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# CRYSTALLIZATION

## CRYSTALLIZATION - is also a solid-liquid separation process in which mass transfer occurs

of a solute from the liquid solution to a pure solid crystalline phase. It is a process where
solid particles are formed from a homogeneous phase.
EQUILIBRIUM SOLUBILITY IN CRYSTALLIZATION
Crystallization Equilibrium is attained when the solution or mother liquor is saturated,
represented by the solubility curve. Solubility is dependent mainly upon temperature and
pressure has a negligible effect on solubility.
YIELDS AND HEAT AND MATERIAL BALANCES IN CRYSTALLIZATION
Yields of Crystals can be calculated knowing the initial concentration of solute, the final
temperature, and the solubility at this temperature.
Material balances the calculations are straightforward when the solute crystals are
anhydrous. Simple water and solute material balances are made. When the crystals are
hydrated, some of the water in the solution is removed with the crystals as a hydrate.
Example: Yield of a Crystallization Process
A salt solution weighing 10,000 kg with 30 wt % Na2CO3 is cooled to 293 K (20%). The
salt crystallizes as the decahydrate. What will be the yield of Na2CO3.10H2O crystals if the
solubility is 21.5 kg anhydrous Na2CO3/100 kg of total water? Do this for the following
cases:
a. Assume that no water is evaporated.
b. Assume that 3% of the total weight of the solution is lost by evaporation of water in
cooling.
Solution:
The molecular weights are 106.0 for Na2CO3, 180.2 for 10H20, and 286.2 for
Na2CO3.10H20.

## Process Flow Diagram:

W kg H2O
10,000 kg salt solution

S kg

solution
30% Na2CO3
Na2CO3/100 kg H2O

21.5 kg

C kg crystals, Na2CO3.10H2O
Where; W is kg H2O evaporated, S is kg solution(mother liquor), and C is kg crystals of
Na2CO3.10H2O.
a. Material Balance for water, where W=0,
(100%-30%)% H2O/100x 10,000 kg salt solution = [100 kg H2O/100 kg H2O + 21.5
kg Na2CO3]S kg solution
+ 180.2/286.2 (C) + 0
0.70(10,000) = 0.823(S) + 0.63(C)
where 180.2/286.2 is wt fraction of water in the crystals
Material Balance for Na2CO3
30% Na2CO3 ( 10,000 kg salt soln.) = [21.5 kg Na2CO3/100 kg H2O + 21.5 kg
Na2CO3] S + 106.0/286.2 (C) + 0
0.30(10,000) = 0.177 (S) + 0.370 (C)
Solving the 2 equations simultaneously,
C = 6370 kg of Na2CO3.10H2O crystals
S = 3630 kg solution
b. W = 30% H2O ( 10,000 kg salt solution ) = 300 kg H2O
Material Balance for H2O;
0.70 ( 10,000 ) = 100/(100 + 21.5 )(S) + 180.2/286.2 ( C) + 300
7,000 = 0.823(S) + 0.63(C) + 300

## HEAT EFFECTS AND HEAT BALANCES IN CRYSTALLIZATION

Heat of Solution is an absorption of heat, when a compound whose solubility increases as
temperature increases dissolves. Most data are given as the change in enthalpy in
kJ/kg mol(kcal/g mol) of solute occuring with the dissolution of 1 kg mol of the solid in a
large amount of solvent at essentially infinite dilution.
Evolution of Heat occurs when a compound dissolves whose solubility decreases as
temperature increases.
Heat of Crystallization at equilibrium, this is equal to the negative of the heat of solution
at the same concentration in solution.
Method of calculating heat effects during crystallization process is to use the enthalpyconcentration chart for the solution and the various solid phases which are present in
the systems. The enthalpy H1 of the entering solution at the initial temperature is read
off the chart, where H1 is kJ(btu) for the total feed. The enthalpy H2 of the final
mixture of crystals and mother liquor at the final temperature is also read off the chart.
If some evaporation occurs, the enthalpy Hv of the water vapor is obtained from the
steam tables. Then the total heat absorbed q in kJ is
q = ( H2 + Hv ) H1
If q is positive, heat must be added to the system. If it is negative, heat is evolved or given
off.
Example: Heat Balance in Crystallization
A feed solution of 2268 kg at 327.6 K (54.4 C) containing 48.2 kg MgSO4/100 kg total
water is cooled to 293.2 K (20 C), where MgSO4.7H2O crystals are removed. The
solubility of the salt is 35.5 kg MgSO4/100 kg total water . The average heat capacity
of the feed solution can be assumed as 2.93 kJ/kg. K. The heat of solution at 291.2 K
(18 C) is 13.31 x 10 kJ/kg mol MgSO4.7H2O. Calculate the yield of crystals and
make a heat balance to determine the total heat absorbed, q, assuming that no water
is vaporized.
Solution;
Process Flow Diagram; Heat of solution at 291.2 K (18 C) is 13.31 x 10 kJ/kg mol
MgSO4.7H2O

Material Balance for H2O; Molecular weight of 7H2O is 126, MgSO4.7H2O is 246.49
2268 kg solution[100 kg total H2O/(100 kg H2O + 48.2 kg MgSO4)] = [100 kg H2O/
(100 kg H2O + 35.5 kg
MgSO4)][S] +
[126/246.49][C]
1,530.354 kg total H2O = 0.738 S + 0.511 C
C = [1,530.354 0.738 S]/0.511
Material Balance for MgSO4;
2268 kg solution[48.2 kg MgSO4/(100 kg H2O + 48.2 kg MgSO4)] = [35.5 kg MgSO4/
(100 kg H2O + 35.5 kg
MgSO4)][S] +
[ 120.49/246.49][C]
737.636 kg MgSO4 = 0.262 S + 0.489 C
S = [737.636 0.489 C]/0.262
Solving simultaneously the 2 equations, therefore;
C = {1,530.354 0.738([737.636 0.489 C]/0.262)}/0.511
C = 616.9 kg MgSO4.7H2O crystals
S = [737.636 0.489( 616.9 )]/0.262
S = 1,651.1 kg solution
Heat Balance at 293 K (20 C)
The enthalpy of the feed , H1
H1 = 2268 kg solution( 327.6 K 293.2 K ) 2.93 kJ/kg . K
= 228,600 kJ
Heat of solution = - (13.31 x 10 kJ/kg mol MgSOI4.7H2O)/246.49 = - 54.0 kJ/kg crystals
Heat of crystallization = -(- 54.0 kJ/kg ) = +54.0 kJ/kg crystals
or
= 54.0 kJ/kg crystals ( 616..9 kg MgSO4.7H2O crystals)
= 33,312 kJ
Total heat absorbed = q = - 228,600 kJ 33,312 kJ = - 261,912 kJ ( - 348,240 btu )
Therefore q is given off and must be removed because the value of q is negative.

## EQUIPMENT FOR CRYSTALLIZATION

Crystallization cannot occur without Supersaturation.
Crystallizer is to cause a supersaturated solution to form.
Methods used to bring about supersaturation is as follows;
1. Supersaturation produced by cooling the solution with negligible evaporation tank and
batch-type crystallizers
- substances must have a solubility curve that decreases markedly with
temperature.
2. Supersaturation produced by evaporation of the solvent with little or no cooling
evaporator-crystallizers and crystallizing evaporators this used when solubility curve
changes little with temperature.
3. Supersaturation by combined cooling and evaporation in adiabatic evaporator-vacuum
crystallizers a hot solution is introduced into a vacuum, where the solvent flashes or
evaporates and the solution is cooled adiabatically.
Methods of classification of crystallizers;
4. Circulating Magma Method the entire magma of crystals and supersaturated liquid is
circulated through both the supersaturation and crystallization steps without separating
the solid from the liquid into two streams. Crystallization and supersaturation are
occuring together in the presence of the crystals.
5. Circulating-liquid method a separate stream of supersaturated liquid is passed through
a fluidized bed of crystals, where the crystals grow and new ones form by nucleation.
Then the saturated liquid is passed through an evaporating or cooling region to produce
supersaturation again for recycling.
Types of Crystallizers;
6. Tank Crystallizers hot saturated solutions are allowed to cool in open tanks. After a
period of time the mother liquor is drained and the crystals are removed.
7. Scraped Surface Crystallizers which consists of an open trough 0.6 m wide with a
semicircular bottom having a cooling jacket outside. A slow-speed spiral agitator rotates
and suspends the growing crystals on turning.
8. Circulating-liquid evaporator-crystallizer supersaturation is generated by evaporation.

and agitated crystals, which are growing size. The leaving saturated liquid then goes back
as a recycle stream to
the heater, where it is joined by the entering
feed. The larger crystals settle out and a slurry of crystals and mother liquor is withdrawn as
product.
4. Circulating-magma vacuum crystallizer the magma or suspension of crystals is
circulated out of the main body through a circulating pipe by a screw pump. The magma
flows through a heater, where its temperature is raised 2 to 6 K. The heated liquor then
mixes with body slurry and boiling occurs at the liquid surface. This causes supersaturation
in the swirling liquid near the surface, which deposits on the suspended crystals until they
leave again via circulating pipe. The vapor leave through the top. A steam-jet ejector
provides the vac