Advanced Mass Transfer Operations

N6CHPE12

Dr. Sudhir Ranganath

Contact Hours/Week: 3 (Lecture) Credits: 3.0

CIE Marks: 50
Total Lecture Hours: 39 (L) SEE Marks: 50
UNIT IV: Crystallization
Introduction to crystallization, concept of solubility curves
and super-saturation

Mechanisms of crystallization, nucleation and ΔL law of

crystal growth

Material and energy balance in crystallization

Crystallization equipment: Swenson-Walker, Vacuum, Oslo

crystallizer, Draft-tube-baffle crystallizer
Material Balance in Crystallization

M kg/h mother liquor

xM

Feed, F kg/h xC
Crystallizer
xF C kg/h crystals

xF = mass fraction of solute in the feed solution

xC = mass fraction of solute in the crystals
xM = mass fraction of solute in the mother liquor

Assuming there is only cooling and no evaporation of the solvent,

Overall material balance is given by: % = ' + )

Material balance for solute is given by: %*+ = '*, + )*-

Material Balance in Crystallization
Yield is defined as the weight of the substance crystallized per unit weight of
the substance in the feed solution.

'()*+, )- .)/*,0 123.,4//5607

% !"#$% = x 100
'()*+, )- .)/*,0 5+ ,80 -007 .)/*,5)+

A.CA
Therefore, % <=>?@ = E FGG
D.CD

Two cases of crystallization:

Anhydrous crystals: Here there is no water content in the solid phase,
hence calculation of yield is simple and straightforward.

Hydrated crystals: Here the crystals (solid phase) contains water of

crystallization and must be taken into account while calculating the yield.
Yield of Crystallization
If the crystal forms a hydrate and there is loss of solvent due to evaporation,
then the yield is calculated using the formula below:

Water vapor, W kg/h

Magma
C kg/h crystals
Feed, F kg/h M kg/h mother liquor
Crystallizer
F0, Y0

$%%&% '((*% '+)

Weight of the crystals in the final magma: !=#
$%%'((#'$)

R = ratio of the MW of hydrate/MW of anhydrous salt

s = solubility at the final temperature, kg anhydrous salt/100 kg solvent
F0 = weight of anhydrous solute in the original solution, kg
Y0 = total weight of the water in the original solution, kg
W = water loss due to evaporation, kg
Energy Balance of Crystallization
The heat effects in a crystallization process can be computed by two methods:

A heat balance of sensible heats required for heating or cooling the

solution and the latent heat of vaporization.
At equilibrium, the heat of crystallization is equal and opposite in sign to the
heat of solution.
Heat of solution is the change in enthalpy (ΔH) accompanying the
dissolution of one mole of substance in an excess of solvent.
For substances whose solubilities increase with T, the heat of solution will
be positive since they absorb heat when they dissolve.
For substances whose solubilities decrease with T, heat is released during
dissolution and the heat of solution will be negative.

An enthalpy balance can be made in which the total enthalpy of all leaving
streams minus the total enthalpy of all entering streams is equal to the heat
absorbed from the external sources by the process
Energy Balance of Crystallization
Case (i): When there is no evaporation of the solvent
Magma
C kg/h crystals
Feed, F kg/h M kg/h mother liquor
Crystallizer
Ti, xF T0

Net heat to be removed from the system = (heat to be removed from the feed
solution over a cooling range) + (heat of crystallization)

! = #$%& '( − '* + $λ-

$%& → Specific heat of the feed solution

λ- → heat of crystallization = ± heat of solution
Energy Balance of Crystallization
Case (ii): When solvent is evaporated

Solvent vapor, W kg/h Magma

C kg/h crystals
Feed, F kg/h M kg/h mother liquor
Crystallizer
Ti, xF T0

Net heat to be removed from the system = (heat to be removed from the feed
solution over a cooling range) + (heat of crystallization) – (heat associated with
evaporated solvent)

! = #$%& '( − '* + $λ- − .λ

$%& → Specific heat of the feed solution

λ- → heat of crystallization = ± heat of solution
λ → heat of vaporization of the solvent
Purity of Products
The main advantage of crystallization is that it can produce high purity
crystalline products.

The crystals recovered from the magma retains substantial quantity of the
mother liquor & other impurities.

If the crystal agglomerates, it leads to entrapment of the solution within the

solid mass.

Such mother liquor is generally separated using filtration or centrifugation

and washing with fresh solvent.

Other solid contaminants are very hard to remove and thus constitute a
crystal’s impurity.

The purity of the final crystalline product is thus dependent on the extent to
which contaminants are present in the solution accompanying the crystals.
Problem 29
A crystallizer is charged with 100 kg of a solution containing 25% Ba(NO3)2 in
water. On cooling, 10% of the original water present evaporates. Calculate the
yield of crystals when the solution is cooled to 283 K. The solubility is 7 kg
Ba(NO3)2 /100 kg water.
Solution to Problem 29

W = 7.5 kg
Magma
C kg crystals
F = 100 kg M kg mother liquor
Crystallizer
T = 283 K
Problem 30
What will be the yield of hypo (Na2S2O3.5H2O) if 100 kg of a 50% solution of
sodium thiosulfate is cooled to 293 K. The solubility at 293 K is 70 parts
Na2S2O3 per 100 parts water.
Solution to Problem 30
Magma
C kg crystals
F = 100 kg M kg mother liquor
Crystallizer
T = 293 K
Problem 31
A continuous evaporative crystallizer operating at 1 kPa is fed with 4000 kg/h
of a 50% (weight) aqueous solution of sodium acetate at 350 K. The heat of
crystallization is -150 kJ/kg. The mean heat capacity of the solution is 3.5
kJ/kg.K and, at 1 kPa, water boils at 290 K at which the latent heat of
vaporization is 2482 kJ/kg. At 290 K, the solubility of sodium acetate in water is
54 kg/100 kg water. Determine the yield of CH3COONa.3H2O crystals and the
evaporation rate.
Solution to Problem 31
Given:

F = 4000 kg/h
xF = 0.5
Ti = 350 K
T0 = 290 K
λ' = - 150 kJ/kg (heat is absorbed)
CPF = 3.5 kJ/kg.K
λ = 2482 kJ/kg
xM = 54 kg of sodium acetate/(54 kg sodium acetate + 100 kg water) = 0.351
M.W. of CH3COONa = 82
M.W. of CH3COONa.3H2O = 136

Overall material balance gives: 4000 = - + / + 0 … (1)

/. 0 45 CH3COONa 82
12 = = = 0.603
/. 0 45CH3COONa. 3;< = 136
Solution to Problem 31
Sodium acetate balance gives:

!"# = %"& + (") = 4000 x 0.5 = 0.351% + 0.603( … (2)

Heat balance is given as:

Heat released on cooling + heat liberated on crystallization = Heat used to

vaporize water (or)

!(2# 34 − 36 + (λ) = 8λ

4000 x 3.5 x 350 − 290 + 150( = 24828 … (3)

Solving Eqs (1), (2) and (3), we get:

W = 525.50 kg/h and C = 3097 kg/h

)<=
Yield = x 100 = 93.3 %
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Thank you