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Unit 3 – Crystallization
By
Evelyn R. Laurito
University of Santo Tomas

Outcomes
• Define crystallization and give industrial
applications involving crystallization
• Get solubility and latent heat of crystallization
of solutions
• Differentiate nucleation and crystal growth
• Identify crystallizers based on method of
inducing supersaturation
• Solve crystallizer and seeding problems using
material and energy balance

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What is Crystallization
• Crystallization refers to the formation of solid
crystals from a homogeneous solution.

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Uses and Examples of

Crystallization
• Used in production, purification or
recovery of solid materials
• Isolation of newly synthesized
substances
• Removing sucrose from beet solutions
• Removing salts like NaCl, KCl from an
aqueous solution

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Crystallization
• It is essentially a solid-liquid mass transfer
technique that requires flow of heat
• Unit Operation that will bring a solute out of
solution as crystals by inducing
supersaturation

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Saturation
• What is the difference between saturation
and supersaturation?
• Saturation – state at which a liquid contains the
maximum amount of solute it can dissolve at a
given temperature

• Supersaturation – state at which a liquid contains

more dissolved solids (solute) than can ordinarily
be accommodated at that temperature

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Solubility
• What is solubility?
• Solubility refers to the maximum amount of solute
that can be dissolved in a given amount of
solvent at a specified temperature
• Solubility Units:
 Wt fraction
 Wt solute per 100 wt units solvent
(i.e. g solute per 100 g solvent)

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Solubility Curves

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Solubility Curves
• Solubility Curves
100
90
Solubility, g salt/100 g w ater

80
70
60
50
40
30
20
10
0
0 10 20 30 40 50 60 70 80 90 100
Temperature, oC

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Hydrated Crystals
• Hydrated crystals are usually formed by
cooling a saturated solution
• Water of crystallization is necessary for
the maintenance of crystalline
properties, but capable of being
removed by sufficient heat.

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Hydrated Crystals Matching

Match the Common Name With the Formula
Glauber’s Salt CaSO4·2H2O
Sal soda CuSO4 . 5H2O
Epsom Salt Na2CO3.10H2O
Copperas Al2(SO4)3.18H2O
Blue Vitriol Na2SO4.10H2O
gypsum MgSO4.7H2O
Alum FeSO4.7H2O

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Parts of Solubility Curves

• Solubility Curves Saturated
solution
curve
Crystal.H2O
Unsaturated
Temperature

Crystal.2H2O
solution Pure
Crystal.10H2O Crystals
Crystal.12H2O line

Solubility
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Solubility Curves

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Solubility Curve for MgSO4

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H-x-T diagam for Na2SO4

150
H-x-T diagram for Na2SO4
Solution - Vapor
two-phase region

150

Solution - Na2SO4
Two-phase region
100 One-phase region 100
Solution

50 50
Enthalpy. BTU/lb

Two-phase region
Solution, Na2SO4.10H20
0 0
Three-phase region
Solution, Na2SO4.10H20, Na2SO4

-50 -50

Three-phase region
Ice, solution, Na2SO4.10H20
Two-phase region
-100 Na2SO4.10H20, Na2SO4 -100
Two-phase region
Ice, solution

Two-phase region Na2SO4.10H20

-150 Ice , Na2SO4.10H20 -150

0 10 20 30 40 50 60 70 80 90 100
Concentration, wt % Na2SO4

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H-x-T diagram
for CaCl2

H-x-T diagram
for MgSO4

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Reference Charts & Tables

• Solubility Curves
 Solubility Curve Diagrams
1. Na2SO4 – Fig. 19.28 Foust
2. CaCl2 – Fig. 19.29 Foust
3. MgSO4 – Fig./MSH
4. FeSO4 – Badger & Banchero
5. Perry’s Handbook (Table 2-120)

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at 50oC.
Seatwork
1. Find the solubility of KCl in g/100 g solvent

2. Find the solubility of NaNO3 in wt fraction at

25oC.
3. At what temperature should a 25% solution
of K2Cr2O7 be cooled to produce a saturated
solution
4. Find the enthalpy and temperature of a 30%
Na2SO4 solution at saturation
5. What is the enthalpy of Na2SO4.10H2O
crystals at 60oF
6. Find the solubility g/100 g of
Al2(SO4)3.18H2O at 32oC

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o Seatwork
1. Find the solubility
at 50 C. (42-44)
of KCl in g/100 g solvent

2. Find the solubility of NaNO3 in wt fraction at

25oC. (0.46-0.49)
3. At what temperature should a 25% solution
of K2Cr2O7 be cooled to produce a saturated
solution (52 – 54oF)
4. Find the enthalpy and temperature of a 30%
Na2SO4 solution at saturation (86-90; 30-32)
5. What is the enthalpy of Na2SO4.10H2O
crystals at 60oF (-94 to -98)
6. Find the solubility g/100 g of
Al2(SO4)3.18H2O at 32oC (41.54)

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Methods of Inducing Supersaturation

• Cooling
• Evaporation of the Solvent
• Evaporation of the solvent with cooling
• Drowning
 addition of a non-solvent to the solution which
decreases the solubility of the solid.
• Chemical reaction
 used to alter the dissolved solid to decrease its
solubility in the solvent, thus working toward
supersaturation.

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Methods of Inducing Supersaturation

• Cooling
 Applicable for solids whose solubility decreases
with temperature
100
90
Cooling
Solubility, g salt/100 g w ater

80
70
60
50
to 20oC
40
30
20
Sat’d sol’n Magma
10 of KNO3 at Crystals
0
0 10 20 30 40 50 60 70 80 90 100
50oC Mother Liquor
Temperature, oC
Solubility=?89 Solubilty=?31

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Methods of Inducing Supersaturation

• Evaporation of the solvent
 Applicable for solids whose solubility do not vary
too much with temperature or decreases with
Temp. Ex. NaCl and Ce2(SO4)3
100
90
Solubility, g salt/100 g w ater

80
70
60 Heat
50
40
30
to 100oC
20
10
0
Sat’d sol’n Magma
0 10 20 30 40 50 60 70 80 90 100
of NaCl at Crystals
Temperature, oC
50oC Mother Liquor

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Methods of Inducing Supersaturation

• Evaporation of the solvent with cooling
 How can you make a solution boil by lowering its
temperature? Apply vacuum pressure
100
90
Solubility, g salt/100 g w ater

80
70
Vacuum
60 Cool
50
40
30
to 20oC
20
10
0
Sat’d sol’n Magma
0 10 20 30 40 50 60 70 80 90 100
of KCl at Crystals
Temperature, oC
50oC Mother Liquor

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Types of Crystallizers
• Tank Crystallizers
 This is probably the oldest and most basic method
of crystallization.
 Example: "pot of salt water"
• Take a pot of boiling water and add table salt while stirring
to make a water-salt solution. Continue adding salt until
no more salt will dissolve in the solution (this is a
saturated solution). Now add one final teaspoon of
salt. The salt that will not dissolve will help the first step in
crystallization begin.
 Controlling nucleation and the size of the crystals is
difficult.
 Labor costs are high

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Crystallizer Design
• Scraped Surface Crystallizers
(Swenson-Walker crystallizer)
Agitator
 Consist of a trough about 2 Feed
feet wide with a semi-circular
bottom. Each unit has a
length of 10 ft or 3.048 m Magma
 The outside is jacketed where
cooling water flows Cooling Water
 An agitator blade removes
crystals that grow on the
vessel wall
 Feed flows countercurrent to
the cooling water

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Types of Crystallizers Vapor

• Forced Circulating Liquid

Evaporator-Crystallizer
 Steam causes evaporation reducing the
amount of solvent in the solution
 A circulating liquid is fed together with
steam into the vapor space of the
crystallization vessel.
 The supersaturated liquor flows down a Steam
fluidized area of crystals and liquor where
crystallization takes place. Crystals
 Larger product crystals are withdrawn
while the liquor is recycled, mixed with the
feed, and reheated. Feed

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Types of Crystallizers Vapor

• Vacuum Crystallizer
 A vacuum in the vapor space
causes boiling at the surface of
the liquid.
 The evaporation causes Feed

crystallization and the crystals

and mother liquor are drawn off
near the bottom of the vessel
body
Magma

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Crystallizer Design
• Scraped Surface Crystallizers (Swenson-Walker)
Mother xL
Feed,F Liquor,L hL
Magma tL
xF Cooling Water Crystals, C
hF
xC
tF
w,t2 w,t1 hC
tL
OMB: F=L+C
SB: FxF=LxL+CxC
xC =MW anhydrous crystal/MW hydrated

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Crystallizer Design
• Scraped Surface Crystallizers (Swenson-Walker)
Mother xL
Feed,F Magma
Liquor,L hL
xF t L xC
Cooling Water Crystals, C h
hF C

w,t1 tL
tF w,t2
EB: FhF+ wh1=LhL+ChC + wh2
EB: wh1 - wh2 = LhL+ChC - FhF Lc =Latent heat
EB: q = wCp(t2-t1) = LhL+ChC - FhF of Crystallization
(see Table 2-182
HB: q = wCp(t2-t1) = FCpF(tF-tL)+CLc HB-Ht of soln)

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The Latent heat of crystallization has a value which is

the negative of the heat of solution.

For Ex. CaCl2.6H2O, the latent heat of crystallization is

+4.11 kcal/gmol

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Crystallizer Design
• Vacuum Crystallizer
Vapor,V
tL OMB: F=L+C+V
P1 SB: FxF=LxL+CxC
T1
EB: FhF=LhL+ChC + VHV
Feed F
HV (BTU/lb)= H1 + 0.45 BPR

BPR = tL – T1
Mother
Liquor,L
Magma
Crystals, C

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