Computers and Chemical Engineering 112 (2018) 292–303

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Computers and Chemical Engineering

journal homepage: www.elsevier.com/locate/compchemeng

Multiobjective optimization and experimental validation for batch

cooling crystallization of citric acid anhydrate
K. Hemalatha a,b, P. Nagveni a,b, P. Naveen Kumar a, K. Yamuna Rani a,b,∗
a
Process Dynamics and Control group, Chemical Engineering Department, CSIR-Indian Institute of Chemical Technology, Hyderabad 500007, India
b
Academy of Scientific and Innovative Research (AcSIR), CSIR-Indian Institute of Chemical Technology, Hyderabad 500007, India

a r t i c l e i n f o a b s t r a c t

Article history: Multiobjective optimization (MOO) of crystallization systems is gaining importance due to its ability to
Received 21 December 2017 handle multiple conflicting objectives together for finding optimal operating policies. The present study
Revised 9 February 2018
focuses on batch cooling crystallization of citric acid. Among the two forms of citric acid, citric acid
Accepted 19 February 2018
anhydride (CAA) is chosen for experimentation as no such study is available. MOO is carried out to
Available online 22 February 2018
seek optimal cooling policy for unseeded cooling crystallization of CAA to maximize mean crystal size
Keywords: while minimizing variance in size. In this procedure, temperature is discretized using piecewise constant-
Multiobjective optimization control vector parameterization which is simple and convenient for practical implementation. The model
Batch cooling crystallization reported in literature is suitably modified for solubility parameters which are verified experimentally, and
Citric acid anhydrate employed for optimization. One of the optimal solutions from the Pareto solution set is implemented
Crystal size distribution through experimentation successfully and the measured product crystal properties are comparable to the
Optimal cooling policy
predicted results obtained through optimization.
Experimental implementation
© 2018 Elsevier Ltd. All rights reserved.

1. Introduction ers can be achieved through supersaturation control by manipulat-

Crystallization processes have been widely used for production,
purification or recovery of solid materials in almost all process
industries. In particular, batch crystallization is primarily used in
pharmaceutical, food, specialty and fine chemical industries. The
solids obtained through crystallization are further processed to
yield powders, pastes, dispersions, tablets, etc. Thus the control of
crystal properties such as size, shape, morphology, and purity that
decides the quality and solid characteristics of the final product is
of major concern in batch crystallization as it has significant ef-
fect on the ease of down-stream processing such as filtration and
drying.
Considerable amount of research has focused on optimization
and control of batch cooling crystallizers including online monitor-
ing that are discussed in recent review papers (Nagy and Braatz,
2012; Nagy et al., 2013; Ulrich and Frohberg, 2013; Samad et al.,
2013; Simon et al., 2015). Majority of the studies have focused on
control of crystal size distribution (CSD) or shape, as these crystal
properties strongly influence the product quality, functionality and
processing (Doherty, 2007). The optimal control of batch crystalliz-
∗
Corresponding author: Process Dynamics and Control group, Chemical Engineer-
ing Department, CSIR-Indian Institute of Chemical Technology, Hyderabad 50 0 0 07,
India.
E-mail address: kyrani@iict.res.in (K.Y. Rani).
ing the temperature with the help of defined performance criteria
throughout the batch. Thus, for batch cooling crystallization pro-
cesses, it is necessary to determine an optimal temperature trajec-
tory satisfying performance objectives through which a desirable
product quality is obtained.
Determination of optimal model-based control policies has
been widely investigated in the literature. The concept of pro-
grammed cooling of batch crystallizers has been introduced by
Mullin and Nyvlt (1971) who proposed that a significant increase
in the crystal size is obtained by implementing a cooling profile
obtained for constant nucleation rate throughout the batch. This
fact has been emphasized by several researchers who ascertained
improvement in crystal size with controlled cooling compared to
different temperature profiles including natural and linear cooling
curves (Mullin and Nyvlt, 1971; Jones and Mullin, 1974; Mayrhofer
and Nyvlt, 1988; Rohani and Bourne, 1990; Bohlin and Rasmuson,
1992; Xie et al., 2001). Several studies have focused on optimal
seeding in a batch crystallizer (Chung et al., 1999; Ma et al., 1999;
Chung et al., 20 0 0; Zhang and Rohani, 2003; Hu et al., 2005; Costa
and Filho, 2005; Shi et al., 2006; Choong and Smith, 2004; Patience
et al., 2004; Aamir et al., 2010). Seed properties such as seed size
and mass and seed loading (Kubota et al., 2002) are also proven
to affect final crystal size distribution in addition to tempera-
ture and have also been optimized. Substantial research activity
has been devoted to closed loop temperature/concentration control

https://doi.org/10.1016/j.compchemeng.2018.02.019
0098-1354/© 2018 Elsevier Ltd. All rights reserved.
 K. Hemalatha et al. / Computers and Chemical Engineering 112 (2018) 292–303
studies including classical control approach and predictive control
approach for control of crystal size distribution (Rawlings et al.,
1993; Miller and Rawlings, 1994; Matthews and Rawlings, 1998;
Zhang and Rohani, 2003; Fujiwara et al., 2002; Lewiner et al.,
2002; Fujiwara et al., 2005; Worlitschek and Mazzotti, 2004; Shi
et al., 2005; Shi et al., 2006; Christofides et al., 2007, 2008; Yu
et al., 2007; Nagy et al., 2008; Nagy, 2009; Aamir et al., 2009;
Hermanto et al., 2009; Mesbah et al., 2011; Kwon et al., 2014;
Kwon et al., 2015; Sheikholeslamzadeh and Rohani, 2013). Few
experimental studies have been reported for implementation of
optimal temperature profiles for some case studies. Jones and
Mullin (1974) compared different cooling curves experimentally for
potassium sulfate-water system and found that the programmed
cooling with constant nucleation control and metastable control
showed improvement in product crystal size compared to natu-
ral cooling. Similarly, Mohameed et al. (2002) have also imple-
mented three different cooling curves and studied the effect of
cooling rate on crystal size distribution for potassium chloride-
water system to choose an optimal trajectory. Worlitschek and
Mazzotti (2004) optimized the temperature trajectory for the batch
cooling crystallization of paracetamol from ethanol with the fi-
nal particle size distribution defined as the control objective.
Aamir et al. (2012) proposed a novel targeted direct design ap-
proach to systematically design different cooling profiles and hence
batch times, with the objective being the desired shape of prod-
uct CSD and validated experimentally for potassium dichromate-
water system. Significant research on batch cooling crystallizers fo-
cused on finding the optimal cooling profiles in order to improve
the process performance using a single objective pertaining to the
product size distribution (Chung et al., 1999; Chung et al., 20 0 0;
Choong and Smith, 2004; Costa and Filho, 2005; Ma et al., 1999;
Mohameed et al., 2003; Ward et al., 2006; Hounslow and Reynolds,
2006; Hsu and Ward, 2013; Tseng and Ward, 2017) while incor-
porating process model equations and temperature magnitude and
rate limits, and optionally minimum yield, as constraints. However,
there has been a lot of interest in seeded cooling crystallization
processes compared to unseeded crystallization processes. The op-
timization or control objectives that are usually considered as mea-
sures of product characteristics in the above cited literature are
large mean size, uniform distribution or minimum coefficient of
variation, desired shape of product size distribution, seed proper-
ties, shorter batch times or high yield. Some of these studies are
dedicated to choice and comparison of objective functions (Ward
et al., 2006; Hsu and Ward, 2013; Tseng and Ward, 2017) used in
batch cooling crystallization processes.
Majority of the literature cited above on cooling crystallization
has concentrated on solving single objective optimization problems
for different crystallization systems. However, crystallization pro-
cesses have multiple objectives that are conflicting in nature and
there exists a trade off between these objectives which makes it
necessary to consider multiobjective optimization to obtain op-
timal operating policies for better CSD. Thus, it is necessary to
study multiobjective optimization (MOO) of batch cooling crys-
tallization processes. Sarkar et al. (2006) have carried out MOO
for the first time for simulation of seeded cooling crystallization
of potassium sulfate from water. Since then, the application of
MOO to crystallization processes has received focus not only in
cooling crystallization but also in reactive or antisolvent crystal-
lization processes. Sarkar et al. (2007) have carried out MOO for
reactive crystallization processes through simulation to find op-
timal feeding policies for maximum weight mean size and min-
imum coefficient of variation for barium sulfate-water system.
Sheikhzadeh et al. (2008) and Trifkovic et al. (2009) have proposed
novel real-time dynamic optimal control methodology for seeded,
anti-solvent crystallization of paracetamol from isopropanol and
water in an offline and online manner. The optimal antisovent (wa-
293
ter) addition profile has been sought with respect to maximum
mean size and high yield through simulation and also validated
experimentally. They even compared the results of MOO with sin-
gle objective optimization and suggested that better crystal growth
and yield are achieved through MOO. Acevedo et al. (2015) have
implemented a multiobjective optimization framework for size and
shape optimization of two systems, potassium dihydrogenphos-
phate and paracetamol. The optimal cooling policies have been de-
termined with mean size and target aspect ratio as objectives for
unseeded cooling crystallization. Hemalatha and Rani (2017) have
studied MOO of batch cooling crystallization of unseeded parac-
etamol crystallization and seeded potassium nitrate crystallization
using maximization of mean size and minimization of CV as the
objectives in the unseeded case and, additionally, minimization of
nucleated mass in the seeded case. Yet, research studies consider-
ing multiple objectives in the context of batch cooling crystalliza-
tion are less explored compared to traditional single objective op-
timization studies. Further, though several simulation studies are
reported on batch crystallization of citric acid anhydrate (CAA)
(which has applications in food, beverage and pharmaceutical in-
dustries), the process has not been studied in the context of MOO
and the experimental validation for such process has also not been
explored. Thus, crystallization of citric acid anhydrate is chosen as
the topic of interest in the present work.
In the present study, unseeded batch cooling crystallization of
citric acid anhydrate is considered for multiobjective optimization
and experimental implementation. In this work, maximizing aver-
age crystal size and minimizing coefficient of variation are consid-
ered as objectives. Average crystal size, expressed in terms of num-
ber mean size, and coefficient of variation are considered based
on the suitability for measurement according to our recent work
(Hemalatha and Rani, 2017). In this recent work, MOO of unseeded
and seeded batch cooling crystallization are studied through simu-
lation only for Paracetamol and Potassium nitrate systems respec-
tively, whereas in the present study, first attempt is made to imple-
ment the optimal cooling policy that is determined through MOO
through experimentation for citric acid anhydrate, and the results
obtained are compared with simulation studies.
2. Experimental system
This section discusses details regarding the system chosen i.e.
CAA including specific literature reported on its crystallization, sol-
ubility characteristics of CAA, experimental setup, the procedure
used to carry out cooling crystallization in a batch crystallizer,
measurement and product characterization techniques used.
2.1. System Overview
Citric acid is widely used in the food, beverage and pharmaceu-
tical industries to impact a clean, refreshing tartness. Its prime use
is as an acidulant, but it is also used as sequestrant of metal ions to
give protection from the development of off-flavours and off-doors
in certain food stuffs (Teixeira et al., 2012). Citric acid is also used
in cosmetics and toiletries as buffer, and in a wide variety of in-
dustrial applications as a buffering and chelating agent. Citric acid
is also a reactive intermediate in chemical synthesis. In addition,
its carboxyl and hydroxyl groups permit the formation of a variety
of complex molecules and reactive products of commercial interest
(Soccol et al., 2006).
Citric acid crystallizes in anhydrous and monohydrate forms.
The transition temperature of CAA to Citric acid monohydrate
(CAM) is first reported by Bennet and Yuill (1935) to be below
36.3 °C. Caillet et al. (2008) studied monitoring of solvent-mediated
phase transition of citric acid anhydrate to monohydrate using in
situ Raman spectroscopy and reported the transition temperature
294 K. Hemalatha et al. / Computers and Chemical Engineering 112 (2018) 292–303
to be below 34 °C. According to several studies reporting the transi-
tion temperature of citric acid, it can be considered to be between
34 °C and 36.5 °C (Nemdili et al., 2016). There has been an in-
creased interest in the study of crystallization of citric acid mono-
hydrate (CAM) compared to CAA through experimentation (Sikdar
and Randolph, 1976; Berglund and Larson, 1984; Bravi and Maz-
zarotta, 1998a, b; Caillet et al., 2007a, b). However, several simu-
lation studies have been reported for crystallization of citric CAA
where crystallization kinetics for CAM has been utilized to sim-
ulate crystallization of CAA (Bohlin and Rasmuson, 1992; Choong
and Smith, 2004). Recent literature on crystallization of CAA in-
cludes experimental investigation of a seeded crystallization pro-
cess on a vibrated bed bath crystallizer by Teixeira et al. (2012) and
measurement of primary nucleation and growth parameters in a
batch crystallizer by Nemdili et al. (2016).
2.2. Solubility Studies
Solubility of a solute in a specific solvent is a key step in the
study of the crystallization processes. Solubility of CAA in water
and other solvents has been discussed in literature. However, in
this study, the solubility of CAA in water has been verified ex-
perimentally first, to choose solubility data for crystallization ex-
periment in comparison with the reported literature. The solubil-
ity of citric acid anhydrate in aqueous solution is determined by
gravimetry and is also confirmed through titrimetry. Gravimetry
is the oldest and simplest analytical method used for determina-
tion of solubility in any solvent. The basic steps involved in gravi-
metric analysis are dissolution, filtration, drying and weighing. To
prepare CAA solution, solid citric acid anhydrate is purchased from
Alfa Aesar (purity ≥ 99.5), distilled water with PH of 6.5 serves as a
solvent. Distilled water is filtered through vacuum filtration setup
through 0.22 μm membrane filter. Saturated solutions are prepared
in100ml beakers. Solubility is measured at temperatures ranging
from 40 °C to 60 °C in 10 °C increments. The temperature is con-
trolled and maintained by thermostat baths, and the actual tem-
perature is validated by a digital calibration thermometer (Wika,
Germany, uncertainty of ±0.05 °C). Syringes (25 mL) fitted with
0.44 μm membrane filters are used to sample 10 mL of solution
into pre-weighed crucibles or conical flasks. Syringes are preheated
when necessary to prevent nucleation inside the syringes during
sampling. The filters are also preheated to exceed the solution tem-
perature.
Equilibrium is established by dissolution to saturation of solid
material. Three dissolution experiments at the same temperature
are conducted by adding an excess amount of commercial citric
acid anhydrate in 20 ml water taken in 100 ml glass beakers. The
beakers are placed on a hot plate provided with magnetic stirring
for three hours. The temperature is monitored and kept constant
throughout the dissolution process. The samples are allowed to
settle down by keeping them in a hot water bath maintained at
constant temperature for 24 h without disturbing them. For gravi-
metric analysis, a sample of 5 ml each is withdrawn from the clear
supernatant solution into pre-weighed crucibles through a syringe
provided with filter. The mass of the crucible with saturated so-
lution is recorded. Drying of samples is conducted by keeping the
crucible in a hot air oven at the constant solubility temperature for
two days. The mass of the samples is recorded repeatedly through-
out the drying process to establish the point at which no water
remains. Complete drying occurs when the mass of the sample re-
mains constant over time. The samples are weighed at this final
time when all the solvent is evaporated. The weight of the solid
is recorded for all the three samples. The average is taken as solu-
bility (kg. acid/kg. water) at that particular temperature. The re-
sults of this gravimetric analysis are confirmed through titrime-
try also. A 5 ml sample of clear supernatant liquid is withdrawn
and is diluted 10 times with distilled water. A sample of which
is titrated against standard sodium hydroxide (1 N) solution stan-
dardized with oxalic acid dihydrate (1 N), using phenolphthalein
(8-12 pH) as indicator in all the cases.
2.3. Cooling crystallization of citric acid anhydrate
The experimental unit consists of a jacketed glass vessel of ca-
pacity 250 ml that serves as a batch crystallizer. Stirring is pro-
vided using a pitched blade of 45 °angle agitator rotating at a con-
stant speed of 300 rpm. The crystallizer is connected to a heating-
cooling system or a bath circulator with temperature controller as
shown in Fig. 1. Pt 100 resistance temperature detectors (RTD’s)
are used for online temperature measurement of the crystallizer
and the jacket. Also all the temperatures are recorded in a com-
puter connected through data acquisition interface using LABVIEW.
The crystallizer is fed with water and solid CAA according to a cho-
sen initial concentration which is more than the saturation con-
centration. The initial conditions are chosen after rigorous simu-
lation as explained in Section 5. The dissolution of CAA in water
is carried out at a temperature higher than 70 °C and held con-
stant while stirring at a speed of 300 rpm for 60 min to ensure
complete dissolution. The contents are quickly cooled to 62 °C and
held constant for 30 min. The crystallization experiment is carried
out by implementing a cooling profile from 62 °C to 41 °C obtained
through MOO. The total batch time is fixed at 2.5 h. As there is no
provision for automatic implementation of crystallizer cooling pro-
file in the experimental setup, the temperature profile is tracked
by adjusting the jacket (coolant) temperature set point in accor-
dance with the crystallizer temperature profile and the actual pro-
cedure is explained in Section 5.3. At the end of the batch time,
the slurry is filtered for product crystals that are later analyzed to
determine crystal size distribution. The results obtained from this
experiment are then compared with the predicted simulation data
obtained using multiobjective optimization.
2.4. Measurement of crystal size distribution
The contents of the crystallizer are filtered using vacuum fil-
tration. The crystals are then washed with acetonitrile solution in
which citric acid is poorly soluble and are dried overnight at 40 °C
in the oven. Following this, a solid sample is taken on a glass slide
using a small spatula and the size is measured with an image anal-
ysis system, which consists of a table microscope, a digital camera
and a computer equipped with Image analysis software. Images of
crystals are taken and properties of final product crystals are mea-
sured using offline Image Pro Premier 9.1 software.
The parameter chosen for the crystal size characterization is the
diameter of the crystal along its major axis as observed by mi-
croscopy. The experimental results are presented in terms of num-
ber average of crystal size and coefficient of variation as obtained
from the image analysis process. The number mean size L̄ is given
as:
1 n
L̄ = Li (1)
N i=1
where Li is the individual crystal size and N is the number of crys-
tals.
Coefficient of variation (CV) is determined from standard devi-
ation (σ ) and mean size as
σ
CV = (2)
L̄
3. Simulation system
Determination of optimal cooling policy for unseeded batch
cooling crystallization of citric acid anhydrate for implementation
 K. Hemalatha et al. / Computers and Chemical Engineering 112 (2018) 292–303 295

Fig. 1. Schematic diagram of experimental setup for cooling crystallization of CAA.

to achieve better product CSD is of interest in this work. For this
purpose, the dynamic model with crystallization kinetics reported
in the literature (Bohlin and Rasmuson, 1992) is chosen for sim-
ulation. The model assumptions are: uniform mixing, size inde-
pendent growth with no growth rate dispersion, no agglomera-
tion or breakage. The crystals formed initially in the process due
to primary nucleation act as seeds for the remaining process and
thus secondary nucleation also plays a role. The population bal-
ance equation (PBE) is solved using method of moments, which
has been used historically by many researchers (Chung et al., 1999;
Choong and Smith, 2004; Shi et al., 2005; Shi et al., 2006), as it is
simple and consumes less time during optimization, and is repre-
sented as follows:
∂n ∂n
+ G(t ) =0
∂t ∂L
This PBE is reduced to moment equations as
d μ0
=B
dt
dμ j
= jGμ j−1
dt
Boundary conditions: μ j = 0 at t = 0 j = 0, 1, 2, 3, 4, 5
where n represents the number density of crystals with length L
at time t. The total nucleation rate B is the sum of primary (BP )
and secondary nucleation (BS ). Primary, secondary nucleation and
growth rate (G) are expressed in the form of power laws as follows.
BP = kP (C − C ∗ )P
BS = kS (C − C ∗ )S
B = BP + BS
G = kg (C − C ∗ )g
The concentration C is a function of the third moment μ3 , due
to the crystal mass balance.
dC d μ3
= −ρc kv (10)
dt dt
where C is the solute concentration, ρ c is the density of the crystal,
kv is the volumetric shape factor for a sphere crystal model and it
is assumed to be constant throughout the crystallization process.
The solubility is a function of temperature which is expressed in
the form of second order polynomial equation.
C ∗ = C0 + C1 T + C2 T 2 + C3 T 3 (11)
To obtain larger and fewer crystals it is desirable to suppress
nucleation and enhance growth. This can be achieved by control-
(3) ling the super saturation, which is the actual driving potential for
both the nucleation and growth rates and is represented as a con-
centration difference C.
(4) C = C − C ∗ (12)
C∗ is solubility in g. of solute/g. of solvent and is a function of
temperature (T in K) as shown in Table 1.
(5) Assuming constant volume, the amount of solute leaving the
solution must be accounted for by crystal growth and nucleation
and the mass balance of solute concentration is given as
dC
= −3ρc kv Gμ2 (13)
dt
where ρ c is the density of the crystal and the solute concentration
C, kg acid/kg. solvent.
(6) The crystallization kinetic parameters used by Bohlin and Ras-
muson (1992) are used for simulation of the CAA-water system.
(7) The properties of CAA and parameters used for simulation of the
model are reported in Table 1. The temperature of the system is
decreased from 62 °C to 41 °C in a batch time of 2.5 h or 90 0 0 s fol-
(8)
lowing any chosen cooling trajectory (to be discussed in Section 5).
The system of equations from Eqs. (1) to (13) is simulated where
(9) at first, the super saturation is calculated from Eqs. (12), and
296 K. Hemalatha et al. / Computers and Chemical Engineering 112 (2018) 292–303

Table 1
Values of Parameters/Variables used for simulation of the model.

Parameters/Variables Value Units

Total batch time tf 90 0 0 sec

Final temparature Tmin 41 °C
Initial temparature Tmax 62 °C
0.08412 + (0.09393)T
Solubility C∗ kg CAA/kg H2 O where T is in °C
−(0.00148)T 2 + (0.0 0 0 0110 0)T 3
Density of crystals ρ 1665 kg/m3
Volume shape factor kv 0.52 -
Primary nucleation rate constant kp 1.0 × 107 no/kg(kg/kg)−p
Primary nucleation rate exponent p 3.54 -
Growth rate exponent g 0.65 -
Secondary nucleation rate constant ks 0.88774 × exp(4781/T) no/kg(kg/kg)−p−1 (no/kg)−b where T is in K
Secondary nucleation rate exponent s 0.543 -
Empirical exponent b 0.84 -
Growth rate constant kg 0.02652 × exp(−3584/T) kg/kg, where T is in K
Heat of crystalization -H 206.09 kJ/kg
Heat capacity CP 1.2538 kJ/(kg.K)
Heat transfer coefficient UA 0.0216 kJ/(s °C)

Eqs. (6) to (9) are employed to calculate nucleation and growth
rates. Subsequently, moment equations, Eqs. (4) and (5) are inte-
grated in order to find the final product crystal properties. The
concentration for the next time instant is calculated through the
mass balance equation Eq. (13). During optimization (discussed in
Section 4), it is assumed that the crystallizer temperature is per-
fectly implemented (perfect control). For the purpose of control
calculations, Tj is used as manipulated input which is utilized for
implementation of optimal temperature trajectory and the energy
balance equation is
dT −UA   −H M
= T − TJ − 3ρ kv Gμ2 sol
dt MsluC p Cp Mslu
where Msol is the mass of the solvent and Mslu is mass of the
slurry.
4. Multiobjective optimization
In the face of the importance of the final CSD in the down-
stream processes and in product applications, the objectives of the
optimization problems in crystallization are normally chosen ac-
cording to specific features related to product quality and market
demands. The most common objective functions in crystallization
optimization problems are maximization of the mean crystal size
at the end of the batch, minimization of the standard deviation of
the final CSD or minimization of its coefficient of variation (CV),
and sometimes minimization of the batch time (Hemalatha and
Rani, 2016, 2017). A desirable change in one objective produces
an undesirable change in another objective. This necessitates the
application of MOO for crystallization processes. Many MOO stud-
ies have dealt with multiple objectives by combining them into
one objective function composed of the weighted sum of indi-
vidual objectives, or by transforming one objective into a single
response function while using others as constraints. Such an ap-
proach requires prior knowledge of weights, which makes it dif-
ficult to properly interrelate the properties and has the disadvan-
tage of masking the physical significance of individual objectives.
Using proper MOO solution strategies, it is possible to consider
multiple objectives all at a time and solve simultaneously (Sarkar
et al., 2006; Hemalatha and Rani, 2017). No studies are reported on
MOO of cooling crystallization of CAA. In the present work, num-
ber mean size (NMS) and number coefficient variation (CV) are the
two objectives considered for MOO of unseeded batch cooling crys-
tallization of CAA and the optimization problem is formulated as
follows.
4.1. MOO problem formulation and solution methodology
As the focus of the present problem is on the practical imple-
mentation of the optimal cooling profile and to compare results
of experimentation and simulation, maximization of average crys-
tal size and minimization of coefficient of variation are chosen as
objective functions as these are popularly studied and can be mea-
sured through experiment. Also, average crystal size is represented
in terms of number mean size and corresponding representation of
coefficient of variation is considered.
The chosen objective functions are NMS and CV and they are
(14) represented by moments of CSD to simultaneously optimize with
respect to the temperature/cooling profile as a function of time.
The appropriate constraints are also incorporated. These individ-
ual objectives are optimized simultaneously (J1 = [J11, J12 ]) and the
optimization problem is represented as follows with the objective
function J11, representing maximization of NMS and minimization
of CV is represented by the objective function J12 .
μ1
max J11 = (15)
T (t ) μ0
 
μ2 μ0
min J12 = −1 (16)
T (t ) μ21
Subject to:
c1 : Tmin ≤ T (t ) ≤ Tmax
dT
c2 : ≤0 (17)
dt
c3 : t ≤ t f
where Tmax is the initial temperature and Tmin is the final temper-
ature.
The temperature should always be a decreasing function of
time for cooling crystallization throughout the batch. The inequal-
ity constraints ensure that the temperature profile can be imple-
mented. Temperature is the manipulated variable and it is usu-
ally parameterized as a piecewise linear function with respect to
time in earlier works related to MOO (Hemalatha and Rani, 2017;
Acevedo et al., 2015; Sarkar et al., 2006). Experimental validation
of such kind of an optimal temperature profile sought through
MOO has been reported by Acevedo et al. (2015) where the tem-
perature is controlled through automated environment. Such kind
of automated environment is unavailable for experimental imple-
mentation for the present work. Hence, the temperature is cho-
sen to be parameterized as a piecewise constant function which is
simple and convenient for practical implementation in the present
situation.
 K. Hemalatha et al. / Computers and Chemical Engineering 112 (2018) 292–303
Fig. 2. Comparison of solubility data with literature.
The solution methodology using Non-dominated sorting ge-
netic algorithm (NSGA-II) as explained in an earlier work by
Hemalatha and Rani (2017) is chosen for MOO problem to obtain
Pareto optimal set in the present study. In order to parameterize
the input temperature trajectories T(t), the time interval (0, tf ) is
divided into P time stages of unequal length and piecewise con-
stant control policy is sought in each time interval (tk, tk +1 ).
T (t ) = T (k ) for t (k ) ≤ t < t (k + 1 )
where T(k) is the temperature at the beginning of kth interval.
The optimal control problem then is to find T(k), k = 1,2…P. In
the present study, P is considered as 11 between the temperatures
Tmax and Tmin . The number of decision variables to the algorithm
which are temperature variables is taken as 9, excluding Tmax and
Tmin which are fixed initial and final temperatures. This temper-
ature profile is used as the input for MOO through NSGA-II. The
time stages are considered according to time instants represented
by t(k). The explanation for considering unequal time intervals for
optimization is given in Section 5.2.
5. Results and Discussion
5.1. Solubility study
Solubility of CAA in water is determined at temperatures of
40 °C, 50 °C and 60 °C respectively. The experimental solubility data
is compared to those reported by several sources (Dalman, 1937;
Bohlin and Rasmuson, 1992; Teixeira et al., 2012; Apelblat, 2014;
Nemdili et al., 2016). Fig. 2 shows comparison of the experimental
results with the available literature. The solubility units reported
in the literature by different studies is converted to weight frac-
tion for the purpose of comparison. The experimental results ob-
tained are comparable to most of those reported in the literature.
The present experimental solubility results are closer to the data
reported by Teixeira et al. (2012). Hence, the solubility curve re-
ported in their work as shown in Table 1, is chosen for simulation
studies.
297
Table 2
Comparison of mean size and coefficient of variation of different cooling profiles.
Profile NMS, μm CV, %
L 274.20 30.47
P3 418.46 41.67
P4 391.72 51.77
CP 364.45 48.02
(18)
5.2. Optimization of batch cooling crystallization of CAA
Different polynomial cooling profiles reported in the literature
that are commonly employed for simulations or implementation
are compared through simulations using the dynamic model for
citric acid anhydrate detailed in Section 3. The cooling profile is
given by the following equation.

T (t ) = Tmax + (Tmin − Tmax )(t/t f )
a
(19)
where exponent a = 1 results in a linear profile, a = 3 results in a
convex profile suggested for controlled cooling of seeded process,
and a = 4 results in a convex profile suggested for controlled cool-
ing for unseeded process. The profiles for a = 3 and 4 are popularly
known as Mullin-Nyvlt profiles for constant rate of nucleation.
For unseeded cooling crystallization of citric acid anhydrate,
Bohlin and Rasmuson (1992) reported that irrespective of cooling
profile followed, larger mean size is achieved at an initial super
saturation of 0.1 kg/ kg. This has been confirmed in our simulations
and thus for the present work, initial super saturation is consid-
ered to be 0.1 kg/ kg and initial concentration of CAA is chosen
accordingly. With C = 2.9403 kg/kg as the initial concentration of
CAA, the simulations are carried out to study the effect of three
different cooling profiles on final achievable mean size and coeffi-
cient of variation. The results are shown in Table 2 and the corre-
sponding profiles are shown in Fig. 3. It is evident from Fig. 3 that
the number mean size and CV obtained through Mullin-Nyvlt tra-
jectory with power 4 denoted by P4 is inferior to those obtained
by other two profiles. The Mullin-Nyvlt profile with power 3, also
known as a cubic cooling profile denoted by P3 gives better mean
size (418.46 μm) compared to the other two profiles but inferior
value of CV (41.6%) compared to the linear profile denoted by ‘L’.
This type of behaviour is concurrent with the results reported by
298 K. Hemalatha et al. / Computers and Chemical Engineering 112 (2018) 292–303
Fig. 3. Comparison of different cooling profiles.
Bohlin and Rasmuson (1992). For the linear profile, for an improve-
ment of approximately 10% of CV, there is a decrease in mean
size by approximately 150 μm which is not desirable. Among the
three polynomial cooling profiles, for practical implementation, cu-
bic profile can be considered as the best operating profile with re-
spect to mean size and coefficient of variation. However, according
to the optimization study reported by Choong and Smith (2004),
slight deviation from the cubic profile is obtained as the optimal
profile through single objective optimization studies. They have
reported various single objective optimization studies with maxi-
mization of mean size, maximization of yield, minimization of co-
efficient of variation and minimization of batch time as different
objectives that yielded different optimal cooling curves for each
case. It is concluded from their study that the objectives are con-
flicting in nature and a desirable change favouring one objective
results in an unfavourable change in the other objectives. Hence,
multiobjective optimization is necessary for determination of an
optimal cooling profile with respect to specific objectives as it has
the potential to consider trade off between multiple objectives.
To carry out MOO of citric acid, mean size and coefficient of
variation are considered as objectives as these two objectives ex-
hibited a trade off between each other in our simulation stud-
ies. A multiobjective optimization problem for unseeded cooling
crystallization is formulated with two objectives as discussed in
Section 4. Usually, the manipulated variable, temperature is param-
eterized as a piecewise linear policy with respect to time. Due to
limitations in practical implementation of such a cooling profile in
terms of a variable set point at every sampling instant, piecewise
constant policy is chosen where the total batch time is discretized
into 11 unequal time stages corresponding to various temperatures
which can be read from the cubic profile:
t (k )={0, 1400, 2300, 3900, 5300, 6200, 6600, 7400, 8000,
830 0, 870 0, 90 0 0};
A controlled cooling profile can be constructed with these time
stages, without any optimization and compared with the other
polynomial profiles as shown in Fig. 3. When the unseeded pro-
cess is simulated with the newly constructed profile CP, the ob-
tained NMS and CV are 364.45 μ and 48.01% respectively and it is
found that this is comparatively inferior to the terminal mean size
and CV obtained for profile P3. Hence, an optimization is consid-
ered to be necessary with chosen objectives NMS and CV, to seek
an optimal cooling profile for practical implementation. The pop-
ular Non-dominated sorting genetic algorithm (NSGA-II) is used
for solving MOO problem. The solution methodology using NSGA-
II and genetic algorithm parameters reported by Hemalatha and
Rani (2017) are used for the present MOO problem. 9 tempera-
ture variables (excluding initial and final temperature values) are
considered as decision variables for NSGA corresponding to the 11
time stages.
Unlike single objective optimization that results in a unique so-
lution, MOO results in a set of optimal solutions known as Pareto
optimal set or Pareto front. The trade off between the objectives
NMS and CV can be observed from the Pareto optimal set of MOO
as shown in Fig. 4.
In order to explore an alternative method of arriving at the so-
lutions using weighted sum approach and to compare with the
solutions of MOO, the single objective optimization (SOO) is con-
sidered with weighted functions of the two chosen objectives. The
following expression is used for SOO where the problem is to min-
imize the objective function J.
J = (x × (−J11 ) ) + ( (1 − x ) × J12 ) (20)
By changing the values of the weighing factor ‘x’ (ranging from
0.0 to 1.0), 25 optimization runs are carried out and the solutions
from these results are used to construct a Pareto set as shown in
the Pareto plot between the two objectives J11 (NMS) and J12 (CV)
in Fig. 5. Whereas a single run of MOO results in a Pareto solu-
tion set which consists of 100 optimal solutions (as the popula-
tion size in NSGA is chosen as 100) that show trade off between
the two objectives. SOO solutions are obtained in the region be-
tween A and Din Fig. 5, whereas the MOO solutions are obtained
between the region B and C. In the region of overlap (region BC),
the solutions of SOO are slightly inferior to solutions of MOO. In
the region BA, for a small drop in CV value, NMS is drastically re-
duced. On the other hand, in the region CD, for a small rise in
WMS, CV is increasing drastically. Therefore, these regions cannot
be considered to provide necessary trade off between the objec-
 K. Hemalatha et al. / Computers and Chemical Engineering 112 (2018) 292–303 299

Fig. 4. Pareto solution set obtained through MOO.

Fig. 5. Comparison of optimization through weighted sum approach and MOO.

tives. Thus choosing MOO methodology over SOO using weighted Table 3
Comparison of objective function values for selective optimal solutions from Pareto
sum approach provides trade off solutions with minimal effort.
solution set.
From the Pareto set of MOO, three representative solutions of
Pareto set from Fig. 4, i.e. end point of the upper Pareto front (UP), Profile NMS, μm CV, %
end point of the lower Pareto front (LP) and the middle point (MP) UP 363.18 42.98
are chosen for comparison in terms of objectives in Table 3, the MP 341.02 37.21
corresponding optimal cooling profiles are shown in Fig. 6. It is LP 310.96 33.22

observed that the range of NMS pertaining to the Pareto set is 310-
363 μm and CV is 42-33%, and thus the constructed profile CP is
5.3. Tracking of optimal cooling profile for cooling crystallization of
not a part of Pareto solution set and is considered suboptimal. MP
CAA
is chosen to be the optimal Pareto point and the corresponding
optimal cooling profile is considered for practical implementation.
Unseeded cooling crystallization of citric acid anhydrate from
aqueous solution is carried out in a batch crystallizer set up ex-
300 K. Hemalatha et al. / Computers and Chemical Engineering 112 (2018) 292–303

Fig. 6. Comparison of cooling profiles for selected solutions from the Pareto set of MOO.

Fig. 7. Comparison of crystallizer temperature profiles through simulation and experiment.

plained in Section 2. The optimal cooling profile obtained through
MOO is considered as a set point trajectory for experimental val-
idation. Here, the controlled variable is the crystallizer tempera-
ture. The contents of the crystallizer are maintained at an ini-
tial temperature of 62 °C. The heating-cooling system used for the
present work does not have a provision for direct control of the
crystallizer temperature (Tc ). The heating-cooling system has pro-
vision to implement a given set point as the input jacket tem-
perature or bath temperature. Trial experiments indicated a differ-
ence of 1 °C between crystallizer temperature and bath tempera-
ture. Therefore, the set point temperature profile for jacket inlet
bath temperature has been calculated from the determined opti-
mal cooling profile. This trajectory so obtained has been used for
tracking.
For the purpose of comparison of experimental results with
simulations, Eq. (14) has also been included in the set of equations
employed for simulations. The crystallizer temperature is consid-
ered as the set point and its optimal set point trajectory is tracked
using the inlet jacket temperature (Tj ) as the manipulated input
using a PI controller. The controller parameters are chosen through
trial and error method and are found to be: control gain Kc = 0.15
and time constant = 10 s. During the experiment, the temperature
data of the crystallizer, jacket inlet and outlet are recorded for ev-
ery 20 s throughout the batch. The bath temperature set point pro-
file is changed manually by giving step changes at specified inter-
vals. The crystallizer temperature obtained through experiment is
plotted along with the optimal cooling profile generated through
offline optimization as shown in Fig. 7. The actual bath tempera-
ture is calculated as the average of jacket inlet and outlet tempera-
tures represented by T̄ j . The manipulated input temperature profile
obtained through simulation and experiment are reasonably com-
parable as shown in Fig. 8. The experiment is continued for 2.5 h
 K. Hemalatha et al. / Computers and Chemical Engineering 112 (2018) 292–303 301

Fig. 8. Comparision of jacket temperature profiles through simulation and experiment.

Fig. 9. Image of Citric acid anhydriate crystals taken using optical microscope with 40X magnification.

Table 4 6. Conclusions
Comparison of results obtained through experiment and simulation.

Profile NMS, μm
Chosen optimal cooling policy (MP) simulation 341.02
Experiment 334.99
and is terminated when the final temperature is reached at the end
of the batch time. The final crystals are analyzed to measure mean
size and variance. Fig. 9 shows an image of few of the experimen-
tally obtained final citric acid crystals taken using an optical mi-
croscope. The number mean size is measured to be 334.99 μm and
coefficient of variation to be 35.01 %. From Table 4, it can be con-
cluded that the experimentally obtained results are in good agree-
ment with the predicted results.
CV, % In the present study, it is attempted to carry out multiobjec-
37.21 tive optimization for cooling crystallization of citric acid anhydrate.
35.01 Firstly, the solubility of citric acid in aqueous solution for differ-
ent temperatures is determined through experiments and is found
to be comparable with the data reported in the literature. Differ-
ent polynomial cooling temperature profiles have been evaluated
through simulation and it has been observed that cubic profile P3
is found to be optimal with respect to larger mean size only. In
order to find a cooling profile for experimental implementation,
the cubic temperature profile is approximated as piecewise con-
stant profile with unequal time intervals. Further, MOO optimiza-
tion problem is considered with NMS and CV as two objectives
to find the piecewise constant crystallizer temperature profile. The
obtained temperature profile is implemented in an experimental
302 K. Hemalatha et al. / Computers and Chemical Engineering 112 (2018) 292–303
crystallizer unit equipped with a heating cooling system. The sim-
ulation results indicate that NMS and CV obtained by implement-
ing cubic profile is found to be closer to the end point of lower
Pareto front, LP in MOO. Whereas, the middle Pareto point, MP is
chosen for experimental implementation. The experimental results
(334.99 μm, 35.01%) are found to be in good agreement with the
optimal solution (341.02 μm, 37.21%) in terms of NMS and CV re-
spectively. This study illustrates the usefulness of MOO for cooling
crystallization process in giving a trade off solution between two
objectives.
Acknowledgement
The first author acknowledges the financial support from De-
partment of Science and Technology (DST), India, under Women
scientist’s program WOS-A, ref. no. SR/WOS-A/ET-40/2013.
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