Crystallization

Crystallization
• FSS
• Need of crystallization:
– Purification and separation of substances
– the production of good-quality crystals.
– To obtain concentrated chemical substances i
n particulate solid form that have desirable pro
perties such as:
• Good flow characteristics
• Easy packing
• Handling ease
• Pleasant appearance
 Terminology
• Crystallization is the formation of solid particles within a homo
geneous phase.
• It may occur as the formation of solid particles in a vapor, as i
n snow; as solidification from a liquid melt, as in the manufact
ure of large single crystals; or as crystallization from liquid sol
ution.
• Magma – In industrial crystallization from solution, the two-ph
ase mixture of mother liquor and crystals of all sizes, which oc
cupies the crystallizer and is withdrawn as product, is called a
magma.
• In the formation of a crystal two steps are required:
1. The birth of a new particle
2. Its growth to macroscopic size.
• The first step is called nucleation.
 Crystallization Methods
• Crystallization is based on production of supersatura
tion.
• Methods to achieve supersaturation:
– Cooling
– Evaporation
– Vacuum or reaction
– Batch and continuous
• The choice depends upon:
– Feed liquid composition
– Product specification
– Solubility curve of product and
– other engineering considerations
 Crystallization Process
• Process achieved by:
– Achievement of supersaturation
– Formation of nuclei
– Growth of nuclei into crystal

• Degree of supersaturation
S=c/c’
or the concentration difference
Δc = c – c’
where
c = concentration of the crystallizing substance in the solution
c’ = equilibrium concentration (solubility) of the crystallizing substan
ce in the solution
• Units for supersaturation: concentration of the supersaturated solutio
n in which the crystal is growing –Concentration of a solution in equil
ibrium with the crystal.
• The two phases are very nearly at the same temperature.
 Nucleation

Nucleation of carbon di
oxide bubbles around fi
gures
COKE + MENTOS !!!!!!!!
Effect of nucleation
 The influence of level of supersaturation on
nucleation and the crystal growth.
• Metastable
– Product feed into crystallizer
– Growth dominating
• Intermediate region
– Nucleation (i.e., formation of
new crystals) rate large
– Actual crystallization
• Labile region
– Last stage
– Visa versa operation of 1st st
age
 The influence of level of supersaturation on
nucleation and the crystal growth.
• Metastable
– Nucleation is very low.
– Growth predominates.
• Intermediate region
– Nucleation (i.e., formation of
new crystals) rate larger.
– Growth is still significant.
• Labile region
– Nucleation predominates.
– Visa versa operation of 1st st
age.
 Degree of freedom

• Number of variables:
– Temperature and flow of process fluid
– Temperature and flow coolant
– Degree of super saturation
– Ratio of mother liquor to crystals which can be varying recycles o
f mother liquor to feed stream
• Number of equation:
– Enthalpy balance based on the Ist law of thermodynamic
– Stoichiometric balance based on solubility curve

• DOF = No. of variables – No. of equation

= 06 - 02
= 04
 Types of crystallizers
• Evaporator crystallizers:
– Indirect heating
• Forced circulated(FC)
• Draft-tube Baffle (DTF)
– Submerged Combustion
– Spray evaporation
• Cooling Crystallizers
– Controlled growth Mag
ma
– Classifying crystallizers
– Direct contact crystallize
r
• Vacuum crystallizer
– Forced circulation(FC)
– Draft tube baffle(DTF)
• Reaction crystallizers
Circulating magma crystallizers
with Indirect heat
• Forced circulated (FC) and draft tube baffl
e (DTB) belongs to this class

• Design consideration:
– The internal recirculation rate and velocity
– The crystallizer hold volume
– The speed of the circulating pump.
 Forced Circulation Crystallizer
1.
(indirect heating)
Feed clear liquor – level c
ontrol to a feed tank. Mix
ed with the mother liquo 4
r.
2. The mixed liquor is fed to
the suction side of the cry
stallizer recirculating pum
p. This feed is adjusted by
a level controller.
3. *The steam flow to the h
eat exchanger – flow cont
rol. An interlock between
the steam and circulating
pump, or the addition of 2
a density recorder.
4. Temperature control in t
he vessel may be achieve
d by controlling the evap
orator chamber pressure 3
by an air bleed.
1

*Once the steam rate is fixed, the production rate is also fixed, provided that the feed composition does not change.
 4

1
Cascade control of indirect heati
ng crystallizer
4
3A The magma density co
ntroller is the cascade
master of the steam f
low controller, and it
varies the heat input i
n order to keep the cr
ystal concentration c
onstant.
2

3B 3A

1
 2

1
 Draft-Tube Baffle Crystallizer
• Produces larger crystals t
han FC.
4
• The baffle controls the cry
stal size by permitting the
separation of unwanted fi
ne crystals.
• Figure shows the control
of the crystal size distribu
tion in a draft-tube baffle
type crystallizer using fine
s removal and their dissol
ution.
3A

3B

1
Submerged-Combustion Crystal
lizer
• used on corrosive applications or in cases where the salts have inv
erted solubility
• Clear liquor is fed under flow control.
• Burner fuel gas – either flow or pressure control.
• A bypass, controls the flow of combustion air to the burner.
 Cooling Crystallizers
• Controlled-growth magma crystallizers,
• Classifying crystallizers,
• Direct contact crystallizers.
Controlled-growth magma crystalliz
ers
• A variety of cradle crystallizers and scraped-s
urface units belong to this category.
• The cradle types are used in small applicatio
ns and involve little instrumental control.
• The various scraped-surface crystallizers are
used in crystallization from high-viscosity liqu
ors or in open-tank crystallizers, as coolers to
induce nucleation.
The basic controls of a refrigera
nt-cooled crystallizer
• evaporating refrigera
nt cools the shell,
• crystallization proces
s – in the tubes
2

1
 The controls of a liquid coolant -
cooled crystallizer
1

2A

2B

The cooling fluid flow is controlled in cascade by the outlet tempera

ture of the product slurry.
 Classifying crystallizer
2 • supersaturation is generated
entirely by cooling
• feed is introduced into a circ
3
ulating loop
1. Flow control of feed liquor –
to maintain constant through
put.
2. Cascade control : Slave – Flo
w of coolant, Master – outlet
temperature of the process fl
uid.
4 3. One refinement is to interloc
k the coolant flow with the ci
4 rculation pump motor.
1 4. Level control – Overflow fro
m the crystallizer & Mother li
quor outflow from the recycl
e vessel.
Classifying crystallizer
2

4
1
 Classifying crystallizer
• supersaturation is generated entirely by cooling
• feed is introduced into a circulating loop
1. Flow control of feed liquor – to maintain constant throughp
ut.
2. Cascade control : Slave – Flow of coolant, Master – outlet t
emperature of the process fluid.
3. One refinement is to interlock the coolant flow with the cir
culation pump motor.
4. Level control – Overflow from the crystallizer & Mother liq
uor outflow from the recycle vessel.
 Direct-Contact Crystallizers
• The coolant is an evaporating refrigerant or b
rine, and it is in direct contact with the proces
s slurry.
• Basic control methods are similar to those in
controlled-growth crystallizers (refrigerant - c
ooled).
• These involve constant feed rate and flow co
ntrols of the evaporating refrigerant, based on
process fluid outlet temperature or on tank le
vel.
 Vacuum crystallizer
• Heat input to produce adiabatic evaporation c
omes entirely from
– the sensible heat of the feed liquor and
– from the heat of crystallization of the crystalline pr
oduct.
• Supersaturation is generated by a combinatio
n of cooling and concentrating the liquor.
• The forced-circulation and draft-tube baffle cr
ystallizer designs are both used in this operati
on mode.
 Vacuum – DTB type
2
1. The vacuum is on contr
ol with steam jet ejecto 3
r. 1

2. Air bleed – pressure co

ntrol,
3. Both the steam and wat
er supplies –automatic
control, which allows ac 5
hieving the minimum c
ost of utilities.

4
 Draft-tube baffle crystallizer with combinatio
n of cooling and vacuum control.
1. Feed – flow control,
2. Product removal control – level measurement, and
3. Temperature control – indirectly by manipulation of jacket coolant.
• Use of suspension density recorder and other refinements can also be used.

2
 Reaction Crystallizers
• Crystallization is associated with a chemical re
action that usually produces the solute directl
y.
• once the reaction mixture is saturated with re
spect to the crystallizing substance, the reacti
on rate would determine the rate of supersat
uration
• the heat of exothermic reaction may be used i
n evaporating the solvent
 The controls of a reaction crystallizer that is
utilizing both gaseous and liquid reactants.
4
1. the aqueous solution 3A
feed – flow control
2. the total liquid feed –
level control
3. the gaseous reactant
is added on pH- 3B
cascaded control.
• The pH metering
lines should be
continuously flushed 1
when this system is
used.

2
 Auxiliary Equipment
1.The feed system, including the feed liquor, recycl
e, and wash streams.
2.Vacuum control to maintain predetermined press
ure in the system as a common means of crystalliz
er temperature control.
3.Dewatering system control. This includes filters or
centrifuges.
4.In the case of external classification equipment, in
order to improve the crystal size distribution of th
e product, hydrocyclones, vibrating screens, and o
ther external classification devices can be used.