CRYSTALLISATION

Crystallization is an operation in which a solute is allowed to be recovered as solid crystals from a

solution. It can be used to purify mixtures or to produce crystal with the desired size range. The
production of sugar from sugar cane or beetroot is an example of a large-scale crystallization process.

Crystall ization is affected by either lowering the temperature of a solution or by evaporating

some of the solvent. The energy that is required during a cooling process includes the sensible heat
of the solution and the heat of crystallization. In the evaporative process the major energy
requirement is the latent heat of vaporization of the solvent. Benzene’s heat of crystallization is
126kJ/kg while the latent heat of vaporization is 394kJ/kg. It is thus clear that from an energy point
of view, cooling is the preferred process.

The crystallization process consists essentially of two stages which proceed simultaneously. The first
is the formation of nuclei which must exist in the solution before crystallization will commence.
This is followed by the growth of the crystals.

Normally a degree of super-cooling is required before crystallization will commence. A metastable

condition thus exists at temperatures that slightly below the temperature where nucleation should
start.

To produce crystals, it is best to start with a saturated solution. A more dilute solution will become
saturated as the air evaporates some liquid, but evaporation takes time (days, weeks) crystals can
be obtained more quickly if the solution is saturated to begin with. A saturated solution can be
made by adding solute (e.g. alum, sugar, salt) to the solvent (usually water, although some
applications may call for other solvents). Stirring the mix would help to dissolve the solute. Heat
may be applied to help the solute dissolve. In evaluating crystallization operations, data on
solubility curves are important. Solubility curves, like the one shown in the figure below, gives
an indication of what mass of solute would dissolve in 100g (100ml) of water over a range of
temperatures.

Crystallization is the process of formation of solid crystals from solution, melt or by deposition
directly from a gas phase. Crystallization is obtained through a variation of the solubility
conditions of the solute in the solvent, by opposition to precipitation that is due to a chemical
reaction. This operation is frequently encountered in the synthesis of pharmaceutical products.
Typically, crystallization separates a product from a liquid feed stream by cooling the stream or
adding precipitants that lower the solubility of the desired product so that it forms crystals. Well-
formed crystals are usually pure, since each molecule or ion must fit perfectly into the lattice as it
leaves the solution. Impurities that do not fit in the lattice remain in solution. Hence, one can say
that molecular recognition is the principle of purification by crystallization. However, there are
instances when impurities incorporate into the lattice, thus decreasing the purity of the final
product. Also, the solvent may remain into the lattice forming a solvate. In addition, the solvent
may be trapped within the crystal, phenomenon known as inclusion. The crystallization process
consists of two major steps, nucleation and crystal growth:
 a. Nucleation
Nucleation is the step where the solute molecules dispersed in the solvent start to gather into
clusters that become stable under 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 (e.g. temperature, super-saturation). At the stage of nucleation, the atoms arrange in a
defined/periodic manner that defines the crystal structure (relative arrangement).

b. Crystal growth
Crystal growth is the subsequent growth of the nuclei. Nucleation and growth continue to occur
simultaneously while the super-saturation exists. Super-saturation is the driving force of
crystallization. This can be achieved by different methods, as cooling, anti-solvent addition,
evaporation, pH adjustment and chemical reaction. Depending on conditions, either nucleation
or growth may be predominant, and as a result crystals with different sizes and shapes are obtained.
Once the super-saturation exhausted, the solid–liquid system reaches equilibrium, unless the
operating conditions are modified, such as supersaturating the solution again.
Note that many compounds may crystallize as different crystal forms, a phenomenon called
polymorphism. Each polymorph is in fact a different thermodynamic solid state. Crystal
polymorphs exhibit different physical properties, such as dissolution rate, shape, and melting point.
For this reason, polymorphism is of major importance in the manufacture of crystalline products.
The tank crystallizer, at atmospheric pressure, under vacuum or under pressure is typically the
main equipment in batch processes, namely in pharmaceutical industry.

Crystallization refers to a solid-liquid separation process in which solid particles are formed within
a homogenous phase. It can occur as:

(1) formation of solid particles in a vapor

(2) formation of solid particles from a liquid melt

(3) formation of solid crystals from a solution

The process usually involves two steps:

1. concentration of solution and cooling of solution until the solute concentration

becomes greater than its solubility at that temperature
2. solute comes out of the solution in the form of pure crystals
Crystal Geometry

A crystal is highly organized type of matter, the constituent particles of which are arranged in an
orderly and repetitive manner; they are arranged in orderly three-dimensional arrays called SPACE
LATTICES

Supersaturation

Supersaturation is a measure of the quantity of solids actually present in solution as compared to

the quantity that is in equilibrium with the solution

Crystallization cannot occur without supersaturation. There are 5 basic methods of generating
supersaturation

(1) EVAPORATION–by evaporating a portion of the solvent

(2) COOLING–by cooling a solution through indirect heat exchange
(3) VACUUM COOLING–by flashing of feed solution adiabatically to a lower temperature
and inducing crystallization by simultaneous cooling and evaporation of the solvent
(4) REACTION–by chemical reaction with a third substance
(5) SALTING–by the addition of a third component to change the solubility relationship

Mechanism of Crystallization Process

There are two basic steps in the over-all process of crystallization from supersaturated solution:

(1) NUCLEATION’

a. Homogenous or Primary Nucleation–occurs due to rapid local fluctuations on a molecular

scale in a homogenous phase; it occurs in the bulk of a fluid phase without the
involvement of a solid-fluid interface
b. Heterogeneous Nucleation–occurs in the presence of surfaces other than those of the
crystals such as the surfaces of walls of the pipe or container, impellers in mixing or
foreign particles; this is dependent on the intensity of agitation
c. Secondary Nucleation–occurs due to the presence of crystals of the crystallizing species

(2) CRYSTAL GROWTH–a layer-by-layer process

a. Solute diffusion to the suspension-crystal interface

b. Surface reaction for absorbing solute into the crystal lattice

Important Factors in a Crystallization Process

(1) Yield
(2) Purity of the Crystals
(3) Size of the Crystals–should be uniform to minimize caking in the package, for ease in
pouring, ease in washing and filtering and for uniform behaviour when used
 (4) Shape of the Crystals

Effects of Temperature on the Solubility of Solutes

In crystallization, equilibrium is attained when the solution (mother liquor) is saturated. This is
represented by a solubility curve.

Solubility is mainly dependent on temperature. Pressure has a negligible effect. In solubility plots,
the solubility data are normally given as parts by mass of anhydrous materials per 100 parts by
mass of solvent.

The solubility of some solutes in water are shown in the following sketch/
Yield of Crystals

The yield of crystals can be calculated by doing solvent and solute balance. The initial and final
concentrations of the solute must be known.

When the solvent is water, hydrated salts can form certain temperature and this aspect must be taken
account of. The initial solvent present is then equal to the sum of the final solvent in the mother
liquor, the crystal water in the hydrated salts and any water that has evaporated.

A solvent (water) balance is then:

Solvent in feed = Solvent evaporated + Solvent in mother liquor + Solvent in hydrated crystals.

𝑦
𝑤1 = 𝑤2 + (𝑦 − 𝑅) + 𝑤1 𝐸 (1)

Where;

w1, w2 are the initial and final masses of solvent (water)

y is the yield of crystals

R is the ratio of molecular mass of hydrate/molecular mass of anhydrous salt

E is the mass of solvent evaporated to mass of solvent initially present

A solute balance gives:

Solute in feed = Solute in product crystals + Solute in the mother liquor.

𝑦
𝑤1 𝑐1 = 𝑤2 𝑐2 + 𝑅 (2)

Where;

c1, c2 are the initial and final concentrations of the anhydrous salt expressed as mass of anhydrous
salt/unit mass of solvent.

From eqn (1) and (2)

𝑦(𝑅−1)
𝑤2 = 𝑤1 (1 − 𝐸) − (3)
𝑅

It can be shown that by substituting (3) in (2) that;

𝑅𝑤1 [𝑐1 −𝑐2 (1−𝐸)]

𝑦= [1−𝑐2 (𝑅−1)]
(4)

Note: mother liquor is a term frequently used instead of solution

Example 1

A solution of 500kg Na2SO4 in 2500kg of water is cooled from 333K to 283K in an agitated mild
steel crystallizer. At 283K, the stable crystalline form is Na2SO4.10H2O. During cooling 2mass%
of water is lost by evaporation. Estimate the yield of crystals. At 283K the solubility of Na2SO4 is
8.9kg/100kg water.

Answer:

R = 322/142 = 2.27

c1 =500/2500 = 0.2kg/kg water

c2 = 8.9/100 = 0.089

w1 = 2500kg water

E = 0.02kg/kg water

Thus, equation 4 gives

2.27 𝑥 2500[0.2−0.089(1−0.02)]
𝑦= = 722kg
1−0.089(2.27−1)

Example 2
Determine the heat that must be removed for the above example given the following:

Mass of mild steel crystallizer = 750 kg

Specific heat of mild steel = 0.5 kJ/kgK

Heat of solution of Na2SO4.10H2O = – 78.5 MJ/kmol

Specific heat of solution = 3.6 kj/kgK

Latent heat of vaporization = 2400kJ/kg

Heat of crystallization is the opposite of the heat solution

= + 78.5MJ/kmol = 78500/322 = 243.8kJ/kg

Thus, heat of crystallization = 243.8 x 723 = 176267kJ

Heat removed to cool crystallizer 750 x 0.5(333 – 283) = 18750kJ

Heat removed by cooling the solution = (500 + 2500) x 3.6 x 50 = 540000kJ

Heat lost by vaporization of 2% water = 2500 x 0.02 x 2400 = 120000kJ

Heat to be removed = 176267 + 18750 + 540000 – 120000 = 615017 kJ

Vacuum Operation
Crystallizers are frequently operated under vacuum. The amount of evaporation can be calculated
by using the following formula that is based on a heat balance.

Heat balance:

Solvent evaporated x latent heat = drop in sensible heat + heat of crystallization

Thus:

𝐸𝑤1 𝜆 = 𝐶𝑝 (𝑇1 − 𝑇2 )𝑊1 (1 + 𝑐1 ) + 𝑞𝑐 𝑦

Substituting eqn (4) in (5) yields

𝑞𝑐 𝑅(𝑐1 −𝑐2 )+𝐶𝑝 (𝑇1 −𝑇2 )(1−𝑐1 )[1−𝑐1 (𝑅−1)]

𝐸= (6)
𝜆[1−𝑐2 (𝑅−1)]−𝑞𝑐 𝑅𝑐 2

Example 3

Determine the yield of sodium acetate trihydrate (CH3COONa.3H2O when an aqueous solution
containing 40% CH3COONa is crystallized in a vacuum crystallizer that operates at 1.33kPa. the
solution is fed to crystallizer at 0.63kg/s at 355K. The solution has a boiling point rise of 11K. The
heat of crystallization is 144kJ/kg while the mean heat capacity of the solution is 3.5kJ/kg. At
1.33kPa water boils at 284.5K and its latent heat of vaporization is 2477kJ/kg.

The solubility data

Temp. (K) 273 283 293 303 303 313

Solubility (kg/kgwater) 36.3 40.8 46.5 54.5 54.5 65.5
Temperature of the liquor = boiling point of water + boiling point rise

= 284.5 + 11 = 295.5 K

At 295.5K the solubility of CH3COONa is found from the graph to be 49kg/100kg water

Thus:

c2 = 49/100 = 0.49kg/kgwater

c1 = 0.4/0.6 = 0.667

R = 136/82 = 1.66

From

𝑞𝑐 𝑅(𝑐1 −𝑐2 )+𝐶𝑝 (𝑇1 −𝑇2 )(1−𝑐1 )[1−𝑐1 (𝑅−1)]

𝐸= (2)
𝜆[1−𝑐2 (𝑅−1)]−𝑞𝑐 𝑅𝑐 2
Example 5

Solve the following problem b material balance and compare the answers with that obtained by
using the formulae given above.

10000kg of a salt solution that contains 30mass% Na2CO3 is cooled to 293K. the salt crystalizes as
the decahydrate. What will be the yield of Na2CO3.10H2O if the solubility at this temperature is
21.5kg NaCO3 per 100kg water

(a) Assume no water is lost by evaporation

(b) Assume that 3% of the total mass of the solution fed is lost by evaporation during the
cooling process.

(a) W = 0

MM of hydrate = (2 x 23) + 12 + 48 + (10 x 18) = 106 + 180 = 286

Water balance: 0.7 x 10000 = 1005/(100 + 21.5) + (180/286)C + 0

Na2CO3 balance: 0.3 x 10000 = 21.5S1(100 + 21.5) + (106/286)C

From these two equations C = 6357 kgS =3643 kg

EVALUATION
Some Types of Crystallizers