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HEAT AND MASS TRANSFER OPERATIONS CRYSTALLIZATION
J. Ulrich and M.J. Jones TVT, Martin-Luther-Univ. Halle-Wittenberg, Germany Keywords: Industrial Crystallization, Solubility, Phase Diagrams, Nucleation, Crystal Growth, Polymorphism, Hydrates and Solvates, Crystal Habit, Crystallization Technology, Melt Crystallization. Contents
This chapter presents an overview of industrial crystallization both from a fundamental, scientific perspective and with an eye on the application of crystallization as a separation process in industrial processes. Crystallization as a separation process yields a solid product from a solution or a melt. The process itself, the product characteristics and the temporal behavior are determined by thermodynamics, i.e. solubility of the materials, and crystallization kinetics, respectively. The thermodynamics of solutions and melts are dependent on a range of physical parameters as discussed within. 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 process and are treated in detail below. Additional factors such as the effect of crystallization on product properties as well as the effect of solid-state properties on the crystallization process are discussed in section 4. Section 5 provides details on commonly used crystallizer designs and highlights the distinction between solution and melt crystallization. 1. Introduction Crystallization is a thermal separation, and therefore a purification process that yields a solid product from a melt, from a solution or from a vapour. As for all thermal separations, non-equilibrium conditions are required as a driving force for the process. Here, evaporation of solvent or temperature reduction (cooling) are the most frequent
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1. Introduction 2. Solid-Liquid Equilibria 3. Kinetics 4. Properties of Crystals 5. Crystallization Technology 6. References Glossary Bibliography Biographical Sketches To cite this chapter
CHEMICAL ENGINEERING AND CHEMICAL PROCESS TECHNOLOGY – Heat and Mass Transfer Operations – Crystallization - J. Ulrich and M.J. Jones
means employed to establish the required non-equilibrium conditions. Pressure can, in principle, also be used to enforce the non-equilibrium state necessary for a phase change. However, in industrial applications this parameter is most frequently kept constant. As a consequence, processes involving pressure change will not be discussed here. 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 (drowningout).Those type of crystallization processes often referred to as precipitation processes will not be covered here [Söhnel/Garside].
Crystallization is a highly selective process and operates at lower temperatures when compared to a separation by distillation for the same material. Melt crystallization has 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 an industrial separation process. On the one hand, many products are solids under ambient conditions, in particular in the specialty chemicals sector, in the pharmaceutical industry and in the manufacture of foods. On the other hand, the ability to manipulate, at a minimum, the macroscopic properties of crystals such as shape and size by judicious choice of crystallization conditions makes the technique a very attractive option in those industry sectors already mentioned, where reproducible product quality with well defined properties (flow properties, color, dissolution characteristics, 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)] In recent years a number of new monographs on industrial crystallization have appeared and these provide a good representation of the state of the art. A good overview of the developments in the field over the past 30 years can be gleaned from the proceedings of the International Symposia on Industrial Crystallization which take place at triennial intervals and are organised by the European Federation of Chemical Engineering (EFCE). [Mullin], [de Jong/Jancic], [Jancic/de Jong 1982], [Jancic/de Jong 1984], [Nývlt/Zacek], [Mersmann], [Rojkowski], [Biscans/Gabas], [Garside 1999], [Chianese], [Ulrich 2005]
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The main feature distinguishing crystallization from other thermal separation processes is the fact that it leads to a solid product. This is one of the key reasons why it lags 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 problems inherent in solids handling. Encrustation and the concomitant heat transfer problems, seizing of moving parts, generation of hazardous dust and the general 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 more widely appreciated. [Mullin], [Myerson], [Mersmann], [Tavare], [Jones], [Nyvlt/Ulrich], [Hartl], [Jancic/Grootscholten], [Ulrich 2002 (in Kirk-Otthmer)]
CHEMICAL ENGINEERING AND CHEMICAL PROCESS TECHNOLOGY – Heat and Mass Transfer Operations – Crystallization - J. Ulrich and M.J. Jones
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. Knowing the theoretical limits of a crystallization process as defined by the thermodynamics is only part of the picture, the other part is knowing what can be achieved in a finite and reasonable time scale and the information on this aspect of crystallization is contained in the process kinetics. Two processes are important in crystallization, both with their own characteristic 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 cases may be ill defined. In addition, further factors that influence the number and nature of particles obtained have to be considered in the design of mass crystallization processes. Whenever suspensions of crystals in solution are involved, attrition and agglomeration have to be taken into account. In this chapter only the “real” kinetic parameters, nucleation and crystal growth, will be discussed. 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 determine many bulk properties of a given crystalline material, such as dissolution rate, bio-availability, color, flow properties etc. A general overview of these properties will also be provided. 2. Solid-Liquid-Equilibria
This section provides an overview of solid-liquid equilibria and the type of information 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. 2.1. Solubilities and Phase Diagrams A solution is a homogeneous mixture of two or more chemical species. For a liquid solution saturation is reached when the liquid phase, in contact with the solid phase, no longer changes its composition. A saturated solution therefore has a constant composition that is not changed by the addition of further amount of the dissolved material. For a two component system, the solubility of one component in the other is dependent on temperature and pressure. For three and more component systems the
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for the first two cases. is shown. In the following the discussion will focus on two component systems only. Jones solubility of one component also depends on the relative amounts of the other components present. The solubility of most materials increases with temperature. The dependence of the solubility upon temperature is best represented graphically in the form of a solubility curve. Various measures of composition are in use to report solubilities and the use of a particular set of units should be carefully selected to suit the purpose the data are required for. Solubilities are determined experimentally and any convenient analytical technique that provides a quantitative measure of composition can be employed. two hydrates and one anhydrous phase. temperature dependence.J. which maps the composition of a solution at the solubility limit onto the temperature. where the solubility shows the reverse trend (sodium sulfate. solvates and hydrates (vide infra) generally have different solubilities. iron sulfate dihydrate. It is common terminology for solutions of solids in liquids to denote the liquid component as the solvent and the solid component as the solute. Ambiguity arises if this is not accounted for. The most common measures are ! ! ! ! ! From the above list it is clear that. 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.CHEMICAL ENGINEERING AND CHEMICAL PROCESS TECHNOLOGY – Heat and Mass Transfer Operations – Crystallization . A change in solid form is normally evidenced by a discontinuity in the solubility curve. The solubility is a continuous function of temperature for a given form of a given material. as many substances can exist as solvated or unsolvated solids (vide infra). to name but a few). However. even if the amount of solute in the solution exceeds the amount of solvent. 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). of the solubility of the respective forms. A generalized solubility curve is shown in Figure 1 below. Moreover. a number of examples exist. it has to be stated explicitly whether composition reported refers to the solvent or the solute in order to avoid confusion. that is. which results from different slope.J. 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. The solubilities of the respective stable phases are indicated by the solid line. Ulrich and M. For example. In Figure 1 the solubility of a fictitious substance A that forms three phases. the solubilities of the different metastable forms are indicated by the dotted line. However. Not every technique ©Encyclopedia of Life Support Systems (EOLSS) N ES SA C M O PL -E E O C LS H AP S TE R Mass of solute per unit mass of solvent (kg/kg) Mass of solute per unit mass of solution (kg/kg) Mass of solute per unit volume of solvent (kg/m3 or g/L) Molar amount of solute per unit volume of solvent (kmol/ m3 or mol/L) Mole fractions (dimensionless number) U . In addition. Polymorphs of the same material. the temperature dependence (and also the pressure dependence providing the difference is sufficiently large. calcium carbonate. it is often necessary to mention the initial state of the solute. two solutions of sodium carbonate in water will have different compositions if in one case the decahydrate is used as starting material and in the other the same mass of monohydrate is employed.
it is important to ensure that the solution is indeed in equilibrium.J. This is particularly important in the case of highly concentrated. 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 given mass of the solution. Figure 1: Typical solubility diagram showing the dependence of solution phase concentration in equilibrium versus temperature. the dashed line represents the solubility of the respective metastable phases. (from [Nordhoff]). evaporating to dryness and weighing the remaining solid (solubility measurements should always be based upon a mass of solution due to the higher accuracy compared to volume measurements). the more difficult it becomes to accurately determine the composition by a single analytical technique. One method to assess whether equilibrium has been reached is to take measurements from two solutions. The full line represents the solubility of the stable phase in a given region. The more components present and the more complex the system.CHEMICAL ENGINEERING AND CHEMICAL PROCESS TECHNOLOGY – Heat and Mass Transfer Operations – Crystallization . A number of factors have to be accounted for when determining solubilities. Here it is important to provide good agitation and to allow for sufficient time before taking a measurement.J. the other where saturation is approached from ©Encyclopedia of Life Support Systems (EOLSS) N ES SA C M O PL -E E O C LS H AP S TE R U . Transition points between different phases are highlighted. viscous solutions where dissolution rates may become vanishingly small the closer one approaches the equilibrium composition. one where saturation is approached from an undersaturated state. First and foremost. Ulrich and M. Jones is suitable for every situation and the decision as to which method is used has to be made on a case by case basis.
Both compositions should be identical within experimental error limits if equilibrium has been achieved. The value of knowing the equilibrium properties of solutions lies in the fact that they dictate the operating conditions for the crystallization process. As is the case for solubility. the relative supersaturation $ # "c / c* # S -1 For melts. the ratio of these two concentrations S # c / c*. see section on kinetics below) increases with increasing supersaturation. Jones a supersaturated state.% . As mentioned above the supersaturation is a measure of the driving force for the crystallization process. be heated) or by evaporation of solvent. Such solutions are called supersaturated solutions and the region of phase space where supersaturated solutions exist is known as the metastable zone. Of course the real yield of the process may differ from the theoretical yield. the driving force is usually expressed in terms of the supercooling "% = % * . and. which represents the difference between the equilibrium temperature of the melt % * and the actual temperature % . Occasionally supercooling also finds use in solution crystallization. that crystallization can only occur at solution compositions where the amount of solute exceeds the solubility limit. As the supersaturation decreases.J. most commonly by cooling a saturated solution (for solutes where solubility increases with temperature. 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.c * . The driving force for crystallization (both nucleation and crystal growth. The driving force required for nucleation and crystal growth is the level of supersaturation in the solution (supercooling in melts). The second reason concerns the theoretical yield of the process. several measures exist to express supersaturation. This means. This definition already accounts for any temperature gradients employed in the process.CHEMICAL ENGINEERING AND CHEMICAL PROCESS TECHNOLOGY – Heat and Mass Transfer Operations – Crystallization . On the other hand. yields ©Encyclopedia of Life Support Systems (EOLSS) N ES SA C M O PL -E E O C LS H AP S TE R (1) (2) (3) (4) U . relating these two. crystal growth rates also decrease and the theoretical yield will only be reached in the limit of infinite time. Quantifying the supersaturation is important for two reasons. At this point it is important to stress that crystallization is a non-equilibrium process. of course. The consequence of this is a lower yield than possible. solutes with reverse temperature dependence must. Ulrich and M.J. These are the difference between the equilibrium composition at the temperature of the supersaturated solution c * and the actual composition in the supersaturated solution c "c # c . Supersaturation can be achieved in a number of ways.
. ©Encyclopedia of Life Support Systems (EOLSS) N ES SA C M O PL -E E O C LS H AP S TE R Figure 2: Stages of stability in solution crystallization (from [Strege]) U . In other words it is defined by those points where the induction time for nucleation vanishes. This can be achieved by optical methods such as turbidity measurements or ATR-FTIR (attenuated total reflectance Fourier transform infrared spectroscopy). or by measuring any other easily measurable physical parameter such as density or conductivity. The Metastable Zone Another important non-equilibrium property of a supersaturated solution is the width of the metastable zone. Ulrich and M. agitation etc. the best method has to be determined after careful consideration of the individual system. by measurement of acoustic properties of the solution (ultrasound). cooling or evaporation rate. The maximum width of the metastable zone is given by those concentrations where instantaneous nucleation occurs once the corresponding temperature has been reached. Unfortunately there is no single analytical technique that is suitable for all substances.J. purity of the solution.CHEMICAL ENGINEERING AND CHEMICAL PROCESS TECHNOLOGY – Heat and Mass Transfer Operations – Crystallization .2. The metastable zone width can be measured by determining the point at which first crystal nuclei are detectable. Jones 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. the metastable zone width is an ill-defined quantity and depends upon time. The metastable zone limit denotes the composition of the solution at a given set of conditions where the solution becomes labile and at which point spontaneous nucleation must occur (vide infra). 2. All points with finite induction times lie within the metastable zone.J. Since nucleation is a kinetically governed process and can be induced by different mechanisms.
The line at tind # 0 defines the limit of the metastable zone. peritectic or compound forming systems) the authors refer to the books by [Walas]. For a binary system only three parameters are required to define the state of the system. However. Both phases coexist only in the region circumscribed by the solidus and liquidus lines. a temperaturecomposition (T-x) diagram is more useful. respectively. The region above the liquidus line is the region of stability of the liquid phase. theoretical yields. Here. Phase diagrams can be represented graphically using any combination of physical variables. it is only this difference of composition that allows the separation of the components from the melt. They are useful for determining equilibrium temperatures. Indeed. Figure 3 shows a generalized ideal temperature composition diagram. temperature and composition. stability regimes of particular phases and the magnitude of the driving force for a given system under given conditions [Ulrich 2003]. In melt crystallization it is not particularly helpful to talk about solubilities. The region below the solidus line is the region where the solid phase is stable and no liquid phase exists. Ulrich and M. The only distinction between a solution and a melt is then the fact that. the equilibrium temperature is plotted against the composition of the solid and the liquid phase. solubility curves are part of the solid-liquid phase diagram and therefore contain the same information. given the fact that the pressure dependence of the solid-liquid equilibrium is usually negligible under ambient conditions. Phase Diagrams for Melt Crystallization A melt is normally understood to be a liquid close to its solidification point. 2. the other the composition of the liquid phase (liquidus). Pressure-temperature diagrams are useful for determining regions of existence of stable modifications. the composition of the solid phase at a given temperature is different from the composition of the liquid phase and the T-x diagram therefore consists of two lines separating three regions in phase space. at least one major component (the solvent) is liquid under ambient conditions. There are a number of types of typical solid-liquid phase diagram representing ideal and different non-ideal behaviors.J. for example. [König].3. usually expressed in terms of mole fractions. ©Encyclopedia of Life Support Systems (EOLSS) N ES SA C M O PL -E E O C LS H AP S TE R U . In the case of the Tx diagram. In principle. For other types of solid-liquid phase diagrams (for example eutectic. In terms of understanding the “possibilities” of a melt crystallization process.CHEMICAL ENGINEERING AND CHEMICAL PROCESS TECHNOLOGY – Heat and Mass Transfer Operations – Crystallization . for the solution. pressure. One of these lines represents the composition of the solid phase (solidus). The discussion here will be restricted to an ideal binary system in order to illustrate pertinent points.J. at higher concentrations of solute at constant temperature the solution is labile. Usage of the term in terms of industrial crystallization is not quite as rigid and encompasses any homogeneous liquid mixture where all major components as individual entities would solidify above ambient temperature. Jones Figure 2 shows a generalized solubility diagram which includes the metastable zone width for different induction times (cf [Mersmann 2001]). solidliquid phase diagrams are the more appropriate point of reference. For an ideal binary system where solid and liquid are in equilibrium. at high pressures pressure can be used to direct a crystallization process in much the same manner as temperature at lower pressures (see [Moritoki]).
Ulrich and M. depending upon the exact starting composition. two regions of coexistence. Figure 3b illustrates this point: starting from a composition xF the temperature is lowered to T& corresponding to point of solidification at the initial composition of the melt. On the right the progress of a crystallization process beginning at a composition F is shown (see [König (in Ulrich/Glade)]). 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. employing the lever rule shows that the solid yield at this point is zero. the composition of the solid is given by xS' and the composition of the liquid phase is xl' . Jones Figure 3: Solid-liquid temperature-composition (Tx) phase diagram for an ideal binary system. The eutectic phase diagram is characterized by four regions. The relative proportions of solid and liquid is given by the ratio of the lengths of the lines R and C. and an ©Encyclopedia of Life Support Systems (EOLSS) N ES SA C M O PL -E E O C LS H AP S TE R 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). 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 . U . the composition of the product at a given final temperature of the process is independent of the starting point.J. Figure 4 shows a simple eutectic phase diagram. The corresponding solid composition is determined by the intersection of the tieline at T& with the solidus line and is represented by xS& . For a crystallization process. the homogeneous liquid. which represents the most common phase behavior of binary organic systems (about 85% of all known organic binary systems are eutectic or pseudo-eutectic). However.J. On the left the three regions of phase space separated by the solidus and liquidus lines can be seen.CHEMICAL ENGINEERING AND CHEMICAL PROCESS TECHNOLOGY – Heat and Mass Transfer Operations – Crystallization . The tie line is a horizontal line (that is a line at constant temperature) that connects the liquidus and the solidus lines. the yield of the solid phase will differ and can be determined by the leverrule. At the final temperature T' . However.
Ulrich and M. no purification is achieved as the liquid and the solid have the same composition [König (in Ulrich/Glade)]. the region to the right of the eutectic point. The two regions of coexistence are separated by the eutectic point. where only pure component B is obtained. pure B cannot be crystallized. which is defined by the minimum in the liquidus curve and where the solid and the liquid have the same composition. In the case of a liquid with composition F2. The right-hand diagram indicates the different outcomes of crystallization from different starting points. 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). for a liquid of composition F3 pure B is obtained together with the eutectic solid. ©Encyclopedia of Life Support Systems (EOLSS) N ES SA C M O PL -E E O C LS H AP S TE R Figure 4: Simple eutectic phase diagram. the yield is no longer a function of the initial composition of the melt alone. the yield decreases. Eutectic behavior has important implications for crystallization. On the left the four regions are shown with their respective phases. no separation is possible as the solid composition is the same as the composition of the liquid. In contrast to the ideal solution.J. For a melt with eutectic composition. in a single separation step. U . describes a system consisting of pure solid B (S2) and the liquid phase. Starting with a melt composition to the left of the eutectic point (F1) yields only pure component A.CHEMICAL ENGINEERING AND CHEMICAL PROCESS TECHNOLOGY – Heat and Mass Transfer Operations – Crystallization . The coexistence region to the left of the eutectic point describes a system consisting of pure solid A (S1) and the liquid phase. in this case a pure component can be obtained. Moreover. it also depends upon the position of the eutectic point in the phase diagram. conversely. For a liquid of composition F1 one obtains pure A and a solid with eutectic composition. Jones 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 detailed discussion of phase diagrams we refer to [König (in Ulrich/Glade)].J. inhomogeneous two-phase solid consisting of pure component A and pure component B. in an ideal case. Whereas in the case of an ideal solution described above any degree of purity can be achieved given sufficient separation stages (the number of stages required to obtain a pure substance is infinite). [Walas].
above the critical radius growth is more favorable as this leads to a reduction of the excess free energy. The critical radius is a measure of the critical nucleus size and is determined by the maximum in the excess free energy curve. critical. these nuclei have to reach a certain. ordered collections of the crystallizing species. The surface excess free energy is proportional to the square of the radius of the particle and is a positive quantity. size. is given by the sum of the surface excess free energy "GS and the volume excess free energy "GV of the particle (Figure 5). Kinetics 3. Nucleation Given a sufficient driving force. the volume excess free energy is a negative quantity and is proportional to r3. The critical nucleus size is governed by the excess free energy "G of the nucleus which.J. Figure 5 shows a qualitative plot of these different quantities. that is supersaturation in the case of solutions or supercooling in the case of a melt. These clusters. are precursors to the crystals eventually formed. In order to grow into a macroscopically detectable crystal.J. a liquid-to-solid phase transformation commences with the initial formation of clusters. Below the critical radius redissolution of the nucleus is energetically favorable as evidenced by the slope of "G.1. ©Encyclopedia of Life Support Systems (EOLSS) N ES SA C M O PL -E E O C LS H AP S TE R Figure 5: Gibbs free energy versus radius of the nucleus U . or nuclei.CHEMICAL ENGINEERING AND CHEMICAL PROCESS TECHNOLOGY – Heat and Mass Transfer Operations – Crystallization . in turn. Jones 3. Ulrich and M.
Jones However. dispersion and circulation of solids) and to transport the suspension. The key power input sources are pumps and impellers. Secondary nucleation rates can be controlled via diameter and tip speed of the impeller blade. crystallization processes. A prerequisite for this behavior is that the growing crystal already has a size larger than the critical nucleus Collision breeding is the most frequently observed and dominant secondary nucleation mechanism. unless measures are taken to reduce the power input into the crystallizer. More important than the magnitude of the power input itself is the means by which the power is brought into the equipment. secondary nuclei are formed by the removal of structured assemblies from the surface of the crystals. As a rule. There are two aspects to secondary nucleation. and these are where most secondary nuclei are produced. Surface roughness of the equipment also falls into this classification. which will occur if the system is free of impurities. The negative aspect is the fact that many more secondary nuclei are produced in an uncontrolled process than are required. Mechanical disturbances result from agitation of the solution or vibrations from ancillary equipment.CHEMICAL ENGINEERING AND CHEMICAL PROCESS TECHNOLOGY – Heat and Mass Transfer Operations – Crystallization . The positive aspect results from the fact that without secondary nucleation as a permanent source of new crystal nuclei.J. mechanically undisturbed and when the thermodynamic non-equilibrium is at or beyond the metastable limit. or crystal-stirrer (-pump) collisions fluid shear: nuclei result from clusters or outgrowths being forced from the solidliquid boundary layer due to shear forces resulting from liquid motion. these are: ! ! ! 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 the crystals collision breeding: nuclei result from fragments of existing crystals which are broken off due to mechanical impact on crystal faces due to crystal-crystal. at least in the majority of industrial.J. Secondary nucleation requires the presence of crystals of the material to be crystallized and occurs at much lower supersaturation than primary nucleation. crystalwall. ©Encyclopedia of Life Support Systems (EOLSS) N ES SA C M O PL -E E O C LS H AP S TE R U . As a result a very fine crystalline product is produced. The most frequently observed nucleation mechanism is called secondary nucleation. Lower tip speeds and larger diameters result in lower secondary nucleation rates. Under normal circumstances there are always impurities in the solution or melt. The more realistic situation is therefore the case of primary heterogeneous nucleation which occurs at a much lower supersaturation and where impurities or rough vessel walls function as nuclei. different nucleation mechanisms exist [Strickland-Constable] and the discussion above applies to primary homogeneous nucleation. Power is required to homogenize the suspension (temperature and concentration. mass production. or particulate impurities such as dust or particles resulting from abrasion from the equipment. a continuous crystallizer with continuous crystal withdrawal would rapidly experience a lack of growing crystals. Ulrich and M. There are different mechanisms which lead to those secondary nuclei. In real life this situation is only rarely achieved. be they other chemical species such as by-products from synthesis.
that all fines smaller than a given particle size passing though this loop are redissolved. 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. In all the other cases a fines trap has to be introduced to the crystallizer. individual growth rate (this phenomenon is called growth rate dispersion). Ulrich and M. In order to conduct the seeding correctly it is necessary to have a deeper understanding of the system than merely knowing the right supersaturation (which differs for each system). On the other hand the seeds should be small enough and low enough in number to produce the desired amount ©Encyclopedia of Life Support Systems (EOLSS) N ES SA C M O PL -E E O C LS H AP S TE R U .J. respectively. as it will not always occur at precisely the same supersaturation: primary heterogeneous nucleation depends on the number and the nature of the impurities and is therefore. Nucleation is also a problem concerning the start-up of a crystallizer. Assuming that nuclei start to grow at high supersaturation. a random event. the seed state (dry or in suspension) and finally where in the crystallizer the seeds should be added. Here it is important always to introduce the seed crystals at the same supersaturation. providing the supersaturation selected coincides with the optimum growth rate for the system under consideration. which is ultimately responsible for the reduction in supersaturation. Jones 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). A fines trap consists of an additional loop within the crystallizer in which the conditions are such. The optimum growth rate is either determined from laboratory tests guided by the rule that a crystallizer should run under such conditions that the concentration in solution remains at the centre of the metastable zone [Hofmann in Hofmann]. In addition. [Doki].CHEMICAL ENGINEERING AND CHEMICAL PROCESS TECHNOLOGY – Heat and Mass Transfer Operations – Crystallization . relevant factors are the seed mass. All of these phenomena lead to poor product purity and quality. In general not all nuclei will grow fast enough to become product size particles due to the fact that each crystal has its own. Some general rules can be stated for seeding [Beckmann]. secondary nucleation by means of seeding is the preferred method of inducing the crystallization process. In some cases small particles will agglomerate. [Warstat/Ulrich]. either as an internal or an external design feature. As a consequence reproducibility of product quality cannot be guaranteed and the performance of the crystallizer will vary. seed surface quality (perfect or irregular). In order to produce high quality crystals in a reproducibly manner. In addition. Keeping the driving force (the supersaturation) constant subsequent to seeding normally results in high quality crystals. otherwise a bimodal crystal size distribution will result. If nucleation commences at a too low a supersaturation. as well as massive formation of small particles that tend to agglomerate. [Heffels/Kind]. the ensuing crystal growth may be slow and will pose a problem with respect to production time or crystallizer size.J. this may lead to strong tendency for caking in storage. within certain limits. Primary nucleation is difficult to control and unreliable. seed size. other measures may have to be taken to control the product. liquid inclusions or dendritic growth (vide infra) are likely. In order to maintain constant growth rates requires good control of the supersaturation and has to take into account the constantly increasing crystal surface area.
v. fluid flow conditions. 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. A properly carried out seeding procedure together with a good control strategy for the supersaturation and an optimised. The crystal growth rate is a physical property of a given material. history of the crystals. 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 ©Encyclopedia of Life Support Systems (EOLSS) N ES SA C M O PL -E E O C LS H AP S TE R As for nucleation. 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 employed. Each of these growth rates can be converted to the others. t the time. However growth rates depend not only on the temperature. 3. Choosing too large a seed crystal size leads to a low yield. Crystal growth rates are of key importance to the engineer since they determine the retention time and therefore the size of the crystallizer.2. U . the nature of the surfaces of crystals and the presence or absence of additives (impurities) in the mother liquor. R. providing the shape of the crystals remains constant during crystal growth. Ulrich and M. Since crystallization is a heat and mass transfer process.J. Growth rates are also measured in terms of mass increase per surface area. or in terms of the displacement of a single crystal face. Crystal growth Linear growth rates for crystals grown from solutions (suspensions) are of the order of 10–7 to 10 –9 m s-1. A the surface area.CHEMICAL ENGINEERING AND CHEMICAL PROCESS TECHNOLOGY – Heat and Mass Transfer Operations – Crystallization . pressure and composition of the mother liquor but also on parameters such as supersaturation (under cooling). Different measures of growth rates are in use other than the increase of a characteristic length denoted by G. too many seed crystals lead to a small product crystal size. In that case the following equations hold: G # 2v # dL / dt # fs /(3 ( ( f v ) A)(dm / dt ) R (5) Here L is the characteristic length. crystal growth only occurs if there is a driving force as a result of non-equilibrium thermodynamic conditions. 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. three steps always have to be considered. ( the density and ( fs ) and ( f v ) the surface and the volume shape factor. respectively. which consequently means the investment costs. Jones of product in the process.J.
As a rule-of-thumb.J. Attrition of the crystals can be neglected in most cases. for example. that an average growth rate for an assembly of crystals is required. Although individual growth rates for single crystals are informative in terms of determining the development of crystal shape (habit) during the growth process. Jones Although these three physical phenomena always occur. This limit coincides with a minimum thickness of the solidliquid boundary layer that determines the mass transfer. 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. The same mechanisms that apply to crystallization also apply to dissolution processes. due to the gentle operating conditions applied in of small fluidized beds. As a rule. supersaturation (supercooling) and the nature of the fluid flow in the vicinity of the crystal surface. [Ulrich 1989]. there exists a limit above which an increase in the flow velocity has no effect on the growth velocity. These individual rates can range from zero to a maximum growth rate characteristic for the material under consideration. However. the dissipation of the heat of crystallization can be neglected. individual face growth rates due to the factors discussed above. the growth velocity is greater the higher the temperature and the higher the supersaturation. 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]. Particles resulting from attrition. This phenomenon crystals displaying individual growth rates despite starting to grow under (nominally) identical conditions with respect to crystal size and growth environment is termed growth rate dispersion (GRD) [Ulrich 1993]. The perfection (or lack thereof) of the surface can influence the growth velocity in both directions. are normally dissolved in that part of the fluidized bed. ©Encyclopedia of Life Support Systems (EOLSS) N ES SA C M O PL -E E O C LS H AP S TE R U . The growth rate is measured monitoring the mass increase over time for a constant number of seed crystals of known size. methods providing access to mass growth rates utilizing either stirred tanks or fluidized beds are to be preferred for this purpose. should they be generated under the operating conditions selected. It is clear from the above discussion. either accelerating or suppressing crystal growth. At this point it should be stressed that each crystal has its own. Ulrich and M. Crystal growth rates depend upon temperature [Ulrich 1993]. one or the other may dominate the crystallization process. The nature of the crystal surface also plays a role in the growth rate and therefore the history of the crystals is an important factor. [Kruse]. 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. In melt crystallization the heat control is generally viewed as the rate determining step.J. where the solution is undersaturated. many crystals would have to be monitored in order to gather statistically significant information that incorporates. Therefore. The influence of the fluid flow is not quite as straightforward.CHEMICAL ENGINEERING AND CHEMICAL PROCESS TECHNOLOGY – Heat and Mass Transfer Operations – Crystallization . [Al-Jabburi]. the effect of GRD and is suitable for use in the design of industrial crystallization equipment. As a consequence and from the point of view of industrial crystallization it is important to collect relevant kinetic data.
As the available crystal surface area increases with growth of the crystals. Especially in the case of batch processes this requires permanent adjustment of the driving force. there exists enough experimental evidence that demonstrates that the liquid and its composition are of great importance in the crystal growth process. for the chemical engineer dealing with mass crystallization they are not of key importance. if the process is operated close to the solubility limit. In order to maintain good yields and high product purity it is desirable to maintain a constant supersaturation throughout the crystallization process.J. The previously mentioned increasing impurity concentration in the remaining mother liquor can not only change the thermodynamics of the system. a small fluctuation in the process variable is sufficient to induce nucleation. If the process operates close to the upper limit of the metastable zone. The ‘birth and spread’ model makes the assumption that growth occurs due to surface nucleation. Conversely. Further details can be found in the standard monographs cited above. For low supersaturation a quadratic dependence of the growth rate as a function of the supersaturation results which changes to a linear dependence at high supersaturation. This would result in a reduction of the crystal size distribution and facilitate oscillations in the of the crystallization process with respect to the output of crystal size distributions. an appropriate cooling or evaporation program must be employed. In some cases the accumulation of impurities may not only affect growth rates but may also influence the resulting crystal habit. These effects have to be understood ©Encyclopedia of Life Support Systems (EOLSS) N ES SA C M O PL -E E O C LS H AP S TE R U . 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. especially when the batch-time is nearing its end and the majority of impurities present have accumulated in the remaining mother liquor. Most crystal growth theories only consider the solid (crystal) and tend to neglect the influence of the conditions in the liquid. Industrial experience suggests that a solution crystallization process should best be operated at the centre of the metastable zone. Ulrich and M. In the case of batch crystallization in particular. [Myerson 2002]. Growth theories are discussed in detail in all standard text books on industrial crystallization [Ohara/Reid]. Neither natural or linear cooling/evaporation provide a constant driving force. Nonetheless. Here the supersaturation dependence of the growth rate is proportional to $ 5/6 . it is extremely important to verify that the laboratory scale crystallization leads to the same quality of product (purity and crystal growth rates). Jones However. insufficient mass per time is produced. [Jancic]. but can also exert a strong influence on the kinetics of crystal growth. 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 and well defined seed crystals.CHEMICAL ENGINEERING AND CHEMICAL PROCESS TECHNOLOGY – Heat and Mass Transfer Operations – Crystallization . [Mullin 1992]. the rate of reduction of supersaturation increases under linear or natural cooling (evaporation) conditions. [Ulrich 2002]. In order to maintain constant supersaturation. The BCF kinetic theory of growth considers the density dislocation leading to spiral growth on a crystal surface and the supersaturation.J.
For this reason the abovementioned terminology. Properties of Crystals 4. is unfortunate and these crystalline materials are better referred to as solvates or.J. This is particularly critical in industries where certain product properties (such as density. 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 processing. the other is common to the different materials. Frequently one substance has several different hydrate forms. liquids and gasses. However.J. Hydrates are often observed in inorganic salts. drying and packaging. bioavailability. Polymorphism has to be taken into consideration in the design of any crystallization process since different polymorphs will exhibit different physical properties as a result of their different crystal structures. in the case of integration of water. symmetry considerations dictate that only a limited number of structures exist in which a space-filling packing of building blocks is possible [Hahn]. or to a lethal dose in the worst case of too rapid dissolution. Unfortunately. the kinetics of transformation to the stable phase may be (infinitely) slow so that these additional crystal modifications must be treated as stable in the context of product properties and life-time. Jones prior to the design of a crystallizer in order to introduce appropriate control measures if required. screening is an important step in the development of a drug substance and polymorph control is essential during the development of a crystallization process: providing a patient the wrong polymorph of a given drug may lead to inefficacy in the best case. hydrates. dissolution rate. one of which is a solvent molecule that forms an integral part of the crystal structure. solubility. This phenomenon. In addition to the polymorphs. Although these structures are thermodynamically metastable. color. Fortunately. though widely used. Pseudopolymorphs are solids that consist of two distinct chemical species. there may also exist a number of so-called pseudopolymorphs for a given species. hardness) are important. depending upon the crystallization conditions. Furthermore. it is not correct to draw the obverse conclusion that only one crystal structure is possible per chemical species. thermodynamically metastable phases alongside the stable phase is known as Polymorphism.1. that is number of different materials exist that vary in the amount of water contained in the crystal lattice. The same behavior can be observed for organic crystals both with water incorporated into the lattice or with an integrated organic solvent. for example in the pharmaceutical industry. Since it is not yet possible to predict polymorphs reliably. since the most stable crystal structure may be different under different conditions of temperature and pressure. The existence of solvates and hydrates ©Encyclopedia of Life Support Systems (EOLSS) N ES SA C M O PL -E E O C LS H AP S TE R U .CHEMICAL ENGINEERING AND CHEMICAL PROCESS TECHNOLOGY – Heat and Mass Transfer Operations – Crystallization . Ulrich and M. a given material may crystallize in different modifications that are not necessarily minimum energy structures at the given conditions. Energy considerations lead to the conclusion that for each substance there is only one minimum energy structure. crystals possess a well defined 3dimensional order. Crystal Structures In contrast to amorphous solids. that is solid-liquid separation. materials have been observed to incorporate more than one type of solvent molecule. the coexistence of chemically identical. 4.
Crystals of the same material grown from different solvents.J. Despite the inherent difficulties. Contact with another solvent may also induce phase transformations. Liquid inclusions are critical in two respects: not only do increasing amounts of included liquid reduce the overall product quality. the product properties can be tailored to suit. their stability window also depends upon the composition of the solvent. on the other hand it retains a large amount of fluid that is difficult to remove using standard solid-liquid separation techniques.e. i. Even solvates and hydrates can exist in different polymorphic forms. This is due to the fact that growth rates of individual crystal faces.2. ©Encyclopedia of Life Support Systems (EOLSS) N ES SA C M O PL -E E O C LS H AP S TE R The existence of polymorphs. poses a difficult task. rapid growth rates have other disadvantages that result in detrimental product quality. Here one may be left with a solid block of an unwanted phase that has to be painstakingly removed and discarded [Ulrich/Jones]. 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. felt-like mass. Ulrich and M. solvates and hydrates leads to the potential for unexpected phase transitions during the production process which may result in unexpected products with unwanted properties. Fast crystal growth encourages liquid inclusions in the crystals and often leads to rough surfaces. 4. This crystalline mass becomes difficult to process. crystals of the same chemical species with the same crystal structure can exhibit different habits. for example. [Malet]. Nonetheless. that is. in particular in the case of drug substances where reproducibility is of paramount importance. desired properties. Jones therefore not only depends upon the temperature and pressure at which they are crystallized. The first case also poses a challenge in solid-liquid separation. are subject to supersaturation effects and the influence of solvent and impurity molecules.CHEMICAL ENGINEERING AND CHEMICAL PROCESS TECHNOLOGY – Heat and Mass Transfer Operations – Crystallization . the internal order of the individual building blocks as determined by the space group symmetry. The accompanying phase transition results in acicular (needle-like) crystals that form a dense. the accumulation of impurities in the mother liquor over the crystallization process also reduces product purity. It is therefore clear that the design and control of reliable and reproducible crystallization processes. Fast growth is desirable from an economic point of view since fast growth means short residence times and smaller equipment. On the one hand it no longer presents a freely flowing slurry. 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.J. For example. that certain hydrates lose their water when brought into contact with organic solvents. Crystal Shape (Habit) The external shape of a crystal is determined by the crystal structure. Apart from the possibility of dendritic growth. may have different aspect ratios or may even display different crystal faces. The crystal faces expressed by the macroscopic crystal always map a lattice plane defined by the microscopic unit cell. in particular if a phase transition occurs during the filtration process. and therefore their relative morphological importance. for example. U . a hydrate may be sensitive to ambient humidity and lose its water if humidity becomes too low. lower investment costs. It has been shown. One substance may crystallize in a number of polymorphic forms and also in the form of different solvates or hydrates.
These small crystals and their controlled production is. it is possible to manipulate the final macroscopic shape of the crystals by deliberately adding an impurity (additive) to the crystallization liquor. filterability etc. however. there are cases where smaller crystals are of key interest. On the other hand. Ulrich and M. since it provides a good fit in many cases. Several so-called ‘tailor-made’ additives have been reported in the literature [Weissbuch]. [Chen]. This can be achieved by identifying additives that fit into the lattice on the fast growing surfaces (but not the others) and therefore block the addition of the regular growth units. Crystal Size and Crystal Size Distribution In mass crystallization crystal sizes are normally discussed in terms of the mean diameter of a size distribution. In terms of postcrystallization processing this can have a negative effect on filterability. agglomeration tendencies. Details of these definitions are not the object of this section. [Clydesdale]. The fastest growing crystal faces grow out and are not observed in the final crystal habit. A quick glance into any book on particle technology will reveal that there are a number of different definitions of “mean diameter” in use. in particular if crystals with an acicular or tabular (platelike) habit are produced. usually the width of the desired distribution. the effect of impurities can be of advantage to tailor the shape of the crystals. Jones 4. ©Encyclopedia of Life Support Systems (EOLSS) N ES SA C M O PL -E E O C LS H AP S TE R The other factor influencing crystal habit mentioned above is the effect of impurities.CHEMICAL ENGINEERING AND CHEMICAL PROCESS TECHNOLOGY – Heat and Mass Transfer Operations – Crystallization . 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 size limit. color. This still leaves the shape of the distribution open. drying.J. Sperling. 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. U . Bennett) distribution. can all depend upon the crystal size. 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. A significant body of work concerning the controlled production of uniformly small crystals has emanated from the photographic materials industry. By exploiting the different interactions of different chemical species with the growing crystal faces. a typical domain of so-called precipitation crystallization which is not the object of this discussion. One means of tightening the specification of a size distribution is to define a second characteristic value.3. Nanotechnology as well as dyes and pigments are two areas where small crystals can exhibit properties that are lost above a certain upper limit. One particular crystal size distribution function that should be named at this point is the RRSB (Rosin. or on the handling of the dry solids. For the 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. Even though larger crystals are often desirable. Rammler. mixing and demixing properties. The size (which from this point onwards should be taken to mean the mean size) of a crystal is important for a variety reasons: flow properties. dissolution rates.J.
This limits the maximum achievable crystal size. minimize or reduce excess nuclei and to produce a product close to the desired size distribution.CHEMICAL ENGINEERING AND CHEMICAL PROCESS TECHNOLOGY – Heat and Mass Transfer Operations – Crystallization . left. Furthermore. typical crystallization equipment frequently found in industrial applications is presented. concentration of impurities or fluid flow patterns). Larger crystals can be obtained using the draft tube baffled crystallizer (DTB. Solution Crystallization Figure 6 shows the three most frequently built. 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 ©Encyclopedia of Life Support Systems (EOLSS) N ES SA C M O PL -E E O C LS H AP S TE R U . In common with all evaporative crystallizers. Ulrich and M.1. together with their heat exchangers. for example. The equipment discussed in the following is based upon “standard” designs frequently sold by the major manufacturers of crystallizers.J. inhomogeneities in the growth conditions can never be excluded (spatial variations in temperature. a distribution with finite width will always be the result. Powders are generally not free-flowing since the attractive forces between the crystals are stronger than the gravitational force. 5. together with some fines. is driven by an axial flow pump that circulates the entire suspension (solution and crystals) through the heat exchanger. centre). The critical lower size limit where powder properties become noticeable is dependent on the material. 5. however. it is often desirable to have a narrow. Even when starting from seed crystals of the same size with the same feedstocks with highly homogeneous growth conditions for all crystals in all regions of the crystallizer. the evaporation zone lies towards the top of the crystallizer at the interface of the solution with the atmosphere. Crystals of table salt (sodium chloride).J. There are several reasons for this. Inside the crystallizers the supersaturation must be kept within the metastable zone at all locations in order to avoid primary nucleation and to provide controlled conditions for crystal growth. Jones Apart from achieving a well defined and often narrow width of the crystal size distribution. yet large enough not to exhibit the typical properties of a powder such as caking. Figure 6. supersaturation. even though many applications require tailor-made solutions. where only the clear solution. As a result all crystals pass through the pump and are therefore liable to impact with the pump impeller. A forced circulation (FC) crystallizer. mono-modal distribution which can be viewed as single-sized. The term ‘narrow distribution’ alone will have different meanings in different situations. continuous evaporative solution crystallizer types. In suspension crystallization it is not possible to produce a narrow. methods exist to control. Special cases are not discussed here. as shown in Figure 6. resulting in attrition and contributing to secondary nucleation. must be small enough to fit through the openings of the salt cellar (generally smaller than 400 µm). single-sized distribution of crystals. Crystallization Technology In this chapter. primarily growth rate dispersion.
the Oslo crystallizer. this area is prone to encrustation due to variable wetting and resultant nucleation. As the liquid interface is subject to periodic variations in height due to the effect of motion in the equipment. right).J. long retention times require large equipment and large equipment results in expensive processes. the forced circulation (FC) crystallizer. Ulrich and M.CHEMICAL ENGINEERING AND CHEMICAL PROCESS TECHNOLOGY – Heat and Mass Transfer Operations – Crystallization . between the tube and the inner wall of the crystallizer. the draft tube baffled (DTB) crystallizer and right. Only cleared solution is circulated through the heat exchanger. The largest crystals can be obtained with the “Oslo”-type crystallizer (Figure 6.J. Images kindly provided by Messo Chemietechnik. 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. Germany In all evaporative crystallizers the liquid layer just beneath the evaporation zone is the region with the highest supersaturation. centre. Figure 6: The three most important types of evaporative solution crystallizers. The low circulation rate results in less attrition of the crystals due to reduced mechanical impact with both pump components and other crystals. Jones tube. Whenever possible. 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. Left. the application ©Encyclopedia of Life Support Systems (EOLSS) N ES SA C M O PL -E E O C LS H AP S TE R U . Large crystals require long retention times.
2. Germany. Figure 7: Process flow sheet for a sodium chloride crystallization plant. a process design avoiding too high a supercooling at the walls or too long a retention time at those locations that are prone to scaling is required.formed crystals). the three forced circulation crystallizers produce standard table salt.J. Jones of FC crystallizers is preferable to DTB or Oslo-type crystallizers due to their lower cost. The first. which is 2000 m2 for such a process. Melt Crystallization Melt crystallization can be subdivided into two distinct methods. settlers for solid-liquid separation.5 t/h. Oslo-type crystallizer produces large sodium chloride crystals. A typical process flow sheet for a solution crystallization process is provided in Figure 7. for example [Arkenbout] or [Ulrich/Glade]. 5. Ulrich and M. which is 30 m. Following the crystallizers. These are suspension based and solid layer based processes. The size of the equipment can be gauged via the total height of the building. Oslo-type crystallizer produces large crystals of the order of 2 mm side length at a rate of 2. Alternatively. Scraped surfaces are used where encrustation does occur (leading to ill. The key problem is to avoid nucleation at the cooled surfaces. and the surface area required. cyclones for fines removal and storage silos can be seen.CHEMICAL ENGINEERING AND CHEMICAL PROCESS TECHNOLOGY – Heat and Mass Transfer Operations – Crystallization . The suspension based processes are frequently combined with so-called wash columns ([Scholz/Ruemekorf ©Encyclopedia of Life Support Systems (EOLSS) N ES SA C M O PL -E E O C LS H AP S TE R U . The different techniques are described in detail in the literature cited. Cooling crystallizers for suspension crystallization techniques can be treated in the same manner as melt crystallization equipment as discussed in the following. Image kindly provided by Messo Chemietechnik. The intake is brine with a flow rate of 60 t/h.J. the remainder of the plant (three successive FC crystallizers followed by post-crystallization processing) produces regular table salt at a rate of 6. Further information on evaporative solution crystallizers can be found in [Hofmann (in Hofmann)]. From the left: the first.5 t/h. The flow sheet represents a four stage sodium chloride purification process.
Ulrich and M. The photograph in Figure 9 illustrates the full scale of the process equipment. Growth rates are about two orders of magnitude higher than in suspension crystallization (10-7 – 10-5 m/s compared to 10-9 – 10-7 m/s).J. Due to the very fast growth rates single stages lead to rather impure products (both crystalline and melt fractions). Solid layer techniques are almost exclusively discontinuous.J. used for p-Xylene purification is shown in Figure 8.CHEMICAL ENGINEERING AND CHEMICAL PROCESS TECHNOLOGY – Heat and Mass Transfer Operations – Crystallization . but they can be staged. These are normally collected and reused in subsequent stages. Heat is withdrawn from the melt through the crystalline layer by means of cooled walls within the crystallizer. Solid layer melt crystallizers follow a different concept. The driving forces are much higher than in the case of suspension crystallization since the feed melt always remains above its melting point. in melt crystallization the surface area of the product is limited and about two orders of magnitude lower than in suspension crystallization. ©Encyclopedia of Life Support Systems (EOLSS) N ES SA C M O PL -E E O C LS H AP S TE R U .. the wash columns (screw-type) are on the left behind the feed heat recovery exchangers. The Netherlands. A flow sheet for a plant from Niro Process Technology B. However. Jones (in Ulrich/Glade)]. The crystallization vessels can be seen on the right hand side of the image. Figure 8: Flow sheet detailing a (generalized) melt crystallization process with wash column. 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. Figure kindly provided by Niro Process Technology B. in order to achieve a better solid-liquid separation.V. Here the product is obtained by enforced encrustation.V.
Jones Figure 9: Melt crystallization plant used for the purification of p-Xylene. To the left of the crystallizer three storage ©Encyclopedia of Life Support Systems (EOLSS) N ES SA C M O PL -E E O C LS H AP S TE R U . Detailed descriptions of melt layer crystallization can be found in [Stepanski/Schäfer (in Ulrich/Glade)].CHEMICAL ENGINEERING AND CHEMICAL PROCESS TECHNOLOGY – Heat and Mass Transfer Operations – Crystallization . Central to the plant is a falling film crystallizer. Ulrich and M. Central to the design is a falling film melt crystallizer. Figure 10 shows a flow sheet for such a design.J. Figure 10: Typical flow sheet for a staged solid layer crystallization plant. The crystallization vessels can be seen to the right. Figure kindly provided by Niro Process Technology B. The Netherlands.V..J.
rinsing or sweating in the case of solid layer crystallization. but are cheaper to implement and run. 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. ©Encyclopedia of Life Support Systems (EOLSS) N ES SA C M O PL -E E O C LS H AP S TE R U . Spain). The role of the wash column used in suspension crystallization is replaced by washing. Switzerland Static solid layer techniques represent the other case encountered in solid layer melt crystallization equipment. Figure 11 provides an example of such a crystallizer. CEPSA. Here. which can then be reused in the process.CHEMICAL ENGINEERING AND CHEMICAL PROCESS TECHNOLOGY – Heat and Mass Transfer Operations – Crystallization . Figure 11: A falling film melt crystallization plant used for the purification of p-xylene (CEPSA. Photograph kindly provided by Sulzer Chemtech Ltd. as no additional equipment such as a circulation pump is required.J. Figure 12 shows an example of a static solid layer melt crystallizer employing cooled plates rather than cooled pipes. (p-Xylene. Jones tanks can be seen. Switzerland. Flowsheet kindly provided by Sulzer Chemtech Ltd. the feed melt is simply filled into the equipment and there is no movement of the feed melt apart from natural convection. These are used to collect residual melt and purified material. Once the crystallization process is sufficiently advanced. Ulrich and M. Spain). the residual melt is drained and replaced by a purer washing liquid in the case of washing or rinsing steps. 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.J.
Glossary Critical cluster size: Growth: A measure of the size of a crystal nucleus required to grow into an energetically stable crystal. Further details on post processing steps can be found in the books on melt crystallization cited. inlets and outlets for feed/product and cooling medium are highlighted.J. in order to drain any impurities or inclusions. the crystalline layer is heated to close to the melting point of the pure substance in the absence of a washing liquid. 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. As a result the technology is competitive in terms of market value. Ulrich and M. Jones Figure 12: Sketch of a simple static melt crystallizer. The process by which crystal nuclei increase in size and develop ©Encyclopedia of Life Support Systems (EOLSS) N ES SA C M O PL -E E O C LS H AP S TE R U .J. For suspension crystallization techniques the advantages and disadvantages are reversed compared to solid layer techniques. All of these post-crystallization techniques lead to purer products and are frequently employed. Switzerland. In the case of sweating. that there is no handling of solids and that the equipment is easy to scale-up.CHEMICAL ENGINEERING AND CHEMICAL PROCESS TECHNOLOGY – Heat and Mass Transfer Operations – Crystallization . The disadvantages that solid layer crystallization is a discontinuous process and provides only limited surface area are often outweighed by the fact that solid-liquid separation is easily achieved in such equipment. Sketch kindly provided by Sulzer Chemtech Ltd. The cooled plates can be seen in the interior of the crystallizer.
Each distinct crystal structure is termed a polymorph and will display different physical properties. Polymorphism in Pharmaceutical Solids. (1994).J. The phenomenon where a chemical entity exhibits more than one crystal structure. Davey R. 39. Impurity Adsorption Mechanism of Borax for a Suspension Growth Condition: A Comparison of Models and Experimental Data. Molecular ©Encyclopedia of Life Support Systems (EOLSS) N ES SA C M O PL -E E O C LS H AP S TE R into fully formed crystals. A measure of the deviation of the system temperature from the equilibrium temperature. Jones Growth rate: Metastable Zone: Nucleation: Nucleation rate: Polymorphism: Phase diagram: Solubility: Supercooling: Supersaturation: Bibliography Al Jibbouri S. France [An overview of progress in scientific research in industrial crystallization over the preceding three years] Brittain H.D. Garside J. (1994). The rate at which crystal nuclei are formed. Once nuclei have formed. New York. G.. USA [An overview of the effect of polymorphism on the properties and manufacture of pharmaceuticals] Chianese A. Different measures of growth rate are in use. Nickisch K. 13th Symposium on Industrial Crystallization. 2(5). The formation of an initial crystalline particle (nucleus) from the supersaturated solution. (1998). 144 (3/4).. Journal of Crystal Growth. Niehoerster S. F. A graphical representation of the state of a system (existence of distinct phases) depending upon selected physical parameters. (2004). (1995). they grow in the metastable zone. and Lewtas K. (1996). 540 – 547 [On the effect of impurities on a crystallization process] Arkenbout G. Solubility is a physical property of a given system. Melt Crystallization Technology. The region in phase space where the solution (melt) is beyond equilibrium but cannot nucleate due to small the small nucleation rate. A measure of the amount of solute that can dissolve in a given solvent. Milano. and Ulrich J. Crystal Research & Technology. 15th Symposium on Industrial Crystallization. (2002). and Gabas N. Organic Process Research & Development. AIDIC.. (1999).D. Italy [An overview of progress in scientific research in industrial crystallization over the preceding three years] Chen B.J. and Budde U. Toulouse.. Roberts K. The nucleation rate depends upon supersaturation. 298 – 304 [An example of seeding techniques applied to a particular crystallization problem] Biscans B. Bergmann D. Ulrich and M. Inc.J.J. 297 – 303 [An account of the effect of additives on crystal shape] Clydesdale G. A measure of the deviation of the solution concentration from the equilibrium concentration. U . Inc. Growth of Meta-Chloronitrobenzene Crystals in the Presence of “Tailor-Made” Additives: Assignment of the Polar Axes from Morphological Changes.. The rate with which crystals grow. Marcel Dekker... USA [An overview of melt crystallization technology] Beckmann W.. Potts G. Computational Modelling Study of the growth Morphology of the Normal Alkane Docosane and its Mediation by “Tailor-Made” Additives. Development of a Seeding Technique for the Crystallization of the Metastable A Modification of Abecarnil. Technomic Publishing Company..CHEMICAL ENGINEERING AND CHEMICAL PROCESS TECHNOLOGY – Heat and Mass Transfer Operations – Crystallization .. Pennsylvania. Lancaster. and Ulrich J.
The Netherlands [A detailed account of fundamentals of crystal symmetry and space groups] Heffels S. Handbook of Crystal Growth. Industrial Crystallization 81.KgaA.. Rugby. Kristallisation in der industriellen Praxis. 2A. Jones Crystals and Liquid Crystals Science and Technology. Handbook of Crystal Growth. 248. Wiley-VCH Verlag GmbH & Co. (1979). (2004).J. and de Jong E. Vol. The Netherlands [Crystallization as a separation technique] ©Encyclopedia of Life Support Systems (EOLSS) N ES SA C M O PL -E E O C LS H AP S TE R .). Wiley-VCH Verlag GmbH & Co. Rugby. The Netherlands [An overview of progress in scientific research in industrial crystallization over the preceding three years] Jancic S.J. Elsevier Science Publisher.CHEMICAL ENGINEERING AND CHEMICAL PROCESS TECHNOLOGY – Heat and Mass Transfer Operations – Crystallization . and van Rosmalen G. (1993).J.. 2A. and de Jong E. Elsevier. ButterworthHeinemann. The Netherlands [An overview of progress in scientific research in industrial crystallization over the preceding three years] Doki N.G.J. Amstersam. 14th Symposium on Industrial Crystallization. Germany [“Crystallization in the industrial practise“. Kristallisation in der industriellen Praxis. The Netherlands [An overview of progress in scientific research in industrial crystallization over the preceding three years] Jancic S. KgaA. and Masumi F. in: Hofmann. Advances in Industrial Crystallization.J. Oxford. Hamada O.A. G. Elsevier Science Publisher. Dordrecht. 6.J. UK [Selective overview lecture on the state-of-the-art in industrial crystallization in 1991] Garside J.J.. D. and Kind M.J.(1999). The Netherlands [An overview of the science if crystal growth] Jancic S. (Ed. Amsterdam. 2527 – 2533 [An example of scaling up a seeded crystallization process] Garside J. (Ed. Institute of Chemical Engineering. Sato A.K.J..M. IchemE. Fractional Crystallisation in: Hurle D. Kluwer Academic Publishers.T. Seeding Technology: An Underestimated Critical Success Factor for Crystallization. Dordrecht. and Jones A. Scaleup Experiments on Seeded Batch Cooling Crystallization of Potassium Alum. materials from a professional development course] Hofmann.) (2002). (1984).). Amsterdam. G. 6. UK [An account of the impact of seeding techniques in crystallization] Hofmann G.J. 45 (12). International Tables for Crystallography. Übersicht über die behandelten Themen. Ulrich and M. and Jancic S. Chap. Amsterdam. and Grootscholten P. UK [An overview of progress in scientific research in industrial crystallization over the preceding three years] Hahn T. North-Holland. North-Holland Publishing Co.J. Germany [An overview of topics discussed in the above book] U Hurle D. (1982). (1994). Vol. Amsterdam. Weinheim. (2004). (1999). Proceedings of the 9th Symposium on Industrial Crystallization.M. The Netherlands [A handbook on industrial crystallization] Jansens P. Weinheim.J. (1999). Industrial Crystallisation '78. Reidel Publishing Co. Industrial Crystallization. 14th International Symposium Industrial Crystallization.. (1991). 751 – 784 [An example of molecular simulations applied to crystallization] de Jong E. (1984). Chap. AIChE Journal. (Ed. Davey R.J.T.. Yokota M.. Kubota N.
). T. Germany [“Growth kinetics in the presence of additives in solution crystallization”] Moritoki. Crystallization. (1992). needle-shaped crystals] Mersmann A. S.. Shaker Verlag. (Eds. Zur Modellierung der Wachstumskinetik in der Lösungskristallisation. de Jong E. Germany [An overview of typical phase behavior encountered in crystallization] Kruse M.J. Butterworth-Heinemann. Handbook of Industrial Crystallisation.. (1999).. Weinheim. UK [A handbook on industrial crystallization] Myerson A.G. and Ulrich J. VCH. in: Ulrich J. 11th Symposium on Industrial Crystallization. Admixtures in Crystallization. (2003). Germany [On the effect of additional components on crystallization processes] Nyvlt J. (Eds. 3 ed. and Jancic S. (1996) Wachstumskinetik in der Lösungskristallisation mit Fremdstoffen. Ulrich and M. USA [A handbook on industrial crystallization] Mullin J. Germany [“On the influence of solvents on pseudopolymorphs“] Nyvlt J.W. Oxford.). USA [A handbook on industrial crystallization and the technology of crystallization] Mohameed H.. Crystallization Technology Handbook. Zur Pseudopolymorphie unter Lösungsmitteleinfluß. Nucleation: Basic Theory with Application. Molecular Modelling Applications in Crystallization. New York. and Coquerel G.(1999). Proceedings of the 10th Symposium on Industrial Crystallization. Germany [“Modelling growth rates in solution crystallization“] Mallet F. Developments in Melt Crystallization. Jones Kashehiev D. UK [An overview of molecular simulation techniques applied to crystallization phenomena] Myerson A. Phase Diagrams in Melt Crystallization. (1990). Industrial Crystallisation. Aachen. New York.-A. (1991).J. Amsterdam. (1979).. New York. Coquerel G. in Industrial Crystallization 78. in: Advances in Industrial Crystallization. (1989). Aachen. in: 10. USA [A handbook on industrial crystallization] Nordhoff.J.. Shaker Verlag.). Inc.S. New York. Petit S. Garmisch-Partenkirchen. USA [An overview of progress in scientific research in industrial crystallization over the preceding three years] ©Encyclopedia of Life Support Systems (EOLSS) N ES SA C M O PL -E E O C LS H AP S TE R Matsuoka M.). (1993). The Netherlands [An account of the effect of pressure on a crystallization process] Mullin J. VDI Fortschrittberichte Nr. Marcel Dekker. 165 – 171 [Tentative growth model of small. 209.. A. Cambridge. (Ed.CHEMICAL ENGINEERING AND CHEMICAL PROCESS TECHNOLOGY – Heat and Mass Transfer Operations – Crystallization . Oxford. Shaker Verlag. Butterworth-Heinemann. (2003).J (Eds. and Jones A. Aachen. Düsseldorf. North-Holland Publishing Company. (1995). Cambridge University Press. BIWIC. Wakabayashi M and Fujikawa.S. New Data and Interpretations on the Formation of Whiskers of Molecular Crystals. Plenum Press. 2nd ed. and Glade H. Aachen. Davey R. Butterworth-Heinemann. Oxford U .W. (1976). Germany [An overview of progress in scientific research in industrial crystallization over the preceding three years] Mersmann A. Verlag Mainz. (2001). M. (2000). Elsevier. (2002). Butterworth-Heinemann. and Zacek S. Garside J. Fractional Crystallization Applying Very High Pressure.. UK [Fundamentals of the initial formation of crystalline solid particles] König.J. VDI-Verlag.
Inc. Jones Ohara M. and Glade H. Germany [Fundamentals of melt crystallization] Ulrich J.D. Aachen. R. (1993). Crystal Research & Technology. J. (2004).C. Aachen. and McGhie A. Germany [A detailed account of the fundamentals and applications of melt crystallization] ©Encyclopedia of Life Support Systems (EOLSS) N ES SA C M O PL -E E O C LS H AP S TE R Söhnel O. E. Proceedings of the 12th Symposium on Industrial Crystallization. and Glade H. Melt Crystallization.A. (2004). and Larson M.). (Eds. Suspension Crystallization from the Melt. (2001). John Wiley & Sons. (1988). UK [A discussion of precipitation techniques] U . (1989). New York. Academic Press. USA Rojkowski Z. Aachen. and Reid R. in: Ulrich J. Separate Organics by Suspension Crystallization. Englewood Cliffs. (Ed. Precipitation: Basic Principles and Industrial Applications. New York. Reihe Verfahrenstechnik. Crystallization. Poland [An overview of progress in scientific research in industrial crystallization over the preceding three years] Scholz. (2002).S. (1988). and Hirasawa I. and Schäfer. Warsaw. in Kirk-Othmer Encyclopedia of Chemical Technology (Online). Germany [A research thesis on phase transitions and their impact on crystallization] Strickland-Constable R.). (2003).. New York. Germany [“Crystal growth rates in suspension crystallization – physical factors and measurement techniques“] Ulrich J. C. Aachen. (Eds. USA [An overview on melt crystallization techniques] Stepanski.CHEMICAL ENGINEERING AND CHEMICAL PROCESS TECHNOLOGY – Heat and Mass Transfer Operations – Crystallization . (Eds. John Wiley & Sons. (1968).F. PhD Thesis. Techniques of Melt Crystallization. in: Ulrich J. Martin-LutherUniversität Halle-Wittenberg. Prentice-Hall Press. USA [On process simulation as a tool in designing crystallization processes] Toyokura K. (1973). Oxford. Industrial Crystallization: process simulation analysis and design. 2nd ed. Growth Rate Dispersion – A Review. R. USA [On the kinetics of crystallization] Tavare N. M. Ulrich and M.).J. (1994). On (Pseudo-) Polymorphic Phase Transformations. Theory of Particulate Processes. New York. Butterworth-Heinemann. Plenum Press New York. 24.J. Academic Press. Separate Organics by Melt Crystallization: A Guide to When and How to Use this Technique. and Garside J. in Mersmann A. and Glade H. Solid Layer Crystallization. Shaker Verlag Aachen. Modelling Crystal Growth Rates from Solution. and Glade H. Kinetics and Mechanism of Crystallization. Inc. USA [A treatise on the fundamental physics of crystal growth] Randolph A. 249 – 257 [An overview of the phenomenon of crystals growing at different rates under otherwise identical conditions] Ulrich J. in: Ulrich J.R.). [An overview of industrial crystallization] Ulrich. and Ruemekorf. Shaker Verlag. (1993). Shaker Verlag. NJ. Kristallwachstumsgeschwindigkeiten bei der Kornkristallisation – Einflussgrößen und Messtechniken. Crystallization Technology Handbook. Marcel Dekker.H.J. (1992). (2003). Germany [An account of suspension crystallization and its application to organic solids] Strege. Shaker Verlag. (2003). Aachen. Shaker Verlag.. Germany [An account of suspension crystallization and its application to organic solids] Sloan G. USA [An account of suspension crystallization from melts] Ulrich J.
CHEMICAL ENGINEERING AND CHEMICAL PROCESS TECHNOLOGY – Heat and Mass Transfer Operations – Crystallization . 381 – 400 [An account of the effect of additives on the solid phase crystallized] Biographical Sketches Joachim Ulrich received the Diplom-Ingenieur degree from the Technical University ClausthalZellerfeld in Germany. HEAT AND MASS TRANSFER OPERATIONS CRYSTALLIZATION.-Ing. Jones. and Bruinsma O.L. Seeding During Batch Cooling Crystallization – An Initial Approach to Heuristic Rules.J. (2001). (2005).J. (1995). Halle (Saale).S.eolss. Japan and in 1999 was appointed chair of thermal process engineering at the MartinLuther-Universität Halle-Wittenberg in Halle (Saale). in Chemical Engineering. [http://www. VDI-Verlag. 53..Martin Molzahn. His interests include all aspects of industrial crystallization. (1985). in: Ulrich J. Andrews and Heriot-Watt University. Advances in Crystal Growth Research. Jones Ulrich J. [Eds. Butterworth-Heinemann.Phase Equilibria in Chemical Engineering. from the Rheinisch-Westfälische Technische Hochschule Aachen and the Habilitation from the Universität Bremen. Nachrichten aus der Chemie.P. (2005). After post-doctoral positions at the University of St. He is currently chair of the European Federation of Chemical Engineering.J. (2004). Matthew Jonathan Jones received the Diplom-Chemiker degree from the Westfälische WilhelmsUniversität Münster in Germany and the PhD from the University of London (University College). Kristalle mit integriertem Lösungsmittel. Oxford . in Hofmann G.UK. VDI-Verlag. Germany in 2003. Kluwer Academic Publishers. Dordrecht. Developed under the Auspices of the UNESCO. London. UK. Crystal Morphology Control with Tailor-Made Additives: A Stereochemical Approach. The Netherlands Walas S.J. Oxford. in Encyclopedia of Life Support Systems (EOLSS). Weinheim. (2005). Lahav M. (2006). Tokio. To cite this chapter J. UK [An account of the impact of thermodynamic properties on engineering] Warstat A. 16th Symposium on Industrial Crystallization Dresden. Ulrich and M. Germany [An report on research to develop rules for seeding techniques] Weissbuch I. Germany [An overview of progress in scientific research in industrial crystallization over the preceding three years] van der Eerden J. and Leiserowiz L. Boston.. the Dr.Ryszard Pohorecki]. he took up the position of senior scientist in the thermal process engineering group at the Martin-Luther-Universität Halle-Wittenberg.M.net] ©Encyclopedia of Life Support Systems (EOLSS) N ES SA C M O PL -E E O C LS H AP S TE R U . 16th Symposium on Industrial Crystallization Dresden. His research interests include the industrial crystallization of proteins and the application of molecular modeling to crystallization and materials in the solid state. Germany [“The effect of additives on crystallization”] Ulrich J. Edinburgh and a teaching fellowship at the University of Leeds. (Ed. Ulrich J. Fremdstoffbeeinflussung in der Kristallisation.). (Ed. Eolss Publishers. Kristallisation in der Industriellen Praxis. He has held a post-doctoral position at the Waseda University. Science and Technology of Crystal Growth. and Jones M. John Bridgwater. 19 – 23 [“Crystals with integrated solvents”] Ulrich J. Ulrich and M. Wiley-VCH.). especially melt crystallization and batch crystallization.
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