Design of continuous ion exchange process for the wastewater treatment

Roman Bochenek, Robert Sitarz, Dorota Antos

n
Department of Chemical Engineering and Processing, Rzeszow University of Technology, ul. W.Pola 2, 35-959 Rzeszow, Poland
a r t i c l e i n f o
Article history:
Received 18 May 2011
Received in revised form
28 August 2011
Accepted 30 August 2011
Available online 7 September 2011
Keywords:
Dynamic simulation
Ion exchange
Optimization
Pollution
Wastewater treatment
Zeolites
a b s t r a c t
A generic design procedure for the continuous ion exchange process is proposed. The procedure is
based on the optimized arrangement of parallel batch columns. The continuity of the process is
achieved by proper shifting of the inlet conditions. The method for the optimization of the process
variables is presented.
The concept is demonstrated on the example of ammonia removal from wastewaters. Two
owsheet schemes are considered utilizing fresh or recycled regenerating agent.
The superiority of the optimized process over the periodic operation is demonstrated.
& 2011 Elsevier Ltd. All rights reserved.
1. Introduction
Ion exchange has numerous applications for industry as well as
laboratory research. It is used in production of various acids, bases,
salts, for industrial drying and treatment of gases, in biomolecular
separations as well as in the food industry. Ion exhange processes is
also commonly used in treatment of drinking and wastewater in
commercial and industrial applications such as water softening,
demineralization and decontamination (Spiro, 2009).
The ion exchange process comprises of the interchange of ions
between a solution and an insoluble solid, i.e., polymeric or
mineralic ion exchangers such as ion exchange resins (functiona-
lized porous or gel polymer), natural or synthetic zeolites,
montmorillonite, clay, etc. In a water treatment system undesir-
able ions in the water supply are replaced with more acceptable
ions. Water decontamination consists of removal of ionic pollu-
tans such as phosphate, nitrate, ammonia, which appear in
various types of agricultural, domestic and industrial wastewaters
or heavy metals discharged in efuent from electroplating plants,
metal nishing operations, as well as a number of mining and
electronics industries (Pintar et al., 2001; Dabrowski et al., 2004;
Spiro, 2009).
Although other physicochemical methods of water purication
such as chemical reactions, electro-otation, reverse osmosis and
adsorption may be under given conditions more effective than
ion exchange (Flores and Cabassud, 1999), the latter process is
considered attractive because of the relative simplicity of applica-
tion (Blanchard et al., 1984) and in many cases is proven to be
economic and effective technique to remove ions from waste-
waters, particularly from diluted solutions (Pintar et al., 2001;
Valverde et al., 2006).
The operating cycle of ion exchange xed bed (column)
consists of two working modes: saturation and regeneration. In
the rst mode the feed stream containing wastewater is delivered
into the column inlet and the efuent free of the polluting ion is
withdrawn at the column outlet. The saturation is interrupted
when the concentration of the polluting ion in the efuent
exceeds a permissible limit. The bed is regenerated in two stages:
elution and re-equilibration. Elution consists of replacing the
retained ions with ions of a regenerant. It is followed by the
column re-equilibration where the regenerant is washed out and
the column is brought back to the initial conditions. The alternate
modes of saturation and regeneration result in a periodic dis-
tribution of concentration in the efuent stream characteristic for
processes of concentration swing adsorption. After a number of
cycles the process attains the cyclic steady state (CSS) in which
distribution of concentration in each cycle is identical.
The process can be realized using a single bed as well as a system
of interconnected beads based on variation of upstream and down-
stream conditions (Nilchan and Pantelides, 1998). The performance of
such a periodic operation is strongly affected by a number of
operating variables. Therefore, the design of effective process requires
solving an optimization problemaimed at minimizing operating costs
of the process subject to the constraints of the product purity
(Nilchan and Pantelides, 1998; Cruz et al., 2003; Jiang et al., 2004;
Cruz et al., 2005; Agarwal et al., 2010).
Contents lists available at SciVerse ScienceDirect
journal homepage: www.elsevier.com/locate/ces
Chemical Engineering Science
0009-2509/$ - see front matter & 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.ces.2011.08.046
n
Corresponding author.
E-mail address: dorota.antos@prz.edu.pl (D. Antos).
Chemical Engineering Science 66 (2011) 62096219
The design procedures for various periodic processes of ion
exchange have been discussed in several publications concerning a
batch system based on a single column operating periodically (Sun
et al., 1990; Lewus et al., 1998; Castel et al., 2000) as well as a
continuous system utilizing multicolumn setups such as the carousel
system (Softening et al., 1990; Ernest et al., 1997; Hritzko et al., 2000;
Huckman et al., 2001; Rochette, 2006). The carousel process refers to
the operation systems in which feed and regenerating streams are
delivered subsequently through the columns mimicking counter-
current movement of the uid ow and the columns. The movement
is realized by switching regenerant and feed ports in equal time
intervals. However, the volume of the feed stream used for the
column saturation typically is much larger compared to that required
in the regenerating stages. The equality of switching intervals may
cause that the owrate of streams delivered in the regeneration mode
has to be set lower compared to that used during the saturation. Such
a forced owrate adjustment is a serious drawback of the carousel
process limiting the process performance.
In this study an alternative procedure for the design of the
continuous ion exchange process in a multicolumn setup has been
proposed. The procedure is based on the parallel delivery of feed and
regenerating streams into the column inlets in such a way that in the
same time interval a certain number of columns operate in the
saturation mode while the rest of them are regenerated. The number
of columns operating in the saturation mode is time-invariant, which
assures the continuity of the process. The operating cycles of
consecutive columns are sequentially shifted in time. The length of
the time intervals for the saturation and regeneration can be adjusted
to assure optimal performance of the overall process.
To verify the concept suggested a model system of ion exchange
process has been selected, i.e., the removal of ammonia ions from
wastewaters on a synthetic zeolite has been analyzed. Two owsheet
schemes have been considered differing in the manner of the column
regenerationin the rst one a fresh solution of the regenerant was
used for the column regeneration whereas in the second one the
exhausted regenerant was partly recycled and reused in the regen-
eration mode. For the process design and optimization a dynamic
model was employed based on the equation of the linear driving force
in the solid phase (i.e., LDF model). The Differential Evolution (DE)
procedure was adopted for the process optimization based on a
simple evolutionary strategy (Storn and Price, 1997) for non-linear,
non-differentiable and non-convex problems with continuous
variables.
The production rate of puried water (process product) was
used as the performance criterion and the goal function of the
optimization procedure.
It has been shown that the optimized continuous process can
signicantly outperform the periodic operation.
2. Principles of the process
2.1. Cyclic process of ion exchange in a single column
In the simplest case, the cyclic ion exchange system comprises a
single batch column operating in a periodic manner, which is based
on alternate stages of the column saturation and regeneration.
The owsheet scheme of the process is presented in Fig. 1.
During the saturation period (stage I) the column is loaded
with wastewater (i.e., with the feed stream), the ionic pollutants
are retained on the stationary phase and the puried water
stream is withdrawn at the column outlet. The operation of
saturation is stopped when the pollutant concentration in the
puried water, C
out,I
P
, exceeds permissible upper limit, Eps
I
.
In the next stage the column has to be regenerated. The
regeneration comprises two operations: elution (stage II) where the
regenerant is delivered into the column to elute the retained ions in
the form of concentrated solutions, and the column re-equilibration
(stage III), where the column is rinsed out to remove the regenerant
and restore initial conditions. The elution stage is stopped when the
concentration of the ionic pollutant in the column efuent, C
out,II
p
,
drops below a threshold concentration, Eps
II
.
The last stage, i.e., of re-equilibration is interrupted when the
concentration of the regenerant in the efuent stream, C
out,III
r
,
decreases below the threshold concentration, Eps
III
.
The stream of the wastewater puried in the saturation mode
is partly consumed for the preparation of regenerating solutions
in the elution and re-equilibration stages (V
II
w
, V
III
w
, see Fig. 1).
To improve the process performance, i.e., to reduce the water
consumption, the efuent from the elution stage (stage II)
Fig. 1. Flowsheet scheme for complete operating cycle on a single column without regenerant recycling, Q
I
, Q
II
, Q
III
are the owrates of the inlet streams in the stages I, II,
III, respectively, Q
recov
is the streams of puried water, V
II
w
, V
III
w
are the volumes of the puried water consumed for supplementing the streams in the elution and the
re-equilibration stages, respectively.
R. Bochenek et al. / Chemical Engineering Science 66 (2011) 62096219 6210
containing exhausted regenerant can be partly recycled (see
Fig. 2). The recycled part is collected and temporarily stored in
a buffer tank to be completely used up in the initial period of the
elution stage II of the consecutive cycle. The exhausted regenerant
is collected within a certain time interval, whose length is
restricted by the threshold concentration of the pollutant in the
buffer tank, C
rec
P
rEps
rec
. Subsequently, in the same stage, the
column is regenerated with a portion of fresh regenerant.
The contribution of the exhausted regenerant to the whole
regeneration stream used in the elution stage is determined by
the recycling ratio U.
Since the last step of re-equilibration is designed for washing
out the regenerant as well as other impurities clogging the bed,
the efuent of the step III is discharged; it is not recycled to the
process.
2.2. Continuous process of ion exchange
The throughput of the ion exchange process can be increased
by utilizing a system of several identical columns arranged in
parallel. If all these columns are simultaneously operated under
the same conditions the node works periodically. The values of
the feed and product owrates of the node are multiplication of
the corresponding owrates of the single column.
The operating cycles for a setup of eight parallel columns are
illustrated in Gantt chart in Fig. 3.
Large-scale processes, which require large amounts of product,
are usually more cost-effective for continuous operations. There-
fore, in this study a continuous process of the wastewater
treatment was considered. In this process the operating cycles
of subsequent columns are shifted in time so that in each time
interval a certain number of columns could operate in the
saturation mode while remaining ones in the regeneration mode.
Because the time length necessary for accomplishing the satura-
tion and regeneration stages are different to assure the process
continuity some of the columns have to wait for the use in a
subsequent cycle in the work stoppage. Therefore, a complete
operating cycle for each column of the continuous node com-
prises four stages: saturation, elution, re-equilibration and the
work stoppage. Gantt chart for an eight-column continuous setup
is presented in Fig. 4. It can be observed that after the startup of
the operation in each time interval four columns are loaded with
the feed stream, i.e., they work in the saturation mode, four are
regenerated or remain in the work stoppage. In this case the
process conditions are optimized for the column operating
Fig. 2. Flowsheet scheme for complete operating cycle on a single column with regenerant recycling.
Fig. 3. Gantt chart for a setup of eight parallel column operating in a periodic node.
R. Bochenek et al. / Chemical Engineering Science 66 (2011) 62096219 6211
individually but not optimized for the column operating jointly in
the multicolumn node.
The work stoppages cause lengthening of the cycle time, which
reduces the process effectiveness. Therefore, optimizing the
process parameters for individual columns (individual column
optimization) and synchronizing their cycles to achieve contin-
uous operation is not sufcient; to upgrade the process perfor-
mance, optimization of the process parameters for the column
operating jointly in the system (node optimization) is required.
Gantt chart for an optimized eight-column node is presented
in Fig. 5.
The throughput of the optimized node is signicantly higher
compared to that obtained for the individual column optimiza-
tion. In the case illustrated in Fig. 5, ve columns are running in
the saturation mode, three in the regeneration mode or in the
work stoppage. In this case the length of the work stoppages is so
short that they are not noticeable in the chart.
To synchronize the runs of columns assembled in the contin-
uous system the shift time between the cycles of consecutive
columns has to be adjusted in such a way that the number of
columns operating simultaneously in each of two modes (i.e.,
saturation and regeneration) is time-invariant, which assures
continuity of the feed delivery and the product withdrawal. The
shift time corresponds to the switching time of the inlet condi-
tions. It can be determined based on the concept of time unit,
which is elucidated as follows.
Each stage consists of a certain number of the time units; the
total number of the time units for all the stages is equal to the
number of columns in the node.
The time units can be divided into two categories: productive units,
N
P
, corresponding to the saturation mode, and non-productive units,
N
R
, corresponding to the periods of elution, re-equilibration and the
work stoppage. The sum of the productive and non-productive units
has to be equal to the number of the column in the node:
N
P
N
R
N
col
1
The number of productive time units can be calculated as
follows:
N
P
INT
t
I
t
c
N
col

2
where INT is an integer function rounding down; t
c
is the total
working cycle time given by the following equation:
t
c
t
I
t
II
t
III
3
where t
I
, t
II
, t
III
are the lengths of the time periods for saturation,
elution and re-equilibration, respectively.
The length of the time unit is expressed as
t
j

t
I
N
P
4
The stoppage time can be calculated as follows:
t
stop
N
R
t
j
t
II
t
III
5
For the total operating time in the node it holds:
t
tot
t
I
t
II
t
III
t
stop
6
Additionally, the following dependence is fullled:
N
col
t
j
t
I
t
II
t
III
t
stop
7
The length of the periods of saturation, elution and re-
equilibration, t
I
, t
II
, t
III
, can be determined on the basis of
simulations of operation cycles for a node column running under
CSS conditions.
Fig. 4. Gantt chart for a setup of eight column operating in the continuous mode; individual column optimization.
Fig. 5. Gantt chart for continuous system of eight-column system, node column optimization.
R. Bochenek et al. / Chemical Engineering Science 66 (2011) 62096219 6212
3. Process optimization
3.1. Optimization procedure
To solve the optimization problem the Differential Evolu-
tion (DE) method was used. It utilizes the evolutionary
algorithm belonging to the class of stochastic population based
methods that proved their efcacy in solving hard nonlinear
global optimization problems involving noncontinuous,
nondifferentiable and nonconvex functions in the optimiza-
tion models (Michalewicz and Fogel, 2002; Onwubolu and
Babu, 2004).
The evolutionary techniques had found wide application for
solving various problems of chemical and process engineering
such as batch operation scheduling, designing various subsys-
tems, e.g., heat exchanger network or water network, molecular
design, designing processes and apparatus (Deb, 2001; Babu et al.,
2005; Jez owski et al., 2005, 2007; Babu and Angira, 2006;
Bochenek et al., 2007; Srinivas and Rangaiah, 2007).
The DE method is a simple evolutionary strategy proposed by
Storn and Price (1997) for solving nonlinear, nondifferentiable
and nonconvex optimization models with continuous variables. It
can handle both unconstrained and constrained optimization
problems and was proved for its high performance for solving
multi-modal problems (Price et al., 2005). The algorithm of the
method is illustrated in Fig. 6.
3.2. Formulation of optimization problem
The problem of the optimal design of the water purication
node that consists of a given number of columns relies on
determining the following process variables:
volumetric owrates Q in the stages I, II, III, which are related
to the time lengths: t
I
, t
II
, t
III
. Increasing the owrates results in
reducing the operation time, which improves the process
performance. On the other hand, it alters the HETP value, i.e.,
it can reduce the column efciency due to worsening condi-
tions for the mass transport. Therefore, determining the values
of owrates for each stage requires solving an optimization
problem.
Typically, the regenerant is not adsorbed; therefore, in the re-
equilibration stage (stage III) the mass transport kinetics does
not affect the process efciency. In such a case the owrate Q
III
can be limited only by the pressure drop in the system or the
pump capacity;
shift time of cycles of subsequent columns (i.e., the switching
time) and the number of columns operating in individual
modes in each time unit. These variables can be calculated
on the basis of the model simulations if the owrates Q
k
(kI,
II, III) are known;
threshold concentration of the polluting ion in the column
efuent in the saturation stage, i.e., the water purity, Eps
I
. This
value can be set arbitrarily according to the permissible
concentration limit;
threshold concentration of the polluting ion at the end of the
elution stage, Eps
II
.
The value Eps
II
should be considered as an indicator of the
regeneration efciency. Complete regeneration, i.e., complete
removal of the ionic pollutant from the column (Eps
II
0)
usually requires long elution time, which reduces the process
effectiveness. On the other hand incomplete regeneration
causes reduction of the loading capacity of the bed. Therefore,
the value of Eps
II
should be optimized;
Fig. 6. Algorithm of the DE method, see details in (Price et al., 2005).
R. Bochenek et al. / Chemical Engineering Science 66 (2011) 62096219 6213
threshold concentration of the regenerant at the end of the re-
equilibration stage, Eps
III
;
the threshold concentration, Eps
III
, can be selected on a level
that mimics the effect of the hardness of the wastewater
contained in the feed stream;
additionally, for the system involving recycling: the recycling
ratio U and the threshold concentration of the pollutant in the
recycled stream, Esp
rec
;
The threshold concentration Eps
rec
should be selected properly;
low value of Eps
rec
results in higher water consumption whereas
too high Eps
rec
causes reduction of the regeneration efciency.
Finding the best values of Eps
rec
and U is an optimization problem.
As a criterion of the process performance the productivity of
pure water can be taken into account. The productivity can be
dened as the volume (or mass) ow of the recovered water,
Q
recov
:
Pr Q
recov

Q
I
w
t
I
V
II
w
V
III
w
t
tot
10
where V
II
w
and V
III
w
are the volumes of the puried water consumed
in the stages II and III, respectively, to supplement the streams Q
II
and Q
III
(see Figs. 1 and 2).
To optimize the process performance the following problem
can be solved:
max Prv 11
where v is a vector of the decision variables.
The optimization problem is solved subject to the constraint
concerning the purity of the recovered water:
C
out,I
P
rEps
I
12
C
out,I
p

Z
t
I
0
C
out,I
p
dt
t
In the recycling mode additional constraint should be added
that is related to the concentration of pollutant in the recycled
stream collected at the column outlet:
C
rec
p
rEps
rec
13
The following decision variables can be taken into account:
v[Q
I
, Q
II
, Eps
II
, Eps
rec
, U]
The two last variables Eps
rec
, U are active for the process
involving the regenerant recycling.
The optimization problem should be solved for the system
operating under CSS conditions, which correspond to repeatabil-
ity of the concentration proles at the column outlet for each
consecutive cycle.
3.3. Modeling of the process dynamics
To predict the process performance a simplied dynamic
model based on the equation of linear driving force (LDF model)
was used (Ruthven, 1984).
The LDF model consists of the mass balance equation in the
mobile phase:
e
t
@C
i
@t
1e
t

@q
i
@t
e
e
D
L
@
2
C
i
@x
2
u
@C
i
@x
14
Eq. (14) is coupled with the following kinetic equation:
@q
i
@t
k
m,i
q
n
i
q
i
15
where i denotes the system component, e.g., eluite (pollutant) ion
ip, and co-ion ico, t, x are the time and the axial coordinates,
respectively; C
i
(t, x) is the concentration in the mobile phase; q
i
(t, x),
q
n
i
t,x are the solid phase concentration and the equilibrium solid
phase concentration, respectively; u is the supercial velocity; e
e
and
e
t
are the external, internal and total porosity; D
L
is the dispersion
coefcient, and k
m,i
is the overall mass transport coefcient.
The coefcient k
m,i
lumps the contribution of external and
internal mass transport kinetics to the overall mass transport
mechanism. It also depends on the isotherm course as follows
(Kaczmarski et al., 2001; Antos et al., 2003):
1
k
mi

k
0
0i
1k
0
0i

2
1
k
1i
1

2
e
e
F
e
e
t
d
p
6k
eff ,i

d
2
p
60D
intra,i
!
16
k
0
0i
F
t
dq
n
i
dC
i
17
k
1i
F
e
e
p
1e
p

dq
n
i
dC
i

18
where F
e
1e
e
=e
e
and F
t
1e
t
=e
t
are the phase ratio:
D
intra, i
e
p
D
peff , i
1e
p
D
seff , i
dq
n
i
dC
i
19
where k
eff
is the effective external mass transport coefcient in
ionic solutions; D
peff
, D
seff
are the effective coefcients of diffusion
in macropores and micropores, respectively; e
p
is the internal
porosity. For a linear isotherm dq
n
i
=dC
i
is the Henry constant.
For self-sharpening fronts the equations presented above can
be used, provided that the isotherm slope dq
n
i
=dC
i
is replaced with
the isotherm chord Dq
n
i
=DC
i
(Lapidus and Amundson, 1952;
Kaczmarski et al., 2001; Antos et al., 2003).
The model is solved with the boundary and initial conditions:
Initial conditions:
C
i
t 0,x C
0
i
20
q
i
t 0,x q
0
i
21
Typically, the column is free of the polluting ions in the initial
state C
0
i
0; q
0
i
0 (i p).
Boundary conditions
At the column inlet the Danckwerts-type boundary conditions
can be assumed:
uC
F
i
tC
i
t,x 0 e
e
D
L
@C
i
t,x 0
@x
22
where C
F
i
t is the prole of concentration at the column intlet. In
the saturation stage C
F
i
t stands for the feed concentration for the
eluite ion as well as the regenerant ions while in the regeneration
stage it describes the regenerant prole. For step changes of the
inlet concentration in k stage it holds:
C
F
i
t C
in,k
i
k I, II, III 23
where C
in, I
i
C
F
i
At the column outlet continuity of the concentration prole is
assumed:
@C
i
t,x L
@x
0 24
The model has to be coupled with the isotherm equation, e.g.,
for the Donnan isotherm model it holds:
q
n
i
C
i
K
i
q
n
c
C
c

z
i
=zc
, K
i

g
m
i
g
s
i
g
s
c
g
m
c

z
i
=zc
25
Eq. (25) is combined with the conditions of electroneutrality in
the mobile phase:
z
i
C
i
z
c
C
c
z
co
C
co
0 26
and in the solid phase:
z
i
q
n
i
z
c
q
n
c
z
m
G0 27
R. Bochenek et al. / Chemical Engineering Science 66 (2011) 62096219 6214
where z is the ionic charge, m denotes the solid matrix (z
m
1
for the cation exchanger); and G is the exchange capacity.
The coefcient K lumps contribution of activity coefcients of
ions in the mobile g
m
and the solid phase g
s
.
Typically, the coefcient K is a function of the regenerant
concentration, r, i.e., salt supplying counter- and co-ions. The
same can holds for G, which can decrease with the increase of the
ionic strength due to the reduction of the electrostatic potential of
the solid matrix. Therefore, additional dependencies should be
quantied (Go rka et al., 2007).
K f C
r
28
Gf C
r
29
4. Results and discussion
4.1. Model parameters
The model parameters used for the simulations were the same
as determined in our previous study for the system of ammonia
removal on a zeolite ion exchanger with NaCl salt as the
regenerant (Go rka et al., 2007).
The bed parameters were assumed as follows:
the column dimensions: column length L25 cm, column dia-
meter d
col
10 cm; the bed porosities were e
t
0.7, e
e
0.5, e
p
0.3.
The following values and dependencies of the isotherm and
kinetic coefcients were used:
empirical dependencies of the isotherm and kinetic coefcients
for the eluite ion, p, on the concentration of counter-ions, C
c
,
supplied by the regenerant, i.e.,
for the isotherm coefcients:
GC
c
2:453:07expC
c
=0:02
K
p
C
c
16:4215:41expC
c
=0:07
To quantify these concentration dependencies the isotherm
course was determined for different contents of the regen-
erant in the mobile phase. For each set of equilibrium data
the isotherm coefcients G and K
p
were estimated. Next, G
and K
p
were appropriately correlated with the regenerant
concentration (see details in Go rka et al., 2007).
Because co-ions were not adsorbed, the coefcient, K
co
was
set equal to zero (K
co
0).
for the effective external mass transport coefcient:
k
eff ,p
1:0 10
5
C
c

0:37
The inuence of owrate variations on the k
eff
value was
accounted for by the relation of Wilson and Geankoplis
(1966), i.e.:

k
eff ,p
f w
0:333
For co-ions the mass transport resistances were neglected.
Note that for non-absorbable species the mass transport
resistances are negligible (see Eq. 16 at k
0
0i
-0).
Diffusion coefcients:
D
seff ,p
4:97 10
211
m
2
=s
The contribution of the pore diffusion D
peff,p
to the mass
transport mechanism could be neglected (Go rka et al., 2007).
Dispersion coefcient:
the dispersion coefcient was calculated according to the
Gunn equation (Gunn, 1987).
All the model parameters were assumed to be time invariant,
i.e., gradual bed destruction or deactivation due to clogging,
ageing, etc., was not taken into account.
The remaining operating variables were set as described
below:
- feed composition, i.e., the inlet composition in the stage I:
C
F
p NH

4
0:0153mol=L
C
F
r NaCl
C
F
co Cl
0:0017mol=L
A relatively low inlet concentration of the ionic pollutant,
C
F
p NH

4
, was selected for the simulations. It corresponded to
weakly non-linear range of the isotherm for which ion-
exchange process can be effective; the use of concentrated
solutions is unprotable due to the fast saturation of the bed
loading capacity. Nevertheless, the principles of the optimiza-
tion procedure presented here are valid for any initial
concentration.
- concentration of the regenerant (salt NaCl) in the stage II:
C
in,II
r
0:5mol=L 3%wt=v
- threshold concentrations:
pollutant concentration in the collected stream (i.e., permis-
sible limit):
Eps
I
1 10
24
mol=L
threshold concentration of the regenerating agent:
Eps
III
C
F
R
0:0017mol=L
- owrate of the water stream in the re-equilibration stage III:
Q
III
6L=min
The value of Q
III
was set as maximal regarding the system
capacity limitation.
4.2. Process simulation
To simulate the process dynamics the model described by Eqs.
(14)(29) was employed with parameters reported above in
Section (5.1). The model was solved for the eluite ion, i.e.,
ammonia ions, NH

4
, and for co-ions, Cl

. The concentration of
the counter-ions was calculated using the electroneutrality con-
ditions (Eqs. (26) and (27)). Note that because the ionic charge of
co-ions was 9z
N
91 the inlet co-ion concentration was equal to
the concentration of the regenerant salt C
in,k
co
C
in,k
r
(kI, II, III).
Local values of the isotherm and kinetic coefcients were
calculated according to the temporal concentration prole of
the counter-ion using Eqs. (28) and (29).
To simulate the breakthrough proles in the saturation mode
the isotherm chord was used in Eqs. (17)(19), whereas for
predicting the regenerating proles the isotherm slope was
calculated. Details of the procedure can be found elsewhere
(Go rka et al., 2007).
The simulation of consecutive stages of the process relied on
proper exchanging the boundary conditions (Eqs. (22) and (23)).
To simulate the process including regenerant recycling the
additional sub-stages in the regeneration mode had to be taken
R. Bochenek et al. / Chemical Engineering Science 66 (2011) 62096219 6215
into account. The efuent containing exhausted regenerant was
assumed to be discharged to the waste within the period (t
I
,
t
collect
). At the time point, t
collect
, the efuent started to be collected
in a buffer tank. The whole storage is used up in stage II of a next
cycle. The value of t
collect
was calculated according to the average
concentration C
rec
P
using the following mass balance equation:
Q
II
C
rec
p
t
rec
Q
II
Z
t
collect
t
II
C
out,II
p
tdt Q
II
Eps
I
t
II
t
collect
30
where t
rec
is the recycling duration. The last term on the left hand
side of the equation corresponds to the mass of the pollutant in
the stream of puried water coming from stage I (see Fig. 2).
The recycling duration t
rec
is determined by the choice of the
recycling ratio U that was dened as follows:
U
C
out,II,max
p
C
U
p
t
rec

C
out,II,max
p
Eps
II
31
where C
out,II,max
p
is the maximum of pollutant concentration in the
regeneration prole, C
U
p
is the concentration corresponding to the
end of the recycling period.
When U is set the outlet concentration C
U
p
can be calculated
according to Eq. (31) and the corresponding time for the elution of
concentration C
U
p
, i.e., t
rec
, can be found.
As mentioned above the optimization problem should be
solved for the system operating in the cyclic steady state. The
CSS was attained after few cycles, i.e., after second cycle for the
column operating without recycling and after fourth for the
recycling mode. The simulation of the start up of the process is
demonstrated in Figs. 7 and 8.
4.3. Optimization results
4.3.1. Single column optimization
The cyclic process of ion exchange was optimized for an single
column operating according to the owsheet scheme involving
the regenerant recycling as well as without recycling. The
objective function was dened by Eq. (10), the consumption of
water V
II
w
, V
III
w
was determined by the water demand in the
regenerating and re-equilibrating streams.
The optimization results are summarized in Table 1. It com-
prises the parameters of the optimization procedure, the searching
range of the decision variables and the optimal solution. It is evident
Fig. 7. Concentration proles of ammonia at the column outlet after two cycles,
for the column without recycling; the re-equilibrating stage III is very short,
therefore not visible on the plot.
Fig. 8. Concentration proles of ammonia in CSS for rst four cycles (column without recycling): (a) complete concentration prole and (b) concentration prole for the
saturation stage I.
Table 1
Optimization results for the single column optimization.
Without recycling With recycling
Parameters of the optimization procedure
CR
a
0.3 0.3
F
a
0.8 0.8
Number of generation 120 150
Number of individuals 10 15
Searching range of the decision variables
Q
I
(L/min) 0.310 0.35
Q
II
(L/min) 0.310 0.35
Eps
II
(mol/L) 10
4
310
3
10
4
410
3
Eps
rec
(mol/L) 10
4
410
3
U 01
Best solution
Objective function OF (L/min) 1.14 1.46
Q
F
Q
I
(L/min) 2.16 2.67
Q
II
(L/min) 1.38 2.88
Eps
II
(mol/L) 8.0610
4
5.0610
4
Eps
rec
(mol/L) 1.3310
3
U 0.710
a
See Fig. 6.
R. Bochenek et al. / Chemical Engineering Science 66 (2011) 62096219 6216
that the process involving recycling performs better compared to that
realized without recycling. The performance improvement for the
process being investigated was ca. 28%.
4.3.2. Node column optimization
As described above, to increase the throughput a multicolumn
node can be used. The node can operate periodicallyit then
comprises a setup of parallel columns operating periodically
under the same conditions (Fig. 3) or continuously, where the
inlet conditions for each column are sequentially changed in time
(Figs. 4 and 5).
The productivity, Pr, of the periodic node is just a multi-
plication of that for a single column presented in Table 1.
The performance optimization for the continuous multicolumn
node was done for three setups comprising 3, 6 and 8 columns.
Two optimization approaches for the optimization were com-
pared: the operating parameters were optimized for a single
column operating individually in the node (individual column
optimization) and for the column operating jointly in the node
(node column optimization).
The optimization results are summarized in Table 2.
It can be observed that for the node column optimization the
system performs markedly better compared to that for the
individual column optimization. The performance differences
result from unproductive gaps in the operating cycles, i.e., the
work stoppages occurring in the continuous operation. The node
column optimization allows minimizing gaps between cycles. The
superiority of the performance of the optimized mode is visua-
lized in Fig. 9a and b.
An important observation is the upgrade of the process
efciency for the system based on the regenerant recycling (even
Table 2
Optimization results for the process of ion exchange in a multicolumn node. Parameters of the optimization procedure and the searching range of the decision variables are
the same as reported in Table 1.
Without recycling With recycling
3 Columns 6 Columns 8 Columns 3 Columns 6 Columns 8 Columns
Q
I
(L/min) 2.01 1.99 2.15 2.26 2.27 2.49
Q
II
(L/min) 1.59 1.54 1.39 2.63 2.79 2.80
Eps
II
(mol/L) 7.9710
4
8.2410
4
8.1910
4
5.1410
4
4.8810
4
4.7510
4
Eps
rec
(mol/L) 1.1210
3
1.2510
3
1.3610
3
U 0.679 0.715 0.744
OF (L/min), node column optimization 3.39 6.78 9.12 4.19 8.54 11.2
OF (L/min) individual column optimization 1.85 5.54 7.39 2.41 7.22 9.62
Fig. 9. Comparison between the optimization results (a) productivity obtained for the individual column optimization and the node column optimization for the owsheet
scheme without regenerant recycling; (b) productivity obtained for the individual column optimization and the node column optimization for the owsheet scheme with
regenerant recycling; (c) comparison between productivity of the nodes with and without recycling.
R. Bochenek et al. / Chemical Engineering Science 66 (2011) 62096219 6217
up to 83% for the three columns system) as demonstrated in
Fig. 9c.
The productivity achieved in the continuous system with node
column optimization is slightly lower than that for the periodic
node (compare Tables 1 and 2). It results from the necessity of
adjustment of the process parameters to achieve the continuous
operation, which reduces the number of degree of freedom in the
optimization procedure. Increase of the column number benets
in a reduction of the time of the work stoppages. Therefore, the
differences between productivity for the periodic and the con-
tinuous setups disappear with the increasing column number.
Nevertheless, the observed superiority of the periodic setup
over the continuous one is only apparent. The periodic system
operates more efciently only if the throughput is also periodic,
i.e., water to be treated is stored in a large amount and is
processed in the purication node in any time.
If the wastewater delivery is continuous the periodic node
performs much worse compared to the continuous system. To
illustrate the problem one can consider a certain wastewater
stream (throughput) to be processed in a purication node. Accord-
ing to the given throughput the number of column has to be
adjusted so that they could operate under optimal conditions. For
instance, for the throughput (feed owrate) 4 L/min a set of three
columns can be used, for 8 L/min six columns while for 10 L/min
eight columns. In the continuous node the given throughput stream
can be processed without storage, i.e., in 3-columns system two
columns are always in the saturation mode, in 6-column system
four columns while in 8-column system ve columns that are
processing required stream of wastewater.
For a periodic node a part of the throughput has to be stored in
a buffer tank and can be processed in a next cycle. In the example
being studied the given throughput can be is processed without
storages only in cycles with even numbers. For cycles with odd
numbers the throughput delivered into the node is in an excess
with respect the column capacity and has to be partly stored (e.g.,
the throughput 4 L/min can be split into the three columns
working parallel into the amount of ca 1.33 L/min per column,
which can be processed within the saturation period making ca.
62% of the total cycle time that gives ca. 2.5 L/min of effective feed
owrate for each odd cycle). The amount of feed stored during
non-productive period of the cycle can be consumed in the next
(even) cycle with maximal productivity.
It is obvious that the operation of storing reduces the effective
throughput of the system. The difference of productivity between
the periodic and optimized continuous node is demonstrated for
the system without recycling in Table 3.
Similar results can be achieved for the columns operating in a
setup involving recycling (not shown here).
As it can be observed, the advantage of the continuous systems
enhances with increase of the column number (see Table 3).
It should be noted that for the simulations presented an ideal
ion-exchange system was assumed; no changes of bed properties
progressing during a long-time operation was assumed. In a real
system a gradual loss of the loading capacity due to the bed
contamination can often be observed. If the isotherm coefcients
are changing from cycle to cycle in a systematic manner, their
values could be correlated with the cycle number. Implementation
of such additional empirical correlations into the dynamic model
and the optimization procedure is straightforward. In such a case
the operating parameters can be periodically adjusted according
to the predicted changes of the bed properties and the process can
be interrupted to discard the adsorbent bed as it approaches
saturation with the contaminant. If an unpredictable bed destruc-
tion is expected, the process controlling has to be used based on
the monitoring of the concentration proles and adjusting accord-
ingly the operating variables. The procedure of the process
modeling and optimization developed in this work could be useful
for the process design also in this case. However, a detailed
analysis of this problem is outside the scope of this study.
5. Conclusions
A design procedure of the continuous ion exchange process for
the wastewater treatment has been proposed. The node for the
wastewater treatment consisted of a multicolumn setup arranged
in such a way that the time-invariant number of columns could
operate in the productive mode (saturation). The operating cycles
of consecutive columns in the node were shifted in time; proper
adjustment of the shift time assured continuity of the operation.
For the process design a model of the process dynamic was
used, i.e., the LDF model, which was incorporated into the
optimization procedure based on the differential evolution
method.
The process conditions were optimized subject to the con-
straint of the pollutant concentration in the output water stream
for the periodic as well as continuous system.
The best results in terms of the process performance were
achieved in case of optimization of the operating conditions for
the columns operating jointly in the purication node.
The optimization results indicated that continuous process can
signicantly outperform the periodic operation.
Additionally, the possibility of the improvement of the process
productivity was analyzed for the owsheet scheme involving
recycling of the exhausted post-regenerating stream. Introducing
the regenerant recycling resulted in reduction of the consumption
of puried water in the regeneration mode and increased the
process performance.
The procedure of the process design suggested in this study
was developed for an ideal ion-exchange system for which
gradual changes of bed properties were neglected. However, after
proper adjustments, it can potentially be used for real systems.
Nomenclature
C concentrations in the mobile phase (mol/L)
D
L
dispersion coefcient (m
2
/s)
D
peff
effective coefcients of diffusion in macropores (m
2
/s)
D
seff
effective coefcients of diffusion in micropores (m
2
/s)
k
eff
effective interparticle mass transport coefcient (m/s)
k
m
lumped mass transport coefcient (1/s)
K isotherm coefcient (dimensionless)
L column length (m)
N number of time units
OF objective function (mol/(L
min
))
Pr productivity
q solid phase concentration (mol/L
solid
)
q
n
solid phase concentration in equilibrium with the liquid
phase (mol/L
solid
)
Q volumetric ow rate (L/min)
u supercial velocity (m/s)
V column volume (m
3
)
Table 3
Performance of different continuous multicolumn setups.
40
(L/min)
80
(L/min)
100
(L/min)
OF, optimized continuous node 3.39 6.78 9.12
OF, periodic node/periodic throughput 3.42 6.84 9.12
OF, periodic node/continuous throughput 2.74 5.48 7.31
R. Bochenek et al. / Chemical Engineering Science 66 (2011) 62096219 6218
x axial coordinate (m)
z ion charge
Greek letters
g activity coefcient
G exchange capacity (mol/L
solid
)
e
e
external porosity
e
p
internal porosity
e
t
total porosity
Subscripts
c counter-ions
co co-ions
p eluite (pollutant) ion
r regenerant
Superscripts
0 initial conditions
in the column inlet
k stage index
F feed
m mobile phase
out column outlet
rec recycling
s solid phase
Acknowledgment
The nancial support of Polish Scientic Committee within the
grant no. N N209 033538 is greatly acknowledged.
References
Agarwal, A., Biegler, L.T., Zitney, S.E., 2010. A superstructure-based optimal
synthesis of PSA cycles for post-combustion CO
2
capture. AIChE J. 56 (7),
18131828.
Antos, D., Kaczmarski, K., Piatkowski, W., Seidel-Morgenstern, A., 2003. Concen-
tration dependence of lumped mass transfer coefcientslinear vs. nonlinear
chromatography and isocratic vs. gradient operation. J. Chromatogr. A. 1006,
61.
Babu, B.V., Pallavi, G.C., Syed Mubeen, J.H., 2005. Multiobjective differential
evolution (MODE) for optimization of adiabatic styrene reactor. Chem. Eng.
Sci. 60 (17), 48224837.
Babu, B.V., Angira, R., 2006. Modied differential evolution (MDE) for optimization
of nonlinear chemical processes. Comput. Chem. Eng. 30, 9891002.
Blanchard, G., Maunaye, M., Martin, G., 1984. Removal of heavy metals from
waters by means of natural zeolites. Water Res. 18, 15011507.
Bochenek, R., Jezowski, J., Bartman, S., 2007. Optimization of heat exchanger
network with xed topology by genetic algorithms. Chem. Eng. Trans. 12,
195200.
Castel, C., Schweizer, M., Simonnot, M.O., Sardin, M., 2000. Selective removal of
fuoride ions by a two-way ion-exchange cyclic process. Chem. Eng. Sci. 55,
33413352.
Cruz, P., Magalh~ aes, F.D., Mendes, A., 2005. On the optimization of cyclic
adsorption separation processes. AIChE J. 51 (5), 13771395.
Cruz, P., Santos, J.C., Magalhaes, F.D., Mendes, A., 2003. Cyclic adsorption separa-
tion processes: analysis strategy and optimization procedure. Chem. Eng. Sci.
58 (14), 31433158.
Dabrowski, A., Hubick, Z., Podkos cielny, P., Rubens, E., 2004. Selective removal of
the heavy metal ions from waters and industrial wastewaters by ion-exchange
method. Chemosphere 56, 91106.
Deb, K., 2001. Multi-objective Optimization Using Evolutionary Algorithms. John
Wiley, Singapore.
Ernest, M.V., Bibler, J.P., Whitley, R.D., Linda- Wang, N.H., 1997. Development of a
carousel ion-exchange process for removal of Cesium-137 from alkaline
nuclear waste. Ind. Eng. Chem. Res. 36, 27752788.
Flores, V., Cabassud, C., 1999. A hybrid membrane process for Cu(II) removal from
industrial wastewater, comparison with a conventional process system.
Desalination 126, 101108.
Go rka, A., Bochenek, R., Warcho", J., Kaczmarski, K., Antos, D., 2007. Ion exchange
kinetics in removal of small ions. effect of salt concentration on inter- and
intraparticle diffusion. Chem. Eng. Sci. 63, 637.
Gunn, D., 1987. Axial and radial dispersion in xed beds. Chem. Eng. Sci. 42,
363373.
Hritzko, B.J., Walker, D.D., Linda- Wang, N.H., 2000. Design of a carousel process
for cesium removal using crystalline silicotitanate. AIChE J. 46 (3), 552564.
Huckman, M.E., Latheef, I.M., Anthony, R.G., 2001. Designing a commercial ion-
exchange carousel to treat DOE wastes using CST granules. AIChE J. 47 (6),
14251431.
Jiang, L., Fox, V.G., Biegler, L.T., 2004. Simulation and optimal design of multiple-
bed pressure swing adsorption systems. AIChE J. 50 (11), 29042917.
Jez owski, J., Bochenek, R., Ziomek, G., 2005. Random search optimization approach
for highly multi-modal nonlinear problems. Adv. Eng. Software 36 (8),
504517.
Jez owski, J., Bochenek, R., Poplewski, G., 2007. On application of stochastic
optimization techniques to designing heat exchanger- and water networks.
Chem. Eng. Process.: Process Intensication 46, 11601174.
Kaczmarski, K., Antos, D., Sajonz, H., Sajonz, P., Guiochon, G., 2001. Comparative
modeling of breakthrough curves of bovine serum albumin in anion-exchange
chromatography. J. Chromatogr. A. 925, 1.
Lapidus, L., Amundson, N.L., 1952. Mathematics of adsorption in beds. the effect of
longitudinal diffusion in ion exchange and chromatographic column. J. Phys.
Chem. 56, 984.
Lewus, R.K., Hakan Altan, F., Carta, G., 1998. Protein adsorption and desorption on
gel-lled rigid particles for ion exchange. Ind. Eng. Chem. Res. 37, 10791087.
Michalewicz, Z., Fogel, D.B., 2002. How to Solve it: Modern Heuristics. Springer
Verlag, Berlin.
Nilchan, S., Pantelides, C.C., 1998. On the optimisation of periodic adsorption
processes. Adsorption 4 (2), 113147.
Onwubolu, G.C., Babu, B.V., 2004. New Optimization Techniques in Engineering.
Springer-Verlag, Heidelberg.
Pintar, A., Batista, J., Levec, J., 2001. Integrated ion exchange/catalytic process for
efcient removal of nitrates from drinking water. Chem. Eng. Sci. 56,
15511559.
Price, K.V., Storn, R.M., Lampinen, J.A., 2005. Differential EvolutionA Practical
Approach to Global Optimization. Springer Verlag, Berlin.
Rochette, F., 2006. Novel technology: fresh approach to countercurrent ion
exchange. Filtration and Separation 43 (7), 1819.
Ruthven, D.M., 1984. Principles of Adsorption and Adsorption Process. John Willey,
New York.
Softening, Y.S., Grevillot, G., Tondeur, D., 1990. Modelling and optimization of the
cyclic regime of an ion-exchange process for sugar juice. Chem. Eng. J. 43,
B53B66.
Spiro, D.A., 2009. Ion exchange resins: a retrospective from industrial and
engineering chemistry research. Ind. Eng. Chem. Res. 48, 388398.
Srinivas, M., Rangaiah, G.P., 2007. Differential evolution with tabu list for solving
non-linear and mixed-integer non-linear programming problems. Ind. Eng.
Chem. Res. 46, 71267135.
Storn, R., Price, K., 1997. Differential evolutiona simple and efcient heuristic for
global optimization over continuous spaces. J. Global Opt. 11, 341359.
Sun, Y., Grevillot, G., Tondeur, D., 1990. Modelling and optimization of the cyclic
regime of an ion-exchange process for sugar juice softening. Chem. Eng. J. 43,
5366.
Valverde, J.L., De Lucas, A., Carmona, M., Pe rez, J.P., Gonza lez, M., Rodrguez, J.F.,
2006. Minimizing the environmental impact of the regeneration process of an
ion exchange bed charged with transition metals. Sep. Purif. Technol. 49,
167173.
Wilson, E.J., Geankoplis, C.J., 1966. Liquid mass transfer at very low Reynolds
number in packed beds. Ind. Eng. Chem. Fund. 5, 914.
R. Bochenek et al. / Chemical Engineering Science 66 (2011) 62096219 6219