Seeding supersaturation

As the smaller seed particles have a higher solubility, the seed supersaturation, or the Si chemical potential between that dissolved in the liquid droplet and... 

Procedure % MSA before seeding Supersaturation ratio Filtration flux (lilers/m /hr) Increase in filtration flux... 

Rain or snow might be made to form by seeding with crushed ice. It is hard, however, to crush ice to a powder, and hence no large number of seeds can be distributed. It was discovered by the American scientist Irving Langmuir that minute crystals of silver iodide, formed by condensation of silver iodide vapor, can serve as seeds for ice crystals. This discovery is the basis of the silver iodide method of making rain or snow by seeding supersaturated parts of the atmosphere. 

Tire usual commercial method of preparation of gibbsite is by cry staUization from a supersaturated caustic aluminate, Na A102, solution. Seed gibbsite crystals are used. 

Several features of secondary nucleation make it more important than primary nucleation in industrial crystallizers. First, continuous crystallizers and seeded batch crystallizers have crystals in the magma that can participate in secondary nucleation mechanisms. Second, the requirements for the mechanisms of secondary nucleation to be operative are fulfilled easily in most industrial crystallizers. Finally, low supersaturation can support secondary nucleation but not primary nucleation, and most crystallizers are operated in a low supersaturation regime that improves yield and enhances product purity and crystal morphology. 

Batch Crystallization. Crystal size distributions obtained from batch crystallizers are affected by the mode used to generate supersaturation and the rate at which supersaturation is generated. For example, in a cooling mode there are several avenues that can be followed in reducing the temperature of the batch system, and the same can be said for the generation of supersaturation by evaporation or by addition of a nonsolvent or precipitant. The complexity of a batch operation can be ihustrated by considering the summaries of seeded and unseeded operations shown in Figure 19. 

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. 

When a process is continuous, nucleation frequently occurs in the presence of a seeded solution by the combined effec ts of mechanical stimulus and nucleation caused by supersaturation (heterogeneous nucleation). If such a system is completely and uniformly mixed (i.e., the product stream represents the typical magma circulated within the system) and if the system is operating at steady state, the particle-size distribution has definite hmits which can be predic ted mathematically with a high degree of accuracy, as will be shown later in this section. 

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 ciystals tends to rob the supersaturation developed in the vaporizer, thereby lowering the efficiency of the recirculation system. 

Control of a batch ciystaUizer is almost always the most difficult part and veiy 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 necessaiy to limit the coohng or evaporation in... 

Garside elal. (1979) measured size distributions of seeondary nuelei and reported their variation with supersaturation. Signifieant inerease of nuelei with supersaturation is observed. Thus the proeess is not simply an attrition event alone, but is also related to the level supersaturation at whieh parent erystal is growing. Jones elal. (1986) also observed anomalous growth of seeondary nuelei in a study of the eontinuous MSMPR erystallization of potassium sulphate with eonsequenees inferred for seeondary nueleation rates. Girolami and Rousseau (1986) demonstrate the importanee of initial breeding meehanism in seeded potash alum bateh erystallization. The number of erystals... 

In all such laboratory studies, plant conditions and compositions should be employed as far as possible. Agglomeration rates tend to increase with the level of supersaturation, suspension density and particle size (each of which will, of course, be related but the effects may exhibit maxima). Thus, agglomeration may often be reduced by operation at low levels of supersaturation e.g. by controlled operation of a batch crystallization or precipitation, and the prudent use of seeding. Agglomeration is generally more predominant in precipitation in which supersaturation levels are often very high rather than in crystallization in which the supersaturation levels are comparatively low. 

A theoretical analysis of an idealized seeded batch crystallization by McCabe (1929a) lead to what is now known as the AL law . The analysis was based on the following assumptions (a) all crystals have the same shape (b) they grown invariantly, i.e. the growth rate is independent of crystal size (c) supersaturation is constant throughout the crystallizer (d) no nucleation occurs (e) no size classification occurs and (f) the relative velocity between crystals and liquor remains constant. 

Thus, if Mp is known, from the initial mass of seeds plus the ehange in solubility over the temperature range, then the growth inerement AL and eonsequent produet CSD eould be evaluated. MeCabe (1929b) verified the method in experimental work. It was observed, however, that nueleation oeeurred despite operation at low supersaturation levels - subsequently referred to as seeond-ary nueleation i.e. nueleation in the presenee of erystals (Chapter 5). 

As seen in Chapter 7, the operation of bateh erystallizers is inherently unsteady-state. Transient values oeeur of the major operating variables sueh as slurry density, supersaturation, temperature and mean partiele size. Methods of operational eontrol sueh as by use of seeding and temperature programming were also eonsidered in detail. 

The most frequent site for erystal enerustation is on a eompatible solid surfaee within a zone of high supersaturation and low agitation. Seleetion of a less eompatible material having a smooth surfaee ean avoid the major exeesses of enerustation. Dunean and Phillips (1979) and Shoek (1983), respeetively, reveal a eonneetion between the metastable zone width of erystallizing solutions and their propensity to enerust. It is well known that judieious erystal seeding ean also help minimize enerustation. Simple laboratory tests are reeommended to determine all these issues before the plant is built. 

At any point in the area above the curve, the sugar solution is supersaturated. This is the case at point B (300 g sugar per 100 g water at 20°C). Such a solution could be formed by carefully cooling a saturated solution at 60°C to 20°C, where a saturated solution contains 204 g sugar per 100 g water. The excess sugar stays in solution until a small seed crystal of sugar is added, whereupon crystallization quickly takes place. At that point the excess sugar... 

Catalytic devices These nonmagnetic devices use a perforated non-ferrous tube to encourage small calcite seed crystals to form and reduce the risk of bulk water scaling. They are promoted for use in hard waters under conditions where supersaturation can easily occur. 

---