CRYSTALLIZATION

CRYSTALLIZATION
a process where solid particles are formed
from a homogeneous phase
a solid-liquid separation process
for control:
yield of crystals
purity of crystals
sizes and shapes of crystals

A crystal is a highly organized

array of atoms, molecules, or ions
arranged in three-dimensional
space lattices.

Common methods to achieve supersaturation

Cooling (with some exceptions)
achieved near a heat-transfer surface

Solvent evaporation
achieved near a heat-transfer surface

Drowning
addition of nonsolvent, which decreases the solubility
of the solid

Chemical reaction
decreases the solubility of the dissolved solvent,
leading to supersaturation

Progression of
crystallization

EQUILIBRIUM SOLUBILITY CURVES FOR

CRYSTALLIZATION
Fig. 18-56 (Perrys CHE Handbook, 7th Ed.) Solubility of MgSO4xH2O in
water at 1 atm
Fig. 12.11-1 (Geankoplis, 4th Ed.) Solubility of Na2S2O3 in water at 1 atm
Fig. 19.27 (Foust et al., 2nd Ed.) Solubility of Na2SO4 in water at 1atm

Fig. 19.28 (Foust et al., 2nd Ed.) Enthalpy-concentration diagram for the
Na2SO4 - H2O system at 1 atm
Fig. 19.29 (Foust et al., 2nd Ed.) Enthalpy concentration diagram for the
CaCl2 - H2O system at 1 atm

Solubilities
of several
solids

MATERIAL BALANCES: YIELD OF CRYSTALS

S
Saturated solution

10,000 KG
30% Na2CO3

T = 293 K
Solubility :
21.5 kg Na2CO3 / 100 kg H2O
C
Na2CO310H2O

Solute Balance

Ma
Fx C
F
Mh

Mh Ma
F1 x F V C

Mh

S'

Total Balance

F V M V CS
C
Ma
Mh
xF
S
F
V
S
M

= mass of crystals in the product magma per unit time

= molecular weight of anhydrous salt or crystal
= molecular weight of hydrated crystal
= mass fraction of anhydrous solute in feed
= solubility of the anhydrous solute at product temperature
= expressed as a weight ratio of anhydrous salt to solvent
= total mass of feed solution per unit time
= evaporation rate in mass of solvent per unit time
= mass of saturated solution produced per unit time
= total mass of product magma produced per unit time
= mass of crystals formed + saturated solution

HEAT BALANCE:

HF HC q HL H V
q
HF
HM
HV
HC

= total heat absorbed in the crystallization/evaporation process

= total enthalpy of entering solution at TF, which is read off
enthalpy-concentration diagram
= total enthalpy of the crystals and saturated solution in the
product magma at the final temperature, TL
= total enthalpy of the vapor
= total heat of crystallization
= positive if crystallization is exothermic
= evaluated as the negative of the heat of solution

HEAT BALANCE (Vacuum Operation)

V V H F H L H C
V

= latent heat of vaporization of the solvent

HF HL

= sensible heat drop

Classification of Crystallization Equipment

According to mode of operation
Batch
Continuous

According to method by which supersaturation

is achieved
Crystallizers that obtain precipitation by cooling a
concentrated, hot solution
Agitated batch crystallizers
Swenson-Walker crystallizers

Crystallizers that obtain precipitation by evaporating a

solution
Salting out evaporators
Draft-tube evaporators
Oslo crystallizers (e.g., Krystal crystallizer for ammonium sulfate
production)

Crystallizers that obtain precipitation by adiabatic

evaporation and cooling
Vacuum crystallizers

TANK CRYSTALLIZERS
Hot, saturated solutions are allowed to cool in open tanks. After
crystallization, the mother liquor is drained and the crystals are
collected.
Controlling nucleation and the size of the crystals is difficult.
The crystallization is essentially just "allowed to happen".
Heat transfer coils and agitation can be used.
Labor costs are high, thus this type of crystallization is typically
used only in the fine chemical or pharmaceutical industries where
the product value and preservation can justify the high operating
costs.

SCRAPED-SURFACE CRYSTALLIZERS
An example may be the Swenson-Walker crystallizer
consisting of a trough about 2 feet wide with a semi-circular
bottom.
The outside is jacketed with cooling coils and an agitator
blade gently passes close to the trough wall removing crystals
that grow on the vessel wall.
FORCED CIRCULATING LIQUID EVAPORATORCRYSTALLIZER
combines crystallization and evaporation, thus the driving
forces toward supersaturation

FORCED CIRCULATING
LIQUID EVAPORATORCRYSTALLIZER
The heated liquid flows into
the vapor space of the
crystallization vessel. Flash
evaporation occurs, reducing
the amount of solvent in the
solution, thus driving the
mother liquor towards
supersaturation.
The supersaturated liquor
flows down through a tube,
then up through a fluidized area
of crystals and liquor where
crystallization takes place via
secondary nucleation. Larger
product crystals are withdrawn
while the liquor is recycled,
mixed with the feed, and
reheated.

CIRCULATING MAGMA VACUUM CRYSTALLIZER

The crystal/solution mixture (magma) is circulated out of the
vessel body.
The magma is heated gently and mixed back into the vessel.

A vacuum in the vapor space causes boiling at the surface of

the liquid.

CIRCULATING MAGMA
VACUUM CRYSTALLIZER

Crystallizer Design

CRYSTAL SIZE DISTRIBUTION

Crystallization is operated to maximize crystal
growth and restrict nucleation.
Product CSD is based on kinetics and nucleation
growth of crystals.
If it is assumed that nucleation does not occur
and that the initial CSD is not known, a rough
estimation of CSD can be calculated.
The McCabe L law is commonly used to
calculate the final CSD if initial CSD in known.

The L Law
If all crystals in magma grow in a uniform
supersaturation field and at the same temperature
and if all crystals grow from birth at the rate
governed by the supersaturation, then all crystals
are not only invariant but also have the same
growth rate that is independent of size.

L = Gt
G f(L) : growth rate
t : time

Calculation of CSD for a seeded crystallizer

L P L S L
LP
LS
L

= characteristic crystal product dimension

= characteristic crystal seed dimension
= change in dimension; constant throughout the
range of sizes present

Relationship between seed mass (mS) and product mass (mP)

m P ' L LS L

3
P

m S ' L3S
Combining:

m P m S 1
LS

= shape factor (different from the usual

shape factor)
= particle density

For the entire crystal mass:

3

L
0 dm P 0 1 L S dm s m P

mP

mS

MSMPR
MSMPR or MIXED-SUSPENSION MIXED-PRODUCT REMOVAL
MODEL

An idealized crystallizer model, which is a basis

for identifying the kinetic parameters and showing
how knowledge of them can be applied to
calculate the performance of such crystallizer.

MSMPR Assumptions
Steady-state
Crystallizer contains a mixed-suspension magma at all
times, with no product classification
Uniform supersaturation exists throughout the magma at
all times
L law of crystal growth applies
No size-classified withdrawal system
No crystals in the feed
Mother liquor in the product magma is saturated
(equilibrium)
No crystal breakage into finite particle size

CRYSTAL POPULATION-DENSITY FUNCTION

dN N
n

dL L
dN
n
dL

Assumptions:
In t time, nL crystals are withdrawn.
The effluent composition in the outflow is Q L/h, which is the same as
that in the crystallizer of volume V.

n L Q t

n L
V
Recall the L law (i.e., L = G t). If G is in mm/h:

n
Q L

n
VG
As both L and n approach 0, and integrating,
n

dn
1
0 n G 0 dL
n

L
n n 0 exp

where = V/Q, which is the total retention time or holding time (in hours)
in the crystallizer, and n0 is the population of nuclei when L = 0.

A solution of 500 kg of Na2SO4 in 2500 kg of

water is cooled from 333 to 283 K in an agitated
mild steel vessel of mass 750 kg, the specific
heat of steel being 0.5 kJ/kg-K. At 283 K the
stable crystalline phase Na2SO410H2O and at
291 K the heat of solution is -78.5 MJ/kgmol.
The mean heat capacity of the solution is 3.6
kJ/kg-K. If, during cooling, 2% by mass of the
water is lost by evaporation, estimate the yield of
crystals formed and the heat to be removed. The
solubility of the anhydrous salt at 283 K is 8.9
kg/100 kg water.

A solute that forms cubic crystals is to be

precipitated from solution at a rate of 10,000 lb/h
of solid (dry basis) using 1,000 lb/h of seed
crystals. If no nucleation occurs and the seed
crystals have the following size distribution,
determine the product size distribution.
Tyler sieve mesh

weight fraction retained

-48+65

0.10

-65+100

0.30

-100+150

0.50

-150+200

0.05

-200+270

0.05