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Crystallization is an important chemical separation technique utilized in the production of

commodity and special chemicals where there is attention to the purity of the product formed.
Crystallizers are the method specific equipment used in crystallization. They are used in
industry to achieve liquid-solid separation. These equipment are capable of generating high
purity products with relatively low energy input.
There are many designs and configurations of crystallizers. The design and operation of
industrial crystallizers are optimized based upon the conditions needed for:

the Size and homogeneity of crystals formed of the desired product

the quantity of agglomerates formed

the quantity of liquid impurities included in crystal agglomerates

the amount of liquid retained by the crystal cake after solid-liquid separation and
washing.

Industrial crystallizers must operate below the solubility curve in order to produce a solid
phase. However; crystallizers must be restricted to the metastable zone and should not be
operated in the unstable zone. It is operated as such is to avoid the creation of a large number
of small particles.
The particle size distribution of an industrial crystallizer depends on the relative rates of
nucleation and growth and on how they relate to the rate of product removal (which depends
on the residence time). Agglomeration and breakage are also major factors in the particle
sizes in industrial crystallizers. Agglomerates form when growing crystals of the same size or
of different sizes collide with each other in a perfectly inelastic way (the particles stick
together to form a new particle). Agglomeration is more extensive if there are more particles
which increases the probability of collision or if the colliding particles tend to stick together

Generally:

Promotion of growth over nucleation leads to smaller numbers of more uniform


crystals

Promotion of material transfer mechanism over product removal leads to larger


crystals

Lower super-saturation promotes growth over nucleation

Higher residence time promote both nucleation and growth over product removal

Hence, for any continuous crystallization application, industrial crystallizers should be


designed to operate in the metastable zone, at lower super-saturations, and with higher
residence times, in order to meet the stated objectives.
All continuous industrial crystallizers must have:

A mechanism to generate super-saturation

A mechanism to relieve the super-saturation

A mechanism to control super-saturation generation

In addition, to manage product crystal size, it is useful for the crystallizers to have a
mechanism for fines dissolution and a mechanism that deals with the removal of classified
product.
Types of Crystallizers

Forced Circulation crystallizers


Forced circulation crystallizers use evaporation or adiabatic evaporative cooling to generate
super-saturation. They create a super-saturated solution by evaporating the solvent of a

saturated solution. The solute of this super-saturated solution then cools, forming crystals.
These types of crystallizers are classified as mixed-suspension, mixed-product-removal
(MSMPR) crystallizers. The key assumption in the operation of an MSMPR crystallizer is
that the slurry is perfectly mixed and uniform throughout the system.
Operation
The feed slurry is pumped through the heat exchanger at high velocity and delivered to the
main body of the crystallizer at a high temperature. Vaporization occurs at the surface of the
slurry, while nucleation occurs near the bottom of the crystallizer body. The crystals are
removed and the vaporized solvent is condensed and sent back to the crystallizer body. There
are modifications available to this type of crystallizer that help them narrow the crystal size
distribution. Modifications such as baffling, provision of a conical entrance and an elutriation
step. The conical entrance promotes more thorough mixing which thereby produces more
uniform slurry. The baffling of the crystallizer reduces the fines from the mixture, so that
they can be recirculated for further growth. Elutriation removes smaller particles from the
slurry, except elutriation separates particles based on weight rather than size. Elutriation is
the process of flowing air over particles. Lighter particles are picked up by the air stream,
while the heavier particles remain in place.
Forced circulation crystallizers are often arranged in stages and are commonly used in
industry to produce salts and chemicals (such as Sodium Sulphate). It is as well used by some
agricultural chemical companies to evaporate phosphoric acid from a mixture and recover
solids.
This type of crystallizer is one of the least expensive types available. This makes it a very
good economic alternative if the product size is of little importance. It ranges quite largely in
sizes available and has a high rate of circulation thereby reducing particle deposits on vessel
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walls. Its only downside is that it is problematic trying to control the crystal size of the
products obtained.

Draft Tube Baffle Crystallizer


Draft tube baffle crystallizers (DTB crystallizers) are usually used in applications in which
excessive nucleation occurs. Small unwanted crystals (fines) are removed from larger
particles using gravitational settling and are recycled through the crystallizer again, resulting
in maximum crystal recovery and larger crystals. They are also used in continuous operations
and when a control of the sizes of crystals formed and the characteristics of the product are of
importance.
Operation
The DTB crystallizers basically consists of a baffle and a draft tube. Inside the baffle is a
vertical draft tube centred by supporting vanes. An agitator, concentrically located, rotates
slowly at the bottom of the draft tube. The feed inlet is located at the base of the bottom of

the cone and is directed into the draft tube and the settling zone provides an outlet for the
mother liquor. In the baffled region gravitational settling separates larger crystals from fines.
The larger crystals settle between the baffle and draft tube and are remover in the product
slurry whiles the fines are recirculated after being dissolved again in the heat exchange. An
elutriation leg is usually fitted to the bottom of the cone to provide classified product
removal.
This kind of crystallizer is used in direct-contact cooling, evaporation or adiabatic
evaporative cooling to generate super-saturation. It provides a mixed suspension as the active
volume for relieving super-saturation. The evaporated solvent obtained is condensed, cooled
and returned to the region of active crystallization. DTB crystallizers generally have a total
residence time of 4 to 6 hours.
The use of this crystallizer allows for the recyclability of fines and control of crystal sizes.
This makes it more economical and in turn, more energy efficient than forced circulation
crystallizers.
Its only disadvantages are that: It cannot handle a high density slurry and it requires regular
flushing to minimize deposits on the walls of the crystallizer.
DTBs are used in the production of Ammonium Sulphate, Sodium Chlorate and Copper
Sulphates. DTBs are also used for the purification of organic compounds.
The evaporated solvent is then condensed, cooled and returned to the region of active
crystallization. DTB crystallizers generally have a total residence time of 4 to 6 hours.

Surface-Cooled Crystallizer
The surface-cooled crystallizer is a version of forced circulation crystallizer which consists of
a shell and tube heat exchanger, a vessel with an internal skirt baffle and a recirculating
pump. The baffle is designed to prevent excessively fine crystals from contacting the growing
magma. This enables control of size and slurry density. The baffle also acts as a partition
between the settling zone and the active crystallization volume. The feed inlet is located on
the recirculating pipe just before the recirculation pump. The settling zone outside the baffle
provides an outlet for the mother liquor. The coolants used are usually either a tempered
water circulated through segmented baffles or a vaporized refrigerant.
Operation
The required super-saturation of the slurry is generated by cooling the mixed stream formed
by the fresh feed and the recirculating slurry within the tubes of the heat exchanger. The
surface of the heat exchanger is the coldest place during the process and causes a build-up of
solids.

Since the tubes within the heat exchanger are the coldest part of the crystallization system,
the temperature differences between the walls and the pumped slurry should be as minute as
practical. Practical values are dependent on the operating cycles and the properties of the
materials utilized. Temperature differences ranging from 5 to 15 are required to achieve
reasonable operating cycles.
This kind of crystallizer is used often in operations where the solutions boiling point is
extremely high, or for operation at temperatures below which it is not economically feasible
to use vacuum equipment.
Applications of this crystallizer are made use of in the production of sodium chloride from
caustic solutions, sodium carbonate decahydrate from waste solutions, and sodium chlorate
from sodium chloride saturated solutions.