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Precipitation and crystallization refer to unit operations that generate a solid from a supersaturated solution.

Crystallization separates a solid product from a liquid feedstream, often in extremely pure form. Well formed crystals are
expected to be pure because each molecule or ion must fit perfectly into the lattice as it leaves the solution. Impurities
would normally not fit as well in the lattice, and thus remain in solution preferentially. Hence, molecular recognition is
the principle of purification in crystallization. However, there are instances when impurities incorporate into the lattice,
hence, decreasing the level of purity of the final crystal product. Also, in some cases, the solvent may incorporate into
the lattice forming a solvate. In addition, the solvent may be 'trapped' (in liquid state) within the crystal formed, and this
phenomenon is known as "inclusion".
The crystallization process consists of two major events, nucleation and crystal growth. Nucleation is the step where the
solute molecules dispersed in the solvent start to gather into clusters, on the nanometer scale (elevating solute
concentration in a small region), that become stable under the current operating conditions. These stable clusters
constitute the nuclei. However, when the clusters are not stable, they dissolve. Therefore, the clusters need to reach a
critical size in order to become stable nuclei. Such critical size is dictated by the operating conditions (temperature,
supersaturation, etc.). It is at the stage of nucleation that the atoms arrange in a defined and periodic manner that defines
the crystal structure note that "crystal structure" is a special term that refers to the relative arrangement of the atoms,
not the macroscopic properties of the crystal (size and shape), although those are a result of the internal crystal structure.
Nucleation, or formation of a new crystal, can be either primary or secondary. Primary nucleation occurs in the absence
of product crystals and usually at high levels of supersaturation. Solute entities cluster together in solution to achieve an
orderly arrangement with minimum free energy. If the clusters exceed a minimum size, they survive and grow. If not,
they dissolve. This mechanism often is the major nuclei source for precipitations created by reaction, salting-out or pH
adjustment since they often have high levels of supersaturation and a low percent solids slurry density. Typically, a thick
mass of small crystals will suddenly appear as the system "crashes out.
In contrast, secondary nucleation requires that product crystals exist in the slurry. Usually the dominant nucleation force
in a mixed-suspension crystallizer operating at low supersaturations, it occurs through contact, fluid shear on semiordered surface layers or attrition or breakage. The mechanism depends on the level of supersaturation, percent solids,
circulation rate, type of agitator, tip speed and power input/unit slurry volume. Contact nucleation is the predominant
type and results from collisions between crystals, or between crystals and walls or agitators.

Crystal growth from an aqueous solution is based on the


existence of metastable regions where spontaneous
formation of crystalline nuclei in the solution is
impossible but in this region is possible to grow a single
crystal from a seed. when the maximum amount of solute
has been dissolved and the solution is saturated.
1. The stable zone of an undersaturated solution where no
nucleation or crystal growth is possible. Existing crystal
will simply dissolve,
2. The supersaturated metastable zone where growth may
occur but spontaneous nucleation does not occur, and
3. The labile supersaturated zone of spontaneous and rapid
nucleation.
The metastable zone width is essential parameter for the
growth of large size crystal from solution, since it is the
direct measure of stability of the solution in its
supersaturated region. Larger the zone width, the stability
is higher.

Operating Curve for Unseeded Batch Cooling

The process follows a path. First, unsaturated feed (A) is


cooled through the solubility curve (B), the metastable
zone (C) and into the labile zone (D). Rapid nucleation
occurs in the labile zone. The concentration then falls out
of the labile zone (E), and growth occurs within the
metastable zone during the reamainder of the cooling (F).
The metastable zone is where growth occurs in the absence
of primary nucleation.

The crystal growth is the subsequent growth of the nuclei that succeed in achieving the critical cluster size. The pattern
of growth resembles the rings of an onion. Nucleation and growth continue to occur simultaneously while the
supersaturation exists. Supersaturation is the driving force of the crystallization; hence the rate of nucleation and growth
is driven by the existing supersaturation in the solution. Depending upon the conditions, either nucleation or growth may
be predominant over the other, and as a result, crystals with different sizes and shapes are obtained (control of crystal
size and shape constitutes one of the main challenges in industrial manufacturing, such as for pharmaceuticals). Once
the supersaturation is exhausted, the solidliquid system reaches equilibrium and the crystallization is complete, unless
the operating conditions are modified from equilibrium so as to supersaturate the solution again.
The main values to control crystal growth are:
Supersaturation value, as an index of the quantity of solute available for the growth of the crystal;
Total crystal surface in unit fluid mass, as an index of the capability of the solute to fix onto the crystal;
Retention time, as an index of the probability of a molecule of solute to come into contact with an existing crystal;
Flow pattern, again as an index of the probability of a molecule of solute to come into contact with an existing crystal
(higher in laminar flow, lower in turbulent flow, but the reverse applies to the probability of contact).
The first value is a consequence of the physical characteristics of the solution, while the others define a difference
between a well- and poorly designed crystallizer.
For crystallization to occur from a solution it must be supersaturated. This means that the solution has to contain more
solute entities (molecules or ions) dissolved than it would contain under the equilibrium (saturated solution). This can be
achieved by various methods, with
(1) removal of solvent by evaporation and solution cooling,
(2) addition of a second solvent to reduce the solubility of the solute (technique known as antisolvent or drown-out),
(3) chemical reaction and
(4) change in pH
(5) changes of temperature or pressure being the most common methods used in industrial practice, and after the
generation of supersaturation subsequent steps are nucleation and growth of the solid; the solid is collected by filtration
or centrifugation.

The solubility of a compound in one solvent can be reduced through the slow introduction of another solvent in which
the solute is not soluble (an anti-solvent). This can either be done by direct contact between the saturated solution and
the anti-solvent (layering) or by allowing the vapours of the anti-solvent to slowly diffuse into a saturated solution.
The solubility of most compounds decreases as the temperature is lowered thus the cooling of a saturated solution will
often produce crystals. Rapid cooling may cause the precipitation of amorphous solid or microscopic crystals; it is
advisable to slow down the rate of cooling to facilitate crystal growth.
The distinction between precipitation and crystallization is quite often based on the speed of the process and the size of
the solid particles produced. The term precipitation commonly refers to a process which results in rapid solid formation
that can give small crystals that may not appear crystalline to the eye. Amorphous solids may also be produced. The
term precipitation also tends to be applied to a relatively irreversible reaction between an added reagent and other
species in solution whereas crystallization products can usually be re-dissolved using simple means such as heating or
dilution. Precipitation processes usually begin at high supersaturation where rapid nucleation and growth of solid
phases occur. In both precipitation and crystallization processes the same basic steps occur: supersaturation, nucleation
and growth. Nucleation does not necessarily begin immediately on reaching a supersaturated condition, except at very
high supersaturation, and there may be an induction period before detection of the first crystals or solid particles.
Nucleation is a phenomenon whereby a nucleus, such as a dust particle or a tiny seed crystal starts a crystallization
process. Nucleation poses a large energy barrier, which is easier to overcome at a higher level of supersaturation.
Common difficulties:
1. If supersaturation is too high, too many nuclei form, hence an overabundance of tiny crystals.
2. In supersaturated solutions that dont experience spontaneous nucleation, crystal growth often only occurs in the
presence of added nuclei or seeds.

Nucleation can occur by both homogeneous and heterogeneous processes. In general, homogeneous nucleation is
difficult to achieve because of the presence of heteronuclei from colloids, dust, or other foreign material in the solution.
This is especially true in industrial practice. The walls of the solution container may also be a source of nucleation sites.
After nucleation the growth phase begins and agglomeration and aging are terms used to describe features of the
changes in the solid particles.
Agglomeration describes the tendency of small particles in a liquid suspension to coalesce into larger aggregates. Other
terms used in the literature include aggregation, coagulation, and flocculation. The term aging refers to a variety of other
processes that change a precipitate after it forms. For example, Ostwald ripening refers to the tendency of larger crystals
to grow at the expense of smaller crystals when the crystals formed after nucleation are smaller than ~1micron. Another
important process is initial nucleation of a metastable solid phase that transforms with aging, e.g., amorphous solid
particles that crystallize with time or a hydrated crystalline solid that converts to a more stable material. Agglomeration
and crystal growth can also be influenced substantially by the presence of impurities in the solution.
The details of performing the precipitation or crystallization process can be very important to produce a pure product
and one that separates well from the liquid phase. Thus, the degree of supersaturation, the order and speed of reagent
addition, the temperature, and the aging time before filtration or centrifugation are used to recover the solid, and the
presence of active impurities can all be important parameters in a precipitation or crystallization process. Usually
aging results in larger particle sizes and may be referred to with terms such as digestion or ripening of the precipitate.
Some measure of control over nucleation and growth, and hence of precipitation, may also be exercised by the addition
of substances, such as surfactants and polyelectrolytes. Impurities in the system, whether deliberately added or already
present, can have a powerful influence on the morphology of the final precipitated particles. Limiting the amount of
added precipitating agent is used to control the initial supersaturation to get larger particle sizes that are readily filtered.
and to limit the formation of soluble complexes which reduce the yield of the product.

Crystal size distribution (CSD)


The appearance and size range of a crystalline product is extremely important in crystallization. If further processing of
the crystals is desired, large crystals with uniform size are important for washing, filtering, transportation, and storage.
The importance lies in the fact that large crystals are easier to filter out of a solution than small crystals. Also, larger
crystals have a smaller surface area to volume ratio, leading to a higher purity. This higher purity is due to less retention
of mother liquor which contains impurities, and a smaller loss of yield when the crystals are washed to remove the
mother liquor.
Crystallization processes
The main factors influencing solubility are, as we saw above:
Concentration
Temperature
So we may identify two main families of crystallization processes:
Cooling crystallization
Evaporative crystallization
This division is not really clear-cut, since hybrid systems exist, where cooling is performed through evaporation, thus
obtaining at the same time a concentration of the solution.
Cooling crystallization
Most chemical compounds, dissolved in most solvents, show the so-called direct solubility that is, the solubility
threshold increases with temperature.

So, whenever the conditions are favourable, crystal formation results from simply cooling the solution. An example of
this crystallization process is the production of Glauber's salt, a crystalline form of sodium sulfate. In the diagram, where
equilibrium temperature is on the x-axis and equilibrium concentration (as mass percent of solute in saturated solution)
in y-axis, it is clear that sulfate solubility quickly decreases below 32.5 C. Assuming a saturated solution at 30 C, by
cooling it to 0 C (note that this is possible thanks to the freezing-point depression), the precipitation of a mass of sulfate
occurs corresponding to the change in solubility from 29% (equilibrium value at 30 C) to approximately 4.5% (at 0 C)
actually a larger crystal mass is precipitated, since sulfate entrains hydration water, and this has the side effect of
increasing the final concentration.

There are of course limitations in the use of cooling crystallization:


Many solutes precipitate in hydrate form at low temperatures: in the previous example this is acceptable, and even
useful, but it may be detrimental when, for example, the mass of water of hydration to reach a stable hydrate
crystallization form is more than the available water: a single block of hydrate solute will be formed this occurs in the
case of calcium chloride);
Maximum supersaturation will take place in the coldest points. These may be the heat exchanger tubes which are
sensitive to scaling, and heat exchange may be greatly reduced or discontinued;
A decrease in temperature usually implies an increase of the viscosity of a solution. Too high a viscosity may give
hydraulic problems, and the laminar flow thus created may affect the crystallization dynamics.
It is of course not applicable to compounds having reverse solubility, a term to indicate that solubility increases with
temperature decrease (an example occurs with sodium sulfate where solubility is reversed above 32.50 C).
The simplest cooling crystallizers are tanks provided with a mixer for internal circulation, where temperature decrease is
obtained by heat exchange with an intermediate fluid circulating in a jacket.
A common practice is to cool the solutions by flash evaporation: when a liquid at a given T0 temperature is transferred in
a chamber at a pressure P1 such that the liquid saturation temperature T1 at P1 is lower than T0, the liquid will
release heat according to the temperature difference and a quantity of solvent, whose total latent heat of vaporization
equals the difference in enthalpy. In simple words, the liquid is cooled by evaporating a part of it.
Evaporative crystallization
Another option is to obtain, at an approximately constant temperature, the precipitation of the crystals by increasing the
solute concentration above the solubility threshold. To obtain this, the solute/solvent mass ratio is increased using the
technique of evaporation. This process is of course insensitive to change in temperature (as long as hydration state
remains unchanged).
Evaporative crystallizers
Most industrial crystallizers are of the evaporative type, such as the very large sodium chloride and sucrose units, whose
production accounts for more than 50% of the total world production of crystals. The most common type is the forced
circulation (FC) model. A pumping device (a pump or an axial flow mixer) keeps the crystal slurry in
homogeneous suspension throughout the tank, including the exchange surfaces; by controlling pump flow, control of the
contact time of the crystal mass with the supersaturated solution is achieved, together with reasonable velocities at the
exchange surfaces.

Forced-Circulation Crystallizer

In the forced-circulation unit,


shown here, a low-head, lowshear axial flow pump is used
to
reduce
secondary
nucleation. Slurry velocities
are about 7 fps, and the
evaporative unit must be
submerged to prevent material
from salting out on the tubes,
and
to
stop
undesired
nucleation.

Crystallization Process
Systems

Agitated Batch crystallizer


Water is circulated though the cooling coils and the solution is agitated by the propellers mounted on the central shaft.

This agitation performs two functions:


1. It increases the rate of heat transfer and keeps the temperature of the solution more uniform.
2. It keeps the fine crystals in suspension, thus it gives them an opportunity to grow uniformly instead of forming large
crystals or aggregates. (Production of uniform crystals)
The product of this operation is not only more uniform but it also very much finer than that from the older tanks.
Disadvantages
1. It is a batch or discontinuous apparatus.
2. The solubility is the least at the surface of the cooling coils. Therefore, crystal growth is most rapid at this point and
the coils rapidly build up with a mass of crystals that decreases the rate of heat transfer.

Swenson Walker Crystallizer

It consists of an open trough A, which is wide, a water jacket welded to the outside of the trough.
It also contains a slow speed spiral agitator set as close as possible to the bottom of the trough.
A number of units may be joined together to give increased capacity.
The hot concentrated solution to be crystallized is fed at one end of the trough and cooling water usually flows
through
the jacket in counter current to the solution.
In order to control crystal size, it is sometimes desirable to introduce an extra amount of water into certain sections in
the jacket.

Functions of the spiral stirrer:


1. It Prevents the accumulation of crystals on the cooling surface.
2. It lifts the crystals that have already been formed and shower them down through the solution.
In this manner, the crystals grow while they are freely suspended in the liquid and therefore they are:
1. Fairly perfect individuals.
2. Uniform in size
3. Free from inclusions or aggregations.
At the end of the crystallizer there may be an overflow gate where crystals and mother liquor overflow to a drain box
from which the mother liquor is returned to the process and the wet crystals are fed to a centrifuge to remove mother
liquor.
Advantages:
1. Large saving in floor space.
2. Large saving in material in process.
3. Saving in labor.
4. Uniform size crystals.
5. Free from inclusions and aggregations.

Vacuum crystallizer

Simple vacuum crystallizer


A, crystallizer body; C, vapor outlet; D, discharge pipe; E, product pump; F, propeller stirrers, G, sight glass; H.
condenser ( Swenson)
It acts by partial removal of vapor by vacuum application which leads to supersaturation and crystal formation. It is used
mainly for crystallizing thermolabile substances.