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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
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:
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
For an
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
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.
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 (
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
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
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