CDB 2063

SEPARATION PROCESS II
CRYSTALLIZATION
Dr Nurul Ekmi Binti Rabat
06 Oct. 2015
1

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

describe crystal growth

discuss about crystallizing equipment

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

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

ease of washing &

filtering

uniform behavior

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

Different size and similar shape

Geometry important to recognize crystal characteristics

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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

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).
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QUESTION?

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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
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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

but can be otherwise

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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

If solute solubility increase strongly with

increase temperature, supersaturation
generated by temperature reduction
If solubility is independent of temperature,
supersaturation generated by evaporating a
portion of the solvent

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)

If a nearly complete precipitaion is required,

PRECIPITATION supersaturation generated by chemical reaction
by adding third component. (e.g. hydrolysis of 16sodium
benzoate with HCl to crystallize benzoic acid)

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
Concentration of solute, C

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

Temperature, T

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FORMATION OF CRYSTALS

Formation of solid crystals from homogeneous

solution
Concentration of solute, C

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

Undersaturated
Temperature, T

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FORMATION OF CRYSTALS

Formation of solid crystals from homogeneous

solution
Concentration of solute, C

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

Supersaturated
Temperature, T

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FORMATION OF CRYSTALS

Formation of solid crystals from homogeneous

solution
Concentration of solute, C

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

Metastable
limit
C

B
A

Nucleation
Temperature, T

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 21
required.

FORMATION OF CRYSTALS

Formation of solid crystals from homogeneous

solution
Concentration of solute, C

Metastable
zone

Growth

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

Metastable
limit
C

B
A

D
Temperature, T

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QUESTION?

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YIELD & MATERIAL BALANCE

material

balance is
straightforward if
solutes

in

are anhydrous

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
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

Crystal stream contains Na2CO310H2O

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

2. Solving the two equation simultaneously,

C = 6370 kg of Na2CO310H2O 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

Hv , Water vapor
Feed,
H1

q = (H2 + HV) H1

CRYSTALLIZER

Two phase mixture

(crystal + saturated
solution), H2

H1

= enthalpy of the entering solution (feed) at the

initial temperature

H2

= enthalpy of the final mixture of crystals and

mother liquor at the final temperature

HV = enthalpy of water vapor (if evaporation occurs)

q

= total heat transferred (kJ) (+ve: heat must be

added (endothermic), -ve: heat must be removed 33
(exothermic))

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

Heat transferred, q = (H2 + HV) H1

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

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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
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NUCLEATION

Types

of nucleation

Primary
Homogeneous (spontaneous)
Heterogeneous (induced by foreign
particles)

Secondary (induced by crystals)

Spurious Nucleation
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PRIMARY NUCLEATION
Primary

nucleation - nucleation takes place in the

absence of crystalline solid phase of the solute.
Occurs at high levels of supersaturation via
homogeneous or heterogeneous means.
When the solution is absolutely clear, nucleation is
referred to as homogeneous/spontaneous
nucleation.
While in the presence of a foreign solid phase (e.g.
dust, colloidal particles), nucleation is referred to as
heterogeneous nucleation.
40

NUCLEATION RATE

Number of new particles formed per unit time

per unit volume of magma (crystal+mother
liquor) or solids-free mother liquor.
Unit = number/cm3 s
B 10
0

25

16 VM 2 N a a 3
exp

3 2 2
3RT s

27.10,[McCabe ])

Rate of nucleation must be estimated to

determine the volume or residence time of
magma
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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

the rate of homogeneous nucleation of

potassium chloride is consistent with an
apparent interfacial tension of 2.8 ergs/cm2 at
300K, and the density of crystals is 1.97 g/cm3
Question : Determine the nucleation rate as a
function of s at a temperature of 300K.

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SECONDARY NUCLEATION

1.

2.

Formation of new particle influence by the

existing macroscopic crystal in the magma
Induced from fragments arising
from the suspended solute
crystals or from seeding
Induced from fluid shear &
collisions between existing
crystals with one another or with
wall of the crystallizer/rotary
impeller
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SPURIOUS NUCLEATION

Nucleation that occurs at large

supersaturations or accompanies poor
(slurry/suspension) magma circulation

Produces irregular crystals

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QUESTION?

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