Multiphase Separation Processes

Crystallisation

Dr. Anand V. Patwardhan

Associate Professor
Chemical Engineering Department
Indian Institute of Technology Kharagpur
Kharagpur−721302

Email: avp@che.iitkgp.ernet.in; dravp63@gmail.com

 Energies of Crystallisation and Distillation
Crystallisation Distillation
total Ratio (heat
Melt. D H CP.D T, Boiling D H CP.D T, total
Substance heat dist / heat
point Cryst. for crys point Dist. for dist heat IN
OUT crys)
0 0
( C) (kJ/kg) (kJ/kg) (kJ/kg) ( C) (kJ/kg) (kJ/kg)

o -cresol 31 115 -2.1 112.9 191 410 336.5 746.5 6.6

m -cresol 12 117 37.6 154.6 203 423 361.6 784.6 5.1
p -cresol 35 110 -10.5 99.6 202 435 359.5 794.5 8.0
o -Xylene -25 128 115.0 243.0 141 347 232.0 579.0 2.4

m -Xylene -48 109 163.0 272.0 139 343 227.8 570.8 2.1
p -Xylene 13 161 35.5 196.5 138 340 225.7 565.7 2.9
o -Nitrotoluene -4 120 71.1 191.1 222 344 401.3 745.3 3.9
m -Nitrotoluene 16 109 29.3 138.3 233 364 424.3 788.3 5.7

p -Nitrotoluene 52 113 -46.0 67.0 238 366 434.7 800.7 11.9

Benzene 5 126 52.3 178.3 80 394 104.5 498.5 2.8
Water 0 334 62.7 396.7 100 2260 146.3 2406.3 6.1

2
 Crystallisation (preamble)

1. Solid-liquid separation process (based on solubility).

2. Mass transfer of a solute from the liquid solution to a

pure solid crystalline phase.

3. Method of purification.

4. Method of providing crystalline materials in a desired

size range (by varying operating conditions).

5. Crystal shape is independent of size.

6. If a crystal grows, each of the faces develops in a

regular manner.
3
 Crystallisation (preamble) …
7. Presence of impurities, however, usually results in the
formation of an irregular crystal.
8. Generally large regular crystals are a guarantee of the
purity of the material, though a number of pair of
materials form “mixed crystals”.
9. For growing perfect single crystals, used in the
production of semiconductor devices, laser beams, and
artificial gems.
10.Crystallisation can offer substantial savings as a
method of separation when compared with distillation,
even though it is more costly to achieve cooling
rather than heating. 4
 Growth & properties of crystals
1. From SOLUTION or from MELT
2. WITH or WITHOUT reaction
3. OCCASIONALLY directly from vapour phase (opposite to
sublimation)
4. DISSOLUTION versus CRYSTALLISATION (differences):
a) Number of nuclei on which material is deposited may increase /
decrease
b) Mass transfer resistance may exist on “Solid-Liquid interface”.
5. Two stages in crystallisation process:
a) Formation of nuclei, which must exist prior to crystallisation
b) Growth of nuclei
The final crystal size may be regulated if the number of nuclei
can be controlled
cooling  saturated solution
unsaturated solution 
cooling
 supersaturation (metastable region)
 crystals + saturated solution
Anand V. Patwardhan 5
 D B
Solubility
Metastable
curve (AB)
region

Conc. c Supersaturation:
b a
C cf: concentration
f cb: temperature
A e

Temperature 
“A-B-D-C”: Metastable region, in which “nucleation
rate” is very low.
Anand V. Patwardhan 6
 Bonds per molecule: ½, 1, 1½
Nucleation:
• Spontaneously, or small crystals may be added, or impurities may
act as nuclei
• Spontaneous nucleation = f (random variations in c, or T, at
molecular level)
• Smaller particles tend to have a greater tendency to solubilise
(owing to lesser bonding / networking amongst molecules)
………… proposed by Lord Kelvin
• Nucleus will grow only if sufficiently large for the solution to be
supersaturated with it.
• Slow cooling: Relatively large crystals, since spontaneous
nucleation is reduced & material is deposited on relatively fewer
nuclei
• Rapid cooling: large crop of small crystals (high number of nuclei)
Anand V. Patwardhan 7
 Growth of crystals:
• Growth rate = f(T & C at the crystal face)
c: necessary for solute transfer from bulk to crystal face
T: necessary for “heat of crystallisation” transfer away
from the crystal face
• Heat & mass transfer resistance: predominantly in laminar
sub-layer close to crystal surface

Crystallisation rate:
cbulk – csat
• f (degree of
 15 supersaturation)
Crystal • Increases rapidly initially
Growth
rate 10 • Levels off later
• Resistance in both liquid
5 and solid phases
Stirring speed 
Anand V. Patwardhan 8
 Concentration profile near crystal surface
cbulk Growing
crystal face
(cbulk – cint)
 cint
Conc.
(cint – csat)
csat

• For crystallisation from solution, very less supercooling is possible

( 1 – 2 0C).
  only mass transfer is important, heat transport is unimportant.
• The two processes, nucleation and growth cannot be separated.
• (cbulk – cint) = concentration gradient required to overcome the
resistance in the liquid film around solid.
• (cint – csat) = concentration gradient required to overcome the
resistance at the solid interface.
• (cbulk – csat) = apparent supersaturation.
Anand V. Patwardhan 9
• (cint – csat) = concentration gradient required to overcome the
resistance at the solid interface.
Lines of constant concentration

 The crystal grows layer-by-layer, and the

growth takes in a spiral manner.
Crystal  The diffusion of material to the crystal face
is controlled by the resistance of the
laminar layer near the crystal face (S-L
interface), therefore,
dm
dt
=
D.A
δ
c
bulk
-c
int 
b
where,
A = area of crystal surface, (m 2 )
D = diffusivity of solute in solution, (m 2 /s)
δ = thickness of laminar layer (decreases as agitation increases), (m)
b
m = mass of material deposited (kg) in time t (s)
Anand V. Patwardhan 10
If it is assumed that the TRANSPORT at INTERFACE is
directly proportional to the SUPERSATURATION at the
interface, then, dm
dt

= K.A. c -c
int sat 
where,
kg kg
K = rate constant for the surface process, or

s.m 2 . kg m3  
s.m 2 . kmol m3 
Eliminating c from the above 2 equations,
B
dm
dt
=
1
A
δ
b 

. c
bulk
-c
sat 
+
K D
Therefore, the LINEAR RATE of CRYSTAL GROWTH is given by,
d
dt
=
1
.
1
. c 
ρ 1 δ b bulk sat
-c = k. c -c
bulk sat  
S +
K D

 cbulk - csat 
dm n
Butler (1970) showed that,  , where n > 1
dt
Anand V. Patwardhan 11
Effect of IMPURITIES on crystal formation:

 Rate of NUCLEATION and rate of CRYSTAL

GROWTH are affected.
 Both these processes are RETARDED due to:
ADSORPTION of impurity on the surface of
NUCLEUS or CRYSTAL.
 May be useful for prevention of SCALING.
 Sometimes, PREFERENTIAL ADSORPTION
of impurities on a particular crystal face 
SHAPE MODIFICATION.

Anand V. Patwardhan 12
 Effect of TEMPERATURE on solubility

FeSO4.4H2O

FeSO4
FeSO4.7H2O
Solubility 

Na2HPO4

Na2HPO4.
2H2O
KClO3
Na2HPO4.7H2O

NaCl
Na2HPO4.12H2O

Temperature 
Anand V. Patwardhan 13
 Fractional crystallisation

40
Solubility of NaCl 

D
36 373
A K

25 C

17 G E
293
K

B F
59 68 88 160 176
Solubility of NaNO3 
EXAMPLE: Effect of NaCl on NaNO3 solubility
Anand V. Patwardhan 14
 Fractional crystallisation (Effect of one salt on the
solubility of other)
Curves EF and CB: effect of NaNO3 on NaCl solubility (mixture
saturated w.r.t.NaNO3 but unsaturated w.r.t. NaCl) at 373 & 293 K
Curves DE and AC: effect of NaCl on NaNO3 solubility (mixture,
saturated w.r.t.NaCl but unsaturated w.r.t. NaNO3) at 373 & 293 K
Points E and C: mixture saturated w.r.t. both salts at 373 & 293 K
Line CE: mixture saturated w.r.t. both salts at intermediate
temperatures
 Form a saturated solution at 373 K (point E)
 Cool the saturated solution 293 K
 At 293 K, saturated solution contains more NaCl and less NaNO3
 NaNO3 gets deposited in pure form
 Crystal size = f (cooling rate, stirring rate)
Anand V. Patwardhan 15
 Phase diagram for o-+m-+p-nitro toluene mixture

para 51.5 0C
P
40 0

30 0
para 324.7 K
Q
20 0

10 0
0 00 R Eutectic –2.8 0C
Eutectic –16.3 0C -10
S
-20 0
-30 0
0

0
-20
-20

-10
-30
-10

0
0

10
0

-30
0

ortho -4 0C meta 16 0C
16
Fractional crystallisation (o-+m-+p-nitro toluene)
For example:
 Point P: 3% o-, 8.5% m-, & 88.5% p- (initial
composition)
 No crystallisation till cooled to 46 0C
 Line PQRS: composition of remaining liquor
 On cooling: only para- is crystallised, and
ortho-/meta- ratio remains constant, till point S is
reached.
 Further cooling: meta- deposits along line SE, till
point E
 Point E: solid as a ternary eutectic
(Eutectic: constant
Anand V.composition
Patwardhan mixture) 17