Crystallization precipitation processes

Jones, A.G., Hostomsky, J. and Waclii, S., 1996. Modelling and analysis of particle formation during agglomerative crystal precipitation processes. Chemical Engineering Communications, 146, 105-130. 

Development and scale-up of reactive crystallization/precipitation processes can present some of the most difficult challenges in the field. The reader is referred to the quotation in Section 10.1.2 above as a reminder of this difficulty. 

The method of preparation of a support material has a tremendous effect on its properties (11). For example, zeoHtes, which are highly stmctured aluminosihcates, are known to be extremely sensitive to the conditions employed both during and after crystallization (12). Also, when siUca—titania is precipitated by a coprecipitation method using ammonia, in which localized hydroxide ion gradients are estabUshed by the precipitation process itself, the product is much more acidic than when it is precipitated using urea, which suppHes hydroxide ion slowly and uniformly during precipitation (13). 

This equation describes the change of population in a well-mixed system and is often used to model fully mixed crystallization and precipitation processes. If the system is imperfectly mixed, however, then the more complicated equation 2.88 can be used provided that the external flow field can be calculated e.g. by use of CFD (see later). 

Thus under ideal circumstances the modes of aggregation can be discriminated by such plots. Deviations below the expected slopes are usually attributed to collision inefficiency leading to imperfect aggregation. In a crystallization or precipitation process, of course, deviations may also occur due to growth and nucleation unless properly accounted for. 

The significance of this novel attempt lies in the inclusion of both the additional particle co-ordinate and in a mechanism of particle disruption by primary particle attrition in the population balance. This formulation permits prediction of secondary particle characteristics, e.g. specific surface area expressed as surface area per unit volume or mass of crystal solid (i.e. m /m or m /kg). It can also account for the formation of bimodal particle size distributions, as are observed in many precipitation processes, for which special forms of size-dependent aggregation kernels have been proposed previously. 

For liquid-liquid crystal precipitation systems where the particle formation processes are fast, mixing becomes an important determiner of performance with a subtle interplay of micro- and mesomixing, which changes as scale of... 

Budz, J., Jones, A.G. and Mullin, J.W., 1987b. Agglomeration of potassium sulphate in an MSMPR crystallizer. In Fundamental aspects of crystallization and precipitation processes, American Institute of Chemical Engineers. Symposium Series, No. 253, 83, New York American Institute of Chemical Engineers, pp. 78-84. 

The reaction is sustained by addition of iron metal which reacts with the sulfuric acid formed, regenerating Fe(n) in solution. To ensure that the desired crystal form precipitates, a seed of a-FeO(OH) is added. However, with appropriate choice of conditions, for example of pH and temperature and by ensuring the presence of appropriate nucleating particles, the precipitation process may be adapted to prepare either the orange-brown y-FeO(OH), the red a-Fe203 or the black Fe304. 

The overall kinetics of crystal precipitation has to consider that the process consists of a series of consecutive processes in simple cases, the slowest is the rate determining step. Assuming the volume diffusion is not the rate determining step, we still have at least the following reaction sequences ... 

Although crystals can be grown from the liquid phase—either a solution or a melt—and also from the vapour phase, a degree of supersaturation, which depends on the characteristics of the system, is essential in all cases for crystal formation or growth to take place. Some solutes are readily deposited from a cooled solution whereas others crystallise only after removal of solvent. The addition of a substance to a system in order to alter equilibrium conditions is often used in precipitation processes where supersaturation is sometimes achieved by chemical reaction between two or more substances and one of the reaction products is precipitated. 

Experiments have determined (8) that mechanical blocking of dislocation motion can be achieved quite directly by introducing tiny particles into a crystal. This process is responsible for the hardening of steel, for instance, where particles of iron carbide are precipitated into iron. 

It should be recognized that a seemingly completed precipitation process can be subject to secondary reactions, designated in the overall scheme as aging, which may involve dehydration, crystallization, recrystallization, ripening, etc. of the original particles. 

Proteins that remain in whey after removing casein from milk are recovered as whey protein concentrates by precipitation with added polyphosphate or other polyvalent anionic compounds, ultrafiltration, ion exchange adsorption, gel filtration, or a combined acid and heat precipitation process. Whey protein concentrates are also manufactured by a combined process involving electrodialysis, concentration, lactose crystallization, and drying (Richert 1975 Morr 1979 Marshall 1982 Anon. 1982 Muller 1982B). 

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