961.
[14] J.P. Vandenhoeck, Classier with gas ow distributor, USA Patent
3006470, 1961.
[15] Buell, A Division of Fisher-Klosterman, Inc., http://www.fjinc.
com/Buell/cat1.html 2003.
[16] V. Galperin, et al., Air Classier, USSR Patent 608568, 1978.
[17] Hosokawa, http://www.hosokawa.com.web/powderequip/
CLASSIFIERS/HTM, Powder and Particle Processing, 2003.
[18] G.K. Smyshliaev, Air Classication in Mineral Processing, Nedra,
Moscow, 1969.
[19] V. Rybin, S. Bockshtein, Investigation of Impingement-Vortex Clas-
sier, Proceedings of the Institute of Building Materials, Gosstrojiz-
dat, 1960.
[20] M. Dubinsky, V. Galperin, Blade Air Classier, USSR Patent 177766,
1965.
[21] I. Klumpar, et al., Air Classiers, Chemical Engineering, 3 March,
1986.
[22] Sturtevant Inc., Whirlwind Air Classiers, http://www.sturtevant.com,
2003.
Chemical Engineering and Processing 44 (2005) 287291
Application of a vertical venturi separator for improved recycling
of automotive tyres
W. McBride
, S. Keys
School of Engineering, Mechanical Engineering Discipline, University of Newcastle, Newcastle, NSW 2308, Australia
Received 1 September 2003; received in revised form 6 January 2004; accepted 11 February 2004
Available online 19 June 2004
Abstract
This paper reports on the successful application of a large vertical venturi separator for the removal of tangled steel and rayon bres from
crumbed rubber product as part of a tyre recycling process. This represents an advance over the other separation units encountered during this
project in cleaning efciency and scalability. The venturi separator was able to unwind the synthetic bres from the steel bre by keeping the
agglomerate in a suspended state within the throat of the venturi. A chaotic particle motion was observed at the throat which aided in teasing
the synthetic away from the steel bre. Overall the venturi separator offered far superior cleaning ability, suitable throughput rates and simple
construction/implementation. The concept could easily be applied to other industries where an aerodynamic classier offering potentially
unlimited particle retention times may be benecial.
2004 Elsevier B.V. All rights reserved.
Keywords: Vertical venturi separator; Tyre recycling; Automotive; Classier
1. Introduction
The work reported on in this paper was in response to an
industry problem on the removal of agglomerated steel and
synthetic bres from the saleable rubber crumb as part of
an automotive tyre recycling plant.
One of the difculties in the conversion of disused tyres
into saleable rubber crumb is the removal of the various
refuse materialsSteel, Rayon and Nylon. The recycling
process for the production of the rubber crumb commences
with primary pulping of the tyres. The pulping can be done
at either ambient or cryogenic temperatures depending on
the process chosen. The cryogenic method provides a lower
level of mechanical work to shred the tyres but this is off-
set by the problems inherent in cryogenic temperatures. In
both ambient and cryogenic processing the primary pulping
is generally a mechanical tearing process working on either
complete tyres or pre-cut sections. In the ambient temper-
ature installation under review material from the primary
mill was transferred to a secondary mill for further size re-
Corresponding author. Tel.: +61 2 4921 5208; fax: +61 2 4921 6946.
E-mail address: william.mcbride@newcastle.edu.au (W. McBride).
duction. In this transportation stage a magnetic separation
unit was in use to collect the liberated steel bre. This pro-
cess consisted of a standard metal tramp belt unit operat-
ing transverse to the product stream from the primary to the
secondary mill. One difculty with the magnetic separation
unit was the need to spread the primary product as a thin
layer onto the transfer belt to assist the magnetic separation.
If the steel bre was buried under any depth of rubber there
was insufcient force generated from the magnet and the
steel bre would remain in the product. After the primary
steel separation phase the product entered the second mill
for further size reduction and more bre liberation. Typical
particle size from the primary mill was +20 mm with the
secondary mill producing 6 mm product.
The primary separation of synthetic bre was achieved
using a number of cyclones assuming that the rubber par-
ticles would dis-engage from the air stream but the bre
would be carried on. Although the cyclones did remove a
large amount of the synthetic bre there was a percentage
of free bre and steel/synthetic bre agglomerate contami-
nating the saleable product.
The formation of the steel/synthetic bre/rubber agglom-
erates is a by-product of the milling process and in part
the tyre manufacturing process. The steel belts used in auto
0255-2701/$ see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.cep.2004.02.023
288 W. McBride, S. Keys / Chemical Engineering and Processing 44 (2005) 287291
Nomenclature
a
p
particle acceleration
A duct area
Cd aerodynamic drag factor (non-dimensional)
F
d
drag force on a particle due to passing air
g acceleration due to gravity
M mass
r, r
p
particle radius
S displacement from origin
U initial velocity
V velocity
Z vertical distance into convergent section
of venturi
a
density of air
s
density of solid
tyres are a twisted strand wire rope and in the shredding pro-
cess these formed short twisted lengths of steel bre. The
rotary nature of the milling process allowed the synthetic
bre to become tangled with the steel bre often trapping
crumb rubber as part of the agglomerate. These agglomer-
ated lumps tended to remain tangled throughout the cleaning
processes and often contained sufcient mass and density
to pass through the separators as product, reducing the -
nal crumb quality.The client trialled a number of secondary
bre removers with little improvement in nal product, a
schematic of a typical secondary fabric separator used at the
plant is shown as Fig. 1.
F
E
E
D
To Filter
Air flow
Cone for material dispersion
Central feed tube
Fig. 1. Typical style fabric separator.
A signicant problem with the style of separator shown
as Fig. 1 is that any feed bias to one location will result
in a reduced local airow rate and subsequent reduction in
the cleaning efciency; an inherent negative feedback loop
exists in the airow path.
The steel/synthetic bre agglomerates formed during the
milling process are extremely difcult to separate using con-
ventional equipment due to the twisted nature of the steel
bres. If sufcient steel is contained in the agglomerate then
the magnetic separation process may remove the entire lump
at the rst stage of product cleaning. However, this then
contaminates the steel refuse with both rubber and bre, re-
ducing both the sale price of the steel refuse and the net
rubber crumb yield available. If the agglomerate passes be-
yond the magnetic separator it is unlikely to be removed by
the air separators as a large lump presented to the separator
unit shown as Fig. 1 is essentially passed through with lit-
tle cleaning. This results in the agglomerate arriving in the
nal products bin, reducing the value of the rubber crumb.
Although a number of air separation units, other than as
shown by Fig. 1, were reported by our client to be available
and trialled, none were reported as being able to adequately
remove the entwined synthetic bre from the steel bre to
release the rubber product, and separate the synthetic bre
from the steel bre.
2. Venturi separator
The difculty with the processing of the agglomerate lies
with the twisted nature of the synthetic and steel bres. The
existing methods of separation were failing as the agglom-
erate only had a short residence time in the air stream. The
concept of the venturi separator was to make use of the dif-
fering velocity proles available in the venturi to prolong
the residence time for the agglomerates. Fig. 2 illustrates the
test facility used in this project.
The testing program investigated different total air ow
rates through the venturi and the effects on particle sizes
trapped by the lters compared to the removal efciency of
the agglomerates.
The results from the testing program were impressive. In
operation the crumb composite (crumbs, synthetic bre and
steel bre) gained momentum from the feed point down to
the mouth of the venturi. With the throat velocity set to
prevent the largest particles from exiting the venturi, an ex-
tremely fast and efcient cleaning was achieved (typically
less than 10 s of residence time). As the material fell down
into the throat it was progressively reacted on by the op-
posing air ow and accelerated back into the venturi dif-
fuser. A large degree of interparticle collision was evident
in the continuous falling/elevating process providing a ran-
dom or chaotic motion. This randomness tended to tease
the loose end of the synthetic bre from the steel bre.
As the particle circulated the synthetic bre was progres-
sively pulled from the steel bre. Once the steel bre was
W. McBride, S. Keys / Chemical Engineering and Processing 44 (2005) 287291 289
To Filters
Central Feed Tube
Screw Feeder
Storage
Hopper
Fig. 2. Venturi separator equipment.
cleaned, now having a low aerodynamic drag/density ratio, it
exited the venturi under gravity. This left a batch of cleaned
rubber crumb in the venturi, free of steel and synthetic
bres.
In order to minimise air separation from the venturi walls
the unit was designed with a 3.3:1 area expansion ratio with
a 6
a
V
2
CdA =
1
2
a
V
2
Cdr
2
(1)
Body force = Mg =
4
3
r
3
s
g (2)
where V is the local air velocity, r the particle radius, g the
acceleration due to gravity,
a
and
s
are the air and particle
density, respectively.
Equating 1 and 2 gives
1
2
a
V
2
dz
Cdr
2
=
4
3
r
3
p
s
g
1
2
a
V
2
dz
Cd =
4
3
r
p
s
g
(3)
If Cd,
a
and
s
are considered as constants then (3) reduces
to
r
p
V
2
dz
With a venturi having an area ratio of 3.3:1, the velocity ra-
tio and thus, particle size range trapped in the venturi is in
theory, 11:1. This means if the velocity at the throat is set
to suspend an 11 mm particle then particles just less than
1 mm would be lost to the lters. In reality this bandwidth
was diminished by the layout of the test facility and vari-
able particle Cd. In the layout shown as Fig. 2 the material
entered from a drop tube at the top of the venturi, this al-
lowed the particles to accelerate for nearly 1.2 m prior to the
venturi constriction. If the throat velocity were set to sus-
pend an 11 mm particle then the gravity force is balanced by
the particle drag at the throat, however, there will be no net
acceleration. This means that if an 11 mm particle entered
the throat with any vertical velocity there would be no de-
celeration of that particle and it would pass through. Thus,
the bandwidth of the unit is limited by the method in which
the particles are introduced into the separator. In the testing
work undertaken, a nominal bandwidth of 6:1 was observed.
This could have been increased by altering the feed from a
vertical drop to a lower horizontal entry.
If a particle enters the converging section of the venturi
with an initial velocity of U then it is possible to predict the
290 W. McBride, S. Keys / Chemical Engineering and Processing 44 (2005) 287291
Z
Z
Vdz
Fig. 4. Elemental slice through a convergent section of the venturi.
maximum particle size that can be captured by the venturi
using
V
2
= U
2
2aS. (4)
From the drag Eq. (1) and noting the F = MA then it can be
shown that the acceleration on a particle at some position
Z (Fig. 4) from the start of the converging section can be
determined by
a
p
=
3
a
Cd
8r
s
V
2
dz
(5)
Where a
p
is the particle acceleration of a particle with radius
r.
If the venturi is segmented into slices Z thick it can be
shown that the velocity exiting the slice is given by
V
exit
= U
entry
+2x(g a
p
)Z (6)
Application of (6) allows evaluation of the lowest point in
the venturi a particle will fall through and (5) will allow for
the calculation of the static suspension position of a given
particle.
Application of these equations for the test data obtained
does not provide a highly accurate match as the equations
are based on particles with a constant Cd. The raw rub-
ber crumb contained a range of particle shapes and corre-
sponding Cds which introduced signicant variances into
the computations. However, the equations clearly indicate
the operational background of the unit.
3. Discussion
The use of a vertical venturi separator was successfully
used to clean steel and synthetic bres from rubber crumb
produced froman automotive tyre recycling plant. The major
advantage of the venturi separator was an inherent positive
feedback loop that exists at the throat. If more material was
introduced to the throat then a higher velocity was generated
at the throat to help retain particles (dependant upon air
mover characteristics). The more conventional cleaning units
observed had a negative feedback inherent in their design,
with an increased local load of product the air velocity would
Screw Feeder
Storage
Hopper
To Filters
Butterfly valve to
dump product
M
a
g
n
e
t
i
c
s
e
p
e
r
a
t
o
r
Crumb Product Belt
Multiple units in series
for continious processing
Fig. 5. Expected batch system layout.
bypass the area resulting in unprocessed material exiting the
system.
From the testing work undertaken it was unclear if the
venturi unit could be operated in a continuous mode with
clean rubber exiting the throat with a continuing input of
product, or if the unit needed to be operated in a batched
mode with a relatively low loading. Given that the cycle
time for the most heavily tangled agglomerate was in the
order of 10 s the batch operation should not present a limi-
tation to throughput with typical crumb plants operating at
around 6 t/h max. From the information gained in the re-
search program it was determined that a single batch mode
venturi with a 250 mm throat would be able to process the
full plants throughput.
Fig. 5 illustrates the proposed concept for the plant im-
plementation of the process. Unfortunately this system was
never trialled as the company in question was liquidated for
other reasons.
W. McBride, S. Keys / Chemical Engineering and Processing 44 (2005) 287291 291
4. Conclusions
Through a program of experiments it was found that the
use of a classically designed venturi could be used to un-
tangle synthetic bre from steel bres formed during the
milling process of automotive tyres. With appropriate air
ow settings the venturi was able to hold the largest particle
sizes in the throat area, allow the clean steel to pass straight
through, and remove only the ner fraction of the rubber
with the synthetic bres. It is believed that the ne rubber
could be easily reclaimed from the bres using a traditional
cyclone separator.
This application of a classic venturi as essentially a
notch pass lter (aerodynamically large sections pass
straight through whilst aerodynamically small particles are
removed through the top) appears a signicant improve-
ment over the alternate separation units witnessed during
this project. The alternate units were quite capable of re-
moving free bre but large particles caused a bias in the
airow pattern away from the lump. This resulted in a
lowered cleaning efciency. The venturi unit displayed
an increase in throat velocity with the introduction of
more material causing an increase in the local cleaning
efciency.
Chemical Engineering and Processing 44 (2005) 293296
Particle movement during granular intermingling
in a pulsated bottom mixer
Mikls Nemnyi
, Attila J. Kovcs
Faculty of Agricultural and Food Sciences, Institute of Agricultural, Food and Environmental Engineering,
University of West Hungary, Vr 2, Mosonmagyarvr H-9200, Hungary
Received 14 August 2003; received in revised form 2 February 2004; accepted 11 February 2004
Available online 28 July 2004
Abstract
Many bulk commodities, such as cereal grains loaded into a silo require active mixing during storage. A special pulsated bottom mixer was
patented at our university for gentle mixing of granular solids stored in large containers or silos. This work intended to reveal the fundamentals
in displacement of single particles mixed by different pulsation orders. A glass-walled simulator (lled with wooden cylinders) was build in
order to be able to follow particles inside the simulated mixer. Three pulsating pistons were attached to the bottom of the simulator. Their
movements provide the mixing effect. Selected cylinders (some with different densities and friction coefcients) were followed during mixing.
Their positions were recorded after certain pulsations. From the measurements the mixing velocity of cylinders was calculated. Examinations
were focused on to give restrictions of the mixing: density and friction of the particles in connection with the pulsation. No correlations were
found between the mixing velocity and density or friction of the particles.
2004 Elsevier B.V. All rights reserved.
Keywords: Particle mixing; Density; Friction; Simulation
1. Introduction
Research on storage, mixing, and preservation techniques
of bulky materials has been initiated 15 years ago at the Uni-
versity of West Hungary, Faculty of Agricultural and Food
Sciences, Institute of Agricultural, Food and Environmental
Engineering. A pilot size storage container was built with in-
atable air tubes at the bottom of the bulk. Inating and de-
ating them with compressed air enable to move and mix the
grain layers being placed above them[1]. Using this patented
method the formation of rotting parts can be prevented and
the existing centers can be eliminated. On the other hand,
the mixing system with ventilation can increase the safety of
storage [2,3]. The investigations proved that this method is
also suitable for other granular materials than cereal grains.
Based on the pilot scale measurements mathematical mod-
eling was started in order to describe the processes. Discrete
element method (DEM) was used to model the mixing. This
was originated from a simple mechanical model to formulate
Corresponding author. Tel.: +36 96 566 635; fax: +36 96 566 641.
E-mail address: nemenyim@mtk.nyme.hu (M. Nem enyi).
the contact forces between two spheres and a particle and
wall, respectively [4,5]. The model considers among others,
the stiffness, damping, and friction coefcients of the par-
ticles. However, the results of modeling of pulsated bottom
mixer were inaccurate and did not follow exactly our mea-
surements. Therefore, examinations were set up to clarify
the principles.
A laboratory glass-walled mixing simulator (dimensions:
0.7 m 0.5 m 0.02 m) was built based on the pilot-scale
apparatus (Fig. 1). Three pulsating pistons were attached at
the bottom of the simulator. The circulation of the particles
is due to the sequence of the pulsation of the pistons. The
pattern of motion using the pistons is similar to the motion
achieved by vibrating processes [6]. The difference between
the two processes is that any kind of motion pattern can be
acquired by using the pulsating mixer independently from
the shape of vessel.
Consequently, the direction of movement of particles with
different densities is independent in our system.
The basic aim of this examination was to nd out the
effects of densities and friction coefcients of particles on
the velocities of movement and mixing.
0255-2701/$ see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.cep.2004.02.024
294 M. Nem enyi, A.J. Kov acs / Chemical Engineering and Processing 44 (2005) 293296
2 1 3
50.00 cm
42.50 cm
17.00 cm (a) (b)
70.00 cm
vessel
pistons
particles
7.00 cm
4.00 cm
Fig. 1. Schematic diagram of the laboratory glass-walled mixing simulator of (a) cylinder in the middle move down; (b) cylinders in the middle move
upwards.
Fig. 2. Photo of the mixing simulator during measurement (1, 2, 3: selected cylinders; sequence: 2). (a) Before movement, (b) after 50 sequences, (c)
after 100 sequences, (d) after 150 sequences, (e) after 200 sequences, and (f) after 250 sequences.
M. Nem enyi, A.J. Kov acs / Chemical Engineering and Processing 44 (2005) 293296 295
Table 1
The sequences of the pistons (starting point: all three cylinders are down)
Steps Sequence 1 (Fig. 1a) Sequence 2 (Fig. 1b)
1 Pistons #2 and #3 Up () Piston #1 Up ()
2 Piston #1 Up () Pistons #2 and #3 Up ()
3 Pistons #2 and #3 Down () Piston #1 Down ()
4 Piston #1 Down () Pistons #2 and #3 Down ()
2. Material and methods
The simulator (Fig. 1) was lled with wooden cylin-
ders with the diameter of 20 mm and the length of 18 mm
( = 700 kg/m
3
, = 0.25). The examined parameters
were: (i) mixing of particles inside the bulk; and (ii)
moving (mixing) characteristics of selected cylinders with
different parameters. In each measurement three cylin-
ders with the same properties were followed. Different
properties of cylinders were studied, such as: wooden
cylinders with coarse surfaces (coated with sandpaper):
ne
= 0.63;
middle
= 0.73;
rough
= 0.91; aluminum
cylinders ( = 0.24, = 2500 kg/m
3
); wooden cylinder
with meat insert ( = 1600 kg/m
3
); hollow metal cylin-
der ( = 0.25, = 6180 kg/m
3
). Figs. 1 and 2 show
the diagram and picture of pulsated bottom mixer. The
lifting of a piston was taken by 0.5 s, and the lowering
was done by 0.1 s. Two moving sequences were utilized
(Table 1).
After 10 sequences the positions of the three selected
cylinders were recorded and a photo was taken from the
Fig. 3. MATLAB-based evaluation of the mixing shown in Fig. 2.
mixer (Fig. 2). Each measurement was taken until 300500
sequences reached that is each selected cylinder rotated at
least two times.
3. Results and discussions
The evaluation of measurements was carried out using the
MATLAB 6.5 software (Fig. 3). The path of the three se-
lected cylinders visualized and the velocity of each cylinder
was calculated. The velocity of a cylinder was calculated
by dividing the sequences by the distance that the cylinder
drove. The velocities of three cylinders were averaged.
Based on the measurements the following was established.
The velocity of cylinder is independent of the friction coef-
cient (Figs. 4 and 5). This means that the smooth surfaced
wooden or aluminum cylinders move with the same speed
as the rough sand-paper covered one. Higher average veloc-
ities with 0.2 cm per movement was found in sequence 2
(where the middle examined cylinder moves upward), than
in sequence 1 (where a cylinder in the middle moves down).
296 M. Nem enyi, A.J. Kov acs / Chemical Engineering and Processing 44 (2005) 293296
0. 0
0. 1
0. 2
0. 3
0. 4
0. 5
0. 6
0. 7
0. 8
0. 0 0.2 0. 4 0.6 0. 8 1.0
Friction coefficient,
V
e
l
o
c
i
t
y
,
v
[
d
i
s
t
a
n
c
e
:
c
m
/
m
o
v
e
m
e
n
t
]
Average: 0.59
Fig. 4. Velocities of the selected cylinders with different friction coef-
cients; middle section moves downwards.
0. 0
0. 1
0. 2
0. 3
0. 4
0. 5
0. 6
0. 0 0.2 0. 4 0.6 0. 8 1.0
Friction coefficient,
V
e
l
o
c
i
t
y
,
v
[
d
i
s
t
a
n
c
e
:
c
m
/
m
o
v
e
m
e
n
t
]
Average: 0. 38
Fig. 5. Velocities of the selected cylinders with different friction coef-
cients; middle section moves upwards.
0
0. 1
0. 2
0. 3
0. 4
0. 5
0. 6
0. 7
0 0 4 6 8 10
De ns ity ratio [ /
wo od
]
V
e
l
o
c
i
t
y
,
v
[
d
i
s
t
a
n
c
e
:
c
m
/
m
o
v
e
m
e
n
t
]
Middle pa rt do wn
Midd le p art up
w
o
o
d
w
o
o
d
+
m
e
t
a
l
a
l
u
m
i
n
u
m
m
e
t
a
l
Fig. 6. Velocities of the selected cylinders with different densities.
One of the reasons of this is that the distance of penetration
of pistons into the bulk was not the same on the sides than
in the middle (Fig. 1).
The densities of cylinders also do not play a role in the
velocities according to our measurements (Fig. 6). It can
be concluded from this that the wooden cylinder with a
density of 700 kg/m
3
moves with the same speed as the
hollow metal cylinder having the density of 6180 kg/m
3
.
These measurements also proved that exact mixing effect
could be reached even under a signicant density difference
(1:10). It was also proved that the denser particles could be
moved in any directions into the bulk.
The results of the above measurements can be used for
improving the mathematical descriptions. However, in this
kind of mixing a major revision and maybe simplication
of the models seems to be suitable.
4. Conclusions
Measurements were carried out in order to correct the
existing discrete element methods that describe mixing ef-
fect of granules in a bulk. Different densities and friction
coefcients of particles were studied to nd correlations
between the parameters and the mixing characteristics.
There was found no effect of these parameters on mixing.
Therefore, the DEM modeling work in this case has to be
reevaluated.
Acknowledgements
The authors express their thanks to Ms. Mrta Varga (Hun-
garian Academy of Sciences, Research Group of Process
Engineering of Agricultural Products) and Mr. Roland Pap,
Ph.D. students for their help; and the founder of Hungarian
Research Funds (OTKA) # T032666 and # F035247.
References
[1] M. Nemnyi, Z. Srkny, K. Kacz, Moving the cereal bulks by pneu-
matic system, Hung. Agric. Eng. 5 (1992) 2425.
[2] K. Kacz, Z. Srkny, Intensive mixing the cereal bulks by pneumatic
method during storage, Hung. Agric. Eng. 6 (1996) 5758.
[3] M. Nemnyi, J. Gyenis, A.J. Kovcs, Intermingling of cohesionless
particles with special regard to grains in pulsated bottom mixer, in:
Proceedings of Third Israeli Conference for Conveying and Han-
dling of Particulate Solids, Dead Sea, Israel, 29 May1 June 2000,
pp. 8.248.28.
[4] Zs. Ulbert, J. Szpvlgyi, J. Gyenis, Y. Tsuji, Modelling and simulation
of particle mixing in gravity and pneumatic mixing tubes containing
helicoidal mixer element, Recents Progres en Genie des Procedes 11
(1997) 299306.
[5] P.A. Cundall, O.D.L. Strack, A discrete numerical model for granular
assemblies, Geotechnique 29 (1979) 4765.
[6] K. Erdsz, Vibrcis technika az lelmiszeriparban, Mezogazdasgi
Kiad, Budapest, 1984 (Vibration technique in food industry, Agri-
cultural Press, Budapest).
Chemical Engineering and Processing 44 (2005) 297302
Estimating the homogenization efciency of mammoth silos
by process dynamics and simulations
Comparing the results of process dynamics with the simulations
D.L. Schott
a,
, L.A. van Wijk
b
, W.J. Vlasblom
a
a
Department of Marine and Transport Technology, Delft University of Technology, Mekelweg 2, 2628 CD Delft, The Netherlands
b
ESI Eurosilo BV, P.O. Box 1047, 1440 BA Purmerend, The Netherlands
Received 26 August 2003; received in revised form 10 March 2004; accepted 19 March 2004
Available online 25 June 2004
Abstract
Previous publications of the authors introduced the homogenization theory of mammoth silos and process dynamics as an indicator of
the homogenization efciency of mammoth silos. Here, it is shown that process dynamics can be used for estimating the homogenization
efciency mainly for silos with a large H/D, given a negative exponential auto correlation function for modeling of the input properties. For
smaller silos with equal volume process dynamics underestimates the homogenization results, due to the existence of top and bottom cones.
2004 Elsevier B.V. All rights reserved.
Keywords: Homogenization efciency; Mammoth silos; Silos; Process dynamics
1. Introduction
In previous articles on Homogenization in mammoth
silos the homogenization theory of these silos was pre-
sented by Schott et al. [1,2], as well as process dynamics
(PD) as a tool to predict the homogenization efciency by
Gerstel and Schott [3,4]. One method to achieve homoge-
nization in mammoth silos is presented in Fig. 1. From the
homogenization theory follows that no analytical solution
can be obtained due to silo geometry, stacking and reclaim-
ing methods. PD does give an analytical solution if the input
auto correlation is known and can be analytically described,
but this solution is based on an innite number of layers
and is valid only for the silo part where the reclaiming and
stacking angle are constant. Or, in other words, PD does not
allow for the start and bottom cones of the homogenization
method. Oosterhuis et al. [5] performed experiments with
an inclined screw conveyor on a free surface. It was inves-
tigated whether this screw can be used to obtain large-scale
homogenization in mammoth silos (Fig. 1). These experi-
ments were carried out at Delft University of Technology.
Corresponding author. Tel.: +31 15 278 3306; fax: +31 15 278 2492.
E-mail addresses: dingenaschott@hotmail.com (D.L. Schott),
avanwijk@eurosilo.com (L.A. van Wijk).
The aim of this paper is to examine the usefulness of pro-
cess dynamics (PD) for obtaining reliable estimations of the
homogenization efciency. Therefore, we will rst briey
discuss the homogenization theory and PD in, respectively,
Sections 2 and 3. Then the results of simulations of the ho-
mogenization theory and PD will be compared. This com-
parison in Section 4 is mainly based on the reduction of the
standard deviation (
y
/
x
) of the material properties. This
paper concludes with a discussion regarding estimating the
homogenization efciency using PD.
2. Modeling using homogenization theory
For the derivation of the homogenization theory is referred
to previous publications of the authors [1,2]. The main result
is the reduction of the standard deviation of the material
property from the output compared to the input as shown in
Eq. (1):
x
=
1
v
slice
m
s=1
(n
s
1)
b
s
i=a
s
b
s
j=a
s
v
i,s
v
j,s
x
(i, j)
m
s=1
n
s
1
(1)
0255-2701/$ see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.cep.2004.03.015
298 D.L. Schott et al. / Chemical Engineering and Processing 44 (2005) 297302
cd
< 0 > 0
Fig. 1. Inclined stacking by controlled dump (left) and reclaiming using
an inclined conveyor (right). The symbols and indicate the stacking
and reclaiming angles.
This equation is valid under the condition that the volumes
of the slices (v
slice
) are mutually equal. As can be seen from
Eq. (1) the reduction of the standard deviation is a function
of:
volume distribution, i.e. the number of layers intersected
by the conveyor during reclamation, and the volume of
each layer in this slice (v
i,s
and v
j,s
). This is xed by the
chosen silo geometry, stacking and reclaiming method,
and number of layers (n
s
) and slices (m);
input properties, i.e. the uctuations of certain physical
or chemical material properties in the input ow modeled
by the auto correlation function
x
.
This equation cannot be solved analytically due to
the volume distribution. Therefore we have built a sim-
ulation program to calculate the homogenization ef-
ciency (
y
/
x
and the improvement of the autocorrelation
function).
3. Modeling using process dynamics (PD)
The homogenization process, existing out of a stacking
and reclaiming process, is linear and due to constant stacking
and reclaiming angles the system is time invariant as well.
Applying s requires a continuous and linear time invariant
system, this rst requirement is met by taking innite thin
slices. How the auto covariance function of the output is
obtained is in detail explained in previous publications of
Gerstel and Schott [3,4], here only the result based on a
rst order negative exponential input correlation function
(Eq. (2)) is presented in Eqs. (3)(5).
x
() = e
||/V
ci
(2)
where V
ci
is the characteristic volume of the input properties
(m
3
).The auto covariance function for 0
z
V
s+r
and
for
z
V
s+r
is, respectively, Eqs. (3) and (4):
yy
(
z
) =
4
2
x
V
ci
3V
4
s+r
2V
3
s+r
+
3
z
+6
z
V
2
ci
3V
2
s+r
z
+(6V
3
ci
3V
2
s+r
V
ci
)e
z
/V
ci
(3V
3
ci
+3V
s+r
V
2
ci
)e
(V
s+r
+
z
)/V
ci
(3V
3
ci
+3V
s+r
V
2
ci
)e
V
s+r
+
z
/V
ci
(3)
yy
(
z
) =
4
2
x
V
2
ci
V
4
s+r
(2V
2
ci
V
2
s+r
e
z
/V
ci
(V
ci
V
s+r
+V
2
ci
)e
(V
s+r
+
z
)/V
ci
+(V
ci
V
s+r
V
2
ci
)e
V
s+r
z
/V
ci
) (4)
The reduction of the standard deviation is obtained by using
z
= 0 in Eq. (3):
x
=
4V
ci
3V
4
s+r
(2V
3
s+r
+6V
3
ci
3V
2
s+r
V
ci
6V
2
ci
(V
ci
+V
s+r
)e
V
s+r
/V
ci
) (5)
4. Results
In order to compare the results from PD with the simula-
tions, the input properties, and silo geometry have to be the
same. As the results of PD in the previous section are based
on a rst order negative exponential correlation function,
this function was used as well for the simulations. Three
different input properties were used with different charac-
teristic volumes (V
ci
): 40 and 400 m
3
. The silo volume was
approximately 40,000 m
3
, with a height of 50 m and a diam-
eter of 32 m. This relatively high silo was chosen because
constant angles over the silo height are required (as indi-
cated in Fig. 1) for a thorough comparison with PD. As the
input properties are realizations of a stochastic process 400
repetitions were done per simulation.
4.1. Process dynamics (PD)
A characteristic volume of the input property (V
ci
) equal
to 40 m
3
means that the signal is very incoherent. This indi-
cates that homogenizing will improve the coherence of the
signal and reduce the amount of uctuations very well. Fig. 2
shows the improvement of the auto correlation function de-
pending on the stacking and reclaiming angles. The y-axis
represents the auto correlation function as a function of
the lag
V
on the x-axis. The plot on the left-hand side shows
the results of the homogenization process with a horizontal
stacking method, whereas the other plot shows the results
on the basis of inclined stacking ( = 30
v
x10
3
[m
3
]
[-] = 0
0 1 2 3 4
0
0.2
0.4
0.6
0.8
1
= 30 = 20
= 10 in
v
x10
3
[m
3
]
[-] =30
0 1 2 3 4
0
0.2
0.4
0.6
0.8
1
= 30 = 20
= 10 = 0 in
Fig. 2. PD results: input and output auto correlation functions with V
ci
= 40 m
3
.
v
x10
3
[m
3
]
[-] = 0
0 1 2 3 4
0
0.2
0.4
0.6
0.8
1
= 30 = 20
= 10 in
v
x10
3
[m
3
]
[-] =30
0 1 2 3 4
0
0.2
0.4
0.6
0.8
1
= 30 = 20
= 10 = 0 in
Fig. 3. PD results: input and output auto correlation functions with V
ci
= 400 m
3
.
correlation functions of the output (dashed lines). The cor-
relation functions of the output differ since the reclaiming
angle is different as indicated in the legend of the plot.
The improvement of the characteristic volume can be de-
rived from the gure. For example: the characteristic volume
of the output property (V
co
) is approximately 2000 m
3
when
the stacking is horizontally ( = 0
. This improves to V
co
4000 m
3
when the
stacking angle = 30
.
A better correlated input signal will leave less space for
improvement compared to the previous. Fig. 3 shows the
improvement of the auto correlation functions for V
ci
=
400 m
3
. It follows that the characteristic volume of the output
property (V
co
) is just slightly higher compared to V
ci
=
40 m
3
: V
co
3400 m
3
versus V
co
3200 m
3
for = 0
and = 30
.
Results of the reduction of the standard deviation obtained
from PD follow in the next subsection.
4.2. Comparison of PD with simulations
Tables 1 and 2 both show the reduction of the standard
deviations relative to the mean value of the input calculated
by the simulations and PD for different stacking () and
reclaiming () angles. V
ci
in the upper left of the tables
indicates the characteristic volume of the input property used
for the calculations and simulations.
The requirement for applying PD is that the system should
be a linear time invariant system. This is the case in the area
where both the reclaiming and the stacking angles are con-
stant. This part is indicated by const in Fig. 5. The top and
bottom cones are indicated by top and bottom respec-
tively. This notation is also used in the following tables.
The stacking method can be implemented in two ways;
using an inclined conveyor (ic) and controlled dump (cd).
The difference is shown in Fig. 4.
These tables show that the PD results match quite
well with the results of the constant part and the total
< 0
cd
< 0
Fig. 4. Inclined stacking using an inclined conveyor (left) and inclined
stacking using controlled dump (right).
300 D.L. Schott et al. / Chemical Engineering and Processing 44 (2005) 297302
Table 1
Results of the reduction of the standard deviation from process dynamics and simulations for V
ci
= 40 m
3
, H = 50 m and D = 32 m.
V
ci
= 40 m
3
PD (
y
/
x
) Average
y
/
x
of 400 simulations
Total Const Top Bottom
0 30 0.119 0.166 0.122 0.246 0.299
10 cd 20 0.123 0.138 0.126 0.140 0.175
10 ic 20 0.123 0.144 0.126 0.170 0.190
20 cd 10 0.123 0.133 0.125 0.138 0.143
20 ic 10 0.123 0.144 0.125 0.178 0.166
30 cd 30 0.085 0.089 0.074 0.087 0.097
30 ic 30 0.085 0.105 0.074 0.113 0.114
Table 2
Results of the reduction of the standard deviation from process dynamics and simulations for V
ci
= 400 m
3
, H = 50 m and D = 32 m
V
ci
= 400 m
3
PD (
y
/
x
) Average
y
/
x
of 400 simulations
Total Const Top Bottom
0 30 0.364 0.385 0.323 0.506 0.580
10 cd 20 0.375 0.361 0.333 0.358 0.432
10 ic 20 0.375 0.364 0.333 0.385 0.438
20 cd 10 0.375 0.350 0.332 0.346 0.371
20 ic 10 0.375 0.361 0.331 0.402 0.385
30 cd 30 0.263 0.240 0.200 0.228 0.260
30 ic 30 0.263 0.258 0.200 0.268 0.274
homogenization efciency of the silo. As we have to deal
with top and bottom cones (Fig. 5) where the homoge-
nization efciency will be less (as shown by the last two
columns in Tables 1 and 2), the question is whether PD
is a good approximation of the whole silo content and not
only for the constant part. Even though the homogenization
of the top and bottom part is less, the approximation of
PD is within 3% of the simulation results. Comparing the
rows with controlled dump and inclined conveyor shows
preferable results for the controlled dump stacking method
over the inclined conveyor method (Tables 1, 2 and 5).
The slightly underestimation of the homogenization ef-
ciency in Table 1 and the slightly overestimation in Table 2
can be a result of the realization of the stochastic input prop-
erties, although these are based on the analytical input auto
correlation function used for PD. Another possible cause is
the number of layers; in practice the layer thickness is 10 cm,
this value was used in the simulations. But, PD is based on
innite thin layers so using layers of 10 cm can make the
difference with the volume distribution of different layers in
a slice (Section 2).
Table 3 gives an overview of the volume in the different
parts of the silo. The inuence of the top and bottom cones
of the small stacking and reclaiming angles seems to be
rather small, and there is no difference between controlled
dump (cd) and inclined conveyor (ic) stacking. So the
difference between cd and ic can be explained only by the
different volume distributions in the top and bottom cones,
Table 3
Volume of the different silo parts of a silo with H = 50 m and D = 32 m
H = 50 m; D = 32 m Volume in parts of silo (m
3
)
Total Const Top Bottom
0 30 40212 32703 2503 5006
10 20 40212 30523 4118 5572
20 10 40212 28100 5733 6379
30 30 40212 13566 12112 14535
where cd is the method to prefer in terms of homogenization
efciency.
For a smaller silo, with equal storage volume, the volume
in the parts of the silo change, the constant part becomes
less and the top and bottom parts have an increasing inu-
ence as can be seen in Table 4 and Fig. 5. The bottom row
shows that due to the stacking and reclaiming angles no part
with stationary homogenization efciency is left. As a re-
Table 4
Volume of the different silo parts of a silo with H = 25 m and D = 45 m
H = 25 m; D = 45 m Volume in parts of silo (m
3
)
Total Const Top Bottom
0 30 39761 19162 6866 13733
10 20 39761 2156 16687 20918
20 10 39761 1357 18204 20200
30 30 39761 0 16527 23234
D.L. Schott et al. / Chemical Engineering and Processing 44 (2005) 297302 301
CL
CL
top
constant
bottom
Fig. 5. Distinction of areas in the mammoth silo for different H/D.
Table 5
Results of the reduction of the standard deviation from process dynamics and simulations for V
ci
= 400 m
3
, H = 25 m, and D = 45 m
H= 25 m; D = 45 m; V
ci
= 400 m
3
PD (
y
/
x
)
y
/
x
simulations
Total Const Top Bottom
0 30 0.364 0.313 0.157 0.353 0.420
10 cd 20 0.375 0.223 0.150 0.195 0.240
10 ic 20 0.375 0.237 0.150 0.219 0.248
20 cd 10 0.375 0.201 0.155 0.192 0.203
20 ic 10 0.375 0.237 0.154 0.242 0.227
30 cd 30 0.263 0.136 0.117 0.145
30 ic 30 0.263 0.182 0.177 0.179
Homogenization of the same amount of material with equal stacking and reclaiming methods in a smaller silo will be better compared to a tall silo
(Fig. 5) because the amount of material between the rst and last intersected layer is larger. So, the auto correlation of the output material will be
improved at a higher extent compared to the silo with a large H/D.
sult the estimation by PD is getting worse, but is at least
an underestimation of the total homogenization results (see
Table 5).
5. Conclusions
With material properties modeled by a negative exponen-
tial auto correlation function we have seen that the estima-
tion by process dynamics is quite well for H = 50 m and D
= 32 m. For silos with a smaller H/D the estimation is get-
ting worse, because the volume where the process dynamics
can be applied is getting smaller and top and bottom cones
dominate the results. Compared to tall silos, the homoge-
nization result in small silos with equal storage volume will
in general be better because the amount of material between
the rst and last intersected layers in a slice is larger. Of
course this is valid for equal stacking and reclaiming meth-
ods.
Appendix A. Nomenclature
m number of slices
n
s
number of layers intersected by slice s
v
i,s
volume of layer i in slice s (m
3
)
v
j,s
volume of layer j in slice s (m
3
)
v
slice
volume of a slice (m
3
)
V
ci
characteristic volume of the input properties
(m
3
)
V
co
characteristic volume of the output
properties (m
3
)
V
s+r
volume of stacking + reclaiming cone (m
3
)
Greek letters
yy
auto covariance function of the output
auto correlation function
x
auto correlation function of the input x
x
standard deviation of the input signal x
,
z
lag (m
3
)
References
[1] D.L. Schott, A.W. Gerstel, L.A. van Wijk, Homogenization theory of
mammoth silos, in: Proceedings of the Seventh ICBMH, University
of Newcastle, NSW, Australia, 2001, pp. 199208.
[2] D.L. Schott, L.A. van Wijk, C. Kraaikamp, Large scale homogeniza-
tion in mammoth silos: importance of modeling input properties, Int.
J. Miner. Process. 71 (14) (2003) 179199.
302 D.L. Schott et al. / Chemical Engineering and Processing 44 (2005) 297302
[3] A.W. Gerstel, D.L. Schott, Homogenisation in mammoth silos, in:
Proceedings of the Seventh ICBMH, University of Newcastle, NSW,
Australia, 2001, pp. 189198.
[4] A.W. Gerstel, D.L. Schott, Upgrading of bulk material in mammoth
silos, Port Technol. Int. 17 (2002) 109116.
[5] E.J. Oosterhuis, D.L. Schott, L.A. van Wijk, Reclaim screw in mam-
moth silos operating on a free surface: comparison between horizontal
and inclined operation on free owing bulk solids, in: Proceedings of
the Fourth CHoPS, Budapest, Hungary, 2003.
Chemical Engineering and Processing 44 (2005) 303313
Assessing the homogeneity of powder mixtures
by on-line electrical capacitance
N. Ehrhardt
a
, M. Montagne
a
, H. Berthiaux
a,
, B. Dalloz-Dubrujeaud
b
, C. Gatumel
a
a
Laboratoire de Gnie des Procds des Solides Diviss, UMR CNRS 2392, Ecole des Mines dAlbi-Carmaux,
Campus Jarlard, route de Teillet, 81 000 ALBI, France
b
Dpartement de Mcanique Energtique, UMR CNRS 6595, Ecole Polytechnique Universitaire de Marseille,
Technop ole de Ch ateau-Gombert, 5, rue Enrico Fermi, 13 453 Marseille, France
Received 27 August 2003; received in revised form 10 March 2004; accepted 19 March 2004
Available online 25 June 2004
Abstract
In this paper, we try to improve our comprehension of one of the most important challenge in the particulate solids industry: the assessment
of the homogeneity of powder mixtures. A two-electrode electrical capacitance method is used to measure the permittivity of mixtures while
owing in a 1-D set up. An emphasis is placed on the possibility of following homogeneity evolution through permittivity measurement,
without the necessity to calculate the volumetric proportions of each component from an effective medium formulation. The methodology is
applied to examine segregation in a funnel, as well as the efciency of a laboratory drum mixer.
2004 Elsevier B.V. All rights reserved.
Keywords: Homogeneity; Capacitance; Powder mixing
1. Introduction
With the increased variety of formulated products of the
particle form that appears every day on the market and
that are issued for a wide range from industry (pharma-
ceutical, agro-food, cement, plastics, . . . ), particulate pro-
cesses in general, and mixing processes in particular, are
pushed to a never-ending battle against their own perfor-
mances. This is due to the fact that the end-used properties of
the products that are manufactured nowadays are more and
more complex, especially because these must cover more
and more functions. Because product engineering had be-
come a major engineering science producing its own tools
both at the research and the educational levels, a prod-
uct ought to become an intelligent delivery system, a
small process able to optimise its own action when it is
used.
However, it is of common knowledge that mixers, as much
other equipment dealing with particles, are all designed and
operated from the purest empiricism. Indeed, there exists an
N
i=1
(x
i
)
2
N
(1)
This latter formula, which is commonly used in the in-
dustrial practice, also holds for the case of an estimation of
the mixture quality using random sampling. However, the
main problem in this global analysis lays in the well-known
(since the famous Danckwerts example in chemical reac-
tors [23]) fact that two different structures can correspond to
the same intensity of segregation criteria. Fig. 1 illustrates
this idea, which has a very practical sense in the context of
pharmaceutical blending.
In effect, let us assume that the two processes depicted
here concern pharmaceutical tablets produced in packages
containing six consecutive unit doses. These are of identi-
cal macromixing state, as standard deviations are equal. But
in one case (namely Fig. 1a), a patient will take a slightly
under-dosed treatment, and another one a slightly overdosed
treatment, while in the second possibility (Fig. 1b), an equi-
librium of the dose will be reached after the second take.
Indeed, structure defaults can provoke negative therapeutic
effects that cannot be diagnosed with a macroscopic index
of segregation intensity.
As introduced by Danckwerts in the mid-fties [24,25],
and more recently reviewed by Gyenis [26], the mixing
structure can be accounted for by the use of the autocorrela-
tion function R(r) (Eq. (2)). The distance r
0
, corresponding
to the equation R(r) = 0, at which two sample compositions
can be considered to be uncorrelated, is a main character-
istic of the structure of the mixture and has an important
practical consequence: tablets should probably be produced
at this segregation scale to statistically ensure that these
have the right (desired) composition. However, the gure
given here is still global, as we do not know anything about
the location and the distribution of the segregated zones in
the mixer, and also on zones of acceptable defaults. As a
consequence, the size of the tablets that corresponds to the
segregation scale may be not so adequate as it is said to be.
R(r) =
Nr
i=1
(x
i
)(x
i+r
)
N
i=1
(x
i
)
2
(2)
An illustrating example for this idea is provided in Fig. 2,
in which a series of consecutive elementary samples con-
taining an active ingredient has been articially generated.
One may easily nd that the mean content is = 5%, while
the global standard deviation is = 1.34%. If we refer to
a pharmaceutical standard, this is not a good mixing, being
the corresponding coefcient of variation equal to 26%. As
it can also be seen from the data, an important deviation
from the mean occurs for sample nos. 11 and 12, which
have the particularity of being corrected at a small scale
(sample nos. 13 and 14). From the point of view of mon-
itoring of the mixing process, it is certainly interesting to
search for this local default that makes the overall mixture
probably inadequate, despite of the fact that other regions
seem to be much better mixed.
If we look at the variations of the corresponding auto-
correlation function (Fig. 3), the characteristic distance r
0
covers between 1 and 2 elementary samples, which means
that these must be grouped two by two or three by three (for
more security) to avoid any correlation. Doing so, six or ten
tablets can be dened depending on the way the elementary
ones were grouped together (see also Fig. 2). However, this
procedure did not really change the situation, as it gave rise
to an overdosed (no. 4) and an under-dosed tablet (no. 5) and
four perfectly dosed tablets (nos. l3 and 6). This is due to
306 N. Ehrhardt et al. / Chemical Engineering and Processing 44 (2005) 303313
Fig. 2. Numerical example showing that a non-randomised structural default (heterogeneous zone between sample nos. 1114) cannot be cleared by
increasing sample size either by a factor 2 (top case) or 3 (bottom case).
the fact that this structural default induces segregation at a
relatively short scale, and cannot be adequately detected by
the criteria r
0
. The reason for this failure is fundamentally
linked to the global (but structural) character of this crite-
rion that characterises homogeneity at the scale of all the
N samples. In other words, this analysis would give a bet-
ter result if the problematic elementary samples were not
placed coast to coast in the mixture, but dispatched along
the whole data set.
2.2. Methodology for detecting structural defaults
Because of the above-mentioned type of problem, it is ad-
visable to have a better insight on the local structure of the
Fig. 3. Autocorrelogram corresponding to the present example, and indicating that a characteristic interval of two samples should be considered for
ensuring homogeneity.
mixture, with the aim of disregarding samples of inadequate
composition rather than grouping them. For this reason, we
derived another type of analysis, which we claim to be more
sensible to structural defaults and also easier to adapt to
on-line measurement of continuous processes in which the
series of data is, in principle, innite. Let us rst dene a
window that consists of n consecutive elementary sam-
ples (of course n < N) placed at the beginning of the data
series. For this packet of samples, a mean
1,n
and a stan-
dard deviation
1,n
can be dened by the following Eqs. (3)
and (4).
1,n
=
1
n
n
i=1
x
i
(3)
N. Ehrhardt et al. / Chemical Engineering and Processing 44 (2005) 303313 307
1,n
=
n
i=1
(x
i
1,n
)
2
n
(4)
Let us further displace this window from one sample to
the right (of, say, Fig. 2), dening thus another mean
2,n
and another standard deviation
2,n
. If the composition of
the newly considered sample (number n + 1) is close to x
1
,
then both
2,n
and
2,n
will be close to
1,n
and
1,n
, re-
spectively. In the contrary, if a small structural default ex-
ists, it will be detected by this analysis because the variation
of the corresponding mean and standard deviation will be
important, even if it concerns segregation at a small scale.
Generalisation of Eqs. (3) and (4) for packets beginning with
sample number k is obviously given by Eqs. (5) and (6).
k,n
=
1
n
n+k1
i=k
x
i
(5)
k,n
=
n+k1
i=k
(x
i
k,n
)
2
n
(6)
For the above example, one can observe that the seventh
packet rst considers the small segregated region, while it is
not touched after the fourteenth if the size of the window is
equal to ve samples. This results in a clearly marked peak
on a graph representing the variation of these local variances
with time, while the means are affected at a much lower
level (see Fig. 4).
The reason for this lays in the fact that even a small
deviation in composition has a consequence on the standard
deviation value, so that the local standard deviations are as
great as many samples in the packet demonstrate a deviation
from the mean. In our case, it can be seen that the number
n
p
of packets that are affected by the perturbation is equal to
8 out of 16, which also helps in magnifying the default. For
instance, it is felt that a smoothed local standard deviation
Fig. 4. Evolution of the local means and standard deviations with the number of packet considered (packet width equal to ve elementary samples),
magnifying the existence and the location of the heterogeneous zone.
curve is the consequence of a good mixture achieved at a
small scale, while a rough one corresponds to the existence
of heterogeneous regions in the blend.
From the graph, it is also possible to calculate the number
of samples n
0
that form part of the default, and should prob-
ably be taken away from the production line. In effect, it is
easy to demonstrate Eq. (7). In the present example, as n
p
= 8 and n = 5, one will verify that the heterogeneous zone
effectively covers four consecutive elementary samples.
n
0
= n
p
n +1 (7)
3. Experimental set up development and methodologies
Like in any micromixing state consideration, the experi-
mental illustration of the concept needs the development of
a sensor. Because even slight structural defaults must be de-
tected, it can be felt that this technique may cover the fol-
lowing properties:
(1) Be adapted on-line: The three dimensional knowledge
of the repartition of the components in a vessel (as in
a batch mixer) is generally of a few interest for the
practitioner, especially because an important disruption
of the mixture occurs when emptying the mixer.
(2) Be non-intrusive: This is the better way to avoid any
cutting error due to the insertion of a probe in the
powder ow.
(3) Be exhaustive: As all defaults are to be screened, no
partial sampling procedures that would induce a statis-
tical bias can be developed. For instance, the derivation
of a certain part of the powder ow for analysis cannot
be considered here.
(4) Have a good spatial and temporal resolution.
On the other hand, as only the global content in the sam-
ple is to be derived, imaging and tomographic techniques
308 N. Ehrhardt et al. / Chemical Engineering and Processing 44 (2005) 303313
Fig. 5. Capacitance sensor developed.
that also provide spatial distributions are perhaps too pow-
erful tools to be employed with respect to the information
effectively needed. From the above-mentioned techniques, it
can be understood that the best method prole should com-
bine the advantages of bre-optics (exibility, global infor-
mation) and ECT (non-intrusive, no sampling) sensors.
3.1. Electrical capacitance set up
Classical ECT set ups are composed by a ring of elec-
trodes (typically 12, see [27,28]), which is generally placed
around the external part of the pipe itself. The correlation
between the dielectric measurements provided by the elec-
trodes allows for a tomographic mapping of the pipe in
the radial direction. In the present case and as commented
above, the radial distribution of the components is of a few
interest (at least in a rst approximation) as we are only
concerned with the overall composition in the measuring
volume. For this reason, we developed a capacitance sensor
with the aim of measuring the variations of the global ca-
pacity of a mixture during its own ow. It thus consists of
only two copper electrodes covering practically the whole
Fig. 6. Sketch of the electronic circuit for capacitance measurements.
section of a glass tube of external diameter 12 mm (see Fig.
5). A PVC screen allows isolating the electrodes from the
aluminium full cylinder (of dimensions 40 mm 30 mm)
that covers the overall measuring cell. This latter also pre-
vents from external disturbances, as well as the coaxial
cables, making the liaison with the capacitance meter.
The sensor is connected to a capacitance meter consisting
of the electronic circuit depicted in Fig. 6, and further to a
computer through an analogic/numeric converter. Measure-
ments are taken at a frequency of 5000 scans per second
and the sensibility of the circuit is high enough (close to
0.1 pF) to detect the capacity variations of some picofarads
provoked by changes in the composition of the measured
volume. Preliminary results also show that capacity and di-
electric permittivity could be linked to each other through a
linear relation over the whole measuring range in which we
work. It must be stated that such a statement is only true if the
measured space between electrodes is fully lled with mate-
rial. Otherwise, the measurements would show very strong
non-linear character.
The calibration of the sensors is performed with a liquid
(namely n-butyl acetate) of known dielectric permittivity,
N. Ehrhardt et al. / Chemical Engineering and Processing 44 (2005) 303313 309
and is repeated every week. Three sensors of exactly the
same characteristics were constructed and can be linked to
the capacitance meter at the same time. As capacitance is
strongly inuenced by temperature and humidity, a cool-
ing air equipment is also placed near the sensors, ensuring
then a temperature comprised between 15 and 16
C. In
the same time, humidity of the laboratory is controlled to
be sure it is rigorously the same for each experimentation.
Each sensor proceeds to measurements on samples whose
volume is approximately 2.3 cm
3
and the electrode area is
approximately 0.38 cm
3
.
3.2. The effective medium theory
The effective medium theory consists in considering
the real medium, which is quite complex, as a ctitious
model medium (the effective medium) of identical prop-
erties. Bruggeman [29] had proposed a relation linking
the dielectric permittivity of the medium to the volumetric
proportions of each component of the medium, including
the air through the porosity of the powder mixture. This
formula has been rearranged under a symmetrical form by
Landauer (see Eq. (8), where
i
is the permittivity of pow-
der i at a dense state,
m
is the permittivity of the mixture
and P
i
the volumetric proportion of powder i) and cited by
Guillot [30] as one of the most powerful model.
N
c
i=1
i
+2
m
P
i
= 0 (8)
3.3. Particulate system considered and characterisation
Because the objective of the study is to calculate the pro-
portion of a denite component in a binary or in a ternary
mixture from the data, the particulate products to be cho-
sen may rst demonstrate a certain permittivity contrast at
a dense state. It must be stated that in the case of a par-
ticulate material, this does not correspond to the dielectric
constant of a massive block of the material for which elec-
tric contacts between grains do not exist. For instance, the
dense state corresponds to a hypothetical block of material
having the same quality of dielectric contact as a granular
material for which porosity is occupied by vacuum.
The method used in determining the dense dielectric per-
mittivity of a denite material consists in dening a uid in
which the material cannot dissolve and further to measure
the effective permittivity of various particulate media/uid
mixtures corresponding to various porosity. The intercep-
tion point of the curves representing the variation of the per-
mittivity of the material with porosity (through the effective
medium equation, see section 3.2) gives the dense state
permittivity.
It is clear that this method does not work in the case of a
particulate medium/uid mixture that saturates the sensor.
In this way, we developed a second method that consists
in lling the sensor with powder, measuring the blend
Table 1
Some characteristics of the products used
Products True density Dense state relative
permittivity
d
50
(m)
Salt 2.21 5.43 565
Silicon carbide 3.15 44.44 565
permittivity, weighting the powder in order to isolate the
porosity and, thanks to the effective medium equation (see
Eq. (8)), to deduce the dense permittivity of the powder.
This method is less precise than the previous one, but we
proceeded to several measurements and we averaged them,
thus obtaining better results.
In this study, commercial sugar, silicon carbide and pow-
der that enter in the composition of cement (AC) were -
nally chosen for their high permittivity difference. Sugar and
SiC were both sieved between 500 m and 630 m in order
to avoid segregation by particle size. Another advantage is
that silicon carbide particles can be separated from sugar in
the blends by water dissolution of the latter, ltration of SiC
and nally drying. Table 1 gives the physical properties of
these powders. Note that true densities were measured by a
classical pycnometric method.
3.4. Experimental rig and mixers
The mixture to be analysed is placed inside vertical walls
in a vibrating channel operating at low amplitude to avoid
Fig. 7. Sketch of the experimental rig showing the intial mixture (1), the
vibrating channel (2), the upper funnel (3), the sensors (4), the static mixer
(5), the lower funnel (6), the belt conveyor (7) and the capacimeter (8).
310 N. Ehrhardt et al. / Chemical Engineering and Processing 44 (2005) 303313
Fig. 8. View of the discharge proles through a funnel.
particle segregation during transport, as well as ensuring
mass ow of the blend. The particles are then falling at the
centre of a funnel (without accumulation) that is connected
to the glass tube surrounded by a rst capacitive sensor (de-
noted sensor H). At the end of the tube, a Sulzer
static
mixer consisting of six mixing elements is placed. These
mainly allow for a radial motion of the particles and few
axial mixing occurs in normal ow regime (see [31]). The
mixture further ows by gravity to another funnel placed in
the upper part of another glass tube that supports the last two
sensors separated by a known distance (see Fig. 7). Assum-
ing mass ow in this last section, the correlation between
the responses of these sensors (denoted M and B) allows for
the calculation of the ow rate and the frequency to consider
avoiding any sample crossing.
For instance, the glass tube must always be full of solids
with a constant ow. To ensure this, the end of each tube
was squeezed and the bottom of these tubes were placed at
a short distance from a conveyor belt operating at constant
speed (5 mmin
1
), thus gently deposing the mixture as a
layer onto the belt. This set up also allows a validation of the
method by comparing the sample compositions in the belt
to the compositions given by the closest sensor. With this
special set up, all particle ow rates become quickly equal
from the vibrating channel to the conveyor belt (in fact, the
amplitude of the vibrations can be adjusted for this task).
4. Results and discussion
4.1. Following the discharge prole through a funnel
In this experiment, we studied the effect of a funnel on
the discharge prole of two different and successive layers
(sugar at the bottom and SiC at the top). This preparation
owed through the glass tube equipped by the rst sensor
and then through a lower funnel equipped by the two other
sensors at its outlet. The discharge proles are represented
in Fig. 8.
The prole in the upper funnel clearly shows the step of
permittivity applied to the system, whereas the prole after
the lower funnel is clearly spread. This shows us that the
Fig. 9. Photograph of the Erweka Rotocube
mixer.
N. Ehrhardt et al. / Chemical Engineering and Processing 44 (2005) 303313 311
Fig. 10. View of the initial discharge proles before and after the static mixer.
SiC is mixed with sugar at the beginning of the experiment
because it ows preferentially in the middle of the funnel,
whereas components situated near the walls are owing at
the end.
We can also conclude that this experimental device gen-
erates a high segregation by density difference that give rise
to a preferential ow in the centre of the funnel. It thus
greatly perturbs the measures and the mixing process. In or-
der to prevent from segregation, it is therefore particularly
important not to ll the funnels, so that a solution could be
to convey powders directly to the centre of it.
Fig. 11. Standard deviation of dielectric permittivity before and after the static mixer versus the number of revolutions in the Rotocube
.
4.2. Kinetics of mixing in a laboratory drum mixer: the
Rotocube
(passage from a
shearing mechanism to a diffusion one), which may change
the mixing structure. Note that the presence of oscillations,
which are softened by the static mixer, may be due to seg-
regation in the Rotocube
k,n
mean for a packet of n samples beginning at
sample number k
k,n
standard deviation for a packet of n samples
beginning at sample k
i
dense dielectric permittivity of the component
i in the powder mixture
m
dielectric permittivity of the powder mixture
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Chemical Engineering and Processing 44 (2005) 315321
Solid transport in a pyrolysis pilot-scale rotary kiln:
preliminary resultsstationary and dynamic results
N. Descoins
a
, J.-L. Dirion
a,
, T. Howes
b
a
UMR CNRS 2392 Laboratoire de Gnie des Procds des Solides Diviss, Centre nergtiqueEnvironnement,
Ecole des Mines dAlbi-Carmaux, Campus Jarlard, 81013 Albi CT Cedex 09, France
b
School of Engineering, The University of Queensland, St. Lucia 4072, Australia
Received 14 July 2003; received in revised form 18 December 2003; accepted 11 February 2004
Available online 26 June 2004
Abstract
Experiments for the investigation of the ow of granular solids in a pyrolysis pilot-scale rotary kiln are presented. These experiments
consisted rst in measuring the volumetric lling ratio (steady-state experiences) for several operating conditions and second in recording the
exit ow rates after a positive or negative step in one of the operating parameters (dynamic experiences). A dynamical model computing the
evolution of the ow rate of granular solids through the kiln has been developed based on Saeman model [Chem. Eng. Prog. 47 (1951) 508].
The simulations are compared with experimental results; the model gives good results for the rolling mode, but for the slipping mode too.
2004 Elsevier B.V. All rights reserved.
Keywords: Rotary kiln; Dynamic; Solid ow-rate; Pyrolysis
1. Introduction
The processes of pyrolysis provide a solution for the
thermal treatment of solid wastes and are a complemen-
tary and often advantageous technology to incineration and
gasication. For example, in comparison with conventional
waste incineration, pyrolysis allows waste treatment with
extremely low dioxin and furan emissions, substitution of
fossil fuels by process gas and pyrolysis coke, and a wide
range of waste materials can be processed. Rotary kilns are
well suited as pyrolysis reactors because of their good mix-
ing capability, ability to use different materials and efcient
heat transfer. In order to develop design tools for industrial
scale pyrolysis rotary kilns adapted to various wastes or
mixed waste, it is necessary to correctly understand and de-
scribe the physicalchemical phenomena occurring inside
the pyrolysis vessel.
Our goal is to develop a global dynamic model of pyrol-
ysis rotary kilns. This global model can be viewed as three
parts with coupling terms:
a solid phase motion part,
C. Nitrogen is used as
a carrier gas for the vapours produced by pyrolysis reactions.
Nitrogen and solids can ow in counter-current or co-current
way. Rotational speed is adjustable between 0.5 and 8 rpm
(8.3 10
3
and 0.13 tr s
1
)and the cylinder can be tilted at
angles of up to 7
_
2H(z)
R
H(z)
2
R
2
_
3/2
(1)
This equation gives the local volumetric solid ow rate (Q
v
)
according to the kiln radius (R), the different operating vari-
ables (, n), the angle of repose of materials () and the local
depth of the solid bed (H). The spatial variable (z) is dened
from the kiln end; for example, H(z = 0) corresponds to the
depth of the solid bed at the exit of the kiln. Two views of
the kiln are presented in Fig. 2 with the main variables used
in the equations.
The equation is obtained by a geometrical analysis of
the path that one particle follows in travelling through the
rotary kiln. For this analysis, the rolling regime is assumed,
i.e. particles roll down continually on the bed surface (the
active layer), then they enter the passive region where they
are carried upward by the rotating wall until they enter the
active layer again. The angle of repose is assumed to be
constant all along the kiln.
In the stationary regime and for a non-reactive solid, the
volumetric solid ow rate is constant and equal to the inlet
ow rate given by the vibrating feeder (Q
E
v
). From Eq. (1),
the following ordinary differential equation is directly ob-
tained and can be solved with a boundary condition (exit
height xed) in order to compute the bed prole along the
kiln:
dH(z)
dz
=
3Q
E
v
tan()
4nR
3
_
2H(z)
R
H(z)
2
R
2
_
3/2
tan()
cos()
(2)
The mass conservation equation is written for the transitory
regime and for a non reactive solid:
S
s
(z, t)
t
=
Q
v
(z, t)
z
(3)
S
s
corresponds to the cross section of solid and can be ex-
pressed in function of the local bed height. The Eq. (1) can be
inserted in the above equation and nally a partial differen-
tial equation can be derived for the computation of the transi-
tory proles of bed (more details are given in Appendix A):
F
1/2
H
H(z, t)
t
U
T
tan()
sin()
F
1/2
H
(1 F
H
)
1/2
H(z, t)
z
=
z
_
U
T
3
Rcot F
3/2
H
H(z, t)
z
_
with F
H
=
2H(z, t)
R
H(z, t)
2
R
2
and U
T
= 2nR (4)
Two boundary conditions are necessary. The rst condition is
always for the constant exit height (at z = 0) and the second
one denes the continuity of the ow between the vibrating
feeder and the kiln at the inlet of the kiln (at z = L):
H(z = 0, t) = H
S
H(t)
z
z=L
=
3Q
E
v
tan()
2U
T
R
2
_
2H(z = L, t)
R
H(z = L, t)
2
R
2
_
3/2
tan()
cos()
(5)
The initial prole is computed by the Saeman model
(Eq. (1)). The inlet ow rate and/or the operating parame-
ters can be modied during the resolution of the dynamic
equation. Spurling et al. [7] give a similar equation, but the
computed variable is not the local height of the bed, but the
maximum half angle subtended by the bed at the cylinder
axis.
The dynamic model can simulate the lling phase of
the kiln, provided there are some physical considerations.
In fact, the volumetric ow rate cannot be set to 0 in the
Saemans equation because a mathematical singularity oc-
curs. So the ow rate is set to a very low value, close to 0,
318 N. Descoins et al. / Chemical Engineering and Processing 44 (2005) 315321
Fig. 3. Dynamic simulation: transient response for the lling phase of the
kiln.
and anyway the mass ow rate will be less than one particle
per second, which is the physical limit for granular matter.
The Fig. 3 shows an example of a lling phase simulation.
The blue line represents the initial steady state prole, i.e.
the kiln is empty. The dynamic simulation starts when
the feeder volumetric ow rate is increased: the bed depth
prole evolution can be seen for different times (200, 500,
1000, 1500 , 2500, 4000 and 8000 s). The bed depth pro-
le converges on a new steady-state prole at 8000 s. This
last prole can be also simulated with the Saemans equa-
tion, the nal value of ow rate being used. The dynamic
model can also simulate one or several transitions occurred
by a change in an operating parameter. For example, Fig. 4
presents the dynamic evolution of the bed depth prole after
a change in the rotational speed. The initial bed depth pro-
le is represented by the blue line. The dynamic simulation
starts when the rotational speed is increased by a factor of
two: the bed depth prole evolution can be seen for differ-
Fig. 4. Dynamic simulation: transient response of the exit ow rate to a
step change in the rotational speed.
ent times (1600, 3200, 48,000, 6400 and 8000 s). The bed
depth prole computed by the dynamic model converges on
the prole computed by the steady state model with the nal
value of rotational speed.
3.2. Steady state results
The volumetric lling ratio, X, can be evaluated from
Eq. (2) in the steady state: the angle subtended by the bed
at the cylinder axis, (z), is computed from the local height
H(z), and the volumetric lling ratio is obtained by numer-
ical integration:
(z) = 2 cos
1
_
1
H(z)
R
_
X =
1
L
_
z=L
z=0
V
solid
(z)
V
cyl
(z)
dz
=
1
L
_
z=L
z=0
R
2
((z) sin((z)))/2
R
2
dz
=
1
2L
_
z=L
z=0
((z) sin((z)))dz
(6)
The experimental and theoretical volumetric lling ratios are
given in Fig. 5 for 12 experiments.
The bed was in slipping mode for all experiments with-
out the grid inside the kiln because of the smoothness of
the inside wall. So, the angle of repose of the bed mate-
rial have been replaced by the wall friction angle in the
Eq. (1). However in spite of this modication, the predic-
tive ability of the Seaman equation is good: the predicted
volumetric lling ratios are very close to the experimental
ones (results for cases 18). When the grid is rolled in-
side the kiln, the rolling regime was observed and the com-
parison between experimental and simulation results stays
good.
It has been noted that the lling ratios obtained with the
grid are generally larger than without; for example, the vol-
umetric lling ratio values can be compared between the
cases 2 and 10 because the experimental conditions are
close.
3.3. Dynamic results: lling phase of the kiln
In course of the twelve previous experiments, the exit
ow rate has been recorded during the lling of the kiln
until the steady state regime was achieved. The transient
volumetric ow rate along the kiln, and more particularly
the exit ow rate, can be evaluated from the bed height
proles obtained by the integration of Eq. (4). In Figs. 6
and 7, the experimental exit ow rates without (Fig. 6) and
with the grid (Fig. 7) for several different rotation speeds
are compared with the theoretical ones. The inclination of
kiln is xed at 1
.
The values of the delay, i.e. the necessary time for the
rst solid particles ow out of the kiln are always well eval-
N. Descoins et al. / Chemical Engineering and Processing 44 (2005) 315321 319
Case Inlet flow
rate
kg.h
-1
Rotation
speed
Rev.min
-1
kiln
inclination
deg.
Grid X exp
%
X theo
%
angle
(used in Eq. 1)
deg.
1 15 1.7 1 No 11 13 21
2 23 2.9 1 No 11 12 21
3 26 4.0 1 No 10 10 21
4 35 5.2 1 No 11 10 21
5 21 1.7 2 No 11 12 21
6 34 2.9 2 No 11 11 21
7 47 4.0 2 No 10 10 21
8 62 5.2 2 No 10 11 21
9 9 1.7 1 Yes 12 12 33
10 20 2.9 1 Yes 15 16 33
11 41 4.0 1 Yes 24 23 33
12 51 5.2 1 Yes 24 24 33
Fig. 5. Experimental and theoretical volumetric lling ratio.
uated. The model gives rather good results for the simula-
tion of the subsequent transient phase; however, a slightly
tendency to overestimates the length of the transition phase
for the cases without grid can be observed. These overesti-
mations can be perhaps explained from some visual obser-
vations: for the slipping regime (cases without grid), some
small oscillations of the angle of repose have been observed
in course of the experiments. Mellmann called this type of
motion surging, which is characterised by periodic alter-
nations between adhesive and kinetic friction of the bed on
Fig. 6. Experimental (markers) and simulated (lines) exit ow rates for a
lling phase. Experiments without grid inside the kiln.
the wall [9]. An assumption of the model is to have a con-
stant angle of repose.
3.4. Dynamic results: transient response to a step in
operating parameters
In order to evaluate the quality of the developed model,
new experiments have been carried out. These experiments
consisted in xing operating parameters (inclination angle,
rotation speed, inlet ow rate), waiting for the steady state
Fig. 7. Experimental (markers) and simulated (lines) exit ow rates for a
lling phase. Experiments with a grid inside the kiln.
320 N. Descoins et al. / Chemical Engineering and Processing 44 (2005) 315321
Fig. 8. Transient responses of the exit ow rate for a positive and negative
step in the rotation speed: experimental (markers) and simulated (lines)
ow rates. Experiments without grid.
regime and applying a step (positive or negative) in one of
the operating parameters. The response of the exit ow rate
have been recorded until the new steady state was achieved.
In this paper, the experimental and theoretical ow rates
are compared only in the case of a positive and negative
step in the rotation speed of the kiln (Figs. 8 and 9). These
gures present respectively results without and with the
grid.
In all presented cases, a large step is initially observed.
The exit ow rate is instantaneously modied from its ini-
tial value (the initial value of the ow rate is equal to the
nal value) as soon as the step is applied. Next, the ow
rate returns slowly to its nominal value, i.e. value of the
inlet ow rate. The magnitude and length of the transient
phase are very well evaluated by the model in the two g-
ures. However, a difference between experimental and the-
Fig. 9. Transient responses of the exit ow rate for a positive and negative
step in the rotation speed: experimental (markers) and simulated (lines)
ow rates. Experiments with a grid.
oretical curves can be observed at the start of the positive
steps.
4. Conclusion
The developed model for the simulation of the dynamic
ow rate in a rotary kiln has been validated for varied exper-
imental conditions: lling phases, transient responses after
a step in the rotation speed or in the feed rate (not presented
here). It is shown that this dynamic model, based on the Sae-
man equation developed for rolling mode, works with the
slipping mode too: the replacement of the angle of repose
by the wall friction angle is sufcient.
From an industrial point of view, this model is able to
predict and study the inuence of the operating parameters
on the lling ratios or the residence times for example. The
model can be used for the design (steady state) and the
control (transient phase) of rotating kilns.
The future steps of the project will be to adapt the model
to the ow of reacting granular solids and to incorporate
this model in a global model with thermal and chemical
parts.
Appendix A. Details for the development of the
dynamic equation
For one reason of simplicity, the indexes relative to the
time (t) or to the axis of the kiln (z) have been omitted.
The mass conservation equation is written for the transi-
tory regime and for a non reactive solid:
S
s
t
=
Q
v
z
=
(S
s
U
s
)
z
= S
s
S
s
z
+U
s
U
s
z
(A.1)
where S
s
and U
s
are, respectively, the cross-sectional area
of bed and the mean axial velocity:
S
s
=
R
2
2
( sin()) (A.2)
U
s
=
Q
v
S
s
=
8
3
nR
_
tan()
sin()
+cot()
R
2
sin
_
2
_
z
_
sin
3
(/2)
sin()
(A.3)
The mean axial velocity is directly given by the Saemans
equation.
If all the terms of Eq. (A.1) are replaced by the Eqs. (A.2)
and (A.3) and by their derivatives respective to the time and
to the space, the new equation is:
(1 cos())
t
=
z
_
4
3
nR
2
cot() sin
4
_
2
_
z
_
+
2nRtan()
sin()
sin
_
2
_
sin()
z
(A.4)
N. Descoins et al. / Chemical Engineering and Processing 44 (2005) 315321 321
The relations between (angle subtended by the bed at
the cylinder axis) and h (height of bed) are:
H = R
_
1 cos
_
2
__
(A.5)
sin
_
2
_
=
_
2H
R
H
2
R
2
_
1/2
(A.6)
cos() = 1 2 sin
2
_
2
_
= 1 2
_
2H
R
H
2
R
2
_
(A.7)
cos
2
_
2
_
= 1 sin
2
_
2
_
= 1
2H
R
+
H
2
R
2
(A.8)
sin() =2 sin
_
2
_
cos
_
2
_
= 2
_
2H
R
H
2
R
2
_
1/2
_
1
2H
R
+
H
2
R
2
_
1/2
(A.9)
z
=
2
Rsin(/2)
H
z
(A.10)
t
=
2
Rsin(/2)
H
t
(A.11)
With the Eqs. (A.5)(A.11), the partial derivative equation
with Eq. (A.4) gives partial derivative equation with the
variable H:
_
2H
R
H
2
R
2
_
1/2
H
t
=
z
_
2
3
nR
2
cot()
_
2H
R
H
2
R
2
_
3/2
H
z
_
+
_
2nRtan ()
sin ()
_
2H
R
H
2
R
2
_
1/2
_
1
2H
R
+
H
2
R
2
_
1/2
_
H
z
(A.12)
The nal Eq. (A.13) can be written:
F
1/2
H
H
t
U
T
tan()
sin()
F
1/2
H
(1 F
H
)
1/2
H
z
=
z
_
U
T
3
Rcot()F
3/2
H
H
z
_
with F
H
=
2H
R
H
2
R
2
and U
T
= 2nR (A.13)
Appendix B. Nomenclature
H bed height (m)
L length of kiln (m)
n rotational speed, rpm (tr s
-1
)
Q
v
volumetric ow rate (m
3
s
1
)
R kiln radius, m
S
s
cross-sectional area of bed (m
2
)
t time (s)
U
s
mean axial velocity (ms
1
)
V
cyl
volume of kiln (m
3
)
V
solid
volume of solid bed (m
3
)
X
exp
experimental volumetric lling ratio
X
theo
theoretical volumetric lling ratio
z axial distance from the cylinder discharge
end (m)
Greek letters
angle subtended by the bed at the cylinder axis,
angle of repose of the granular solid,
angle between the kiln and the horizontal,
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dimensional and rheological analysis, Can. J. Chem. Eng. 68 (1990)
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[6] D.V. Khakhar, J.J. Mc Carthy, T. Shinbrot, J. Ottino, Transverse ow
and mixing of granular materials in a rotating cylinder, Phys. Fluids
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[7] R.J. Spurling, J.F. Davidson, D.M. Scott, The transient response of
granular ows in an inclined rotating cylinder, Trans. I. Chem. E. 79
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[9] J. Mellmann, The transverse motion of solids in rotating
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Chemical Engineering and Processing 44 (2005) 323326
Controlling dust emissions and explosion hazards in
powder handling plants
Peter Wypych, Dave Cook
, Paul Cooper
Centre for Bulk Solids and Particulate Technologies, Faculty of Engineering, University of Wollongong, Wollongong NSW 2522, Australia
Received 27 August 2003; received in revised form 2 January 2004; accepted 11 February 2004
Available online 17 July 2004
Abstract
This paper presents results from investigations into quantifying and modelling the dust generation and air entrainment mechanisms that
occur during free-falling streams of material. Emphasis is placed on the effects of drop height and product temperature. This information is
important for the efcient design and operation of dust control systems, as well as minimising the risk and severity of dust explosions.
2004 Published by Elsevier B.V.
Keywords: Dust generation; Drop height; Product temperature
1. Introduction
The efcient control of dust or particulate emissions in
the workplace and general environment is becoming increas-
ingly important in industry for many reasons:
more stringent OH&S legislation;
decreasing allowable emission levels;
loss of material (e.g. spillage, dust emissions);
risk of dust explosions when handling combustible solids;
maintenance and clean-up costs;
damage to process equipment;
premature failure of dust control systems, especially for
hot processes;
aesthetics;
increasing pressure from the government and/or commu-
nity;
society becoming more environmentally conscious.
The design of a suitable dust control system for a par-
ticular application requires knowledge of dust generation
and air entrainment. The interaction of these two parameters
with the process (e.g. solids throughput, powder properties,
temperature, drop height, velocity) also must be considered
for this purpose. Unfortunately, the existing techniques to
Corresponding author. Tel.: +61 2 4221 3488; fax: +61 2 4221 4577.
E-mail address: peter wypych@uow.edu.au (D. Cook).
predict such information are inaccurate and unreliable. This
paper aims to:
describe and examine dust generation and air entrainment
mechanisms;
present some of the latest research work and results in
trying to quantify and model air entrainment and dust
generation/control;
examine process effects on dust generation;
describe some techniques to minimise/eliminate dust gen-
eration and emissions (e.g. velocity control);
explore the implications of the above ndings for dust
explosion hazards.
Some case studies are included to provide examples and
also demonstrate some of the more important issues.
2. Dust generation and air entrainment
One of the most difcult processes in which to control dust
generation is that where a bulk material is dropped under
free-fall conditions to impact on a stockpile or other surface.
Examples of this type of situation are shown in Fig. 1.
The approach generally taken to control the dust in such
situations is to partially or fully enclose the process. A very
common example of this is the case of conveyor transfer
stations, where bulk material is dropped from the end of
one conveyor onto the start of another. Even when only a
0255-2701/$ see front matter 2004 Published by Elsevier B.V.
doi:10.1016/j.cep.2004.02.026
324 P. Wypych et al. / Chemical Engineering and Processing 44 (2005) 323326
Fig. 1. Examples of dust generation processes involving free-fall of bulk material.
very small fraction of the parent bulk material is liberated
as fugitive dust the total quantity of dust generated may be
enormous due to the very large throughput of the parent
material.
For the designer of such enclosures there are two major
questions that need to be answered:
(a) what is the volume of dusty air that should be extracted
from the enclosure?
(b) what is the concentration of dust in the air?
As yet, there is no reliable method of answering either of
these questions. This paper considers the most fundamental
situation of a product free falling under steady-state condi-
tions from a hopper at a given height above a stockpile. It
also examines briey the effect of product temperature on
dust generation.
3. Previous research
The rst serious attempt to predict the quantity of air
entrained by a falling stream theoretically was that of
Hemeon [1]. Hemeon modelled the air entrainment process
as one whereby the drag force exerted by each solid parti-
cle was essentially equal to that of a single particle falling
through a quiescent uid. He deduced that the induced
(entrained) air ow, Q
ind
, is given by (converted here to SI
units):
Q
ind
=
0.66g m(hA)
2
(d
p
p
)
1/3
m
3
/s
(1)
where g = gravitational acceleration, m = mass ow rate of
solids, h = drop height, A = cross-sectional area of material
stream, d
p
= particle diameter and
p
= particle density.
Tooker [2] then used this approach to formulate a means
of calculating the extract air requirements for enclosures,
such as conveyor transfer stations. The equations of Hemeon
[1] and Tooker [2], and variations thereon, are used widely
in industry. However, they generally grossly over-predict the
rate of air entrainment unless empirical correction factors
Fig. 2. Dust generation and air entrainment for falling stream of material.
are applied. This is a result of the inherent assumption that
the ow in the stream is made up of particles that act in-
dependently, whereas the reality is that: the stream of parti-
cles form a relatively coherent stream, Fig. 2; and particles
within the stream interact with the quiescent ambient to a
much lesser extent than if they were falling independently
through the uid.
4. Experimental facility and results
Two experimental rigs were used for this study. The rst
rig comprised a double-feed hopper arrangement to ensure
a virtually constant mass ow rate of powder during each
test. The hopper arrangement was mounted on a frame that
could be raised or lowered to change drop height and was
suspended on cables connected to three load cells to en-
able the mass ow rate to be recorded. The bulk material
dropped through a hole in a shelf above the stockpile and
air was extracted from underneath the shelf at a rate such
that the air pressure under the shelf was kept exactly equal
P. Wypych et al. / Chemical Engineering and Processing 44 (2005) 323326 325
Fig. 3. Experimental rig used to measure entrained air and dust generation.
to that of the external ambient air, as shown in Fig. 3. A
pressure observation port between the space under the shelf
and outside allowed the pressure to be equalised between
the surrounding air and the underside of the shelf by smoke
visualisation. Under these conditions, the volume of air ex-
tracted from beneath the shelf was equal to the total vol-
ume of air and bulk material falling through the aperture.
A relatively inert and robust powder, alumina (median size
= 96 m, particle density = 2465 kg/m
3
; loose-poured bulk
density = 1010 kg/m
3
), was selected for testing.
The second rig involved the release of approximately 2 kg
of hot alumina from an electrically heated hopper in a sealed
box. The alumina was dropped onto a plate at the bottom
of the box and the dust liberated during the fall and subse-
quent impact was collected in petri dishes and weighed to
determine the specic dust generation rate G = (dust liber-
ated/mass of parent material). The motivation for this work
came from the need to understand the fundamentals of dust
generation during hot solids handling processes, such as
those involved in cement and coke production.
5. Results and discussion
The volume of entrained air was found to be proportional
to the drop height raised to the power of approximately 5/3.
This is in contrast to Eq. (1) where the expected index is
2/3 [3]. This is an important result and suggests that a better
approach to modelling of the air entrainment process might
come from the use of a modied plume theory.
The specic air entrainment (i.e. air entrainment per unit
mass of parent bulk material) was found to decrease with
increasing mass ow rate of solids, Fig. 4. The solid line
correlates the results of Smithers [4] and Glutz [5] and shows
that specic air entrainment is proportional to m
0.67
. If the
particles in the falling stream behaved independently of one
another, each interacting in the same way with the ambient
air, then the specic air entrainment would be constant with
respect to mass ow rate. The experimental results show that
this is not the case.
Fig. 4. Specic air entrainment results of Smithers (x symbols) and Glutz
( symbols) using alumina with drop heights of 625650 mm.
Fig. 5. Dust generation from a falling stream of alumina as a function of
temperature difference (drop height = 500 mm, mass = 2.0 kg).
The results of the experiments to determine how the rate
of dust generation is inuenced by the temperature differ-
ence between the bulk material and the surrounding ambient
air are shown in Fig. 5 [6]. Clearly, temperature difference
has a very strong inuence on dust generation rates for
materials with a relatively high proportion of nes. For the
alumina used in these experiments a temperature difference
of 140
Department of Chemical and Biomolecular Engineering and Energy and Environment Research Center,
Korea Advanced Institute of Science and Technology, DaeJeon 305-701, South Korea
Received 31 July 2003; received in revised form 12 December 2003; accepted 11 February 2004
Available online 25 June 2004
Abstract
The effects of the ratio of TiO
2
/silica gel, supercial gas velocity (U
g
), solid circulation rate (G
s
), initial trichloroethylene (TCE) concen-
tration, wavelength of UV light, and concentrations of H
2
O and O
2
on photodegradation of TCE over TiO
2
/silica gel have been determined
in a circulating uidized bed (CFB) photoreactor. The TCE conversion decreases with wavelength of the UV light, the initial TCE and H
2
O
concentrations in the CFB reactor. The optimum concentration of O
2
for TCE degradation is found to be approximately 9 vol.% in the CFB
photoreactor. The CFB photoreactor is an effective tool for high TCE degradation with efcient utilization of photon energy.
2004 Elsevier B.V. All rights reserved.
Keywords: TiO
2
/silica gel; Solid circulation rate and holdup; Circulation uidized bed (CFB) photoreactor
1. Introduction
The degradation of trace contaminants from polluted air
and water by using photocatalytic reactor systemhas been in-
vestigated [1]. The photocatalytic degradation technologies
have several attractive advantages such as complete and ef-
cient remediation of a broad range of pollutants under certain
operating conditions at ambient temperature and pressure
without any chemical additives. Also the most commonly
employed TiO
2
photocatalyst is inexpensive, safe, and very
stable with high photocatalytic activity [1]. Therefore, pho-
tocatalytic degradation systems are being actively used as an
economical remediation method for various purication ap-
plications. Studies of heterogeneous photocatalysis involv-
ing gas-solid interfaces are relatively sparse compared to
those of water-solid interfaces. Photocatalytic gas treatment
systems are under developing since they exhibit much higher
photocatalytic activity than the water treatment system [2].
Typical phocatalytic degradation efciencies in water
treatment are a few percent at best or less than 1% in most
Corresponding author. Tel.: +82 42 869 3913; fax: +82 42 869 3910.
E-mail address: kimsd@kaist.ac.kr (S.D. Kim).
cases whereas the efciency of gas treatment is commonly
above 10%. Such higher photocatalytic efciencies in the
gas-solid interface provide a motivation to develop efcient
photocatalytic reactors. The photocatalytic water remedi-
ation systems have been studied in suspensions whereas
gas remediation systems usually employed immobilized
photocatalysts on solid substrates except for reactors using
packed powder layer. The most common immobilized pho-
tocatalytic reactors for gas treatment are annular plug ow
reactors and honeycomb monolith reactors [1].
The idea of using uidized bed as both uniform light
distribution and an immobilizing support for photocatalysts
has been originally proposed and theoretically evaluated by
Yue and Khan [3]. Experimental application of this idea has
been demonstrated by Dibble and Raupp [4] who designed
a bench scale at plate uidized bed photoreactor for pho-
tocatalytic oxidation of trichloroethylene (TCE). Recently,
Lim et al. [5,6] have developed a modied two-dimensional
uidized bed photocatalytic reactor system and determined
the effects of various operating variables on decomposi-
tion of NO
x
. Fluidized bed photocatalytic reactor systems
have several advantages over conventional immobilized or
slurry-type photocatalytic reactors [7,8]. The unique reac-
0255-2701/$ see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.cep.2004.02.027
328 T.H. Lim, S.D. Kim/ Chemical Engineering and Processing 44 (2005) 327334
tor conguration provides both exposure of photocatalyst to
UV light and good penetration of the light into the photo-
catalyst bed that allows more contact of photocatalyst and
reactant gas [8]. Also, UV light can be more evenly dis-
tributed within the given catalyst bed. Furthermore, a newly
developed circulating uidized bed (CFB) photoreactor sys-
tem enables remote delivery of UV light to the photocata-
lyst, which is ideally suited to the gas remediation since it
provides good contact between UV light and photocatalyst
with reaction gas, higher reactant throughputs, reduces mass
transport limitations [9] and lower pressure drops compared
to conventional bubbling uidized beds [10]. Although the
two-dimensional uidized bed photocatalytic reactor system
can be applied to water and gas treatments, a CFB photore-
actor system for gas phase treatment has not been reported
yet.
In the present study, the effects of the initial TCE con-
centration, wavelength of the UV light, H
2
O concentration,
O
2
concentration, the ratio of TiO
2
/silica gel, supercial gas
velocity (U
g
), solid circulation rate (G
s
) on photodegrada-
tion of TCE have been determined in a CFB photoreactor
system.
2. Experimental
2.1. Photocatalyst
In general, TiO
2
powder is classied into Geldart C group
having a poor uidization behavior [5,6]. Therefore, silica
gel (Aldrich, USA) with size of 3060 mesh and surface area
of 490 m
2
g
1
was used as a support to enhance uidization
quality. This support is transparent to near UV light. Precur-
sor solutions for TiO
2
coating on silica gel were prepared by
using titanium ethoxide, ethanol, HCl, hexylene glycol and
milli-Q water. Titanium ethoxide (5 g) and hexylene glycol
(2.8 cc) were dissolved in ethanol (50 g). After mixing vig-
orously at room temperature for 90 min, water (0.4 cc) and
37 vol.% HCl (0.1 cc) were added to the solution. The molar
ratios of water and HCl to the titanium ethoxide were 1 and
0.11, respectively. After mixing vigorously at room tempera-
ture for 90 min, silica gel was added to the aqueous colloidal
suspensions of TiO
2
. Then, it was dried at 80
C for 24 h
and calcined at 450
s
= 1
g
(1)
330 T.H. Lim, S.D. Kim/ Chemical Engineering and Processing 44 (2005) 327334
Fig. 2. Effect of TiO
2
/silica gel ratio on TCE conversion with a variation
of U
g
.
P
riser
L
= (1
g
)(
s
g
)g (2)
where, P
riser
, L,
g
,
s
,
g
are pressure drop across the riser
(P
RB
P
RT
), length of the measuring height, gas holdup,
solid density and gas density, respectively.
The TCE conversion with a variation of wavelength of UV
light as a function of G
s
and
s
is shown in the Fig. 4. As can
be seen, TCE conversion increases linearly with increasing
Fig. 3. Effect of U
g
on TCE conversion with a variation of G
s
.
Fig. 4. Effect of solid circulation rate on TCE conversion with a variation
of wavelength of UV light U
g
.
G
s
at the given wavelengths (254 and 365 nm). With the ger-
micidal white lamp at G
s
= 9.2 kg m
2
s
1
(
s
= 0.018),
more than 80% of TCE is degraded, and the TCE conversion
increases up to 90% with increasing G
s
(15.4 kg m
2
s
1
)
at
s
= 0.031. Therefore, it can be seen that solid holdup
(
s
) affects the performance of CFB photoreactor since the
optimum
s
provides better contact between the catalyst
(TiO
2
/silica gel) and the reactant gas (TCE) at the given
UV light irradiation as reported in the surface modica-
tion of HDPE powders in a circulating uidized bed reactor
[10].
The effect of initial TCE concentration on TCE conver-
sion in the CFB photoreactor is shown in Fig. 5 where the
conversion decreases linearly with increasing the initial TCE
concentration at the given U
g
(1.3 and 1.5 ms
1
). It may in-
dicate that the limited and xed amounts of active sites on
TiO
2
/silica gel are present before degradation of TCE as ob-
served for decomposition of toluene and formaldehyde by
UV/TiO
2
at the saturated adsorption with the xed active
sites [1,7,11].
The effect of wavelength of the UV light (germicidal
white and uorescent black lamps) on TCE conversion in
the CFB photoreactor is shown in Fig. 6. As can be seen,
the germicidal white lamp (254 nm) exhibits higher TCE
conversion than the uorescent black lamp (365 nm). It has
been reported that variation of photon energy in excess of
band gap of TiO
2
does not affect the product mixture from a
photocatalyst reactor [12]. The increase of TCE conversion
is caused by higher photon ux, rather than by increases
T.H. Lim, S.D. Kim/ Chemical Engineering and Processing 44 (2005) 327334 331
Fig. 5. Effect of initial TCE concentration on TCE conversion with a variation of U
g
.
in the energy of individual photons. Germicidal white
lamps are about 25% more efcient than uorescent black
lights to producing photons with wavelengths less than
385 nm [11]. In addition, it has been reported that shorter
Fig. 6. Effect of wavelength of UV light on TCE conversion with a variation of U
g
.
wavelength light is adsorbed more strongly by TiO
2
/silica
gel than the longer one. Therefore, penetration distance
of photons into TiO
2
/silica gel is shorter and electrons
and holes are formed closer to the surface of TiO
2
/silica
332 T.H. Lim, S.D. Kim/ Chemical Engineering and Processing 44 (2005) 327334
Fig. 7. Effect of O
2
concentration on TCE conversion with a variation of U
g
.
gel. Therefore, photons take less time to migrate onto
TiO
2
/silica gel surface and hence have less time to par-
ticipate in energy wasting recombination reactions before
useful surface (or near-surface) chemical reaction take place
[5]. Therefore, the shorter wavelength (245 nm) irradiation
is more effective to enhance photodegradation of TCE than
the longer wavelength (365 nm) irradiation in the CFB
photoreactor.
The effect of O
2
concentration on TCE conversion with
variation of U
g
is shown in Fig. 7 where the TCE conversion
increases with increasing O
2
concentration up to 9 vol.%
and remains constant with a further increase in O
2
con-
centration. The role of molecular O
2
in the photocatalytic
gas-treatment is three-fold: (1) a conduction band for elec-
tron scavenger to reduce fast electronhole recombination,
(2) a precursor of active oxygen species (e.g. HO
2
, HO, O)
that initiate decomposition reactions, and (3) a replenishing
source of the lattice oxygen that could be depleted during
the photocatalytic degradation [9]. Therefore, increasing
oxygen content up to 9 vol.% enhances TCE conversion.
Above 9 vol.% of O
2
, TCE conversion remains constant
that may indicate a sign of O
2
saturation. In the absence
of O
2
at U
g
= 1.5 ms
1
, it can be noticed that the conver-
sion reaches 0.75 that may imply the lattice oxygen took
part in the photocatalytic degradation of TCE [9]. From
this study, the optimum O
2
concentration is approximately
9 vol.% for the maximum TCE conversion in the CFB
photoreactor.
The effect of H
2
O concentration on the TCE conversion
in the CFB photoreactor is shown in Fig. 8. As can be seen,
TCE conversion decreases with H
2
O concentration at the
given U
g
(1.3, 1.5 ms
1
). The presence of H
2
O could en-
hance or reduce the photocatalytic reaction rates that depend
on the reactant and H
2
O concentrations [4]. The water vapor
in this study negatively affects the photocatalytic conversion
of TCE as reported previously [13]. In general, the presence
of water vapor in photocatalytic reactions is considered to be
favorable because water molecules react with valence band
holes to produce reactive hydroxyl radicals. Indeed, a small
amount of preadsorbed water is found to be essential in pho-
tocatalytic degradation of TCE [9]. Although no water was
added in this study except when the effect of water vapor
on the TCE conversion was determined, water molecules
generated in situ from various reactions byproduct of TCE
photo-degradation seem to be a sufcient source of OH rad-
ical in the photoreaction of TCE. Also, TCE molecules are
oxidized through direct hole transfer pathway that does not
involve OHradical mediators [4]. It can be reasonably accept
that both the hydroxyl radical and the direct hole pathways
are operating in the photocatalytic conversion of TCE. In ei-
ther case, excess water molecules compete for active surface
sites on TiO
2
/silica gel photocatalyst with TCE molecules
T.H. Lim, S.D. Kim/ Chemical Engineering and Processing 44 (2005) 327334 333
Fig. 8. Effect of H
2
O concentration on TCE conversion with a variation of U
g
.
to reduce the photodegradation conversion. Therefore, it can
be claimed that TCE conversion decreases with increasing
H
2
O concentration with a variation of U
g
in the CFB pho-
toreactor.
4. Conclusion
The photocatalytic degradation characteristics of trichlo-
roethylene have been determined in a CFB (circulating u-
idized bed) photoreactor over TiO
2
/silica gel photocatalyst.
The performance of the CFB photoreactor is governed by
solid holdup as a function of supercial gas velocity and
solid circulation rate to provide the optimum contact be-
tween TiO
2
/silica gel and TCE gas at the given UVlight. The
TCE conversion decreases with wavelength of the UV light
and H
2
O concentration in the CFB reactor. The optimum
concentration of O
2
for the maximum TCE degradation is
found to be approximately 9 vol.% in the photoreactor.
Acknowledgements
The authors would like to thank for a grant in aid of re-
search to Dr. S.D. Kim from the LG-Caltex Co. in the frame
of the Brain Korea 21 Project. Also, this work was supported
by Korea Research Foundation Grant (KRF-2000-E00442).
Appendix A. Nomenclature
C
O
2
concentration of O
2
in gas phase (ppmv)
C
H
2
O
concentration of H
2
O in gas phase (ppmv)
C
TCE
concentration of TCE in gas phase (ppmv)
g acceleration due to gravity (ms
2
)
G
s
solid circulation rate (kg m
2
s
1
)
L length of the measuring height (m)
P pressure (kPa)
U
mf
minimum uidization gas velocity (cms
1
)
U
g
supercial gas velocity (cms
1
)
X fractional conversion of TCE ()
Greek letters
g
gas holdup ()
s
solid holdup ()
g
gas density (g cm
3
)
s
solid density (g cm
3
)
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| |
| |
CHEMICAL ENGINEERING AND PROCESSING
Editors:
Prof. Dr.-lng. A. Go rak
Universitat Dortmund
Lehrstuhl fur Thermische Verfahrenstechnik
Fachbereich Chemietechnik
Emil-Figge-Strasse 70
D-44221 Dortmund
Phone: 49 721 608 2391
Fax: 49 721 608 3490
e-mail: gorak.CEP@ct.uni-dortmund.de
Prof. Dr.-Ing. A. Wild
Laboratoire des Science du Genie Chimique
Groupe ENSIC
1 rue Grandville
BP 451
F-54001 Nancy
France
Phone: 49 231 755 2323
Fax: 49 231 755 3035
e-mail: Gabriel.Wild@ensic.inpl-nancy.fr
Founding Editor:
Prof. Em. Dr.-lng. Dr. h.c. mult. E.-U. Schlunder, Universitat Karlsruhe, Germany
Honorary Editor:
Dr. lng. V. Gnielinski, Universitat Karlsruhe, Germany
Editorial Board:
P. Aptel, Universite Paul Sabatier, France
P.I. Barton, Massachusetts Institute of Technology, Cambridge, Massachusetts, USA
P. Bekiaroglou, University of Thessaloniki, Thessaloniki, Greece
P. Burghardt, Instytut Inzynierii Chemicznei l, Gliwice, Poland
K.J. Carpenter, Syngenta Global Specialist Technology, Hudderseld, UK
E. Drioli, Universita Della Calabria, Italy
J. Gyenis, Hungarian Academy of Sciences, Veszprem, Hungary
K. Jelemensky, Slovak Technical University, Bratislava, Slovak Republic
J.T.F. Keurentjes, Eindhoven University of Technology, The Netherlands
B. Kraushaar-Czarnetzki, University of Karlsruhe, Karlsruhe, Germany
F. Larachi, Universite Laval, Canada
R. Marr, Technische Universitat Graz, Graz, Austria
D. Mewes, University of Hanover, Hanover, Germany
H. Mu ller-Steinhagen, German Aerospace Centre, Stuttgart, Germany
K.D.P. Nigam, Indian Institute of Technology Delhi, New Delhi, India
A. Olcay, Ankara University, Ankara, Turkey
L. Puigjaner, Universitat Politencnica de Catulunya, Barcelona, Spain
H. Schoenmakers, BASF AG, ZAT-L540, Ludwigshafen, Germany
S. Skogestad, Norwegian University of Science and Technology, Trondheim, Norway
A. Stankiewicz, DSM Research, The Netherlands
K. Sundmacher, Universitaet Magdeburg, Germany
J. Werther, Technische Universitat of Hamburg-Harburg, Hamburg, Germany
K.R. Westerterp, Twente University of Technology, Enschede, The Netherlands
Aims and Scope
Chemical Engineering and Processing is a journal intended for practising engineers in industry and academia. The aim of the published articles is to demonstrate
how novel discoveries, developments and theories may be used for improved analysis and design of chemical engineering equipment and processes. The Journal
offers space for articles on any branch of chemical engineering and is particularly concerned with mechanical, thermal, chemical and bioengineering processes and
also includes analyses relating to environmental chemical engineering and sustainable industrial development. Advanced knowledge on engineering fundamentals
and processes is presented in such a form that it can be readily implemented into practical application. From time to time, review papers will be published for
individual elds of activity to illustrate and summarise scientic and/or technological progress.
*1 The paper used in this publication meets the requirements of ANSI/NISO Z39.48-1992 (Permanence of Paper).
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