Crystallization
What is Crystallization
Formation of solid particles within a homogenous phase
e.g. formation of solid NaCl from salt solution
Formation of ice, snow from water vapor
Natural minerals, e.g. gemstones, diamonds
Significance of study of crystallization:
Crystals are very pure form of materials
Crystals formed from impure solution are still pure
Very practical method of obtaining very high purity
Rock salt crystals
material
in satisfactory condition for storage
Natural diamond crystal
Snow flakes
Terms
Magma: two phase mixture of mother liquor and crystals of all sizes
Mother liquor: the part of a solution left over after crystallization
Supersaturated solution: solution with concentration greater
than equilibrium concentration
Invariant crystal: the crystal maintains geometric similarity
Characteristic length: definition of size of crystal
L
6v
s
p
sp is surface area of the crystal
vp is the volume of the crystal
Overlapping principle: different faces of crystal grow at a different
rate and later the shape and appearance of the crystal
Faces with low velocity survive crystal growth
Equilibrium Curve
Solubility
KNO3
NaCl
MnSO4
Temperature
Solubility-supersolubility
diagram
Solubility is usually a strong function of temperature, e.g. KNO3, MnSO4
Most inorganic substances crystallize with water of crystallization
In some systems several hydrates might be formed
Fundamental driving force for crystallization is change in chemical potential but
mostly expressed as concentration driving force
Supersaturation
From
solutions
solution with concentration greater than equilibrium concentration
Generated using
Temperature change (cooling or heating)
Evaporating the solvent
Addition of third component (salting out, precipitation)
Degree of supersaturation is given by
c y c c
Saturation ratio is given by S c
*
Relative supersaturation: c S 1
c
Example
At 293 K, a supersaturated solution of sucrose contains 2.45 kg sucrose/kg water. If
the equilibrium saturation value is 2.04 kg/kg water, what is the supersaturation
ratio in terms of kg/kg water and kg/kg solution?
Formation of Crystals
Rupture of existing crystals
Nucleation
Primary nucleation (homogenous nucleation)
Solute molecules clustering to form aggregates or embryos that grow into
nuclei
Secondary nucleation (heterogeneous nucleation)
Contact nucleation
Breakage of dendritic growths on the crystals
Catalytic effect of solid particles in the supersaturated solution
Fluid shear nucleation
Sonication, shear due to impellers, etc
Formation of Crystals
Caking
Frequently cake or cement together on storage
Depend on crystal size, shape, moisture content, storage
conditions
Minimized by airtight packing, deposition of inert dust on crystals
Washing
To remove mother liquor content and for removal of impurities
Crystals are separated using filtration, centrifugation
Cake is washed with another insoluble liquid
Multiple washing stages might be required
Crystal Growth
Design of crystallizers
Set supersaturation limit in the crystallizer
Calculate solution recirculation rate from material balance
Estimate maximum growth rate assuming cubic crystals for given
supersaturation
Calculate crystal growth for different desupersaturations
Mass of crystals in suspension and the suspension volume are
calculated assuming a value for the voidage which is often about 0.85
Solution up-flow velocity is calculated for very small crystals
Usually measured exerimentally
Crystallizer area and diameter are calculated, and height is estimated
using (volume of suspension/cross-sectional area)
Equipment
Cooling Crystallizers
Agitated vessels
Scraped surface crystallizers
Evaporating crystallizers
Vacuum cooling crystallizers
Equipment
Cooling Crystallizers
Agitated vessels
Scraped surface crystallizers
Evaporating crystallizers
Vacuum cooling
Forced circulation
Forced circulation Swenson crystallizer
Equipment
Cooling Crystallizers
Agitated vessels
Scraped surface crystallizers
Evaporating crystallizers
Vacuum cooling
Forced circulation
Fluidized bed
Oslo fluidized bed crystallizer
