Crystallization

• Crystallization is a solid-liquid separation process in which mass transfer of a solute from the liquid
solution to a pure solid crystalline phase occurs

• In crystallization, the solution is CONCENTRATED and usually cooled until the solute concentration
greater than it solubility at that temperature.

• Then, the solute comes out of the solution forming CRYSTAL of approximately pure solute.

• Example : Production of sucrose from sugar beet, where the sucrose is crystallized out from an aqueous
solution

• This process can occur in:

 freezing of water to form ice,
 formation of solid particles from liquid melts,
 formation of snow particles from vapor or
 formation of solid crystals from a liquid solution
 Crystallization process
• Crystallization Steps :

Nucleus Crystal
Formation Growth

• The driving force for nucleus formation and crystal growth is

SUPERSATURATION
• These 2 steps will NEVER happen in saturated or under
saturated solution.
 Supersaturation
• Supersaturation is a state of a solution that contains more of the
dissolved material – supersaturated solution.

• Three methods to produce supersaturation:

• Cooling the solution with negligible evaporation (tank/batch

crystallizer).
• Evaporation of the solvent with little or no cooling (crystallizing
evaporator)
• Combination of cooling and evaporation (vacuum crystallizer)

Nucleation
Primary nucleation
Homogenous nucleation
• Crystallization occur at high
supersaturation.
• No agitation needed
• Initial formation of crystal The
crystal size distribution begins to
take shape.
Crystallization process steps
Crystal growth
Secondary nucleation • Once the first small crystal
forms, the nucleus start to
increases its own dimension.
• Growth rate is influenced by
Contact nucleation
several physical factors, such as
surface tension of solution,
• Crystallization occur at low
pressure, temperature, relative
supersaturation
crystal velocity in the solution,
• Secondary nucleation requires
Reynolds number.
"seeds" or existing crystals to
perpetuate crystal growth.
• The crystal growth is initiated
with contact between solution
and other crystal, a mixer
blade, a pipe, a vessel wall, etc.
Example of crystallization process
~ Salt crystal production ~
• Take a pot of boiling water and add table salt while stirring to
make a water-salt solution.
• Continue adding salt until no more salt will dissolve in the
solution (this is a saturated solution).
• Now add one final teaspoon of salt. The salt that will not
dissolve will help the first step in crystallization begin.
 Advantages of crystallization
Able to obtain very high purity products
(>99.9%)

Products are with good appearances

such as the sizes and shapes
crystallization

Crystals formed are the most

concentrated form of the chemical
possible

Requires less energy input

 Types of Crystals
Cubic – three equal axes at right angles to each other

Tetragonal – three axes at right angles to each other, one axis longer
than the other two

Orthorhombic – three axes at right angles to each other, allof

different lengths

Hexagonal – three equal axes in one lane at 60° to each other and a
fourth axis at right angles to this plane

Monoclinic – three unequal axes, two at right angles in a plane and a third at
some angle to this plane

Triclinic – three unequal axes at unequal angles to each other and

not 30, 60 or 90°

Trigonal – three equal and equally inclined axes

Types of Crystals
 Equilibrium Solubility in Crystallization

• In crystallization equilibrium is
attained when the solution or
mother liquor is saturated.
• Represented by a SOLUBILITY
CURVE.
• Solubility is dependent mainly on
temperature.
• In general, the solubilities of most
salts increase slightly or markedly
with increasing temperature.
 Solubility Curve

 anywhere on the solubility curve -

saturated solid crystals
 above the solubility curve -
supersaturated solid crystals
 below the solubility curve -
unsaturated solution.

Solubility of sodium thiosulfate, Na2S2O3, in water

• Solubility increases rapidly with temperature, but there are definite breaks in the
curve which indicate different hydrates.
• Up to 50°C, the solid crystals formed are Na2S2O3·5H2O
• From 50°C to 65°C, the solid crystals formed are Na2S2O3·2H2O
• From 65°C to 70°C, the solid crystals formed are Na2S2O3·½H2O
• Above 70°C, anhydrous solid crystals formed are Na2S2O3
 Yields and Heat and Material Balances in Crystallization

1) Material balances in crystallization

• The yield of crystals from a crystallization process can be calculated knowing the initial
concentration of solute, the final temperature and the solubility at this temperature.

W kg H2O

F kg feed Cooler or S kg solution (T)

(T) crystallizer

C kg crystals
2) Heat effects and heat balances in crystallization

• When a compound (whose solubility increases as temp. increases) dissolves, there is an

absorption of heat called heat of solution.
• At equilibrium, the heat of crystallization is equal to the negative of heat of solution at
the same concentration.
• If some evaporation occurs, the enthalpy, Hv of the water vapor is obtained from the
steam tables.
• Total heat absorbed, q :
q = H2 + H v - H 1

H1 = enthalpy of the entering solution

H2 = enthalpy of the final mixture of crystals and mother liquor
Hv = enthalpy of the water vapor

• If q is positive, heat must be added to the system.

• If q is negative, heat is evolved or given off.
Example 12.11-1
• A salt solution weighing 10 000 kg with 30% Na2CO3 is cooled to 293 K (200°C). 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?
(a) Assume that no water is evaporated.

V kg H2O

10,000 kg solution S kg solution

COOLER &
CRYSTALLIZER
30% Na2CO3 21.5 kg Na2CO3/100 kg H2O
70% H2O

C kg crystals, Na2CO3 ·10H2O

1. Perform material balance for water and Na2CO3
100 180.2
H2O balance: 0.7(10000)  (S )  (C )  0
100  21.5 286.2

21.5 106
Na2CO3 balance: 0.3(10000)  (S )  (C )
100  21.5 286.2

Molecular Weight: 10H2O = 180.2

Na2CO3 = 106
Na2CO3·10H2O = 286.2

2. Solving the two equation simultaneously,

C = 6370 kg of Na2CO3·10H2O crystals
S = 3630 kg solution
(b) Assume that 3% of the total weight of the solution is lost by evaporation of water in cooling.

0.03(10000)  300 kg H 2 O

Balance for water and Na 2 CO 3 :

100 180.2
0.70(10000)  (S )  (C )  300
100  21.5 286.2

21.5 106
0.3(10000)  (S )  (C )  0
100  21.5 286.2

Solving the two equation simultaneously,

C = 6630 kg of Na2CO3·10H2O crystals
S = 3070 kg solution
Example 12.11-2
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 crystal 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
103 kJ/kg mol MgSO4·7H2O. Calculate the yield of crystals and make a heat balance to
determine the total heat adsorbed, q assuming no water is vaporized.

W= 0

F=2268kg
(327.6K) S (293.2 K) 35.5 kg MgSO4
Crystallizer
100kg H2O
48.2 kg MgSO4
100 kg H2O
C kg MgSO4 . 7H2O
1. Perform material balance for water and MgSO4
 100  100 126
H2O balance:  2268  (S )  (C )  0
 100  48 . 2  100  35 . 5 246 . 49

MgSO4 balance: 
48.2  35.5 120.49
2268  (S )  (C )
 100  48 . 2  100  35 . 5 246 . 49

Molecular Weight: 7H2O = 126

MgSO4 = 126
MgSO4 ·7H2O = 246.49

2. Solving the two equation simultaneously,

C = 616.9 kg of MgSO4 ·7H2O crystals
S = 1651.1 kg solution
To make heat balance, a datum of 293.2 K will be used.

The enthalpy of feed, H1 = 2268(327.6K - 293.2K)(293) = 228600 kJ H = FCpΔT

Heat of solution is = - 13.31 x 103 kJ/ kgmol MgSO4

Heat of crystallization, H2 = (- 13.31 x 103 kJ/ kgmol MgSO4·7H2O) / (246.49 kg/kgmol MgSO4·7H2O)
= (- 54.0 kJ/kg crystals) x 616.9 kg crystals
= -33312 kJ
Assume value at 291.2 K is the same as at 293.2 K
The total heat absorbed, q:
q = H 2 + Hv - H1
= -33312 - 228600
= -261912 kJ
Since q is –ve , heat is evolved or given off.