Circulating Liquor Crystallizers Figure

CUMULATIVE % RETAINED

18-63 Calculated product-size distribution for a crystallizer operation at different fine-crystal-separation sizes.

Crystallizers Process Equipment
FIG. 18-64 Forced-circulation (evaporative) crystallizer. (Swenson Process Equipment, Inc.)

vaporization to achieve equilibrium between liquid and vapor, the supersaturation which is created causes deposits on the swirling body of suspended crystals until they again leave via the circulating pipe. The quantity and the velocity of the recirculation, the size of the body, and the type and speed of the circulating pump are critical design items if predictable results are to be achieved. A further discussion of the parameters affecting this type of equipment is given by Bennett, Newman, and Van Buren [Chem. Eng. Prog., 55(3), 65 (1959); Chem. Eng. Prog. Symp. Ser., 65(95), 34, 44 (1969)].

If the crystallizer is not of the evaporative type but relies only on adiabatic evaporative cooling to achieve the yield, the heating element is omitted. The feed is admitted into the circulating line after withdrawal of the slurry, at a point sufficiently below the free-liquid surface to prevent flashing during the mixing process.

Draft-Tube-Baffle (DTB) Evaporator-Crystallizer Because mechanical circulation greatly influences the level of nucleation within the crystallizer, a number of designs have been developed that use circulators located within the body of the crystallizer, thereby reducing the head against which the circulator must pump. This technique reduces the power input and circulator tip speed and therefore the rate of nucleation. A typical example is the draft-tube-baffle (DTB) evaporator-crystallizer (Swenson Process Equipment, Inc.) shown in Fig. 18-65. The suspension of product crystals in maintained by a large, slow-moving propeller surrounded by a draft tube within the body. The propeller directs the slurry to the liquid surface so as to prevent solids from short-circuiting the zone of the most intense supersaturation. Slurry which has been cooled is returned to the bottom of the vessel and recirculated through the propeller. At the propeller, heated solution is mixed with the recirculating slurry.

The design of Fig. 18-65 contains a fines-destruction feature comprising the settling zone surrounding the crystallizer body, the circulating pump, and the heating element. The heating element supplies sufficient heat to meet the evaporation requirements and to raise the temperature of the solution removed from the settler so as to destroy

Draft Tube Centrifugal Pump
FIG. 18-65 Draft-tube-baffle (DTB) crystallizer. (Swenson Process Equipment, Inc. )

any small crystalline particles withdrawn. Coarse crystals are separated from the fines in the settling zone by gravitational sedimentation, and therefore this fines-destruction feature is applicable only to systems in which there is a substantial density difference between crystals and mother liquor.

This type of equipment can also be used for applications in which the only heat removed is that required for adiabatic cooling of the incoming feed solution. When this is done and the fines-destruction feature is to be employed, a stream of liquid must be withdrawn from the settling zone of the crystallizer and the fine crystals must be separated or destroyed by some means other than heat addition—for example, either dilution or thickening and physical separation.

In some crystallization applications it is desirable to increase the solids content of the slurry within the body above the natural consistency, which is that developed by equilibrium cooling of the incoming feed solution to the final temperature. This can be done by withdrawing a stream of mother liquor from the baffle zone, thereby thickening the slurry within the growing zone of the crystallizer. This mother liquor is also available for removal of fine crystals for size control of the product.

Draft-Tube (DT) Crystallizer This crystallizer may be employed in systems in which fines destruction is not needed or wanted. In such cases the baffle is omitted, and the internal circulator is sized to have the minimum nucleating influence on the suspension.

In DTB and DT crystallizers the circulation rate achieved is generally much greater than that available in a similar forced-circulation crystallizer. The equipment therefore finds application when it is necessary to circulate large quantities of slurry to minimize supersaturation levels within the equipment. In general, this approach is required to obtain long operating cycles with material capable of growing on the walls of the crystallizer. The draft-tube and draft-tube-baffle designs are commonly used in the production of granular materials such as ammonium sulfate, potassium chloride, photographic hypo, and other inorganic and organic crystals for which product in the range 8 to 30 mesh is required.

Surface-Cooled Crystallizer For some materials, such as sodium chlorate, it is possible to use a forced-circulation tube-and-shell exchanger in direct combination with a draft-tube-crystallizer body, as shown in Fig. 18-66. Careful attention must be paid to the temperature difference between the cooling medium and the slurry circulated through the exchanger tubes. In addition, the path and rate of slurry flow within the crystallizer body must be such that the volume contained in the body is "active." That is to say, crystals must be so suspended within the body by the turbulence that they are effective in relieving supersaturation created by the reduction in temperature of the slurry as it passes through the exchanger. Obviously, the circulating pump is part of the crystallizing system, and careful attention must be paid to its type and its operating parameters to avoid undue nucleating influences.

The use of the internal baffle permits operation of the crystallizer at a slurry consistency other than that naturally obtained by the cooling of the feed from the initial temperature to the final mother-liquor temperature. The baffle also permits fines removal and destruction.

With most inorganic materials this type of equipment produces crystals in the range 30 to 100 mesh. The design is based on the allowable rates of heat exchange and the retention required to grow the product crystals.

Direct-Contact-Refrigeration Crystallizer For some applications, such as the freezing of ice from seawater, it is necessary to go to such low temperatures that cooling by the use of refrigerants is the only economical solution. In such systems it is sometimes impractical to employ surface-cooled equipment because the allowable temperature difference is so small (under 3°C) that the heat-exchanger surface becomes excessive or because the viscosity is so high that the mechanical energy put in by the circulation system requires a heat-removal rate greater than can be obtained at reasonable temperature differences. In such systems, it is convenient to admix the refrigerant with the slurry being cooled in the crystallizer, as shown in Fig. 18-67, so that the heat of vaporization of the refrigerant cools the slurry by direct contact. The successful application of such systems requires that the refrigerant be relatively immiscible with the mother liquor and be capable of separation, compression, condensation, and subsequent recycle into the crystallizing system. The operating pressures and temperatures chosen have a large bearing on power consumption.

This technique has been very successful in reducing the problems associated with buildup of solids on a cooling surface. The use of direct-

FIG. 18-66 Forced-circulation baffle surface-cooled crystallizer. (Swenson Process Equipment, Inc. )
Agitated Batch Crystallizer
FIG. 18-67 Direct-contact-refrigeration crystallizer (DTB type). (Swenson Process Equipment, Inc. )

contact refrigeration also reduces overall process-energy requirements, since in a refrigeration process involving two fluids a greater temperature difference is required on an overall basis when the refrigerant must first cool some intermediate solution, such as calcium chloride brine, and that solution in turn cools the mother liquor in the crystallizer.

Equipment of this type has been success: fully operated at temperatures as low as -59°C (-75°F).

Reaction-Type Crystallizers In chemical reactions in which the end product is a solid-phase material such as a crystal or an amorphous solid the type of equipment described in the preceding subsections or shown in Fig. 18-68 may be used. By mixing the reactants in a large circulated stream of mother liquor containing suspended solids of the equilibrium phase, it is possible to minimize the driving force created during their reaction and remove the heat of reaction through the vaporization of a solvent, normally water. Depending on the final particle size required, it is possible to incorporate a fines-destruction baffle as shown in Fig. 18-68 and take advantage of the control over particle size afforded by this technique. In the case of ammonium sulfate crystallization from ammonia gas and concentrated sulfuric acid, it is necessary to vaporize water to remove the heat of reaction, and this water so removed can be reinjected after condensation into the fines-destruction stream to afford a very large amount of dissolving capability.

Other examples of this technique are where a solid material is to be decomposed by mixing it with a mother liquor of a different composition, as shown in Fig. 18-69. Carnallite ore (KClMgCl2'4H2O) can be added to a mother liquor into which water is also added so that decomposition of the ore into potassium chloride (KCl) crystals and magnesium chloride-rich mother liquor takes place. Circulated slurry in the draft tube suspends the product crystals as well as the incoming ore particles until the ore can decompose into potassium chloride crystals and mother liquor. By taking advantage of the fact that water must be added to the process, the fines-bearing mother liquor can be removed behind the baffle and then water added so that the finest particles are dissolved before being returned to the crystallizer body.

Crystallizer
FIG. 18-68 Swenson reaction type DTB crystallizer. (Swenson Process Equipment, Inc.)

Other examples of this technique involve neutralization reactions such as the neutralization of sulfuric acid with calcium chloride to result in the precipitation of gypsum.

Mixed-Suspension, Classined-Product-Removal Crystallizers Many of the crystallizers just described can be designed for classified-product discharge. Classification of the product is normally done by means of an elutriation leg suspended beneath the crystallizing body as shown in Fig. 18-66. Introduction of clarified mother liquor to the lower portion of the leg fluidizes the particles prior to discharge and selectively returns the finest crystals to the body for further growth. A relatively wide distribution of material is usually produced unless the elutriation leg is extremely long. Inlet conditions at the leg are critical if good classifying action or washing action is to be achieved.

If an elutriation leg or other product-classifying device is added to a crystallizer of the MSMPR type, the plot of the population density versus L is distorted in the region of largest sizes. Also the incorporation of an elutriation leg destabilizes the crystal-size distribution and under some conditions can lead to cycling. The theoretical treatment of both the crystallizer model and the cycling relations is discussed by Randolph, Beer, and Keener (loc. cit.). Although such a feature can be included on many types of classified-suspension or mixed-suspension crystallizers, it is most common to use this feature with the forced-circulation evaporative-crystallizer and the DTB crystallizer.

Classified-Suspension Crystallizer This equipment is also known as the growth or Oslo crystallizer and is characterized by the production of supersaturation in a circulating stream of liquor. Supersaturation is developed in one part of the system by evaporative cooling or by cooling in a heat exchanger, and it is relieved by passing the liquor through a fluidized bed of crystals. The fluidized bed may be contained in a simple tank or in a more sophisticated vessel arranged

Dtb Crystallizer
FIG. 18-69 Swenson atmospheric reaction-type DTB crystallizer. ( Swenson Process Equipment, Inc. )

for a pronounced classification of the crystal sizes. Ideally this equipment operates within the metastable supersaturation field described by Miers and Isaac, J. Chem. Soc., 1906, 413.

In the evaporative crystallizer of Fig. 18-70, solution leaving the vaporization chamber at B is supersaturated slightly within the metastable zone so that new nuclei will not form. The liquor contacting the bed at E relieves its supersaturation on the growing crystals and leaves through the circulating pipe F. In a cooling-type crystallization hot feed is introduced at G, and the mixed liquor flashes when it reaches the vaporization chamber at A. If further evaporation is required to produce the driving force, a heat exchanger is installed between the circulating pump and the vaporization changer to supply the heat for the required rate of vaporization.

The transfer of supersaturated liquor from the vaporizer (point B, Fig. 18-69) often causes salt buildup in the piping and reduction of the operating cycle in equipment of this type. The rate of buildup can be reduced by circulating a thin suspension of solids through the vaporizing chamber; however, the presence of such small seed crystals tends to rob the supersaturation developed in the vaporizer, thereby lowering the efficiency of the recirculation system.

An Oslo surface-cooled crystallizer is illustrated in Fig. 18-71. Supersaturation is developed in the circulated liquor by chilling in the cooler H. This supersaturated liquor is contacted with the suspension of crystals in the suspension chamber at E. At the top of the suspension chamber a stream of mother liquor D can be removed to be used for fines removal and destruction. This feature can be added on either type of equipment. Fine crystals withdrawn from the top of the suspension are destroyed, thereby reducing the overall number of crystals in the system and increasing the particle size of the remaining product crystals.

Scraped-Surface Crystallizer For relatively small-scale applications a number of crystallizer designs employing direct heat exchange between the slurry and a jacket or double wall containing a cooling medium have been developed. The heat-transfer surface is scraped or agitated in such a way that the deposits cannot build up.

The scraped-surface crystallizer provides an effective and inexpensive method of producing slurry in equipment which does not require expensive installation or supporting structures.

Double-Pipe Scraped-Surface Crystallizer This type of equipment consists of a double-pipe heat exchanger with an internal agitator fitted with spring-loaded scrapers that wipe the wall of the inner pipe. The cooling liquid passes between the pipes, this annulus being dimensioned to permit reasonable shell-side velocities. The scrapers prevent the buildup of solids and maintain a good film coefficient of heat transfer. The equipment can be operated in a continuous or in a recirculating batch manner.

Such units are generally built in lengths to above 12 m (40 ft). They can be arranged in parallel or in series to give the necessary liquid velocities for various capacities. Heat-transfer coefficients have been reported in the range of 170 to 850 W/(m2K) [30 to 150 Btu/(hft2°F)] at temperature differentials of 17°C (30°F) and higher [Garrett and Rosenbaum, Chem. Eng., 65(16), 127 (1958)]. Equipment of this type is marketed as the Votator and the Armstrong crystallizer.

Batch Crystallization Batch crystallization has been practiced longer than any other form of crystallization in both atmospheric tanks, which are either static or agitated, as well as in vacuum or pressure vessels. It is still widely practiced in the pharmaceutical and fine chemical industry or in those applications where the capacity is very small. The integrity of the batch with respect to composition and history can be maintained easily and the inventory management is more precise than with continuous processes. Batch crystallizers can be left unattended (overnight) if necessary and this is an important advantage for many small producers.

In any batch process the common mode of operation involves charging the crystallizer with concentrated or near-saturated solution, producing supersaturation by means of cooling the batch or evaporating solvent from the batch, seeding the batch by means of injecting seed crystals into the batch or by allowing homogeneous nucleation to occur, reaching the final mother-liquor temperature and concentration by some time-dependent means of control, and stopping the cycle

Oslo Krystal Cooler Crystalliser

FIG. 18-70 OSLO evaporative crystallizer.

Circulating pump

FIG. 18-70 OSLO evaporative crystallizer.

so that the batch may be dumped into a tank for processing by successive steps, which normally include centrifugation, filtration, and/or drying. In some cases, a small "heal" of slurry is left in the batch crystallizer to act as seed for the next batch.

Control of a batch crystallizer is almost always the most difficult part and very often is not practiced except to permit homogeneous nucleation to take place when the system becomes supersaturated. If control is practiced, it is necessary to have some means for determining when the initial solution is supersaturated so that seed of the appropriate size, quantity, and habit may be introduced into the batch. Following seeding, it is necessary to limit the cooling or evaporation in

Oslo Cooling Crystallizer
FIG. 18-71 OSLO surface-cooled crystallizer.

the batch to that which permits the generated supersaturation to be relieved on the seed crystals. This means that the first cooling or evaporation following seeding must be at a very slow rate, which is increased nonlinearly in order to achieve the optimum batch cycle. Frequently, such controls are operated by cycle timers or computers so as to achieve the required conditions. Sugar, many pharmaceutical products, and many fine chemicals are produced this way. Shown in Fig. 18-72 is a typical batch crystallizer comprising a jacketed closed tank with top-mounted agitator and feed connections. The tank is equipped with a short distillation column and surface condenser so that volatile materials may be retained in the tank and solvent recycled to maintain the batch integrity. Provisions are included so that the vessel may be heated with steam addition to the shell or cooling solution circulated through the jacket so as to control the temperature. Tanks of this type are intended to be operated with a wide variety of chemicals under both cooling and solvent evaporation conditions.

Recompression Evaporation-Crystallization In all types of crystallization equipment wherein water or some other solvent is vaporized to produce supersaturation and/or cooling, attention should be given to the use of mechanical vapor recompression, which by its nature permits substitution of electrical energy for evaporation and solvent removal rather than requiring the direct utilization of heat energy in the form of steam or electricity. A typical recompression crystallizer flowsheet is shown in Fig. 18-73, which shows a singlestage evaporative crystallizer operating at approximately atmospheric pressure. The amount of heat energy necessary to remove 1 kg of water to produce the equivalent in crystal product is approximately 550 kilocalories. If the water evaporated is compressed by a mechanical compressor of high efficiency to a pressure where it can be condensed in the heat exchanger of the crystallizer, it can thereby supply the energy needed to sustain the process. Then the equivalent power for this compression is about 44 kilocalories (Bennett, Chem. Eng. Progress, 1978, pp. 67-70).

Although this technique is limited economically to those large-scale cases where the materials handled have a relatively low boiling point elevation and in those cases where a significant amount of heat is required to produce the evaporation for the crystallization step, it nevertheless offers an attractive technique for reducing the use of heat energy and substituting mechanical energy or electrical energy in those cases where there is a cost advantage for doing so. This technique finds many applications in the crystallization of sodium sulfate, sodium carbonate monohydrate, and sodium chloride. Shown in Fig. 18-74 is the amount of vapor compressed per kilowatt-hour for water vapor at 100°C and various ATs. The amount of water vapor compressed per horsepower decreases rapidly with increasing AT and, therefore, normal design considerations dictate that the recompression evaporators have a relatively large amount of heat-transfer surface so as to minimize the power cost. Often this technique is utilized only with the initial stages of evaporation where concentration of the solids is relatively low and, therefore, the boiling-point elevation is negligible. In order to maintain adequate tube velocity for heat transfer and suspension of crystals, the increased surface requires a large internal recirculation within the crystallizer body, which consequently lowers the supersaturation in the fluid pumped through the tubes. One benefit of this design is that with materials of flat or inverted solubility, the use of recompression complements the need to maintain low ATs to prevent fouling of the heat-transfer surface.

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  • stephan schreiber
    What are the operating system of circulating liquid crystalizer equipment?
    3 years ago

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