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INDUSTRIAL CRYSTALLIZATION AND PRECIPITATION

FROM SOLUTIONS: STATE OF THE TECHNIQUE

Abstract - Crystallization and precipitation from solutions are


responsible for 70% of all solid materials produced by the chemical
industry. Competing with distillation as a separation and purification
technique, their use is widespread. They operate at low
temperatures with low energy consumption and yield with high
purifications in one single step. Operational conditions largely
determine product quality in terms of purity, filterability, flowability
and reactivity. Producing a material with the desired quality often
requires a sound knowledge of the elementary steps involved in the
process: creation of supersaturation, nucleation, crystal growth,
aggregation and other secondary processes. Mathematical models
coupling these elementary processes to all particles in a crystallizer
have been developed to design and optimize crystallizer operation.
For precipitation, the spatial distribution of reactants and particles in
the reactor is important; thus the tools of computational fluid
dynamics are becoming increasingly important. For crystallization of
organic chemicals, where incorporation of impurities and crystal
shape are critical, molecular modeling has recently appeared as a
useful tool. These theoretical developments must be coupled to
experimental data specific to each material. Theories and
experimental techniques of industrial crystallization and
precipitation from solutions are reviewed, and recent developments
are highlighted.
Keywords: Crystallization, precipitation, computational fluid
dynamics.

INTRODUCTION
The continuous development of the chemical process industry has been
accompanied by rising demands for product quality. Crystallization is
one of the methods to produce particulate material in the chemical
industry. In fact, crystallization is a separation technique which has
been used for centuries. In the twenties, the first definition of
crystallization as a unit operation appeared (Walker et al., 1923). This
concept was used until the sixties when Randolph and Larson (1971)
took population balance into account for mathematical treatment for

crystallization analysis and design. After that, crystallization became


recognized as a more complex field and as a part of the chemical
engineering sciences. Many approaches appeared to establish the
foundations of industrial crystallization, including chemical precipitation
(Nielsen, 1964; Strickland-Constable, 1968; Nvlt, 1971; Mullin, 1972
and Garside, 1985). Presently, several textbooks on industrial
crystallization are available: Jancic and Grootscholten (1984), Nvlt et
al. (1985), Shnel and Garside (1992), Myerson (1993), Mersmann
(1994), Tavare (1995) and Mullin (1997).
Crystallization is often critical because it largely determines product
purity and handling characteristics such as caking, wetting or losses
due to dusting. Crystallization is employed in many cases as an
energetically advantageous way to separate an individual compound
from a mixture of substances represented by raw materials or byproducts of reaction. Crystallization may occur as the formation of solid
particles from a vapor, as solidification from a liquid melt or as the
formation of dispersed solids from a solution.
The aim of this paper is to review the basic aspects of industrial
crystallization from solutions for analysis and design purposes and to
present its recent advances.

SOLUBILITY AND DRIVING FORCE


In a two-component system with two coexisting solid and liquid
phases, assuming that one component crystallizes as a chemical entity,
i.e., that it doesn't form solid solutions with the solvent, the
thermodynamic condition for isobaric equilibrium can be expressed as
the equality of chemical potentials of the component in both phases:

where is the chemical potential of component 1 in the liquid (') and


solid (") phases, for which:

We choose the pure anhydrous component at the temperature and


pressure of the system as the standard state; 1 is its activity, 1 its
activity coefficient and x1 its mole fraction in the solution. The solubility
of component 1 in the solvent is the total amount dissolved at
equilibrium state. In general solubility depends on temperature, so
solubility curves or tables have been compiled (Seidell and Linke,

1958; Mullin, 1997; Nvlt et al., 1985). If the system is near ideal,
concentration units can represent the relations above.
The solubility or saturation condition is experimentally determined by
heating a suspension and observing the temperature at which the
solids are completely dissolved. Above this temperature the solution is
undersaturated. When again cooling this same solution, temperatures
below that of saturation can be reached without the formation of any
crystals. In this region the solution is called supersaturated. The
difference between the concentration of the supersaturated solution, c,
and the saturated concentration, c*, is the so-called absolute
supersaturation, which is the driving force for the crystallization
process:

Other important definitions are the supersaturation ratio, S, and the


relative supersaturation, :

If the solution mentioned previously is further cooled, a new solid


phase is formed by nucleation at a specific point, which define the
metastable zone, as indicated in Figure 1.

The shift of the equilibrium state from one local energy minimum to
another constitutes a first-order phase transition, induced by a change
in a thermodynamic parameter such as temperature or concentration.
The two states related to a first-order phase transition are distinct,
occurring in separate regions of the thermodynamics configuration
space (Callen, 1985).
In industrial practice, starting with a saturated binary solution,
supersaturation can be generated in the following ways, depending on
the solubility of the solute or more precisely on the slope of the
solubility-temperature curve, dc*/dT (Figure 2):

i) For very soluble substances (C* > 0.2 g/g), by cooling the solution;
ii) For soluble substances (C* < 0.2 g/g), by cooling or evaporating the
solution or by combining them by flash evaporation;
iii) For substances with a small dc*/dT (< 0.005 g/g.C), by
evaporating the solution;
iv) For slightly soluble substances (C* < 0.01 g/g), supersaturation
can be created by the chemical reaction of two or more reactants.
v) In all cases, the addition of a new solvent, miscible with the solvent
present, where the solute is less soluble, can also be applied.
The choice of method for generation of supersaturation to crystallize a
substance also depends on the product properties desired and
economic aspects. In all cases, it is always possible to establish
adequate mathematical expressions for the supersaturation in terms of
known properties (Hurle, 1994).

ELEMENTARY PROCESSES
Nucleation

In a supersaturated solution, part of the solute tends to reorganize


itself into the solid form. However, the formation of the solid phase
(energetically favorable) implies the generation of an interface
(energetically unfavorable). Therefore, if nucleation is to occur, an
energy barrier has to be overcome. This barrier is particularly
important in the early stages of the nucleation process, when only a
few molecules or ions in solutions gather to form clusters with a
high surface/volume ratio.
When nucleation from a clear solution takes place, it is known as
primary homogeneous nucleation and is characterized by an
exponential dependence on supersaturation as well as by very large
metastable zone widths. One first defines the rate of primary
nucleation, J, as the number of new particles, N, generated per unit
time per unit volume of solution V (Volmer, 1939; Becker and Dring,
1935):

Starting with the basic Gibbs-Thomson relationship and with the


definition of the Gibbs free energy, it is possible to obtain the equation
for the homogenous primary nucleation rate which takes the following
form (Mullin, 1997):

In industrial practice, this type of nucleation seldom occurs because


solutions usually contain foreign particles that act as substrates for
nucleation, known as primary heterogeneous nucleation. Due to the
availability of a solid surface, the effective activation energy, eff, is
lower for heterogeneous nucleation than it is for homogeneous
nucleation (often eff = 1/2 to 1/3 of) as is the pre-exponential term,
Ahetero (Nielsen and Shnel, 1971):

The metastable zone width is large, and due to the exponential


dependence on supersaturation, the process is explosive and difficult
to reproduce and should thus be avoided wherever possible in
industrial practice. It always takes place in the early stages of
unseeded batch processes. For other operating modes, primary
heterogeneous nucleation occurs when the rate of supersaturation
generation is higher than the capacity of the system to absorb it
through crystal growth (Nvlt et al., 1985).
When a supersaturated solution is in contact with particles of the
crystallizing compound, secondary nucleation occurs. Particles collide
with the agitator blades, with the crystallizer walls and with each other,
thereby promoting their abrasion. Tiny crystals under 100 m in size
that behave as nuclei are thus generated. Attrition takes place
preferentially at specific locations on the crystal surface such as the
edges and corners. For high supersaturations, more of these
preferential locations appear, since the crystal surfaces become
atomically rough, macro-steps or even dendritic growth may occur
(Denk and Botsaris, 1972). There are many empirical expressions that
correlate the secondary nucleation with crystallization parameters. The
most accepted is given by (Nvlt et al., 1985)

where B0 is defined as the secondary nucleation rate similarly to the


primary nucleation rate, J. The average power input from the
agitator, (k = 0.6 to 0.7), is associated with the collision energy, and
the solids concentration, M, is related to the frequency of crystalcrystal collisions (j=2) or crystal-impeller and crystal-wall collisions
(j=1). The dependence on supersaturation, b, is usually in the range of
1 to 3. Supersaturation is important not only because it defines the
surface characteristics of the crystals, but also because it determines
whether secondary nuclei survive: these small crystals frequently have
internal stresses which make them more soluble than their parent
crystals so that they dissolve if the supersaturation is not high enough
(Nvlt et al., 1985).
Secondary nucleation is particularly important for coarse products
(sizes of 500 m and above) due to the enhanced collision energy of
larger crystals. On the other hand, if crystals are smaller than the
Kolmogorov length scale (which defines the smallest eddies in a
turbulent field, usually 50 to 150 m within agitated reactors), they are
encapsulated within the viscous limits of the Kolmogorov eddies and do
not generate secondary nuclei.
Crystal Growth

If crystal size is characterized by a characteristic dimension, L, we can


define its linear growth rate, G, and the mass growth rate can be
defined as

Crystal growth involves transport of the so-called growth units


(molecules or ions of solute) from the bulk solution to the surface of
the crystal and their incorporation into the crystal lattice. For growth
controlled by diffusion (e.g., some cases of crystallization of
compounds with a high solubility, static crystallization and
crystallization from viscous solutions) the growth rate becomes

The mass transfer coefficient, kd = D/ can be derived from several


correlations for the Sherwood number, Sh = kdL/D, such as Sh = 2
+ 0.6 Re1/2 Sc1/3.
For growth controlled by surface integration, the three mechanisms
shown below can be distinguished (Mullin, 1997).

(a) Spiral Growth (Figure 3)


For small supersaturations, growth units are incorporated only at kinks
on the crystal surface: first a defect has to be generated on the surface
and then growth proceeds layer by layer upon this defect so that a
spiral dislocation forms; this spiral is self-propagating and never dies.
The surface is thus smooth at the atomic level (Burton et al., 1951).

(b) Growth by Two-Dimensional Nucleation (Figure 4)


For relatively larger supersaturations, two-dimensional nucleation
appears on the crystal surface, thereby generating the necessary kinks
for further growth. If the rate of lateral growth of the 2D nuclei is high
in comparison to the nucleation rate, the surface is smooth. For higher
supersaturations the nucleation rate dominates the process and the
surface becomes rough (Nielsen, 1984).

Rough Growth (Figure 5)


For even higher supersaturations, growth units attach anywhere on
the crystal surface (terraces, steps or kinks) so the crystal surface
becomes rough. For organic compounds, the transition between
smooth and rough growth can be achieved by increasing not only
the supersaturation, but also the temperature.

Growth controlled by surface integration can be described by the


general empirical equation (Mullin, 1997)

Theoretical considerations show that spiral growth at very low


supersaturations results in g=2 and for large supersaturations, g=1.
For a 2D nucleation mechanism, g is greater than 2 and for rough
growth, g=1. Experimental determination of the growth kinetics
supported by microscopic examination of crystals often allows the
determination of the prevailing growth mechanism. The most
frequently found mechanism is spiral growth. As mentioned in the
nucleation section, the rough regime should be avoided wherever
possible, as it results in excessive secondary nucleation. Whichever the
prevailing growth mechanism, the constant, kg, is proportional to
solute concentration, i.e., soluble compounds grow faster than slightly
soluble ones (G values in the ranges 10-7-10-8 and 10-9-10-10 m/s,
respectively).
As noted before, small crystals generated by secondary nucleation may
have varying degrees of mechanical stress, so they have a higher
solubility and thus lower growth rate than larger crystals. They heal as
they grow so their growth behavior becomes similar to that of the
larger crystals. This behavior explains two phenomena commonly
observed during mass growth of crystals: growth rate dispersion,
whereby different individual crystals show varying growth rates and
size-dependent growth, whereby smaller crystals grow slower than
large ones.

MODE OF OPERATION AND MATHEMATICAL REPRESENTATION


Continuous operation is usually applied for large capacities. It offers
good control of average product size. Continuous processes are easier
to operate than batch ones, requiring less manpower and less physical
space for the same production capacity. They are not recommended for
products with a strong scaling tendency. Continuous processes can be
represented by a simple mathematical treatment that takes population
density (n), defined as the number of crystals of a specific size per unit
volume of crystallizer as the basic variable. The mass balance in the
crystallizer can be obtained using the equilibrium data (solubility
curve) and definition of the moments of distribution as pointed by
Randolph and Larson (1988). The third moment of the distribution
correspond to the mass of crystals produced in the crystallizer. A
population balance for the crystallizer is coupled to mass balance as
well as to crystallization kinetic parameters as shown in Figure 6,
where the population balance does not take into account breakage and
agglomeration processes.

For an

MSMPR (Mixed Suspension,


without
breakage,
the solution of
(Randolph and

Mixed Product Removal) crystallizer


agglomeration and
operating at steady state,
population balance is
Larson, 1988)

A straight line on a mono log scale (Figure 7) can represent this. The
slope is (-1/G) where G is the growth rate and is the average crystal
residence time. From the intercept with the y-axis, no, it is possible to
estimate the nucleation rate (B0) from

With this formulation, the average product size for any operational
condition can be easily obtained.
Batch operation is usually preferred for small-scale production, but
there are exceptions. Batch operation normally involves simpler
equipment and the same crystallizer can be used for more than one
product. Batch is the recommended mode of operation for
crystallization of substances with low growth rates. Good practices for
batch operation involve a sound selection of cooling profiles and
seeding procedures since they influence product quality (Giulietti et al.,
1995; Giulietti et al., 1996; Derenzo et al., 1996; Giulietti et al.,
1999a).
Cooling Profile
Curve 3 in Figure 8 shows a typical cooling curve found in industrial
practice derived from a constant flow rate of the cooling fluid. Several
families of particles are generated by sequential nucleation bursts due
to higher supersaturation in the early stages of the process, resulting
in a product with a wide crystal size distribution (CSD) and a large
number of fines. Also, the CSD changes from batch to batch due to
excessive primary nucleation. All these problems can be avoided if only
one nucleation step (or seeding) occurs at the beginning of the
process. This situation can be achieved with the cooling profile shown

by curve 1 in the same figure. This curve was theoretically derived,


assuming that only growth (no nucleation) dominates the process
(Nvlt et al., 1985). A similar curve can be obtained for evaporation
crystallization. This "ideal cooling", however, is expensive in practice
due to the control hardware and the high cooling capacity required
(van Rosmalen, 1999). Curve 2 in Figure 8 shows a linear cooling
profile, an intermediary situation, which is a reasonable compromise
between the "ideal" and "industrial" situations.

Seeding is frequently applied to avoid the supersaturation peak at the


beginning of the process. The chosen mass of seeds is around 0.5 to
2% of the crystal mass to be obtained (Myerson, 1993). Seeds are
normally obtained by screening the product in a narrow range. A good
seeding procedure involves pre-washing the crystal seeds with a nearly
saturated solution to dissolve small particles adhering to their surfaces.
Seeds should be fed into the crystallizer during the cooling process just
after the solution has become supersaturated. When seeding a large
quantity of crystals, a large surface area is provided for solute
incorporation, lowering the average supersaturation of the batch
process and resulting in a product with a narrow CSD (Jagadesh,
1996).
In normal operation, product size can vary from batch to batch. The
best way to have a more stable size is to control the time from the

beginning of supersaturation to the end of the cooling process, the real


crystallization batch time. Figure 9 shows an overview of the effect of
average supersaturation on nucleation and growth rates and on
average product size. In a faster crystallization, average
supersaturation increases (Nvlt, 1985). Therefore, for each system,
the adequate minimum batch time has to be observed in order to
produce a more or less stable average crystal size.

Due to the transient nature of batch processes, their mathematical


description is not as simple as that of the continuous mode of
operation. A typical batch population density distribution is shown
in Figure 10. It is composed of an initial family of crystals from the
seeds combined with another generated during the process to give the
final distribution.

Experimental Determination of Crystallization Kinetics


Growth and nucleation kinetics can be measured either simultaneously
or independently. By operating an MSMPR at steady state, with a
varying degree of supersaturation (e.g., by changing the crystal
residence time and temperature), nucleation and growth parameters, g
and kg and n and kN, can be estimated using the plot of ln n against L
(Fig.7). In this method, it is necessary to confirm that steady state was
achieved before sampling. Generally this occurs within 8 to 16
residence times from the beginning of operation (Garside et al., 1990).
In batch mode, nucleation and growth kinetic parameters can be
derived by monitoring at least supersaturation or CSD and ideally both
(Gutwald and Mersmann, 1990; Myerson, 1993). Supersaturation can
be monitored in an indirect way, i.e., using any solution property, such
as refractive index, density, conductivity, etc. (Nvlt et al., 1985;
Garside et al., 1990). Monitoring CSD allows estimation of the growth
rate and population density (Myerson, 1993). If the only monitored
variable is the CSD at the end of the run, the average growth and
nucleation kinetics throughout the run could be obtained (Nvlt et al.,
1985). In this case more than three experiments at varying batch time
or average supersaturation are needed. The conditions should be in the
range of unstable operation shown in Figure 9 so that substantially
different average crystal sizes are experimentally derived (Derenzo,
1994).

Independent measurement of the growth kinetics is achieved in a fluid


bed crystallizer: a known number or mass of uniformly sized crystals is
fluidized in a solution of known supersaturation for a fixed time. At the
end of the experiment, average product size or total mass is measured
again to calculate the size increment (Garside et al., 1990). Nucleation
kinetics may be independently determined by induction period
measurements, defined as the time required after saturation of the
solution to observe the formation of the first crystals when cooling the
system at a linear rate. At least three experiments are needed with
different cooling rates (Nvlt et al., 1985).

BASIC DESIGN
The design of industrial crystallizers has been sometimes called an art
rather than a science due to the high complexity of the system:
simultaneous heat and mass transfer with a strong dependence on
fluid and particle mechanisms; multiphase and multicomponent
system; concentration, particle size and size distribution that could
vary with time; scarcity of data; low reproducibility in the experiments
to determine both nucleation and growth rates; secondary effects like
agglomeration and the effect of impurities that can alter the
morphology and the quality of the crystalline product. Some authors
have proposed methods for design of crystallizers, among them Mullin
(1997), Randolph and Larson (1988), Nvlt et al. (1985), Jancic and
Grootscholten (1984), Mersmann (1994) and Toyokura et al. (1976).
The strategy of basic design of industrial cristallizers can be divided
into three steps: choice of the solvent, basic design and detailed
design.
Choice of the Solvent
The solvent chosen should give the desired polymorph and the optimal
shape of the crystals. In general this choice is made based on
experimental tests, but also using molecular modeling techniques. The
use of additives often helps to change the crystal shape or the
crystallization kinetics. The textbooks of Nvlt and Ulrich (1995) and
Myerson (1999) give detailed information on the effect of additives on
several systems of industrial interest.
Basic Design of the Process
This design involves the following steps: definition of design
specifications and information, crystallization method (cooling,
evaporation, flash, precipitation or second solvent addition), mode of
operation (batch or continuous, single or multistage), type of industrial
crystallizer and estimation of the basic dimensions of the crystallizer.

This basic process design is the traditional way of designing an


industrial crystallizer (McCabe et al., 1993).
Some design specifications are defined first: the yield, the mean
crystal size (for a good estimeted value, this specification must be
defined by laboratory tests or taken from the literature) and the final
purity of the product. At this stage, other specifications such as
polymorphs and crystal inclusions are not taken into account.
In addition, some design information is needed: the feed composition,
temperature, concentration and presence of crystals; physical and
transport properties for solute and solvent, such as densities,
viscosities, heat conductivities and heat capacities and their
dependence on temperature; thermodynamic properties such as
solubility curve and other phase diagrams; and for systems with more
than one solvent, the mutual solubility.
After these definitions and a survey of the data, a number of design
decisions have to be made. The crystallization method is in general
chosen on the basis of the physical and thermodynamic properties of
the solute and solvent and the required purity of the final crystalline
product (van Rosmalen, 1999). Chemical reaction or anti-solvent
crystallization is chosen when the solute is slightly soluble in the
solvent (c*<0.01). An adequate choice of reactant and solvent can
result in a good yield and purity of the final product (Giulietti and
Danese, 1993).
The second criterion for the choice of the crystallization mode is based
on the solubility curve. For highly soluble materials (c*>0.2) with a low
dependence on temperature (dc*/dT <0.005), evaporative
crystallization is recommended. In other cases (c*>0.2 and dc*/dT
>0.005), the cooling mode is recommended.
The choice of mode of operation follows. Multiple effect crystallizers are
used to save energy and to provide products with a narrower CSD.
Investment costs can play an important role in this decision.
The type of industrial crystallizer can be selected from the mean
crystal size specified. Some well-known textbooks (Mullin, 1997;
Myerson, 1993; Jancic and Grootscholten, 1984; Nvlt, 1992;
Mersmann, 1994; Toyokura et al., 1976) give detailed information on
industrial crystallizer types and selection criteria.
At this stage, design calculations are performed in order to obtain the
general dimensions of the crystallizer, making use of mass (overall and
component) and energy balance equations. The solution of these
equations provides the feed and product flow rates, the heat duties for
the heat exchangers and the evaporation or cooling rates for the
crystallization process. If product purity needs to be considered,

impurity balances must be done. Using an adequate distribution factor,


the purge stream is derived to ensure the required impurity level of the
magma. The mean residence time
of the magma in continuous
crystallizers can be estimated by using the equation

where Lm is the mass mean crystal size of the product and Gm the
mean crystal growth rate. For rough calculations, Lm can be assumed
to vary from 200 to 1000 m for highly soluble materials and Gm in the
range of 4.10-8 to 10-7 m/s. For practical purposes, the fraction of solids
in the magma suspension (

can be assumed to be in the range

of
The volume (V) of the crystallizer can be calculated by
multiplying the production rate by the mean residence time. Assuming
that the cylindrical crystallizer vessel has a height/diameter ratio of
3/2, its diameter becomes

For the calculation of the heat exchange area, the mean temperature
difference between the exchange fluid and the magma should be
between 1 and 3C for cooling and from 10 to 30C for evaporation
surfaces. The mean heat transfer coefficient can be assumed to be in
the range of 800 to 1100 W/m2.K. These average values were taken
from Seckler (2000). The mixing inside the crystallizer is important
and will be discussed later in this paper.
The method presented above is a practical short-cut method to
evaluate the main parameters of the industrial crystallizer that allows
an initial estimate of the investment cost of the plant. A complete basic
design procedure can be found in Nvlt (1992) and Mersmann (1994).
Detailed Crystallizer Design
The detailed scale design of the industrial crystallizer can be based on
the required product quality. Extended models can be used to describe
the interactions of hydrodynamics and to include the crystallization
kinetics in different parts of the industrial crystallizer, where nonuniform conditions occur (Bermingham et al., 1998; Eek et al., 1995;
Gahn and Mersmann, 1997; Neumann et al., 1998). Molecular
modeling can be used to predict the shape of the crystals, the possible
formation of polymorphs and the influence of additives on the

characteristics of the final product. At this stage, the optimization of


the global process can be an important tool to improve product quality.
The CSD can be manipulated by using process actuators like fines
removal and product classification, which in many cases have a great
effect on the crystallizer's process dynamics (Neumann et al., 1998).

MIXING OF SUSPENSIONS IN CRYSTALLIZATION


The design of the mixing system interferes with crystallizer behavior in
several ways. Since it is impossible to obtain a perfectly homogeneous
suspension, differences in solid and liquid residence times arise. In
addition, regions of high solids concentration consume solute more
eagerly and thus have a lower supersaturation. Part of the mixing
power introduced into the crystallizing medium is consumed in
collisions between the particles, thus generating secondary nucleation,
so low power inputs and low blade tip velocities are preferred. For
precipitation systems, effective liquid mixing on the molecular level
(micromixing) is often required at the location where reactants are
added to reduce variability in product quality.
The main goal of solid-liquid agitation in crystallizing systems is to
keep crystals in suspension and to promote interphase mass transfer
by inducing turbulence in the liquid phase. To date, the most widely
used basis for the design of solid-liquid suspension systems is the
critical speed, which corresponds to the minimum agitation speed for
complete off-bottom solid suspension, Njs. Under this condition, the
surfaces of all the particles are exposed to the fluid, thereby ensuring
that the maximum surface area is available for mass transfer.
Considerable attention has been devoted to determining this minimum
agitation speed. Zwietering (1958), who was the first to apply this
criterion, determined the minimum impeller speed at which complete
suspension is achieved, with the aid of dimensional analysis and
experiments with a wide range of impeller types, sizes and off-bottom
clearances, vessel sizes and physical properties of fluid and solid.
Many other works like Baresi and Baldi (1987), Wichterle (1988), Rao
et al. (1988), Thring (1990), Rewatkar and Joshi (1991), Janzon
(1994) and Myers (1994), Armenante (1998) have been published on
this subject. Despite these, it is recommended that Zwietering's
correlation be used for small-scale predictions except (a) where special
geometries are involved and (b) where the correlations of others have
been based on experimental conditions well away from those covered
by Zwietering (Harnby, 1992).
This correlation takes the following form

For paddle stirrers with D/W=2, the dimensionless constant S can be


calculated from the following equation, adapted from the original work
of Zwietering (1958):

PRECIPITATION
Precipitation is a subclass of crystallization that has been characterized
by one or more of the following features: formation of a slightly soluble
compound, generation of supersaturation by chemical reaction, fast
processing, and production of small particles. All these features are in
fact connected. For a compound with a very low solubility, it is possible
to generate a very high supersaturation almost instantly, e.g., by
mixing two reactants. At high supersaturation, precipitation proceeds
rapidly and a large number of nuclei are generated so a fine product
results. This effect is enhanced by the fact that compounds with low
solubility grow slowly (see the section on crystal growth).
Precipitation processes proceed according to the same elementary
steps presented earlier for crystallization of highly soluble compounds.
Supersaturation is usually achieved by chemical reaction, addition of
an anti-solvent, addition of a saline solution (salting out), or a change
in pH. Due to high supersaturation, heterogeneous primary nucleation
is usually dominant, and in some cases even homogeneous nucleation
can take place. Crystal growth often follows the rough growth
mechanism identified by irregular crystal surfaces. Besides these
elementary steps, other secondary processes play a very important
role in determining final product properties.
Polymorphism occurs when there is more than one possible
arrangement of solutes in a crystalline lattice. Polymorphs are thus
chemically identical compounds, but with different crystalline
structures. Polymorphs behave differently in terms of their solubility,
nucleation and growth rates, etc. Calcium carbonate, for instance, can
precipitate as aragonite, valerite and calcite, all having the chemical
formula CaCO3. For ionic salts, pseudo polymorphs, i.e., salts
containing varying amounts of hydration water, occur. Due to their
large sizes, organic molecules and biomolecules have many
polymorphs, wich are often very similar to each other, so precipitation
products are frequently mixtures of polymorphs. When supersaturation
is high enough, precipitation is so fast that the building units of the

crystal do not have enough time to adequately arrange themselves


according to a thermodynamically stable configuration, and a partially
or fully amorphous product results. The degree of crystallinity may
often be correlated with synthesis conditions (Seckler et al., 1999a;
Seckler et al., 1999b).
A practical rule that holds true for most precipitation systems is the
Ostwald rule of stages, according to which the first phase formed is the
most soluble. This derives from the fact that polymorphs with higher
solubilities precipitate faster (Calmanovici et al., 1996). After being
formed, the polymorph redissolves as new phases of decreasing
solubility are formed. At the end, only the polymorph with the lowest
solubility survives. All precursors are called metastable phases, and the
surviving polymorph is the only thermodynamically stable phase.
In industrial practice, one should conduct precipitation at a sufficiently
low supersaturation in order to avoid the presence of difficult-to-handle
colloidal amorphous phases. In addition, the choice of precipitation
conditions should take into account the solubilities of the possible
polymorphs so that only the desired phase is formed. For instance, if a
salt with only a few water molecules is required, precipitation should
be conducted at a high temperature. When it is not possible to isolate
the desired compound on the basis of solubility differences, the
precipitation time should be adjusted: a short time is preferred if the
desired polymorph is a metastable phase, whereas a long time may be
used to obtain stable modification.
Aging
The thermodynamic stability of a solid compound arises from the
ordered arrangement of its molecules in a crystal lattice in an infinite
medium. For particles of finite size, the average particle stability is an
average of its volume and surface contributions. Since surfaces have a
low stability, the smaller the particle, the lower its stability, i.e., the
high its solubility.
This effect is important for particles of 1 m m or less. In late stages of
batch precipitation, when supersaturation is low, smaller particles tend
to redissolve (Shnel and Garside, 1992). The residual supersaturation
is slowly consumed by larger particles. Aging can take days or even
months, and in general, it helps to improve product quality as it results
in larger crystal sizes and improved product crystallinity.
Agglomeration is present in almost all precipitation processes and in
some crystallization systems as well (Derenzo et al., 1996), particularly
during start-up, where higher supersaturations prevail (Eek, 1995).
When solid-liquid separation is critical, agglomeration is desired since it
leads to larger, easy-to-filter particles. When products of high purity
are needed, however, agglomeration should be avoided since

agglomerates trap impure mother liquor in their interstices. For low


solids contents (below 1 vol%) in the precipitator, agglomeration of
these solids on large seeds in a fixed or fluid bed can be
advantageously applied (Seckler et al., 1996a,b,c; Seckler et al.,
1995).
The process of agglomeration starts with the transport of particles
towards one another. When the particles have enough kinetic energy to
overcome the repulsion due to their surface potential, they collide. If
they remain in contact long enough for growth to take place and
thereby bind the particles together, an agglomerate is formed. Having
this picture of agglomeration in mind, one understands the variables
affecting agglomeration during industrial precipitation. Mixing intensity
improves the particle collision frequency and thus agglomeration.
However, a mixing intensity that is too high promotes particle
disruption. Solids concentration also increases the collision frequency
to the second power (since two particles are involved in each collision).
pH has a very strong effect on the surface potential, for every
compound there is a pH where the particle surface is electrically
neutral (the isoelectric point). At this pH, particle-particle repulsion
vanishes and agglomeration is highest. A high ionic strength depresses
the double layer, thus stimulating agglomeration. A high
supersaturation decreases the time needed for binding particles
together, thereby facilitating agglomeration.
Jones et al. (1996) review quantitative descriptions of agglomerative
precipitation systems using population balance based models. Since
such models are computationally intensive and parameter fitting is
difficult, Seckler (1994) proposed a simple model based on the
moments of CSD. The model was successfully applied to the
agglomeration of amorphous calcium phosphate. Recently, Hounslow et
al. (1999) have proposed a universal model for agglomeration with a
population balance structure coupled a phenomenological
dimensionless number. Hounslow and coworkers have been studying
agglomeration of calcium oxalate and calcium carbonate for several
years. In this model, it is assumed that solid bridge is formed before
its rupture by fluctuations in flow field. They propose the nondimensional number M:

The parameter * derives from parameters of limited usefulness: the


material mechanical resistance, a factor that relates bridge growth rate
and crystal growth rate and a bridge shape factor. The agglomeration
efficiency is defined as the ratio between experimental
agglomeration rate and average collision rate. It was found that the

reactant concentration does not affect agglomeration and that a slight


positive effect of particle size is present. The mixing intensity was
inversely proportional to the agglomeration rate for both systems
studied. The authors postulate that agglomeration mechanism for both
compounds is identical.
Mixing
Precipitation is often conducted either by chemical reaction or antisolvent processes. In both cases, mixing has to take place on the
molecular level before precipitation proceeds. Since many precipitation
processes are conducted at very high supersaturations, the
characteristic reaction time is of the same order of magnitude or even
smaller than the mixing time. When this situation prevails, the course
of the mixing process helps to determine the course of
supersaturation. This explains why mixing conditions affect crystal
shape, purity, crystallinity, and in some cases, even the phase
modification (e.g., polymorph) that is formed. When one wishes to
produce large crystals of high crystallinity and purity, precipitation
should be conducted at low supersaturation. Therefore, reactants
should be added near areas of high mixing intensity, and as far as
possible from each other, i.e., a good dispersion of the concentrated
reactant with the reactor contents should be stimulated. If fine
particles with a narrow size distribution are desired, intense mixing
should provide rapid contact between concentrated reactants.
Mersmann et al. (1994) give a nice review on this topic and Tosun
(1988) showed how the proper selection of addition points can be
effective in controlling the particle size of barium sulfate crystals.

NEW TRENDS IN INDUSTRIAL CRYSTALLIZATION


The recent developments in industrial crystallization from solutions are
considerable (Price, 1997). The commercial availability of software for
molecular modeling (Myerson, 1999) has led to new advances in the
use of alternative solvents in crystallization of organic materials as well
as to the development of tailor-made additives for the modification of
the crystal habit (Winn and Doherty, 1999). Additives have been
receiving increased attention (Nvlt and Ulrich, 1995; Myerson, 1993)
due to the possibilities they offer of changing the crystal habit (Giulietti
et al., 1999a; Leo et al., 1996), inhibiting scaling and product caking
(Veiga et al., 1999).
Continuous research efforts are being devoted to the field of secondary
nucleation. Meadhra et al. (1996) have set a new approach for the
scale-up of this phenomenon. Gahn and Mersmann (1999) have
developed a detailed mechanistic model for secondary nucleation. The
model was applied within the framework of a population balance based

model to successfully describe the steady state behavior of a 1


m3 crystallizer (van Rosmalen and Kramer, 1999).
Computational fluid dynamics (CFD) is becoming an important tool for
describing solid-liquid mixing in crystallization. This technique allows
the prediction of flow patterns, local solids concentration and local
kinetic energy values, taking into account vessel as well as agitator
shape. It has been used to assess the effect of mixing variables and
system geometry on mixing performance. As an example, Figure
11 shows the distribution of solid phase concentration within an
industrial scale vessel originally agitated by paddle impeller and after
optimization of agitation parameters, with 45 pitched blade impeller.
It is possible to see that after optimization the degree of
homogenization is much higher. For precipitation, CFD has been
successfully applied to describe local concentrations (Seckler et al.,
1995; van Leeuwen et al., 1996); however, new developments are
needed to better describe the distributed micromixing behavior in
precipitators.

Mathematical modeling of crystallization processes by neural networks


has been successfully applied to batch systems (Giulietti et al., 1999b)
and is a promising alternative for improving control of industrial
crystallizers by prediction of CSD based on plant's historical data.
The action of external fields on crystallization has shown promising
results in recent years. Ultrasound waves applied to crystallization
magma reduce agglomeration and create a narrower CSD (Martinez et
al., 1999). Sonochemistry is an emerging field of research that can
offer an enormous contribution to industrial crystallization development

(Thompson and Doraiswamy, 1999). Despite their exoteric character,


magnetic fields seem to open up new possibilities for the control of the
solubility and the kinetics of crystallization of diamagnetic materials
(Freitas et al., 1998; Freitas et al., 1999) in view of their industrial
applications.
New techniques for the production of spherical particles, such as quasiemulsion crystallization (R and Biscans, 1999), are promising
alternatives for obtaining particles with special properties and
characteristics, especially for the pharmaceutical, cosmetic and fine
chemistry industries.
Downstream processing in biotechnology offers new challenges for the
separation and purification of biomolecules such as enzymes and
proteins by crystallization (Miranda and Berglund, 1995). Chernov and
Komatsu (1995) have reviewed the fundamentals of this type of
process.
Improvements in the understanding of the fundamental aspects of
crystallization have led to the successful solution of problems found in
industrial practice, such as a reduction in process variability and
improvements in product quality (crystal shape, product handling,
downstream processing performance, etc.). Often such gains are
achieved by the mere adjustment of operational procedures with no
need for investment.
The developments just presented show that the technology of
industrial crystallization and precipitation is becoming more and more
exciting and challenging in the world of chemical engineering.

NOMENCLATURE
A

area,m2

weightofsolids/weightoffluidx100,dimensionless

B0

secondarynucleationrate,#/m3.s

concentration,mol/m3

particlesize,m

D
crystallizerdiameter,m

impellerdiameter,m

crystalgrowthrate,m/s

gravitationalconstant,9.81m/s2

orderofcrystalgrowthkinetics

ateofprimarynucleation,#/m3.s

Boltzmannconstant,1.3805x1023J/K

constantofcrystallizationkinetics

kd

masstransfercoefficient,mol/m2.s

crystalsize,m

concentrationofsolidsinsuspension,kg/m3

dimensionlessagglomerationnumber

mass,kg

orderofnucleationkinetics

populationdensity,#/m4

Njs

minimumagitationspeedforcompleteoffbottomsolidsuspension,1/s

volumetricflowrate,m3/s

R
gaslawconstant,8.3130J/mol.K

Re

Reynoldsnumber

dimensionlessconstant

supersaturationrate

Sc

Schmidtnumber

Sh

Sherwoodnumber

T/C

offbottomclearanceratio

T/D

impellerratio

temperature,K

time,s

crystallizervolume,m3

Vm

molecularvolume,m3/mol

Wi

stressenergyinthecrystal,J

molefraction

GreekLetters

agglomerationefficiency

kinematicviscosity,m2/s

densitydifferencebetweenparticleandfluid,kg/m 3

difference

activity,mol/m3

agitatorpowerinput,J/kgandsolidfractioninsuspension

activitycoefficient,interfacialtension,J/m 2andshearstress,J/m2

chemicalpotential,Jand,dynamicviscosity,kg/m.s

density,kg/m3

relativesupersaturation

residencetime,s

Subscripts
1

component,solute

area

cryst

crystallizer

eff

effective

growth

impeller

in

inlet

liquid

mean

nucleation

initial

out

outlet

total

volume

Superscripts
0

standard

'

liquidphase

''

solidphase