CRYSTALLIZATION

What is
Crystallization
???

Crystallization is solidliquid separation

process, where solid
particles are formed
from a homogenous
phase.

 In crystallization, the solution is CONCENTRATED and

usually cooled until the solute concentration greater than
its solubility at that temperature.
Then, the solute comes out of the solution forming
CRYSTAL of approximately pure solute.

CRYSTALLIZATION PROCESS
Crystallization Steps :

Nucleus
Formati
on

Crystal
Growth

The driving force for nucleus formation and crystal

growth is SUPERSATURATION
These 2 steps will NEVER happen in saturated or under
saturated solution.

Nucleation
initiation of phase change in small
region

Primary nucleation
(initial formation of
crystal where there are
no other crystal
present)
Condition
Homogenous
nucleation
Nucleation that is
not influenced in
any way by solid
include the wall of
crystallizer vessel
or particles of any
foreign substances

Heterogenous
Nucleation
Occurs when solid
particles of foreign
substances cause
an increase in the
rate of nucleation
that otherwise not
be seen without the
existances of these
foreign particles

Secondary nucleation

Secondary nucleation
requires "seeds" or
existing crystals to
perpetuate crystal
growth. In our salt
example, we bypassed
primary nucleation by
"seeding" the solution
with a final teaspoon of
salt. Secondary
nucleation can be
thought of as the
workhorse of
crystallization.

Crystal Growth
Once the first small crystal, the nucleus, forms it acts
as a convergence point that it increases its own
dimension in successive layers.
Growth rate is influenced by several physical factors,
such as surface tension of solution, pressure,
temperature, relative crystal velocity in the solution,
Reynolds number

Cubic system

Hexagonal

triclinic

tetragonal

Types
of
crystal
geome
try

trigonal

orthorhombi
c

APPLICATION OF CRYSTALLIZATION
IN INDUSTRY
Application
of
Crystallizati
on in
Industry

Food
Industry

Pharmaceuti
cal Industry

APPLICATION : FOOD INDUSTRY

Purpose

Important
Factor

Preserving food
Example:
Shelf Stability
Freezing of food

Reference: Hartel, R. W. (2001).Crystallization in Foods.Aspen Publisher

Types of Crystal and Its Role in

Foods
Food item

Type of crystal

Crystal Role and

Development in Foods

Fondant

Sugar

Fondant is a two-base
system: sucrose crystals in
syrup.
For good crystal formation
the syrup needs to be
sufficiently supersaturated.
The presence of acid as an
interfering agent makes
both the final temperature
and the cooking time critical
for optimum crystal size.

Food
item

Type of crystal

Crystal Role and Development in

Foods

Grape
Juice

tartrate crystals:
Ca tartrate
Potassium
hydrogen
tartrate

Sherbet

Ice

In solution the K2H2 tartrate gives

the juice a cloudy appearance and
an acid flavor.
Bulk storage at low temperatures
(less than 40F) allows for
precipitation of an crystals prior to
packaging.
Precipitation can be brought about
in as little as 24 hours using rapid
The
ice crystals
give
frozen
freezing,
thawing,
andthe
filtering.
dessert its hardness.
Sherbet is a two-phase system: ice
crystals in syrup.
In sherbets the amount of sugar is
very high to counteract the acid
which serves to lower temperature
at which the crystals form.
Sugar also acts as an interfering
agent to help keep the crystal size
small.

Pharmaceutical Industry

Purpose
Preparation of pharmaceuticals for
pulmonary delivery
Micro-crystallization

Separation of chiral isomers

Direct crystallization

Reference: Rohani, S. (2010).Application of the Crystallization Process in the Pharmaceutical Industry. Front. Chem. Eng. China 201, 4(1): 29. Higher Education Press and Springer-Verlag Berlin Heidelberg 2010

Equipment for
Crystallization
Tank Crystallizers:
-hot saturated solution is
allowed to cool by open tank
or coil and a jacket and agitator
-Produce fine chemical and
pharmaceutical product
- Size of crystal are difficult to
control.

 Scraped Surface Crystallizers:

I.

Swenson-Walker crystallizer
produce wide crystal size

II.

double-pipe scraped surface

crystallizer (votator)

use in crystallizing ice-cream and

plasticizing margarine.

Circulating-Liquid
Evaporator-Crystallizer
combination evaporatorcrystallizer
Also called Oslo
crystallizer
Supersaturation is reach
by evaporation.

Circulating-magma
Vacuum Crystallizer
Continuous crystallizers
The following features are
achieved:
An increase in the spacetime
yield

A reduction in the
requirements manpower
A more uniform quality of
product

What are the advantages

of crystallization
compared to other solidliquid separation?

Able to obtain very high

purity products (>99.9%)

crystallization

Products are with good

appearances such as the sizes
and shapes
Crystals formed are the most
concentrated form of the
chemical possible
Requires less energy input

 Product purity
Crystals can be produced from an impure
solution in only a single process step. Examples of
the impurities can be water or any kinds of
reagent.
Good appearance of the products:
1. Sizes: give good handling characteristic.
2. Shapes: requires certain shape according to the
uses and industrial demand.
. Very concentrated form of chemical possible:
solution is concentrated and usually cooled until
the solute concentration becomes greater
. Requires less energy input: reduce cost

THEORY

 Rate of crystal growth and growth coefficient

NA/Ai = (yA - yAe)/(1/ky + 1/ks) = K (yA yAe)
NA = rate of crystal growth in kg.mol A/s
Ai = area in m2 of surface i
yA = supersaturation concentration of A
ky = mass transfer coefficient in kg.mol/s.m2.mol frac
ks = surface reaction coefficient in kg.mol/s.m2.mol frac
yAe = saturation concentration of A
K = overall transfer coefficient

 L law of crystal growth

L = D2 D1 = G(t2 t1)

D = linear dimension of one crystal in mm

t = time in h
G = growth rate (a constant) in mm/h
*The law is reasonably accurate in many situation
eventhough it is not applicable in all cases.

 Particle size distribution of Crystal

CV = 100 [(PD16% - PD84%)/ 2PD50%]

CV = coefficient of variation
PD16% = particle diameter at 16% retained
PD50% = mean particle diameter