CRYSTALLIZATION

Instructor: Zafar Shakoor

 Defining, Crystallization !!!
• Crystallization refers to the formation of solid crystals
from a homogeneous solution.
• It may occur as the formation of solid particles in a
vapor, as in snow; as solidification from a liquid melt.
• Crystallization is an important operation in
processing as a method of both purification and of
providing crystalline materials in a desired size range.
• Technique used to purify solid compounds.
 Defining, Crystallization !!!
 Based on the principles of solubility.
• Impurities are excluded from the growing crystals and
the pure solid crystals can be separated from the
dissolved impurities by filtration.
• A few parts per million may alter the product beyond
recognition.
Magma
It is the two phase mixture of mother liquor & crystals
of all sizes, which occupies the crystallizer & is with
drawn as product, is called magma.
 Crystallisation, one of the oldest of unit operations.
 It is used to produce vast quantities of materials,
including sodium chloride, sodium & aluminium
sulphates & sucrose which all have production rates
in excess of 108 tonne/year on a world basis.
 Many organic liquids are purified by crystallisation
rather than by distillation since, as shown by MULLIN,
enthalpies of crystallisation are generally much
lower than enthalpies of vaporisation.
 Crystallisation may be carried out closer to ambient
temperature thereby reducing energy requirements.
 Crystallisation is rarely the last stage in a process &
solvent separation, washing & drying stages are
usually required.
 Crystallisation is also a key operation in the
 freeze-concentration of fruit juices.
 desalination of sea water.
 recovery of valuable materials i.e. metal salts from
electroplating processes.
 production of materials for the electronic
industries.
 in biotechnological operations such as the
processing of proteins.
Energy requirements for crystallisation and distillation
Slow Cooling
Fast Cooling
 Kinetics and Mechanisms of Crystallization
Crystallization process consists of two stages
• Formation of small particles or nuclei;
• Growth of the nuclei

If the number of nuclei can be controlled then the

size of the crystal can also be controlled.
1. Crystal Nucleation
The creation of crystalline bodies within a supersaturated fluid,
is a complex, often ill-defined event, and nuclei may be
generated by many different mechanisms
The rate of nucleation is the number of new particles formed
per unit time per unit volume of magma or solids free mother
liquor.
– Primary Nucleation—in the absence of crystals
• primary nucleation are based on sequences of bimolecular
collisions and interactions in a supersaturated fluid, which
result in the buildup of lattice-structured bodies that may
or may not achieve thermodynamic stability.
– Secondary Nucleation—in the presence of crystals
• can take place only if crystals of the species under consideration
are already present.
• This is mainly the case in working crystallizers

where
• B is the rate of secondary nucleation (birthrate),
• Kb is the birthrate constant,
• MT is the slurry concentration (magma density),
• N is a term that gives some measure of the intensity of agitation in
the system (e.g., the rotational speed of an impeller), and
• ΔC is the supersaturation.
• The exponents j, l, and b vary according to the operating
conditions
2. Crystal Growth
1.mass transport, either by diffusion or convection from
the bulk solution to the crystal face
2.Surface reaction in which the growth units are
integrated into the crystal lattice

where
• D is the diffusion coefficient,
• v the molar volume,
• ΔC the supersaturation, and
• L the crystal size; i.e., the diffusion-controlled growth
rate is directly proportional to the degree of
supersaturation
3. Growth–Nucleation Interactions
• Crystal nucleation and growth in an industrial
crystallizer cannot be considered in isolation
because they interact with one another and with
other system parameters in a complex manner.
• The rate of growth of a crystal in a solution is
dependent on the temperature and
concentration of the liquid at the crystal face.
Pictorial Representation Of The Process
 Designing a Crystallizer
Five main types of information are generally
required to design a crystallization process:
1) Solubility and phase relationships
2) Metastability limits
3) Nucleation characteristics
4) Crystal growth characteristics
5) Hydrodynamics of crystal suspensions
 Solubility & Phase Relationships

• Solubility and phase relationships influence

the choice of crystallizer and method of
operation.
• These data must be obtained by using the
materials to be encountered in the plant
because traces of impurity often have a
considerable effect on phase relationships.
 Metastability Limits
• Metastable limits define acceptable operating
conditions for the minimization of
uncontrolled nucleation
 Nucleation characteristics
• The processes of nucleation and growth are
both exceedingly complex
• They are influenced greatly by temperature,
supersaturation and impurities.
• A knowledge of these system characteristics is
essential in design.
 Crystal growth characteristics

• Specify the type of crystal growth like veild

growth, Spikewise growth
• The crystals are present in large quantities,
settling is hindered;
• Further complications can arise if their shapes
are irregular.
Hydrodynamics of crystal suspensions

• Crystal suspension velocities must also be

known so that liquor circulation rates in
fluidized-bed crystallizers maintained
accordingly

• Agitation rates in stirred vessels can be

specified
Desalination of Seawater by Freezing
 Direct-Contact Freezing
Direct-contact freezing processes utilise inert, immiscible
refrigerants and are suitable for desalination. A typical scheme
is shown in Figure. Sea-water, at a temperature close to its
freezing point, is fed continuously into the crystallisation vessel
where it comes in direct contact with a liquid refrigerant such
as n-butane which vaporises and causes ice crystals to form
due to the exchange of latent heat. The ice-brine slurry is fed
to a wash column where it is washed counter currently with
fresh water. The emerging brine-free ice is melted by the
enthalpy of the condensation of the vapour released from the
compressed refrigerant. A major part of the energy input is
that required for the compressors.
Continuous
Crystallization Process
Vacuum Crystallizer
 Applications of Crystallization
• Detergents
• Fertilizers
• Food stuff (Protein, etc.)
• Catalysts
• Dyestuffs
• Electronic Materials
• Pharmaceuticals
 Caking of Crystals
Crystalline materials frequently cake or cement together on storage & crystal size,
shape, moisture content, and storage conditions can all contribute to the caking
tendency. In general, caking is caused by a dampening of the crystal surfaces in storage
because of inefficient drying or an increase in atmospheric humidity above some
critical value that depends on both substance and temperature. The presence of a
hygroscopic trace impurity in the crystals, can also greatly influence their tendency to
absorb atmospheric moisture. Moisture may also be released from inclusions if crystals
fracture under storage conditions and, if crystal surface moisture later evaporates,
adjacent crystals become firmly joined together with a cement of re-crystallised solute.
Caking may be minimised by efficient drying, packaging in airtight containers, and
avoiding compaction on storage. In addition, crystals may be coated with an inert dust
that acts as a moisture barrier. Small crystals are more prone to cake than large crystals
because of the greater number of contact points per unit mass, although actual size is
less important than size distribution and shape and the narrower the size distribution
and the more granular the shape, the lower is the tendency of crystals to cake. Crystal
size distribution can be controlled by adjusting operating conditions in a crystalliser
and crystal shape may be influenced by the use of habit modifiers.
 Crystalliser selection
The temperature–solubility relationship for solute and solvent is of prime importance
in the selection of a crystalliser and, for solutions that yield appreciable amounts of
crystals on cooling, either a simple cooling or a vacuum cooling unit is appropriate. An
evaporating crystalliser would be used for solutions that change little in composition
on cooling and salting out would be used in certain cases. The shape, size and size
distribution of the product is also an important factor and for large uniform crystals, a
controlled suspension unit fitted with suitable traps for fines, permitting the discharge
of a partially classified product, would be suitable. This simplifies washing and drying
operations and screening of the final product may not be necessary. Simple cooling-
crystallisers are relatively inexpensive, though the initial cost of a mechanical unit is
fairly high although no costly vacuum or condensing equipment is required. Heavy
crystal slurries can be handled in cooling units without liquor circulation, though
cooling surfaces can become coated with crystals thus reducing the heat transfer
efficiency. Vacuum crystallisers with no cooling surfaces do not have this disadvantage
but they cannot be used when the liquor has a high boiling point elevation. In terms
of space, both vacuum and evaporating units usually require a considerable height.
 Design Procedures
MULLIN has given details of a procedure for the design of classifying crystallisers in
which the calculation steps are as follows.
(a) The maximum allowable supersaturation is obtained and hence the working
saturation, noting that this is usually about 30 per cent of the maximum.
(b) The solution circulation rate is obtained from a materials balance.
(c) The maximum linear growth-rate is obtained based on the supersaturation in the
lowest layer which contains the product crystals.
(d) The crystal growth time is calculated from the growth rate for different relative
desupersaturations (100 per cent desuperation corresponding to the reduction of
the degree of supersaturation to zero).
(e) The mass of crystals in suspension and the suspension volume are calculated
assuming a value for the voidage which is often about 0.85.
(f) The solution up-flow velocity is calculated for very small crystals (< 0.1 mm) using
Stokes’ Law although strictly this procedure should not be used for particles other
than spheres or for Re > 0.3. In a real situation, laboratory measurements of the
velocity are usually required.
(g) The crystalliser area and diameter are first calculated and then the height which is
taken as (volume of suspension/cross-sectional area).
Cooling crystallisers (Batch Crystallisers)
Non-agitated vessels
The simplest type of cooling crystalliser is an unstirred tank in
which a hot feedstock solution is charged to an open vessel and
allowed to cool, often for several days, by natural convection.
Metallic rods may be suspended in the solution so that large
crystals can grow on them thereby reducing the amount of
product that sinks to the bottom of the unit. The product is
usually removed manually. Because cooling is slow, large
interlocked crystals are usually produced. These retain mother
liquor and thus the dried crystals are generally impure. Because of
the uncontrolled nature of the process, product crystals range
from a fine dust to large agglomerates. Labour costs are high, but
the method is economical for small batches since capital,
operating, and maintenance costs are low, although productivity is
low and space requirements are high.
 Agitated Vessels

Installation of an agitator in an open-tank crystalliser gives

smaller & more uniform crystals & reduces batch times.
Because less liquor is retained by the crystals after filtration &
more efficient washing is possible, the final product has a
higher purity. Water jackets are usually preferred to coils for
cooling because the latter often become encrusted with
crystals and the inner surfaces of the crystalliser should be
smooth and flat to minimise encrustation (hard coating on the
surface of something). Operating costs of agitated coolers are
higher than for simple tanks &, although the productivity is
higher, product handling costs are still high. Tank crystallisers
vary from shallow pans to large cylindrical tanks.
 Agitated Vessels

The typical agitated cooling

crystalliser, shown in Figure
15.14a, has an upper conical
section which reduces the
upward velocity of liquor and
prevents the crystalline product
from being swept out with the
spent liquor. An agitator, located
in the lower region of a draught
tube circulates the crystal slurry
through the growth zone of the
crystalliser; cooling surfaces may
be provided if required.
 Agitated Vessels

External circulation, as shown in

Figure b, allows good mixing inside the
unit and promotes high rates of heat
transfer between liquor and coolant,
and an internal agitator may be
installed in the crystallisation tank if
required. Because the liquor velocity
in the tubes is high, low temperature
differences are usually adequate, and
encrustation on heat transfer surfaces
is reduced considerably. Batch or
continuous operation may be
employed.
 Vacuum (adiabatic cooling) crystallisers

A vacuum crystalliser operates on a slightly different

principle from the reduced-pressure unit since
supersaturation is achieved by simultaneous evaporation
and adiabatic cooling of the feedstock. A hot, saturated
solution is fed into an insulated vessel maintained under
reduced pressure. If the feed liquor temperature is higher
than the boiling point of the solution under the low
pressure existing in the vessel, the liquor cools
adiabatically to this temperature and the sensible heat
and any heat of crystallisation liberated by the solution
evaporate solvent and concentrate the solution.
 Continuous Crystallizers
The majority of continuously operated crystallisers are of three basic
types: forced circulation, fluidised-bed and draft-tube agitated units.
Forced-circulation crystallisers
A Swenson forced-circulation crystalliser operating at reduced
pressure is shown in Figure . A high recirculation rate through the
external heat exchanger is used to provide good heat transfer with
minimal encrustation(hard coating on the surface of something) . The crystal
magma is circulated from the lower conical section of the
evaporator body, through the vertical tubular heat exchanger, and
reintroduced tangentially into the evaporator below the liquor level
to create a swirling action and prevent flashing. Feed-stock enters on
the pump inlet side of the circulation system and product crystal
magma is removed below the conical section.
 Fluidised Bed Crystallisers
In an Oslo fluidised-bed crystalliser, a bed of crystals is suspended in
the vessel by the upward flow of supersaturated liquor in the annular
region surrounding a central downcomer, as shown in Figure.
Although originally designed as classifying crystallisers, fluidised-bed
Oslo units are frequently operated in a mixed-suspension mode to
improve productivity, although this reduces product crystal size.
With the classifying mode of operation, hot, concentrated feed
solution is fed into the vessel at a point directly above the inlet to
the circulation pipe. Saturated solution from the upper regions of the
crystalliser, together with the small amount of feedstock, is
circulated through the tubes of the heat exchanger and cooled by
forced circulation of water or brine. In this way, the solution
becomes supersaturated although care must be taken to avoid
spontaneous nucleation. Product crystal magma is removed from the
lower regions of the vessel.
 Draught-tube Agitated vacuum Crystallisers
A Swenson draught-tube-baffled (DTB) vacuum unit is shown in Figure .
A relatively slow-speed propellor agitator is located in a draught tube
that extends to a small distance below the liquor level. Hot,
concentrated feed-stock, enters at the base of the draught tube, and
the steady movement of magma and feed-stock to the surface of the
liquor produces a gentle, uniform boiling action over the whole cross-
sectional area of the crystalliser. The degree of super cooling thus
produced is less than 1 deg K and, in the absence of violent vapour
flashing, both excessive nucleation and salt build-up on the inner walls
are minimised. The internal baffle forms an annular space free of
agitation and provides a settling zone for regulating the magma density
and controlling the removal of excess nuclei. An integral elutriating
(Elutriation is a process for separating particles based on their size) leg may be installed below

the crystallisation zone to effect some degree of product classification.

THANKS