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CRYSTALLIZATION

•  saturated solution cooled/evaporated forms crystal

•  important industrially because:

i) a crystal formed from an impure solution and itself pure

ii) Practical method of obtaining pure chemical substances in a


satisfactory condition for packaging and storing

•  solid-liquid separation process

•  yield , purity, sizes & shapes of crystals important

•  crystals - uniform in size


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SOLUBILITY CURVE

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SOLUBILITY CURVE

•  equilibrium is attained when the solution or mother liquor is saturated


(represented by solubility curve)

•  solubility dependent mainly on temperature (pressure negligible effect)


•  solubilities of most salts increase slightly or markedly with temperature

Solubility curve for some typical salts in water Solubility curve for sodium thiosulfate

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SOLID-LIQUID PHASE DIAGRAM

Solid-liquid phase diagram for the MgSO4-nH2O system at 1 atm

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YIELD & HEAT & MATERIAL BALANCES
•  yield of crystals can be calculated by knowing:
initial concentration of solute
final temperature
solubility at this temperature
•  material balances Mass balance :
kg H2O evaporate
Water balance : Input = Output
Solute balance : Input = Output
F kg Hot solution S kg solution

X1 kg solute/ X2 kg solute/
100 kg H2O 100 kg H2O

C kg Crystal
solute crystals are anhydrous - simple water & solute material balances
crystals are hydrated - some water in the solution is removed with crystals
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EXAMPLE 12.11-1

A salt solution weighing 10 000 kg with 30 wt % Na2CO3 is cooled to 293K (20oC). The salt
crystallized 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 evaporated.

b)  Assume that 3% of the total weight of the solution is lost by evaporation of water in
cooling.
Ans: 6370 kg, 6630 kg

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EXAMPLE 12.11-1
Solution:    
Molecular weights: Na2CO3 = 106.0, 10H2O = 180.2, Na2CO3 •10H2O = 286.2

(a)  W = 0, water balance:

Na2CO3 balance:

C = 6370 kg of Na2CO3 •10H2O crystals and S = 3630 kg solution


(b) W = 0.03(10000) = 300 kg, water balance:

C = 6630 kg of Na2CO3 •10H2O crystals and S = 3070 kg solution.


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EXAMPLE 27.1(McCabe,   Smith & Harriott)
A solution consisting of 30 wt% MgSO   4 is cooled to 60oF. During cooling, 5 %
 
of the total water in the system evaporates. How kg of crystals are obtained per
1000 kg of original mixture?
Data: Molecular weight of MgSO4 = 120.4
Ans: 261 kg

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EXAMPLE (P12.11-3)

A hot solution containing 1000 kg of MgSO4 and water having a concentration


of 30 wt% MgSO4 is cooled to 288.8 K (60oF) where crystals of MgSO4.7H2O
are precipitated. The solubility at 288.8 K is 24.5 wt % anhydrous MgSO4 in
the solution. Calculate the yield of crystals obtained if 5 % of the original
water in the system evaporates on cooling.
Data: Molecular weight of MgSO4 = 120.4
Ans: 261 kg

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HEAT BALANCES IN CRYSTALLIZATION


normally, crystallization is exothermic W kg H2O
HV kJ/kg

F kg Hot solution S kg solution

hF kJ/kg hS kJ/kg

Total heat absorbed, q (kJ): C kg Crystal


hC kJ/kg
When Tdatum = 32oF ,
FhF + q = (S + C)hM + WHV
or
FhF + q = ShS + ChC + WHV
When Tdatum = Tequil./sat. , FhF + q = Wλ + ChC = Wλ + CΔH∞crys
#
heat of crystallization, ΔHcrys = - heat of solution at infinite dilution, "H
soln
Heat absorbed, q = + ve ,Heat given off , q = - ve

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ENTHALPY-CONCENTRATION DIAGRAM

Enthalpy-concentration diagram for the MgSO4-


nH2O system at 1 atm
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ENTHALPY-CONCENTRATION DIAGRAM

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EXAMPLE

A 32.5% solution of MgSO4 at 120oF


(48.9oC) is cooled, without appreciable
evaporation to 70oF (21.1oC) in a batch-
cooled crystallizer. How much heat must be
removed from the solution per 100 Ib of the
feed solution? The average heat capacity of
the feed solution is 0.72 Btu/Ib oF and the
heat of solution at 18oC is 23.2 Btu/Ib of
MgSO4.7H20.
Ans: -4260 Btu

Enthalpy-concentration diagram for the MgSO4-


nH2O system at 1 atm
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EXAMPLE 12.11-2

A feed solution of 2268 kg at 327.6 K


(54.4oC) containing 48.2 kg MgSO4/100
kg total water is cooled to 293.2 K (20oC)
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 (18oC) 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 evolved and
removed from the crystalliser, q,
assuming that no water is vaporized.
Data: Molecular weight of MgSO4•7H20
is 246.49
Ans: 616.9 kg crystal, -261 912 kJ
Enthalpy-concentration diagram for the MgSO4-
nH2O system at 1 atm
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EXAMPLE 12.11-2
Solution:    
Molecular weights: MgSO4 = 120.4, 7H2O = 126, MgSO4 •7H2O = 246.4

2268 kg S kg solution
48.2 kg MgSO4/100 kg H2O 35.5 kg MgSO4/100 kg H2O

C kg MgSO4 •7H2O

! 100 $ ! 100 $ ! 126 $


W = 0, water balance: 2268 # &= S# &+C# &
" 48.2 +100 % " 35.5+100 % " 246.4 %

! 48.2 $ ! 35.5 $ ! 120.4 $


MgSO4 balance: 2268 # &= S# &+C# &
" 48.2 +100 % " 35.5+100 % " 246.4 %

Total balance: 2268 = C + S

C = 631.9 kg MgSO4•7H2O crystals, S = 1636.1 kg solution.


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EXAMPLE 12.11

Solu&on  
Tref. = 293.2K (Tdatum)
Heat balance :
FhF + q = Wλ + ChC = Wλ + CΔH∞crys
Enthalpy of the feed , hF = CpΔT = (2.93)(327.6-293)

Heat of solution = 13.31x103/246.49 = 54.0 kJ/kg crystals.


Heat of crystallization = -(54.0) = -54.0 kJ/kg crystals
Total heat absorbed, q
2268(2.93)(327.6-293) + q = 631.9(54.0)
q = 631.9(54.0) - 2268(2.93)(327.6-293) = -262 689 kJ

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EXAMPLE

A solution of 500 kg of Na2SO4 in 2500 kg water is cooled from 333K to 283K in


an agitated mild steel vessel. At 283K, the solubility of the anhydrous salt is 8.9
kg/100kg water and the stable crystalline phase is Na2SO4.10H2O. At 291K, the
heat of solution is -78.5 MJ/kmol and the specific heat capacity of the solution is
3.6 kJ/kg.K. If, during cooling, 2% of the water initially present is lost by
evaporation, estimate the heat which must be removed.
Ans: 240 407 kJ

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CRYSTALLIZER

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