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Crystallization Notes 1 PDF
Crystallization Notes 1 PDF
Crystallization Notes 1 PDF
CRYSTALLIZATION
Compilation of Lectures and Solved Problems
CHEMICAL ENGINEERING SERIES 2
CRYSTALLIZATION
CRYSTALLIZATION
Refers to a solid-liquid separation process in which solid particles are formed within a homogenous phase.
It can occur as:
(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
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
Crystallization Process
WATER
SOLUTION
CRYSTALS
The concentrated
solution is cooled until
Solution is concentrated the concentration
by evaporating water becomes greater than
its solubility at that
temperature
(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
Magma
It is the two-phase mixture of mother liquor and crystals of all sizes, which occupies the crystallizer and is
withdrawn as product
CHEMICAL ENGINEERING SERIES 4
CRYSTALLIZATION
Classification of Crystallizer
(1) May be classified according to whether they are batch or continuous in operation
(2) May be classified according on the methods used to bring about supersaturation
(3) Can also be classified according on the method of suspending the growing product crystals
Expressions of Solubilities
Parts by mass of anhydrous materials per 100 parts by mass of total solvent
Mass percent of anhydrous materials or solute which ignores water of crystallization
CHEMICAL ENGINEERING SERIES 5
CRYSTALLIZATION
200
(1) TYPE I: Solubility increases with temperature
150
and there are no hydrates or water of
crystallization 100
50
0
0 20 40 60 80 100
Temperature, °C
250
150
0
0 20 40 60 80 100
Temperature, °C
Solubility of NaCl (CHE HB 8th edition)
250
Solubility, gram per 100 gram water
200
0
0 20 40 60 80 100
Temperature, °C
Solubility of Na2HPO4 (CHE HB 8th edition)
60
Solubility, gram per 100 gram water
50
40
(4) TYPE IV: Unusual Curve; Solubility increases Na2CO3·H2O
0
0 20 40 60 80 100
Temperature, °C
Solubility of Na2CO3 (CHE HB 8th edition)
SUPERSATURATION BY COOLING
Crystallizers that obtain precipitation by cooling a concentrated hot solution; applicable for substance that
have solubility curve that decreases with temperature; for normal solubility curve which are common for
most substances
CHEMICAL ENGINEERING SERIES 6
CRYSTALLIZATION
Pan Crystallizers
Batch operation; seldom used in modern practice, except in small scale operations, because they are
wasteful of floor space and of labor; usually give a low quality product
Consist of an agitated tank; usually cone-bottomed, containing cooling coils. It is convenient in small scale
or batch operations because of their low capital costs, simplicity of operation and flexibility
A continuous crystallizer consist of an open round bottomed-trough, 24-in wide by 10 ft long, and containing
a long ribbon mixer that turns at about 7 rpm.
CALCULATIONS:
L
F XL
XF hL where:
hf tL = mass of the feed solution
tF = mass of the mother liquor, usually saturated solution
W = mass of the crystals
W
t1 C
t2 = mass of the cooling water
XC
= mass solute (salt) in the feed solution per mass of feed solution
hC
tC = mass of solute (salt) in the mother liquor per mass of mother liquor
= mass of solute (salt) in the srystals per mass of crystals
= enthalpy of the feed solution
Over-all material Balance:
= enthalpy of the mother liquor
= enthalpy of the crystals
= heat absorbed by the cooling water
Solute Balance:
= heat loss by the crystals
= specific heat of the feed solution
Enthalpy Balance: = specific heat of cooling water
= heat of crystallization
= over-all heat transfer coefficient
Heat Balance: = heat transfer area
= temperature of the feed solution
( ) = temperature of the mother liquor
( ) = inlet temperature of cooling water
= outlet temperature of cooling water
Heat Transfer Equation
( ) ( )
[ ]
CHEMICAL ENGINEERING SERIES 7
CRYSTALLIZATION
Crystallizers that obtain precipitation by evaporating a solution; applicable for the substance whose solubility
curve is flat that yield of solids by cooling is negligible; acceptable to any substance whose solubility curve is
not to steep
Salting Evaporator
The most common of the evaporating crystallizers; in older form, the crystallizer consisted of an evaporator
below which were settling chambers into which the salt settled
Oslo Crystallizer
Modern form of evaporating crystallizer; this unit is particularly well adopted to the production of large-sized
uniform crystals that are usually rounded; it consists essentially of a forced circulation evaporator with an
external heater containing a combination of salt filter and particle size classifier on the bottom of the
evaporator body
CALCULATIONS:
V where:
hV L = mass of the feed solution
F XL = mass of the mother liquor, usually saturated solution
XF hL = mass of the crystals
hf tL = mass of the cooling water
tF = mass of the evaporated solvent
W = mass solute (salt) in the feed solution per mass of feed
W
t1 C solution
t2
XC
= mass of solute (salt) in the mother liquor per mass of
hC
mother liquor
tC
= mass of solute (salt) in the srystals per mass of crystals
Over-all material Balance: = enthalpy of the feed solution
= enthalpy of the mother liquor
= enthalpy of the crystals
Solute Balance:
= enthalpy of the vapor
= heat absorbed by the cooling water
= heat loss by the crystals
Solvent Balance:
( ) ( ) ( ) = specific heat of the feed solution
= specific heat of cooling water
Enthalpy Balance: = heat of crystallization
= latent heat of vaporization
= over-all heat transfer coefficient
Heat Balance: = heat transfer area
= temperature of the feed solution
( ) = temperature of the mother liquor
( ) = inlet temperature of cooling water
= outlet temperature of cooling water
CHEMICAL ENGINEERING SERIES 8
CRYSTALLIZATION
V where:
hV
= mass of the feed solution
= mass of the mother liquor, usually saturated solution
F = mass of the crystals
XF = mass of the cooling water
hf
= mass of the evaporated solvent
L = mass solute (salt) in the feed solution per mass of feed
XL
M hL solution
= mass of solute (salt) in the mother liquor per mass of
C
XC
mother liquor
hC = mass of solute (salt) in the srystals per mass of crystals
= enthalpy of the feed solution
Over-all material Balance: = enthalpy of the mother liquor
= enthalpy of the crystals
= enthalpy of the vapor
Solute Balance: = heat of crystallization
= temperature of the feed solution
= temperature of the mother liquor
Solvent Balance: = inlet temperature of cooling water
( ) ( ) ( ) = outlet temperature of cooling water
Enthalpy Balance:
CRYSTALLIZATION BY SEEDING
ΔL Law of Crystals
States that if all crystals in magma grow in a supersaturation field and at the same temperature and if
all crystal grow from birth at a rate governed by the supersaturation, then all crystals are not only
invariant but also have the same growth rate that is independent of size
The relation between seed and product particle sizes may be written as
Where:
= characteristic particle dimension of the product
= characteristic particle dimension of the seed
= change in size of crystals and is constant throughout the range of size present
CHEMICAL ENGINEERING SERIES 9
CRYSTALLIZATION
Since the rate of linear crystal growth is independent of crystal size, the seed and product masses may
be related for
( )
( )
( )
[ ]
( )
( )
All the crystals in the seed have been assumed to be of the same shape, and the shape has been assumed
to be unchanged by the growth process. Through assumption is reasonably closed to the actual conditions
in most cases. For differential parts of the crystal masses, each consisting of crystals of identical
dimensions:
∫ ∫ ( )
∫ ( )
CHEMICAL ENGINEERING SERIES 10
CRYSTALLIZATION
( )( ) ( )( ) ( )( )
Substitute in
( )
Magma composition:
% Recovery:
( )( )
( )( )
CHEMICAL ENGINEERING SERIES 11
CRYSTALLIZATION
( )( ) ( ) ( )( )
THE PROBLEM CAN BE SOLVED BY TRIAL AND ERROR SINCE TEMPERATURE OF THE
SOLUTION AFTER CRYSTALLIZATION IS UNKNOWN AND ENTHALPIES ARE DEPENDENT
ON TEMPERATURE
Substitute to equation
Substitute to equation
th
From figure 27-4 (Unit Operations by McCabe and Smith, 7 edition)
[( )( )]
( )( ) ( )( ) ( )( ) ( )( )
Since % error is less than 5%, assumed value can be considered correct.
Product temperature
Operating Pressure
From steam table for vapor temperature of 50°F
PROBLEM # 03 :
SOLUTION:
Assume that the liquor entering the crystallizer is a saturated solution at 0°C
PROBLEM # 04 :
1,200 lb of barium nitrate are dissolved in
V
sufficient water to form a saturated solution at
90°C. Assuming that 5% of the weight of the
C
original solution is lost through evaporation, F
T = 20 C
1,200 lb BaNO3
calculate the crop of the crystals obtained CRYSTALLIZER
when cooled to 20°C. solubility data of barium T = 90 C
nitrate at 90°C = 30.6 lb/100 lb water; at 20°C = L
9.2 lb/100 lb water T = 20 C
( ) ( )
( )
( )
( )
( )
( ) ( )
( )
( )
( )( ) ( )( )
Substitute in
( )
[( )( )]
CHEMICAL ENGINEERING SERIES 15
CRYSTALLIZATION
PROBLEM # 05:
SOLUTION:
( )( ) ( )( ) ( )( )
Equate and
( )
CHEMICAL ENGINEERING SERIES 16
CRYSTALLIZATION
[( )( )( ) ]
[( )( )]
( )
( )( )
( ) ( )
( ) ( )
( )( )
CHEMICAL ENGINEERING SERIES 17
CRYSTALLIZATION
PROBLEM # 06:
Crystals of Na2CO3·10H2O are dropped into a saturated solution of Na2CO3 in water at 100°C.
What percent of the Na2CO3 in the Na2CO3·H2O is recovered in the precipitated solid? The
precipitated solid is Na2CO3·H2O. Data at 100°C: the saturated solution is 31.2% Na 2CO3;
molecular weight of Na2CO3 is 106
SOLUTION:
PROBLEM # 07:
per hour?
SOLUTION:
( )
th
From table 27-3 (Unit Operations by McCabe and Smith, 7 edition), at 50°F
( )( ) ( )( ) ( )( )
Equate and
CHEMICAL ENGINEERING SERIES 19
CRYSTALLIZATION
PROBLEM # 08:
F L
The solubility of sodium bicarbonate in water tF = 60 F tL = 20 F
is 9.6 g per 100 g water at 20°C and 16.4 g 16.4 g
NaHCO3 /100 g
per 100 g water at 60°C. If a saturated H2O
COOLING CRYSTALLIZER
solution of NaHCO3 at 60°C is cooled to 20°C,
what is the percentage of the dissolved salt C,
that crystallizes out? 9.6 g NaHCO3
per 100 g H2O
tC = 20 F
SOLUTION:
( )
( )
( )( ) ( )( ) ( )( )
Equate and
( )( )
V
L
F tL = 20 C
tF = 20 C
8.4% Na2SO4
CRYSTALLIZER
C,
tC = 20 C
CHEMICAL ENGINEERING SERIES 20
CRYSTALLIZATION
PROBLEM # 09:
Glauber’s salt is made by crystallization from a water solution at 20°C. The aqueous solution at
20°C contains 8.4% sodium sulfate. How many grams of water must be evaporated from a liter of
such solution whose specific gravity is 1.077 so that when the residue solution after evaporation
is cooled to 20°C, there will be crystallized out 80% of the original sodium sulfate as Glauber’s
salt. The solubility of sodium sulfate in equilibrium with the decahydrate is 19.4 g Na2SO4 per 100
g H2O.
SOLUTION:
Basis: 1 L feed
( )( )
( )( )
Substitute to equation
( )
( )( )
Substitute to equation
CHEMICAL ENGINEERING SERIES 21
CRYSTALLIZATION
PROBLEM # 10:
A hot solution of Ba(NO3)2 from an evaporator
contains 30.6 kg Ba(NO3)2/100 kg H2O and
goes to a crystallizer where the solution is
cooled and Ba(NO3)2 crystallizes. On cooling, V
10% of the original water present evaporates.
For a feed solution of 100 kg total, calculate L
F
the following: 30.6 kg Ba(NO3)2/100 kg H2O
CRYSTALLIZER
a) The yield of crystals if the solution is
cooled to 290K, where the solubility is 8.6
C
kg Ba(NO3)2/100 kg total water
b) The yield if cooled instead to 283K, where
the solubility is 7 kg Ba(NO 3)2/100 kg total
water
SOLUTION:
( ) ( )
( )
( )( ) ( )( ) ( )( )
Equate and
CHEMICAL ENGINEERING SERIES 22
CRYSTALLIZATION
( ) ( )
( )
( )( ) ( )( ) ( )( )
Equate and
CHEMICAL ENGINEERING SERIES 23
CRYSTALLIZATION
PROBLEM # 11:
A batch of 1,000 kg of KCl is dissolved in
sufficient water to make a saturated solution at
363 K, where the solubility is 35 wt % KCl in
V
water. The solution is cooled to 293 K, at
L
which temperature its solubility is 25.4 wt %. F
293K
1,000 kg KCl
a) What are the weight of water required for 363K
CRYSTALLIZER
the solution and the weight of KCl crystals
obtained?
C
b) What is the weight of crystals obtained if 293K
5% of the original water evaporates on
cooling?
SOLUTION:
( )( ) ( )( )
Equate and
( )( )
CHEMICAL ENGINEERING SERIES 24
CRYSTALLIZATION
( )
( )( ) ( )( )
Equate and
CHEMICAL ENGINEERING SERIES 25
CRYSTALLIZATION
PROBLEM # 12:
The solubility of sodium sulfate is 40 parts
Na2SO4 per 100 parts of water at 30°C, and
13.5 parts at 15°C. The latent heat of
crystallization (liberated when crystals form) is
L
18,000 g-cal per gmol Na2SO4. Glauber’s salt tL = 15 C
F
(Na2SO4·10H2O) is to be made in a Swenson- tF = 30 C
SWENSON-WALKER
CRYSTALLIZER
Walker crystallizer by cooling a solution,
saturated at 30°C, to 15°C. Cooling water
C, 1 ton/h
enters at 10°C and leaves at 20°C. The over- W
t2 = 20 C Na2SO4·10H2O
t1 = 10 C
all heat transfer coefficient in the crystallizer is tC = 15 C
2
25 BTU/h·ft ·°F and each foot of crystallizer
has 3 sq ft of cooling surface. How many 10-ft
units of crystallizer will be required to produce
1 ton/h of Glauber’s Salt
SOLUTION:
( )
( )
( )
Equate and
CHEMICAL ENGINEERING SERIES 26
CRYSTALLIZATION
th
From Table 2-194 (CHE HB 8 edition)
[( )( ) ( )( )]
[( )( )( ) ]
[( )( )]
( ) ( )
( ) ( )
( )( )
CHEMICAL ENGINEERING SERIES 27
CRYSTALLIZATION
PROBLEM # 13:
A continuous adiabatic vacuum crystallizer is
to be used for the production of MgSO4·7H2O
V
crystals from 20,000 lb/h of solution containing
0.300 weight fraction MgSO4. The solution
enters the crystallizer at 160°F. The C = 6,000 lb/h
F, 20,000 lb/h
crystallizer is to be operated so that the xF = 0.3000 ADIABATIC VACUUM
MgSO4·7H2O
mixture of mother liquor and crystals leaving tF = 160 F CRYSTALLIZER
the crystallizer contains 6,000 lb/h of
MgSO4·7H2O crystals. The estimated boiling L
point elevation of the solution in the BPE = 10 F
crystallizer is 10°F. How many pounds of
water are vaporized per hour?
SOLUTION:
( )( ) ( )( ) ( )( )
THE PROBLEM CAN BE SOLVED BY TRIAL AND ERROR SINCE TEMPERATURE OF THE
SOLUTION AFTER CRYSTALLIZATION IS UNKNOWN AND ENTHALPIES ARE DEPENDENT
ON TEMPERATURE
b. Compute for hV
c. Using the enthalpy balance equation, compute for “V” using the value of “L” from step
3
6. Compare values of “V” from step 4 with that from step 5-c
7. If not the same (or approximately the same), conduct another trial and error calculations
Substitute to equation
Substitute to equation
th
From figure 27-4 (Unit Operations by McCabe and Smith, 7 edition)
[( )( )]
( )( ) ( )( ) ( )( ) ( )( )
PROBLEM # 14:
Crystals of CaCl2·6H2O are to be obtained
from a solution of 35 weight % CaCl2, 10
V
weight % inert soluble impurity, and 55
weight % water in an Oslo crystallizer. The
solution is fed to the crystallizer at 100°F M (magma)
F C
and receives 250 BTU/lb of feed from the CaCl2 = 35% Inert
OSLO CRYSTALLIZER
external heater. Products are withdrawn Inert = 10% L
H2O = 55% tF = 40 F
from the crystallizer at 40°F. tF = 100 F
a) What are the products from the
crystallizer? L
CENTRIFUGE
b) The magma is centrifuged to a moisture
content of 0.1 lb of liquid per lb of
CaCl2·6H2O crystals and then dried in a
conveyor drier. What is the purity of the
final dried crystalline product? C’’ DRYER
CaCl2·6H2O
nd
Source: Principles of Unit Operations 2
edition (Foust, et al)
SOLUTION:
where T is in K
At 100°F (310.93 K)
At 40°F (277.59 K)
̅
CHEMICAL ENGINEERING SERIES 30
CRYSTALLIZATION
th
From table 2-224 (CHE HB 8 edition), heat of solution of CaCl2·6H2O = -4,100 cal/mol;
in the absence of data on heat of crystallization, heat of solution can be used instead but
of opposite sign
( )( ) ( )( )( ) ( )( ) ( )( )
Substitute in
( )
( )
( )
( )( ) ( )( ) ( )( )
Equate and
( )
( )
CHEMICAL ENGINEERING SERIES 31
CRYSTALLIZATION
( )
lb %
CaCl2·6H2O 0.0056 4.89
H2O 0.0090 7.85
inerts 0.1000 87.26
0.1146 100.00
PROBLEM # 15:
SOLUTION:
( )
( )
( )( ) ( )( ) ( )( )
Equate and
CHEMICAL ENGINEERING SERIES 33
CRYSTALLIZATION
[( )( )( ) ] [( )( )]
[( )( )]
CHEMICAL ENGINEERING SERIES 34
CRYSTALLIZATION
PROBLEM # 16:
Sal soda (Na2CO3·10H2O) is to be made by dissolving soda ash in a mixture of mother liquor and
water to form a 30% solution by weight at 45°C and then cooling to 15°C. The wet crystals
removed from the mother liquor consist of 90% sal soda and 10% mother liquor by weight. The
mother liquor is to be dried on the crystals as additional sal soda. The remainder of the mother
liquor is to be returned to the dissolving tanks. At 15°C, the solubility of Na 2CO3 is 14.2 parts per
100 parts water.
The latent heat of crystallization of sal soda at 15°C is approximately 25,000 cal/mol. The
specific heat of the solution is 0.85 BTU/lb·°F. A production of 1 ton/h of dried crystals is desired.
Radiation losses and evaporation from the crystallizer are negligible.
a) What amounts of water and sal soda are to be added to the dissolver per hour?
b) How many units of crystallizer are needed?
c) What is to be the capacity of the refrigeration plant, in tons of refrigeration, if the cooling
water is to be cooled and recycled? One ton of refrigeration is equivalent to 12,000 BTU/h.
F (Soda Ash)
W (Water)
V
A B D
DISSOLVER CRYSTALLIZER FILTER DRYER
45C 15C
R (remainder
mother liquor)
C (Sal Soda)
SOLUTION:
( )( )
CHEMICAL ENGINEERING SERIES 35
CRYSTALLIZATION
Substitute to equation
( )( ) ( )( )
( )
( )( )
Substitute to equation
( )
( )( ) ( )( ) ( )( )
Equate and
( )
[( )( )( ) ] [( )( )]
( ) ( )
[( ) ( )]
( )( )
Refrigeration capacity:
CHEMICAL ENGINEERING SERIES 37
CRYSTALLIZATION
PROBLEM # 17:
One ton of Na2S2O3·5H2O is to be crystallized per hour by cooling a solution containing 56.5%
Na2S2O3 to 30°C in a Swenson-Walker crystallizer. Evaporation is negligible. The product is to
be sized closely to approximately 14 mesh. Seed crystals closely sized to 20 mesh are
introduced with the solution as it enters the crystallizer. How many tons of seed crystals and how
many tons of solutions are required per hour? At 30°C, solubility of Na 2S2O3 is 83 parts per 100
parts water
Source: Unit Operations (Brown, et al)
SOLUTION:
∫ ∫ ( )
th
From table 19-6 (CHE HB 8 edition)
( )
( )
∫ ∫ ( )
Equate and
( )
( )( ) ( )( ) ( )( )
Equate and
CHEMICAL ENGINEERING SERIES 38
CRYSTALLIZATION
PROBLEM # 18:
SOLUTION:
th
From figure 27-3 (Unit Operation 7 edition, McCabe and Smith) at 110°F
th
From figure 27-3 (Unit Operations 7 edition, McCabe and Smith) at 40°F
( )( ) ( )( ) ( )( )
Equate and
∫ ∫ ( )
[ ]
th
From table 19-6 (CHE HB 8 edition)
( )
( )√
th
From table 19-6 (CHE HB 8 edition)
CHEMICAL ENGINEERING SERIES 39
CRYSTALLIZATION
PROBLEM # 19:
SOLUTION:
∫ ∫ ( )
∫ ( )
∫ ( )
∫ ( )
( )
1. Assume value of
2. Solve for ( ) for each size range, use the mean ̅ for each size range
3. Solve for
4. Get the total
5. If ∑ , then assumed is correct; if not, redo another trial
CHEMICAL ENGINEERING SERIES 40
CRYSTALLIZATION
TRIAL 1: Assume
̅ ( ) ( )
̅ ̅
( ̅ )
( )( ) ( )( ) ( )( )
CHEMICAL ENGINEERING SERIES 41
CRYSTALLIZATION
( )
th
From table 2-120 (CHE HB 8 edition)
50°C 43 lb/100 lb H2O
60°C 55 lb/100 lb H2O
Cooling Duty:
[( )( )( ) ] [( )( )]
CHEMICAL ENGINEERING SERIES 42
CRYSTALLIZATION
PROBLEM # 20:
How much CaCl2·6H2O must be dissolved in 100 kg of water at 20°C to form a saturated
solution? The solubility of CaCl2 at 20°C is 6.7 gmol anhydrous salt (CaCl2) per kg of water.
SOLUTION:
Since there should only be total of 100 kg water in the solution, the amount of free water (net
of water of hydration)
( )
6. Amount of CaCl2·6H2O required for every 100 kg free water (net of water of hydration)