crystallization

CHE133
 CRYSTALLIZATION

• Process where solutions become supersaturated as

to cause the formation of crystals.
 Methods of Supersaturating a
Solution
• 1. Supersaturation by cooling.

• 2. Supersaturation by evaporation.

• 3. Supersaturation by evaporation and cooling.

 Methods of Supersaturating a
Solution
• 4. Addition of a third component that reduces the
solubility of substance of interest. SEEDING.
Common ion effect.

• 5. Addition of a third component to form

precipitate. Precipitation Reaction.
 Equilibrium in Crystallization

• Generally it is said that equilibrium is reached in

crystallization when the solution above the solid or
crystals is a saturated solution.
 General types
1. cooling crystallizer-
of Crystallizers
supersaturate solution by
cooling

crystallizes material whose

solubility increases greatly
with temperature.

Agitated batch crystallizer

Swenson Walker Continuous
Cooling Crystallizer
Semicircular bottom
•
Swenson-Walker
A scraped-surface crystallizer.
Crystallizer
• Open through 0.6 m wide
with a semi circular bottom.
• With a cooling jacket outside.
 Swenson-Walker Crystallizer

• A slow-speed spiral agitator rotates and

suspends the growing crystals on
turning.

• The blades pass close to the wall and

break off any deposits of crystal on the
cooled wall.

• The product has a wide crystal

distribution.
Agitated Batch Crystallizer
 Agitated Batch Crystallizer

• Old Method

• Hot saturated solution is

allowed to cool in tank.

• After a period of time the

mother liquor is drained and
the crystal removed.
 Agitated Batch Crystallizer

• The tank is cooled by jacket or

coils.

• Agitator improves heat transfer rate.

• Crystals often build up on surfaces.

• Use: Pharmaceutical products

 Agitated Batch Crystallizer

• Disadvantages
• 1. Crystal size is difficult to
control.

• 2. Crystal contain considerable

amount of occluded mother liquor.

• 3. High labor cost.

 2. Evaporator crystallizer/
crystallizing evaporator
This type of evaporator
supersaturate a solution by
evaporation.

These equipment crystallizes

material whose solubility s not
affected by temperature.
OSLO (evaporative) crystallizer
 Oslo Crystallizer

• A circulating – liquid evaporator

crystallizer.

• A screw type pump pumps the liquid

into the tube side of Heat exchanger
heated by steam.

• The heated liquid goes to the “vapor

space” where flash evaporation
occur.
 Oslo Crystallizer
• The supersaturated liquid flows
down the downflow tube.

• Then up through the bed of

crystals which are growing in size.

• The leaving saturated solution

then goes back to the heat
exchanger.
•
Oslo
Where it is joined by the
Crystallizer
feed.

• The larger crystal goes to the

bottom and withdrawn as
product.
Forced circulation (evaporation)
crystallizer
 Forced circulation (evaporation)
• A circulating magma crystallizer
vacuum crystallizer

• A heat exchanger heats the

magma.

• A Screw type pump pumps

the magma.
 Magma

• In industrial crystallization from a solution, this

refer to the the two phase mixture of mother liquor
and crystal of all sizes, which occupy the
crystallizer and can be withdrawn as the actual
product.
 3. Vacuum Crystallizers
Supersaturating solution by combined cooling and evaporation in
adiabatic evaporator.

Most important in large

scale production.

A hot solution is introduce in

vacuum, the solvent
evaporate cooling the
solution adiabatically.
Direct Contact Refrigeration
crystallizer
Draft-tube-baffle (DTB)
crystallizer
 4. Reaction type crystallizer
Supersaturate solution by precipitation reaction or common ion
effect.
Swenson reaction type
crystallizer
Swenson-atmospheric reaction
type crystallizer
Melt Crystallization vs Solution
Crystallization
• Melt crystallization – separation of components of
a binary mixture without addition of solvent.

• Solution crystallization – a diluent is added to the

mixture, then the solution is cooled and/or solvent
is evaporated to effect evaporation.
Table 2-122 page 2-126 to 2-129
8th ed
 Old board question

• The solubility of soda ash at 30°C in g/100g water

is _______
• A. 9.6
• B. 21.5
• C. 11.1
• D. 38.8
 Old board question

• The solubility of sal ammoniac at 70°C in g/100g

water is______.
• A. 116.8
• B. 60.2
• C. 55.2
• D. 126
 Seat work

• The solubility of epsom salt (magnesium sulfate) in

equilibrium with the saturated solution at 10°C in
g/100g water is _______.
• A. 30.90
• B. 53.23
• C. 59.5
• D. 62.9
Assignment: Google common names
of chemical list
 Sample Problem

• The enthalpy of saturated MgSO4 solution at 150°F

in Btu/lb is _____________.
• A. -25
• B. -30
• C. -20
• D. -40
Material Balance
F=L+V+C

Solute balance
F (Xf) = L(Xl) + C(Xc)
Solvent balance
F(1-Xf) = L(1-Xl) + C(1-Xc) + V
Sample Problem 1
Sample Problem 1
Seat work 1
 heat balance in crystallization

q = F Cp ∆T + C λc
Heat Balance
Seat work 2
 Old board problem

• The solubility of sodium bicarbonate in water is 9.6

g/100 g of water at 20C and 16.4 g/100 g of water
at 60C. If a saturated solution of sodium
bicarbonate at 60C is cooled to 20C, the percentage
of dissolved salt that crystallizes out is
• A. 14.5% B. 15.4% C. 41.5% D. 48%
MCL Chem Eng Quiz Question

• A saturated solution containing 1500 kg of KCl at

360 K is cooled in an open tank to 290K. The
solubility of KCl per 100kg of water is 53.55 kg at
360K and 34.5 kg at 290K. Calculate the mass of
crystal obtained. Assume no evaporation.
 Old board problem

• Glaubers salt is made by crystallization by

evaporation. The original solution contains 8.4%
sodium sulfate. How many g of water must be
evaporated from 1.00 L solution with a density of
1.077 g/ml. 80% of original sodium sulfate will
crystallized as decahydrate. The solubility of
sodium sulfate is 19.4 g Na2SO4/ 100 g water.
• A. 821.52 B. 721 C. 850.52 D. 801.52
 Old board problem

• A batch of 1000 kg of KCl is dissolved in water to

make a saturated solution at 363K. Where the
solubility is 35% wt KCl in water. The solution is
cooled to 293K where the solubility is 25.4% wt.
5% of the original water evaporates. Calculate the
weight of crystal.
• A. 400 kg b. 238 kg c. 200 kg d. 480 kg
 Old board problem/seat work

• 1200 lb of barium nitrate is dissolved in sufficient

water to form a saturated solution at 90⁰C.
Assuming that 5% of the original solution
evaporates. Calculate the weight of crystal at 20⁰C.
Solubility for barium nitrates is 30.6% at 90⁰C and
8.6% at 20⁰C.
 Old board question

• The heat of solution of saltpeter kcal/mol is

• A. -5.23
• B. -6.23
• C. -8.633
• D. -4.6
Table 2-182 p. 2-203 to 2-205
 Old board question/seat work

• The heat of solution of hydroxybenzene in cal/mol

is
• A. -2605
• B. -3960
• C. -3705
• D. -5210
 Old board question

• The enthalpy of a saturated MgSO4 at 150F in

btu/lb solution is.
• A. -25
• B. -30
• C. -20
• D. -40
 Old board problem

• The enthalpy of a 25% MgSO4 at 82.2C in btu/lb is

• A. 45
• B. 50
• C. 40
• D. 35
 Mc Cabe example 27.2

• A 32.5 % solution of MgSO4 at 120F is cooled to

70F without evaporation. How much heat must be
removed per ton of crystal.
 Hand book problem

• Example 2: Yield from a Crystallization Process A 10,000-

lb batch of a 32.5 percent MgSO4 solution at 120°F is cooled
without appreciable evaporation to 70°F. What weight of
MgSO4⋅7H2O crystals will be formed (if it is assumed that
the mother liquor leaving is saturated)?From the solubility
diagram in Fig. 18-56 at 70°F the concentration of solids is
26.3 lb MgSO4 per 100-lb solution.
• The mole weight of MgSO4 is 120.38.
• The mole weight of MgSO4⋅7H2O is 246.49.
 Coulson

• Consider the evaporative cooling of a 1000 lb of water in a

solution containing NaCl and KCl. Initially the solution
contains 27.0 g NaCl per 100 g of water and 34.3 g KCl per
100 g of water at 100°C. Applying vacuum results to boiling
of solution at lower temperature of 40°C. The solution now
has a concentration of 28.4 g NaCl per 100 g of water and
20.4 g KCl per 100 g of water. Calculate the amount of KCl
that precipitates. Assume all NaCl remains in the solution.

• Answer: 149 lb KCl

 Coulson

Answer:
 Seat work/old board
problem

• A Swenson-Walker crystallizer is used to produced 1

ton per hour of copperas crystals by cooling a saturated
solution at 120°F to 80°F. Cooling water enter the
cooling jacket at 60°F and exits at 70°F. U for
crystallization is 35 btu/h.ft2.°F. Heat of solution is 4400
cal/mol. Cpf is 0.70btu/lb.°F. Solubility at 120°F is 140
kg copperas/100 kg water. Solubility at 80°F is 74 kg
copperas/100 kg water. Calculate the crystallizer area.
 Old board question

• If an aqueous solution of 25% MgSO4 at 140F is

cooled to 30F the type of crystal formed is
• A. MgSO4.12H2O
• B. MgSO4.2H2O
• C. MgSO4.7H2O
• D. MgSO4.10H20
P18.40 8th ed. Perry
 Old board question

• The mother liquor concentration will be ____%

MgSO4.
• A. 10
• B. 18
• C. 24
• D. 4
P18.40 8th ed. Perry
 “supersaturation”

• The term used to refer to the difference in

concentration between a supersaturated and
saturated solution.
Coulson
 nucleation

• cluster→embryo→nucleus→crystal
 Kelvin Equation

• α is ratio of concentration of supersaturated solution and saturated solution.

• L is the crystal size.
• v is number of ions per molecule.
• Vm is the molar volume in cc/mol.
• R is gas constant used 8.314 X 10 7 ergs/mol.K.
• T is temp in K.
• σ is interfacial tension in ergs/cm2.
 McCabe 27.3

• Assuming that the rate of nucleation of potassium

chloride is consistent with interfacial tension of 2.5
ergs/cm2, determine the size of the nucleus at 300
K. The molar mass of KCl is 74.56 g/mol and its
crystal density is 2.000 g/cm3. The ratio of
concentration of supersaturated solution and
saturated solution is 1.029.
• Answer: 2.60 nm
 McCabe 27.4

• What would be the size of a nucleus in equilibrium

with a fractional supersaturation of 0.029, under
the same condition as example 27.3.

• Answer: 2.63 nm