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Crystallization

Crystallization
• Crystallization is a solid-liquid operation used to separate solutes
from a solution in the form of crystals.

• In this unit operation, mass is transferred from the liquid phase

(solution) to the solid phase/the crystal surface.

• It involves simultaneous heat and mass transfer.

• Crystallization is normally carried out in process industry, either

from solution or melt(polymer melts).
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• This operation gives almost pure products from

relatively impure solutions in a single processing step in
the form of crystals of the desired size range.

• Crystallization is carried out at low temperatures.

• From energy point of view, crystallization requires

much low energy for separation as compared to other
purification methods( distillation, etc).
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Crystallization usually involves….

i. Concentration of solution (evaporating a part of solvent)

ii. Cooling of the solution until the concentration of the solute

becomes greater than its solubility at the prevailing
temperature. Then the solute comes out of the solution in
the form of crystals.

• Performance of a crystallization process is evaluated in

terms of size, shape, structure, yield and purity of
crystals.

• In commercial crystallization the size and shape of the

crystals are as important as the yield and purity of
crystals.

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• Solubility: The solubility of a solute in a given solvent is the

concentration of the solute in a saturated solution at a given
temperature.

• Saturation: A saturated solution is defined as the one, which is

in equilibrium with an excess of solid solute at a given
temperature.

• Solubility Curves:

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Mechanism of Crystallization

• The formation of crystals from solution involves three steps.

1. Supersaturation
2. Nucleus formation
3. Crystal growth

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Mier’s Supersaturation theory

• Mier and Issac proposed a theory explaining a relationship between
Supersaturation and spontaneous crystallization.

Mier’s theory points out that…

1. The greater the degree of Supersaturation, the more chance is of
nuclei formation

2. if the Supersaturation passes a certain range of values, nucleus

formation is extremely rapid.
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Assumptions of Mier’s Supersaturation theory

1. The solute and the solvent must be pure.

2. The solution must be free from solid solute particles.

3. The solution must be free from foreign solid particles.

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Solubility – super-solubility diagram

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• The theory can be explained with the help of solubility – super-

solubility diagram.
• Here the curve AB is the ordinary solubility (equilibrium) curve
represents the maximum concentration of solutions that can be
obtained by bringing solid solute into equilibrium with solvent.

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• If a sample of solution having a temperature and composition of

point C is cooled in the direction of CD, it first crosses the solubility
curve AB, but no nucleus will be formed.

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• When it reaches some where in the neighbourhood of the point D

(according to Mier’s theory) crystallization begins.
• As the crystallization proceeds the concentration of the solution
follows roughly according to the curve DE and reaches the solubility
curve.

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• In the absence of any solid particles the curve FG represents the

limit at which nucleus formation begins spontaneously and,
consequently crystallization starts – this line (FG) is called the
super solubility curve.

• According to Mier’s theory at any point between C and D point

nuclei cannot form and crystallization cannot occur.

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Figure shows Saturation-

supersaturation diagram
showing the 1. stable
2. metastable and 3. labile
zones for the crystallization of
a solid from solution.

The solid line represents the equilibrium solubility curve and the dashed line
represents the maximum supersaturation or nucleation curve. The separation
of the two curves represents the metastable zone width (MZW).
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The process follows a path….

• First, unsaturated feed (A) is cooled through the solubility curve (B),
the metastable zone (C) and into the labile zone (D).
• Rapid nucleation occurs in the labile zone.
• The concentration then falls out of the labile zone (E), and growth
occurs within the metastable zone during the reamainder of the
cooling (F).
• The metastable zone is where growth occurs.

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Discuss following Crystallizer in detail

1. Draft Tube Baffle (DTB) Crystallizer
2. Forced Circulation Crystallizer
3. Surface Cooled Crystallizer
4. Batch Vacuum Crystallizer

• Construction
• Working
• Schematic Diagram
• Advantages
• Disadvantages
• Application
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