Table of Contents

Summary: ......................................................................... 2
Introduction ................................................................... 3

CH1 : nucleation: ........................................................... 3-4

ch2 : Growth: ................................................................... 4

ch3 : CRYSTALLIZERS and crystallization application
in industry: ................................................................ 5-13
FORCED-CIRCULATION: .......................................... 5-8

DRAFT TUBE BAFFLE: .............................................. 8-11

SURFACE-COOLED: ................................................... 11-12
BATCH VACUUM: ....................................................... 12-13
Conclusion: ..................................................................... 14
references : ................................................................... 15

Summary :
introduction talk about what is the crystallization and And the importance of it .
in ch1: talk about nucleation generality and we will talk about the two step of
nucleation primary and secondary nucleation in primary we talk about
Homogeneous and heterogeneous nucleation . in ch2 talk about what is the
growth . in ch3 talk about some of kinds of CRYSTALLIZERS and their importance
and advantages and disadvantages and examples of their uses

introduction:
definition :
Crystallize Definition: crystallization is the slow precipitation of crystals from a solution of a
substance. Crystallization can also refer to the solid-liquid separation and purification
technique in which mass transfer occurs from the liquid solution to a pure solid crystalline
phase.[1]
Crystallization touches every aspect of our lives from the foods we eat and the medicines we
take, to the fuels we use to power our communities. The majority of pharmaceutical
products go through at least one crystallization step during their manufacture. Salt and
sugar are delivered to our dinner tables as crystals. The unwanted crystallization of gas
hydrates played a role in the recent Deepwater Horizon oil spill.
crystallization introduction Scientists and engineers working in many industries around the
world are required to understand, optimize and control crystallization processes every day
We can start with a few definitions:
Crystal: Solid particles in which the constituent molecules, atoms or ions are arranged in
some fixed and rigid repeating three-dimensional pattern or lattice.
Precipitation: It is a little bit difficult to define the term precipitation. For some, it is simply a
fast, perhaps uncontrolled, crystallization process. For others, it is crystal formation resulting
from a chemical reaction. It can also vary by industry; in the pharmaceutical industry,
crystallization is common and in the chemical industry precipitation is the vernacular.
For the purpose of this blog, the two will be used interchangeably.
The prevalence of crystallization processes in industry can probably be attributed to
the fact that crystallization acts as both a separation and purification step. In one fell
swoop, crystal product of the desired purity can be created and then isolated. Despite
this obvious advantage, crystallization processes still need to be understood an
controlled to ensure the desired crystal product quality is achieved and to ensure an
efficient and cost-effective crystallization process.[2]
the crystallization process consists of two major events, nucleation and crystal growth

nucleation:
Nucleation, the initial process that occurs in the formation of a crystal from a solution, a
liquid, or a vapour, in which a small number of ions, atoms, or molecules become
arranged in a pattern characteristic of a crystalline solid, forming a site upon which
.additional particles are deposited as the crystal grows

Primary nucleation:
is the initial formation of a crystal where there are no other crystals present or where, if
there are crystals present in the system, they do not have any influence on the process. This
can occur in two conditions. The first is homogeneous nucleation, which is nucleation that is
not influenced in any way by solids. These solids include the walls of the crystallizer vessel
and particles of any foreign substance. The second category, then, is heterogeneous
nucleation. This occurs when solid particles of foreign substances cause an increase in the
rate of nucleation that would otherwise not be seen without the existence of these foreign
particles. Homogeneous nucleation rarely occurs in practice due to the high energy
necessary to begin nucleation without a solid surface to catalyse the nucleation.[3]

Homogeneous and heterogeneous nucleation:

Heterogeneous nucleation begins on alien surfaces or particles, or preexisting nuclei in the old phase. Dust or atmospheric aerosols can serve as
heterogeneous nucleation centers for water condensation in the
atmosphere. Likewise, the microscopically rough surface of a soda glass
offers nucleation sites for CO2 bubbles.
We can also induce heterogeneous nucleation in a one-component system
by seeding nuclei of the new phase into the metastable old phase. For
instance, we can easily trigger the crystallization of a saturated saline
solution or a supercooled liquid by adding just a few grains of the salt to the
solution. In the following video, this is demonstrated by dropping a few icecrystals into a bottle of supercooled water, which then completely freezes
within seconds:
Heterogeneous nucleation typically has a much smaller barrier towards the
phase transition and most phase transitions occurring in experiments or
nature are started by heterogeneous nucleation. Still, the focus in
nucleation research often lies on the underlying homogeneous nucleation:
the formation of the new phase solely from fluctuations within the old
phase.[4]

Secondary nucleation:
Secondary nucleation is the formation of nuclei attributable to the
influence of the existing microscopic crystals in the magma .The first type
of known secondary crystallization is attributable to fluid shear, the other
due to collisions between already existing crystals with either a solid
surface of the crystallizer or with other crystals themselves. Fluid shear
nucleation occurs when liquid travels across a Crystal at a high speed,
sweeping away nuclei that would otherwise be incorporated into a
Crystal, causing the swept-away nuclei to become new crystals. Contact
nucleation has been found to be the most effective and common method

for nucleation. The benefits include the following[5]

Growth:
Once the first small crystal, the nucleus, forms it acts as a convergence point (if
unstable due to supersaturation) for molecules of solute touching or adjacent
to the crystal so that it increases its own dimension in successive layers. The
pattern of growth resembles the rings of an onion, as shown in the picture,
where each colour indicates the same mass of solute; this mass creates
increasingly thin layers due to the increasing surface area of the growing crystal.
The supersaturated solute mass the original nucleus may capture in a time unit
is called the growth rate expressed in kg/(m2*h), and is a constant specific to the
process. Growth rate is influenced by several physical factors, such as surface
tension of solution, pressure, temperature, relative crystal velocity in the
solution, Reynolds number, and so forth.

CRYSTALLIZERS and crystallization

application in industry:
Crystallizers are used in industry to achieve liquid-solid separation. They are an
important piece of chemical processing equipment because they are capable of
generating high purity products with a relatively low energy input.

(figure 1)[3]

FORCED-CIRCULATION
Forced-circulation crystallization is the most widely used crystallization method in
industry.

(figure 2 FORCED-CIRCULATION)[3]
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.

(figure 3)[3]

EQUIPMENT DESIGN
The feed slurry is first heated in a heat exchanger, then pumped to the main body
of the crystallizer. Vaporization occurs at the top surface of the slurry,
while nucleation occurs near the bottom of the crystallizer body. The crystals are
removed and vaporized solvent is condensed and returned to the crystallizer body.

(figure 4 )[3]

There are several adaptations that can be added to a forced-circulation

crystallizer to help narrow the crystal size distribution. Options include
baffling, a conical entrance, and an elutriation step. A conical entrance
promotes more thorough mixing, which creates a more uniform slurry
mixture. Baffling is used to remove fines from the mixture, so that they can
be recirculated for further growth. Elutriation, like baffling, 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
heavier ones remain in place.
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.

(figure 5)
Forced-circulation crystallizers are often arranged in stages. The two-stage
crystallizer shown below is used by an agricultural chemical company to evaporate
phosphoric acid from a mixture and recover solids.

(figure 6)

ADVANTAGES

DISADVANTAGES

Least expensive type of

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

Crystal size difficult to control

DRAFT TUBE BAFFLE

Draft tube baffle crystallizers are used to control crystal size and characteristics.

(figure 7)
GENERAL INFORMATION
Draft Tube Baffle (DTB) crystallizers, such as the one shown below, are used in
applications in which excessive nucleation occurs. Small, unwanted crystals, called
fines, are removed from larger particles using gravitational settling and recycled
through the crystallizer again, resulting in maximum crystal recovery and larger
crystals.

(figure 8)

EQUIPMENT DESIGN
DTB crystallizers have two distinct volumes. In the baffled region
gravitational settling separates larger crystals from fines. The larger crystals
settle between the baffle and draft tube, as shown below, and are removed
in the product slurry, while the fines are recirculated after being
redissolved in a heat exchanger. The evaporated solvent is then condensed,
cooled, and returned to the region of active crystallization.

(figure 9)
DTB crystallizers typically have circulation rates of 1 to 4 times/min and a total
residence time of 4 to 6 hours.
USAGE EXAMPLES
The two DTB crystallizers shown below are used to produce ammonium sulfate.
DTB crystallizers are also used for the purification of organic compounds as well as
the production of salts.

(figure 10)
Examples of crystals that are formed using a DTB crystallizer are shown below.

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(figure 11)

ADVANTAGES

DISADVANTAGES

Crystal size easy to control

Economic due to recyclability of
fines
More energy efficient than forcedcirculation crystallizers

Frequent flushings required to

minimize deposits on the
crystallizer wall
Cannot effectively handle a high
density slurry

SURFACE-COOLED
GENERAL INFORMATION/EQUIPMENT DESIGN
Surface-cooled crystallizers combine a draft tube baffle crystallizer body with a
heat exchanger. Slurry is drawn from the crystallizer body and then cooled before
being pumped back into the crystallizer body.
Crystallizers such as these are the most useful for operations in which the solution's
boiling point is extremely high, or when such low temperatures are required that
evaporation by vacuum is not possible.

(figure 12 )

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USAGE EXAMPLES
Surface-cooled crystallizers such as the one shown here are used to produce
sodium chloride from caustic solutions, sodium carbonate decahydrate from waste
solutions, and sodium chlorate from sodium chloride saturated solutions.

(figure 13)

BATCH VACUUM
GENERAL INFORMATION/EQUIPMENT DESIGN
Vacuum crystallizers use a condenser with a booster to maintain a vacuum inside
the crystallizer body. This vacuum makes it possible to generate a supersaturated
solution when very low operating temperatures are needed. Vacuum crystallizers
may be continuous or batch. The batch vacuum crystallizer is particularly useful
when processing materials that tend to grow on the walls of continuous
crystallization equipment.

(figure 14)

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USAGE EXAMPLES
The vacuum crystallizer shown below is used to produce Glauber's Salt at a
mineral plant. The crystallizer body can be seen on the left, with the condenser
and booster slightly above and to the right of it.

(figure 15)

SCRAPED SURFACE
GENERAL INFORMATION
Scraped surface crystallizers such as the one shown below are used as low energy,
low cost means of crystallization for small scale operations. They are used primarly
for the crystallization of melts.

(figure 16)

EQUIPMENT DESIGN
A scraped surface crystallizer consists of a jacketed pipe in which a cooling
medium between the pipe wall and the jacket remove heat from the slurry,
causing crystallization. Inside the pipe, large scrapers wipe the solid
deposits from the wall to prevent build up. Scraped surface crystallizers are
often grouped together in assemblies, as shown below. [7]

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Conclusion:
The Crystallization is very important for each chemical engineer because it
is one of the important processes in the classroom and purification
Crystallization touches every aspect of our lives from the foods we eat and
the medicines we take, to the fuels we use to power our communities. The
majority of pharmaceutical products go through at least one crystallization
step during their manufacture. Salt and sugar are delivered to our dinner
tables as crystals. The unwanted crystallization of gas hydrates played a
role in the recent Deepwater Horizon oil spill. Advise everyone to learn at
least the basics in the crystal because it is one of the most important
processes

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references :
[1] (http://chemistry.about.com/od/chemistryglossary/g/crystallizedef.htm)
[2] (http://blog.autochem.mt.com/2011/01/introduction-crystallization-andprecipitation/).
[3] (Tavare, N.S. (1995). Industrial Crystallization Plenum Press, New York)
[4](http://www.ffn.ub.edu/davidr/index.php?option=com_content&view=article&id=
44:introduction-to-nucleation&catid=34:nucleation&Itemid=58)
[5] (McCabe & Smith (2000). Unit Operations of Chemical Engineering' McGraw-Hill, New York)
[6] Wikipedia
[7](Genck, Wayne J. A Clearer View of Crystallizers. Chemical Engineering.
7(2011): 28 - 32.
Print.
Mersmann, A. Crystallization Technology Handbook. New York, NY: Marcel
Dekker, Inc., 1995.
Print.
Mullin, J.W. Crystallization. 3rd ed. Stoneham, MA: ButterworthHeinemann, 1993. Print.
Myerson, Allan S. Handbook of Industrial Crystallization. Stoneham, MA:
ButterworthHeinemann, 1993. Print.
Perry, Robert H., and Don W. Green. Perry's Chemical Engineers' Handbook.
7th ed. New
York: McGraw-Hill Inc., 1997. Print.
Walas, Stanley M. Chemical Process Equipment Selection and Design.
Stoneham, MA:
Butterworth-Heinemann, 1990. Print.)

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