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CRYSTALLIZATION

Dr. Leonardo C. Medina Jr.


Perry’s Chemical
Engineers Handbook
8th Edition 7th Edition
Table 2-122 Solubilities of Table 2-120 Solubilities of
Inorganic Compounds in Inorganic Compounds
Water at Various in Water at Various
Temperature Temperature
Tables 2-182 & 2-183 Tables 2-224 & 2-225
Heats of Solution Heats of Solution
Tables 2-33 to 2-122 Tables 2-31 to 2-117
Densities of Aqueous Densities of Aqueous
Inorganic & Organic Inorganic & Organic
Solutions at 1 atm Solutions at 1 atm
Sections 18-39 to 18-58 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 25°C
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:
Over-all Material Balance: F  C  L V
Solute Balance: Fx F  Cx c  Lx L
Solvent Balance: F 1  xF   C1  xc   L1  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 VL  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:

 k  f  x  x i 
dW
dt
Volume of crystal: V  aD 3

or
dV  3aD dD 2
also
dW   dV

Substituting:  3aD2dD 
 k  f x  xi 
dt
 K  f  x  x i 
dD
dt
Relation between seed and product
crystals: D  D  D
p s

For ideal growth, is the same for all


crystals: W  aD3  a D  D 3
p p  s 
but WS  aDS
3
therefore: for a single sized crystal
3
 D 
WP   1   W S
 DS 

For an entire range of particle sizes:


3
 D 
1   dWS
WS
WP  o
 DS 
which is solved by trial and error.
Effect of Supersaturation on Crystal
Growth Quality and Type of Nucleation for
MgSO4 7H2O