CHAPTER

CRYSTALLIZATION
8

Lecturer: Dr. Tran Tan Viet

  Basic principles and
applications of
crystallization
process.
 CALCULATION of
yields, material and
energy balance in
crystallization.
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 CRYSTALLIZATION
• Process of producing crystals from a homogeneous
phase which is obtained from a solution.
• Capable of producing bioproducts at very high
purity and considered to be a polishing step and a
purification step
• Two different application of crystallization:
i. Crystallization for polishing and purification
ii. Crystallization for crystallography

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 Comparison of Crystallization and
Precipitation
Description Crystallization Precipitation
Solubility Wide range, usually Sparingly soluble
medium to high
Relative Low High
supersaturation
Product morphology Well-defined Ill-defined
Product crystal size Large Small
Nucleation Secondary Primary
mechanism
Nucleation rate Low High
Growth Rate Wide Range Low
Controllability
2/2/2020 Controllable
Lecturer: Dr. Tran Tan Viet Difficult to control 4
 Crystallization from Supersaturated Solutions of
Sodium Acetate

• Description: A supersaturated solution of sodium

acetate is crystallized by pouring it onto a seed
crystal, forming a stalagmite-like solid. Heat is
radiated from the solid.

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 Crystallization Principles
Crystals
• Can appear as polyhedrons, or solids formed by plane faces when
allowed to form freely.
• Angles made by the corresponding faces of the same material do not
vary – can be classified by this characteristics.
• Relative sizes of the faces 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 stunt the growth of a crystal in certain directions.

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 POLYHEDRONS SHAPE

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 TABULAR
Book-like (tablets) that are thicker than platy
but not as longated as bladed. Wulfenite
forms crystals that are a good example of
tabular crystals.

PRISMATIC
One of the most common of crystal habits. Prismatic crystals
are "pencil-like", elongated crystals that are thicker than
needles (see acicular). Indicolite (a variety of elbaite) forms
good examples of prismatic crystals.

ACICULAR
Long and needle-like, thinner than
prismatic but thicker than fibrous. Natrolite
crystals can be good examples of acicular crystals.

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 Crystals grow in 2
steps:

1. Nucleation - first aggregation.

2. Growth.
– Thermodynamically
distinct
– Want a few nuclei to grow
big
– Use thermodynamics to
understand the required
conditions

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 Crystallization Principles
Nucleation
• The generation of ultramicroscopic particles in the process of
nucleation is the sum of contributions by primary nucleation and
second nucleation.
• Primary nucleation : occurs in the absence of crystals, secondary
nucleation: attributed to the influence of existing crystals
• Primary nucleation can be either homogeneous (no foreign particles
are present) or heterogeneous (foreign particles present during
heterogeneous nucleation)
• Rate of primary nucleation has been modeled by the following power
law expression: B: number of nuclei formed per unit volume per unit time;
N: number of nuclei per unit volume; kn : rate constant;
c: instantaneous solute concentration; c*: solute
concentration at saturation. (c-c*) term : supersaturation,
(1) the exponent of n can range up to 10 but typically is in
the range of 3 to 4.
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 Crystallization Principles
• Two types of secondary nucleation : shear nucleation (occurs as a
result of fluid shear on growing crystal faces), contact nucleation (
happens because of crystals colliding with each other and with the
impeller and other vessel internal surfaces.
• Rate of secondary nucleation in crystallization is the following:

(2)

k1 : rate constant; MT : suspension density,

b : can range up to 5 but has a most probable value of 2;
j: ranges up to 1.5 with 1 being the most probable value

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 Crystallization Principles
- The supersaturation must be above the a certain
value before nucleation will begin
- Metastable region : the supersaturation is low that
nucleation will not start
- Once the supersaturation has been raised enough to
be in the labile region, nucleation can begin.
- At this point, crystals begin to grow, and the
supersaturation decreases
- If the supersaturation becomes too high, the
nucleation rate will be too great, and amorphous
precipitate will result.

Figure 1: Typical phase diagram. The components in solution consist of the product (ordinate) and the
precipitating reagent (abscissa). The lines with arrows out line one possible way of performing the
crystallization.

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 Phase diagram
Solute concentration

Nucleation
and growth

Heterogeneous while
Stable region crystal growth
(homogeneous solution)
Reagent concentration
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 Crystallization Principles
Nucleation

Super saturation

Nucleation
Solute concentration

Prismatic form Growth

2/2/2020 time
Lecturer: Dr. Tran Tan Viet 14
 Phase diagrams
Supersaturation

Precipitation zone

Nucleation zone
concentration

Metastable zone
Protein

Solubility Crystals grow, but

curve Nuclei form only infinitely
Under-saturation slowly
(protein remains soluble; crystals dissolve)
Precipitatant concentration (salt, PEG etc.)

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 Course of Crystallization Experiment
Metastable
Precipitation
Nucleates
Protein concentration

here Nucleation
Crystal grows
Sequesters protein
[protein] drops
Crystal stops growing @
solubility curve
Start w/ soluble protein
(undersaturated or
metastable)
Expt incr. [protein], [precipitant]
Xtl grows again, until hits curve
[Precipitatant]
Repeats as follows solubility curve

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 Crystallization Principles
Crystal Growth
• Post nucleation process in which molecules in solution are added to
the surface of existing crystals
• The rate of mass deposition R during crystal growth is:
W: mass of crystals per volume of solvent;
A : the surface area of crystals per volume of
(3) solvent;
kG : overall mass transfer coefficient (depends on
temperature, crystal size, hydrodynamic
conditions, the presence of impurities);
g : usually 0 and 2.5

• Overall linear growth rate can also be expressed as:

L : characteristics single dimension of the crystal, such as length

(4)
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 Crystallization Principles
• Crystal growth is a process that consists of two steps in
series – diffusion and surface integration

(5)
(6)

ci : concentration at the interface between the liquid and solid phase; kd

and kr : mass transfer coefficients

When the exponents are unity, combining Equation 3, 5, 6

gives
Thus, if surface integration is very fast
(7) compared with bulk diffusion, then kr >> kd,
and kG , kd.
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 Yields and Heat and Material Balances in
Crystallization
• Yields and material balance in crystallization
• The solution (mother liquor) and the solid crystals are in contact for
enough time to reach equilibrium. Hence, the mother liquor is
saturated at the final temperature at the final temperature of the
process, and the final 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.
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 Example 1
Yield of a Crystallization Process
A salt solution weighing 10000 kg with 30 wt % Na2CO3 is cooled
to 293 K (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.

FIGURE3. Process flow

for crystallization

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 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, with W being kg H2O
evaporated, S kg solution (mother liquor), and C kg
crystals of Na2CO3 •10H2O.Making a material balance
around the dashed line box for water for part
(a), where W = 0.

(13)

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

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 Example 1
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.

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 Yields and Heat and Material Balances in
Crystallization
Heat effects and heat balances in crystallization
• 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 H1 of the entering solution at the initial temperature is
read off the chart, where H1 is kJ for the total feed. The enthalpy H2 of
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
(16)

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

heat is evolved or given off. Lecturer: Dr. Tran Tan Viet
2/2/2020 23
 Example 2
Heat Balance in Crystallization
A feed solution of 2268 kg at 327.6 K (54.4 °C) containing
48.2 kg MgSO4/100 kg total water is cooled to 293.2 K
(20°C), where MgSO4•7H2O crystals are removed. The
solubility of the salt is 35.5 kg MgSO4/100 kg total water.
The average heat capacity of the feed solution can be
assumed as 2.93 kJ/kg• K. The heat of solution at 291.2
K (18 °C) is -13.31 x 103 kJ/kg mol 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.

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 Example 2
Solution
Making a water balance and a balance for MgSO4using
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:

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 Example 2
The heat of solution is -(13.31x103)/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.

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 Equipment for Crystallization
Agitaged batch crystallizer Uniform and fine crystals Batch operation
Heat transfer rate
decreases at the
surface due to crystals
Swenson Walker crystallizer Continuouslu operation Scrappers may break
Uniform crystal crystals
Krystal Large capacity of controlled size Large size equipment
crystals
Vacuum crystallizer Very simple configuration
Suitable for corrosive solution
Batch and continuously operation
Tank crystallizer
Forced circulation
crystallizer
Scraped surface crystallizer
Circulating magma vacuum
crystallizer
Oslo2/2/2020
crystallizer Lecturer: Dr. Tran Tan Viet 27
 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.

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 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.

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 Equipment for Crystallization
Circulating-liquid evaporated-crstallizer
• 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.
• 2/2/2020
Also called Oslo crystallizer. Lecturer: Dr. Tran Tan Viet 30
 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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 CHAPTER
CRYSTALLIZATION
8