Crystallizatio 1

Introduction

o Crystallization is a operation in which solid particles are formed from a liquid solution
.
o It is a solid-liquid operation used to separate a solute from its solution in the form of
crystals.
o In this operation, mass is transferred from the liquid phase (solution) to a pure solid
crystalline phase. This operation gives pure product in the form of crystals of a desired
size ranging from relatively impure solutions in a single processing step.
o Crystallization is an important operation in the chemical industry as the number of
salable products has to be in the forms of crystals.
o From energy point of view, crystallization requires much less energy for separation as
compared to other method. It may be carried out at relatively low temperatures.
o The process of crystallization takes place in three stages: nucleation, crystal growth,
and laboratory uses of crystallization.
o Crystallization usually involves:
1. Concentration of solution (by evaporating a part of the solvent)
2. Cooling of solutions until the concentration of solute becomes higher than its
solubility at the prevailing temperature..
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What is Crystallization?

 Crystallization is a technique used for the purification of substances. A

separation technique to separate solids from a solution.
 Crystallization can be defined as the process through which the
atoms/molecules of a substance arrange themselves in a well-defined three-
dimensional lattice and consequently, minimize the overall energy of the
system. When a substance is subjected to crystallization, its atoms or molecules
bind together through well-defined angles.
 Crystallization can be defined as the solidification of a liquid substance into a
highly structured solid whose atoms or molecules are placed in a well-defined
three-dimensional crystal lattice. The smallest individual part of a crystal is
called a unit cell. The crystal is made up of millions of such unit cells.
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Stages of Crystallizations:
o Nucleation: The first stage or step in the process of crystallization is nucleation.
Among the atoms, the first to form a crystal becomes the center of the nucleation and
more atoms are formed around that nucleus. In the whole process of crystallization,
nucleation is most crucial as it determines the structure of the entire crystal. Any liquid
on the edge of solidifying is known as a super cooled liquid for which an initial
nucleus must form. The process of crystallization will continue to revolve around this
nucleus. The nucleus forms when atoms or molecules in a cooling liquid lose their

capacity to bounce off each other. Instead, they start interacting and forming solid
crystal structures. Larger molecules may be difficult to crystallize at normal
temperatures and pressures, although pure elements usually form a crystal structure.
The solvent containing the desired crystal is full in a supersaturated solution. The
solubility of the atoms or molecules in the solution decreases when the temperature
drops or the acidity rises, and the solvent can hold fewer of them.
o Crystal Growth: Other molecules and atoms that surround the nucleus branch off
from the established symmetry, adding to the seed crystal. Depending on the
circumstances, this procedure can occur very rapidly or slowly. Water may turn into
ice in seconds, whereas rock crystals like quartz and diamonds take millennia to
create. The entire crystal structure is determined by the basic formation set up around
the nucleus. From the uniqueness of a snowflake to the purity of a diamond, variances
in crystal formation account for the disparities in crystals. Crystals can only accept a
limited number of geometric shapes determined by the bonds and interactions of the
molecules. Different bond angles of atoms based on the initial nucleus cause various
forms. Impurities in the solution or the material will cause the pattern to deviate from
the expected one. Even minor imperfections in the nucleus can result in wholly
distinct and unique designs, as seen in snowflakes
o Laboratory uses of Crystallization: The method of crystallization is a frequent and
helpful one in the lab. It may be used to purify chemicals and coupled with
sophisticated imaging methods to learn about the crystallized substances' composition.
Material can be dissolved in a suitable solvent in laboratory crystallization. Heat and
acidity changes can aid in the dissolution of the substance. The components in the
solution precipitate out at various rates when the circumstances are reversed. Pure
crystals of the required material can be obtained by carefully controlling the
environment
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Application of Crystallization:
1) Purification of seawater
2) Separation of alum crystals from impure samples
3) In the pharmaceutical industry, crystallization is used as a separation and purification
process for the synthesis and isolation of co-crystals, pure active pharmaceutical
ingredients (API), controlled release pulmonary drug delivery, and separation of chiral
isomers.

Separating Substances via Crystallization

Activity:

Here is an experiment to understand crystallization clearly:

Step 1: Take 50 ml water in a beaker
Step 2: Add sugar in it and stir it
Step 3: Now heat the solution
Step 4: Repeat the process continuously
Step 5: After some time there will be a point at which no more sugar can be dissolved in water. This stage is
the saturation point, and the solution is referred to as a saturated solution
Step 6: Now filter the sugar with the help of a filter paper
Step 7: Collect the filtrate in a glass bowl and cool it
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Step 8: We will observe that some fine crystals are formed in the bowl
Step 9: The process of filtration can separate these crystals. The liquid left after the removal of crystals is
known as mother liquo

What are the two primary types of crystallization?

Crystallization processes can be broadly categorized into the following two types:
 Evaporative crystallization.
 Cooling crystallization

List some examples of crystallization.

Some common examples of crystallization are listed below. What are the various factors that
affect the rate of crystallization?
Crystallization refers to the solidification of a liquid substance into a highly structured solid
whose atoms or molecules are placed in a well-defined three-dimensional crystal lattice.
Various factors like temperature, concentration, nature of the crystallizing substance,
impurities present in the solution and agitation affect the crystallization rate.
 The crystallization of honey when it is placed in a jar and exposed to suitable
conditions.
 The formation of stalagmites and stalactites (especially in caves).
 The deposition of gemstone crystals.
 The crystallization of water to form ice cubes and snow.

What are the advantages of crystallization?

The key advantages of crystallization are listed below.
 A product of high purity can be obtained from one single step via the process of
crystallization.
 The dry products formed from crystallization can be directly packaged and stored.
 The energy requirements and the operating temperatures of this process are relatively
low.
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Mechanism of crystallization.

 The generations of a new solid phase (i.e. new small particles) either on an inert
material in the solution or in the solution itself is called nucleation. The increase in
size of these nuclei with a layer-by-layer addition of solute is called crystal growth.
 super saturation is the common driving force for nucleation and crystal growth.
Crystals can neither form nor grow unless a solution is supersaturated.
Methods of super saturation:
1. By cooling a concentrated, hot solution through indirect heat exchange.
2. By evaporating a part of solvent/ By evaporating a solutions.
3. By adiabatic evaporation and cooling(i.e., vacuum cooling) : by flashing of a feed
solution adiabatically to a lower temperature and inducing/causing crystallization by
simultaneous cooling and evaporation of solvent.
4. By adding a new substance (i.e., a third substance) which reduces the solubility of the
original solute i.e., by salting.
5. By chemical reaction with a third substance.
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Optimizing Crystallization Systems

To achieve optimum efficiency, each crystallization system should be designed on an

individual basis, as different types of equipment are more suitable for different applications.
This differentiation largely depends on the substances in the mixture, the amount of energy
input, and desired crystal size.

At Thermal Kinetics, our team of engineers, developers, and designers can construct a wide
array of custom crystallization equipment to match your unique needs. Whether your
crystallizer is a standalone system or part of a larger operation, we can configure it to fit any
industry application. From circulating batch models to continuous crystallizers, each of our
systems can be adjusted to meet your operational requirements.
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Classification of crystallizers
Two schemes have been employed to classify crystallization equipment. One uses the
method of generating super saturation, while the other scheme uses the method by which the
growing crystals are suspended.
When classifying according to the method of suspending the growing crystals, crystallizers
fall into one of four basic types:
1) Mixed-suspension, mixed product removal (MSMPR) crystallizers.
Also sometimes called circulating magna crystallizers, this type of equipment circulates the
growing crystals through the zone of the crystallizer where the supersaturation conditions are
generated. This may be accompanied by mixed- or classified-product removal, and with or
without destruction of fines.
2) Circulating liquor/classified- suspension crystallizers.
In this type, only the liquor or a weak slurry is circulated, while the bulk of the growing
crystals are not circulated. Supersaturation is imparted to the liquor in one part of the
equipment, whereupon this liquor is circulated to another area where it relieves the super
saturation on growing crystals. This type of crystallizer is also available with or without fines
destruction capabilities. The units are usually identified as Krystal- or Oslo-type
crystallizers.
3) Scraped-surface crystallizers.
Crystallization is induced by indirect heat exchange with a cooling medium at the heat-
transfer surface, which is continuously scraped and agitated to minimize fouling. This type
of equipment employs vertical tanks with scrapers or horizontal pipes.
4) Tank crystallizers.
Crystallization is produced by cooling the feed solution in either static or agitated tanks by
natural convection and radiation, by surface cooling through coils or a jacket, programmed
evaporative cooling, reaction or antisolvent methods.

Types of crystallizer.
There are two main types of crystallizers: evaporative and cooling.

Evaporative Crystallizers

Evaporative crystallization increases the concentration of the solution by evaporating the

solvent. As the concentration increases, the solution becomes supersaturated and nucleation
begins. Upon further concentration, the nuclei begin to grow and distinct crystals appear.

TYPES OF EVAPORATIVE CRYSTALLIZER.

1. Draft Tube Crystallizers 

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Submerge Circulating Crystallizers .

Cooling Crystallizers
Cooling crystallization, the process of crystallizing solutions based on solubility temperature
dependence, is conducted through indirect heat transfer or directly under vacuum. These
methods cause some of the solution to evaporate and then cool to a temperature in equilibrium
with the reduced pressure. In essence, a small amount of the solvent flashes off the latent heat, subsequently
lowering the temperature of the solution.

While this process does cause a reduction in solvent, the crystallization is mainly due to the
change in temperature of the solution. Decreasing the temperature supersaturates the
solution, developing the nuclei and encouraging crystal growth to force the salt out of
solution and crystallize.

The cooling crystallization process is performed using one of three systems:

vacuum cooling crystallizers

continuous cooling crystallizers

Scraped surface crystallizers.

 Agitated Tank Crystallizer

Is also known as a stir-tank crystallizer Or agitated batch crystallizer. This is the simplest
and perhaps the most economical unit. In this crystallizer, super saturation is generated by
cooling so it is a cooling crystallizer.

Construction:

 Agitated tank crystallizer consists of a cylindrical tank provided with a low-speed agitator
and a cooling coil. The tank has a conical bottom through which the product is withdrawn.
The agitator improves the heat transfer rate keeps the temperature of the solution uniform
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and keeps the fine crystals in suspension which is essential for uniform growth of the
crystals, and simplicity of operation.

 Crystallizer Work:

1. A known quantity of hot solution is charged to the crystallizer, cooling is applied by

circulating a coolant through the coil, and the agitator is started. The mass in the crystallizer
cools due to heat transfer to the circulated coolant and as the temperature decreases, crystals
are formed due to a decrease in the solubility of the solute. The mass is cooled to a
predefined temperature and finally, a product stream containing crystals plus mother liquor is
withdrawn from the bottom of the crystallizer.
2. This type of crystallizer is used to produce fine chemicals, pharmaceutical products, and
dye intermediates.

Advantages :
This type of crystallizer is commonly employed in small-scale production or batch
processing due to several advantages, such as low initial cost, simplicity in construction, and
flexibility. These are having capacities more than tank crystallizers.

Disadvantages:
One of the drawbacks of this crystallizer is that the solids deposited on the surface of the coil
add resistance to heat transfer so that it ceases to function efficiently. High super
saturation at a cooling surface is unavoidable and because of this, the cooling surface gets
rapidly fouled with adhering crystals so the surface might therefore require frequent washing
and scrapping. Other disadvantages include difficulty in controlling nucleation and size of
crystals and high labour costs.
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Conclusion
Crystallization is the process by which solid forms, where the atoms or molecules are highly
organized into a structure known as a crystal. Some ways by which crystals form are
precipitating from a solution, freezing, or more rarely deposition directly from a gas.
Attributes of the resulting crystal depend largely on factors such as temperature, air pressure,
and in the case of liquid crystals, time of fluid evaporation.
Crystallization occurs in two major steps. The first is nucleation, the appearance of a
crystalline phase from either a super cooled liquid or a supersaturated solvent. The second
step is known as crystal growth, which is the increase in the size of particles and leads to a
crystal state. An important feature of this step is that loose particles form layers at the
crystal's surface and lodge themselves into open inconsistencies such as pores, cracks, etc.
The majority of minerals and organic molecules crystallize easily, and the resulting crystals
are generally of good quality, i.e. without visible defects. However, larger biochemical
particles, like proteins, are often difficult to crystallize. The ease with which molecules will
crystallize strongly depends on the intensity of either atomic forces (in the case of mineral
substances), intermolecular forces (organic and biochemical substances) or intermolecular
forces (biochemical substances).
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Crystallization is also a chemical solid–liquid separation technique, in which mass transfer of

a solute from the liquid solution to a pure solid crystalline phase occurs. In chemical
engineering, crystallization occurs in a crystallizer. Crystallization is therefore related to
precipitation, although the result is not amorphous or disordered, but a crystal.
Crystallization is a key technique for various sectors of the chemical process industries
(CPI).
Several approaches for industrial crystallization have evolved over time, and highly
specialized crystallizer designs have been developed, especially in long-established
industries. solution crystallization is an important unit operation because the process can
generated high-purity products from solutions containing significant levels of impurities with
relatively low energy input.
conventional crystallization mechanisms consists of nuleation, growth, and maturation of the
crystals, thus resulting in a crystalline lattice.

References:
1. http://www.vpscience.org/materials/crystallisation-U-3-US05CICV24.pdf .
2. https://www.chemengonline.com/a-clearer-view-of-crystallizers/?printmode=1 .

3. Facts at your Fingertips, MSMPR Crystallization. Chem. Eng.,

October 2010, p. 31.
4. Sutradhar, B., Coping with Crystallization Problems, Chem.
Eng., March 2004, pp. 46–52.
5. Schweitzer, P.A., “Handbook of Separation Techniques for
Chemical Engineers,” 3rd ed. McGraw Hill, New York, 1997.
6. “Perry’s Chemical Engineer’s Handbook,” 8th ed., McGraw Hill,
New York, 2008.
7. Couper, James. “Chemical Process Equipment: Selection and
Design.” Gulf Professional Publishing, Houston, 2010.
8. https://en.wikipedia.org/wiki/Crystallizatio.
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9. Ronald W. Rousseau, in Encyclopedia of Physical Science and

Technology (Third Edition), 2003.
10. Peter Crafts, in Computer Aided Chemical
Engineering, 2007