Ciystallization crystals

The "natural" shape or habit of a crystal obtained in the medium from which it is crystallized is of minus) importance in designing an industrial-scale ciystallizer. Crystal habit is also of extrema interest to crystallization thcorisia, Many anicles have been writtno describing variables ther affect natural habit, and)... 

This is because on one hand, heav wave is weaker and on the other hand, photoelastic testing method is unfavorable for observing the sound field of axial symmetry. The sound field (see Fig.4) excited by strip ciystal in solid is observed with photoelastic testing method. The wavefront of head wave can be see in Fig.4, which is a circumstantial evidence of wavefront of head wave excited just by point-shape crystal. We can calculate... 

Fig. VIII-8. Surface structures (a) (1 x 1) structure on the (100) surface of a FCC crystal (from Ref. 76) (b) C(2 x 1) surface structure on the (100) surface of a FCC ciystal (from Ref. 76). In both cases the unit cell is indicated with heavy lines, and the atoms in the second layer with pluses. In (b) the shaded circles mark shifted atoms. (See also Ref. 77.)...

Cooling Ciystalli rs use a heat sink to remove both sensible heat from the feed stream and the heat of crystallization released as crystals are formed. The heat sink may be no more than the ambient surroundings of a batch crystallizer, or it may be cooling water or another process stream. 

Piezoelectric Transducers Certain ciystals produce a potential difference between their surfaces when stressed in appropriate directions. Piezoelectric pressure transducers generate a potential difference proportional to a pressure-generated stress. Because of the extremely high electrical impedance of piezoelectric crystals at low frequency, these transducers are usually not suitable for measurement of static process pressures. 

Thermal decrepitation occurs frequently when crystals are rearranged because of transition from one form to another or when new compounds are formed (i.e., calcination of limestone). Sometimes the strains in cases such as this are sufficient to reduce the particle to the basic ciystal size. 

CiystaUization may be carried out from a vapor, from a melt, or from a solution. Most of the industrial applications of the operation involve crystalhzation from solutions. Nevertheless, crystal sohdifica-tion of metals is basically a crystalhzation process, and much theoiy has been developed in relation to metal ciystallization. This topic is so specialized, however, that it is outside the scope of this subsection, which is hmited to ciystaUization from solution. 

Another method of fractional crystallization, in which advantage is taken of different ciystallization rates, is sometimes used. Thus, a solution saturated with borax and potassium chloride will, in the absence of borax seed ciystals, precipitate only potassium chloride on rapid coohng. The borax remains behind as a supersaturated solution, and the potassium chloride crystals can be removed before the slower borax crystalhzation starts. 

Crystal Formation There are obviously two steps involved in the preparation of ciystal matter from a solution. The ciystals must first Form and then grow. The formation of a new sohd phase either on an inert particle in the solution or in the solution itself is called nucle-ation. The increase in size of this nucleus with a layer-by-layer addition of solute is called growth. Both nucleation and ciystal growth have supersaturation as a common driving force. Unless a solution is supersaturated, ciystals can neither form nor grow. Supersaturation refers to the quantity of solute present in solution compared with the quantity which would be present if the solution were kept for a veiy long period of time with solid phase in contac t with the solution. The latter value is the equilibrium solubility at the temperature and pressure under consideration. The supersaturation coefficient can be expressed... 

Nucleation due to crystal-to-ciystal contact is greater for equal striking energies than ciystal-to-metal contact. However, the viscous drag of the liquid on particle sizes normaUy encountered hmits the velocity of impact to extremely low values. The assumption that only the largest crystal sizes contribute significantly to the nucleation rate by ciystal-to-crystal contact permits a simple computation of the rate ... 

Crystallizers with Fines Removal In Example 3, the product was from a forced-circulation crystallizer of the MSMPR type. In many cases, the product produced by such machines is too small for commercial use therefore, a separation baffle is added within the crystallizer to permit the removal of unwanted fine crystalline material from the magma, thereby controlling the population density in the machine so as to produce a coarser ciystal product. When this is done, the product sample plots on a graph of In n versus L as shown in hne P, Fig. 18-62. The line of steepest ope, line F, represents the particle-size distribution of the fine material, and samples which show this distribution can be taken from the liquid leaving the fines-separation baffle. The product crystals have a slope of lower value, and typically there should be little or no material present smaller than Lj, the size which the baffle is designed to separate. The effective nucleation rate for the product material is the intersection of the extension of line P to zero size. 

In some crystalhzation apphcations it is desirable to increase the solids content of the shiny within the body above the natural consis-tencw, 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 shiny within the growing zone of the crystallizer. This mother liquor is also available for removal of fine ciystals for size control of the product. 

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 ciystals in the suspension chamber at E. At the top of the suspension chamber a stream of mother hquor D can be removed to be used for fines removal and destruction. This feature can be added on either type of equipment. Fine ciystals withdrawn from the top of the suspension are destroyed, thereby reducing the overall number of ciys-tals in the system and increasing the particle size of the remaining product ciystals. 

Scraped-Surface Crystallizer For relatively small-scale apph-cations a number of ciystallizer designs employing direct neat exchange between the shiny 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. 

In the forced-circulation-type crystallizer (Fig. 19-43) primaiy control over particle size is exercised by the designer in selecting the circulating system and volume of the body. From the operating standpoint there is little that can be done to an existing unit other than supply external seed, classify the discharge ciystals, or control the shiny... 

Because crystallizers can come with such a wide variety of attachments, capacities, materials of constrnc tion, and designs, it is very difficult to present an accurate picture of the costs for any except certain specific types of equipment, ciystallizing specific compounds. This is illustrated in Fig. 18-75, which shows the prices of equipment for ciystallizing two different compounds at various production rates, one of the compounds being produced in two alternative crystallizer modes. Installed cost (including cost of equipment and accessories, foundations and supporting steel, utility piping. 

In the case of lactose manufacture, crystals of uniform size are produced by first grinding part of a previous batch and taking a quantity with the required nunriiber of particles, then introducing these as seed crystals into a solution that is gradually cooled with gentle stirring. Variation in size of the seed ciystals does not affec t me size of the produc t ciystals. 

Purification of a chemical species by solidification from a liquid mixture can be termed either solution crystallization or ciystallization from the melt. The distinction between these two operations is somewhat subtle. The term melt crystallization has been defined as the separation of components of a binaiy mixture without addition of solvent, but this definition is somewhat restrictive. In solution crystallization a diluent solvent is added to the mixture the solution is then directly or indirec tly cooled, and/or solvent is evaporated to effect ciystallization. The solid phase is formed and maintained somewhat below its pure-component freezing-point temperature. In melt ciystallization no diluent solvent is added to the reaction mixture, and the solid phase is formed by cooling of the melt. Product is frequently maintained near or above its pure-component freezing point in the refining sec tion of the apparatus. 

Performance information for the purification of p-xylene indicates that nearly 100 percent of the ciystals in the feed stream are removed as produc t. This suggests that the liquid which is refluxed from the melting section is effectively refrozen oy the countercurrent stream of subcooled crystals. A high-meltingproduct of 99.0 to 99.8 weight percent p-xylene has been obtained from a 65 weight percent p-xyfene feed. The major impurity was m-xylene. Figure 22-12 illustrates the column-cross-section-area-capacity relationship for various product purities. 

One important factor influencing the solubility of rosin derivatives is its tendency to crystallize. Initially, a rosin product may appear to be soluble in a given solvent, but on standing, the rosin will crystallize out of soluble solution. This tendency of rosin to ciystallize can be overcome by derivatization, mainly esterification. 

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