Crystallization

Crystallization is the (natural or artificial) process for the formation of solid crystals from a uniform solution. A complete crystallization plant includes a crystallization unit, centrifuge, pump and condenser.

Crystallization types
1-Cooling crystallization Whenever the conditions are favorable, crystal formation results from simply cooling the solution. An example of this crystallization process is the production of Glauber's salt, a crystalline form of sodium sulfate. Cooling crystallizers The simplest cooling crystallizers are tanks provided with a mixer for internal circulation, where temperature decrease is obtained by heat exchange with an intermediate fluid circulating in a jacket. These simple machines are used in batch processes, as in processing of pharmaceuticals and are prone to scaling. Batch processes normally provide a relatively variable quality of product along the batch. A common practice is to cool the solutions by flash evaporation: when a liquid at a given T0 temperature is transferred in a chamber at a pressure P1 such that the liquid saturation temperature T1 at P1 is lower than T0, the liquid will release heat according to the temperature difference and a quantity of solvent, whose total latent heat of vaporization equals the difference in enthalpy. In simple words, the liquid is cooled by evaporating a part of it. 2-Evaporative crystallization Another option is to obtain, at an approximately constant temperature, the precipitation of the crystals by increasing the solute concentration above the solubility threshold. To obtain this, the solute/solvent mass ratio is increased using the technique of evaporation. This process is of course insensitive to change in temperature. Evaporative crystallizers Most industrial crystallizers are of the evaporative type, such as the very large sodium chloride and sucrose units. The most common type is the forced circulation (FC) model. A pumping device keeps the crystal slurry in homogeneous suspension throughout the tank, including the exchange surfaces; by controlling pump flow, control of the contact time of the crystal mass with the supersaturated solution is achieved, together with reasonable velocities at the exchange surfaces. 3-Draft tube-baffle technology: This type of crystallization is especially designed for low viscosity products when a narrow crystal size distribution is expected. Super saturated product enters into a chamber containing (mixture of solids and solution). Instantaneously, the product crystallizes around the crystals that are already inside the vessel so that the solution reaches the saturation point. Inside the chamber, a stirrer creates a high circulation flow in order to give a good repartition of the crystals. On the side of the vessel, baffles create a quiet zone where an upward flow brings the smallest crystals out of the vessels. They are re-melted and put back in the vessel.

Process
The crystallization process consists of two major events, nucleation and crystal growth. Nucleation is the step where the solute molecules dispersed in the solvent start to gather into clusters, on the nanometer scale (elevating solute concentration in a small region), that become stable under the current operating conditions. These stable clusters constitute the nuclei. However, when the clusters are not stable, they re-dissolve. Therefore, the clusters need to reach a critical size in order to become stable nuclei. Such critical size is dictated by the operating conditions (temperature, supersaturation, etc.). Crystal growth is the subsequent growth of the nuclei that succeed in achieving the critical cluster size. Nucleation and growth continue to occur simultaneously while the supersaturation exists. Supersaturation is the driving force for crystallization. Hence the rate of nucleation and growth is driven by the existing supersaturation in the solution. Depending upon the conditions, either nucleation or growth may be predominant over the other, and as a result, crystals with different sizes and shapes are obtained (control of crystal size and shape constitutes one of the main challenges in industrial manufacturing, such as for pharmaceuticals).

Industrial applications of crystallization

There are two major groups of applications for the artificial crystallization process: Crystal Production and Purification Crystal production 1. Powder salt for food industry 2. Silicon crystal wafer production 3. Production of sucrose from sugar beet, where the sucrose is crystallized out from an aqueous solution 4. Ionic and covalent crystal production 5. Powder, sand and smaller sizes crystals 6. Mass-production: on chemical industry, like salt-powder production 7. Sample production: small production of tiny crystals for material characterization 8. Thin film production Crystal Purification 9. Used to improve (obtaining very pure substance) and/or verify their purity. 10. Crystallization separates a product from a liquid feed stream, often in extremely pure form, by cooling the feed stream or adding precipitants which lower the solubility of the desired product so that it forms crystals. 11. Well formed crystals are expected to be pure because each molecule or ion must fit perfectly into the lattice as it leaves the solution. Impurities would normally not fit as well in the lattice, and thus remain in solution preferentially. Hence, molecular recognition is the principle of purification in crystallization. However, there are instances when impurities incorporate into the lattice, hence, decreasing the level of purity of the final crystal product. Also, in some cases, the solvent may incorporate into the lattice forming a solvate. In addition, the solvent may be 'trapped' (in liquid state) within the crystal formed, and this phenomenon is known as inclusion. 12. More than 80% of the substances used in pharmaceuticals, fine chemicals, agrochemicals, food and cosmetics are isolated or formulated in their solid form. Crystallization is in general the last chemical purification step in the production of ingredients.