CHC3170: Process Equipment Design – Unit IV: Deign of Crystallizer, Agitated Vessels and

Reactors

CRYSTALLIZERS:
Crystallization is a separation and purification technique employed to produce a
wide variety of materials. Crystallization may be defined as a phase change in which
a crystalline product is obtained from a solution. A solution is a mixture of two or
more species that form a homogeneous single phase. Solutions are normally thought
of in terms of liquids, however, solutions may include solids and even gases.
Typically, the term solution has come to mean a liquid solution consisting of a
solvent, which is a liquid, and a solute, which is a solid, at the conditions of interest.
The term melt is used to describe a material that is solid at normal conditions and is
heated until it becomes a molten liquid. Melts may be pure materials, such as molten
silicon used for wafers in semiconductors, or they may be mixtures of materials. In
that sense, a homogeneous melt with more than one component is also a solution,
however, it is normally referred to as a melt. A solution can also be gaseous; an
example of this is a solution of a solid in a supercritical fluid.
There is a wide variety of equipment used to carry out the crystallization process,
called crystallizers. Such equipment can be classified into four broad types:
1. Bulk solution crystallizers: Crystals are suspended in solution for a significant
time while nucleation and growth occurs.
2. Precipitation vessels: Feed streams entering the vessel generate high super
saturation levels (by chemical reaction, drowning or salting out), very rapidly
forming large numbers of small crystals.
3. Melt crystallizers forming multiple crystals. The bulk (typically > 90%) of the
solution or melt forms crystals either in suspension or on a cooled surface.
Impurities remain in the small amount of un-crystallized mother liquor.
4. Melt crystallizers forming large high-purity single crystals. Crystals form very
slowly from high-purity melts, yielding large, pure and defect-free crystals.
These are typically used for semiconductor manufacture.
All these type of equipment have aspects in common:
 A region where super saturation is generated to drive the crystallization.
 A region where crystals are in contact with supersaturated solution for crystal
growth. In some cases, crystals are present throughout the vessel, suspended
by some form of agitation; in other cases, the crystals occupy only part of the
vessel, typically as a fluidized bed.
CHC3170: Process Equipment Design – Unit IV: Deign of Crystallizer, Agitated Vessels and
Reactors

Equipment Types
1. Batch Crystallizers: For applications involving relatively small amounts of
material or when the material being processed must be handled on other than a
continuous basis, it is often convenient to use a batch vacuum crystallizer similar
to that shown in Figure 1.

Figure 1: Swenson Batch Vacuum Crystallizer without Booster

CHC3170: Process Equipment Design – Unit IV: Deign of Crystallizer, Agitated Vessels and
Reactors

Typically, the cycle on batch equipment of this type ranges from 2-8 h. At the
conclusion of the cycle, the material is dumped to an agitated tank from which it is
removed on either a batch or continuous basis for separation and drying. The time
required for filling the crystallizer and dumping the crystallizer must be added to the
time actually used for processing the material within the crystallizer to calculate the
batch cycle time.

2. Fluidized Suspension Crystallizer: Shown in Figure 2 is a fluidized suspension

crystallizer, or Oslo crystallizer as it is sometimes known.

Figure 2: Swenson Fluidized Suspension Crystallizer

This design was one of the earliest available for the crystallization of coarse
materials and operates by mixing a hot concentrated feed solution with a
circulated stream of liquid pumped to the vaporizer where solvent is evaporated
adiabatically. Liquid that is supersaturated at this point leaves the vaporizer
through the downcomer and enters the suspension chamber at the lowest portion.
Here the incoming fluid agitates the largest crystals present in the suspension
chamber and maintains them in a fluidized condition in the incoming stream of
supersaturated solution. A portion of the coarsest crystals can be removed
continuously as shown by pumping the slurry directly from the lower portion of
CHC3170: Process Equipment Design – Unit IV: Deign of Crystallizer, Agitated Vessels and
Reactors

the suspension chamber. In the upper portion of the suspension chamber, the
product crystals separate from the mother liquor leaving only a small quantity of
fines to recirculate with the incoming feed solution. Unwanted fine crystals are
dissolved by mixing with water and returned to the crystallizer where the water
must be evaporated.
This design has been widely used for the production of some coarse materials
such as ammonium sulfate. Its best field of application is for crystals of very high
settling rate such as nickel sulfate.

3. Forced-Circulation Crystallizer: The crystallizer, shown in Figure 3, is known

as forced-circulation (FC) crystallizer, or the mixed suspension, mixed product
removal (MSMPR) crystallizer.

Figure 3: Swenson Forced-Circulation Crystallizer

CHC3170: Process Equipment Design – Unit IV: Deign of Crystallizer, Agitated Vessels and
Reactors

The crystallizer consists of a body that is sized for vapor release with a liquid
level high enough so as to enclose a volume sufficient for retention of the growing
crystals. The circulation rate must be large enough to maintain suspension of the
crystals present. Suction from the lower portion of the body passes through a
circulation pump, through a heat exchanger back to the body through a tangent
inlet or a vertical inlet. The heat exchanger is omitted in those cases where
adiabatic cooling is sufficient to produce a yield of crystals.
The most common use of this crystallizer is as an evaporative crystallizer with
materials having relatively flat solubility or inverted solubility. It is also useful
for evaporation from solutions where there are scaling components.
This type of crystallization equipment is probably the most widely used of any
and is found in sizes ranging from 0.6 m for laboratory equipment up to over 12
m in diameter. Per pound of product produced, it is normally the least expensive
type of equipment available, particularly when substantial amounts of
evaporation are required.
The FC crystallizer is recommended for the crystallization of a wide range of
organic and inorganic compounds, such as NaCl, sodium sulfate, sodium
carbonate monohydrate, citric acid, urea, sugar, etc.

4. Draft Tube Baffle (DTB) Crystallizer: The DTB crystallizer shown in Figure 4,
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.
Typically, crystallizers of this type operate with a suspension of solids that is 25-
50% apparent settled volume. The low temperature drop at the boiling surface
and the uniform distribution of boiling created by the circulation pattern and the
uniform distribution of boiling created by the circulation pattern minimizes
crystallization buildup on the walls of the crystallizer and extends the operating
cycle.
Control of the population of fine particles by the mother liquor pumped from the
baffle zone permits crystallization of products such as ammonium sulfate, KCl,
and (NH4)2HPO4 in the range of 6-20 mesh.
CHC3170: Process Equipment Design – Unit IV: Deign of Crystallizer, Agitated Vessels and
Reactors

Figure 4: Swenson DTB Crystallizer

CHC3170: Process Equipment Design – Unit IV: Deign of Crystallizer, Agitated Vessels and
Reactors

5. Spray Crystallization: For applications where waste heat at very low temperature
is available and where the product will not be contaminated by atmospheric air
nor contaminate the air itself, it is possible to use spray crystallization. A cross-
section of a typical unit is shown in Figure 5. In this type of equipment, the slurry
to be crystallized is sprayed into a stream of air where cooling takes place, thereby
supersaturating the solution circulating with the suspended crystals. Systems of
this type can operate during the winter months and produce end temperatures that
are lower than 0°C, and can condense the heat from a multiple-effect evaporator,
thereby adding one additional crystallizing stage and eliminating the need for a
source of cooling water or a cooling tower. Although such equipment is relatively
new, its use is increasing and it shows great potential, particularly for applications
where crystal size and final liquid temperature are not critical, such as in the
recovery of KCl, Na2CO3 • 10H2O, and Glauber's salt from purge brines.

Figure 5: Typical Flowsheet of Spray Evaporator Crystallizer

CHC3170: Process Equipment Design – Unit IV: Deign of Crystallizer, Agitated Vessels and
Reactors

Design Procedure:
The following steps are outlined for the design of a crystallizer of the FC type.
Although these calculations are limited to that style, the procedure has general
application to other types of equipment.
1. Choose the type of crystallizer that best meets the requirements for (a) product
size, (b) product quality, (c) process economics, and (d) scale of operation.
2. It is convenient to make a listing of the temperatures and physical properties
required for the calculations, which is called a temperature frame. As the
calculation procedure proceeds, the table can be filled out and serves as a
summary of the calculated values.
3. Make a material balance, heat balance, and flow sheet.
4. Decide what retention time is required to make the required product, (a) by
experience, and (b) from growth and nucleation rate data.
5. Size the body on the basis of the controlling volume required for crystal
retention with due consideration for the minimum cross-section required for
vapor (evaporation) release.
6. Size the heat-transfer surface (for evaporative types) and the recirculation rate.
7. Size the condenser and vapor pipe, and entrainment separators (for
evaporative types).
8. Select the vacuum equipment (for vacuum types).
9. Select the circulating pump or agitator.
10.Select the slurry, feed, condensate, and related pumps.
11.Specify the mechanical requirements and construction codes (such as ASME,
UPV Section VIII) required.

Super-Saturation Generation:
Five main methods can be used to generate super-saturation:
a) Cooling, using the vessel walls, internal coils, or by pumping mother liquor
through an external heat exchanger. This is used when solubility changes
significantly with temperature and when the feed stream is near saturation at
a high temperature.
b) Evaporation, by heating the mother liquor or reducing the pressure to form a
boiling zone at the top of the vessel. This can be used for a wide range of
systems, although it is more energy-intensive than cooling.
CHC3170: Process Equipment Design – Unit IV: Deign of Crystallizer, Agitated Vessels and
Reactors

c) Reaction, where feed streams enter and mix resulting in a chemical reaction
generating the product, usually at high levels of super-saturation.
d) Drowning out, where a miscible solvent is added resulting in a mixture in
which the product is less soluble. This has similar characteristics to reaction
crystallization.
e) Salting out, where a salt with a common ion is added to precipitate the product
from solution. Again, this has similar characteristics to reaction
crystallization.

Crystallizer Mode:
Crystallizers can be designed to operate in either batch or continuous mode (and,
rarely, combinations of the two).
a) Batch crystallization is generally easier to control and is more flexible. It can
operate over a wide range of conditions. Generally, the key parameter is the
rate of generation of super-saturation expressed in terms of the cooling,
evaporation or addition rate.
b) Continuous crystallizers produce a consistent product and are generally
smaller and more energy efficient than batch equipment for the same
production rate as they operate at steady-state. Thus, continuous crystallizers
are favored for high-production rate systems. However, they operate over only
a narrow range of conditions, so more process knowledge is generally
required to make sure they produce the required product specification. The
only adjustable parameters are usually the feed rate (and hence residence time)
and the super-saturation generation rate.