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SEPARATION PROCESS II
CRYSTALLIZATION
Dr Nurul Ekmi Binti Rabat
06 Oct. 2015
1
TOPIC OUTCOMES
By end of topic, students should be able to
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, antisolvent 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
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).
OBJECTIVE OF CRYSTALLIZATION
Important objectives in crystallization
good yield
high purity
size uniformity
minimize caking
ease of pouring
uniform behavior
CRYSTAL GEOMETRY
appear as polyhedrons
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
QUESTION?
11
SOLUBILITY IN CRYSTALLIZATION
Solubility - maximum
amount of solute that can be
dissolved in a given solvent at
a given temperature
SOLUBILITY IN CRYSTALLIZATION
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
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SOLUBILITY CHART
line = saturated
above line = supersaturated
below line = undersaturated
generally, the
solubilities of most
salts increase with
increasing temperature
SUPERSATURATION
Saturated solution
Solution that is in
thermodynamic
equilibrium with the
solid phase of its solute
at a given temperature.
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 cs (molar concentration); or y = y ys (molar fraction)
where c and cs are the solution conc., and equilibrium
saturation conc. at a given T, respectively.
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GENERATION OF SUPERSATURATION
Techniques to generate supersaturation
COOLING
SOLVENT
EVAPORATION
SALTING
FORMATION OF CRYSTALS
Prerequisites
formation
of crystals - 2 steps :
1.
2.
neither
driving
FORMATION OF CRYSTALS
Solubility curve
[saturation
concentration, C*(T)]
Temperature, T
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FORMATION OF CRYSTALS
Solubility curve
[saturation
concentration, C*(T)]
A
Undersaturated
Temperature, T
19
FORMATION OF CRYSTALS
Solubility curve
[saturation
concentration, C*(T)]
B
A
Supersaturated
Temperature, T
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FORMATION OF CRYSTALS
Metastable
zone
Solubility curve
[saturation
concentration, C*(T)]
Metastable
limit
C
B
A
Nucleation
Temperature, T
FORMATION OF CRYSTALS
Metastable
zone
Growth
Solubility curve
[saturation
concentration, C*(T)]
Metastable
limit
C
B
A
D
Temperature, T
22
QUESTION?
23
balance is
straightforward if
solutes
in
are anhydrous
crystallization
some
some
MATERIAL BALANCE
W kg H2O
L kg solution
(solute + solvent)
COOLER &
CRYSTALLIZER
S kg solution
xi,S
C kg crystals
xi,C
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MATERIAL BALANCE
L kg solution
xi,L
W kg H2O
= 0 (no evap)
xi,W
COOLER &
CRYSTALLIZER
L xi , L S xi , S W xi ,W C xi ,C
i water, solute
S kg solution
xi,S
C kg crystals
xi,C
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MATERIAL BALANCE
Example:
A salt solution weighing 10 000 kg with 30%
Na2CO3 is cooled to 293 K (20C). The salt
crystallizes as the decahydrate. What will be the
yield of Na2CO310H2O crystals if the solubility
is 21.5 kg anhydrous Na2CO3 per 100 kg of total
water? Assume that no water is evaporated.
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MATERIAL BALANCE
W kg H2O
=0, no evap.
10,000 kg
solution
30% Na2CO3
COOLER &
CRYSTALLIZER
S kg soln
21.5 kg Na2CO3/
100 kg H2O
Molecular Weight:
10H2O = 180.2
Na2CO3 = 106
Na2CO3 10H2O = 286.2
C kg crystals,
Na2CO310H2O
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MATERIAL BALANCE
1. Perform material balance for water and Na2CO3
Feed = Solution stream + Crystals stream + Vapor stream
Feed stream: given
Solution stream
Given: 21.5 kg Na2CO3 per 100 kg H2O in Solution stream
xwater, S
kg Na2CO3
kg H2O
, xNa2CO3 , S
kg H2O kg Na2CO3
kg H2O kg Na2CO3
xwater,C
MW Na2CO3
MW H2O
, xNa2CO3 ,C
MW Na2CO3 10H2O
MW Na2CO3 10H2O
Vapor stream
W = 0 as no evaporation
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MATERIAL BALANCE
Feed = Solution stream + Crystals stream + Vapor stream
L xi , L S xi , S W xi ,W C xi ,C
i water, solute
Water:
Na2CO3:
100
180.2
0.7(10000)
(S )
(C ) 0
100 21.5
286.2
21.5
106
0.3(10000)
(S )
(C ) 0
100 21.5
286.2
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MATERIAL BALANCE
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MATERIAL BALANCE
32
q = (H2 + HV) H1
CRYSTALLIZER
H1
H2
Example
A feed of 10000 lbm solution is flowed into the
system at 130F. The concentrated solution is
flowed out at 80F. The yield of crystals
FeSO4.7H2O is 2750 lbm. The average heat
capacity of the feed is 0.70 btu/lbmF. The heat of
solution at 80F is -28.47 btu/lbm FeSO4.7H2O.
Heat of feed, H1 = 10000(0.70)(130-80) = 350000 btu
Heat of crystallization, H2
= 28.47 2750 lbm FeSO4.7H2O
= 78300 btu
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Example
= 78300 + 0 350000
= 428300 btu
Since q is ve, heat is removed (exothermic)
35
QUESTION?
36
NUCLEATION THEORIES
The first formed embryos due to clustering or
aggregation of ions or molecules in a supersaturated
solution.
Minute solid particles, seeds, small crystals- alternative
form of nucleation
Act as centers for crystal growth.
37
NUCLEATION
Sequence of stages for crystal evolution
Cluster Several particles accumulate to form
loose aggregate
Embryo Enough particles to form a new and
separate phase
Nucleus Smallest group of particles, not
redissolve and grow to form crystal
38
NUCLEATION
Types
of nucleation
Primary
Homogeneous (spontaneous)
Heterogeneous (induced by foreign
particles)
PRIMARY NUCLEATION
Primary
NUCLEATION RATE
25
16 VM 2 N a a 3
exp
3 2 2
3RT s
27.10,[McCabe ])
NUCLEATION RATE
VM = Molar volume of crystals, cm3/g mol
Na = Avogadro constant, 6.022 x 1023 molecules/g mol
a = Average interfacial tension between solid and
liquid, ergs/cm2
R = Gas constant, 8.3143 x 107 ergs/g mol K
T = Temperature, K
= Number of ions per molecule of solute
s
= Fractional supersaturation = ln
= Ratio of concentrations of supersaturated and
saturated solutions = c/cs
4VM
, L= crystal size .
(27.8, [McCabe])
ln
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RTL
NUCLEATION RATE
43
SECONDARY NUCLEATION
1.
2.
SPURIOUS NUCLEATION
45
QUESTION?
46