CRYSTALLIZER SELECTION

Crystallization is an important separation process in the production of

commodity and special chemicals
The design and operation of an industrial crystallizer are optimized based
upon the conditions needed for:
Producing larger and more uniform crystals of the desired product
Reducing the formation of agglomerates
Reducing the amount of liquid impurities included in the crystal
agglomerates
Reducing the liquid retained by the crystal cake after solid-liquid
separation and washing

The key factors in the design of any thermal separation process are the
thermodynamics of the system under consideration as well as its kinetics.
The thermodynamics defines the limits of what can be achieved, the kinetics
define the time-scale and therefore the size of the equipment required. This
general statement also holds for crystallization. As a consequence,
fundamental knowledge of phase diagrams and solubility of the materials to
be separated is required prior to the design of any industrial process.
Definition of Terms

Growth: The process by which crystal nuclei increase in size and develop
into fully formed crystals.
Growth rate: The rate with which crystals grow. Different measures of
growth
rate are in use.
Metastable Zone: The region in phase space where the solution (melt) is
beyond equilibrium but cannot nucleate due to small the small nucleation
rate. Once nuclei have formed, they grow in the metastable zone.
Nucleation: The formation of an initial crystalline particle (nucleus) from the
supersaturated solution.
Nucleation rate: The rate at which crystal nuclei are formed. The
nucleation rate depends upon supersaturation.
Polymorphism: The phenomenon where a chemical entity exhibits more
than one crystal structure. Each distinct crystal structure is termed a
polymorph and will display different physical properties.
Phase diagram: A graphical representation of the state of a system
(existence of distinct phases) depending upon selected physical parameters.
Solubility: A measure of the amount of solute that can dissolve in a given
solvent. Solubility is a physical property of a given system.
Supercooling: A measure of the deviation of the system temperature from
the equilibrium temperature.
Supersaturation: A measure of the deviation of the solution concentration
from the equilibrium concentration.
Mechanisms
Reasons for choosing batch operation

Evaporating Crystallizers
If the solubility of a solute in a solvent is not appreciably decreased by
lowering the temperature, the appropriate degree of solution supersaturation
can be achieved by evaporating some of the solvent. Evaporation techniques
have been used for centuries to crystallize salts; the simplest
method utilization of solar energy is still employed commercially

throughout the world [58]. Common salt is produced widely from brine in
steam-heated evaporators, and similar evaporating crystallizers, often in
multiple-effect series, are used in sugar refining. Many types of forcedcirculation evaporating crystallizers are now in large-scale use

Oslo Crystallizer
also called classified-suspension crystallizer
oldest design developed for the production of large, coarse crystals.

DESIGN

desupersaturation of the mother liquor by contact with the

largest crystals present in the crystallization chamber
keeping most of the crystals in suspension without contact by a
stirring device, thus enabling the production of large crystals of
narrow size distributio

HOW IT WORKS
A bed of crystals is suspended in the vessel by the upward flow of
supersaturated liquor in the annular region surrounding a central downcomer. Originally designed as classifying crystallizers, 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 crystallizer, 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.
Most of the Oslo type crystallization units are of the "close type." However,
the "open" type is worth to be considered when very large settling areas are
required or when the vessel must be fabricated out of high cost alloys or
metals.

Figure 1 Oslo Type Crystallizer

Crystallizer Open Type

Figure 2 Oslo Type

KEY ADVANTAGES
Operating costs are much lower than that of any other type of
crystallizer
Low maintenance
Allows long production cycles between washing periods
TYPICAL PRODUCTS

(NH4)2 SO4
Na2SO4
AgNO3
hydrated mono sodium glutamate
mono ammonium phosphate (MAP)

SUPERSATURATION GENERATION:

FORCED CIRCULATION EVAPORATORS

GENERAL INFORMATION

Forced-circulation crystallizers, such as the one shown below, are

evaporative crystallizers. They create a super-saturated solution by
evaporating the solvent of a saturated solution. The solute of this
supersaturated solution then cools, forming crystals. These types of
crystallizers are classified as mixed-suspension, mixed-product-removal
(MSMPR) crystallizers. The key assumption of an MSMPR crystallizer is that
the slurry is perfectly mixed and uniform throughout the system.

USAGE EXAMPLES
Forced-circulation crystallizers are commonly used to produce salts and
chemicals in industry. The forced-circulation crystallizer shown on the left is
used to produce sodium sulfate, while that on the right is used in the
agricultural industry.
LIMITATIONS
Usually, they operate from low vacuum to atmosphere pressure. As a rule,
these units are used for high evaporation rates and when crystal size is not
of the utmost importance or if crystal grows at a fair rate. Almost any
material of construction can be considered for the fabrication of these
crystallizers.

TYPICAL PRODUCTS

NaCl (food or technical grade)

KNO3

Na2, SO4, K2 SO4

NH4Cl

Na2CO3H2O

Citric acid

ADVANTAGES

Least expensive type of crystallizer

Large range of sizes available
High rate of circulation reduces particle deposits on vessel walls

The Draft Tube Baffle (DTB) Crystallizer

The DTB crystallizer shown in Figure 5.18 consists of a body in which growing
crystals are circulated from the lower portion to the boiling surface by means
of a large, slow-moving propeller circulator. Surrounding the suspended
magma of growing crystals is an annular settling zone from which a stream
of mother liquor can be removed bearing fine crystals. The fine crystals
separate from the growing suspension of crystals by gravitational settling in
the annular baffle zone. Fine crystals in the mother liquor leaving the baffle
zone are sent to a following stage, settler, or heat exchanger in the case of
an evaporative-DTB crystallizer. The mother liquor is returned to the sucdon
of the propeller circulator after the fines have beendestroyed by heating,
mixing with dilute feed, or water, depending on the flow sheet. Incoming
feed is also mixed at the eye of the propeller, and in the case of adiabatic
cooling crystallizers or evaporative crystallizers, the temperature rise in the
circulated magma caused by the mixing of the feed or heated mother liquor
is in the order of 1 C. This low temperature rise can be achieved at very low

power consumption because of the small head loss in the circulated liquidsolid circulation path.
The Draft Tube Baffle (DTB) Crystallizer, used in applications requiring narrow
crystal distribution, and larger average crystal size, has been examined widely in
crystallisation theory. The basic choices of the type of crystallizer for continuous
operation are few: the design engineer has to choose between a mixed tank, a
fluidised bed (also known as "Growth" type or OSLO) crystallizer, and a Draft Tube
Baffle (DTB) crystallizer.

This type of equipment is especially useful in multiple-stage cooling

crystallizer applications where the cooling of the feed solution

Relieving the Supersaturation

Mixed suspension
Classified suspension

Control of supersaturation generation

Magma Recirculation
Liquor Circulation