Crystallization

COURSE OUTCOME
 Describe the basic principles and applications of
crystallization processes.
 Analyze the solubility data and binary mixture phase
diagram.
 Calculate the yield, heat and mass balances in
crystallization.
 Distinguish different type of equipment in crystallization
process.
 Crystallization
 Crystallization is the (natural or artificial) process for
the formation of solid crystals from a homogenous single
phase solution.

 Crystallization is also a chemical solid-liquid separation

technique, in which isolation of a solute from the liquid
solution to a pure solid crystalline phase occurs.

 Generally, crystallization is the last chemical purification

step. More than 80% of the substances used in pharmaceuti -
cals, fine chemicals, agrochemicals, food and cosmetics are
isolated or formulated in their solid form.
 In order for crystallization to take place, a solution must be
"supersaturated".

 Crystallization is based on the principles of

solubility:
 Compounds (solutes) tend to be more soluble in hot liquids
(solvents) than they are in cold liquids.
 If a saturated hot solution is allowed to cool, the solute is no
longer soluble in the solvent and forms crystals of pure
compound.
 Impurities are excluded from the growing crystals and the pure
solid crystals can be separated from the dissolved impurities by
filtration.
 EQUILIBRIUM, SOLUBILITY AND PHASE DIAGRAM
 Equilibrium in crystallization
processes is reached when the
solution is saturated and the
equilibrium relationship for bulk
crystals is the solubility curve.

 Figure shows the solubility curve

as a function of temperature.
 Most materials follow curves similar
to curve 1 for KNO3; that is their
solubility increases more or less
rapidly with temperature.
 A few substances follow curves like
curve 2 for NaCl, with little change
in solubility with temperature.
 Other have what is called an
inverted solubility curve (curve 3
for Ce2(SO4)3), which means that
their solubility decreases as the
temperature is raised.
EQUILIBRIUM, SOLUBILITY AND PHASE DIAGRAM
 The solubility characteristic of a solute in a particular solvent is
by far the most important property for determining (1) the best
method for causing crystallization and (2) the ease or
difficulty is growing crystals.

 Crystallization by cooling is only attractive for compounds

having a solubility that decreases rapidly with decreasing
temperature above ambient temperature. For instance, for
NaCl, crystallization by cooling would be undesirable because
the solubility decreases only by about 10% when the
temperature decreases from 100 until 0oC. For most soluble
inorganic compounds, cooling by evaporation is the preferred
technique.

 Many important inorganic substances crystallize with water of

crystallization. In some systems, several different hydrates are
formed, depending on the concentration and temperature and
phase equilibrium in such systems can be quite complicated.
EQUILIBRIUM, SOLUBILITY AND PHASE DIAGRAM

 Figure shows the solid-liquid phase-equilibrium diagram for naphthalene and benzene.
 Point A and B are the melting (freezing) points of pure benzene (5.5 oC) and naphthalene (80.2
oC).

 Point E is the eutectic point. Eutectic point in this case represent the binary mixture of
naphthalene and benzene, as separate solid phases, with the lowest freezing(melting) point.
 Points located above the curve AEB correspond to a homogeneous liquid phase.
 Curve AE is the solubility curve for benzene in naphthalene.
 Curve EB is the solubility curve for naphthalene in benzene.
 For this mixture, as with most mixtures, solubility increases with increasing temperature.
EQUILIBRIUM, SOLUBILITY AND PHASE DIAGRAM

 If a liquid solution of composition and temperature represented by point P is cooled along the vertical, dashed
line, it will remain a liquid until the line intersects the solubility curve at point F.
 If temperature is lowered further, crystals of naphthalene form and the remaining liquid, called mother liquor,
becomes richer in benzene.
 Example: when point G is reached, pure naphthalene crystals and a mother liquor, given by point H on solubility
curve EB, coexist at equilibrium, with the composition of the solution being 37 wt% naphthalene.
 The fraction of the solution crystallized can be determined by applying the inverse-lever-arm-rule.
 As the temperature is lowered further until line CED, corresponding to the eutectic temperature, is reached at
point J, the two-system consists of naphthalene crystals and a mother liquor of the eutectic composition given by
point E.
 Any further removal of heat causes the eutectic solution to solidify.
 Mechanism of Crystallization
 Crystallization from solution can be thought of as a 3 step
processes which are :
 Supersaturation -The formation of supersaturated solution
 Nucleation - The formation of crystal nuclei.
 Crystal growth - The growth of the nuclei to larger size
 Supersaturation
 Supersaturation refers to a state in which the liquid (solvent) contains
more dissolved solids (solute) than can ordinarily be accommodated at that
temperature.

 Based on Ostwald-Miers, the field of supersaturation consists of three regions

and the relationship between supersaturation and spontaneous crystallization
led to the diagrammatic representation (Fig.1). The regions of
supersaturation are describe as follows

 The stable (undersaturated) zone –

Crystallization is impossible. The solutions have concentrations lower than the
solubility curve at a specific temperature, are considered as being
undersaturated. In such solutions, any crystals present will re-dissolve.

 The metastable (supersaturated) zone-

Spontaneous nucleation does not occur. However existing crystals may grow if a
surface on which growth can occur is present
 The unstable or labile (supersaturated) zone –
Spontaneous nucleation is probable and so the growth. Nuclei are formed
spontaneously from a clear solution.

The upper dashed line is referred

to as the super-solubility line and
denotes the temperatures and
concentration where spontaneous
nucleation occurs.
 Supersaturation can be achieved using several methods. These
include :

 Changing solution temperature (cooling crystallization)

 Evaporation of solvent (evaporative crystallization),
 Changing the solvent composition (antisolvent crystallization).
 Chemical reactions (reactive crystallization/precipitation)

 Each process has its possibilities and limitations.

 Nucleation
Primary Nucleation
 The formation of a new crystalline entity from a solution starts
through the nucleation process.
 Nucleation is defined as the series of atomic or molecular processes
by which the atoms or molecules of a reactant phase rearrange into a
cluster of the product phase large enough as to have the ability to
grow irreversibly to a macroscopically larger size.
 The cluster is defined as nucleus or critical nuclei.
 Nucleation can be homogeneous, in the absence of foreign particles
or crystals in the solution, or heterogeneous, in the presence of
foreign particles in the solution.
Secondary Nucleation
 Secondary nucleation takes place when nucleation is induced by the
presence of crystals of the same substance.
 Secondary nucleation requires "seeds" or existing crystals to perpetuate
crystal growth
 Crystal Growth
 Crystal growth is the series of processes by which an atom or a molecule is
incorporated into the surface of a crystal, causing an increase in size.

 These different processes can be summarized into four steps which are:
1) transport of atoms through solution
2) attachment of atoms to the surface
3) movement of atoms on the surface
4) attachment of atoms to edges and kinks.

 The first process is the so-called transport process, whereas 2–4 are
referred to as surface processes (and may involve several sub steps).
 Since these different steps normally occur in series, the slowest process will
control the overall crystal growth.
 Therefore, growth can be transportted (when step 1 is the slowest) or
surface controlled (when steps 2–4 are the slowest).
 Crystals
 Can appear as polyhedrons, or solids formed by plane faces when
allowed to form freely.
 Shape is determined by atomic arrangements .Some directions grow
faster than others
 Morphology can be distinct for the conditions and speed of crystal
nucleation/growth.
 Relative sizes of a crystal in a particular system can vary
considerably –resulting in a variety of crystal shapes. This variation is
called a habit.
 Crystal habit is influence by the conditions of crystallization,
particularly by the impurities present and by the particular solvent or
solvents used.
 Impurities can inhibit the growth of a crystal in certain directions.
Polyhedrons Shape
CALCULATION IN CRYSTALLIZATION
 Material Balances
 The solution and the solid crystals are in contact for enough time to
reach equilibrium. Hence, the solution is saturated at the final
temperature of the process, and the final concentration of the solute in
the solution can be obtained from the solubility curve.

 The yield can be calculated knowing the initial concentration of solute,

the final temperature, and the solubility at this temperature.

 In making the material balances, the calculations are straightforward

when the solute crystals are anhydrous. Simple water and solute
material balances are made. When the crystallizations are hydrated,
some of the water in solution is removed with the crystals as a hydrate.
 Example 1

A salt solution weighing 10000kg with 30wt% Na2CO3 is cooled

to 293K (20°C). The salt crystallizes as the decahydrate.What will
be the yield of Na2CO3•10H2O crystals if the solubility is
21.5 kg anhydrous Na2CO3/100 kg of total water? Do this for the
Following cases:

(a) Assume that no water is evaporated.

(b) Assume that 3% of the total weight of the solution is lost by
evaporation of water in cooling.
 Example 1
Solution
The molecular weights are 106.0 for Na2CO3, 180.2 for
10H20, and 286.2 for Na2CO3 •10H2O.The process
flow diagram is shown in Fig. 3, withW being kg H2O
evaporated, S kg solution (mother liquor), and C kg
crystals of Na2CO3 •10H2O.
Making a material balance :
(a), where W = 0.

(13)

where (180.2)/(286.2) is wt fraction of water in the crystals.

 SOLUTION:
Making a balance for Na2CO3,
(14)

Solving the two equations simultaneously, C = 6370 kg of Na2CO3

•10H2O crystals and S = 3630 kg solution.

For part (b), W = 0.03(10000) = 300 kg H2O. Equation (13)

becomes
(15)

Equation (14) does not change, since no salt is in the W stream.

Solving Eqs. (14) and (15)simultaneously, C = 6630 kg of Na2CO3
•10H2O crystals and S = 3070 kg solution.
 Heat Balance
 When a compound whose solubility increases as temperature increases
dissolves, there is an absorption of heat, called the heat of solution–occurs
when the solubility decreases as the temperature increases
 At equilibrium the heat of crystallization is equal to the negative of the heat
of solution at the same concentration in solution.
 The enthalpy H1of the entering solution at the initial temperature is read off
the chart, where H1is kJ for the total feed. The enthalpy H2of the final
mixture of crystals and mother liquor at the final temperature is also read
off. If some evaporation occurs, the enthalpy Hv of the water vapor is
obtained from the steam tables. Then the total heat absorbed q in kJ is

 If q is positive, heat must be added to the system. If it is negative,

heat is evolved or given off.
 Example 2
A feed solution of 2268kg at 327.6K(54.4°C) containing
48.2kg MgSO4/100kg total water is cooled to 293.2K (20°C),
where MgSO4•7H2O crystals are removed. The solubility of the
salt is 35.5kg MgSO4/100 kg total water. The average heat
capacity of the feed solution can be assumed as 2.93kJ/kg•K.
The heat of solution at 291.2K(18°C) is 13.31x103 kJ/kgmol
MgSO4•7H2O.

Calculate the yield of crystals and make a heat balance to

determine the total heat absorbed, q ,assuming that no water is
vaporized
 SOLUTION:
Solution
Making a water balance and a balance for MgSO4
using equations similar to (13) and (14) in
Example 1, C = 616.9 kg MgSO4•7H2O crystals
and S = 1651.1 kg solution.
To make a heat balance, a datum of 293.2 K
(20°C) will be used. The molecular weight
of MgSO4•7H20 is 246.49. The enthalpy of the
feed is H1:
 SOLUTION: 3
The heat of solution is -(13.31x10 )/246.49 = -54.0 kJ/kg crystals.
Then the heat of crystallization is -(-54.0) = +54.0 kJ/kg crystals,
or 54.0(616.9) = 33312 kJ. This assumes that the value at 291.2 K
is the same as at 293.2 K. The total heat absorbed, q,
is

Since q is negative, heat is given off and must be removed.

 Equipment for Crystallization
Tank Crystallization
 Hot saturated solutions are allowed to cool in open tanks
 After a period of time, the mother liquor is drained and the crystals removed
 Nucleation and the size of crystals are difficult to control
 Labor cost are very high
 Has limited application; used to produce certain fine chemical and
pharmaceutical products.
 Equipment for Crystallization
Scraped surface crystallizers
 One type of scraped surface crystallizer is
the Swenson-Walker crystallizer,
which consists of an open trough 0.6 m
wide with a semicircular bottom having a
cooling jacket inside.
 Slow-speed spiral agitator rotates and
suspends the growing crystals on turning.
 Blades pass close to the wall and break off
any deposits of crystals on the cooled wall.
 Used in crystallizing ice cream and
plasticizing margarine.
 Equipment for Crystallization
Circulating-liquid evaporated-crystallizer
 Supersaturation is generated by evaporation.
 Circulating liquid is drawn by the screw pump down inside
the tube side of condensing steam heater
 Heated liquid then flows into the vapor space, where flash
evaporation occurs, giving some supersaturation.
 The vapor leaving is condensed.
 The supersaturated liquid flow down the downflow tube and
then up through the bed fluidized and agitated crystals,
which are growing in size.
 The living saturated liquid then goes back as a recycle stream
to the heater, where it is joined by the entering feed.
 The larger crystals settle out and a slurry of crystals and
mother liquor is withdrawn as product.
 Also called Oslo crystallizer.
 Equipment for Crystallization
Circulating-magma vacuum
crystallizer
 The magma or suspension of crystals is circulated
out the main body through a circulating pipe by a
screw pump
 Magma flows through a heater, where its
temperature is raised 2-6 K.
 The heated liquor then mixes with body slurry and
boiling occurs at liquid surface
 This cause supersaturation in the swirling liquid
near the surface, which results in deposits on the
swirling suspended crystals until they leave again via
the circulating pipe
 The vapors leave through the top
 A steam-jet ejector provides the vacuum
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