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CCB 2063
SEPARATION PROCESSES
CRYSTALLISATION
Dr Taslima Khanam
28 May 2014
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TOPIC OUTCOMES
By end of topic, students should be able to
understand the concept of crystallization
understand equilibrium solubility of materials
perform material & heat balance for crystallization process
understand Nucleation Theories
discuss basis of equipment
describe types of crystallizers

3
TODAYS LESSON OUTCOMES
By end of lesson, students should be able to
understand the concept of crystallization
understand equilibrium solubility of materials
perform material balance for crystallization process
understand Nucleation Theories

4
CRYSTALLISATION THEORY
Crystallization is a particle formation process by which
solute molecules in a solution are transformed into a
solid phase of regular lattice structure
occurs by precipitation process where particles
form by decreasing solute solubility (i.e. increasing
supersaturation) by cooling, evaporation, anti-
solvent addition, etc.
mass transfer of a solute from liquid solution to
form pure solid crystalline phase
Key point: solid-liquid separation process>>>driving
force: supersaturation
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APPLICATION
One of the oldest and most important unit operation with
enormous economic importance.
- Widely used in fine chemical and pharmaceutical
industries for purification, separation, production step(s).
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OBJECTIVE OF CRYSTALLIZATION
Important objectives in crystallization
good yield
high purity
size uniformity
minimize caking
ease of pouring
ease of washing &
filtering
uniform behavior
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CRYSTAL GEOMETRY
Crystal solid composed of atoms, ions or molecules
which are arranged in organized, orderly and repetitive
manner
appear as polyhedrons
flat faces and sharp corners
All crystals of same material possess
equal angle between the corresponding faces
(particular shape)
relative sizes of faces can be different
same particular characteristics
Geometry important to recognize crystal characteristics

Different size and similar shape
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CRYSTAL GEOMETRY
Crystal structure maintain lattice structure

A point lattice is a set of points arranged so that each point has
identical surroundings.

A unit cell is a single cell constructed employing the same
parameters (e.g. bond angles) as those of lattice.
Point lattice Unit cell
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CRYSTAL GEOMETRY
Crystal classification based on the interfacial angle & length of axes
Seven Crystallographic systems
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TYPES OF CRYSTALLINE SOLID
Crystalline solids can be classification based on type of bond to
hold the particles in place in crystal lattice
i.Ionic crystals - charged ions held in place in the lattice by
electrostatic forces (e.g. sodium chloride).
ii.Covalent crystals - constituent atoms do not carry effective
charges; connected by a framework of covalent bonds, the atoms
sharing their outer electrons (e.g. diamond).
iii.Molecular crystals - discrete molecules held together by weak
attractive forces (e.g. VDW force or H bonds) (e.g. organic
compounds, sugar).
iv.Metallic crystals - ordered arrays of identical cations held by
sharing of outer electrons between constituent atoms (e.g.
copper).



QUESTION?
11
12
SOLUBILITY IN CRYSTALLIZATION
Solubility - maximum
amount of solute that can be
dissolved in a given solvent at
a given temperature




EQUILIBRIUM in crystallization is attained
when the solution is SATURATED
Represented by a SOLUBILITY CURVE
Solubility is dependent mainly on
TEMPERATURE
SOLUBILITY IN CRYSTALLIZATION
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Solubility measurements
Polythermal methods heating solutions
initially containing excess solutes.
Isothermal methods adding solvents at
constant temperature.

Magnitude of solubility depends on unit used.
Mass (or moles) solute/mass (or moles) solvent
Mass (or moles) solute/mass (or moles) solution
Mass (or moles) solute/volume solution



14
SOLUBILITY CHART
generally, the
solubilities of most
salts increase with
increasing temperature
line = saturated
above line = supersaturated
below line = undersaturated
but can be otherwise
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SUPERSATURATION
Supersaturated solution
Solution containing more dissolved solute than that given by
the equilibrium saturation value.
Degree of supersaturation (conc. driving force) is given by: c
= c c
s
(molar concentration); or y = y y
s
(molar fraction)

where c and c
s
are the solution conc., and equilibrium
saturation conc. at a given T, respectively.
Saturated solution
Solution that is in
thermodynamic
equilibrium with the
solid phase of its solute
at a given temperature.
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GENERATION OF SUPERSATURATION
If solute solubility increase strongly with
increase temperature, supersaturation
generated by temperature reduction
COOLING
If solubility is independent of temperature,
supersaturation generated by evaporating a
portion of the solvent
SOLVENT
EVAPORATION
If solubility is very high (NEITHER cooling &
evaporation is desirable), supersaturation is
generated by addition of common ion salt to
decrease solubility. (e.g. adding ammonium sulphate to protein
solution)
SALTING
Techniques to generate supersaturation

PRECIPITATION
If a nearly complete precipitaion is required,
supersaturation generated by chemical reaction
by adding third component. (e.g. hydrolysis of sodium
benzoate with HCl to crystallize benzoic acid)

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FORMATION OF CRYSTALS
Prerequisites for the formation of crystal is
supersaturation
formation of crystals - 2 steps :
1. birth of new particle - nucleation
2. its growth to macroscopic size
neither crystal growth nor formation of nuclei
from the solution can occur in a saturated or
unsaturated solution
driving potential for both rates is supersaturation



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FORMATION OF CRYSTALS
Formation of solid crystals from homogeneous
solution
C
o
n
c
e
n
t
r
a
t
i
o
n

o
f

s
o
l
u
t
e
,

C

Temperature, T
Solubility curve
[saturation
concentration, C*(T)]
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FORMATION OF CRYSTALS
Formation of solid crystals from homogeneous
solution
C
o
n
c
e
n
t
r
a
t
i
o
n

o
f

s
o
l
u
t
e
,

C

Temperature, T
Solubility curve
[saturation
concentration, C*(T)]
A
Undersaturated
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FORMATION OF CRYSTALS
Formation of solid crystals from homogeneous
solution
C
o
n
c
e
n
t
r
a
t
i
o
n

o
f

s
o
l
u
t
e
,

C

Temperature, T
Solubility curve
[saturation
concentration, C*(T)]

A
B
Supersaturated
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FORMATION OF CRYSTALS
Formation of solid crystals from homogeneous
solution






Nucleation
C
o
n
c
e
n
t
r
a
t
i
o
n

o
f

s
o
l
u
t
e
,

C

Temperature, T
Solubility curve
[saturation
concentration, C*(T)]
Metastable
limit
Metastable
zone
C
A
B
Metastable limit is influenced by saturation temperature, rate of supersaturation
generation, impurity level, mixing
For nucleation in metastable zone, seeding (adding small crystal particles) is
required.
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FORMATION OF CRYSTALS
Formation of solid crystals from homogeneous
solution
Growth
C
o
n
c
e
n
t
r
a
t
i
o
n

o
f

s
o
l
u
t
e
,

C

Temperature, T
Solubility curve
[saturation
concentration, C*(T)]
Metastable
limit
D
Metastable
zone
C
A
B
QUESTION?
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YIELD & MATERIAL BALANCE
material balance is
straightforward if
solutes are anhydrous
in crystallization
some water is removed as water
some water in the solution is
removed with the crystals as
hydrate
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MATERIAL BALANCE
COOLER &
CRYSTALLIZER
L kg solution
(solute + solvent)
W kg H
2
O

S kg solution
x
i,S
C kg crystals
x
i,C
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MATERIAL BALANCE
COOLER &
CRYSTALLIZER
L kg solution
x
i,L
W kg H
2
O
= 0 (no evap)
x
i,W

S kg solution
x
i,S
C kg crystals
x
i,C
solute water,

i
x C x W x S x L
C i W i S i L i , , , ,
MATERIAL BALANCE
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Example:
A salt solution weighing 10 000 kg with 30%
Na
2
CO
3
is cooled to 293 K (20C). The salt
crystallizes 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
per 100 kg of total
water? Assume that no water is evaporated.

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MATERIAL BALANCE
COOLER &
CRYSTALLIZER
10,000 kg
solution
30% Na
2
CO
3
W kg H
2
O
=0, no evap.
S kg soln
21.5 kg Na
2
CO
3
/
100 kg H
2
O
C kg crystals,
Na
2
CO
3
10H
2
O
Molecular Weight:
10H
2
O = 180.2
Na
2
CO
3
= 106
Na
2
CO
3
10H
2
O = 286.2
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MATERIAL BALANCE
O 10H CO Na MW
O H MW
2 3 2
2

C water
x
,
3 2 2
2
CO Na O H
O H
kg kg
kg
x
S water

,
3 2 2
3 2
CO Na O H
CO Na

kg kg
kg
x
S CO Na

,
3 2
,
1. Perform material balance for water and Na
2
CO
3
Feed = Solution stream + Crystals stream + Vapor stream
Solution stream
Given: 21.5 kg Na
2
CO
3
per 100 kg H
2
O in Solution stream
Vapor stream
W = 0 as no evaporation
Feed stream: given
Crystal stream contains Na
2
CO
3
10H
2
O
O 10H CO Na MW
CO Na MW
,
2 3 2
3 2
CO Na
3 2

C
x
,
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MATERIAL BALANCE
Feed = Solution stream + Crystals stream + Vapor stream
Water:
0 ) (
2 . 286
2 . 180
) (
5 . 21 100
100
) 10000 ( 7 . 0

C S
Na
2
CO
3
:

0 ) (
2 . 286
106
) (
5 . 21 100
5 . 21
) 10000 ( 3 . 0

C S
solute water,

i
x C x W x S x L
C i W i S i L i , , , ,
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MATERIAL BALANCE
2. Solving the two equation simultaneously,
C = 6370 kg of Na
2
CO
3
10H
2
O crystals
S = 3630 kg solution
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MATERIAL BALANCE
Assume that 6% of the total weight of the
solution is LOST by evaporation of water in
cooling, recalculate C and S ????
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HEAT BALANCES IN CRYSTALLIZATION
q = (H
2
+ H
V
) H
1
H
1
= enthalpy of the entering solution (feed) at the initial
temperature
H
2
= enthalpy of the final mixture of crystals and mother
liquor at the final temperature
H
V
= enthalpy of water vapor (if evaporation occurs)
q = total heat transferred (kJ) (+ve: heat must be added
(endothermic), -ve: heat must be removed (exothermic))
CRYSTALLIZER
Feed, H
1
H
v
, Water vapor


Two phase mixture
(crystal + saturated
solution), H
2
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Example
A feed of 10000 lb
m
solution is flowed into the
system at 130F. The concentrated solution is
flowed out at 80F. The yield of crystals
FeSO
4
.7H
2
O is 2750 lb
m
. The average heat
capacity of the feed is 0.70 btu/lb
m
F. The heat of
solution at 80F is -28.47 btu/lb
m
FeSO
4
.7H
2
O.
Heat of feed, H
1
= 10000(0.70)(130-80) = 350000 btu
Heat of crystallization, H
2

= 28.47 2750 lb
m
FeSO4.7H
2
O
= 78300 btu
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Heat transferred, q = (H
2
+ H
V
) H
1

= 78300 + 0 350000
= 428300 btu
Since q is ve, heat is removed (exothermic)
Example