CRYSTALLIZATION

Unit Operations 3
Submitted by:

Cortez, Jan Kyle Aubrey M.

Dimatatac, Joshua Vincent A.

Hermosura, Richelle B.

Malleon, Vanessa Ashley A.

ChE-4101

Submitted to:

Engr. Reggie Duenas

Professor, UOPs 3
CRYSTALLIZATION
Crystallization is the (natural or artificial) process by which a solid forms, where the atoms
or molecules are highly organized into a structure known as a crystal. Some of the 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 supercooled 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 lodge
themselves into open inconsistencies such as pores, cracks, etc.

PROCESS
The crystallization process consists of two major events, nucleation and crystal growth
which are driven by thermodynamic properties as well as chemical properties. In crystallization
Nucleation is the step where the solute molecules or atoms dispersed in the solvent start to gather
into clusters, on the microscopic scale (elevating solute concentration in a small region), that
become stable under the current operating conditions. These stable clusters constitute the nuclei.
Therefore, the clusters need to reach a critical size in order to become stable nuclei. Such critical
size is dictated by many different factors (temperature, supersaturation, etc.). It is at the stage of
nucleation that the atoms or molecules 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 or molecules, not the macroscopic properties of the crystal (size and
shape), although those are a result of the internal crystal structure.

The crystal growth is the subsequent size increase of the nuclei that succeed in achieving
the critical cluster size. Crystal growth is a dynamic process occurring in equilibrium where solute
molecules or atoms precipitate out of solution, and dissolve back into solution. Supersaturation is
one of the driving forces of crystallization, as the solubility of a species is an equilibrium process
quantified by Ksp. Depending upon the conditions, either nucleation or growth may be predominant
over the other, dictating crystal size.

Crystallization is the process of forming solid material from a liquid solution or melt, where
the solid material formed has crystalline (as opposed to amorphous) structure. A crystallization
process generally has the following characteristics:

 The feed material is either in solution or is a liquid above the melting point of the solid
phase. If in solution, there may be more than one solvent present.
 There may be dissolved or solid impurities present. Some impurities may have very similar
properties to the solute (especially for side-products from organic reactions). During
crystallization, impurities may remain in solution, crystallize separately, or incorporate in
some way into the product crystals.
 The product material is solid, and present as particles in a range of sizes.
 The product is generally surrounded by mother liquor.
 The waste stream from the process is liquid, containing both residual dissolved product
and impurities.

The general advantages of crystallization as a process are:

 High purification can be obtained in a single step.

 Produces a solid phase which may be suitable for direct packaging and sale.

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  Operates at a lower temperature and with lower energy requirements than corresponding
distillation separations.
 Plant can be simple and easy to construct and maintain.
 May be more economic than alternative separation processes.

The general disadvantages are:

 Generally only purifies one component.

 Yield is limited by phase equilibria.
 Process kinetics are more complex and less well-understood than some alternatives;
obtaining detailed kinetic parameters involves complex experimental procedures.

Crystallization is used industrially in a wide variety of processes. Typical applications include bulk
chemicals, such as salt, sugar and fertilizers; high value-added products such as specialty
chemicals and pharmaceuticals; and difficult separations such as ortho- and para-xylene.

EQUIPMENT FOR CRYSTALLIZATION

Crystallization is often carried out in a stirred tank or vessel. Depending on the type of
crystallization different configurations of the tank/vessel are used. The crystallizers are in some
processes combined with external equipment like heat exchangers, settlers/cyclones, etc.

There are 3 main different types of commercial evaporative crystallizers:

 Forced Circulation (FC) Crystallizers in which the heat for evaporation is added to a
circulated suspension. In the evaporator the circulated stream is flashed and the mixing is
originating from the impulse of the circulated suspension
 Draft Tube Baffled (DTB) Crystallizers in which the heat for evaporation is added to a
crystal lean stream of liquid which is taken from the settling zone in the crystallizer. The
slurry is kept in suspension by a propeller type stirrer in combination with the draft tube.
 OSLO or fluidized bed crystallizers in which the heat for evaporation is added to the
almost crystal-free top stream leaving the fluid bed. After flashing the overheated stream
in the evaporator the resulting supersaturated liquid is circulated over the fluidized bed,
where the supersaturation is deposited on the crystals in the bed.

The FC crystallizer is the simplest and most robust type of the three, whereas the OSLO
crystallizers is the most complex and less robust type. The OSLO crystallizer, however, usually
delivers a higher quality of crystals with a larger average size and a narrower size distribution.

There are many different configurations of commercially available cooling crystallizers. The
most important types are the batch or continuous Stirred Tank Crystallizers, Fluid Bed
Crystallizers or Crystallizers with a Scraped Heat Exchanger. The previously mentioned and FC
and DTB crystallizers are examples of Stirred Tank Reactors. The OSLO crystallizer is an example
of a FB Crystallizer. In cooling crystallization applications the liquid is not overheated, but
undercooled in the heat exchanger. The circulation flow is set at a rate that the fluidized bed can
be maintained, while the undercooled solution can remain within the metastable zone to prevent
spontaneous nucleation. Usually the temperature difference between the coolant and the
crystallizing solution is less than 2°C in crystallizers with non-scraped heat exchangers. The fines
removal can be accomplished with equipment like a cyclone. The most common type of
crystallizer with a scraped heat exchanger is the double tube configuration. Crystallization takes
place in the inner tube, while the coolant flows through the outer tube. The surface of the inner
tube is kept free from solids by rotating scrapers. Armstrong Chemtec is a leading supplier of
tubular crystallizers with a scraped heat exchanger.

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 For flash cooling the same crystallizers can be used as for evaporative crystallization (FC,
DTB, OSLO). There are less problems with encrustation on the wall as the heat is not withdrawn
via the wall. However, problems can occur in the boiling zone and/or near the feed point(s) where
locally high supersaturations may be formed. Another potential problem is that the gaseous solvent
needs to be recovered and/or purified for recycling or disposal.

Direct contact cooling is also applied to prevent problems with encrustation and it is typically
used at low temperatures, where flash crystallization cannot be used easily. A special point of
attention is that the coolant may not interfere with the crystallization process. The cooling power
for the crystallization is supplied by the evaporation energy or by the cooling caused by the coolant.
The recovery and/or purification of the coolant is a potential drawback of direct cooling.

Precipitation is usually carried out in Batch or Continuous Stirred Tank Reactors.

TYPES OF CRYSTALLIZATION
Crystallization processes/techniques can be distinguished by the manner in which the
supersaturation is created. The most frequently applied types of crystallization are:

 Evaporative crystallization
 Cooling crystallization from solution or the melt
 Reactive crystallization or precipitation.

The choice for a certain method depends on the properties of the compound to be
crystallized, the feed and the thermodynamics of the system. For compounds with a low solubility
the standard option is reactive crystallization/precipitation. As a rule of thumb, a compound has a
low solubility when the equilibrium concentration in solution is lower than 10 g/kg. For
compounds with a solubility higher than 200 g/kg, a choice has to be made between evaporative
and cooling crystallization. Evaporative crystallization is typically the preferred option when the
solubility is hardly dependent on T, which implies that cooling the saturated solution will not result
in a significant amount of crystals. Kramer and Bruinsma[2] mentioned that evaporative
crystallization is usually the preferred method when the amount of dissolved product decreases
with less than 5 g/kg per °C (or dC/dT < 0.005 g/g.°C).

Evaporative Crystallization

In evaporative crystallization, the crystallization is resulting from the evaporation of the

solvent. So, this process creates a vapor and a suspension of crystals in mother liquor. The heat of
evaporation that has been added is in principle captured in the vapor stream. In principle this
energy can be recovered, but the energy will be available at a lower T. The mother liquor will still
contain the equilibrium concentration of product. It is possible to harvest this residual amount of
product by recycling the mother liquor to the feed. The possibility to recycle the mother liquor will
be restricted by the impurities. At a certain moment the concentration of impurities will become
so high that they can influence the crystallization and/or the product purity. If that is the case, the
mother liquor stream cannot be recycled any longer and the remaining mother liquor has to be
discharged via a bleed or purge stream.

Cooling Crystallization

Cooling crystallization is attractive when the solubility of the product increases

significantly with increasing temperature. In those cases, cooling crystallization is usually more
energy friendly than evaporative crystallization. In a cooling crystallization process the feed is
cooled in a heat exchanger, which can be situated inside the crystallizer or an external loop. The
wall of the crystallizer can be used as internal heat exchanger, but the heat exchanger can also be
integrated in the crystallizer in the form of cooled tubes or plates. Crystallization can take place

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when the liquid is cooled to a temperature below the equilibrium solubility. The lowest temperature
in the system is at the surface of the heat exchanger. Therefore the cooling needs to be done
carefully to prevent nucleation on the cold surface of the heat exchanger, which will lead to
encrustation. Typically measures to prevent this unwanted phenomenon is to reduce the
temperature difference between the coolant and the crystalizing solution, to increase the liquid
velocity along the surface of the heat exchanger to level out the temperature difference over the
length of the heat exchanger or to use a scraper to keep the surface of the heat exchanger free of
solids. Alternative methods of cooling that not require a heat exchanger are flash cooling which
involves (partial) evaporation of the solvent or direct cooling via insertion of a cold gas or coolant.

Melt crystallization can be regarded as a special form of cooling crystallization process.

The main difference with cooling crystallization from solution is the absence of solvents, which
implies that most melt crystallization processes are operated close to the melting point of the pure
product. The feed for a melt crystallization process is an impure melt. Cooling this melt below the
equilibrium temperature will typically result in the formation of a solid phase that is purer than the
feed, while the impurities prefer to stay in the impure mother liquor. Section 2.2 will give more
background information on melt crystallization, which is also known as fractional crystallization.

Precipitation

In precipitation the supersaturation is created by the mixing of two streams. The most
common forms of precipitation are: (1) reactive crystallization, (2) pH shift crystallization and (3)
anti-solvent (or extractive) crystallization. In reactive crystallization, the solid phase is formed due
to a reaction between components that were originally present in the (two) feed streams, for
instance A (aq) + B (aq) ® AB (s). pH-shift crystallization often makes use of the change in the
chemical state/charge of ionic species with pH. Well known examples of ions that change state
with pH are for instance carbonate and phosphate. In a pH shift crystallization, typically a reaction
takes place between an acid and a base. Such a reaction is usually very fast and can be quite
exothermic, especially when the reactants are present in relatively high concentrations. In an anti-
solvent crystallization the anti-solvent is usually mixed with a (concentrated) solution. The anti-
solvent is typically well-mixable with the solvent, the crystalizing product has a low(er) solubility
in the anti-solvent and for economic and environmental reasons it should be possible to recover
the anti-solvent.

Precipitation can be fast or slow. A precipitation is called fast of one of the underlying
processes in crystallization, e.g. the nucleation, is fast compared to the mixing. A fast conversion
step does not necessarily imply that the residence time in all precipitation processes are short.
Long(er) residence times are for instance required when a coarser product or a different polymorph
needs to be made than in the primary conversion/precipitation step. The size of a precipitate can
be increased by ripening or ageing of the suspension. Ripening typically runs at relatively low
supersaturation, which prolongs the residence time. Precipitation is also known for its
characteristic that metastable intermediates can be formed around the inlets of the feed streams.
These intermediates can be amorphous or (pseudo)polymorphs of the desired, thermodynamically
stable end product. The transition from the metastable phase to the thermodynamically stable
product requires a liquid mediated recrystallization step, which runs at a relatively low
supersaturation and thus requiring relatively long residence times. An advantage of such a slow
re-crystallization is that it is typically accompanied by a strong increase of the purity of the product.

Fractional Crystallization

Fractional crystallization is a term that is used to describe a process where repeated

crystallization steps are used to increase the purity of the product and/or to increase the yield of
the process. Applications can be found in metal (metal refining/zone melting), oil & gas (e.g. oil
dewaxing), food (e.g. palm oil fractionation and freeze concentration) and in chemistry/chemical
industries (e.g. paraffin wax de-oiling or the ultra-purification of chemicals). In a fractional
crystallization process the crystals formed in the first stage are separated from the mother liquor
with devices like filters, centrifuges or wash columns and remolten to be used as feed in a second

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crystallization stage. Alternatively, the crystals are not remolten, but re-suspended in a liquid with
a higher product concentration at a higher operating temperature. After re-suspending, the crystals
may be allowed to grow if that is needed/beneficial. The choice between re-melting or re-
suspending depends on the quality of the crystals. Re-suspension is the preferred option when the
crystals already have more or less the right internal purity, shape and size. If one or more of these
parameters significantly differs from the specifications of the end product re-melting/re-
crystallization is usually the best option. This second crystallization stage will operate at a higher
temperature than the first stage due to the higher purity of the feed in the second stage. If the
mother liquor still contains a significant amount of product, it may also be used as feed for an
additional crystallization stage. This stage will then be operated at a lower temperature than the
first crystallization, because the mother liquor has a lower concentration of product than the feed
of the first crystallization stage. In the described process the solids and liquid move in different
directions: the crystals go up in temperature while the mother liquor faces a decrease in
temperature. Therefore, this staged crystallization processes is also known as a counter-current
cascade. A well-known example of a process deploying the counter-current cascade principle is
the TSK-CCCC process[3]. The crystal transport/separation in this process is done by cyclones,
while the liquid transport is achieved by gravity.

In principle, fractional crystallization can refer to crystallization from solution as well as

to crystallization from the melt. In practice, it is used more in relation with melt crystallization,
which probably explains why the term fractional crystallization is sometimes used as a synonym
for melt crystallization. Melt crystallization is particularly interesting for the separation and ultra-
purification of organic chemicals due to their favourable melting points. Ulrich and Glade[4] found
out that 71% of the organic chemicals in the Merck catalogue from 1991 had a melting point
between 0 and 200°C.

Fractional/melt crystallization is a separation method that can be an attractive alternative

for distillation for the separation of organic mixtures. Distillation is by far the most frequently used
separation process in chemical industry, but there are also distinct disadvantages such as thermal
degradation of product, excessive consumption of energy, poor performance in case of azeotropes.
In 1989, TNO [5]compared in a desk study the energy consumption of conceptual separation
processes using distillation with that of melt crystallization for the purification of 5 bulk chemicals:
benzene, styrene, phenol, caprolactam and dimethyl terephthalate (DMT). For all products melt
crystallization required much less energy than distillation: 27% less for benzene; 32% less for
styrene, 63% less for phenol; 50% less for caprolactam and an impressive 96% less for DMT.
Moreover, distillation requires large reflux ratios and a large number of stages when the feed
contains compounds with similar boiling points/volatility. These disadvantages can be overcome
using melt crystallization, making use of the fact that for organic chemicals the melting enthalpy
is typically only 1/3 of the enthalpy of vaporization, its high selectivity and its relatively low
operating temperature. Melt crystallization avoids the use of solvents, which implies that volumes
of process streams can be kept small and that no processes/equipment are needed for recovery and
recycling of the solvents.

There are two different methods for melt crystallization which differ in the way that the
solid crystals are growing. In a layer melt crystallization the crystals grow as a layer on a cold wall
of a heat exchanger. The liquid phase is either stagnant in static layer crystallization or mixed
(mechanically or as a falling film) in dynamic layer crystallization. The heat exchanger can have
different shapes like plates or tubes. When the layer has reached the required thickness, the
remaining mother liquor is drained and the layer is molten off with or without layer purification
steps like sweating and/or washing. In suspension melt crystallization the crystals grow freel y
suspended in the liquid phase. The liquid/suspension is often cooled with a heat exchanger, but in
this case it is designed and operated to prevent that the solid is forming on the wall. Although,
layer crystallization and suspension crystallization are based on the same physical principles there
are characteristic difference between the options. Layer crystallization is typically a batch process
and high growth rates in the order of 10-5-10-6 m/s are required to compensate for the relatively
small surface area on which the growth takes which is in the order of 50-100 m2/m3. Suspension
crystallization is typically a continuous process and the large surface area of the suspended

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crystals, which can be as high as 5000-10000 m2/m3, implies that the required production rate can
be reached at relatively low growth rates in the order of 10 -7-10-8 m/s. A consequence of a low
growth rate is that the kinetic incorporation of impurities in the crystalline phase is strongly
suppressed, which explains why the solid material (crystals) made in a suspension growth process
is significantly purer than the solid layer in the layer growth process. Therefore a layer growth
process will require more stages than a suspension growth process to compensate for the lower
purification efficiency per stage. The specific energy consumption of layer grow is significantly
higher than for suspension growth due to the higher number of stages and the subsequent heating
and cooling cycles inherent to a batch process. In an EU-funded project the purification of
caprolactam and naphthalene was investigated for both the layer and the suspension melt
crystallization. For the same separation target, the suspension growth option required 66% less
energy than the layer growth process for the purification of naphthalene, while for caprolactam the
difference was even larger, namely a 75% lower energy consumption for the suspension-based
process

The main requirement for deploying the larger purification and energy efficiency of
suspension melt crystallization is that it is possible to grow crystals of sufficient size and suitable
shape for the solid-liquid separation that follows the crystallization step. A Hydraulic Wash
Column, that combines continuous solid-liquid separation with a highly efficient counter-current
washing step at throughputs as high as 5-20 tonnes of product per hour per m2 wash column,
requires crystals with an average crystal size of 50-100 µm. Wash column operation is easy with
hard crystals with a reasonable 3-dimensional shape (cubes, spheres, needles, …), but can be
challenging for soft and/or plate-like, or hair-shaped crystals as these properties strongly reduce
the porosity of the crystal bed. Frequently mentioned points of attention for suspension melt
crystallization is the handling of slurries and scale up. Of course slurry handling requires more
attention than liquid handling, but there are many industrial processes and products where slurry
handling is done without any problem at small (e.g. pharmaceuticals) and very large scale (e.g.
sugar, soda ash). Scale up of scraped heat exchanger suspension crystallizers and the Hydraulic
Wash Column is not a problem: the tubular design of the Armstrong scraped Surface Continuous
Crystallizer has a beneficial surface to volume ratio and the modular design allows for an easy
expansion with growth in demand. The scale up principle of the Hydraulic Wash Column, where
the number of filter tubes is increased proportional with the cross-sectional surface area is
straightforward and proven up to a diameter of 55 cm. The production capacity of this column was
more than 5 tonne per hour. A further scale up to 1.13 m, resulting in a HWC with a cross-sectional
surface area of 1 m2, is considered feasible, which will push the production capacity up to 20 tonne
per hour for a single HWC.

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