966 II / CRYSTALLIZATION / Melt Crystallization

Melt Crystallization
P. J. Jansens, Delft University of Technology, melt crystallization entirely depend on its solid}liquid
The Netherlands phase equilibrium (SLE). A survey of SLE data in
M. Matsuoka, Tokyo University of Agriculture and 1986 demonstrated that more than 70% of organic
Technology, Japan substances have melting points between 03C and
Copyright ^ 2000 Academic Press 2003C, indicating that no special thermal media are
needed to achieve separation (Figure 1).
The classiRcation of about 1500 binary systems in
the International Critical Tables (Figure 2) has re-
Introduction vealed that more than 50% form simple eutectic
Melt crystallization, sometimes referred to as frac- mixtures and 25% form an intermolecular solid com-
tional crystallization, is a collective term for physical pound which forms simple eutectics with the two
separation processes aimed at puriRcation of organic constituent components. This type also includes the
compounds from a multi-component mixture by crys- formation of more than two solid compounds. The
tallization without addition of a solvent. The driving formation of a pure solid phase in one crystallization
force for crystallization is created by cooling, evapor- step is feasible for roughly 85% of the systems. The
ating or pressuring the melt. formation of solid-solutions is limited to only 10%,
The main advantage of this separation technique is for which complete separation in a single crystalliza-
the superior selectivity of the crystallization process tion step is fundamentally impossible.
caused by restricted mobility in the crystal lattice and Even for eutectic systems, however, the product
strong molecular bonds. The energy consumption can from industrial crystallizers is not 100% pure. This is
be low because the heat of fusion of most organic caused by the adherence of mother liquor to the
compounds is two to four times smaller than their heat crystal surface and by the inclusion/entrapment of
of evaporation and the operating conditions are gener- mother liquor inside the crystals. Further puriRcation
ally mild. Finally, the absence of hazardous solvents is is required and this can be achieved by washing and
important from an environmental point of view. Dis- by sweating.
advantages are the inherent slowness of crystal growth
E Washing is done by contacting the crystals with
leading to voluminous equipment and the need for
a fresh solvent or, preferably, with pure melted
intensive slurry handling in certain process designs.
product. This operation removes adhering impu-
Balancing the merits and drawbacks, melt crystalli-
rities and is widely used in commercial plants.
zation is usually applied for ultrapuriRcation
E Sweating can be induced by exposing the impure
('99.99%), separation of isomers and puriRcation
solid phase to slightly elevated temperatures. This
of thermally unstable components. Some examples of
operation removes locally dispersed included im-
industrial applications are acrylic acid, bisphenol A,
purities. Upon a temperature increase, the fraction
caprolactam, cresol, dichlorobenzene, fatty acids,
of liquid inside the crystals increases according to
naphthalene, parafRn and xylene.
the lever-rule whereby the more impure sections
In this chapter, the designs of conventional and
emerging melt crystallization processes are described
and evaluated. Also the related Reld of freeze-concen-
tration of aqueous solutions is brieSy touched upon.
Extensive coverage of all types of equipment on dif-
ferent scales is beyond the scope of this article. There
is a focus on large-scale applications with a bias on
state-of-the-art equipment provided by equipment
manufacturers rather than the proprietary processes
of end-users. More elaborate overviews of the prin-
ciples and applications of melt crystallization are
given in the Further Reading.

Theory
The technical feasibility and economic viability of Figure 1 Distribution of atmospheric melting points of organic
separation and puriRcation of an organic mixture by components (after Matsuoka and Fukushima, 1986).
 II / CRYSTALLIZATION / Melt Crystallization 967

Figure 2 Distribution of binary phase diagrams of organic mixtures (after Matsuoka and Fukushima, 1986).

melt preferentially due to a lower melting point. Industrial layer growth equipment is normally
The impure liquor comes out of the crystalline operated batch-wise, whereby static and dynamic
body through cracks and pores. Sweating can also processes can be distinguished. In static equipment,
be applied to solid solution systems and plays an crystal growth occurs from a stagnant melt. Commer-
important role as a puriRcation mechanism in layer cial equipment is manufactured by BEFS Technolo-
and suspension growth processes. gies (France) and Sulzer Chemtech (Switzerland).
Their similar designs feature a closed rectangular
vessel equipped with a high heat-exchange area in the
Process and Equipment Design form of Rnned tubes or structured plates (Figure 3).
Indirect cooling is the most widely applied technique One full operating cycle takes about one day and
to produce crystals from a melt. In this context the comprises Rve steps: (1) Rlling of the vessel, (2)
term indirect refers to the mechanism of heat trans- crystallization by programmed cooling, (3) sweating
fer from the melt to the cooling medium, which takes by gradual heating, (4) draining of residual mother
place via the wall of a heat exchanger. Crystal growth liquor and (5) melting and draining of the product
may either take place as a layer on a cooled surface or layer. Equipment sizes range from 0.1 to 35 m3.
freely suspended in the mother liquor. The principles Typical growth rates are in the order of 10\6 m s\1
of both techniques and their large-scale applications but the overall separation efRciency of a full operat-
are discussed below. See Table 1 for an overview and ing cycle is relatively good (up to 99.9 wt% product
an evaluation of both techniques. purity).
In dynamic processes, there is forced mixing of the
mother liquor during the crystallization step. The
Layer Growth
mixing is usually achieved by circulating the liquor as
In this technique the crystals grow as a layer Rxed and a falling Rlm or as a fully developed Sow over vertical
perpendicular to a cooled wall. The heat of crystal- heat-exchanger tubes. Other designs whereby mixing
lization is removed through the crystal layer and the was achieved by stirring, pulsation or bubbling-
wall. At low growth rates (typically(10\7 m s\1) through an inert gas, were not successfully commer-
and proper mixing of the mother liquor, a stable cialized. Sulzer Chemtech provides the dynamic
crystal morphology can be maintained, which results falling Rlm system whereby both the melt as well as
in a good selectivity of the crystallization step. In the coolant are circulated as falling Rlms over the tube
industrial practice, however, very high growth rates wall (Figure 4).
(10\6}10\5 m s\1) must be applied leading to The turbulent Sow regime of the mother liquor
roughening of the crystal surface (cellular and den- enhances heat and mass transfer, which enables
dritic growth) and consequently to entrapment of higher growth rates of typically 10\6}10\5 m s\1.
impure liquor in the layer. High growth rates are Similar to the static process, one full operating cycle
required to achieve a reasonable productivity since comprises Rve stages but is completed in 1.5 h. Tubes
the growth area is limited to the heat-exchange area are about 0.1 m in diameter and 12-m long while up
(4100 m2 m\3). to 1250 tubes are Rtted in one shell.
968 II / CRYSTALLIZATION / Melt Crystallization

Table 1 Comparison of layer and suspension growth processes (values represent order of magnitude; operation/maintenance
relative to distillation)

Parameter Layer growth Suspension growth

Crystal surface area Up to 100 m2 m\3 Up to 10 000 m2 m\3

Growth rate 10\6}10\5 m s\1 10\8}10\7 m s\1
Mixing intensity Poor (static)/good (dynamic) Good
Separation efficiency Good (static)/moderate (dynamic) Excellent
Product purity in one stage 499.9% 599.95%

Mode of operation Repetitive batch Once through, continuous

Heat transfer coefficient &200 W m\2 K\1 &1250 W m\2 K\1
Energy efficiency Good (static)/moderate (dynamic) Good

Slurry handling No Yes

Solid}liquid separation No Yes
Design Simple Complex

Operational attention Normal Above average

Maintenance intensity Normal Above average

Scale-up Mutiplication of units Engineering

Economy of scale Not good Good
World-scale plant capacity &150 kT year\1 &350 kT year\1

Feed concentration Preferably '90% Preferably (99%

Viscosity (10 cP (50 cP
Purification of solid solutions Suitable Less suitable
Freeze concentration Less suitable Suitable

The overall separation efRciency of one dynamic ery. The stages are actually operating cycles which
operating cycle is moderate relative to a static process can be executed in the same crystallizer (Figure 5).
but the short cycle time makes the dynamic process One of the drawbacks of the dynamic process until
well suited to sequential countercurrent staging. Stag- now has been its poor energy efRciency resulting from
ing requires intermediate storage tanks but makes it the need to repeatedly crystallize and melt a product
possible to produce ultrapure products at good recov- to attain the desired purity. This problem was

Figure 4 Dynamic falling film crystallizer. (Courtesy of Sulzer

Figure 3 Static crystallizer. (Courtesy of Sulzer Chemtech.) Chemtech.)
 II / CRYSTALLIZATION / Melt Crystallization 969

speciRc productivity can be achieved at low growth

rates because the crystal surface area is very large (up
to 10 000 m2 m\3). Typical growth rates in industrial
units are only 10\8}10\7 m s\1 which contributes to
an excellent selectivity of the crystallization process.
Suspension growth processes generally comprise
separate sections for crystallization and solid}liquid
Figure 5 Multistage operation of layer growth processes (tem-
peratures T1(T2(T3).
separation. The effectiveness of the Rnal solid}
liquid separation has a major impact on the overall
separation efRciency. The design of the crystallization
addressed by the introduction of heat integration in section should be focused therefore on producing
1996. The principle is based on a heat pump where crystals with a good Rlterability which means essen-
a crystallizer alternatively acts as a condensor or as an tially growing large crystals with a narrow size distri-
evaporator for the cooling agent (Figure 6). bution. The fundamentals of modelling particulate
Continuous processes, whereby the layer growth processes are also applicable to suspension growth
occurs on a rotary drum or an endless belt, have been from the melt.
designed but are not applied commercially for puriR-
cation of organics for various reasons (low selectivity, Crystallization section Single-stage crystallization is
mechanical complexity, economy of scale). often unfavourable because the nucleation and
Static and dynamic layer growth equipment are growth of all crystals occurs at the lowest operating
applied commercially to a wide range of products temperature, which is determined by the yield, from
(e.g. acrylic acid, p-xylene, naphthalene, bisphenol an impurity-rich mother liquor. The simplicity of this
A and parafRn). A relatively high feed purity is re- design often does not outweigh the potential disad-
quired, particularly for the dynamic processes, since vantages:
this promotes the adhesion of the crystal layer to the
cooled surface. E poor Rlterability of crystals due to high nuclea-
tion : growth ratio;
E reduced selectivity due to inclusion or incorpora-
Suspension Growth
tion of impurities;
In this technique, the crystals form and grow freely E moderate energy efRciency;
suspended in the mother liquor. The heat of crystalli- E difRcult solid}liquid separation.
zation is absorbed by the supercooled liquor. High
Cascades of crystallizers, operated either cocurrent
or countercurrent, are found in most processes. In
cocurrent cascades crystals and mother liquor are
transported in parallel from stage to stage at decreas-
ing temperature. The GMF-CDC (Figure 7) is an
example of a cocurrent cascade, where the crystal
slurry Sows freely from one compartment to the next
via openings in the cooling elements. Along the Sow
direction, the impurities are concentrated in the
mother liquor but the nucleation rate and the crystal
growth rate decrease. As a result, the Rlterability of
the crystals improves throughout the cascade while
a good selectivity is maintained. The product crystals
suspended in the impure mother liquor are with-
drawn from the cold end of the cascade, which is
a major drawback for solid}liquid separation.
In countercurrent cascades crystals and mother
liquor are transported in opposite directions. TSK
(Japan) and Niro-PT (Netherlands) provide similar
countercurrent cascades, although the design of the
individual stages differs considerably (Figure 8; see
Figure 6 Heat integration of dynamic falling film crystallizers. also Figure 17). The feed is usually supplied to the hot
(Courtesy of Sulzer Chemtech.) end of the cascade making sure that here too a large
970 II / CRYSTALLIZATION / Melt Crystallization

Figure 7 Cocurrent cascade of crystallizers. (Courtesy of

GMF-Gouda.)

part of the crystal production occurs at high temper-

ature from a relatively pure mother liquor. PuriRca-
tion of the crystals by Ostwald ripening (growth of
large crystals by dissolution of Rnes driven by a reduc-
tion of surface energy) can play a role but it is doubt-
ful whether there is a contribution from sweating.
Product withdrawal occurs from the hot end, which
simpliRes solid}liquid separation. Figure 8 Countercurrent cascade of crystallizers. (Courtesy of
A comparison of cocurrent and countercurrent Tsukishima Kikai Co. (TSK).)
crystallizers is shown in Table 2.

Solid}liquid separation section Product recovery is The crystal bed can be transported under gravity,
more and more executed in wash columns, which by hydraulic pressure or via a mechanical aid
combine an effective solid}liquid separation with (screw/piston). The direction of transport is normally
a pure melt wash and a single recrystallization step. downwards for organic crystals and upwards for ice.
The principle of wash columns is illustrated by Fig- If the temperature of the feed slurry is low (single-
ure 9. A crystal slurry is pumped into the column, stage or cocurrent cascade crystallization), more
where the mother liquor escapes via a Rlter leaving wash liquid will recrystallize causing a large drop in
behind the crystals as a packed bed. This bed is porosity over the wash front. At a given transport
transported upwards by means of a rotating screw. At force exerted on the crystal bed, the throughput re-
the top, the crystals are scraped off, suspended in duces with decreasing porosity due to an increased
wash liquid (recycled pure melt) and melted in an back-pressure from the wash liquid. Alternatively at
external melter. The wash-liquid circuit is kept press- constant throughput, the compressive stresses exerted
urized, which causes the wash liquid to Sow down- on the crystals increase considerably which may
ward (reSux). The wash liquid does not leave the result in deformation of some organic crystals, which
column but recrystallizes on the cold crystal bed, are mechanically weak. Ideally, the temperature in-
thereby producing the so-called wash front. This crease over a wash column should be 2}53C.
front marks steep gradients in concentration, temper- Mass and heat transfer in the wash columns are
ature and porosity. governed by axial dispersion of the liquid phase while

Table 2 Comparison of crystallization sections consisting of a single-stage, a cocurrent cascade or a countercurrent cascade

Parameter Single Cocurrent Countercurrent

Operating temperature Constant low Decreasing Increasing

Product withdrawal Cold Cold end Hot end
Product crystal filterability Moderate Good Good
Product liquor Impure Impure Relatively pure
Internal slurry handling None Limited Intensive
Equipment and process design Simple More complex Complex
 II / CRYSTALLIZATION / Melt Crystallization 971

Figure 10 Classification of wash columns based on the crystal

transport mechanism (after Jansens and Van Rosmalen, 1994).

Figure 9 Principle of wash column. (Courtesy of Niro-PT.) duction rate is limited by the capacity of the wash
columns (41500 kg m\2 h\1). A new development
heat-transfer limitation in the solid phase may be by Matsuoka is the inclined column crystallizer.
neglected. In the more densely packed hydraulic and The inclination promotes settling and reduced axial
mechanical wash columns, puriRcation occurs almost dispersion (Figure 11).
exclusively by displacement washing. In the loosely
packed gravity wash columns, further puriRcation by Alternative Process Designs
sweating occurs because of the longer residence time.
Gravity and mechanical wash columns have been Evaporative Melt Crystallization
commercialized by TSK and Niro-PT, respectively. Direct cooling is the driving force for evaporative
TNO (Netherlands) has developed a hydraulic wash crystallization. The heat of crystallization is with-
column equipped with separate Rlter tubes. See Fig- drawn by evaporation of a portion of the mother
ure 10 and Table 3 for a more detailed comparison. liquor, which is induced by a reduction of the operat-
Suspension growth equipment is applied commer- ing pressure. The vapour phase is condensed in an
cially to purify various organic products (e.g. p- overhead condensor and reSuxed to the crystallizer.
xylene, naphthalene and p-dichlorobenzene) but also Crystal formation and growth take place freely sus-
for concentration of aqueous solutions (freeze con- pended in the bulk of the mother liquor. The main
centration, see below). There are virtually no restric- advantage of direct over indirect cooling is that the
tions on feed purity, while a product purity heat of crystallization is transferred to the cooling
599.99% is feasible. medium via a clean condensing duty rather than via
a (scraped) heat exchanger. Hence the heat transfer is
Column crystallizers Column crystallizers are de- more effective while the design and scale-up of equip-
signs where a single-stage crystallizer and a gravity- ment can be simpliRed.
wash column have been integrated in one shell In conventional evaporative crystallization pro-
(similar to distillation columns). The back- cesses, low boiling solvents (propane and carbon di-
mixing column, for example, has been successfully oxide) are used to crystallize heavier organic compo-
commercialized by Nippon Steel Chemical Co. nents but the addition of solvents is not desirable
(Japan) for the puriRcation of naphthalene. The pro- for various reasons (equipment size, safety and the

Table 3 Comparison of wash columns

Parameter Gravity Hydraulic Mechanical

Height : diameter ratio 4}6 1 1

Minimum crystal size 500
m 150
m 150
m
Residence time: whole column 1h 10}15 min 10}15 min
Residence time: wash section 30 min 3}5 min 3}5 min
Purification mechanism Washing and sweating Washing Washing
Maximum temperature rise 10}153C 5}103C 5}103C
Compressive stress Negligible Considerable Considerable
Capacity 500}1500 kg m\2 h\1 5000}10 000 kg m\2 h\1 5000}10 000 kg m\2 h\1
Scale-up Proven to 2 m Under study Proven to 1.2 m
Equipment design Simple More complex Complex
972 II / CRYSTALLIZATION / Melt Crystallization

shows the pressure temperature}fraction temperature

(PT}XT) phase diagrams where the three-phase equi-
librium curve (ScLV) stretches from the triple point of
caprolactam (Tc) to the quadruple point of the binary
system (Tq). Lowest operating cost can obviously be
achieved near 5 wt% water, where the operating pres-
sure is maximum and the temperature fairly high.
Deep vacuum would be required for water concentra-
tions below 1 wt% and above 20 wt%. Operating at
a high temperature generates cost savings for the
condensor (low area, no chilled cooling water).
Figure 14 shows the PT-trajectory for the batch-
wise crystallization of caprolactam from a melt con-
taining 4 wt% of water. Starting from point A, the
pressure in the crystallizer is reduced until the va-
pour}liquid equilibrium is reached at point B and the
melt starts to boil. Upon a further reduction of pres-
sure, the evaporation of mainly water causes the melt
Figure 11 Inclined column crystallizer. (A) Schematic pre- to cool down but the composition of the melt does
sentation of flows. (B) Experimental facility. (Reproduced with not change since the vapour is condensed and re-
permission from Matsuoka M, Takiyama H and Soutome O (1997) Suxed. At point C the solid}liquid}vapour equilib-
Separation characteristics of an inclined column crystallizer. rium is reached and caprolactam starts to solidify.
Transactions of the Institution of Chemical Engineers
75(A): 206}212.)
From C to D the crystal content steadily increases to
20 wt%, while the water concentration in mother
liquor increases to 5 wt%.
environment, product purity). The potential of ap- Scale-up to 50}100 m3 crystallizers appears to be
plying direct cooling to melt crystallization, however, feasible, which is world scale for suspension crystalli-
was not recognized until recently. zation equipment. Until now, there are few commer-
In 1993 TSK proposed a puriRcation processes cial installations with limited capacity. TSK has
based on evaporative melt crystallization for cap- installed two units for caprolactam with a capacity of
rolactam, acrylic acid and bisphenol A. Figure 12 2500 tons per year.
illustrates the set-up of a continuous process featuring
a single-crystallization stage and a wash column
Pressure Crystallization
(puriRer).
In recent years, a batch-wise evaporative melt-crys- In this technique, crystallization is induced by com-
tallization process with caprolactam}water as a model pression rather than by cooling. The solid phase of
system has been developed and optimized. Figure 13 most (organic) materials has a higher density than the
liquid phase and consequently the melting point rises
with increasing pressure. Benzene, for example, has
an atmospheric melting point of 5.53C but solidiRes
at room temperature when the pressure is about
2 MPa. Not only the melting points but also
solid}liquid phase equilibria shift upward upon
a pressure increase, which is illustrated for a mixture
of cresols in Figure 15.
An additional advantage of pressure crystallization
is found in the transmission of pressure being much
faster than the transfer of heat in both liquid and solid
phases. This means that a uniform pressure can be
established quickly throughout the system. Therefore
local variations in supercooling of the mother liquor
can easily be avoided.
Figure 12 Continuous evaporative crystallization. ML, mother
The separation of cresol isomers by conventional
liquor; Con., condensate; Prod., product; STM, steam; CW, cool- (atmospheric) cooling crystallization is rather difR-
ing water. (Courtesy of Tsukishima Kikai Co. (TSK).) cult due to a high viscosity of the melt. Kobe Steel
 II / CRYSTALLIZATION / Melt Crystallization 973

Figure 14 Part of pressure}temperature diagram of
-caprolac-

tam}water. (Reproduced with permission from: Diepen PJ (1998)
Cooling Crystallization of Organic Compounds. PhD thesis, Tech-
nical University Delft.)

Figure 13 Pressure}temperature}composition diagram of
-

caprolactam}water. Tt,i"triple point component i; Tq"quadru- E high yield, limited only by the solid}liquid equilib-
ple point; Tcrys"crystallizer temperature; Tcon"condenser tem- rium of a given system;
perature; Si, Li, Vi"solid, liquid, vapour phase component i; (LV)i, E short cycle times, only a few minutes per cycle, due
(SL)i, (SV)i liquid}vapour, solid}liquid, solid}vapour equilibrium to rapid penetration of pressure;
curves pure component i; x, y"liquid, vapour concentration
E low energy consumption } only mechanical energy
(wt%) at three-phase equilibrium; SiLV"three-phase equilibrium
line with solid phase of component i. (Reproduced with per- used for compression;
mission from Diepen PJ (1998) Cooling Crystallization of Organic
Compounds. PhD thesis, Technical University Delft.)

(Japan) developed in the 1970s a pressure-crystalliza-

tion process, which was applied for the separation of
p-cresol from its isomers on a commercial scale.
A given amount of slurry from a chiller is fed to
a cylindrical pressure vessel, compressed to crystallize
and drained to remove residual impure melt (Fig-
ure 16). During the subsequent depressuring, puriR-
cation by sweating can occur. Finally, a cylindrical
block of puriRed crystals is taken out as the product.
The operating temperature is 62.53C at 200 MPa
(versus 12.53C at atmospheric pressure) which
effectively reduces the viscosity of the mother liquor.
Under these conditions, the selectivity and the rate of
crystal growth rate are enhanced while solid}liquid
separation is facilitated. PuriRcation by sweating dur-
ing depressuring is analogous to (thermal) sweating at
elevated temperatures.
The features of pressure crystallization can be sum-
marized as follows:
Figure 15 Phase diagram of mixture of p-cresol and m-cresol.
E batch-wise operation; (Reproduced with permission from Yasuda M, Sato Y and
E product purity up to 99.5%, feasible in one operat- Suematsu H (1991) p-Cresol with high pressure crystallization.
ing cycle from 70 to 80% in feed; Kagaku Kogaku 55(4): 290}291.)
974 II / CRYSTALLIZATION / Melt Crystallization

Figure 16 Operating cycle of pressure crystallization process. (Reproduced with permission from Yasuda M, Sato Y and Suematsu
H (1991) p-Cresol with high pressure crystallization. Kagaku Kogaku 55(4): 290}291.)

E simple process design } crystallization, separation pension growth in terms of process synthesis and
and sweating are carried out in a single vessel; equipment design.
E complex mechanical design } materials selection Commercial processes feature a countercurrent cas-
and construction of mechanical parts are critical cade of crystallizers while the Rnal solid}liquid separ-
factors for success. ation takes place in mechanical wash columns (Fig-
ure 17). Indirect cooling is usually preferred over direct
The scale-up of pressure-crystallization equipment cooling to prevent contamination of the concentrate
is not easy due to mechanical complexity, and it and to contain the volatile components. Large spherical
becomes increasingly difRcult at larger vessel dia- ice crystals can be grown relatively easily through Os-
meters to remove residual melt from the centre of the twald ripening. The individual stages of the cascade
cake by compression. The production capacity of therefore feature separate sections for nucleation and
a single plant is in the order of 500 tons per year. growth. Crystallization (nucleation) takes place on the
surface of the external scraped surface heat exchangers.
Freeze Crystallization
Ripening (growth) occurs in large stirred vessels.
Freeze concentration is a separation technology Nearly identical process Sow schemes and equip-
aimed at concentration of aqueous solutions by ment designs can also be found in some melt-crystalli-
means of cooling crystallization. This technology is zation processes, e.g. to separate p-xylene from its
closely related to melt crystallization based on sus- isomers.

Figure 17 A three-stage countercurrent freeze concentration process. (Courtesy of Niro-PT.) (A) Simplified process flow scheme.
(B) Cross-section of a scraped surface heat exchanger. 3Bx is a measure for concentration of water phase (based on the breaking
index).
 II / CRYSTALLIZATION / Polymorphism 975

Traditionally, most applications are found in the speciRc productivity of crystal growth in a suspen-
food industry for the concentration of fruit juice, sion create a huge potential, which can be further
wine, beer and coffee extract. In this Reld, the advant- exploited by simpliRcation of equipment design
ages of freeze concentration over competing tech- and minimization of slurry handling.
nologies (membranes and evaporation) are the superb E Evaporative melt crystallization is a relatively young
preservation of aromas and colour while decay reac- technology which combines the merits of suspension
tions are slowed down by the low operating temper- growth with a minimum of slurry handling. For
ature. certain applications, such as caprolactam, this tech-
Recently, world-scale installations have come on- nique is expected to take off in coming years.
stream where wastewater from chemical plants is E Pressure crystallization is an alternative techno-
concentrated. The produced melt water can be re- logy, which is well suited to purify components
used as process water while the residual concentrate with a very low melting point at ambient temper-
is incinerated. Here the advantages of freeze concen- ature but elevated pressure. Outside this niche use,
tration are the low energy costs and the capability to pressure crystallization probably cannot compete
concentrate beyond the eutectic point, where salts with indirect/direct cooling crystallization due to
start to precipitate. high equipment cost.
Drawbacks of freeze crystallization are the rela-
tively high investment cost and the above-average See Colour Plate 36.
maintenance intensity (there are many pieces of
rotating equipment). Further Reading
Arkenbout GF (1995) Melt Crystallization Technology.
Basel: Technomic Publishing AG.
Conclusion and Future Outlook Jansens PJ and Van Rosmalen GM (1994) Fractional crys-
tallisation. In: Hurle DJT (ed.) Handbook of Crystal
Melt crystallization is the third most applied physical
Growth, Vol. 2A, ch. 6. Amsterdam: Elsevier Science.
separation technology after distillation and extrac- Matsuoka M and Fukushima H (1986) Determination of
tion. Conventional processes are based on layer or solid}liquid equilibrium. Bunri Gijutsu (Separation Pro-
suspension growth by indirect cooling. cess Engineering) 16: 4}10.
Matsuoka M, Takiyama H and Soutome O (1997) Separ-
E Layer growth may be considered as proven and ation characteristics of an inclined column crystallizer.
mature technology, whereby the absence of slurry Transactions of the Institution of Chemical Engineers
handling is a major advantage. Fully automated 75(A): 206}212.
semi-continuous units can be delivered as turnkey Moritoki M (1984) Crystallisation and sweating of p-cresol
projects. The need for repeated recrystallization by application of high pressure. Industrial Crystalliza-
steps to achieve a high product purity, however, tion 84: 369}380.
Randolph AD and Larson MA (1988) Theory of Particulate
increases both investment and operating cost. The
Processes, 2nd edn. San Diego: Academic Press.
desire to develop economically attractive continu- Sloan GJ and McGhie AR (1988) Techniques of Melt Crys-
ously operated equipment seems to be in conSict tallization. New York: John Wiley.
with the basic characteristic of layer growth on Yasuda M, Sato Y and Suematsu H (1991) p-Cresol with high
a cooled surface. pressure crystallization. Kagaku Kogaku 55(4): 290}291.
E Suspension growth is also proven but not yet ma- Zief M and Wilcox WR (1967) Fractional SolidiTcation.
ture technology. The superior selectivity and high New York: Marcel Dekker.

Polymorphism
M. R. Caira, University of Cape Town, Rondebosch, structure arrangement, the substance is said to dis-
South Africa play polymorphism. This phenomenon was dis-
covered in the early nineteenth century but only since
Copyright ^ 2000 Academic Press
the middle of the twentieth century have its wider
implications been appreciated by scientists investigat-
Introduction ing the crystallization, properties and interconversion
When the molecules of a chemical substance are able of solid phases. These implications stem from the fact
to crystallize in more than one three-dimensional that different polymorphs of a given substance may