Journal of Chemical Engineering of Japan, Vol. 42, No. 4, pp.

231–240, 2009 Research Paper

Model for Batch Crystallization of Bisphenol-A Adduct under the

Influence of Industrial Impurities
Ehsan NOURAFKAN and Abdolmohammad ALAMDARI
Chemical and Petroleum Engineering Department,
School of Engineering, Shiraz University,
Zand St., Shiraz, 7134851154, Iran

Keywords: Adductive Crystallization, Bisphenol A, Impurities, Kinetic Parameters, Modeling

The present study investigates the crystallization kinetics of bisphenol A-phenol adduct under the
influence of impurities present in industrial liquors. Crystallization experiments were carried out in a
2 L stainless-steel jacketed reactor. Impurities in a sample of industrial liquor were analyzed using gas
chromatography and the morphology of adduct particles were illustrated using method of scanning elec-
tron microscopy. A population balance equation coupled with a mass balance equation was used in model
development. These model equations were solved simultaneously using the finite difference method of
Crank–Nicolson. Kinetic parameters of the rate equations of growth, nucleation, and agglomeration
were estimated by minimizing the difference between the model predictions and the experimental data.
The estimation of kinetic parameters revealed that the impurities decrease the mechanisms of growth
and nucleation but increase the agglomeration of adduct particles. Therefore, the plant impurities detri-
mentally affect the quantity and quality of the adduct product.

Introduction such as heating and extraction (Mullin, 2001). The ac-

Bisphenol A (BPA) is generally used in the indus-
tries of polycarbonate plastics and resins of epoxy,
phenoxy, and polysulfone. Two phenolic rings join to-
gether through a bridging group of isopropylidene, to
form BPA. A reaction between phenol and acetone in
the presence of acidic catalysts or cationic exchange
resins produces BPA as shown below.
CH3COCH3 + 2C6H5OH → (CH3)2C(C6H4OH)2 + H2O
companied or co-builder molecule in the case of BPA
adduct is phenol, which comprises about 30% of the
adduct mass and is removed later by distillation. The
structure of adduct crystals may be represented by the
following reaction in which one molecule of BPA is
attached to one molecule of phenol through a physical
bond to form the complex compound of adduct.
C6H5OH + (CH3)2C(C6H 4OH)2
→ C6H 5OH·(CH3)2C(C6H 4OH)2

BPA is separated from the reaction products in the
industrial practice through the consecutive processes
of crystallization of BPA adduct from the reaction so-
lution, washing the adduct crystals by fresh phenol,
dissolving the washed crystals in phenol, recrystallization
of adduct crystals from phenolic solution for further
purification, filtration and melting of adduct crystals,
distillation of phenol from melt, and flaking of the BPA
melt.
The crystallizing compound in adductive crystal-
lization includes the main desired product accompa-
nied by an extra organic or inorganic constituent. Usu-
ally, only a part of the auxiliary compound contributes
physically in the crystal structure; thus, the structure
of adduct crystal may break easily through operations
Received on July 4, 2008; accepted on October 16, 2008.
Correspondence concerning this article should be addressed to
A. Alamdari (E-mail address: alamdari@shirazu.ac.ir).
The mother solution of crystallizing BPA adduct
contains many impurities which are generated by side
reactions. Light and heavy phenolic compounds are
side products of the BPA reaction. These side products
have been reported to reduce the efficiency of the BPA
production process by up to about 20% (Bodiger et al.,
2004). The impurities may affect the crystallization
kinetics, the morphology, and the physical properties
of the crystals (Mullin and Garside, 1974; Moyers,
1986; Nokhodchi et al., 2005). Generally, impurities
reduce the product purity and disturb the product size
distribution, and consequently make the downstream
processes of filtration, drying and storage more diffi-
cult.
Moyers (1986) studied the kinetics of BPA-adduct
crystallization in a full scale MSMPR crystallizer. He
measured the size distribution of particles in the
crystallizer and calculated the population densities

Copyright © 2009 The Society of Chemical Engineers, Japan 231

 Table 1 Quantitative analysis of a sample taken from the output of an industrial BPA reactor

Concentration [wt%] Retention time [min] Component

66.59 1.85 Phenol
0.62 4.30 4-Isopropenylphenol (PRF)
0.56 4.85 2,2,4-Trimethyl chromen (TMC)
0.05 6.31 1,1,3-Trimethyl-5-indenol (TMI)
1.36 7.67 9,9-Dimethylxanthene (M210)
0.15 9.32 Dimethylhydroxybiphenyl (M198)
1.42 10.93 o,p-BPA
3.23 12.27 2,2,4-Trimethyl-4-(4′-hydroxyphenyl) chroman
17.14 13.24 p,p-BPA
7.38 16.39 1,1,3-Trimethyl-3-(4-hydroxyphenyl)-5-indanol

against the particle size. The linear behavior on a semi- 1. Experimental

log scale indicated the relevance of the MSMPR theory
The first and the second set of experiments were
used for modeling and simulation of BPA-adduct crys-
carried out in the presence of high and low concentra-
tallization. The resulting equation of Moyers describ-
tions of impurities, respectively, similar to the impu-
ing the nucleation rate is shown below.
rity concentrations in the plant cycles of crystalliza-
tion and recrystallization.
B° = knG1.14M T1.17
1.1 Analysis of impurities
The impure samples were analyzed by GC method
in which a 2 m-glass-packed column with an internal
Here, B° is the nucleation rate, G is the growth rate,
diameter of 2.2 mm was used. The packing was 10%
MT is the suspension density, and kn is the coefficient
Silicone OV-17 on Chromosorb WHP 80–100 Mesh.
of nucleation rate.
The initial and the final temperatures of the column
Using HPLC technique, Poskrobko et al. (2000)
were 130 and 260ºC, respectively, and the flow rate of
developed a method for the analysis of impurities in
the carrier gas N2 was 0.66 mL/s. The samples for GC
the process streams of a BPA plant. Many patents have
analysis were prepared by dissolving 0.2 g of the sam-
been granted to the BPA makers, mostly about the pro-
ple solution in 15 mL of dioxane solvent.
duction process of BPA (Saruwatari, 2004; Webb and
The results of GC analysis of the sample from the
Spivck, 2006). However, almost no research can be
plant liquor taken from the reactor outlet are reported
found in the literature about the impurity effects on
in Table 1. The concentrations were calculated using
the kinetic mechanisms of BPA-adduct crystallization.
the method of area normalization. Para-para BPA and
Lack of published materials about the impurity effects
phenol constitute 17.14 and 66.59 wt% of the plant liq-
necessitates implementation of more research in this area.
uor, respectively; therefore, 16.27% of the liquor may
The present study aims at investigating the kinet-
be considered to be impurities.
ics of BPA-adduct crystallization under the influence
1.2 Seed preparation
of impurities found in the liquors of a local BPA plant.
The initial seeds necessary for experiments were
In this plant, the reaction of BPA production is
prepared through the primary nucleation mechanism
catalyzed by cation exchange resins. The reaction prod-
in a pure phenolic solution containing 18% BPA un-
ucts, soluble in a phenolic solution, after dewatering
dergoing a natural cooling program.
and removal of acetone in a distillation tower, are sent
1.3 Crystallization experiments
to the crystallization stage, where the BPA adduct crys-
It is essential that the supersaturation generated
tallizes from the solution upon cooling. A branch of
at the commencement of the cooling process is con-
the product stream is returned to the adduct crystallizers
sumed on the growth mechanism; otherwise, primary
as a seed stream. A portion of the mother liquor from
nucleation would be inevitable. Addition of enough
the centrifuges is returned to the reactor and another
seed and an appropriate low rate of cooling are neces-
portion of the mother liquor is thermally catalyzed in
sary to prevent primary nucleation. A very low rate of
order to decompose the heavy phenolic compounds to
cooling or a very high amount of seed, on the other
lighter compounds and phenol. The residual liquor from
hand, makes an industrial process of crystallization
the thermal decomposition process comprising heavier
more expensive. In the present study, a third-order-
compounds is treated as residual waste.
cooling profile was used to prevent excessive genera-
tion of supersaturation at the early stages of cooling
when enough surface area is not available (Nyvlt et

232 JOURNAL OF CHEMICAL ENGINEERING OF JAPAN


Fig. 1 Experimental setup for batch cooling crystalliza-
tion of BPA-phenol adduct
al., 1973). The employed temperature profile is shown
by Eq. (1).
T0 − T  t 
3
= (1)
T0 − Tf  τ 
Here, T is the temperature at time t, T 0 is the commenc-
ing temperature, Tf is the terminating temperature and
τ is the total cooling time. However, at the end when
enough surface area of seed has been generated, higher
cooling rates are suggested by the profile in order to
minimize the experiment course.
A specified amount of adduct particles as initial
seed was added to the feed solution of all experiments
before the commencement of the cooling process. How-
ever, the optimum amount of seed is generally deter-
mined practically (Choong and Smith, 2004). The
amount of seed was chosen as 5 wt% of the initial so-
lution in the crystallizer vessel.
The experimental setup used in the present study
is schematically shown in Figure 1. The stainless steel
crystallizer in each experiment was filled with 2 L of
phenolic solution containing 18% BPA and different
amounts of impurity (0.0, 0.8, 1.5, 5, and 9 wt%). The
temperature of crystallizer was lowered by circulating
a stream of water from a bath equipped with an electrical
heater and a cooling coil. The water temperature in the
bath was controlled by a PT100 controller, and the so-
lution temperature was monitored by a thermometer.
A 45º pitched four-blade agitator with a large diameter
was used to suspend the particles and to accelerate the
heat transfer from the jacket to the solution. The large
blades of the agitator and its low speed (55 rpm) mini-
mized crystal breakage while sufficiently suspending
the particles.
The solution was prepared and maintained at 72ºC
before cooling for about half an hour. Then, the tem-
perature was lowered to 70ºC at which the seed parti-
cles were added to the solution and the cooling profile
was started. Cooling from 70 to 55ºC on the profile
lasted about 3 h. Sampling from solid phase for deter-
mination of CSD was carried out twice: after 2.5 h from
VOL. 42 NO. 4 2009
Table 2 Experimental conditions of different
crystallization runs
Experimental conditions Value
BPA-Phenol solution in crystallizer 2 kg
BPA concentration 18 wt%
Initial seed concentration 5 wt%
Initial temperature 70°C
Final temperature 55°C
Speed of agitator 55 rpm
Total cooling time 3h
Impurity concentration [wt%]
1st experiment 0.8%
2nd experiment 1.5%
3rd experiment 5%
4th experiment 9%
the start, and at the end of the cooling program. The
solids were separated from the solution through filtra-
tion by a Buchner funnel under vacuum. The filter cake
was immediately reslurried in n-hexane, and was well
agitated for about 10 min. The solids were filtered,
dried and analyzed for size distribution using a sieve
set of ASTM (E: 11). Each filtrate sample was analyzed
for BPA concentration using the GC method. The ex-
perimental conditions of different crystallization runs
are reported in Table 2.
Supersaturation was calculated using the results
of GC analysis and the equilibrium data at the corre-
sponding temperatures. Each experiment was repeated
twice to ensure the results were reproducible. Scan-
ning Electron Microscopy (Oxford 5526, Link Pentafet
operating at 20 kV) was used to investigate the mor-
phology and agglomeration tendency of the adduct
particles.
Experiments were carried out batch-wise due to
easy operation and control of a batch-bench-scale set
up and high toxicity of phenol, which is the solvent of
BPA-adduct crystallization. Phenol is highly corrosive
and is absorbed rapidly through the skin, and affects
the central nervous system and causes damage to the
liver and kidney. When heated, phenol will produce
toxic vapors which at a low concentration of a few ppm
in the air may be harmful to the eyes. Therefore, all
the experiments and operations of solution preparation
were performed under a well-ventilated hood. During
the filtration and sampling operations, anti-acid cloths,
gloves, safety glasses, and masks were used.
2. Mathematical Modeling
Crystallization mechanism functions of growth,
nucleation, agglomeration, and breakage were em-
ployed in the theory of population balance by Randolph
and Larson (1988) to predict the size distribution of
crystals produced in a crystallization process. The
233
 Table 3 Some important physical properties of adduct crystals

Properties of adduct crystals Value

Molecular weight 322.3 g/gmol
Melting point 98–100˚C
Shape factor of particles from pure solution 0.27
(Shariatnasab et al., 2006)
Shape factor of particles from impure solution 0.39
(estimated at this study)
Solubility in phenol
45˚C 11.87 g/100 g
75˚C 39.92 g/100 g

Skeletal density, ρ, measured by liquid pycnometry

(Shariatnasab et al., 2006)
25˚C 1.357 g/cm3

population balance for a perfectly mixed batch shown in Table 3. The mass balance equation is sub-
crystallizer of constant volume under conditions of ject to the initial condition CBPA (t = 0) = Co, where Co
negligible breakage is shown by Eq. (2). is the BPA concentration in the feed solution.
The supplementary relations to mass and popula-
∂n(v, t ) ∂(Gv n(v, t ))
tion balances are the nucleation, the growth, and the
+ = B(v, t ) − D(v, t ) (2 ) agglomeration rate equations. The nucleation rate is
∂t ∂v given by Eq. (7) (Bransom, 1960).
Here, n(v, t) is the population density of v-size crystals
at time t, Gv is the crystal growth rate, and D and B are B° = kn MT S i (7)
the death and birth functions for v-size particles due to
agglomeration, respectively. The initial and boundary Here, kn is the coefficient of nucleation rate and i is
conditions are given by Eqs. (3) and (4), respectively. the supersaturation order of the nucleation rate. The
growth rate is given by Eq. (8).
n(v, 0) = ns (v) (3)
dv
Gv = = kg S a v 2 3 (8)
B° dt
n(0, t ) = ( 4)
Gv (v = 0)
Here, kg is the coefficient of growth rate and a is the
supersaturation order of growth rate. The birth and
Here, B° is the nucleation rate and ns is the population death functions of agglomeration mechanism are shown
densities of seed crystals. by Eqs. (9) and (10), respectively.
The mass balance for a cooling adductive crystal-
lization system with constant volume is Eq. (5).
1 v
B(t, v) = ∫
2 0
C(t, u, v − u)n(v − u, t )n(u, t ) d u ( 9)
d CBPA d ∞
dt
= − ρk
dt 0 ∫
n(v, t )v d v (5)
∞
D(t, v) = nv (v, t )∫ C(t, v, u)n(u, t ) d u (10)
0
Here, CBPA is the BPA concentration in the crystalliz-
ing solution, ρ is the density of adduct crystals, and k Here, C is the agglomeration kernel, and u and v are
is the mass fraction of BPA in adduct crystals, which the particle volumes. Due to some similarities between
is given by Eq. (6). the mixing pattern in the crystallizer of the present
study and that of the shear stream, and a strong de-
MBPA pendency of agglomeration to supersaturation, the ker-
k= = 0.7081 (6 )
Mphenol + MBPA nel function shown in Eq. (11), was used in the formu-
lation (Smoluchowski, 1917).
Here, M is the molecular weight of constituents. Some
C(v, u) = kc S m (u1 3 + v1 3 )
3
important physical properties of adduct crystals are (11)

234 JOURNAL OF CHEMICAL ENGINEERING OF JAPAN

Table 4 The solubility parameters of Eq. (12) presenting
the experimental solubility data at different im-
purity concentrations
Impurity concentration [wt%] β [—] α [K– 1 ]
0.0 –0.424 2.25 × 10 – 2
1.5 –0.540 2.38 × 10 – 2
9 –0.642 2.46 × 10 – 2
Here, kc is the agglomeration rate coefficient and m is
the supersaturation order of the agglomeration kernel.
Solubility of BPA in a phenolic solution with the
presence of different concentrations of plant impuri-
ties was studied by Alamdari et al. (2006). They re-
ported that both the meta-stable zone width and the
BPA solubility decrease under the influence of the plant
impurities. The data of BPA solubility from their work
was correlated satisfactorily to the expression of Eq. (12).
log C ∗ = αT + β (12)
Here, C* is the saturation concentration of BPA at tem-
perature T, and α and β are the parameters of the equa-
tion. These parameters depend on the concentration of
impurities in the saturated solution. The solubility pa-
rameters of Eq. (12) (α and β) are listed in Table 4.
The supersaturation used in the rate equations was ex-
pressed as Eq. (13).
C − C∗
S= (13)
C∗
Here, the value of C* was calculated using Eq. (12).
2.1 Model solution
The methods of moment transformation, finite
difference, and Laplace and Fourier transformations
are available to solve the population balance equations.
There are also some recent methods for more complex
population equations (Bennett and Rohani, 2001; Lim
et al., 2002). It is necessary to solve the model equa-
tions accurately with reasonable speed. In the present
study, the finite difference method of Crank–Nicolson
was used to solve the population and mass balance
equations (Schilling and Harris, 2000).
The accuracy of a numerical solution by the finite
difference method increases as the number of size and
time intervals increases; on the other hand, the CPU
computation time also increases. Therefore, the opti-
mum numbers of intervals corresponding to appropri-
ate size and time steps give good accuracy and a rea-
sonable CPU computation time. In order to find the
appropriate value of size step, the CPU time for differ-
ent size steps of ∆x equal to 0.5, 1, 2, 5, and 10 µm,
but for a constant time step of 30 s, was recorded. It
was found that there were small differences between
VOL. 42 NO. 4 2009
Fig. 2 Smooth curve fitted to the cumulative size distri-
bution of seed measured by sieve analysis
model outputs for ∆x smaller than 2 µm. However, the
CPU time for size steps less than 2 µm increased
sharply. Thus, based on the CPU computation time and
the insignificant difference between the model outputs,
the size step of 2 µm was chosen for further calcula-
tions. Choice of a size step equal to 2 µm divided the
applicable size range to 235 intervals.
Since the number of sieves used in the size analy-
sis was less than the number of size steps used in the
program, a smooth curve was fitted to the data of sieve
analysis and some more data corresponding to the
number of steps in the program were extracted from
the fitted curve using the method of Piecewise Cubic
Hermite Interpolating Polynomial (Fritsch and Carlson,
1980). Figure 2 shows the seed size distribution mea-
sured by sieve analysis and the curve fitted to the data
points.
The accuracy of the model solution by the Crank–
Nicolson method was verified by comparing the nu-
merical solutions with the analytical solutions for very
few limited cases for which the analytical solutions
were reported in the literature (Gelbard and Seinfeld,
1978).
Shariatnasab et al. (2006) calculated the volume
shape factor of adduct crystals using Eq. (14) and
counting and weighing around two thousand crystals
in a narrow size range in the distribution taken between
two successive sieves in the analysis.
M
kv = (14)
NρL3
Here, M is the weight of crystals, N is the number of
crystals, ρ is the density, and L is the average size of
two successive sieves which crystals were taken from.
2.2 Parameter estimation
The model solution can predict the PSD of the
adduct crystals during the course of crystallization at
different times. In order to solve the model equation,
235

Fig. 3 The effect of different concentrations of the plant
impurities on the crystallization productivity of BPA
adduct after 3 h
it is necessary that the parameters in the rate equations
be estimated. The values of parameters may be esti-
mated by minimizing the deviations between the model
predictions of PSD and those measured experimentally.
Therefore, the optimal sets of parameters for pure and
impure liquors were found by solving the following
nonlinear optimization problem.
min Φ( Mexp , M , Sexp , S;θ )
Here, for crystallization from the pure liquor, θ, is given
by the below function.
θ = [kg , kn , a, i ]
For crystallization from the impure liquor, θ is given
by the following function.
θ = [ kg , k n , k c , m ]
The objective function, Φ, was defined as the sum of
the squared deviations between the experimental data
and the model predictions as Eq. (15).
Φ(θ ) = Φ1 (θ ) × Φ 2 (θ )
Ne  N M
 Mexp ( j ) − M ( j ) 
2
= ∑ ∑    × ∑
i =1  j =1  Mexp ( j )   k =1  Sexp ( k ) 

Here, Φ1 is the solid information in terms of the differ-
ence between the model calculated mass of particles
larger than a specified size and those calculated from
the experimental measurements, Φ2 is the liquid infor-
 NS  Sexp ( k ) − S( k )  2
(15)
mation in terms of the difference between the model
calculated supersaturations of BPA and the
supersaturations calculated from the GC analysis, Ne
is the number of the sampling operations from the solid
phase, NM is the number of sieves used in the size analy-
sis, and NS is the number of measurements of BPA con-
centration. Each sieve corresponds to a specific size in
the distribution. The counters i, j, and k count the sam-
pling operations from the solid phase, the sieves used,
and the concentration measurements, respectively. Use
of information from both phases maximizes the accu-
racy and reliability of the optimized parameters.
MATLAB software was used for programming of
this study, and due to a nonlinear multivariable opti-
mization problem, the interior-reflective Newton
method was employed (Coleman and Li, 1994).
3. Results and Discussion
The adduct particles crystallized from the pure
solution were bright white, while the particles crystal-
lized from the impure solution tended to be dark red.
The extent of the tendency for color change was al-
most proportional to the impurity concentration. The
higher the impurity concentration was in the solution,
the darker the crystals were. Impurities may adsorb on
the crystal surface and change the color of the crystals
or alternatively substitute in the crystal lattice and make
the crystals darker. Figure 3 shows the productivity at
different concentrations of plant impurities. As the level
of impurity concentration in the liquor increases, the
inhibition effect on the productivity increases, indicat-
ing blockage of growth sites by the impurity molecules.
However, it was anticipated that not all the active sites
on the crystal faces would be blocked by the impuri-
ties due to a minimum yield at high concentrations of
impurities. The exponential form of the curve in Fig-
ure 3 and its similarity with the isotherms of adsorp-
tion postulates a mechanism of adsorption for the in-
hibition observed. Figure 3 shows that the slope of in-
hibition for lower concentrations of impurity is higher,
which suggests that a possible process for impurity
removal may be more effective if implemented prior
to the crystallization stage. However, the process of
impurity removal or disposal in industry is commonly
carried out after the crystallization stage.
Figure 4 shows SEM representative photomicro-
graphs of adduct particles crystallized from the pure
and impure liquors. The agglomeration increase shown
in photomicrograph (b) for the impure crystallization
appears to be due to connections between small ad-
duct crystals by means of the molecules of organic
compounds. Perhaps this connection appears by a kind
of polymerization of organic molecules and adsorp-
tion of their free branches on the small adduct crys-
tals. Alternative to association of individual particles,
nucleation on the surface and further growth of the

236 JOURNAL OF CHEMICAL ENGINEERING OF JAPAN


Fig. 4 SEM representative photo-micrographs of adduct
particles crystallized from: (a) the pure liquor; and
(b) the impure liquor
nuclei possibly created the agglomerate appearance.
It is worthy to note that large molecules of impu-
rities having several phenol rings may enhance agglom-
eration by different mechanisms. They may act as a
bridge combining two particles or they may enhance
surface nucleation by blocking the growth sites and
directing the supersaturation release on the surface
nucleation. Agglomeration might cause pockets of
mother liquid to be trapped in the agglomerates as oc-
clusions. The trapped impurities in agglomerates,
which cannot be removed by washing, are transferred
to the solution of recrystallization cycle during the
melting process.
However, the SEM photomicrograph of the adduct
particle crystallized from the impure solution shows
the particle has a compact appearance and has negligi-
ble voids between the primary particles; therefore, the
density of adduct particles crystallized from the im-
pure solutions was assumed to be skeletal and equal to
that of the single adduct particles crystallized from the
pure solution (1.357 g/cm3). The shape of this particle
approaches a more rounded shape as the agglomera-
tion proceeds, and thus the volume shape factor in
model solution was chosen as an average between the
shape factor of a single adduct particle (0.27) and that
of a fully rounded agglomerate (π/6).
The optimized values of parameters calculated
from model fitting to the experimental data in the case
of a pure solution are shown in Table 5. Due to a short
temperature range of cooling operations in adductive
crystallization of BPA in both the experimental and
industrial trials, the kinetic parameters of kg, kn, and k c
were considered independent of temperature in the
VOL. 42 NO. 4 2009
Table 5 The optimized values of kinetic
parameters of adductive crystal-
lization of BPA from pure phe-
nolic solution
Parameter Value
–1
kg [µm s ] 0.0459
kn [# (kg cry stal)– 1 s – 1 ] 398.59
kc [kg so lu tio n # – 1 µm– 3 s – 1 ] 0.0
i 0.44
a 0.51
Table 6 The optimized values of kinetic parameters of
adductive crystallization of BPA from phenol
solution under the influence of different concen-
trations of impurities
Parameter 9 % impurity 1.5% impurity
kg [µm s ] –1
5.58 × 10 –3
0.0144
kn [# (kg cry stal)– 1 s – 1 ] 71.59 181.59
kc [kg so lu tio n # – 1 µm– 3 s – 1 ] 3.46 × 10 – 1 7 2.85 × 10 – 1 7
m 2.81 2.81
range 70 to 55ºC. The supersaturation orders of rate
equations for the impure crystallization were consid-
ered equal to those for the pure crystallization in order
to transfer the effect of impurities to the rate coeffi-
cients of kg, kn, and kc. Observation of SEM photographs
from this study and from other references (Moyers,
1986; Shariatnasab et al., 2006) shows that particles
crystallized from pure solutions are mostly singular and
do not demonstrate agglomerate appearances. There-
fore, kc for crystallization from the pure solution in this
study was considered zero. Additionally, the size dis-
tribution predicted by the model for pure crystalliza-
tion when kc kept as zero was close enough to experi-
mental data and justified neglecting the agglomeration
mechanism for the pure crystallization. However, the
optimized value of supersaturation order of agglom-
eration kernel for the impure crystallization was m = 2.81.
The optimized values of coefficient parameters for the
impure crystallization are shown in Table 6. It is nota-
ble that the optimized parameters shown in Tables 5
and 6 are intermediate values and are valid for the tem-
perature range of 55–70ºC. The supersaturation order
of growth rate (a) less than unity reported in Table 5
indicates that variations of G with supersaturation at
low values of S is larger than its variations at high val-
ues of S. This suggests that at low values of supersatu-
ration when the growth rate is low, the generation of
new sites for growth on the crystal surface is more;
therefore, growth rate increases considerably with a
supersaturation increase. However, at high values of
supersaturation when the growth rate is high, the site
generation on the crystal surface is correspondingly
237
Fig. 5 Sensitivity of objective function with changes of
agglomeration coefficient near the optimum point for
the case of impure solution containing 9 wt% plant
impurities (constant parameters: m = 2.81, a = 0.51,
i = 0.44, k g = 5.58 × 10–3, kn = 71.59)
Fig. 6 The cumulative mass distribution of particles crys-
tallized from the pure and impure solutions after
2.5 hours, predicted by the model and measured dur-
ing the course of experiments

less; therefore, growth rate increases less with a su-

persaturation increase.
In order to verify the reliability of model param-
eters, and clarify the model sensitivity to parameters,
the value of each parameter around its optimum point
was varied when other parameters were kept constant,
and the change in objective function was monitored.
The sufficient variations in the values of objective func-
tion for parameters of growth, nucleation, and agglom-
eration rates were suggestive of the reliability of these
parameters. For brevity, the sensitivity of objective
function with respect to agglomeration coefficient is
only shown in Figure 5.
The cumulative mass undersize predicted by the
model using the optimized parameters have been com-
pared to the corresponding experimental data taken
after 2.5 and 3 h in Figures 6 and 7. The closeness of
the model predictions and the experimental data indi- Fig. 7 The cumulative mass distribution of particles crys-
cates the validity and accuracy of the parameter val- tallized from the pure and impure solutions after 3
ues obtained by optimization. Figure 8 shows the su- hours, predicted by the model and measured dur-
persaturation values predicted by the model during the ing the course of experiments
crystallization progress. As shown in Figure 8, in the
impure liquor, the supersaturation is higher than in the
pure liquor, indicating that impurities inhibit supersatu- growth rate coefficients in crystallization from the
ration release on nucleation and growth mechanisms; impure solution shown in Table 6 will also justify a
therefore, a decrease in productivity occurs as shown lower productivity observed in the impure crystalliza-
in Figure 3. Impurity adsorption on the growth and tion of BPA adduct.
nucleation sites, and resulting site blockage, is the sug- During the first hour of experimental runs, when
gestive mechanism for decrease in supersaturation re- the cooling rate is very low, the generation of super-
lease. Additionally, in impure solutions, the surface saturation is less than its consumption; therefore, su-
area of crystals available for deposition of mass by persaturation decreases as shown in Figure 8. This ef-
growth would be lower due to a high rate of agglom- fect is more sensible for pure crystallization in which
eration. The lower values estimated for nucleation and active sites on the crystal faces are not blocked by

238 JOURNAL OF CHEMICAL ENGINEERING OF JAPAN

 Accumulation of impurities in the cycling solu-
tions of BPA plants and their detrimental effects on
product quality and quantity through changing the
mechanisms of agglomeration and growth suggest thor-
ough removal or conversion of impurities.

Fig. 8 The experimentally measured and the model pre-
dictions of supersaturation in the pure and impure
solutions during the course of crystallization
Conclusions
The mechanisms of nucleation, growth and ag-
glomeration for BPA adductive crystallization from a
phenolic solution containing plant impurities were
mechanistically modeled and the rate equation param-
eters were optimized. The presence of impurity in the
liquor reduced both growth and nucleation, but inten-
sified agglomeration. These effects reduce the produc-
tivity and the quality of BPA product.
A color change of crystals was observed due to
adsorption of impurities on the crystal faces and prob-
ably due to their incorporation in the crystal lattice.
Results showed that plant impurities even at low con-
centrations are detrimental to productivity. Therefore,
it is essential in industrial practice that the process of
impurity removal be implemented before the
recrystallization stage.

Acknowledgments
The authors are grateful to the Iranian Company of Petro-
chemical Research and Technology for financial support of this re-
search.

Nomenclature
a = supersaturation order of growth rate rate, [—]
B(v, t) = birth function [# (kgsolution)–1 s –1 µm –3]
B° = nucleation rate [# (kg solution)–1 s –1]
C = agglomeration kernel [# –1 s –1 kg solution]
C* = saturation concentration of BPA[kg BPA (kgsolution)–1]
C BPA = concentration of BPA [kg BPA (kgsolution)–1]
D(v, t) = death function [# (kgsolution)–1 s –1 µm –3]
Fig. 9 The experimentally measured and the model pre- Gv = volumetric growth rate [µm 3 s –1]
dictions of BPA concentration in the pure and im- i = supersaturation order of nucleation rate [—]
pure solutions during the course of adductive crys- i = counter of solid phase sampling operations [—]
tallization j = counter of sieves [—]
k = counter of concentration measurements [—]
k = BPA mass fraction in adduct crystals
[kg BPA (kgcrystal)–1]
impurities and can grow fast. However, after about 1.5 h kc = agglomeration rate coefficient
[kg solution #–1 µm–3 s –1]
when the cooling rate is higher, the generation of su- kg = coefficient of growth rate [µm s –1]
persaturation is more than its consumption; therefore, kn = coefficient of nucleation rate [# (kg solution)–1 s –1]
supersaturation increases with time. This effect is more kv = volume shape factor of crystals [—]
sensible for impure crystallization in which active sites Mexp = experimental cumulative mass undersize
on the crystal faces are blocked by plant impurities and [kg crystal (kg solution)–1]
MT = magma density of adduct crystals
cannot consume the supersaturation, as seen from about [kg crystal (kg solution)–1]
1.5 to about 2.5 h. After 2.7 h, when supersaturation is m = supersaturation order of agglomeration kernel
at its highest value, and at the same time the magma [—]
density is also at the highest value, secondary nuclea- n = crystal population density [# (kg solution)–1 µm –3]
tion is high enough to produce enough surface area to ns = initial crystal population density
[# (kg solution)–1 µm –3]
provide enough sites for supersaturation release, result- S = supersaturation [—]
ing in a decrease in supersaturation for the second time. Sexp = experimental supersaturation [—]
Concentrations predicted by the model and those mea- T = temperature [K]
sured through the experiments are shown in Figure 9. t = time [s]

VOL. 42 NO. 4 2009 239

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