Journal of Crystal Growth 198/199 (1999) 729—737

Design of industrial crystallisers for a given product quality

Herman J.M. Kramer*, Sean K. Bermingham, Gerda M. van Rosmalen
Laboratory for Process Equipment, Technische Universiteit Delft, Leeghwaterstraat 44, 2628 CA Delft, The Netherlands

Abstract

The main challenge in the design of industrial crystallisers is to predict the influence of crystalliser geometry, scale,
operating conditions and process actuators on the process behaviour and product quality. The quality characteristics,
such as the crystal size distribution, inclusion content and morphology determine to a large extent the product
performance and are therefore of importance. The quality of the product crystals is basically determined by the rates at
which crystals are born and attrited, grow or dissolve and agglomerate in the different regions of the crystalliser. An
analysis technique is therefore introduced to describe the various crystallisation phenomena as a function of local process
conditions such as supersaturation and energy dissipation. This technique is based upon:

E the derivation of pure kinetic parameters from an MSMPR experiment.

E setting up compartmental models for design alternatives in order to separate kinetic and hydrodynamic phenomena.
E analysis of the process behaviour of the design alternatives by applying the same kinetic model and parameters for
each compartments.
E optimisation of the design alternatives with respect to product quality using crystalliser geometry, operating
conditions and the appropriate process actuators, like a fines removal system, as degrees of freedom.

The advantage of this technique over conventional techniques is illustrated for an evaporative DTB crystalliser.  1999
Elsevier Science B.V. All rights reserved.

1. Introduction glomeration and purity, i.e. uptake of mother

The performance of a crystal product, such as its
filterability, flowability, drying, caking and tablet-
ting behaviour is mainly determined by the product
quality, which is expressed in terms of crystal size
distribution, morphology, polymorph, degree of ag-
* Corresponding author. Tel.: #31 15 278 5593;
#31 15 278 6975; e-mail: h.j.m.kramer@wbmt.tudelft.nl.
liquid, foreign molecules or ions into its lattice.
The quality characteristics of a crystalline prod-
uct are a complex function of the physical and
thermodynamic properties of the solvent—solute
system on the one hand and the various process
conditions experienced by the crystals during their
stay in the different regions of the crystalliser vessel
on the other.
fax: In order to predict product quality, and
thus product performance, a priori for a certain

0022-0248/99/$ — see front matter  1999 Elsevier Science B.V. All rights reserved.
PII: S 0 0 2 2 - 0 2 4 8 ( 9 8 ) 0 1 1 7 9 - 8
730 H.J.M. Kramer et al. / Journal of Crystal Growth 198/199 (1999) 729–737
solvent—solute system, crystalliser geometry and
set of operating conditions, it is thus necessary to
take into account the non-uniform distribution
throughout the vessel of process variables, such as
the solids density, crystal size distribution (CSD),
supersaturation and energy dissipation, and also
the system dynamics, an inherent quality of most
crystallisation processes.
Traditional scale-up strategies for crystallisers do
not take these geometric and time-dependent vari-
ations into account, and it is therefore hardly sur-
prising that these strategies practically fail without
exception. In this paper, we will discuss an ap-
proach to the full scale design of industrial crystal-
lisers for a predefined set of product specifications.
Main emphasis will be upon:
1. The need for a more detailed and separate de-
scription of the hydrodynamics and kinetics to
analyse and optimise the behaviour of design
alternatives.
2. Setting up hydrodynamic models for industrial
scale crystallisers (typically non-MSMPR), in
which the crystalliser volume is divided into
hydrodynamically well-defined regions, i.e. re-
gions in which the supersaturation, energy dissi-
pation, solids density and CSD are uniformly
distributed.
3. Obtaining scale and geometry independent kin-
etic parameters, for a certain kinetic model, from
laboratory scale (MSMPR) experiments. The
key problem here is how to obtain pure kinetic
parameters, that are not polluted with hy-
drodynamic information.
4. Description of the crystallisation phenomena
in full scale crystallisers as a function of local
process conditions, in order to properly predict
the influence of changes in crystalliser geo-
metry, scale and operating conditions on the
resulting product quality and its related product
performance.
2. Drawback of current design practice
The main problem with the current design prac-
tice, is the lacking of an adequate tool to predict the
influence of geometry, scale and operating condi-
tions on crystallisation behaviour. Although it has
already long been recognised, that industrial crys-
tallisers are far from ideally mixed, geometrically
lumped descriptions of the crystallisation phe-
nomena in a vessel and their effect on product
quality still prevail.
The need for a description of the crystallisation
phenomena on a local scale in an industrial crystal-
liser, i.e. on a scale where process conditions are
uniform, is widely recognised:
E A geometrically lumped description only yields
one average value for the supersaturation, thus
ignoring possible peak values. In evaporative
crystallisers the supersaturation will be above
average in the boiling zone and lower, possibly
undersaturated, after the heat exchanger. Near
feed points of a cooling crystalliser, where
a saturated stream is mixed with the much cooler
contents of the vessel, high supersaturation
values can be expected, possibly leading to pri-
mary nucleation or scaling. In both these exam-
ples, a lumped description of the crystallisation
process will probably ignore or definitely under-
estimate the occurrence of certain phenomena,
such as dissolution and primary nucleation.
E Whenever there is a difference in material density
of the solid and liquid phase, particle segregation
will occur to some extent. To what extent, de-
pends on the internal circulation rate, which is
related to the specific power input of a circula-
tion pump or impeller. If particle segregation is
such that large particles will have a significantly
shorter residence time in the boiling zone,
the growth rate of these particles will appear to
be below average. In a geometrically lumped
description of such a process, this effect can only
be described by lowering the growth rate con-
stant of the larger particles. The error in this
approach becomes evident when the internal cir-
culation rate is increased, particle segregation
decreases and the growth rate of these particles
approaches average values.
These examples also obviate the problems en-
countered in practice, when a kinetic model, of
which the parameters were estimated from the be-
haviour of a non-ideally mixed crystalliser, is
applied to another crystalliser. These kinetic
 H.J.M. Kramer et al. / Journal of Crystal Growth 198/199 (1999) 729–737
parameters will undoubtedly contain hy-
drodynamic information, such as the above-men-
tioned particle segregation effect, that is specific for
a certain crystalliser and operating conditions. It is
therefore not surprising that simple scale-up rules,
based on geometrically lumped descriptions of the
process behaviour, fail for crystallisation processes.
We therefore stress the need for laboratory scale,
MSMPR experiments for the derivation of ‘pure’
kinetic parameters, i.e. parameters that are not hy-
drodynamically polluted.
As a consequence, the design procedure which is
proposed in the next section, is partly based upon
a kinetic model of which the parameters are derived
from MSMPR experiments, and partly upon a hy-
drodynamic analysis of the full scale crystalliser.
3. Proposed design procedure
Crystalliser design is a complex task in which
many degrees of freedom are present. As a conse-
quence it is convenient to decompose these degrees
of freedoms into sets related to the chemical envi-
ronment, the basic unit operation design and the
detailed, full scale crystalliser design (Fig. 1).
1. Design alternatives are first of all generated by
selecting a solvent and possibly additives, in
order to obtain the desired polymorph, the opti-
mal crystal morphology and an acceptable solu-
bility for the main compound as well as for the
present impurities. The influence of solvent and
additives upon morphology and polymorphism
is determined by means of molecular modelling
calculations in combination with laboratory ex-
periments. These calculations are based purely
on physical and thermodynamic data of the
materials involved. No process or equipment
information is needed.
2. ¹he basic unit operation design. For the alterna-
tives resulting from level one, the crystallisation
method, the operation mode and the crystalliser
type need to be selected. This part of the design
task has a strong empirical nature. The crystal-
lisation method, i.e. evaporation, cooling or
flash cooling, is mainly determined by the tem-
perature dependence of the saturation concen-
731
Fig. 1. Multi-level design strategy.
tration as well as its absolute value (Fig. 2).
Criteria such as the production capacity, scaling
tendency and width of the CSD determine the
operation mode, i.e. (semi-)batch or continuous.
The crystalliser type, i.e. DTB, FC, Oslo or stir-
red tank, strongly influences the maximum crys-
tal size that can be obtained. This is related to
the severity of the mechanical interactions be-
tween the crystals and the crystalliser hardware.
In addition, calculations need to be performed
to determine residence time, solids concentra-
tion, operation temperature and pressure, main
crystalliser and heat exchanger dimensions, as
well the various flows rates. At this stage only
specifications for the yield, average crystal size
and overall purity of the crystals are used.
3. Full-scale crystalliser design. At this stage, de-
tailed analyses will be performed of the design
alternatives generated in the previous level. The
main objective is to check whether a certain
crystalliser is capable of producing crystals of
the desired quality. The main degrees of freedom
that are manipulated in this stage are the crystal-
liser geometry, the process conditions and the
type and dimensions of the process actuators.
This task requires a detailed model, which can
use the kinetic models and parameters obtained
from laboratory scale experiments to predict
the product quality of the full scale, typically
732 H.J.M. Kramer et al. / Journal of Crystal Growth 198/199 (1999) 729–737
Fig. 2. Heuristics for crystallisation method selection.
non-ideally mixed crystalliser as a function of
local process conditions. For this purpose,
a compartmental modelling approach is applied,
to divide the crystalliser volume into a number
of well-mixed regions, with respect to super-
saturation, energy dissipation, solids density and
CSD.
To perform a detailed analysis of the behaviour of
full-scale crystalliser design alternatives, for a par-
ticular solute—solvent—additive system, the follow-
ing steps are required:
E Select a kinetic model structure with the appro-
priate mechanistic relations for the various crys-
tallisation and hydrodynamic phenomena.
E Analyse the laboratory scale crystalliser with re-
spect to MSMPR behaviour, i.e. uniform process
conditions.
E Perform experiments to derive the ‘pure’ kinetic
parameters, i.e. parameters which contain no hy-
drodynamic information. Also the dependency of
the hydrodynamics variables like e must be de-
termined.
E Set up the compartmental models for the full-
scale crystalliser design alternatives.
E Analyse the process behaviour of the design al-
ternatives, by combining compartmental models
with the kinetic model and parameters.
E Subsequently, optimise the design alternatives
with respect to product quality, using crystalliser
geometry, operating conditions and the appro-
priate process actuators as degrees of freedom.
The remainder of this paper will focus on level 3 of
this proposed crystalliser design procedure. First of
all, a methodology is discussed to derive a compart-
mental model for a particular crystalliser. This
methodology is subsequently applied to both la-
boratory- and industrial-scale crystallisers. Labor-
atory scale crystallisers need to be identified as an
MSMPR crystalliser for a specific solute—solvent—
additive system and for the applied process condi-
tions. This check is essential, as the technique in
this design procedure for the analysis of full-scale
crystalliser performance, requires a kinetic model
with parameters that are not hydrodynamic pol-
luted. Compartmental models also need to be
derived for these large-scale crystallisers in order to
account for the non uniformly distributed process
conditions.
4. Deriving a compartmental model
In this section a heuristic approach for the deri-
vation of a compartmental model for suspension
crystallisers [2] is summarised. Setting up a com-
partmental model comprises of determining the
location and size of the various compartments, as
well as the interconnecting flow rates and corre-
sponding cross-sectional areas. The compartments
in a compartmental model must be chosen such,
that they contain negligible internal gradients with
respect to supersaturation, energy dissipation and
crystal size distribution. The steepness of these
gradients is influenced by the kinetics and material
properties of the material to be crystallised, the
geometry of the crystalliser vessel and the operating
conditions. As a consequence, a compartmental
model is not specific for a certain crystalliser, but
may need to be re-derived for different operating
conditions or another solute—solvent—additive
system.
Four steps can be distinguished in the derivation
of a compartmental model:
E First of all, compartments are selected to repres-
ent the overall flow pattern within the crystal-
liser. This is done on the basis of crystalliser
 H.J.M. Kramer et al. / Journal of Crystal Growth 198/199 (1999) 729–737 733

dimensions, geometry and operating conditions.
In this phase, the majority of the rates of flows
connecting the various compartments is deter-
mined roughly.
E Secondly, the compartments are checked for in-
ternal gradients in local energy dissipation.
Strong gradients may be expected around the
impeller or inside the pump and near feed loca-
tions. If they are indeed present, one or more of
the compartments selected in the first step will be
split up.
E In the third place, all compartments are checked
for the presence of internal supersaturation
gradients, or in other words the degree of liquid-
phase mixing is analysed. For this purpose, the
half lifetime for supersaturation decay must
be one order of magnitude larger than the resi-
dence time in the compartment. Depending on
the crystallisation system, the half lifetime varies
from a few seconds to several minutes.
E Finally, classification functions are calculated to
describe particle segregation or the non-uniform
distribution of the solids phase. These functions
act upon the flows connecting the individual
compartments, which effectively makes the resi-
dence time of the crystals in a compartment size
model, is illustrated for ammonium sulphate in
water using a 22 l evaporative DT crystalliser. For
this system, first of all the kinetic model derived by
Ö Meadhra et al. [7] was selected. This model is
discussed below, in order to highlight the depend-
encies of the various kinetic phenomena on super-
saturation and crystal size. Note that no intrinsic
dependency of changes in energy dissipation are
present in the model.
In a recently published new model for secondary
nucleation [5], the direct relation is formulated
between the crystallisation kinetics and the fre-
quency and energy of particle—impeller collisions
depending on a number of material properties of
the crystals. This promising new model, which is
discussed in the contribution of Neumann et al. [8],
will open the possibilities for the formulation of the
direct relation between the energy dissipation and
crystallisation kinetics.
The growth kinetics are dependent on both the
supersaturation and the crystal size. The size de-
pendency is a result of internal stress in the smaller
particles. This stress is a consequence of the attri-
tion process, by which these particles were formed
(secondary nucleation).


¸ N
dependent. The classification function of a slurry G (¸,p)"p pN 1!(1!p ) exp . (1)
    p
stream is related to its superficial flow velocity, 
flow direction, viscosity and density difference The attrition rate function accounts for the fact that
between the liquid and solid phases. the smaller particles do not develop sufficient kin-
etic energy to undergo attrition. From a certain
It must be noted that the same material, energy
size onwards the crystals become more and more
and population balances are used to describe each
susceptible to attrition:
compartment in a compartmental model [1]. This


also applies to the physical and thermodynamic 1
G (¸)"p 1! . (2)
property relations as well as the kinetic rate expres-   1#(¸/p )N
sions. Different nucleation, growth, dissolution, at- 
trition, breakage and aggregation rates are purely The effective growth rate of a crystal thus depends
a result of different local conditions, not of different on its size and the supersaturation:
sets of parameters. G (¸,p)"G (¸,p)!G (¸). (3)
   
The volumetric rate of attrition is given by


5. Crystallisation kinetics derived from laboratory 
scale experiments »Q "3k G (¸)n(¸)¸ d¸. (4)
  

The analysis of a kinetic model structure and of The secondary nucleation rate is related to the
a particular laboratory scale crystalliser’s suitabil- attrition rate by means of a supersaturation-depen-
ity to derive pure kinetic parameters for that kinetic dent survival efficiency ("p p). Furthermore, an

734 H.J.M. Kramer et al. / Journal of Crystal Growth 198/199 (1999) 729–737

experimentally determined size distribution of

nuclei has been incorporated:
B(¸)"p p»Q H(¸). (5)
 
For undersaturated conditions, the kinetic model
was extended with a dissolution model given by
Jager [6]. The kinetic dissolution rate is calculated
as a function of a mass transfer coefficient and
relative supersaturation. Using a diffusion control-
led model and experimental results of Daudey [3]
the mass transfer coefficient for ammonium sul-
phate at 50°C was estimated:
G (¸,p)"!k (¸)p, (6)
 
2D
k (¸)" #constant. (7)
 ¸
The 22 l DT evaporative crystalliser is equipped
Fig. 4. Simulated trend of the median crystal size in a 22 l DT
with an internal heat exchanger, to avoid the use of crystalliser obtained with both the MSMPR and the six com-
an external loop and have it resemble MSMPR partment model.
behaviour as much as possible. At a first glance,
internal turnover times of 1—3 s compared to
a characteristic time for supersaturation depletion
of 50 s and vertical fluid velocities of 0.7 m/s,
should ensure ideal mixing. To check the heuristics, A mean residence time of 4500 s and a heat input of
presented in the compartmental modelling section, 120 kW/m were used for these simulations. The
a more detailed study was required. Using a six- response of the median crystal size after start-up of
compartment model (see Fig. 3), derived from CFD the 0.022 m DT crystalliser, calculated with the
studies, of this crystalliser on the one hand and an one-compartment model is shown in Fig. 4. The
MSMPR approach on the other, simulations of this trend of the median size calculated with the six-
crystalliser’s process behaviour were performed. compartment model could not be distinguished
from the one obtained with the one compartment
approach. The validity of the MSMPR assumption
for this laboratory scale evaporative DT crystalliser
is also confirmed by the fact that the relative super-
saturations in the different compartments were all
in a range of 0.0045 (in the boiling zone) to 0.0041
(inner draft tube).

6. Analysis of full-scale crystalliser design

alternatives

The analysis of full scale crystalliser design alter-

natives will be illustrated for DTB crystallisers. The
design of this type of crystalliser is a delicate task as
DTB crystallisers have a tendency towards unsta-
Fig. 3. Six compartment model of a 0.022 m DT crystalliser. ble process behaviour. In this respect, the design of
 H.J.M. Kramer et al. / Journal of Crystal Growth 198/199 (1999) 729–737
Fig. 5. Six compartment model of a 1.1 m DTB crystalliser.
the external circulation loop in which fine
crystals are dissolved and the internal circulation
through the draft tube are essential for larger
crystallisers.
Changes in the fines removal rate influence the
cut size of the fines classification system, as a direct
consequence of an increased vertical velocity in
the annular zone. This flow rate also determines
the residence time in the heat exchanger and the
temperature rise of the fines flow. The degree of
dissolution is determined by a combination of these
effects.
The behaviour of a DTB crystalliser is thus
strongly influenced by its geometry, actuator design
and operating conditions. The analysis of DTB
crystalliser design alternatives therefore requires
a detailed description of crystallisation phenomena
on a local scale. Such a detailed analysis will be
illustrated for a 1.1 m evaporative DTB crystal-
liser. For this purpose, a six-compartment model
was derived, consisting of a boiling zone, a stirrer
zone, two zones for the inner and outer sections
735
Fig. 6. Simulated trend of the median crystal size for a 1.1 m
MSMPR crystalliser (Q "0 l s\) and a 1.1 m DTB crystal-

liser using the one compartment model with ideal fines dissolver
(Q "2.5 and 3 l s\).

of the draft tube, a compartment to describe the
classification in the annular zone and temperature
increase in the external heat exchanger, and a
compartment in which fine particles are dissolved
after the heat exchanger (see Fig. 5). For compari-
son purposes, the crystalliser was also modelled as
a classical one-compartment model with an ideal
fines dissolver [7]. In both the six- and one-com-
partment model, the particle segregation in the
annular zone was described using a model de-
veloped by Eek et al. [4], which was based on CSD
measurements of the fines and product streams.
The median crystal size trend after start-up
simulated with the one compartment model and
ideal fines dissolver is shown in Fig. 6 for fines
flows of 2.5 and 3 l s\. Comparison with the
MSMPR trend given in the same figure, denotes
that ideal fines dissolution strongly affects the me-
dian crystal size, while the process dynamics are
hardly affected. In reality, however, often a much
smaller effect is observed on the steady-state value
of the median crystal size, whereas the dynamics are
strongly affected, occasionally resulting in severe
cyclic behaviour of the crystalliser [4,8,9]. This
discrepancy between model and reality, makes the
736 H.J.M. Kramer et al. / Journal of Crystal Growth 198/199 (1999) 729–737
Fig. 7. Simulated trend of the median crystal size for a 1.1 m
DTB crystalliser using the six compartment model (Q "2.5 and

3 l s\)
Fig. 8. CSD of the removed and returned fines flows, simulated
with the six compartment model of a 1.1 m DTB crystalliser.
design of the fines removal and dissolution system
almost impossible, when idealised models are used.
The simulation results using the six-compart-
ment model, which includes a physical dissolution
model, are given in Figs. 7 and 8. Fig. 7 shows
the trends of the median crystal size for two fines
removal rates in combination with two different
volumes of the dissolution vessel (V ). In Fig. 8 the

population density of the streams to and from the
dissolution compartment are given. Depending on
the volume of the compartment, only a small part
of the fines dissolve. These results show that when
the partial dissolution of crystals is taken into ac-
count, a much more realistic trend in the simulated
median crystal size is obtained for the steady-state
values as well as the dynamics.
7. Conclusions
Simulations of a large-scale DTB crystalliser
were performed with a one-compartment model
with ideal fines dissolution on the one hand and
with a multi-compartment models with a physical
dissolution model on the other.
Comparison of the results showed that the sensi-
tivity of crystalliser design for geometry, process
actuators and operating conditions can only be
described using the extended analysis technique
presented in this paper.
It was shown, that the same analysis technique
can be applied to determine whether a laboratory
scale crystalliser is suitable to estimate kinetic param-
eters for a certain crystallisation system.
Acknowledgements
The Dutch Foundation of Technology (STW),
AKZO-Nobel, BASF, Bayer A.G., Dow Chemicals,
DSM, DuPont de Nemours and Purac Biochem
are gratefully thanked for their support of the
UNIAK research program.
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