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Research Paper

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8575

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.

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

Published on Web 07/31/2009

8576

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.

growth, breakage, and aggregation. Both methods calculate the

moments of the distribution defined by,

j )

fn(L) Lj dL,

j ) 1, 2, ...,

(2)

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

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)

length L and a well-mixed crystallizer with growth and

nucleation as the only dominating phenomena, the population

balance equation (PBE) has the form

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

Efficient Solution of PBEs

(1)

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)

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)

i ) t and the

characteristic equations are given by the following system of

ODEs:

dL

) G(S, L;g)

dt

(8)

dG(S, L;g)

dfn(L, t)

) -fn(L, t)

+ B(S;b) (r0, L)

dt

dL

(9)

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)

seeding crystallization, secondary nucleation is considered as

solution of PBEs.

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))

calculating the initial conditions for the method of characteristics in the

case of growth and nucleation mechanisms.

(11)

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

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

and unseeded batch cooling crystallizers.

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)

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)

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)

experiments. (a) Experiment A: Ssp ) 0.6 wt %, used for parameter

identification. (b) Experiment B: Ssp ) 0.3 wt %, used for validation.

8579

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

slurry)

parameter

value

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

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

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

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)

Broucker mean diameter during the entire batch of experiment A.

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

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

t ) 30 min (experiment B).

function (b) for the simulated experiment A.

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

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).

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

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

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

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

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.

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ReVised manuscript receiVed June 13, 2009

Accepted July 10, 2009

IE900430T

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