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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

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yield , purity, sizes & shapes of crystals important

crystals - uniform in size

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

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Solubility curve for sodium thiosulfate

SOLID-LIQUID PHASE DIAGRAM
Solid-liquid phase diagram for the MgSO 4 -nH 2 O 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 H
2 O evaporate
Water balance : Input = Output
Solute balance : Input = Output
S kg solution
F kg Hot solution
X 1 kg solute/
100 kg H 2 O
X 2 kg solute/
100 kg H 2 O
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 % Na 2 CO 3 is cooled to 293K (20 o C). The salt crystallized as the decahydrate. What will be the yield of Na 2 CO 3 .10H 2 O crystals if the solubility is 21.5 kg anhydrous Na 2 CO 3 /100 kg of total water?

a)

b)Assume that 3% of the total weight of the solution is lost by evaporation of water in

cooling. Ans: 6370 kg, 6630 kg

Assume

that no water evaporated.

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EXAMPLE 12.11-1

Solution: !! Molecular weights: Na 2 CO 3 = 106.0, 10H 2 O = 180.2, Na 2 CO 3 •10H 2 O = 286.2

(a) W = 0, water balance:

Na 2 CO 3 balance:

C = 6370 kg of Na 2 CO 3 •10H 2 O crystals and S = 3630 kg solution (b) W = 0.03(10000) = 300 kg, water balance:

C = 6630 kg of Na 2 CO 3 •10H 2 O 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 60 o F. 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 MgSO 4 = 120.4
Ans: 261 kg
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EXAMPLE (P12.11-3)

hot solution containing 1000 kg of MgSO 4 and water having a concentration

A

of

are precipitated. The solubility at 288.8 K is 24.5 wt % anhydrous MgSO 4 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 MgSO 4 = 120.4

Ans: 261 kg

30 wt% MgSO 4 is cooled to 288.8 K (60 o F) where crystals of MgSO 4 .7H 2 O

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HEAT BALANCES IN CRYSTALLIZATION

W kg H 2 O H V kJ/kg

normally, crystallization is exothermic

S kg solution
F kg Hot solution
h F kJ/kg
h S kJ/kg
Total heat absorbed, q (kJ):
C kg Crystal
h C kJ/kg
Fh F + q = (S + C)h M + WH V
or
Fh F + q = Sh S + Ch C + WH V
Fh F + q = W λ + Ch C = W λ + C ΔH ∞ crys
#
soln

When T datum = 32 o F ,

When T datum = T equil./sat. ,

heat of crystallization, ΔH crys = - heat of solution at infinite dilution, "H Heat absorbed, q = +ʼve ,Heat given off , q = -ʼve

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ENTHALPY-CONCENTRATION DIAGRAM
Enthalpy-concentration diagram for the MgSO 4 -
nH 2 O system at 1 atm
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ENTHALPY-CONCENTRATION DIAGRAM
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EXAMPLE
A 32.5% solution of MgSO 4 at 120 o F
(48.9 o C) is cooled, without appreciable
evaporation to 70 o F (21.1 o C) 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 o F and the
heat of solution at 18 o C is 23.2 Btu/Ib of
MgSO 4 .7H 2 0.
Ans: -4260 Btu
Enthalpy-concentration diagram for the MgSO 4 -
nH 2 O system at 1 atm
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EXAMPLE 12.11-2
A feed solution of 2268 kg at 327.6 K
(54.4 o C) containing 48.2 kg MgSO 4 /100
kg total water is cooled to 293.2 K (20 o C)
where MgSO 4 .7H 2 O crystals are removed.
The solubility of the salt is 35.5 kg
MgSO 4 /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 o C) is 13.31 x 10 3
kJ/kg mol MgSO 4 .7H 2 O. 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 MgSO 4 •7H 2 0
is 246.49
Ans: 616.9 kg crystal, -261 912 kJ
Enthalpy-concentration diagram for the MgSO 4 -
nH 2 O system at 1 atm
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EXAMPLE 12.11-2
Solution: !!
Molecular weights: MgSO 4 = 120.4, 7H 2 O = 126, MgSO 4 •7H 2 O = 246.4
2268 kg
48.2 kg MgSO 4 /100 kg H 2 O
S kg solution
35.5 kg MgSO 4 /100 kg H 2 O
C kg MgSO 4 •7H 2 O
!
\$
!
\$
!
\$
1
0 0
1
0 0
1
2 6
W = 0, water balance:
2
2 6 8 #
& = S #
%
& + C #
&
"
4 8 . 2 + 1 0 0
"
3 5 . 5 + 1 0 0
%
"
2 4 6 . 4
%
!
!
\$
! \$
4
8 . 2
\$
& = S #
3
5 . 5
1 2 0 . 4
MgSO 4 balance:
2
2 6 8 #
& + C #
&
"
4 8 . 2 + 1 0 0
%
"
3 5 . 5 + 1 0 0
%
"
2 4 6 . 4
%
Total balance:
2268 = C + S
C = 631.9 kg MgSO 4 •7H 2 O crystals, S = 1636.1 kg solution.
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!

!

!

!

EXAMPLE 12.11

!

Solu&on! T ref. = 293.2K (T datum ) Heat balance :

Fh F + q = W λ + Ch C = W λ + C ΔH crys

Enthalpy of the feed , h F = C p Δ T = (2.93)(327.6-293)

Heat of solution = 13.31x10 3 /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 Na 2 SO 4 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 Na 2 SO 4 .10H 2 O. 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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