Master of Crystallography and Crystallization October 2012-Sevilla

Crystallization reactors

Béatrice Biscans
Université de Toulouse.
CNRS -Laboratoire de Génie Chimique UMR 5503 –FRANCE

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Crystallizer selection
Method of creation of supersaturation
Can be imposed:
precipitation, extractive crystallization, salting out
Must be determined
From the temperature-solubility relationship
high variation: cooling
weak variation: evaporation (or vacuum cooling)

Type of crystallizer
Batch crystallizer : low production, incrustation problems
Continuous crystallizer: high production, controlled crystallization

Type of contactor
Stirred vessel: high energy cost and maintenance
Recycling slurry: efficient but risk of incrustation
Recycling liquor
Fluidized bed (classification): narrower product size distribution
easier solid-liquid separation

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Continuous crystallizers
Advantages:
Economical in operating and labour costs
Reduced space
Amount of mother liquor needed reworking is small
Elimination of impurities by flushing out
Higher reproducibilty of crystal size distribution
High production rate

Drawbacks:
Encrustation of heat exchangers and pipes
Problem of continuous withdrawal
Need denses slurry for limitation of the volumes of filtration
Periodical stops problem of steaty state recovery
Difficulty for controlling secondary nucleation
Seeding: more difficult

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Batch crystallizers
Advantages
Interesting for 1 to 100t/week productions
Simplicity of equipment without complicated mechanical systems
Easy scale-up
Minimization of encrustation on heat exchangers
Can be cleaned thoroughly at the end of each batch
Large crystals easy to obtain because nucleation can be controlled
at the beginning of the batch cycle
Seeding: easy
Easy cleaning

Drawbacks:
The product is not regular, lack of reproducibility
High labour costs , high working costs
High size
Small production
Cycles rather long

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Cooling crystallizers
Non agitated vessels

The simplest type of cooling crystallizer is the unstirred tank:

A hot feedstock solution is charged to the open vessel where it is
allowed to cool, often for several days, predominantly by natural
convection. Metallic rods may be suspended in the solution so that large
Crystals can grow on them and reduce the amount of product that sinks
to the bottom of the crystallizer. The product is removed by hand

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Cooling crystallizers
Agitated vessels
External circulation through an heat exchanger

The design of tank crystallizers varies

from shallow pans to large cylindrical
tanks.
The use of external circulation allows
mixing inside the crystallizer and high
rates of heat transfer between the liquor
and coolant. An internal agitator may
be installed in the crystallization tank if
needed.
The liquor velocity in the tubes is high,
therefore, small temperature differences
are usually adequate for cooling
purposes and encrustation on heat
transfer surfaces can be reduced
Batch or continuous

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Cooling crystallizers
Agitated vessels
Internal circulation with a draft tube

The large agitated crystallizer

shown here has an upper conical
section which slows down 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 draft tube
circulates the crystal slurry through
the growth zone of the crystallizer.
If required cooling surfaces may be
provided inside the crystallizer.

Batch or continuous
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Cooling crystallizers
Agitated vessels

It consists of two interconnected Twin or double crystallizer:

simple crystallizers, each section
operating at a different
temperature. Hot feed liquor enters
and mixes with the circulating
contents of the crystallizer, which
pass downwards through the
water-cooled draft tube A, under
the influence of an agitator. Part of
the cold magma passes under the
adjustable gate B, into the second
compartment of the crystallizer,
where it mixes with the circulating
magma in the second draft tube C, Batch or continuous
operated at a lower temperature
(crystallizers in series)

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Cooling crystallizers
Trough crystallizers
It consists of a long shallow through, about 1.2m wide,
rocked on supporting rollers. The solution to be crystallized is fed in
at one end and the crystals are discharged at the other end continously.
The slope of the trough towards the discharge end, is varied according
to the required residence time of the liquor in the crystallizer. Heat is
lost by natural convection in the atmosphere.

The Wulff-Bock crystallizer

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Cooling crystallizers
Trough crystallizers
The Swenson Walker crystallizer is a trough crystallizer with internal
agitation and a cooling system. 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 Swenson-Walker
crystallizer

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Cooling crystallizers
Oslo-Krystal cooling crystallizer
A small quantity of warm concentrated
feed solution enters the crystallizer vessel
at point A, located directly above the inlet to
the circulation pipe B. Saturated solution from
the upper regions of the vessel together with
The small amount of feed liquor, is circulated
by pump C through the tubes of heat
exchanger D, which is cooled rapidly by a
forced circulation of water or brine. On cooling
the solution becomes supersaturated, but not
sufficiently for spontaneous nucleation to
occur (metastable). The supersaturated
solution flows down pipe E and emerges from
the outlet F, directly into a mass of crystals
growing in the vessel. The rate of the liquor is
such that the crystals are maintained in a continuous
fluidized state

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Cooling crystallizers

Direct contact cooling crystallizer

Avoid the use of conventional

heat exchanger and
encrustation. The coolant is
insoluble in the solution and
its latent heat of phase change
(sublimation or vaporization)
is the main cause of heat
removal.The low density
coolant collects in the upper
layers and passes to a cyclone
to separate aqueous solution
droplets before being recycled

The Cerny direct coolant crystallizer (continuous)

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Evaporating crystallizers
Steam heated evaporators
Most evaporation units are steam
heated and a typical evaporator body
used in evaporative crystallization is
the short tube vertical type in
which steam condenses on the
outside of the tubes. A steam chest
or calandria with a large central
downcomer allows the magma to
circulate through the tubes; during
operation the tops of the tubes are just
covered with liquor. To increase the
rate of heat transfer, especially in
dealing with viscous liquors, a forced
circulation of liquor may be effected
by installing an impeller in the Typical evaporating crystallizer with a
downcomer. calandria with a large central downcomer

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Evaporating crystallizers
Forced circulation evaporators
The typical forced circulation
evaporator-crystallizer is a
circulating magma unit operated
under reduced pressure. Magma is
circulated from the conical base 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.

Forced circulation evaporative crystallizer

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Evaporating crystallizers
Oslo-Kristal evaporating crystallizer
The principle of the Oslo-Krystal process, already shown in cooling
crystallizer, can also be applied to evaporative crystallization.
Three forms of the Oslo-Krystal evaporating crystallizer are shown here
The vaporizer is directly connected with the crystallizer body to form
a sealed unit.

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Vacuum crystallizers
Draft tube agitation
A vacuum unit capable of producing
large crystals of narrow size
distribution is the Swenson draft-tube-
baffled (DTB) crystallizer.
A slow-speed propeller agitator is
located in a draft tube .The internal
baffle in the crystallizer forms an
annular space in which agitation
effects are absent. This provide a
settling zone that provide regulation
of the magma density and control of
the removal of excess nuclei. An
integral elutriating leg may be installed
underneath the crystallization zone to
effect some degree of product
classification.
Swenson draft-tube-baffled (DTB) crystallizer

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Vacuum crystallizers
Draft tube agitation
The standard Messo turbulence
crystallizer is another draft tube
agitated unit. Two liquor flow circuits are
created by concentric
pipes: an outer injector tube with a
circumferential slot and an inner
guide tube. Circulation is effected by a
variable speed agitator in the
guide tube. The principle of the Oslo
crystallizer is used in the growth
zone; partial classification occurs in the
lower regions, and fine crystals
segregate in the upper regions. Feedstock
is introduced into the guide tube in the
lower region of the vessel and passes into
the vaporizer
section where flash evaporation takes
place. Nucleation therefore Standard Messo turbulence crystallizer
occurs in this region and nuclei are swept
into the primary circuit
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Vacuum crystallizers
Fluidized bed agitation
The Oslo-Krystal unit is a fluidized bed agitated crystallizer in which
the gentle action minimizes secondary nucleation allows large crystals
to grow. Two different methods of operation exist: classified suspension
(circulating liquor) or mixed suspension (circulating magma)

Oslo-Krystal vacuum crystallizer showing two different methods of operation:

a) classified suspension b) Mixed suspension
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Vacuum crystallizers
Multistage vacuum crystallizer

The standard Messo multistage vacuum

crystallizer provides a number of cooling
stages in one vessel. The horizontal
cylinder is divided into several
compartments by vertical baffles that permit
underflow of magma from one section to
another but isolate the vapor spaces. Each
vapor space is kept at its operating pressure
by a thermocompressor, which discharges
to a barometric condenser. Hot feedstock is
sucked into the first compartment which is Standard Messo multistage vacuum
crystallizer
operated at the highest pressure and
temperature. Flash evaporation and cooling
occur and the resulting crystal slurry passes
into the successive compartments

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reactive crystallizers

Swenson atmospheric up-pumping

reaction-type DTB crystallizer
Swenson reaction-type DTB crystallizer

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