CRYSTALLIZATION

Defining, Crystallization !!!

Crystallization refers to the formation of solid crystals from a homogeneous solution. Technique used to purify solid compounds. Based on the principles of solubility. Impurities are excluded from the growing crystals and the pure solid crystals can be separated from the dissolved impurities by filtration. A few parts per million may alter the product beyond recognition.

Possibilities of Crystallization

Formation of solid particles in vapor (formation of snow) Solidification from a liquid melt (formation of water into ice) Crystallization from a solution (formation of sugar from sugarcane)

Importance of Crystallization

It gives uniform product It gives solids of beautiful shapes, so marketing is easier Packing & storage of solids is easier Energy required is much less thank distillation

Applications of Crystallization

Detergents Fertilizers Food stuff (Protein, etc.) Catalysts Dyestuffs Electronic Materials Pharmaceuticals

Slow Cooling

Mechanism of Crystallization

Basic mechanism is Supersaturation this is obtained by Cooling ( NaNO3) Evaporation (common salt) Fractional Crystallization (salting)

Kinetics and Mechanisms of Crystallization

Crystallization process consists of two stages Formation of small particles or nuclei; Growth of the nuclei

If the number of nuclei can be controlled then the size of the crystal can also be controlled.

1.

Crystal Nucleation
The creation of crystalline bodies within a supersaturated fluid, is a complex, often ill-defined event, and nuclei may be generated by many different mechanisms

Primary Nucleationin the absence of crystals

primary nucleation are based on sequences of bimolecular collisions and interactions in a supersaturated fluid, which result in the buildup of lattice-structured bodies that may or may not achieve thermodynamic stability.

Secondary Nucleationin the presence of crystals

can take place only if crystals of the species under consideration are already present. This is mainly the case in working crystallizers

where

B is the rate of secondary nucleation (birthrate), Kb is the birthrate constant, MT is the slurry concentration (magma density), N is a term that gives some measure of the intensity of agitation in the system (e.g., the rotational speed of an impeller), and C is the supersaturation. The exponents j, l, and b vary according to the operating conditions

2.

Crystal Growth
1. 2.

mass transport, either by diffusion or convection from the bulk solution to the crystal face Surface reaction in which the growth units are integrated into the crystal lattice

where D is the diffusion coefficient, v the molar volume, C the supersaturation, and L the crystal size; i.e., the diffusion-controlled growth rate is directly proportional to the degree of supersaturation

3.

GrowthNucleation Interactions Crystal nucleation and growth in an industrial crystallizer cannot be considered in isolation because they interact with one another and with other system parameters in a complex manner. The rate of growth of a crystal in a solution is dependent on the temperature and concentration of the liquid at the crystal face.

Pictorial Representation Of The Process

Solubility-Supersolubility Diagram
Understanding phase equilibria is crucial to crystallizer operation Undersaturated : Crystals will dissolve Metastable : Crystals will grow Labile : Solution will nucleate spontaneously

Designing a Crystallizer
Five main types of information are generally required to design a crystallization process: 1) Solubility and phase relationships 2) Metastability limits 3) Nucleation characteristics 4) Crystal growth characteristics 5) Hydrodynamics of crystal suspensions

Solubility & Phase Relationships

Solubility and phase relationships influence the choice of crystallizer and method of operation. These data must be obtained by using the materials to be encountered in the plant because traces of impurity often have a considerable effect on phase relationships.

Metastability Limits

Metastable limits define acceptable operating conditions for the minimization of uncontrolled nucleation

Nucleation characteristics

The processes of nucleation and growth are both exceedingly complex They are influenced greatly by temperature, supersaturation and impurities. A knowledge of these system characteristics is essential in design.

Crystal growth characteristics

Specify the type of crystal growth The crystals are present in large quantities, 4so normally settling is hindered Further complications can arise if their shapes are irregular.

Hydrodynamics of crystal suspensions

Crystal suspension velocities must also be known so that liquor circulation rates in fluidized-bed crystallizers
Agitation rates in stirred vessels can be specified

Types of Crystallizers

Forced Circulating Liquid Evaporator Crystallizer Circulating Magma Vacuum Crystallizer Draft Tube Baffle Crystallizer Tank Crystallizer

Forced Circulating Liquid Evaporator Crystallizer

FCLEC

Supersaturation is reached by evaporation. The circulating liquid is drawn down inside the tube side of the condensing stream heater. The heated liquid then flows into the vapor space, where flash evaporation occurs, giving some supersaturation. The vapor leaving is condensed. The supersaturated liquid flows down the downflow tube and then up through the bed of fluidized and agitated crystals, which are growing in size. The leaving saturated liquid then goes back as a recycle stream to the heater, where it is joined by the entering fluid. The larger crystals settle out and slurry of crystals and mother liquid is withdrawn. these units are used for high evaporation rates and when crystal size is not of the utmost importance

Circulating Magma Vacuum Crystallizer

CMVC

The magma or suspension of crystals is circulated out of the main body through a circulating pipe . The magma flows though a heater, where its temperature is raised & The heated liquor mixes with body slurry and boiling occurs at the liquid surface. This causes supersaturation in the swirling liquid near the surface, which deposits in the swirling suspended crystals until they leave again via the circulating pipe. The vapors leave through the top. A steam-jet ejector provides vacuum.

Draft Tube Baffle Crystallizer

This is a tubular baffled crystallizer that offers plug flow under lamina flow conditions (low flow rates) with superior heat transfer coefficient, allowing controlled cooling profiles Body is equipped with a draft tube which also act as baffle to control the circulation of magma and agitator This gives much better control over crystal size, morphology and consistent crystal products.

Tank Crystallizers
Tank crystallization is an old method still used in some specialized cases. Saturated solutions, in tank crystallization, are allowed to cool in open tanks. After a period of time the mother liquid is drained and the crystals removed. Nucleation and size of crystals are difficult to control. Typically, labor costs are very high.