cRYSTALLIZATION

Dr. KSHITIZ KUMAR

 Syllabus

Crystal geometry,
Equilibria and yields,
Nucleation,
Crystal growth,
Crystallization equipments,
Crystallization from melts.
Introduction
 Crystallization is also a solid-liquid separation process
in which mass transfer occurs of a solute from liquid
solution to pure solid crystalline phase.
 Crystallization is the formation of solid particles
within homogeneous phase.
 It may occur as formation of solid particle in:
 Vapour: Example: Snow
 Liquid melt: Formation of large single crystal
 Liquid solution: To be discussed in this chapter
 Concept applied to crystallization of solute from
saturated solution and crystallization of part of
solvent itself.
Introduction
 Application:
 Formation of pure crystal from impure solution
 Production of sucrose from sugar beet
 Magma: The two phase mixture of mother liquor
and crystal of all sizes which occupies the crystallizer
and is withdrawn as product is called magma.
 The retained mother liquor is separated from crystal by
filtration, centrifugation and washing with fresh solvent
 Along with good yield and high purity the appearance
and size range (uniformity) of crystal are also
significant.
 Crystal size distribution (CSD) must be under control.
Crystal geometry
 Crystal: A crystal is most highly
organised type of non-living
matter. Its constituent particle
(atom, molecules, ion) are
arranged in orderly three-
dimensional arrays called
space lattice.
 The relative size of the faces and
edges of the various crystals
may be different but angles
made by corresponding faces of
all crystals of the same material
are equal and characteristic of
that material under a given
condition.
Crystal geometry
 The smallest geometric portion, which
repeats to build up the whole crystal is
called a UNIT CELL.
 A finite number of symmetrical
arrangement are possible for a crystal lattice
and these may termed as crystal forms or
crystal system.
 A chemical substance may exists more
than one crystalline form is called
polymorphs and these phenomenon is
called polymorphism.
 Crystallographic System
 As all crystals of a definite substance have
same interfacial angle crystal forms are
classified on the basis of angles
Crystal geometry
 A given material may crystallize in two or more
different classes depending upon condition of
crystallization.
 For Example: Calcium carbonate occur in hexagonal
(more common) and orthorhombic form.
 Invariant Crystals: A growing crystal maintains
geometric similarity during growth . Such crystals
are called invariant.
Invariant Crystals:
 The center point may be thought as nucleus
from where crystal grow.
 Rate of growth of any face is measured by
velocity of translation of the face away from
center in a direction perpendicular to face.
 Unless crystal is regular polyhedron the rate of
growth of various faces of invariant crystal are
not equal.
 Size of crystal is denoted by characteristic
length, L
 : Sphericity
Vp and Sp: volume and surface area of crystal
 This is true for sphericity value close to 1 but
not for very low sphericity value
 The concept of invariant growth is useful in
analyzing the crystallization process.
 In real case growth is far from invariant.
 In extreme case very rapid growth of one face
will lead to needle like crystal while slow
growth of one face may give rise to thin-plate
or disc-shaped crystals.
Overlapping principle
 Even in invariant crystals the different faces of a
growing crystal have different translational
velocities.
 This alter the shape and appearance of crystal.
 Faces with low translational velocities
dominate the growth process such that faces
with high velocities diminish and ultimately
disappear.
 Only faces with lowest velocities survive.
 When the crystal is being dissolved, faces
with low translational velocities disappear
and only with highest velocities survive.
Equilibria and yields
 Equilibrium in crystallization
process is reached when the
solution is saturated, and the
equilibrium relationship for bulk
crystal is the solubility curve
 There are three types of solubility
curve observedfor materials
 Curve 1: KNO3 type (Solubility
increases with increase in temp.)
 Curve: 2: NaCl type (Solubility is
constant with increase in temp.)
 Curve 3: MnSO4 type , Inverted
solubility curve (Solubility
decreases with increase in temp.)
Phase diagram of magnesium
sulphate + water at 1 atm
Yields
 In most industrial crystallization process, the solution
(mother liquor) and the solid crystal are in contact for
long enough time to reach equilibrium.
 Hence mother liquor is saturated at the final temperature
of the process and the final concentration of the solute
in the solution can be obtained from solubility curve
 The yield of crystals from the crystallization process is then
calculated knowing the initial concentration of solute, the
final temperature and the solubility at this temperature.
 Simple water and solute material balance equation are
used to calculate the yield.
Yield of a crystallization process
Solution
Supersaturation
 In the formation of a crystal two steps are required:
 1. The birth of new particle: Nucleation
 2. Its growth to macroscopic size: Crystal growth
 CSD is dependent on the kinetics of both nucleation
and crystal growth.
 Driving force for both the process is supersaturation.
 Neither of the above process can take place in saturated
or unsaturated solution.
 Supersaturation can be generated by one or more of
four method
Method of Generation of Supersaturation
By Cooling and
• If solubility of solute increases strongly
Temperature with increase in temperature
Reduction

Evaporating a portion • If the solubility is independent of

of solvent temperature

• If cooling and evaporation is undesirable as when solubility

By adding third is very high
• Third component forms mixed solvent with original one and
component
reduces the solubility of solute. This is called salting

• New solute reacts with original solute

By adding new solute and form an insoluble substance
Units of Supersaturation
 Supersaturation is the concentration difference
between that of supersaturated solution in which
crystal is growing and that of a solution in
equilibrium with crystal.
 Concentration may be either mole fraction of solute
denoted by ‘y’ or in mole fraction of solute in unit
volume of solution, denoted by ‘c’.
 The two supersaturations are defined by equation:
The above two equation can be related as (considering the molar
density of solution and saturated solution equal)

Where is molar density of solution

 The concentration ratio ‘α’ and the fractional
supersaturation ‘s’ are defined by:

 In practice value of s is about 0.02

 100s represents percentage of supersaturation.
Supersaturation is generally less than about 2 percent.
 Nucleation
•Nucleation refers to the birth of very small bodies of a
new phase within a supersaturated homogeneous
existing phase.
•Nucleation may be classified into three groups

Nucleation

Primary Secondary Spurious

Homoge Heterog Fluid Initial Needle Veiled

Contact Attrition Growth
neous eneous Shear Breeding Breeding
Primary Nucleation
 Nucleation is a consequence of rapid local
fluctuations on a molecular scale in a homogeneous
phase that is in state of metastable equilibrium.
 Homogeneous Nucleation: Formation of new
particle within a phase uninfluenced in any way
by solids of any sort, including the walls of
container or even the most minute particles of
foreign substance.
 Heterogeneous nucleation: Solid particles of
foreign substance influence the nucleation
process by catalysing an increase in nucleation
rate.
Homogeneous Nucleation
 In crystallization from solution it almost Never
Happens .
 Crystal nuclei may form from various kind of particle:
molecules, atom, ions.
 The sequence of stages in evolution of crystal is

Cluster Embryo Nucleus Crystal

Homogeneous Nucleation
 Cluster: A loose aggregation of components which disappears
quickly.
 Because of their random motion, in any small volume several particles
associate to form cluster.
 Embryo: Association of enough particle in which there are beginning
of lattice arrangement and formation of new and separate phase.
 Have short life and revert to cluster or individual particles

 Nucleus: Smallest assemblage of particles that will not redissolve

and can therefore grow to form crystal.
 If supersaturation is large enough embryo grows to such a size that it is in
thermodynamic equilibrium with solution and it is called nucleus.
 The number of particles needed for stable nucleus ranges from few to
several hundred. (For water it is 80)
 Crystal: If the nucleus gains unit it grows and becomes crystal
Ostwald ripening
 Small particles have more surface energy than large
one.
 Hence solubility of smaller crystal is larger than the
large crystal and small crystal can be in equilibrium with
supersaturated solution.
 Such equilibrium is unsatble, because if large crystal is
present, the smaller crystal will dissolve and the
larger will grow until the small crystal disappears.
 This phenomena is called Ostwald ripening.
Kelvin Equation
 The solubility of a substance is related to its particle
size by Kelvin equation:

 where
 L= Crystal size

 α=Ratio of concentration of supersaturated and saturated

solutions
 VM= Molar volume of crystal

 σ= average interfacial tension between solid and liquid

 ν= number of ions per molecules of solute

Rate of Nucleation

 B0= Nucleation rate, number/cm3.s

 Na=Avogadro constant, 6.022 X 1023
 R = Gas constant, 8.313 X 107 ergs/g mol.K
 C= Frequency factor
Heterogeneous Nucleation
 The catalytic effect of solid particles on nucleation rate
is the reduction of energy required for nucleation.
 If the nucleus “wets” the surface of the catalyst, the
work of nucleus formation is reduced by a factor
that is a function of the angle of wetting between
nucleus and catalyst.
 The rate of nucleation is given by:
Secondary Nucleation
 The formation of nucleus attributable to the influence
of the existing macroscopic crystals in the magma is
called secondary nucleation.
 There are two kinds of secondary nucleation known:
 1. Fluid Shear Nucleation
 2. Contact Nucleation
Fluid Shear Nucleation

The supersaturated Swept nuclei

The shear stress in
solution moves past incorporated into
the boundary layer
the surface of a growing crystal and
may sweep away
growing crystal at a so appear as new
embryos or nuclei
substantial velocity crystal.
Contact Nucleation
 Nucleation influenced by intensity of agitation.
 Most common type of nucleation.
 Occurs at low supersaturation where growth of
crystal is at optimum for good quality.
 It is proportional to the first power of supersaturation.
 It is combination of
 Breakage of microscopic dendritic growth on the surface
of growing crystal
 Interference by the contacting object with cluster of
solute particle moving to become organized into the
crystal
 In commercial crystallization equipment nucleation
results from both homogeneous and contact
nucleation.
 The overall rate B0 can be written as:
 B0=Bss + Be +Bc
 Where Bss= Rate of homogeneous nucleation due to
supersaturation driving force
 Be= Nucleation rate from contact of crystal with impeller

 Bc= Nucleation rate from crystal-crystal contact

Summary

High • Homogeneous
supersaturation
and no agitation
Nucleation

Low • Contact
supersaturation
and agitation
Nucleation
Spurious Crystallization
Attrition • Internal agitators break small crystal into fragment and give rise
to new crystal

Crystallization • Independent of supersaturation

• Seed crystals originating in previous crystallization system carry

Initial Breeding small crystal on their surface.
• The small crystals soon wash off and grow.

• Abnormal needlelike or whiskerlike growth from the ends of

Needle crystal, which grow much faster than the sides if supersaturation
is large or magma circulation poor.
Breeding • Spikes break off to give new crystal origin.

• It is result off occlusion of mother liquor into crystal face.

Veiled Growth • There is too rapid crystal growth which traps mother liquor into
crystal face
Crystal Growth
 Crystal growth is a diffusional process, modified by
effect of solid surface.

Solute molecule Solute are

Solute organized
reach the growing accepted by the
into space lattice
face of the crystal crystal

 None of the process can proceed unless the solution is

supersaturated.
 Growth occurs layer by layer on the crystal face and
each new layer begins as two-dimensional nucleus
attached to the face.
Crystal Growth
 y= mole fraction of
solute in bulk solution
 ys= Mole fraction of
solute in saturated
solution
 y’= Mole fraction of
solute at interface
between crystal and
liquid
Crystal Growth
 The equation for mass transfer for crystallization can
be written as:

.
 Where NA= molar flux, moles per unit time per unit area

 sp= surface area of crystal

 K= overall mass transfer coefficient
 ky= mass transfer coefficient from solution to crystal face
 ks= coefficient of interfacial reaction
Crystal Growth
 The growth rate is given by:

 Where G= Growth rate of crystal, m/h

 ρM= Molar density of solution, g mol/cm3
The ΔL law of crystal Growth
 If all the crystal in magma grow in uniform
supersaturation field and at the same temperature and
if all the crystal grow from birth at a rate governed by
supersaturation, then all crystals are not only
invariant but also have the same growth rate that is
independent of size.

 It is highly idealised and not realistic in all situation.

 When above equation is not applicable and
the growth is called size dependent
Equipment for Crystallization
 Classification of crystallizer on method of achieving
supersaturation
Method of
achieving
supersaturation

Supersaturation
Supersaturation by Adiabatic Supersaturation
by cooling alone evaporation and by evaporation
cooling alone

Vacuum
Agitated tank Swenson Walker Krystal Draft Tube
Crystallizer
 Agitated Tank Crystallizer
 Simplest and most economical unit
 Supersaturation generated by
cooling
 Construction:
 Consist of cylindrical tank with low
speed agitator and a cooling coil.
 The tank has conical bottom
through which product is
withdrawn.
 The agitator improves the heat
transfer rate, keeps the temperature
of solution uniform, and keeps fine
crystal in suspension
 Agitated Tank Crystallizer
 Working
 Hot solution is discharged to the
crystallizer.
 The mass cools due to heat
transfer to the circulating
coolant.
 With decrease in temperature
crystal is formed due to
decrease in solubility of solute
 Product stream containing
crystal plus mother liquor is
withdrawn from bottom.
 Swenson Walker Crystallizer/Scraped Surface
Crystallizer
 It is a cooing type, continuous, jacketed
trough crystallizer.
 Contruction:
 An helical agitator-conveyor rotates at a
slow speed inside the trough to aid the
growth of the crystals by lifting them and
then allowing them to fall back through the
solution.
 The trough is jacketed externally for
circulating of coolant during operation.
 At one end inlet for hot solution is provided
while at other end overflow gate for crystal
and mother liquor discharge is provided
 Swenson Walker Crystallizer/Scraped Surface
Crystallizer
 Working:
 A hot concentrated solution is fed at
one end of the open trough and flows
slowly towards the other end.
 Water flows in jacket in
countercurrent direction to solution.
 The solution cools by heat transfer to
water and become supersaturated.
 Crystal start forming and building
 A spiral agitator keeps the crystal in
suspension so that previously formed
crystal grow in size.
 Used in crystallizing ice cream and
plasticizing margarine.
 Vacuum Crystallizers/Circulating
Magma Vacuum Crystallizer
 It is closed vessel in which vacuum
is maintained by a condenser.
 Feed solution enters the downpipe
before the suction of circulating
pump.
 Mother liquor and crystals are
drawn off through discharge pipe
upstream from the feed inlet in the
downpipe.
 Mother liquor is separated from the
crystal in a continuous centrifuge.
 The crystals are taken off as product
and the mother liquor is recycled to
the downpipe.
Vacuum Crystallizers
 Magma circulates from cone bottom of
crystallizer through a downpipe to a low
speed low head circulating pump.
 Magma then passes upward through vertical
tubular heater with condensing steam in the
shell and then into crystallizer body.
 The heated stream enters through tangential
inlet just below the level of magma surface
which imparts swirling motion to the magma
and facilitates flash evaporation
Vacuum Crystallizers
 Adiabatic evaporative cooling is used to create
the supersaturation.
 The temperature of entering solution is well
above the boiling point at the pressure in the
crystallizer.
 The feed solution cools spontaneously to the
equilibrium temperature.
 A portion of solvent evaporate (Enthalpy of
cooling and enthalpy of crystallization appear as
enthalpy of vaporization).
 Supersaturation generated by cooling and
evaporation causes nucleation and growth.
 Krystal or Oslo Cooler Crystallizer
 Used when large quantities of
crystals of controlled size are
required.
 Supersaturation is generated by
indirect cooling.
 Consist of:
 crystallizing chamber
 a circulating pump
 a external cooler.
 The solution is fed from top.
 Mother liquor is withdrawn
near the feed point with help of
circulating pump.
 Krystal or Oslo Cooler Crystallizer
 It is admitted to cooler where
supersaturation is achieved by
cooling.
 Supersaturated solution is fed
back to bottom of crystallizing
unit through a central pipe.
 Nuclei formed circulate with the
mother liquor and once crystal
grow to required size they are
removed from bottom as these
cannot be retained in the
fluidised bed by circulating
velocity
 Equipment for Crystallization
Circulating-liquid evaporated-
crstallizer
 Supersaturation is generated by evaporation.
 Circulating liquid is drawn by the screw pump
down inside the tube side of condensing steam
heater
 Heated liquid then flows into the vapor space,
where flash evaporation occurs, giving some
supersaturation.
 The vapor leaving is condensed.
 The supersaturated liquid flow down the
downflow tube and then up through the bed
fluidized and agitated crystals, which are growing
in size.
 The living saturated liquid then goes back as a
recycle stream to the heater, where it is joined by
the entering feed.
 The larger crystals settle out and a slurry of crystals
and mother liquor is withdrawn as product.
 Also called Oslo crystallizer.