CRYSTALLIZATION

Dr. Leonardo C. Medina Jr.

Perrys Chemical
Engineers Handbook
8th Edition
Table 2-122 Solubilities of
Inorganic Compounds in
Water at Various
Temperature
Tables 2-182 & 2-183
Heats of Solution
Tables 2-33 to 2-122
Densities of Aqueous
Inorganic & Organic
Solutions at 1 atm
Sections 18-39 to 18-58

7th Edition
Table 2-120 Solubilities of
Inorganic Compounds
in Water at Various
Temperature
Tables 2-224 & 2-225
Heats of Solution
Tables 2-31 to 2-117
Densities of Aqueous
Inorganic & Organic
Solutions at 1 atm
Sections 18-35 to 18-55

Crystallization process whereby a

solution is super saturated so as to

cause the formation of crystals.
Methods of Supersaturating a Solution:
1. Super saturation by cooling e.g.
Swenson-Walker Crystallizer
2. Super saturation by evaporation of
solvent Salting-out evaporator,
Oslo crystallizer
3. Adiabatic evaporation with cooling
Vacuum crystallizer
4. Adding a third component where the
solubility of the solute is simply
reduced by seeding.
5. Addition of a third component to form
precipitates.

Solubility Curves for (1) KNO3, (2) NaCl and

(3)MnSO4 H2O in Aqueous Solution

Phase Diagram MgSO4 H2O

System

Integral Heats of Solution for

Sulfates in Water at 25C

Enthalpy Concentration Diagram

MgSO4 H20 System

Swenson Walker Continuous

Cooling Crystallizer

Circulating Batch Cooling

Crystallizers

Swenson Draft Tube Baffled

Crystallizer

Continuous Crystallizer

Draft Tube Baffle Crystallizer with internal

system for fines separation and removal

Brodie Purifier Countercurrent

Cooling Crystallizer

Process for the Production of

MgSO4 7H2O

Crystallizer for Production of

MgSO4 7H2O Crystals

Principles of Crystallization

xF

xL

xc

MATERIAL BALANCE:

F C L V

Over-all Material Balance:

Solute Balance:

Fx F Cx c Lx L

Solvent Balance: F 1 xF C1 xc L1 xL + V
where: XL is the solubility
of the solute at TL
XC is the MW of
solute/MW of hydrated
crystal
For the solubility of some
solids, see Fig. 18-56;
Fig. 18-57 Perry

NOTE: Tie substance method may be

applied:
(a) If the crystals are anhydrous,
water becomes the tie substance
between the original solution and
the mother liquor
(b) If the crystals are in the form of
hydrates, free or excess water is
the tie substance.

ENTHALPY BALANCE
If Enthalpy-Concentration data
are available:

Fh F VH V Lh L Chc q
HEAT BALANCE

If the specific heats, heat of solution and heat

of crystallization are available

q VL FcF TF Tc CHc

For the area of the crystallizer

q UA T t ln

L
L

CRYSTALLIZATION BY SEEDING
Mechanism of crystallization:
(a) Nucleation and (b) Crystal
Growth
Assumptions in the use of seed
crystals:
1. no new nucleation occurs
2. uniform linear growth, i.e., the L
or D law applies
L or D law = the rate of linear
growth is independent of size.

Rate of Deposition of crystals:

dW
k f x x i
dt
Volume of crystal:

V aD

or

dV 3aD dD
2

also

dW dV

Substituting: 3aD2dD
k f x xi
dt
dD
K f x x i
dt
Relation between seed and product
crystals:
D D D
p

For ideal growth, is the same for all

crystals: W aD3 a D D 3
p

but

WS

3
aDS

therefore:

for a single sized crystal

WP

D
1
DS

W S

For an entire range of particle sizes:

3

WS
o

WP

D
dWS
1
DS

which is solved by trial and error.

Effect of Supersaturation on Crystal

Growth Quality and Type of Nucleation for
MgSO4 7H2O