Ind. Eng. Chem. Res.

2009, 48, 85758584

8575

Combined Quadrature Method of Moments and Method of Characteristics

Approach for Efficient Solution of Population Balance Models for Dynamic
Modeling and Crystal Size Distribution Control of Crystallization Processes
E. Aamir, Z. K. Nagy,*, C. D. Rielly, T. Kleinert, and B. Judat
Loughborough UniVersity, Loughborough, LE11 3TU, United Kingdom, and BASF SE, Ludwigshafen,
D-67056, Germany

The paper presents a novel methodology for the estimation of the shape of the crystal size distribution (CSD)
during a crystallization process. The approach, based on a combination of the quadrature method of moments
(QMOM) and the method of characteristics (MOCH), provides a computationally efficient solution of the population
balance equation (PBE) and hence a fast prediction of the dynamic evolution of the CSD for an entire batch.
Furthermore, under the assumption that for supersaturation-controlled crystallization the main phenomenon is growth,
an analytical CSD estimator is derived for generic size-dependent growth kinetics. These approaches are evaluated
for the crystallization of potassium alum in water. The model parameters are identified on the basis of industrial
experimental data, obtained using an efficient implementation of supersaturation control. The proposed methods
are able to predict and reconstruct the dynamic evolution of the CSD during the batch. The QMOM-MOCH
solution approach is evaluated in a model-based dynamic optimization study, which aims to obtain the optimal
temperature profiles required to achieve desired target CSDs. The technique can serve as a soft sensor for predicting
the CSD, or as a computationally efficient algorithm for off-line design or online adaptation of operating policies
based on knowledge of the full CSD data.
1. Introduction
Crystallization from solution is an industrially important unit
operation due to its ability to provide high purity separation. It
is widely used in industries such as petrochemicals, pharmaceuticals, microelectronics, and food processing. Batch cooling
crystallization provides the advantages of being simple, flexible,
and generally requiring less process development and investment
than many other separation/purification techniques. However,
despite the long history and widespread application of batch
crystallization, there are a disproportionate number of problems
associated with its control. The crystal size distribution (CSD)
is a key factor in the production of a high quality product and
determines the efficiency of the downstream processes.1,2
Therefore many problems in downstream processes can be
attributed to poor particle characteristics established in the
crystallization step. The control objectives for batch crystallization processes can be defined in terms of product purity,
crystal habit, morphology, average particle size, crystal size
distribution, bulk density, product filterability, and dry solid flow
properties, which all depend on the CSD. The main difficulty
in batch crystallization is to accomplish a uniform and reproducible CSD.3 Online control during the process allows for
improved crystalline product quality, shorter process times, and
reduction or elimination of compromised batches. Even if some
of these objectives can be expressed in terms of the moments
of the distribution, knowing and predicting the entire shape of
the distribution allows the design and adaptation of operating
policies to achieve improved product quality.
A potential way to enhance the control of CSD is to use
supersaturation control,4-10 or direct nucleation control,11,12
which drives the process within the metastable zone to avoid
nucleation or to generate controlled nucleation/dissolution
* To whom correspondence should be addressed. E-mail: z.k.nagy@
lboro.ac.uk. Tel.: +44 1509 222516. Fax: +44 1509 223923.

Loughborough University.

BASF SE.

events. Although these approaches can provide improved

consistency of the CSD, the actual prediction and estimation
of the shape of the distribution at the end of the batch can
provide useful information for monitoring or designing the
operating curve for the supersaturation controller. Model-based
approaches can be used for better control13-21 but also for
product design by reverse engineering the process to achieve
the desired CSD and shape.22-25
Population balance models have been widely used for
modeling crystallization processes.26,27 The solution of the
generic population equation (PBE) usually requires computationally expensive, complex numerical solution techniques.28,29
The variety of solution approaches proposed for the PBE include
the standard method of moments (SMM), the quadrature method
of moments (QMOM),30-32 the method of characteristics
(MOCH),22 the method of classes (MOC),33,34 direct numerical
solution (DNS) techniques, such as finite volume and finite
difference schemes,35,36 and dynamic Monte Carlo (DMC)
simulation approaches.31-37 The first two methods only provide
average characteristics of the CSD expressed in terms of low
order moments (e.g., the mean and standard deviation), whereas
the last two methods are usually computationally too expensive
for online real-time applications. Both SMM and QMOM
provide efficient solutions of the PBE and have been widely
used in the literature for optimization and control purposes.4,14
However, these approaches only provide the moments of the
CSD and not the entire distribution. Several techniques are
available to reconstruct the distribution from its moments, for
example, using linear or nonlinear inversion approaches. These
techniques have the disadvantage that they require a larger
number of moments and generally suffer from solution multiplicity and ill-conditioning problems. Approximate distribution
functions (e.g., polynomial, normal, gamma, or log-normal), or
a weighted sum of distributions, using for example orthogonal
polynomials as weighting functions, can also be used to
approximate the shape of the distribution based on the

10.1021/ie900430t CCC: $40.75 2009 American Chemical Society

Published on Web 07/31/2009

8576

Ind. Eng. Chem. Res., Vol. 48, No. 18, 2009

moments.27,38 However, the solution of such inverse problems

is usually not unique. There is also a lack of systematic
methodologies for the choice of the suitable type and number
of base functions and distributions. Hence the approximate
distribution functions resulting from both categories of reconstruction methods are subject to spurious oscillations and the
correctness of the resultant shape of distribution is difficult to
evaluate in most practical cases. The method of characteristics
(MOCH) in combination with the SMM has been used successfully for processes with size-independent growth and
nucleation,22 including the modeling and control of polymorphic
transformations.10,39 However this approach does not apply in
the more generic case of a PBE with size-dependent growth
and dissolution, or when breakage and agglomeration mechanisms need to be considered.
The approach presented in the paper combines the advantages
of QMOM and the MOCH to provide a computationally efficient
technique for the prediction of the entire CSD. The algorithm
can be applied for the solution of population balance equations
with generic size-dependent growth and nucleation kinetics and
can provide a more general framework for the efficient solution
of PBEs even in the case of breakage and agglomeration.
According to the authors knowledge, this is the first time that
these two approaches have been combined to provide an efficient
solution approach for a model-based control of distribution
shape, with the original idea first presented by the authors in
Aamir et al.45
The method has also been used to identify the kinetic
parameters for the batch cooling crystallization of potash alum
from water using industrial experimental data. An analytical
CSD estimator is also presented for the first time, which can
be used in the case of supersaturation controlled, growthdominated processes. It is shown that the proposed approach
provides a computationally efficient CSD estimation technique,
which can be used for off-line parameter estimation, crystallization design, or for online estimation and control. The
approach is applied in a model-based optimal control approach
to determine optimal temperature trajectories to achieve desired
target CSDs.

of moments (in more generic cases including size-dependent

growth, breakage, and aggregation. Both methods calculate the
moments of the distribution defined by,
j )

fn(L) Lj dL,

j ) 1, 2, ...,

(2)

The QMOM is a generic solution approach for the PBE.30,32,40

It employs a quadrature approximation of the distribution
function
Nq

fn(L, t)

w (t) (L (t), L)
i

(3)

i)1

where Nq is the number of quadrature points and the corresponding weights, wi, and abscissas, Li, can be determined
through the product-difference (PD) algorithm41 or via direct
solution of a differential-algebraic (DAE) system,42 based on
the idea of minimizing the error committed by replacing the
integral from the moment definition with its quadrature
approximation,
j )

Nq

fn(L) Lj dL

wL

j
i i

(4)

i)1

Applying the moment transformation to eq 1 with the quadrature

approximation of eq 4 the resulting moment equations have the
form32,40
d0
) B(S;b)
dt
N

q
dj
)j
wiLj-1
i G(S, Li ;g) +
dt
i)1

B(S;b)rj0,

j ) 1, 2, 3,...

(5)

Considering a single growth direction with one characteristic

length L and a well-mixed crystallizer with growth and
nucleation as the only dominating phenomena, the population
balance equation (PBE) has the form

The generic PBE eq 1 can be reduced to a system of ODEs by

applying the MOCH. The aim of the MOCH is to solve the
PBE by finding characteristic curves in the L - t plane that
reduce the partial differential equation to a system of ODEs.
The L - t plane is expressed in a parametric form by L ) L(Z
i)
and t ) t(Z
i ), where the parameter Z
i gives a measure of the
distance along the characteristic curve. Therefore, fn(L,t) )
i ),t(Z
i )), and applying the chain rule gives
fn(L(Z

fn(L, t)
(G(S, L;g)fn(L, t))
+
) B(S;b)(r0, L)
t
L

dfn
dL fn
dt fn
)
+
dZ
i
dZ
i L
dZ
i t

2. Combined QMOM-MOCH Approach for the

Efficient Solution of PBEs

(1)

where fn(L,t) is the crystal size distribution expressed as a

number density function (number of crystal per unit mass of
slurry), t is time, G(S,L;g) is the rate of crystal growth, B(S;b)
is the nucleation rate, S ) (C - Csat) is the absolute supersaturation, C is the solute concentration, Csat ) Csat(T) is the
saturation concentration with T being the temperature, r0 is the
size of nuclei, (r0,L) is the Kronecker delta ( ) 1 if L ) r0
and ) 0 if L * r0) and g and b are vectors of growth and
nucleation kinetic parameters, respectively. The solution of eq
1 is an initial value problem, with initial condition given by
the size distribution of seed, fn(L,0) ) fn,0(L0).
Equation 1 can be transformed into a system of ODEs by
applying the standard method of moments (in the case of sizeindependent growth and nucleation) or the quadrature method

(6)

In the case of generic growth kinetics, eq 1 can be rewritten in

the form of
fn(L, t)
fn(L, t)
dG(S, L;g)
+ G(S, L;g)
) -fn(L, t)
+
t
L
dL
B(S;b) (r0, L)

(7)

Comparing eqs 6 and 7 it can be shown that Z

i ) t and the
characteristic equations are given by the following system of
ODEs:
dL
) G(S, L;g)
dt

(8)

Ind. Eng. Chem. Res., Vol. 48, No. 18, 2009

dG(S, L;g)
dfn(L, t)
) -fn(L, t)
+ B(S;b) (r0, L)
dt
dL

(9)

with initial conditions L ) L0 and fn(L,0) ) fn,0(L0), that is, the

seed CSD. To obtain the dynamic evolution of the crystal size
distribution fn(L,t), eqs 8 and 9 with prescribed nucleation and
growth expressions can be integrated repeatedly for different
initial values [L0,fn,0(L0)]. The initialization of the integrations
in the L-t plane are illustrated in Figure 1, showing typical
evolutions of the characteristic lines during the integration. To
simulate the growth of the seed, the initial conditions start from
along the L axis of the L-t plane, with values calculated by
choosing a discretization interval L0 and using t0 ) 0 and L0
) max (0,L0,max - kL0), k ) 0,1, ..., N, where N is the number
of discretization points for the seed distribution and L0.max is
chosen to be greater or equal to the maximum size range of the
seed crystals. The discretization interval L0 will determine the
number of integrations (the number of characteristic lines) and
hence the resolution of the dynamic evolution of the seed CSD.
For this part of the integration the initial values for the
probability distribution function are calculated from the seed
distribution fn,0(L0) ) fseed(L0), and all integrations start from
an initial time t0 ) 0.
Figure 1 also shows the method employed to represent the
contribution to the overall distribution function from nucleation
events, which may occur during the batch. In this case, the
characteristic lines for nucleation and growth of new particles,
start from initial conditions along the t axis of the L-t plane,
using L0 ) 0, fn,0(L0) ) 0, and t0 ) tnext. The initial time for the
next integration, tnext, is calculated by interpolating the characteristic line for L ) r0, as shown in Figure 1. The number of
integrations within this part of the algorithm is not predetermined
and will depend on the evolution of the characteristic lines
governed by the growth kinetics. This is an adaptive feature of
the algorithm, which allows the high resolution prediction of
the part of the CSD that results from nucleation events. The
iterations are stopped when tnext g tf where tf is the end time of
the batch. For the solution of eqs 8-9, it is considered that at
the moment of nucleation, nuclei can have any size between 0
and r0. This is described by the modified delta function defined
as
(r0, L) )

1 if L [0, r0]
0 if L [0, r0]

8577

(10)

Thus nucleation events are assumed to occur for L e r0. For

seeding crystallization, secondary nucleation is considered as

Figure 2. Flowchart of the combined QMOM-MOCH approach for the

solution of PBEs.

the dominating nucleation phenomenon, which is generally

expressed as a function of the supersaturation and the volume
of the existing crystals, given by the third-order moment of the
size distribution. Hence in the model, B ) kbSb3. The
formulation given by eq 10 allows the direct consideration of
apparent nucleation kinetics in the model, where r0 is the size
of the particles when they are first detected with a particular
measurement approach. In this study r0 ) 1 m is used since it
represents approximately the size of particles which can be
detected by typical in situ process analytical tools based on
image analysis or focused beam reflectance measurements.
Both the growth and nucleation rates are functions of the
supersaturation, S, which can be calculated from the material
balance. The solute concentration is given by
C(t) ) C(0) - kvFc(3(t) - 3(0))

Figure 1. Evolution of characteristic lines with the generic approach of

calculating the initial conditions for the method of characteristics in the
case of growth and nucleation mechanisms.

(11)

where Fc is the density of crystals and kv the volumetric shape

factor. The solution of eqs 8, 9, and 11 requires a priori
knowledge of the dynamic evolution of the supersaturation, S(t)
and/or the third moment 3(t), which can be obtained by using
the moment transformation of eq 1 via the SMM or QMOM.
The main steps of the proposed algorithm are shown in Figure
2. In the case of secondary nucleation and size-dependent
growth, the ODEs from the QMOM have to be integrated
together with eq 11 once for the duration of the batch to predict
the evolution of 3 and the variation of supersaturation with
time, then S(t) and 3(t) are used in the nucleation and growth
kinetic expressions during repeated integrations of eqs 8,9 with
different initial conditions, to map out the complete evolution
of the full CSD via the MOCH. When nucleation is included

8578

Ind. Eng. Chem. Res., Vol. 48, No. 18, 2009

fn(L) ) fn,0(L0) 1 +

Figure 3. Operating curves represented in the phase diagram for seeded

and unseeded batch cooling crystallizers.

in the model, an iterative integration of eqs 8-9 is needed, since

the number of initial conditions along the t axis, for nucleating
and growing particles, is not known a priori. Note that the
method also applies for dissolution problems and can be
extended for certain breakage and agglomeration mechanisms,
which would appear as extra terms on the right-hand side of eq
9 and would be computed using the evolution of the weights
and abscissas from the solution of the QMOM part of the
algorithm.
3. Analytical CSD Estimator for Growth-Dominated
Crystallization Systems
The traditional way of controlling cooling crystallization
processes is to follow a predetermined temperature profile in
time. Recent developments in the direct design of crystallization
systems have led to a widespread application of supersaturation
control.4,5,7 The direct design approach is based on the idea of
operating the system within the metastable zone bounded by
the nucleation and solubility curves (see Figure 3). In this
technique a supersaturation set point profile is chosen experimentally and it is followed in the phase diagram using a
supersaturation controller based on concentration measurement.
The supersaturation is usually chosen to be constant and with
the application of properly designed control algorithms, in the
case of seeded crystallization the process is maintained at the
desired constant supersaturation throughout the entire batch.
For constant supersaturation controlled seeded crystallization,
seed is added to suppress nucleation, and the operation will be
dominated by growth. Considering the generic case of sizedependent growth given by
G ) kgSg(1 + L)p

kgSg(1 - p)t
(1 + L0)1-p

p/(p-1)

(16)

Discretizing the initial seed size distribution fn,0(L0) for

different values of L0, eqs 15, 16 can be used to compute the
dynamic evolution of the CSD for a generic growth-dominated
process (the solution is valid for p * 1 and * 0; for p ) 1
and/or ) 0 the analytical expressions can also be derived).
Equations 15, 16 are of significant practical importance, because
they show that if the initial seed distribution and growth kinetics
of a supersaturation controlled crystallization process are known,
the evolution of the CSD can be estimated/predicted by using
concentration (supersaturation) measurements.
4. Model Identification and Validation
The QMOM-MOCH approach has been validated for the
batch cooling crystallization of the inorganic compound, potash
alum (KAl(SO4)2) in water. The experimental data were obtained
using an industrial pilot-plant crystallization system located at
BASF (Ludwigshafen, Germany). A supersaturation controller
was implemented in the process and seeded experiments were
carried out at constant supersaturation set-points. The CSD was
measured at different time intervals using laser-diffraction,
whereas concentration measurements were obtained based on
density measurements of the slurry. The results from two
experimental runs (experiments A and B) are shown in Figure
4. Experiment A was conducted at a supersaturation set-point
Ssp ) 0.6% (weight percent in kg solute/kg slurry), whereas
experiment B was at Ssp ) 0.3% (weight percent). Seed was
introduced in both cases shortly after the supersaturated state
had been reached. In the case of experiment A it can be seen
that the supersaturation controller exhibits an overshoot during
the initial part of the operating curve, which leads to secondary
nucleation. Since experiment A captures both the growth and
the nucleation mechanisms, it was used for model parameter

(12)

where g )[kg,g,,p] is the growth parameter vector, for growthdominated systems (B ) 0) the model eqs 8-9, reduce to the
form:
dL
) kgSg(1 + L)p
dt

(13)

dfn(L, t)
) -kgSgp(1 + L)p-1fn(L, t)
dt

(14)

In the case of well-controlled constant supersaturation, which

follows the desired set-point value, Ssp, eqs 13, 14, can be solved
analytically, with the solution:
L ) (((1 + L0)1-p + kgSg(1 - p)t)1/

(1-p)

- 1)/
(15)

Figure 4. Experimental results in the case of supersaturation controlled

experiments. (a) Experiment A: Ssp ) 0.6 wt %, used for parameter
identification. (b) Experiment B: Ssp ) 0.3 wt %, used for validation.

Ind. Eng. Chem. Res., Vol. 48, No. 18, 2009

8579

Table 1. Size-Dependent Growth and Nucleation Parameters for the

Crystallisation of Potash Alum in Water (Units for S ) kg/kg
slurry)
parameter

value

growth rate constant (kg), m s-1

growth constant (), m-1
growth constant (p), -growth order constant (g), -nucleation rate constant (kb), m-3 s-1
nucleation order constant (b), --

8.5708
0.0050
1.5777
1.0000
0.0380
3.4174

identification using the QMOM-MOCH approach described in

section 2, whereas experiment B was used for validation of the
analytical estimator. For the potash alum system, size-dependent
growth has been reported in the literature,44 and was observed
experimentally. Hence a generic size-dependent growth expression given by eq 12 was used in the model identification.
The nucleation and growth parameters were determined to
capture the dynamic evolution of the shape of the size
distribution, as well as the experimental concentration profile.
The optimization problem for the parameter estimation is given
by
K

min{wf

Nd

(f

Figure 5. Dynamic evolution of the modeled and experimental CSD for

experiment A.

exp
2
V,k(Ll)-fV,k (Ll)) + wC

k)1 l)1

(C

2
- Cexp
k ) }

k)1

(17)
subject to
(18)

min e e max

with ) [kg,g,,p,b,kb] being the model parameter vector with

the growth and nucleation kinetic parameters, min and max are
vectors with specified minimum and maximum bounds for each
parameter, respectively, Ck and Ckexp are the simulated and
experimental concentration values at the discrete time steps k
exp
are the values of the simulated and
) 1, ..., K, fv,k and fV,k
experimental volume probability distribution functions, corresponding to the discretized size Ll, l ) 1, ..., Nd, with Nd being
the number of experimental size bins, and wf, wC are objective
function weighting factors. The volume distribution function is
calculated as
Nd

(f

(19)

Figure 6. Experimental and simulated results: (a) concentration and (b) de

Broucker mean diameter during the entire batch of experiment A.

The optimization problem is solved using a sequential

quadratic programming (SQP)-based optimization approach
implemented in the Matlab function fmincon. Note that finding
the best kinetic parameters is generally a difficult optimization
problem due to the strong correlation between the parameters
and the generally nonconvex optimization problem 17, 18.
Supersaturation controlled experiments can be used to design
experiments which allow to decouple the identification of the
kinetic parameters or quick metastable zone determination
experiments can be used for providing experimental data based
initial guesses for the parameter identification process.43 The
resultant model parameters for the potash alum system are
presented in Table 1.45 The dynamic evolution of the modeled
and experimental CSDs are in very good agreement during the
entire batch, as shown in Figure 5. It can be seen that due to
the particular size-dependent growth kinetics of this system, the
CSD broadens with decreasing height during the batch. The
formation of a secondary CSD peak can also be observed, which
is the result of secondary nucleation. The QMOM-MOCH

approach with the model using the identified growth and

nucleation parameters is able to describe the main features of
the CSD throughout the entire batch. Figure 6 shows the
comparison between the experimental and modeled concentration and weight mean size throughout the batch, which are also
in relatively good agreement.
Figure 7 illustrates the evolution of the characteristic lines
and the discretized number distribution function predicted by
the simulation of experiment A, using the combined QMOMMOCH. The evolution of the characteristic lines show the
broadening of the distribution function due to the size-dependent
growth kinetics, as can be observed from Figure 5. The
distribution function is initialized at t ) 0 with values obtained
from the seed distribution, after which the values of fn decrease
as the distribution broadens. At different time steps new nuclei
and new characteristic lines appear using the methods described
in section 2. The discretization intervals along the time axis
depend on the growth kinetics according to the approach
described in section 2 and illustrated in Figures 1 and 2. It can
be observed that during 10-30 min into the batch, when the

fV,l ) fn,lLl /
3

n,lLl

Ll)

l)1

8580

Ind. Eng. Chem. Res., Vol. 48, No. 18, 2009

Figure 9. Performance of the analytical estimator initialized with CSD at

t ) 30 min (experiment B).

Figure 7. Evolution of characteristic lines (a) and number distribution

function (b) for the simulated experiment A.

growth is faster (and the nucleation rate is also more significant),

the discretization is finer, compared to the later stages of the
batch characterized by slower growth.
The combined QMOM-MOCH can be used not only for the
model identification, but also for CSD prediction. The simulation
time for the reconstruction of the entire evolution of the CSD
during the batch, only takes a few seconds on a standard PC
running Matlab. For even faster computational performance, the
analytical estimator given by eqs 15 and 16 can be used in the
case of growth-dominated processes. Figure 8 shows the CSD
for the seed, selected times during the batch, and the final CSD
for experiment B, compared to predictions from the analytical
estimator with initial concentration, temperature profile, and seed
distribution set to match the experiment, along with kinetic
parameters deduced from experiment A (see Table 1). In this
case the supersaturation was well maintained at its constant setpoint. The simulated and experimental CSDs are in good
agreement overall. However, the experimental CSD shows
evidence of secondary nucleation during the batch, indicated
in Figure 8 by the secondary CSD peak developed during the

crystallization. The analytical estimator is derived based on the

assumption of constant supersaturation and no nucleation.
Therefore, initializing it with the seed CSD and applying it in
open-loop, the analytical estimator is not able to predict the
development of the secondary peak. However, in the case of
many practical applications, an online measurement of the CSD
is available typically with a sampling time in the range of 1-15
min (e.g., by using focused beam reflectance measurement
coupled with inverse geometric modeling to transform chord
length distributions into size distributions).46,47 In these cases
the analytical estimator can be used in closed-loop, initializing
it with the new CSD measurement every time it becomes
available. Figure 9 illustrates the results when the estimator was
initialized using the measured CSD after 30 min. The effect of
the secondary nucleation, which occurred in the first 30 min of
the batch, on the final CSD is partially predicted. The proposed
method can be used as an efficient estimator for monitoring
and predicting the CSD at the end of the batch, or in off-line or
on-line optimization approaches for designing crystallization
systems to produce consistently the desired final CSD. These
results show that in practical applications the analytical estimator
can be used for prediction of the CSD even if during the initial
phase of the batch the supersaturation is not constant. As new
CSD measurements become available and the supersaturation

Figure 8. Comparison between measured and simulated CSD using the analytical CSD estimator (experiment B).

Ind. Eng. Chem. Res., Vol. 48, No. 18, 2009

8581

Figure 10. Simulated dynamic evolution of CSD with optimal temperature profile throughout the batch.

reaches its constant set point value, the predicted CSD will
converge to the correct value.
5. Model-Based Dynamic Optimization of Temperature
Trajectories for Shaping the CSD
The combined QMOM-MOCH approach described in section 2 was used to solve the PBM in a model-based dynamic
optimization scheme, with the aim to determine optimal
temperature trajectories which yield desired target CSDs at the
end of the batch. The final CSD is dependent on the supersaturation profile created over the batch time, hence the cooling
trajectory is of critical importance for the final CSD. In the
optimization both the temperature trajectory and the batch time
were optimized. For the solution of the dynamic optimization
problem the batch time horizon [0, tf] is divided into Nb equally
spaced time intervals of t (stages), with discrete time steps tk
) jt, j ) 0, 1, ..., Nb, and the temperature trajectory is
approximated by a piece-wise linear function determined by the
fixed initial temperature at t ) 0, T(0), and the slopes RT(j) in
each discretized period t. Note, that since the batch time is
also optimized the duration of the time interval t changes
during the optimization, but the number of disretizations Nb is
fixed. This formulation allows an easy incorporation of the
temperature rate constraints (as bounds on the decision variables
RT(j)), which are very important to obtain a practically implementable temperature trajectory. The optimization problem is
formulated as follows:
K

min

RT(j),tf

Nd

(f

target
2
v,k(Ll)-fV,k (Ll))

k)1 l)1

(20)

subject to
RT,min e RT( j) e RT,max,

j ) 0, 1, ..., Nb

(21)

0 e tf e tf,max

(22)

C(tf) e Cf,max

(23)

with RT(j) the elements of the vector containing the slopes, (dT/
dt) for the temperature trajectories and tf is the total batch time,
C(tf) is the solute concentration at the end of the batch and Cf,max
is the maximum acceptable concentration at the end of the batch
target
are the values of the
to achieve the required yield, fV,k and fV,k
simulated and the target volume probability distribution functions at the discrete time steps k ) 1, ..., K, where measurement
data were available, corresponding to the discretized sizes Ll, l
) 1, ..., Nd, with Nd being the number of experimental size bins.
The optimization problem is solved using a sequential quadratic
programming (SQP) approach implemented in the Matlab
function fmincon. The kinetic parameters used are described in
Table 1.
Figures 10 and 11 show the results of the distribution shaping
optimal control. The seed and target distributions are shown
on the first plot (at t ) 0) in Figure 10. The target CSD is a
fictitious bimodal distribution. For simulation purposes a monomodal seed was selected, represented by a Gaussian distribution
with mean of 54 m and standard deviation of 15 m, chosen
based on CSD measurement of the seed used in the experiments.
Figure 10 shows the dynamic evolution of the CSD toward the
target bimodal distribution, when the optimal temperature
trajectory shown in Figure 11a is implemented in the simulation.
The final CSD is in good agreement with the target distribution.

8582

Ind. Eng. Chem. Res., Vol. 48, No. 18, 2009

Figure 11. Optimal control results of the simulations for bimodal target distribution with pronounced secondary peak: (a) optimized temperature profile with
50 discretization points, (b) phase diagram showing solubility and optimal operating curve, (c) concentration profile during the batch (d) supersaturation
profile (kg/kg slurry) during the batch, (e) nucleation rate profile during the batch, (f) growth rate profile during the batch.

Figure 12. Optimal control results for bimodal target distribution with minimized fines due to secondary nucleation: (a) comparison of model and target
distribution, (b) optimized temperature profile with 30 discretization intervals, (c) concentration profile during the batch, (d) supersaturation profile during
the batch.

The first 10-15 min of the batch are devoted mainly to the
growth of the seed crystals, which approach rapidly the larger
size mode of the target distribution, due to the high driving force
in this periodslarge supersaturation as can be seen on Figure
11b,d. The supersaturation achieves its peak value at about 10
min (see Figure 11d) yielding the appearance of a second mode
due to secondary nucleation, which develops clearly by t ) 17
min. The optimal temperature profile, shown in Figure 11a, was

obtained using 50 discretization points in the optimization. The

selection of the number of discretizations is a trade-off between
computational time and accuracy. No significant improvement
in the objective function was achieved when the discretization
was increased from 30 to 50 and hence a finer discretization
was not considered necessary. The target CSD can be achieved
within the temperature range of 40 to 5 C during a batch period
of approximately 1 h with the desired yield of 60%, as shown

Ind. Eng. Chem. Res., Vol. 48, No. 18, 2009

in Figure 11c. The temperature profile shows several distinguishing slope changes, which correspond to secondary nucleation events generated to achieve the desired shape of the target
distribution. After the initial peak at around 10 min, the
supersaturation raises again between 25-40 min and subsequently toward the end of the batch between 50-55 min, as
can be seen in Figure 11d. These increases in the supersaturation
lead to additional nucleation events and growth, required to
achieve the target distribution, as shown in Figure 11e,f. Figure
10 shows that the first mode of the bimodal target distribution
is skewed requiring the subsequent nucleation events to improve
the shape of the obtained CSD. The third region of increased
supersaturation has significantly smaller values and is mainly
to facilitate growth of the larger particles to give a better fit to
the second mode of the target CSD; Figure 10 shows no
significant change in the first mode of the CSD after t ) 41
min, indicating mainly the growth of the second mode.
The previous target CSD showed a pronounced secondary
peak to illustrate the ability of the approach to achieve a bimodal
distribution. In industrial scenarios, the major emphasis is to
suppress the nucleation and minimize the formation of small
particles during the crystallization process. Therefore the
temperature profile was optimized for another fictitious target
distribution, with a significantly smaller fraction of fine particles.
Figure 12a shows that the CSD predicted by the model is very
close to the target distribution. The slight deviation in the fitting
of the first peak of the target distribution indicates that it is not
possible to achieve any arbitrary target distribution by designing
the cooling profile only. There are limitations on the potentially
attainable CSD shapes given by the particular nucleation and
growth kinetics, as well as the shape of the seed distribution.
The optimized temperature profile ranges from 40 to 7 C in
Figure 12b and shows a sequence of gradually increasing cooling
rate until t ) 60 min, when the nucleation of the particles
required for the second small peak occurs. Figure 12d shows
that this nucleation event leads to a decrease in the supersaturation, to a level which is maintained for the next 20 min of
the batch, initially by reducing the cooling rate. The cooling
rate then is gradually increased again to produce a slightly higher
supersaturation level to complete the growth of the particles to
the required size and to achieve the required yield of 60%; see
Figure 11c. The batch time for this case has increased
significantly compared to the previous case to approximately
95 min. The number of discretizations used is 30 since the
previous case showed that no significant improvement was
obtained by increasing the discretization to 50. Although the
secondary peak is significantly reduced in the second case, note
that with the desired shape of the primary mode of the target
distribution and required yield it is not possible to eliminate
completely the secondary peak from the resulting CSD. However
the two case-studies illustrate that the proposed method can be
used to obtain optimal temperature trajectories for designing
different target distributions. The combined QMOM-MOCH,
model can predict the CSD efficiently and can be used with
off-line or online optimization approaches for designing crystallization systems to produce consistent target CSDs.
6. Conclusions
The paper describes a new methodology of solving population
balance equations. The approach combines the quadrature
method of moments (QMOM) with the method of characteristics
(MOCH), and provides a computationally efficient method of
reconstructing the crystal size distribution (CSD). The approach
can also be used to design optimal temperature profiles for

8583

crystallization product design with a desired shape of the final

CSD. By applying the approach in conjunction with control at
constant supersaturation, analytical expressions can be derived
for the estimation of the CSD for growth-dominated processes.
The QMOM-MOCH approach and the analytical CSD estimator are evaluated in the case of the seeded crystallization of
potash alum in water with size dependent growth. Experimental
and simulation results demonstrate the efficiency of the proposed
approach. Optimal temperature trajectories have also been
designed for various bimodal target CSDs, suggesting that the
approach based on the combined QMOM-MOCH model has
the ability to be used for off-line or online optimization of batch
crystallization processes.
Acknowledgment
Financial support provided by the Engineering and Physical
Sciences Research Council (EPSRC), U.K., (grant EP/E022294/
1) is gratefully acknowledged. BASF, Ludwigshafen, Germany,
is also acknowledged for partial financial support and for
providing experimental data for model identification.
Literature Cited
(1) Chung, S. H.; Ma, D. L.; Braatz, R. D. Optimal model-based
experimental design in batch crystallization. Chemom. Intell. Lab. Syst. 2000,
50, 83.
(2) Mullin, J. W. Crystallisation, 4th ed.; Butterworth Heinemann:
Oxford, U.K., 2001.
(3) Braatz, R. D. Advanced control of crystallization processes. Annu.
ReV. Control 2002, 26, 87.
(4) Fujiwara, M.; Nagy, Z. K.; Chew, J. W.; Braatz, R. D. First-principles
and direct design approaches for the control of pharmaceutical crystallization. J. Process Control. 2005, 15, 493.
(5) Nagy, Z. K.; Chew, J. W.; Fujiwara, M.; Braatz, R. D. Comparative
performance of concentration and temperature controlled crystallizations.
J. Process Control. 2008, 18, 399.
(6) Liotta, V.; Sabesan, V. Monitoring and feedback control of supersaturation using ATR-FTIR to produce an active pharmaceutical ingredient
of a desired crystal size. Org. Process Res. DeV. 2004, 8, 488.
(7) Zhou, G. X.; Fujiwara, M.; Woo, X. Y.; Rusli, E.; Tung, H. H.;
Starbuck, C.; Davidson, O.; Ge, Z. H.; Braatz, R. D. Direct design of
pharmaceutical antisolvent crystallization through concentration control.
Cryst. Growth Des. 2006, 6, 892.
(8) Doki, N.; Seki, H.; Takano, K.; Asatani, H.; Yokota, M.; Kubota,
N. Process control of seeded batch cooling crystallization of the metastable
alpha-form glycine using an in-situ ATR-FTIR spectrometer and an insitu FBRM particle counter. Cryst. Growth Des. 2004, 4, 949.
(9) Gron, H.; Borissova, A.; Roberts, K. J. In-Process ATR-FTIR
spectroscopy for closed-loop supersaturation control of a batch crystallizer
producing monosodium glutamate crystals of defined size. Ind. Eng. Chem.
Res. 2003, 42, 198.
(10) Hermanto, M. W.; Chiu, M.-S.; Woo, X. Y.; Braatz, R. D. Robust
optimal control of polymorphic transformation in batch crystallization.
AIChE J. 2007, 53, 2643.
(11) Abu Bakar, M. R.; Nagy, Z. K.; Saleemi, A. N.; Rielly, C. D. The
impact of direct nucleation control on crystal size distribution in pharmaceutical crystallization processes. Cryst. Growth Des. 2009, 9 (3), 1378.
(12) Woo, X. Y.; Nagy, Z. K.; Tan, R. B. H.; Braatz, R. D. Adaptive
concentration control of cooling and antisolvent crystallization with laser
backscattering measurement. Cryst. Growth Des. 2009, 9, 182.
(13) Rawlings, J. B.; Miller, S. M.; Witkowski, W. R. Model identification and control of solution crystallization processes: A review. Ind. Eng.
Chem. Res. 1993, 32, 1275.
(14) Nagy, Z. K.; Braatz, R. D. Robust nonlinear model predictive
control of batch processes. AIChE J. 2003, 49, 1776.
(15) Larsen, P. A.; Patience, D. B.; Rawlings, J. B. Industrial crystallization process control. IEEE Control Syst. Mag. 2006, 26, 70.
(16) Ward, J. D.; Mellichamp, D. A.; Doherty, M. F. Choosing an
operating policy for seeded batch crystallization. AIChE J. 2006, 52, 2046.
(17) Nagy, Z. K.; Fujiwara, M.; Braatz, R. D. Modelling and control of
combined cooling and anti-solvent crystallization processes. J. Process
Control. 2008, 18, 856.

8584

Ind. Eng. Chem. Res., Vol. 48, No. 18, 2009

(18) Worlitschek, J.; Mazzotti, M. Model-based optimization of particle

size distribution in batch-cooling crystallization of paracetamol. Crys.
Growth Des. 2004, 4, 891.
(19) Sheikhzadeh, M.; Trifkovic, M.; Rohani, R. Fuzzy logic and rigid
control of a seeded semi-batch, anti solvent, isothermal crystallizer. Chem.
Eng. Sci. 2008, 63, 991.
(20) Sheikhzadeh, M.; Trifkovic, M.; Rohani, R. Adaptive MIMO neurofuzzy logic control of a seeded and an unseeded anti-solvent semi-batch
crystallizer. Chem. Eng. Sci. 2008, 63, 1261.
(21) Zhang, G. P.; Rohani, S. On-line optimal control of a seeded batch
cooling crystallizer. Chem. Eng. Sci. 2003, 58, 1887.
(22) Hounslow, M. J.; Reynolds, G. K. Product engineering for crystal
size distribution. AIChE J. 2006, 52, 2507.
(23) Lee, K., Lee, J. H., Fujiwara, M., Ma, D. L., Braatz, R. D. Runto-run control of multidimensional crystal size distribution in a batch
crystallizer, Proceedings of the American Control Conference; IEEE Press:
Piscataway, NJ, 2002; p 1013.
(24) Rusli, E., Lee, J. H., Braatz, R. D. Optimal distributional control
of crystal size and shape. Proceedings of the Fifth World Congress on
Particle Technology; Orlando, FL, 2006; Paper 240f.
(25) Nagy, Z. K. Model based robust control approach for batch
crystallization product design. Comput. Chem. Eng., doi:10.1016/j.compchemeng.2009.04.012.
(26) Hulburt, H. M.; Katz, S. Some problems in particle technologysA
statistical mechanical formulation. Chem. Eng. Sci. 1964, 19, 555.
(27) Randolph, A. D., Larson, M. A. Theory of Particulate Processes:
Analysis and Techniques of Continuous Crystallization; Academic Press:
San Diego, CA, 1971.
(28) Ramkrishna, D. Population Balances, Theory and Applications to
Particulate Systems in Engineering; Academic Press: San Diego, CA, 2000.
(29) Gerstlauer, A.; Gahn, C.; Zhou, H.; Rauls, M.; Schreiber, M.
Application of population balances in the chemical industryscurrent status
and future needs. Chem. Eng. Sci. 2006, 61, 205.
(30) McGraw, R. Description of aerosol dynamics by the quadrature
method of moments. Aerosol Sci. Technol. 1997, 27, 255.
(31) Rosner, D. E.; McGraw, R. L.; Tandon, P. Multi-variate population
balances via moment- and Monte Carlo simulation methods. Ind. Eng. Chem.
Res. 2003, 42, 2699.
(32) Marchisio, D. L.; Ptkturna, J. T.; Vigil, R. D.; Fox, R. O. Quadrature
method of moments for population balance equations. AIChE J. 2003, 49,
1266.
(33) Marchal, P.; David, R.; Klein, J. P.; Villermaux, J. Crystallization
and precipitation engineeringsI. An efficient method for solving population
balance in crystallization with agglomeration. Chem. Eng. Sci. 1988, 57,
1107.
(34) Puel, F.; Fevotte, G.; Klein, J. P. Simulation and analysis of
industrial crystallization processes through multidimensional population

balance equations. Part 1: A resolution algorithm based on the method of

classes. Chem. Eng. Sci. 2003, 58, 3715.
(35) Gunawan, R.; Fusman, I.; Braatz, R. D. Parallel high resolution
simulation of particulate processes with nucleation, growth, and aggregation.
AIChE J. 2008, 54, 1449.
(36) Zhang, T.; Tade, M. O.; Tian, Y. C.; Zang, H. High-resolution
method for numerically solving PDEs in process engineering. Comput.
Chem. Eng. 2008, 2, 2403.
(37) Haseltine, E. L.; Patience, D. B.; Rawlings, J. B. On the stochastic
simulation of particulate systems. Chem. Eng. Sci. 2005, 60, 2627.
(38) Flood, A. E. Thoughts on recovering particle size distributions from
the moment form of the population balance. DeV. Chem. Eng. Mineral
Process. 2002, 10, 501.
(39) Ono, T.; Kramer, H. J. M.; Ter Horst, J. H.; Jansens, P. J. Process
modeling of the polymorphic transformation of L-glutamic acid. Cryst.
Growth Des. 2004, 4, 1161.
(40) Marchisio, D. L.; Vigil, R. D.; Fox, R. O. Quadrature method of
moments for aggregation-breakage processes. J. Colloid Interface Sci. 2003,
258, 322.
(41) Gordon, R. G. Error bounds in equilibrium statistical mechanics.
J. Math. Phys. 1968, 9, 655.
(42) Gimbun, J., Nagy, Z. K., Rielly, C.D. Simultaneous quadrature
method of moments for the solution of population balance equations, using
a differential algebraic equation framework. Ind. Eng. Chem. Res., 10.1016/
j.compchemeng.2009.04.012.
(43) Nagy, Z. K.; Fujiwara, M.; Woo, X. Y.; Braatz, R. D. Determination
of the kinetic parameters for the crystallization of paracetamol from water
using metastable zone width experiments. Ind. Eng. Chem. Res. 2008, 47,
1245.
(44) Brecevic, L.; Garside, J. On the measurement of crystal size
distributions in the micrometer size range. Chem. Eng. Sci. 1980, 36, 867.
(45) Aamir, E.; Nagy, Z. K.; Rielly, C. D.; Kleiner, T.; Judat B. Efficient
crystal size distribution estimation approach for growth dominated crystallisation processes. Proceedings of 17th International Symposium of
Industrial Crystallisation, Maastricht, The Netherlands, 14-17th September,
2008; Vol 3 p 1733.
(46) Ruf, A.; Worlitschek, J.; Mazzotti, M. Modeling and experimental
analysis of PSD measurements through FBRM. Part. Part. Syst. Charact.
2000, 17, 167.
(47) Hukkanen, E. J.; Braatz, R. D. Measurement of particle size
distribution in suspension polymerization using in situ laser backscattering.
Sens. Actuators, B 2003, 96, 451.

ReceiVed for reView March 16, 2009

ReVised manuscript receiVed June 13, 2009
Accepted July 10, 2009
IE900430T