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Unesco - Eolss Sample Chapter: Heat and Mass Transfer Operations - Crystallization
Unesco - Eolss Sample Chapter: Heat and Mass Transfer Operations - Crystallization
Contents
1. Introduction
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2. Solid-Liquid Equilibria
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3. Kinetics
4. Properties of Crystals
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5. Crystallization TechnologyO
6. References
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Glossary
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Bibliography
Biographical Sketches
To cite this chapter AP
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Summary
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a solid product from a solution or a melt. The process itself, the product characteristics
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and the temporal behavior are determined by thermodynamics, i.e. solubility of the
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Crystallization kinetics can be divided into two separate processes, nucleation and
crystal growth. Both play a significant role in the design of equipment for a given
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1. Introduction
Other technical routes to leading to crystalline products may involve chemical reactions
(reactive crystallization), change of dielectric constant/ionic strength of a solution
(salting-out) or crystallization induced by a change in solvent composition (drowning-
out).Those type of crystallization processes often referred to as precipitation processes
will not be covered here [Söhnel/Garside].
The main feature distinguishing crystallization from other thermal separation processes
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is the fact that it leads to a solid product. This is one of the key reasons why it lags
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behind separation techniques involving liquid-liquid or liquid-gaseous phase change
processes in terms of research effort expended and knowledge available. In the past
chemical engineering has tended to avoid the solid state as far as possible due to the
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problems inherent in solids handling. Encrustation and the concomitant heat transfer
problems, seizing of moving parts, generation of hazardous dust and the general
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difficulty inherent in solid-liquid separation are just some of the issues involved.
However, the attitude towards crystallization is changing and the positive aspects of the
techniques, low energy consumption and the potential for high-purity products, are
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more widely appreciated. [Mullin], [Myerson], [Mersmann], [Tavare], [Jones],
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the additional advantage of not requiring a solvent, although it is not a method suitable
for all materials. Manifold reasons exist for the growing importance of crystallization as
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an industrial separation process. On the one hand, many products are solids under
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industry and in the manufacture of foods. On the other hand, the ability to manipulate,
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option in those industry sectors already mentioned, where reproducible product quality
with well defined properties (flow properties, color, dissolution characteristics,
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polymorphic form etc.) are of utmost importance. [Ulrich/Glade], [Ulrich (in Hofmann
2004)], [Arkenbout], [Jansens/van Rosmalen (in Hurle)], [Matsuoka (in Garside)],
[Sloan/McGhie], [Toyokura/Hirasawa (in Mersmann)], [Ulrich 2002 (in Myerson)]
The key factors in the design of any thermal separation process are the thermodynamics
of the system under consideration as well as its kinetics. The thermodynamics defines
the limits of what can be achieved, the kinetics define the time-scale and therefore the
size of the equipment required. This general statement also holds for crystallization. As
a consequence, fundamental knowledge of phase diagrams and solubilities of the
materials to be separated is required prior to the design of any industrial process. In
many instances the literature only provides phase diagrams for pure materials. With
increasing number of components phase diagrams become progressively more complex.
Realistic systems generally contain many components and determining phase behavior
under operating conditions is one of the greatest challenges in crystallization.
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achieved in a finite and reasonable time scale and the information on this aspect of
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crystallization is contained in the process kinetics.
Two processes are important in crystallization, both with their own characteristic
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kinetics. One of these processes is nucleation [Kashehiev], the other is crystal growth.
Both of these phenomena are dependent on a large number of variables that in some
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cases may be ill defined.
In addition, further factors that influence the number and nature of particles obtained
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have to be considered in the design of mass crystallization processes. Whenever
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Finally crystals possess an internal structure, an external shape and consequently a finite
size (or size distribution in the case of a quantity of crystals). These parameters
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determine many bulk properties of a given crystalline material, such as dissolution rate,
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bio-availability, color, flow properties etc. A general overview of these properties will
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also be provided.
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2. Solid-Liquid-Equilibria
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This section provides an overview of solid-liquid equilibria and the type of information
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useful to crystallization that can be gleaned from their representation in the form of
phase diagrams. Different types of – idealized – phase and solubility diagrams shall be
discussed together with associated phenomena.
solubility of one component also depends on the relative amounts of the other
components present. For liquid solutions the pressure dependence is negligible if the
pressure difference is small (which is the case in most applications) and will not be
considered here. However, the temperature dependence (and also the pressure
dependence providing the difference is sufficiently large, see [Moritoki]) of the
solubility can be considerable and it is therefore important to state the temperature for
which the solubility is reported even under ‘normal’ conditions. In the following the
discussion will focus on two component systems only.
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selected to suit the purpose the data are required for. The most common measures are
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• Mass of solute per unit mass of solvent (kg/kg)
• Mass of solute per unit mass of solution (kg/kg)
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• Mass of solute per unit volume of solvent (kg/m3 or g/L)
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• Molar amount of solute per unit volume of solvent (kmol/ m3 or mol/L)
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• Mole fractions (dimensionless number)
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From the above list it is clear that, for the first two cases, it has to be stated explicitly
whether composition reported refers to the solvent or the solute in order to avoid
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confusion. Moreover, it is often necessary to mention the initial state of the solute, as
many substances can exist as solvated or unsolvated solids (vide infra). For example,
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two solutions of sodium carbonate in water will have different compositions if in one
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case the decahydrate is used as starting material and in the other the same mass of
monohydrate is employed. Ambiguity arises if this is not accounted for.
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examples exist, where the solubility shows the reverse trend (sodium sulfate, calcium
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carbonate, iron sulfate dihydrate, to name but a few). The dependence of the solubility
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upon temperature is best represented graphically in the form of a solubility curve, which
maps the composition of a solution at the solubility limit onto the temperature. A
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material, solvates and hydrates (vide infra) generally have different solubilities. A
change in solid form is normally evidenced by a discontinuity in the solubility curve,
which results from different slope, that is, temperature dependence, of the solubility of
the respective forms. In Figure 1 the solubility of a fictitious substance A that forms
three phases, two hydrates and one anhydrous phase, is shown. Two discontinuities can
be seen marking the transition points between the stable regions for the trihydrate and
monohydrate (left) and the monohydrate and anhydrous phase (right). The solubilities
of the respective stable phases are indicated by the solid line. In addition, the solubilities
of the different metastable forms are indicated by the dotted line.
Solubilities are determined experimentally and any convenient analytical technique that
provides a quantitative measure of composition can be employed. Not every technique
is suitable for every situation and the decision as to which method is used has to be
made on a case by case basis.
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stable phase in a given region, the dashed line represents the solubility of the respective
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metastable phases.
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In the simplest case of a two component system containing a solute that is non-volatile
and stable with respect to temperature the composition can be determined by taking a
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given mass of the solution, evaporating to dryness and weighing the remaining solid
(solubility measurements should always be based upon a mass of solution due to the
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higher accuracy compared to volume measurements). The more components present and
the more complex the system, the more difficult it becomes to accurately determine the
composition by a single analytical technique.
A number of factors have to be accounted for when determining solubilities. First and
foremost, it is important to ensure that the solution is indeed in equilibrium. This is
particularly important in the case of highly concentrated, viscous solutions where
dissolution rates may become vanishingly small the closer one approaches the
equilibrium composition. Here it is important to provide good agitation and to allow for
sufficient time before taking a measurement. One method to assess whether equilibrium
has been reached is to take measurements from two solutions, one where saturation is
approached from an undersaturated state, the other where saturation is approached from
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commonly by cooling a saturated solution (for solutes where solubility increases with
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temperature, solutes with reverse temperature dependence must, of course, be heated) or
by evaporation of solvent. As is the case for solubility, several measures exist to express
supersaturation. These are the difference between the equilibrium composition at the
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temperature of the supersaturated solution c * and the actual composition in the
supersaturated solution c
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Δc = c - c * , (1)
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the ratio of these two concentrations
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S = c / c*, (2)
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σ = Δc / c* = S -1
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(3)
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For melts, the driving force is usually expressed in terms of the supercooling
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Δθ = θ * - θ , (4)
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which represents the difference between the equilibrium temperature of the melt θ * and
the actual temperature θ . Occasionally supercooling also finds use in solution
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crystallization.
Quantifying the supersaturation is important for two reasons. As mentioned above the
supersaturation is a measure of the driving force for the crystallization process. The
second reason concerns the theoretical yield of the process. The theoretical yield of any
crystallization is easy to calculate as it is given by the difference between the actual
composition of the feed solution at the starting point of the process and the equilibrium
composition at the end-point of the process. This definition already accounts for any
temperature gradients employed in the process. Of course the real yield of the process
may differ from the theoretical yield. As the supersaturation decreases, crystal growth
rates also decrease and the theoretical yield will only be reached in the limit of infinite
time. The consequence of this is a lower yield than possible. On the other hand, yields
may be higher than theoretically possible if growth is fast and if the crystals obtained
contain a significant amount of liquid and/or impurity inclusions.
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temperature has been reached. In other words it is defined by those points where the
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induction time for nucleation vanishes. All points with finite induction times lie within
the metastable zone. The metastable zone width can be measured by determining the
point at which first crystal nuclei are detectable. This can be achieved by optical
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methods such as turbidity measurements or ATR-FTIR (attenuated total reflectance
Fourier transform infrared spectroscopy), by measurement of acoustic properties of the
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solution (ultrasound), or by measuring any other easily measurable physical parameter
such as density or conductivity. Unfortunately there is no single analytical technique
that is suitable for all substances; the best method has to be determined after careful
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consideration of the individual system.
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Figure 2 shows a generalized solubility diagram which includes the metastable zone
width for different induction times (cf [Mersmann 2001]). The line at tind = 0 defines
the limit of the metastable zone, at higher concentrations of solute at constant
temperature the solution is labile.
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In melt crystallization it is not particularly helpful to talk about solubilities. Here, solid-
liquid phase diagrams are the more appropriate point of reference. In principle,
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solubility curves are part of the solid-liquid phase diagram and therefore contain the
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same information. They are useful for determining equilibrium temperatures, theoretical
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yields, stability regimes of particular phases and the magnitude of the driving force for a
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given system under given conditions [Ulrich 2003].
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Phase diagrams can be represented graphically using any combination of physical
variables. For a binary system only three parameters are required to define the state of
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composition (T-x) diagram is more useful, given the fact that the pressure dependence of
the solid-liquid equilibrium is usually negligible under ambient conditions. However, at
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high pressures pressure can be used to direct a crystallization process in much the same
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diagram, the equilibrium temperature is plotted against the composition of the solid and
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the liquid phase, usually expressed in terms of mole fractions, respectively. There are a
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number of types of typical solid-liquid phase diagram representing ideal and different
non-ideal behaviors. The discussion here will be restricted to an ideal binary system in
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order to illustrate pertinent points. For other types of solid-liquid phase diagrams (for
example eutectic, peritectic or compound forming systems) the authors refer to the
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Here the composition of the respective phases in equilibrium with each other at any
given temperature is determined by the end points of the tie line (Figure 3a). The tie line
is a horizontal line (that is a line at constant temperature) that connects the liquidus and
the solidus lines. For a crystallization process, the composition of the product at a given
final temperature of the process is independent of the starting point. In this example,
any melt with a composition in the range between xAs and xAl will lead to a solid
product enriched in component A with composition xAs and a liquid enriched with
component B with the composition xAl . However, depending upon the exact starting
composition, the yield of the solid phase will differ and can be determined by the lever-
rule. Figure 3b illustrates this point: starting from a composition xF the temperature is
lowered to Tα corresponding to point of solidification at the initial composition of the
melt. The corresponding solid composition is determined by the intersection of the tie-
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line at Tα with the solidus line and is represented by xSα . However, employing the
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lever rule shows that the solid yield at this point is zero. At the final temperature Tω , the
composition of the solid is given by xSω and the composition of the liquid phase is xlω .
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The relative proportions of solid and liquid is given by the ratio of the lengths of the
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lines R and C.
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system.
On the left the three regions of phase space separated by the solidus and liquidus lines
can be seen. Within the two-phase region the composition of the respective phases is
determined by the locus of the end-points on the respective equilibrium lines. On the
right the progress of a crystallization process beginning at a composition F is shown
(see [König (in Ulrich/Glade)]).
Figure 4 shows a simple eutectic phase diagram, which represents the most common
phase behavior of binary organic systems (about 85% of all known organic binary
systems are eutectic or pseudo-eutectic). The eutectic phase diagram is characterized by
four regions, the homogeneous liquid, two regions of coexistence, and an
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the eutectic point (F1) yields only pure component A, pure B cannot be crystallized.
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Moreover, the yield decreases, the closer the initial melt composition is to the eutectic
point. The same holds for the situation where the initial composition is to the right of
the eutectic point (F3), where only pure component B is obtained. For a melt with
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eutectic composition, no separation is possible as the solid composition is the same as
the composition of the liquid.
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In principle all other types of phase diagram (compound forming and peritectic systems)
can be derived from the ideal solution and the simple eutectic system. For a more
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detailed discussion of phase diagrams we refer to [König (in Ulrich/Glade)], [Walas].
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On the left the four regions are shown with their respective phases. The right-hand
diagram indicates the different outcomes of crystallization from different starting points.
For a liquid of composition F1 one obtains pure A and a solid with eutectic
composition, for a liquid of composition F3 pure B is obtained together with the eutectic
solid. In the case of a liquid with composition F2, no purification is achieved as the
liquid and the solid have the same composition [König (in Ulrich/Glade)].
3. Kinetics
3.1. Nucleation
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quantity, the volume excess free energy is a negative quantity and is proportional to r3.
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Figure 5 shows a qualitative plot of these different quantities. The critical radius is a
measure of the critical nucleus size and is determined by the maximum in the excess
free energy curve. Below the critical radius redissolution of the nucleus is energetically
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favorable as evidenced by the slope of ΔG, above the critical radius growth is more
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favorable as this leads to a reduction of the excess free energy.
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The most frequently observed nucleation mechanism is called secondary nucleation.
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Secondary nucleation requires the presence of crystals of the material to be crystallized
and occurs at much lower supersaturation than primary nucleation. As a rule, secondary
nuclei are formed by the removal of structured assemblies from the surface of the
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crystals. There are different mechanisms which lead to those secondary nuclei, these
are:
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• initial breeding: nuclei result from simply placing crystals into a supersaturated
solution or supercooled melt via the washing off of dust particles from the surface of
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the crystals
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• collision breeding: nuclei result from fragments of existing crystals which are
broken off due to mechanical impact on crystal faces due to crystal-crystal, crystal-
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liquid boundary layer due to shear forces resulting from liquid motion. A
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prerequisite for this behavior is that the growing crystal already has a size larger
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Collision breeding is the most frequently observed and dominant secondary nucleation
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There are two aspects to secondary nucleation. The positive aspect results from the fact
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Should control of tip speed and enlargement of impeller diameter not be sufficient to
reduce the amount of fines to below a value of the order of 1010 in terms of number per
cm3 (while still less than 1% in terms of mass percentage), other measures may have to
be taken to control the product. In general not all nuclei will grow fast enough to
become product size particles due to the fact that each crystal has its own, individual
growth rate (this phenomenon is called growth rate dispersion). In some cases small
particles will agglomerate. In all the other cases a fines trap has to be introduced to the
crystallizer, either as an internal or an external design feature. A fines trap consists of an
additional loop within the crystallizer in which the conditions are such, that all fines
smaller than a given particle size passing though this loop are redissolved.
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the same supersaturation: primary heterogeneous nucleation depends on the number and
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the nature of the impurities and is therefore, within certain limits, a random event. As a
consequence reproducibility of product quality cannot be guaranteed and the
performance of the crystallizer will vary. Assuming that nuclei start to grow at high
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supersaturation, liquid inclusions or dendritic growth (vide infra) are likely, as well as
massive formation of small particles that tend to agglomerate. All of these phenomena
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lead to poor product purity and quality. In addition, this may lead to strong tendency for
caking in storage. If nucleation commences at a too low a supersaturation, the ensuing
crystal growth may be slow and will pose a problem with respect to production time or
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crystallizer size, respectively.
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Keeping the driving force (the supersaturation) constant subsequent to seeding normally
results in high quality crystals, providing the supersaturation selected coincides with the
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optimum growth rate for the system under consideration. The optimum growth rate is
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either determined from laboratory tests guided by the rule that a crystallizer should run
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under such conditions that the concentration in solution remains at the centre of the
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increasing crystal surface area, which is ultimately responsible for the reduction in
supersaturation.
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Some general rules can be stated for seeding [Beckmann], [Heffels/Kind], [Doki],
[Warstat/Ulrich]. The surface area of the seeds added has to be large enough to avoid
any additional nucleation at the moment the process is started or while it is in its early
stages, otherwise a bimodal crystal size distribution will result. On the other hand the
seeds should be small enough and low enough in number to produce the desired amount
of product in the process. Choosing too large a seed crystal size leads to a low yield, too
many seed crystals lead to a small product crystal size. A properly carried out seeding
procedure together with a good control strategy for the supersaturation and an
optimised, gentle agitation provides the basis for a reproducible and controlled
crystallization process in terms of number and size (size distribution) of crystals in the
product.
Many open questions remain in this area and until a complete model or theory regarding
seeding is available this will remain an active field of investigation.
As for nucleation, crystal growth only occurs if there is a driving force as a result of
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non-equilibrium thermodynamic conditions. The crystal growth rate is a physical
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property of a given material. However growth rates depend not only on the temperature,
pressure and composition of the mother liquor but also on parameters such as
supersaturation (under cooling), fluid flow conditions, history of the crystals, the nature
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of the surfaces of crystals and the presence or absence of additives (impurities) in the
mother liquor. Crystal growth rates are of key importance to the engineer since they
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determine the retention time and therefore the size of the crystallizer, which
consequently means the investment costs.
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Linear growth rates for crystals grown from solutions (suspensions) are of the order of
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10–7 to 10 –9 m s-1. For melt layer growth the processes can feature growth rates in the
range of 10 –5 to 10 –7 m s-1 where forced circulation of the homogeneous melt is
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employed.
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Different measures of growth rates are in use other than the increase of a characteristic
length denoted by G. Growth rates are also measured in terms of mass increase per
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surface area, R, or in terms of the displacement of a single crystal face, v. Each of these
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growth rates can be converted to the others, providing the shape of the crystals remains
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constant during crystal growth. In that case the following equations hold:
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Here L is the characteristic length, t the time, A the surface area, ρ the density and ( fs )
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Since crystallization is a heat and mass transfer process, three steps always have to be
considered. These are:
• transport of material to be crystallized from the bulk solution to the vicinity of
the crystal surface
• transfer of material from the solution boundary layer to the solid state (generally
referred to as surface integration)
• dissipation of the heat of crystallization liberated at the point of growth
Although these three physical phenomena always occur, one or the other may dominate
the crystallization process. As a rule-of-thumb, the dissipation of the heat of
crystallization can be neglected. In solution crystallization the processes occurring for
the remaining two cases are referred to either as “surface integration controlled” or
“diffusion controlled” growth if one or the other step is rate determining. In melt
crystallization the heat control is generally viewed as the rate determining step. The
same mechanisms that apply to crystallization also apply to dissolution processes.
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on the growth velocity. This limit coincides with a minimum thickness of the solid-
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liquid boundary layer that determines the mass transfer.
The nature of the crystal surface also plays a role in the growth rate and therefore the
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history of the crystals is an important factor. The perfection (or lack thereof) of the
surface can influence the growth velocity in both directions, either accelerating or
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suppressing crystal growth.
At this point it should be stressed that each crystal has its own, individual face growth
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rates due to the factors discussed above. These individual rates can range from zero to a
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maximum growth rate characteristic for the material under consideration. This
phenomenon crystals displaying individual growth rates despite starting to grow under
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(nominally) identical conditions with respect to crystal size and growth environment is
termed growth rate dispersion (GRD) [Ulrich 1993], [Ulrich 1989].
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to collect relevant kinetic data. It is clear from the above discussion, that an average
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growth rate for an assembly of crystals is required. Although individual growth rates for
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single crystals are informative in terms of determining the development of crystal shape
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(habit) during the growth process, many crystals would have to be monitored in order to
gather statistically significant information that incorporates, for example, the effect of
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GRD and is suitable for use in the design of industrial crystallization equipment.
Therefore, methods providing access to mass growth rates utilizing either stirred tanks
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or fluidized beds are to be preferred for this purpose. Here fluidized beds operated with
seed crystals of known size and quality are the better choice since all parameters of
interest (vide supra) can be varied independently [Mohameed], [Kruse], [Al-Jabburi].
The growth rate is measured monitoring the mass increase over time for a constant
number of seed crystals of known size. Attrition of the crystals can be neglected in most
cases, due to the gentle operating conditions applied in of small fluidized beds.
Particles resulting from attrition, should they be generated under the operating
conditions selected, are normally dissolved in that part of the fluidized bed, where the
solution is undersaturated.
Classical crystal growth theories are of course important for an understanding of the
growth process and a number have been developed and improved over the years.
However, for the chemical engineer dealing with mass crystallization they are not of
key importance. Growth theories are discussed in detail in all standard text books on
industrial crystallization [Ohara/Reid], [Mullin 1992], [Jancic], [Myerson 2002], [Ulrich
2002].
Most crystal growth theories only consider the solid (crystal) and tend to neglect the
influence of the conditions in the liquid. Nonetheless, there exists enough experimental
evidence that demonstrates that the liquid and its composition are of great importance in
the crystal growth process.
The most important growth models are the spiral growth model incorporated in the
Burton-Cabrera-Frank (BCF) theory of crystal growth and the so-called ‘birth and
spread’ model. The BCF kinetic theory of growth considers the density dislocation
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leading to spiral growth on a crystal surface and the supersaturation. For low
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supersaturation a quadratic dependence of the growth rate as a function of the
supersaturation results which changes to a linear dependence at high supersaturation.
The ‘birth and spread’ model makes the assumption that growth occurs due to surface
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nucleation. Here the supersaturation dependence of the growth rate is proportional to
σ 5/6 . Further details can be found in the standard monographs cited above.
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The normal engineering approach to growth rates is to determine these experimentally
as a function of supersaturation at a given temperature using the original mother liquor
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and well defined seed crystals. In the case of batch crystallization in particular, it is
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extremely important to verify that the laboratory scale crystallization leads to the same
quality of product (purity and crystal growth rates), especially when the batch-time is
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nearing its end and the majority of impurities present have accumulated in the
remaining mother liquor. In some cases the accumulation of impurities may not only
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affect growth rates but may also influence the resulting crystal habit.
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In order to maintain good yields and high product purity it is desirable to maintain a
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batch processes this requires permanent adjustment of the driving force. Industrial
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experience suggests that a solution crystallization process should best be operated at the
centre of the metastable zone. If the process operates close to the upper limit of the
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oscillations in the of the crystallization process with respect to the output of crystal size
distributions. Conversely, if the process is operated close to the solubility limit,
insufficient mass per time is produced. Neither natural or linear cooling/evaporation
provide a constant driving force. As the available crystal surface area increases with
growth of the crystals, the rate of reduction of supersaturation increases under linear or
natural cooling (evaporation) conditions. In order to maintain constant supersaturation,
an appropriate cooling or evaporation program must be employed.
4. Properties of Crystals
In contrast to amorphous solids, liquids and gasses, crystals possess a well defined 3-
dimensional order. Fortunately, symmetry considerations dictate that only a limited
number of structures exist in which a space-filling packing of building blocks is
possible [Hahn]. The crystal structure is important even in industrial mass
crystallization as the internal arrangement of the building blocks defines the
macroscopically observable shape of the crystal and thus influences post-crystallization
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processing, that is solid-liquid separation, drying and packaging. Energy considerations
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lead to the conclusion that for each substance there is only one minimum energy
structure. However, it is not correct to draw the obverse conclusion that only one crystal
structure is possible per chemical species, since the most stable crystal structure may be
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different under different conditions of temperature and pressure. Unfortunately,
depending upon the crystallization conditions, a given material may crystallize in
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different modifications that are not necessarily minimum energy structures at the given
conditions. Although these structures are thermodynamically metastable, the kinetics of
transformation to the stable phase may be (infinitely) slow so that these additional
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crystal modifications must be treated as stable in the context of product properties and
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therefore not only depends upon the temperature and pressure at which they are
crystallized, their stability window also depends upon the composition of the solvent.
One substance may crystallize in a number of polymorphic forms and also in the form
of different solvates or hydrates. Even solvates and hydrates can exist in different
polymorphic forms. It is therefore clear that the design and control of reliable and
reproducible crystallization processes, in particular in the case of drug substances where
reproducibility is of paramount importance, poses a difficult task. Despite the inherent
difficulties, polymorphism can also be viewed as an opportunity for overcoming
problems with perhaps undesirable physical properties of energetically stable structures:
by judicious choice of crystallization conditions and by producing a particular
polymorph with certain, desired properties, the product properties can be tailored to suit.
The existence of polymorphs, solvates and hydrates leads to the potential for
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unexpected phase transitions during the production process which may result in
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unexpected products with unwanted properties. For example, a hydrate may be sensitive
to ambient humidity and lose its water if humidity becomes too low. Contact with
another solvent may also induce phase transformations. It has been shown, for example,
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that certain hydrates lose their water when brought into contact with organic solvents.
The accompanying phase transition results in acicular (needle-like) crystals that form a
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dense, felt-like mass. This crystalline mass becomes difficult to process. On the one
hand it no longer presents a freely flowing slurry, on the other hand it retains a large
amount of fluid that is difficult to remove using standard solid-liquid separation
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techniques. The first case also poses a challenge in solid-liquid separation, in particular
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if a phase transition occurs during the filtration process. Here one may be left with a
solid block of an unwanted phase that has to be painstakingly removed and discarded
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[Ulrich/Jones], [Malet].
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The external shape of a crystal is determined by the crystal structure, that is, the internal
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order of the individual building blocks as determined by the space group symmetry. The
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crystal faces expressed by the macroscopic crystal always map a lattice plane defined by
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the microscopic unit cell. Nonetheless, crystals of the same chemical species with the
same crystal structure can exhibit different habits. This is due to the fact that growth
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rates of individual crystal faces, and therefore their relative morphological importance,
are subject to supersaturation effects and the influence of solvent and impurity
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molecules. Crystals of the same material grown from different solvents, for example,
may have different aspect ratios or may even display different crystal faces. Fast growth
due to high supersaturation has a great effect on crystal habit and in extreme cases leads
to dendritic growth resulting in highly branched and fragile crystals. Fast growth is
desirable from an economic point of view since fast growth means short residence times
and smaller equipment, i.e. lower investment costs. Apart from the possibility of
dendritic growth, rapid growth rates have other disadvantages that result in detrimental
product quality. Fast crystal growth encourages liquid inclusions in the crystals and
often leads to rough surfaces. Liquid inclusions are critical in two respects: not only do
increasing amounts of included liquid reduce the overall product quality, the
accumulation of impurities in the mother liquor over the crystallization process also
reduces product purity.
The other factor influencing crystal habit mentioned above is the effect of impurities.
No mother liquor is ever truly free of impurities and it has long been recognized that
these impurities can lead to changes in the observed crystal shape. In terms of post-
crystallization processing this can have a negative effect on filterability, drying, or on
the handling of the dry solids, in particular if crystals with an acicular or tabular (plate-
like) habit are produced. On the other hand, the effect of impurities can be of advantage
to tailor the shape of the crystals. By exploiting the different interactions of different
chemical species with the growing crystal faces, it is possible to manipulate the final
macroscopic shape of the crystals by deliberately adding an impurity (additive) to the
crystallization liquor. The fastest growing crystal faces grow out and are not observed in
the final crystal habit. One strategy to influence the shape of the crystal is therefore to
find an additive that reduces the growth rate of faster growing faces while leaving the
growth rates of the slower growing faces unchanged. This can be achieved by
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identifying additives that fit into the lattice on the fast growing surfaces (but not the
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others) and therefore block the addition of the regular growth units. Several so-called
‘tailor-made’ additives have been reported in the literature [Weissbuch], [Chen],
[Clydesdale].
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4.3. Crystal Size and Crystal Size Distribution
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In mass crystallization crystal sizes are normally discussed in terms of the mean
diameter of a size distribution. A quick glance into any book on particle technology will
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reveal that there are a number of different definitions of “mean diameter” in use. For the
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purpose of this discussion it is important to point out that any researcher dealing with
size distribution has to be careful to select the correct definition for the problem in hand.
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In industry requirement are often stated quite generally such that a product has to meet a
certain specification with regard to the proportion of particles above or below a certain
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size limit. One means of tightening the specification of a size distribution is to define a
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second characteristic value, usually the width of the desired distribution. This still
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leaves the shape of the distribution open. One particular crystal size distribution
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function that should be named at this point is the RRSB (Rosin, Rammler, Sperling,
Bennett) distribution, since it provides a good fit in many cases.
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The size (which from this point onwards should be taken to mean the mean size) of a
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crystal is important for a variety reasons: flow properties, color, dissolution rates,
agglomeration tendencies, mixing and demixing properties, filterability etc. can all
depend upon the crystal size.
Even though larger crystals are often desirable, there are cases where smaller crystals
are of key interest. Nanotechnology as well as dyes and pigments are two areas where
small crystals can exhibit properties that are lost above a certain upper limit. A
significant body of work concerning the controlled production of uniformly small
crystals has emanated from the photographic materials industry. These small crystals
and their controlled production is, however, a typical domain of so-called precipitation
crystallization which is not the object of this discussion.
Apart from achieving a well defined and often narrow width of the crystal size
distribution, it is often desirable to have a narrow, mono-modal distribution which can
be viewed as single-sized. The term ‘narrow distribution’ alone will have different
meanings in different situations. Crystals of table salt (sodium chloride), for example,
must be small enough to fit through the openings of the salt cellar (generally smaller
than 400 µm), yet large enough not to exhibit the typical properties of a powder such as
caking. Powders are generally not free-flowing since the attractive forces between the
crystals are stronger than the gravitational force. The critical lower size limit where
powder properties become noticeable is dependent on the material.
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regions of the crystallizer, a distribution with finite width will always be the result.
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There are several reasons for this, primarily growth rate dispersion. Furthermore,
inhomogeneities in the growth conditions can never be excluded (spatial variations in
temperature, supersaturation, concentration of impurities or fluid flow patterns),
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however, methods exist to control, minimize or reduce excess nuclei and to produce a
product close to the desired size distribution.
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5. Crystallization Technology
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In this chapter, typical crystallization equipment frequently found in industrial
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applications is presented. Special cases are not discussed here, even though many
applications require tailor-made solutions. The equipment discussed in the following is
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Figure 6 shows the three most frequently built, continuous evaporative solution
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crystallizer types, together with their heat exchangers. In common with all evaporative
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crystallizers, the evaporation zone lies towards the top of the crystallizer at the interface
of the solution with the atmosphere. Inside the crystallizers the supersaturation must be
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kept within the metastable zone at all locations in order to avoid primary nucleation and
to provide controlled conditions for crystal growth.
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Larger crystals can be obtained using the draft tube baffled crystallizer (DTB, Figure 6,
centre), where only the clear solution, together with some fines, is circulated through the
heat exchanger, while the crystals are circulated at low speed in the apparatus by means
of a very large impeller pump (often exceeding 1 m in diameter) located within the draft
tube. The low circulation rate results in less attrition of the crystals due to reduced
mechanical impact with both pump components and other crystals.
The largest crystals can be obtained with the “Oslo”-type crystallizer (Figure 6, right).
Here crystals grow in a fluidized bed created by the supersaturated solution circulating
from the evaporation zone down the central draft tube towards the bottom of the
equipment and from there back upwards to create the fluidized bed that is located in the
lower part of the crystallizer, between the tube and the inner wall of the crystallizer.
Only cleared solution is circulated through the heat exchanger. Gentle flow conditions
and longer retention times are required in order to obtain larger crystals and there is no
size reduction due to pumps or impellers.
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Figure 6: The three most important types of evaporative solution crystallizers. Left, the
forced circulation (FC) crystallizer, centre, the draft tube baffled (DTB) crystallizer and
right, the Oslo crystallizer. Images kindly provided by Messo Chemietechnik, Germany
In all evaporative crystallizers the liquid layer just beneath the evaporation zone is the
region with the highest supersaturation. As the liquid interface is subject to periodic
variations in height due to the effect of motion in the equipment, this area is prone to
encrustation due to variable wetting and resultant nucleation.
Large crystals require long retention times, long retention times require large equipment
and large equipment results in expensive processes. Whenever possible, the application
A typical process flow sheet for a solution crystallization process is provided in Figure
7. The flow sheet represents a four stage sodium chloride purification process. The
intake is brine with a flow rate of 60 t/h. The first, Oslo-type crystallizer produces large
crystals of the order of 2 mm side length at a rate of 2.5 t/h, the remainder of the plant
(three successive FC crystallizers followed by post-crystallization processing) produces
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regular table salt at a rate of 6.5 t/h. The size of the equipment can be gauged via the
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total height of the building, which is 30 m, and the surface area required, which is 2000
m2 for such a process. Further information on evaporative solution crystallizers can be
found in [Hofmann (in Hofmann)].
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Figure 7: Process flow sheet for a sodium chloride crystallization plant. From the left:
the first, Oslo-type crystallizer produces large sodium chloride crystals, the three forced
circulation crystallizers produce standard table salt. Following the crystallizers, settlers
for solid-liquid separation, cyclones for fines removal and storage silos can be seen.
Image kindly provided by Messo Chemietechnik, Germany.
Melt crystallization can be subdivided into two distinct methods. These are suspension
based and solid layer based processes. The different techniques are described in detail in
the literature cited, for example [Arkenbout] or [Ulrich/Glade]. The suspension based
processes are frequently combined with so-called wash columns ([Scholz/Ruemekorf
(in Ulrich/Glade)], in order to achieve a better solid-liquid separation. A flow sheet for a
plant from Niro Process Technology B.V. used for p-Xylene purification is shown in
Figure 8.
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Figure 8: Flow sheet detailing a (generalized) melt crystallization process with wash
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column. Figure kindly provided by Niro Process Technology B.V., The Netherlands.
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Solid layer melt crystallizers follow a different concept. Here the product is obtained by
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enforced encrustation. Heat is withdrawn from the melt through the crystalline layer by
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means of cooled walls within the crystallizer. The driving forces are much higher than
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in the case of suspension crystallization since the feed melt always remains above its
melting point. Growth rates are about two orders of magnitude higher than in
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suspension crystallization (10-7 – 10-5 m/s compared to 10-9 – 10-7 m/s). However, in
melt crystallization the surface area of the product is limited and about two orders of
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The photograph in Figure 9 illustrates the full scale of the process equipment. The
crystallization vessels can be seen on the right hand side of the image, the wash
columns (screw-type) are on the left behind the feed heat recovery exchangers.
Solid layer techniques are almost exclusively discontinuous, but they can be staged.
Due to the very fast growth rates single stages lead to rather impure products (both
crystalline and melt fractions). These are normally collected and reused in subsequent
stages. Further purification and higher yield can be achieved in this manner. Storage
tanks are cheaper than crystallizers and for this reason all stages of a given process are
usually carried out in a single crystallizer and the intermediate products are stored in
tanks until such a time that enough material has accumulated for the next stage.
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Figure 9: Melt crystallization plant used for the purification of p-Xylene. The
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crystallization vessels can be seen to the right. Figure kindly provided by Niro Process
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Figure 10 shows a flow sheet for such a design. Central to the plant is a falling film
crystallizer. Detailed descriptions of melt layer crystallization can be found in
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Figure 10: Typical flow sheet for a staged solid layer crystallization plant. Central to the
design is a falling film melt crystallizer. To the left of the crystallizer three storage
tanks can be seen. These are used to collect residual melt and purified material, which
can then be reused in the process. Flowsheet kindly provided by Sulzer Chemtech Ltd,
Switzerland.
The falling film equipment shown above represents the so-called dynamic solid layer
technique which requires forced circulation of the melt passing over the cooled surface.
Figure 11 provides an example of such a crystallizer. (p-Xylene, CEPSA, Spain).
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Figure 11: A falling film melt crystallization plant used for the purification of p-xylene
(CEPSA, Spain). Photograph kindly provided by Sulzer Chemtech Ltd, Switzerland
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Static solid layer techniques represent the other case encountered in solid layer melt
crystallization equipment. Here, the feed melt is simply filled into the equipment and
there is no movement of the feed melt apart from natural convection. Figure 12 shows
an example of a static solid layer melt crystallizer employing cooled plates rather than
cooled pipes. Static processes require slower crystallization rates and therefore higher
volumes in order to achieve the same product purity and the same production rate as
falling film equipment, but are cheaper to implement and run, as no additional
equipment such as a circulation pump is required. The role of the wash column used in
suspension crystallization is replaced by washing, rinsing or sweating in the case of
solid layer crystallization. Once the crystallization process is sufficiently advanced, the
residual melt is drained and replaced by a purer washing liquid in the case of washing or
rinsing steps.
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Figure 12: Sketch of a simple static melt crystallizer. The cooled plates can be seen in
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the interior of the crystallizer, inlets and outlets for feed/product and cooling medium
are highlighted. Sketch kindly provided by Sulzer Chemtech Ltd, Switzerland.
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In the case of sweating, the crystalline layer is heated to close to the melting point of the
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pure substance in the absence of a washing liquid, in order to drain any impurities or
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inclusions. All of these post-crystallization techniques lead to purer products and are
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frequently employed. Further details on post processing steps can be found in the books
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separation is easily achieved in such equipment, that there is no handling of solids and
that the equipment is easy to scale-up. As a result the technology is competitive in terms
of market value. For suspension crystallization techniques the advantages and
disadvantages are reversed compared to solid layer techniques. General rules for the
selection of the one or the other technique are still not available and a decision as to
which technique is more suitable for a given problem must be made on a case-to-case
basis.
Glossary
Critical cluster A measure of the size of a crystal nucleus required to grow into
size: an energetically stable crystal.
Growth: The process by which crystal nuclei increase in size and develop
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polymorph and will display different physical properties.
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Phase diagram: A graphical representation of the state of a system (existence of
distinct phases) depending upon selected physical parameters.
Solubility: A measure of the amount of solute that can dissolve in a given
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Supercooling:
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A measure of the deviation of the system temperature from the
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equilibrium temperature.
Supersaturation: A measure of the deviation of the solution concentration from
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Biographical Sketches
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Joachim Ulrich received the Diplom-Ingenieur degree from the Technical University Clausthal-
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Zellerfeld in Germany, the Dr.-Ing. from the Rheinisch-Westfälische Technische Hochschule Aachen and
the Habilitation from the Universität Bremen. He has held a post-doctoral position at the Waseda
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University, Tokio, Japan and in 1999 was appointed chair of thermal process engineering at the Martin-
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Matthew Jonathan Jones received the Diplom-Chemiker degree from the Westfälische Wilhelms-
Universität Münster in Germany and the PhD from the University of London (University College), UK.
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After post-doctoral positions at the University of St. Andrews and Heriot-Watt University, Edinburgh and
a teaching fellowship at the University of Leeds, he took up the position of senior scientist in the thermal
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