Crystallization
MASS TRANSFER PROCESSES AND EQUIPMENTS
(CH2051)
Dr Nonni Soraya Sambudi
By end of topic, students should be able to
understand the concept of crystallization
understand equilibrium solubility of materials
understand Nucleation Theories
describe crystal growth
perform material balance
2
Introduction:
Crystallization of Copper Sulphate
FORMATION OF CRYSTALS
• Formation of solid crystals from homogeneous
solution
Concentration of solute, C
Solubility curve
[saturation
concentration, C*(T)]
A - Undersaturated
Temperature, T
4
FORMATION OF CRYSTALS
• Formation of solid crystals from homogeneous
solution
Concentration of solute, C
Solubility curve
[saturation
concentration, C*(T)]
B
A
B - Supersaturated
Temperature, T
5
FORMATION OF CRYSTALS
• Formation of solid crystals from homogeneous
solution
Metastable
zone
Concentration of solute, C
Metastable Solubility curve
limit [saturation
concentration, C*(T)]
C B
A
C - Nucleation
Temperature, T
• Metastable limit is influenced by saturation temperature, rate of supersaturation generation, impurity level,
mixing
• For nucleation in metastable zone, seeding (adding small crystal particles) is required.
6
FORMATION OF CRYSTALS
• Formation of solid crystals from homogeneous
solution
Metastable
zone
Concentration of solute, C
Metastable Solubility curve
limit [saturation
concentration, C*(T)]
C B
A
D - Growth
D
Temperature, T
7
Draw a solubility curve of this
material
Yields and Heat and Material
Balances in Crystallization
xi,S q = (H2 + HV) – H1
xi,L
H1
Hydrate eg: sodium thiosulfate pentahydrate, Na2S2O3. 5 H2O
H2 xi,C
9
YIELD AND MATERIAL
BALANCES
W kg H2O
L kg solution
(solute + solvent)
COOLER &
CRYSTALLIZER
S kg solution
xi,S
C kg crystals
xi,C
10
W kg H2O
= 0 (no evap)
L kg solution xi,W
xi,L COOLER &
CRYSTALLIZER
S kg solution
xi,S
C kg crystals
L ⋅ xi , L = S ⋅ xi , S + W ⋅ xi ,W + C ⋅ xi ,C xi,C
i = water, solute
11
Example 1
A salt solution weighing 10 000 kg with 30%
Na2CO3 is cooled to 293 K (20°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 per 100 kg of total
water?
Assume that no water is evaporated.
12
W kg H2O
=0, no evap.
10,000 kg
solution S kg soln
COOLER &
CRYSTALLIZER
30% Na2CO3 21.5 kg Na2CO3/
100 kg H2O
Molecular Weight:
10H2O = 180.2
C kg crystals,
Na2CO3 = 106
Na2CO3•10H2O
Na2CO3 • 10H2O = 286.2
13
1. Perform material balance for water and Na2CO3
Feed = Solution stream + Crystals stream + Vapor stream
Feed stream: given
Solution stream
Given: 21.5 kg Na2CO3 per 100 kg H2O in Solution stream
kg H2O kg Na 2CO3
xwater , S = , x Na CO , S =
kg H O + kg Na CO
2 3
kg H2O + kg Na 2CO3
2 2 3
Crystal stream contains Na2CO3•10H2O
MW H2O MW Na 2CO3
xwater ,C = , xNa2CO3 ,C =
MW Na 2CO3 ⋅10H2O MW Na 2CO3 ⋅10H2O
Vapor stream
W = 0 as no evaporation
14
Feed = Solution stream + Crystals stream + Vapor stream
L ⋅ xi , L = S ⋅ xi , S + W ⋅ xi ,W + C ⋅ xi ,C
i = water, solute
Water:
100 180.2
0.7(10000) = (S ) + (C ) + 0
100 + 21.5 286.2
Na2CO3:
21.5 106
0.3(10000) = (𝑆𝑆) + (𝐶𝐶) + 0
100 + 21.5 286.2
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2. Solving the two equation simultaneously,
C = 6315.8 kg of Na2CO3•10H2O crystals
S = 3684.2 kg solution
16
Example 2
A salt solution weighing 10 000 kg with 30%
Na2CO3 is cooled to 293 K (20°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 per 100 kg of total
water?
Assume that 3% of the total weight of the
solution is lost by evaporation of water in cooling.
Solution
Feed = Solution stream + Crystals stream + Vapor stream
L ⋅ xi , L = S ⋅ xi , S + W ⋅ xi ,W + C ⋅ xi ,C
i = water, solute
Water:
100 180.2
0.7(10000) = (𝑆𝑆) + (𝐶𝐶) + 300
100+21.5 286.2
Na2CO3: 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
Exercise 1
A salt solution weighing 10 000 kg with 35%
FeSO4 is cooled to 293 K (20°C). The salt
crystallizes as the heptahydrate. What will be
the yield of FeSO4•7H2O crystals if the
solubility is 30.5 kg anhydrous FeSO4 per 100
kg of total water?
Assume that no water is evaporated.
HEAT EFFCTS IN CRYSTALLIZATION
Heat of solution
• Definition: the absorption of heat when the solubility of
a compound increases as temperature increases.
• As change in enthalpy in kJ/k mol
• Data in handbook always has (-) sign but depends on
process.
1. Endothermic = temperature decreases, cooling, + value
2. Exothermic = temperature increases, heating, - value
Heat of crystallization
• The opposite of heat of solution
• Negative of heat of solution at the same concentration in
solution.
HEAT BALANCES IN CRYSTALLIZATION
Hv , Water vapor
Feed,
H1
q = (H2 + HV) – H1 CRYSTALLIZER
Two phase mixture
(crystal + saturated
solution), H2
H1 = enthalpy of the entering solution (feed) at the initial temperature
H2 = enthalpy of the final mixture of crystals and mother liquor at the
final temperature
HV = enthalpy of water vapor (if evaporation occurs)
q = total heat transferred (kJ) (+ve: heat must be added
(endothermic), -ve: heat must be removed (exothermic))
23
Example 3
A feed solution of 2268 kg at 327.6 K (54.4°C) containing
48.2kg MgSO4/100kg total water is cooled to 293.2 K
(20°C), where MgSO4.7H2O crystals are removed. The
solubility of the salt is 30.5kg MgSO4/100kg total water.
The average heat capacity of the feed solution is 2.93
kJ/kg.K. The heat of solution at 291.2 K (18°C) is -
13.31×103 kJ/kgmol MgSO4.7 H2O. Calculate the yield of
crystals and make a heat balance. Assume that no water
is vaporized.
24
Solution
Balance for water
100/148.2 (2268) = 100/(100+35.5) (S) + 127.4/246.49 (C) + 0
Balance for MgSO4
48.2/148.2 (2268) = 35.5/(100+35.5) (S) + 119.09/246.49 (C) + 0
Solving 2 equations simultaneously,
C = 616.9
S = 1651.1
To make a heat balance, a datum for 293.2 K (20°C) will be
used. MW of MgSO4.7H2O is 246.49 kg/kgmol.
H1 = 2268 (327.6 – 293.2) (2.93) = 228 600 kJ
The heat of solution = -13.31×103/246.49 = -54 kJ/kg
crystals
The heat of crystallization = -(-54) = +54 kJ/kg crystals or
54(616.9) = 33 312 kJ
This assumes that the value at 291.2 K is the same as at
293.2 K.
The total heat absorbed,
q = -228 600 – 33 312 = -261 912 kJ
Problem 1
A hot solution of Ba(NO3)2 from an evaporator contains
30.6 kg Ba(NO3)2/100 kg H2O and goes to a crystallizer,
where the solution is cooled, and Ba(NO3)2 crystallizes.
On cooling, 10% of the feed evaporates. For a feed
solution of 100 kg total, calculate the following:
a) The yield of crystals if the solution is cooled to 290 K
(17˚C), where the solubility is 8.6 kg Ba(NO3)2/100 kg
total water.
b) The yield of crystals if cooled instead to 283 K, where
the solubility is 7.0 kg Ba(NO3)2/100 kg total water.
Answer
a) 10% of the original water present evaporates;
W = 10% of Fx FH2O
Water balance;
100/130.6 (100) = 100/(100+8.6) (S) + 0.1 [100/130.6(100)]
S = 74.8 kg solution
Ba(NO3)2 balance;
30.6/130.6 (100) = 8.6/(100+8.6) (S) + C
C = 17.47 kg crystals
Problem 2
A batch of 1000 kg of KCl is dissolved in sufficient
water to make a saturated solution at 363 K, where
the solubility is 35 wt% KCl in water. The solution is
cooled to 293 K, at which temperature its solubility
is 25.4 wt%.
a) What is the weight of water required for solution
and the weight of crystals of KCl obtained?
b) What is the weight of crystals obtained if 5% of
the feed evaporates on cooling?
