Crystallizat ION: Chemical Engineering Series

CHEMICAL ENGINEERING SERIES
CRYSTALLIZAT
ION
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) formation of solid particles in a vapor
(2) formation of solid particles from a liquid melt
(3) formation of solid crystals from a solution
The process usually involves two steps:
(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
parts solute
100 parts solvent
S=
parts solute at equilibrium
100 parts solvent
Crystallization cannot occur without supersaturation.
supersaturation
There are 5 basic methods of generating
(1) EVAPORATION by evaporating a portion of the solvent

(2) COOLING by cooling a solution through indirect heat exchange
(3) VACUUM COOLING by flashing of feed solution adiabatically to a lower temperature and inducing
crystallization by simultaneous cooling and evaporation of the solvent
(4) REACTION by chemical reaction with a third substance
(5) SALTING by the addition of a third component to change the solubility relationship
Mechanism of Crystallization Process

CRYSTALLIZATION
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
(2) CRYSTAL GROWTH a layer-by-layer process
a. Solute diffusion to the suspension-crystal interface
b. Surface reaction for absorbing solute into the crystal lattice
Crystallization Process
Important Factors in a Crystallization Process

(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
Types of Crystal Geometry

CRYSTALLIZATION
(1)
(2)
(3)
(4)
CUBIC SYSTEM 3 equal axes at right angles to each other

TETRAGONAL 3 axes at right angles to each other, one axis longer than the other 2
ORTHOROMBIC 3 axes at right angles to each other, all of different lengths
HEXAGONAL 3 equal axes in one plane at 60 to each other, and a fourth axis at a right angle to this
plane and not necessarily at the same length
(5) MONOCLINIC 3 unequal axes, two at a right angles in a plane, and a third at some angle to this
plane
(6) TRICLINIC 3 unequal axes at unequal angles to each other and not 30, 60, or 90
(7) TRIGONAL 3 unequal and equally inclined axes
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
Equilibrium Data (Solubilities)
Either tables or curves

Represent equilibrium conditions
Plotted data of solubilities versus temperatures
In general, solubility is dependent mainly on temperature although sometimes on size of materials and
pressure
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
Types of Solubility Curve

CRYSTALLIZATION
(1) TYPE I: Solubility increases with temperature

and there are no hydrates or water of
crystallization
(2) TYPE II: Solubility increases with temperature

but curve is marked with extreme flatness
(3) TYPE III: Solubility increasing fairly rapid with

temperature but is characterized by breaks
and indicates different hydrates or water of
crystallization
(4) TYPE IV: Unusual Curve; Solubility increases

at a certain transition point while the solubility of
the hydrate decreases as temperature
increases
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
Pan Crystallizers

CRYSTALLIZATION
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
Agitated batch Crystallizers
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
Swenson Walker Crystallizer
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:
where:
F = mass of the feed solution

L = mass of the mother liquor, usually saturated solution
C = mass of the crystals
W
Over-all material Balance:
F=L+ C
= mass of the cooling water
X F = mass solute (salt) in the feed solution per mass of feed

solution
X L = mass of solute (salt) in the mother liquor per mass of mother
Solute Balance:
X F F=X L L+ X C C
liquor
X C = mass of solute (salt) in the srystals per mass of crystals

Enthalpy Balance:
h f F=hL L+h c C+ q
h F = enthalpy of the feed solution

h L = enthalpy of the mother liquor
Heat Balance:
hC = enthalpy of the crystals
q water=qcrystals
q crystals=F C pF ( t F t L ) +C H C
q water=W C p H O ( t 2t 1)
2
Heat Transfer Equation
q water = heat absorbed by the cooling water

q crystals = heat loss by the crystals
C pF = specific heat of the feed solution
Cp H
= specific heat of cooling water

CRYSTALLIZATION
q=UA T lm
q=UA
H C = heat of crystallization
( t F t2 ) ( t L t1 )
ln
t F t 2
t Lt 1
= over-all heat transfer coefficient
= heat transfer area
t F = temperature of the feed solution

t L = temperature of the mother liquor
t 1 = inlet temperature of cooling water
t 2 = outlet temperature of cooling water
SUPERSATURATION BY EVAPORATION OF SOLVENT

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:
where:

W
= mass of the evaporated solvent

CRYSTALLIZATION
F=L+ C+V
X F = mass solute (salt) in the feed solution per mass of

feed solution
X L = mass of solute (salt) in the mother liquor per mass of
Solute Balance:
X F F=X L L+ X C C
mother liquor
X C = mass of solute (salt) in the srystals per mass of

crystals
Solvent Balance:
( 1 X F ) F=V + ( 1X L) L+( 1 X C ) C

Enthalpy Balance:
h f F=hV V + h L L+hc C +q

hV
Heat Balance:
= enthalpy of the vapor
q water=qcrystals
q water = heat absorbed by the cooling water
q crystals=F C pF ( t F t L ) +C H C V V
q crystals = heat loss by the crystals
C pF = specific heat of the feed solution
Cp H
= specific heat of cooling water
V
= latent heat of vaporization
= over-all heat transfer coefficient
= heat transfer area

SUPERSATURATION BY ADIABATIC EVAPORATION OF SOLVENT

CRYSTALLIZATION
where:

W
= mass of the evaporated solvent
X F = mass solute (salt) in the feed solution per mass of

F=L+ C+V
Solute Balance:
X F F=X L L+ X C C
feed solution
X L = mass of solute (salt) in the mother liquor per mass of

mother liquor
X C = mass of solute (salt) in the srystals per mass of

crystals
Solvent Balance:
( 1 X F ) F=V + ( 1X L) L+( 1 X C ) C
Enthalpy Balance:
h f F=hV V + h L L+ hc C

hV
= enthalpy of the vapor
CRYSTALLIZATION BY SEEDING
L 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

CRYSTALLIZATION
The relation between seed and product particle sizes may be written as
LP =LS + L
D P =DS + D
Where:
LP D P = characteristic particle dimension of the product

LS DS = characteristic particle dimension of the seed
L D = change in size of crystals and is constant throughout the range of size present
Since the rate of linear crystal growth is independent of crystal size, the seed and product masses may
be related for
W P=a D P3=a ( D S + D )3
W S =a D S3
W P=
WS
DS
( D S + D )
DS + D
DS
W P=W S
W P=W S
W P=W S
DS + [ D PD S ]
DS
(
( )
DP
DS
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:
WP
WS
d W P= 1+
0
D 3
dWS
DS

CRYSTALLIZATION
WS
W P=
0
D 3
1+
d WS
DS
C=W PW S
PROBLEM # 01:
A 20 weight % solution of Na2SO4 at
200F is pumped continuously to a
vacuum crystallizer from which the
magma is pumped at 60F. What is
the composition of this magma, and
what percentage of Na2SO4 in the
feed is recovered as Na2SO410H2O
crystals after this magma is
centrifuged?
SOLUTION:
Basis: 100 lb feed
From table 2-122 (CHE HB), solubility of Na2SO410H2O
T,C
g/100 g H2O
10
9.0
Consider over-all material balance:
F=C+ L
L=100C eqn 1
Consider solute balance:
X F F=X C C+ X L L
15
19.4
20
40.8

CRYSTALLIZATION
XC=
M Na SO
2
M Na SO 10 H O
2
lb Na2 SO 4
142
=0.4410
322
lb Na2 SO 4 10 H 2 O
At 60F, solubility is 21.7778 g per 100 g water
X L=
lb Na2 SO 4
21.7778
=0.1788
100+21.7778
lb liquor
Na SO
SO
(C )
(0.20 lblbfeed
) ( 100lb feed )=(0.1788 lblbNaliquorSO ) ( L )+(0.4410 lb NalbSONa 10
H O)
2
20=0.1788 L+0.4410 C eqn2

Substitute
1 in 2
20=0.1788 ( 100C ) + 0.4410C

C=8.0854 lb crystals
L=1008.0854
L=91.9146 lb
Magma composition:
C=
8.0854
x 100=8 .0854
100
L=
91.9146
x 100=91 .9146
100
% Recovery:
recovery =
XCC
x 100=
XF F
0.4410
recovery =17 . 83 ANSWER
PROBLEM # 02:
lb Na2 SO 4
( 8.0854 lb Na2 SO 4 10 H 2 O )
lb Na2 SO4 10 H 2 O
lb Na2 SO4
0.20
( 100 lb feed )
lb feed
x 100

CRYSTALLIZATION
A solution of 32.5% MgSO4 originally
at 150F is to be crystallized in a
vacuum adiabatic crystallizer to give
a product containing 4,000 lb/h of
MgSO47H2O crystals from 10,000
lb/h of feed. The solution boiling
point rise is estimated at 10F.
Determine the product temperature,
pressure and weight ratio of mother
liquor to crystalline product.
SOLUTION:
F=V + L+C
V =10,000L4,000
V =6,000L equation 1
Consider solute balance:
x F F=x C C + x L L
x C=
M Mg SO
M Mg SO 7 H
4
lb Mg SO 4
120.38
=0.4884
246.49
lb Mg SO 4 7 H 2 O
lb Mg SO
lb
= X ( L ) + (0.4884
4,000
(0.325 lblbMgfeedSO )(10,000 lb feed
)
(
h
lb Mg SO 7 H O )
h)
4
x L L=1,296.4 equation 2
Consider enthalpy balance:
THE PROBLEM CAN BE SOLVED BY TRIAL AND ERROR SINCE TEMPERATURE OF THE
SOLUTION AFTER CRYSTALLIZATION IS UNKNOWN AND ENTHALPIES ARE DEPENDENT
ON TEMPERATURE
1. Assume temperature of the solution
2. From figure 27-3 (Unit Operations by McCabe and Smoth 7 th edition), obtain mass fraction of
MgSO4 at the assumed temperature of the solution
3. Solve for L using equation
4. Solve for V using equation
5. Check if assumed temperature is correct by conducting enthalpy balance

a. Obtain values of hF, hC and hL from figure 27-4 (Unit Operations by McCabe and
Smith 7th edition) at the designated temperatures and concentrations

CRYSTALLIZATION
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
TRIAL 1: Assume temperature of the solution at 60F
From figure 27-3 (Unit Operations by McCabe and Smith 7 th edition)
x L =0.245
lb Mg SO 4
lb liquor
Substitute to equation
L=
1,296.4
=5,291.43 lb
0.245
V =6,0005,291.43=708.57 lb
From figure 27-4 (Unit Operations by McCabe and Smith, 7th edition)
h F at 150 F32.5 Mg SO 4 =10
BTU
lb
hC at 60 F48.84 Mg SO 4 =158
h L at 60 F24.5 Mg SO 4=50
BTU
lb
BTU
lb
Temperature of vapor is 60 10 = 50F
hV =H V +C P x BPE
From steam table at 50F,
[(
H V =1,083.3
hV =1,083.3
BTU
BTU
+ 0.45
( 10 F )
lb
lb F
hV =1,087.8
BTU
lb
BTU
lb
(10 )( 10,000 ) =( 1087.8 )( V ) + (50 ) ( 5,291.43 )+ (158 ) ( 4,000 )

V =732.28 lb

CRYSTALLIZATION
Since % error is less than 5%, assumed value can be considered correct.
Product temperature
T =60 F ANSWER
Operating Pressure
From steam table for vapor temperature of 50F
P=0 . 17803 psi ANSWER
Ratio of mother liquor to crystalline product
L 5,291.43
=
C
4,000
L
=1 .32 ANSWER
C
PROBLEM # 03 :
A plant produces 30,000 MT of anhydrous
sulfate annually by crystallizing sulfate brine at
0C, yields of 95% and 90% in the
crystallization and calcinations operations are
obtained respectively. How many metric tons
of liquor are fed to the crystallizer daily? Note:
300 working days per year
CHE BP January 1970
SOLUTION:
Assume that the liquor entering the crystallizer is a saturated solution at 0C
From table 2-120 (CHE HB), solubility at 0C:
5 g Na 2 SO 4 10 H 2 O
100 g H 2 O
mass Na 2 SO4 10 H 2 O=30,000
MT Na2 SO 4
1 MTmol Na2 SO 4 1 MTmol Na 2 SO 4 10 H 2 O 32
1
x
x
x
x
yr
0.95 142 MT Na2 SO 4
1 MTmol Na2 SO 4
M

CRYSTALLIZATION
mass Na2 SO4 10 H 2 O=71,608.60 MT x
mass Na2 SO 4 10 H 2 O=
F=
1 yr
300 days
238.6953 MT
day
238.6953 MT Na2 SO 4 10 H 2 O
105 MT feed
x
day
5 MT Na2 SO 4 10 H 2 O
F=5 , 012. 60
MT
ANSWER
day
PROBLEM # 04 :
1,200 lb of barium nitrate are dissolved in
sufficient water to form a saturated solution at
90C. Assuming that 5% of the weight of the
original solution is lost through evaporation,
calculate the crop of the crystals obtained when
cooled to 20C. solubility data of barium nitrate
at 90C = 30.6 lb/100 lb water; at 20C = 9.2
lb/100 lb water
CHE BP July 1968
SOLUTION:
x F =0.306
lb Ba ( NO 3 )2
lb Ba ( NO 3 )2
100lb water
x
=0.2343
lbwater
lb feed
( 100+30.6 ) lb feed

CRYSTALLIZATION
x F F=1,200 lb Ba ( NO 3 )2
F=1,200lb Ba ( N O3 )2 x
lb feed
0.2343 lb Ba ( N O3 ) 2
F=5,121.5686lb
x L =0.092
lb Ba ( NO3 )2
lb Ba ( NO 3 )2
100 lb water
x
=0.0842
lb water
lbliquor
( 100+ 9.2 ) lb liquor
Consider over-all material balance around the crystallizer
F=V + L+C
V =0.05 F
L=0.95 ( 5,121.5686 )C
L=4,865.4902C equation 1
Consider Ba(NO3)2 balance
x F F=x L L+ x C C
1,200=( 0.0842 ) ( L ) + ( 1.0 ) (C )
1,200=0.0842 L+C equation 2
Substitute
1 in 2
1,200=0.0842 ( 4,865.4902C ) +C
C=
1,200[ ( 0.0842 )( 4,865.4902 ) ]

0.9158
C=862 .9894 lb ANSWER

CRYSTALLIZATION
PROBLEM # 05:
A Swenson-Walker crystallizer is to be used to
produce 1 ton/h of copperas (FeSO 47H2O)
crystals. The saturated solution enters the
crystallizer at 120F. The slurry leaving the
crystallizer will be at 80F. Cooling water
enters the crystallizer jacket at 60F and
leaves at 70F. It may be assumed that the U
for the crystallizer is 35 BTU/hFft2. There
are 3.5 ft2 of cooling surface per ft of
crystallizer length.
a) Estimate the cooling water required
b) Determine the number of crystallizer
section to be used.
Data:
specific heat of solution = 0.7
BTU/lbF; heat of solution= 4400 cal/gmol
copperas; solubility at 120F = 140 parts
copperas/100 parts excess water; solubility at
80F = 74 parts copperas/100 parts excess
water
SOLUTION:
F=L+ C
L=F2,000 equation1
Consider copperas (FeSO47H2O) balance:
x F F=x C C + x L L
x C =1.0
xL=
74 lb Fe SO 4 7 H 2 O 100 lb H 2 O
lb Fe SO 4 7 H 2 O
x
=0.4253
100 lb H 2 O
174 lb liquor
lbliquor
xF =
140 lb Fe SO 4 7 H 2 O 100 lb H 2 O
lb Fe SO 4 7 H 2 O
x
=0.5833
100 lb H 2 O
240 lb feed
lb feed
( 0.5833 ) ( F )= (1.0 )( 2,000 ) + ( 0.4253 )( L )

L=1.3715 F4,702.5629 equation2
Equate
1 and 2
F2,000=1.3715 F4,702.5629

CRYSTALLIZATION
F=7,274.73
lb
h
L=5,274.73
lb
h
Consider heat balance:
q water=qcrystals
q crystals=F C pF ( t F t L ) +C H C
[ (
BTU
lb
BTU (
lb
cal
gmol
lb
q crystals= 7,274.73
0.70
12080 ) F + 2,000
4,400
x
x
h
lb F
h
gmol 277.85 g
cal
0.55556
g
[(
)(
q crystals=260,701.1615
](
BTU
h
2
260,701.1615
W=
BTU
h
(1.0 lbBTU F ) ( 7060) F
W =26,070.1162
W =52. 14
lb
1 ft 3
7.481 gal
1h
x
x
x
3
h 62.335 lb
60 min
ft
gal
ANSWER
min
q=UA T lm
T lm=
( t Ft2 ) ( t L t1 )
ln
T lm=
t F t 2
t L t 1
( 12070 )( 8060 )
12070
ln
8060
)]

CRYSTALLIZATION
T lm=32.7407 F
260,701.1615
A=
BTU
h
( 32.7407 F )
( 35 h BTU
ft F )
2
A=227.5029 ft 2
of units=227.5029 ft 2 x
1 ft lengt h 1 unit
x
10 ft
3.5 ft 2
of units=6 .5 7 units ANSWER
PROBLEM # 06:
Crystals of Na2CO310H2O are dropped into a saturated solution of Na 2CO3 in water at 100C.
What percent of the Na2CO3 in the Na2CO3H2O is recovered in the precipitated solid? The
precipitated solid is Na2CO3H2O. Data at 100C: the saturated solution is 31.2% Na 2CO3;
molecular weight of Na2CO3 is 106
SOLUTION:
Assume 100 g of Na2CO310H2O added into the saturated solution
wt Na2 CO 3 H 2 O=100 g Na 2 CO 3 10 H 2 O x
124 g Na 2 CO3 H 2 O
286 g Na2 CO3 10 H 2 O
wt Na2 CO 3 H 2 O=43.3566 g
wt Na2 CO 3=100 g Na2 CO3 10 H 2 O x
106 g Na 2 CO3
286 g Na 2 CO 3 10 H 2 O

CRYSTALLIZATION
wt Na2 CO 3=37.0629 g
wt H 2 O=100 g Na2 CO 3 10 H 2 O x
180 g H 2 O
286 g Na2 CO3 10 H 2 O
wt H 2 O=62.9371 g
Na 2 CO 3 satd solnat 100 C=
X
x 100=31.2
X +62.9371
X =28.5412 g
wt Na2 CO 3 precipitated =37.062928.5412=8.5217 g
wt Na2 CO 3 H 2 O precipitated=8.5217 g Na 2 CO 3 x
wt Na2 CO 3 H 2 O precipitated=9.9688 g
Na 2 CO 3 H 2 O precipitated=
9.9688
x 100
43.3566
Na 2 CO 3 H 2 O precipitated=22. 99 ANSWER
PROBLEM # 07:
A solution of MgSO4 at 220F containing 43 g
MgSO4 per 100 g H2O is fed into a cooling
crystallizer operating at 50F. If the solution
leaving the crystallizer is saturated, what is the
124 g Na 2 CO 3 H 2 O
106 g Na 2 CO 3

CRYSTALLIZATION
rate at which the solution must be fed to the
crystallizer to produce one ton of MgSO 47H2O
per hour?
SOLUTION:
F=L+ C
L=F1 equation1
Consider MgSO4 balance
x F F=x L L+ x C C
xF =
43 ton MgSO4
100 ton H 2 O
ton Mg SO 4
x
=0.3007
100 ton H 2 O ( 100+43 ) ton feed
ton feed
x C=
120.38 ton MgSO 4

ton MgSO 4
=0.4884
246.49ton MgSO 4 7 H 2 O
ton MgSO4 7 H 2 O
From table 27-3 (Unit Operations by McCabe and Smith, 7th edition), at 50F
x L =0.23
ton MgSO4
tonliquor
( 0.3007 ) ( F ) =( 0.23 ) ( L ) + ( 0.4884 ) (1 )

L=1.3074 F2.1235 equation2
Equate
1 and 2
F1=1.3074 F2.1235
F=3 .65
ton
ANSWER
h

CRYSTALLIZATION
PROBLEM # 08:
The solubility of sodium bicarbonate in water
is 9.6 g per 100 g water at 20C and 16.4 g
per 100 g water at 60C. If a saturated
solution of NaHCO3 at 60C is cooled to 20C,
what is the percentage of the dissolved salt
that crystallizes out?
SOLUTION:
Basis: 100 kg feed
F=L+ C
L=100C equation1
Consider NaHCO3 balance
x F F=x L L+ x C C
xF =
16.4 kg NaHCO3
100 kg H 2 O
kg NaH CO 3
x
=0.1409
100 kg H 2 O
(100+ 16.4 ) kg feed
kg feed
x C =1.0
xL=
9.6 kg NaHCO 3
100 kg H 2 O
kg NaH CO 3
x
=0.0876
100 kg H 2 O
( 100+9.6 ) kg liquor
kg liquor
( 0.1409 ) ( 100 )=( 0.0876 )( L ) + ( C ) ( 1 )

L=160.844711.4155 C equation 2
Equate
1 and 2
100C=160.844711.4155C
C=5.8417 kg

CRYSTALLIZATION
NaHCO 3 crystallized=
C
x 100
xF F
NaHCO 3 crystallized=
5.8417 kg
x 100
( 0.1409 ) ( 100 kg )
NaHCO 3 crystallized=41. 46 ANSWER
PROBLEM # 09:
Glaubers salt is made by crystallization from a water solution at 20C. The aqueous solution at
20C 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 20C, there will be crystallized out 80% of the original sodium sulfate as Glaubers
salt. The solubility of sodium sulfate in equilibrium with the decahydrate is 19.4 g Na 2SO4 per 100
g H2O.
SOLUTION:
Basis: 1 L feed
F=1 L x
1.077 kg
=1.077 kg
L
F=V + L+C
L=1.077V C equation 1
x C C=0.80 x F F

CRYSTALLIZATION
x F F=( 1.077 kg feed )
( 8.4100kgkgNafeedSO )=0.0905 kg Na SO
2
x C C=( 0.80 ) ( 0.0905 kg Na2 SO 4 )=0.0724 kg Na2 SO 4

x C=
M Na SO
2
M Na SO 10 H
2
C=
kg Na 2 SO 4
142
=0.4410
322
kg Na2 SO 4 10 H 2 O
0.0724 kg Na2 SO 4
=0.1642 kg
kg Na2 SO 4
0.4410
kg Na2 SO 4 10 H 2 O
L=1.077V 0.1642
L=0.9128V equation 2
Consider Na2SO4 balance
x F F=x L L+ x C C
xL=
19.4 kg Na 2 SO 4
100 kg H 2 O
kg Na2 SO 4
x
=0.1625
100 kg H 2 O
( 100+19.4 ) kg liquor
kg liquor
0.0905= ( 0.1625 )( L ) +0.0724

L=0.1114 kg
0.1114=0.9128V
V =0.8014 kg
V =801 . 4 g ANSWER
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,
10% of the original water present evaporates.
For a feed solution of 100 kg total, calculate

CRYSTALLIZATION
the following:
a) The yield of crystals if the solution is
cooled to 290K, where the solubility is 8.6
kg Ba(NO3)2/100 kg total water
b) The yield if cooled instead to 283K, where
the solubility is 7 kg Ba(NO3)2/100 kg total
water
Source:
Transport Processes and Unit
Operations (Geankoplis)
SOLUTION:
a) If solution is cooled to 290K
F=V + L+C
L=100V C
L=100V C
If water evaporated is 10% of the original water present
V =0.10 ( 1x F ) F
xF=
30.6 kg Ba ( NO 3) 2
100 kg H 2 O
100 kg H 2 O
( 100+30.6 ) kg feed
=0.2343
kg Ba ( NO 3) 2
kg feed
V =0.10 ( 10.2343 )( 100 kg )

V =7.657 kg
L=1007.657C
L=92.343C equation 1
x F F=x L L+ x C C
xL=
8.6 kg Ba ( NO 3 )2
kg Ba ( NO 3 )2
100 kg H 2 O
x
=0.0792
100 kg H 2 O
kg liquor
( 100+8.6 ) kg liquor
x C =1.0
( 0.2343 ) ( 100 )=( 0.0792 ) ( L )+ (1.0 )( C )

L=295.833312.6263C equation 2

CRYSTALLIZATION
Equate
1 and 2
92.343C=295.833312.6263 C
C=17 .5026 kg ANSWER
b) If solution is cooled to 283 K

F=V + L+C
L=100V C
L=100V C
If water evaporated is 10% of the original water present
V =0.10 ( 1x F ) F
xF =
30.6 kg Ba ( NO 3) 2
kg Ba ( NO 3) 2
100 kg H 2 O
x
=0.2343
100 kg H 2 O
kg feed
( 100+30.6 ) kg feed
V =0.10 ( 10.2343 )( 100 kg )

V =7.657 kg
L=1007.657C
L=92.343C equation 1
x F F=x L L+ x C C
xL=
7.0 kg Ba ( NO3 ) 2
100 kg H 2 O
100 kg H 2 O
(100+ 7 ) kg liquor
x C =1.0
( 0.2343 ) ( 100 )=( 0.0654 )( L ) + ( 1.0 ) ( C )

L=358.256915.2905C equation 2
Equate
1 and 2
92.343C=358.256915.2905 C
=0.0654
kg Ba ( NO 3 )2
kg liquor

CRYSTALLIZATION
C=18 .6077 kg ANSWER
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
water. The solution is cooled to 293 K, at
which temperature its solubility is 25.4 wt %.
a) What are the weight of water required for
the solution and the weight of KCl crystals
obtained?
b) What is the weight of crystals obtained if
5% of the original water evaporates on
cooling?
Source:
Transport Processes and Unit
Operations (Geankoplis)
SOLUTION:
c) Assume crystallization by cooling (without evaporation)
F=L+ C

CRYSTALLIZATION
F=1,000 kg KCl x
100 kg soln
=2,857.14 kg feed
35 kg KCl
Consider KCl balance
x F F=x L L+ x C C
x L =0.254
kg KCl
kg liquor
x C =1.0
1,000=( 0.254 ) ( L ) + ( 1.0 )( C )
L=3,9373.937 C equation 2
Equate
1 and 2
2,857.14C=3,9373.937 C
C=367 . 67 kg ANSWER
H 2 Ofeed=100 KCl=10035=65
H 2 Ofeed=
wt H 2 O
x 100
wt feed
wt H 2 O=( 2,857.14 kg feed )
65 kg H O
( 100
kg feed )
wt H 2 O=1 ,857 . 14 kg ANSWER
d) Crystallization with evaporation

F=V + L+C
V =0.05 ( 1,857.14 kg )
V =92.8571kg

CRYSTALLIZATION
L=2,857.1492.8571C
L=2,764.2829C equation3
Consider KCl balance
x F F=x L L+ x C C
x L =0.254
x C =1.0
1,000=( 0.254 ) ( L ) + ( 1.0 )( C )
L=3,9373.937 C equation 4
Equate
3 and 4
2,764.2829C=3,9373.937 C
C=399 .29 kg ANSWER

CRYSTALLIZATION
PROBLEM # 12:
The solubility of sodium sulfate is 40 parts
Na2SO4 per 100 parts of water at 30C, and
13.5 parts at 15C.
The latent heat of
crystallization (liberated when crystals form) is
18,000 g-cal per gmol Na2SO4. Glaubers salt
(Na2SO410H2O) is to be made in a SwensonWalker crystallizer by cooling a solution,
saturated at 30C, to 15C. Cooling water
enters at 10C and leaves at 20C. The overall heat transfer coefficient in the crystallizer is
25 BTU/hft2F 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 Glaubers Salt
Source: Unit Operations (Brown)
SOLUTION:
F=L+ C
L=F1 equation1
Consider Na2SO4 balance
x F F=x L L+ x C C
xF =
40 ton Na 2 SO 4
100 ton H 2 O
ton Na 2 SO 4
x
=0.2857
100ton H 2 O ( 100+ 40 ) tonfeed
ton feed
xL=
13.5 ton Na2 SO 4

100 ton H 2 O
ton Na2 SO 4
x
=0.1189
100 ton H 2 O
( 100+13.5 ) ton liquor
tonliquor
x C=
142 ton Na2 SO 4

ton Na2 SO 4
=0.4410
322ton Na 2 SO 4 10 H 2 O
ton Na 2 SO4 10 H 2 O
0.2857 F=0.1189 L+0.4410 ( 1.0 )

L=2.4029 F3.709 equation 2
Equate
1 and 2
F1=2.4029 F3.709
F=1.931
ton
h

CRYSTALLIZATION
q crystal=F C P ( t Ft C ) +C H C
C P=
( m C P )Na SO + ( m C P ) H O
2
From Table 2-194 (CHE HB 8th edition)
C PNa
C P=
SO4
=32.8
cal
BTU
=0.231
C mol
lb F
[ ( 0.2857 ) ( 0.231 ) + ( 0.7143 ) ( 1.000 ) ] =0.7803
[(
q crystal= 1.931
)(
BTU
h
q=UA T lm
( t Ft2 ) ( t L t1 )
ln
t F t 2
t L t 1
t F =30 C=86 F
t L =15 C=59 F
t 1 =10 C=50 F
t 2 =20 C=68 F
T lm=
] [(
ton 2,000 lb
BTU
1.8 F
ton 2,000lb lbmol 454 gm
x
0.7803
( 3015 ) C x
+ 1
x
x
x
h
ton
lb F
C
h
ton
322 lb
lbmo
q crystal=282,656.8961
T lm=
BTU
lb F
( 8668 )( 5950 )
=12.9842 F
8668
ln
5950

CRYSTALLIZATION
262,656.8961
A=
BTU
h
( 12.9842 F )
( 25 h BTU
ft F )
2
A=870.7718 ft 2
1 ft lengt h
1unit
x
2
10 ft lengt h
3 ft
of units=29 . 03 30 units ANSWER
PROBLEM # 13:
A continuous adiabatic vacuum crystallizer is
to be used for the production of MgSO47H2O
crystals from 20,000 lb/h of solution containing
0.300 weight fraction MgSO4. The solution
enters the crystallizer at 160F.
The
crystallizer is to be operated so that the
mixture of mother liquor and crystals leaving
the crystallizer contains 6,000 lb/h of
MgSO47H2O crystals. The estimated boiling
point elevation of the solution in the
crystallizer is 10F. How many pounds of
water are vaporized per hour?
Source: Unit Operations (Brown)
SOLUTION:
F=V + L+C

CRYSTALLIZATION
L=20,0006,000V
L=14,000V equation 1
x F F=x L L+ x C C
x F =0.3000
x C=
lb Mg SO 4
lb feed
120 lb Mg SO 4
lb Mg SO 4
=0.4878
246lb Mg SO 4 7 H 2 O
lb Mg SO 4 7 H 2 O
( 0.30 ) ( 20,000 )=( x L ) ( L )+ ( 0.4878 ) ( 6,000 )

L=
3,073.2
equation2
xL
Consider enthalpy balance:
THE PROBLEM CAN BE SOLVED BY TRIAL AND ERROR SINCE TEMPERATURE OF THE
SOLUTION AFTER CRYSTALLIZATION IS UNKNOWN AND ENTHALPIES ARE DEPENDENT
ON TEMPERATURE
1. Assume temperature of the solution
2. From figure 27-3 (Unit Operations by McCabe and Smoth 7 th edition), obtain mass fraction of
MgSO4 at the assumed temperature of the solution
3. Solve for L using equation
4. Solve for V using equation
5. Check if assumed temperature is correct by conducting enthalpy balance

a. Obtain values of hF, hC and hL from figure 27-4 (Unit Operations by McCabe and
Smith 7th edition) at the designated temperatures and concentrations
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
TRIAL 1: Assume temperature of the solution at 60F
From figure 27-3 (Unit Operations by McCabe and Smith 7 th edition)
x L =0.245
lb Mg SO 4
lb liquor

CRYSTALLIZATION
L=
3,073.2
=12,543.67lb
0.245
V =14,00012,543.67=1,456.33 lb
From figure 27-4 (Unit Operations by McCabe and Smith, 7th edition)
h F at 160 F30 Mg SO 4=5
BTU
lb
hC at 60 F48.78 Mg SO 4 =158
h L at 60 F24.5 Mg SO 4=50
BTU
lb
BTU
lb
Temperature of vapor is 60 10 = 50F
hV =H V +C P x BPE
From steam table at 50F,
[(
H V =1,083.3
hV =1,083.3
BTU
BTU
+ 0.45
( 10 F )
lb
lb F
hV =1,087.8
BTU
lb
BTU
lb
( 5 ) ( 20,000 )=( 1087.8 ) ( V )+ (50 )( 12,543.67 ) + (158 ) ( 6,000 )

V =1,539.97 lb
Since % error is about 5%, assumed value can be considered correct.
V =1 , 539. 97
lb
lb
1, 456 . 33 ANSWER
h
h

CRYSTALLIZATION
PROBLEM # 14:
Crystals of CaCl26H2O are to be obtained
from a solution of 35 weight % CaCl 2, 10
weight % inert soluble impurity, and 55
weight % water in an Oslo crystallizer. The
solution is fed to the crystallizer at 100F
and receives 250 BTU/lb of feed from the
external heater. Products are withdrawn
from the crystallizer at 40F.
a) What are the products from the
crystallizer?
b) The magma is centrifuged to a moisture
content of 0.1 lb of liquid per lb of
CaCl26H2O crystals and then dried in a
conveyor drier. What is the purity of the
final dried crystalline product?
Source: Principles of Unit Operations 2nd
edition (Foust, et al)
SOLUTION:
Basis: 1 lb of inert soluble-free feed
from table 2-120 (CHE HB 8th edition), solubilities of CaCl26H2O
0C
59.5 lb/100 lb H2O
10C
65 lb/100 lb H2O
20C
74.5 lb/100 lb H2O
30C
102 lb/100 lb H2O
At 100F (37.8C), solubility is (by extrapolation), 123.45 lb/100 lb H 2O
At 40F (4.4C), solubility is 61.92 lb/100 lb H2O
Since the equipment is Oslo crystallizer, there the process is supersaturation by evaporation
By heat balance around the crystallizer
q=F C P ( t F t L )+ C H C V V
From table 2-194, specific heat of CaCl2, cal/Kmol
C P=16.9+ 0.00386T
where T is in K
At 100F (310.93 K)

CRYSTALLIZATION
BTU
cal
1mol
lb F
BTU
C P=18.1
x
x
=0.1632
mol K 110.9 g
cal
lb F
1
g F
1
At 40F (277.59 K)
BTU
1
cal
1 mol
lb F
BTU
C P=17.97
x
x
=0.1620
mol K 110.9 g
cal
lb F
1
g F
P= 0.1632+0.1620 =0.1626 BTU
C
2
lb F
For the feed
C P=
BTU
BTU
( 0.35 lbCa Cl2 ) 0.1626 lbCa Cl F + ( 0.55 lb H 2 O ) 1 lb H O F

2
2
( 0.35+0.55 ) lb feed
C P=0.6743
BTU
lb F
From table 2-224 (CHE HB 8th edition), heat of solution of CaCl 26H2O = -4,100 cal/mol; in
the absence of data on heat of crystallization, heat of solution can be used instead but of
opposite sign
H C =4,100
cal
cal
BTU
=18.73
=33.71
mol
g
lb
From the steam table, at 40F,
=1,070.9 BTU / lb
( 250 ) (1 )=( 1 )( 0.6743 )( 10040 ) + ( 33.71 ) ( C ) ( 1,070.9 )( V )

V =0.0315 C0.1957 equation 1
F=V + L+C
L=1V C equation 2

CRYSTALLIZATION
Substitute
1 in 2
L=1 ( 0.0315C0.1994 )C
L=0.80061.0315 C equation3
Consider solute (CaCl26H2O) balance, inert soluble-free
x F F=x L L+ x C C
lbCaCl2 6 H 2 O
lbmol CaCl2 6 H 2 O
=0.7676
lb CaCl2
110.9
lbmol CaCl2
218.9
xF =
35lb CaCl2
1lbmol CaCl2 6 H 2 O
x
x
lbmol CaCl2
(35+ 55 ) lb feed
xL=
61.92lbCaCl 2 6 H 2 O
100 lb H 2 O
x
=0.3824
100lb H 2 O
( 100+61.92 ) lbliquor
x C =1
( 0.7676 ) ( 1 )=( 0.3824 )( L ) + ( 1 ) (C )

L=2.00732.6151C equation 4
Equate
3 and 4
0.80061.0315C=2.00732.6151C
C=0.7620 lb(inert soluble free)
L=0.0146 lb (inert soluble free )

V =0.2234 lb
Composition of the liquor (including the inert soluble)
wt CaCl2 6 H 2 Oliquor=0.0146lb liquor x
61.92 lbCaCl2 6 H 2 O
100 lb H 2 O
x
100 lb H 2 O
( 100+61.92 ) lbliquor
wt CaCl2 6 H 2 Oliquor=0.0056lb
wt H 2 Oliquor=0.01460.0056=0.0090 lb
CaCl26H2O
H2O
inerts
lb
0.0056
0.0090
0.1000
0.1146
%
4.89
7.85
87.26
100.00

CRYSTALLIZATION
For the crystals leaving the centrifuge:
wt liquor ad h ered crsytals=0.7620 lb crsytals x
0.1 lb liquor
=0.0762 lb
lb crystals
Composition of crystals leaving the centrifuge

lb
CaCl26H2O
crystallized
from liquor
0.0762 x 0.0489
0.7620
0.0037
H2O
inerts
0.0762 x 0.0785
0.0762 x 0.8726
0.0060
0.0665
In the dryer, assume all free water has been removed

Composition of dried crystals
CaCl26H2O
inerts
lb
0.7657
0.0665
0.8322
%
92.01
7.99
100.00
Purity=92 .01 ANSWER
PROBLEM # 15:
Lactose syrup is concentrated to 8 g lactose
per 10 g of water and then run into a
crystallizing vat which contains 2,500 kg of the
syrup. In this vat, containing 2,500 kg of
syrup, it is cooled from 57C to 10C. Lactose
crystallizes with one molecule of water of
0.7657
0.0060
0.0665
0.8382

CRYSTALLIZATION
crystallization. The specific heat of the lactose
solution is 3470 J/kgC. The heat of solution
for lactose monohydrate is -15,500 kJ/kmol.
The molecular weight of lactose monohydrate
is 360 and the solubility of lactose at 10C is
1.5 g/10 g water. Assume that 1% of the
water evaporates and that the heat loss
trough the vat walls is 4 x 10 4 kJ. Calculate
the heat to be removed in the cooling process.
SOLUTION:
Consider over-all material balance
F=L+ V +C
wt H 2 O feed=2,500 kg feed x
10 kg H 2 O
=1,388.89 kg
( 10+8 ) kg feed
V =0.01 ( 1,388.89 kg ) =13.89 kg

L=2,50013.89C
Consider lactose balance
x F F=x L L+ x C C
xF =
kg C 12 H 22 O11
8 kg
=0.4444
10+ 8
kg feed
x L=
kg C12 H 22 O11
1.5
=0.1304
10+ 1.5
kg liquor
x C=
MC
MC H
12
12
H 22 O11
22
O11 H 2 O
kg C12 H 22 O11
342
=0.95
360
kg crystal
( 0.4444 ) ( 2,500 )= ( 0.1304 ) ( L )+ ( 0.95 )( C )

L=8,519.93867.2853C equation2
Equate
1 and 2
2,486.11C=8,519.93867.2853 C
C=959.99 kg

CRYSTALLIZATION
L=1,526.12 kg
q crystals=F C P ( t F t L ) +C H C V V
At 10C (50F),
=1,065.2
BTU
kJ
=2,472.47
lb
kg
H C =15,500
kJ
kmol
kJ
x
=43.06
kmol 360 kg
kg
q crystals= ( 2,500 kg ) 3.47
][
)]
kJ
kJ
kJ
( 5710 ) C + ( 959.99 kg ) 43.06
( 13.89 kg ) 2,472.47
kg C
kg
kg
q crystals=414.7196 x 103 kJ
qT =414.7196 x 103 kJ + 4 x 10 4 kJ
qT =454 . 72 x 10 3 kJ ANSWER
)]

CRYSTALLIZATION
PROBLEM # 16:
Sal soda (Na2CO310H2O) is to be made by dissolving soda ash in a mixture of mother liquor and
water to form a 30% solution by weight at 45C and then cooling to 15C. 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 15C, the solubility of Na 2CO3 is 14.2 parts per
100 parts water.
Crystallization is to be done in a Swenson-Walker crystallizer. This is to be supplied with water at
10C, and sufficient cooling water is to be used to ensure that the exit water will not be over 20C.
The Swenson-walker crystallizer is built in units 10 ft long, containing 3 ft 2 of heating surface per
foot of length. An over-all heat transfer coefficient of 35 BTU/ft 2hF is expected.
The latent heat of crystallization of sal soda at 15C is approximately 25,000 cal/mol. The
specific heat of the solution is 0.85 BTU/lbF. 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.
SOLUTION:

CRYSTALLIZATION
Basis: 2,000 lb/h (1 ton/h) of sal soda
Consider over-all material balance of the system
W + F=V +C
V =W + F2,000 equation 1
Consider Na2CO3 balance around the system
x F F=x C C
x F =1.0
x C=
M Na CO
2
M Na CO 10 H
2
F=
0.3706
lb Na 2 CO 3
106
=0.3706
286
lb Na2 CO3 10 H 2 O
lb Na 2 CO3
lb Na2 CO 3 10 H 2 O
2,000
lb Na 2 CO 3 10 H 2 O
h
)(
1.0
F=741. 2
lb Na 2 CO 3
lb soda as h
lb
ANSWER
h
V =W + 741.22,000
V =W 1,258.8 equation2
Consider solute (Na2CO3) balance around the dryer
x D D=x C C
xD =
D=
1lb D
x D =0.3460
0.3706
106lb Na CO
14.2 lb Na CO
2
3
2
3
( 0.90lb Na2 CO 3 10 H 2 O ) 286 lb Na CO 10 H O + ( 0.10lb L )
( 100+14.2 ) lb L
2
3
2
lb Na 2 CO3
lb D
lb Na2 CO 3
lb Na2 CO3 10 H 2 O
2,000
lb Na2 CO3 10 H 2 O
h
)(
0.3460
lb Na2 CO3
lb D

CRYSTALLIZATION
D=2,142.20
lb
h
Consider over-all material balance around the dryer
D=V +C
V =2,142.202,000
V =142.20
lb
h
142.20=W 1,258.8
W =1, 401
lb
ANSWER
h
Consider solute (Na2CO3) balance around the dissolver
x F F+ x R R=x A A
x A=0.30
xR =
lb Na2 CO 3
lb A
14.2 lb Na 2 CO3
lb Na2 CO 3
=0.1243
( 100+14.2 ) lb R
lb R
( 1.0 ) (741.2 ) + ( 0.1243 )( R ) =( 0.30 ) ( A )

A=2,470.67+0.4143 R equation 3
Consider over-all material balance around the dissolver
F+W + R= A
A=741.2+1,401+ R
A=2,142.2+ R equation 4
Equate
3 and 4
2,470.67+0.4143 R=2,142.2+ R
R=560.8
lb
h

CRYSTALLIZATION
A=2,973.0
lb
h
Consider heat balance around the crystallizer
q crystals= A C P ( t A t B ) + C ' H C
C' =0.90 D=0.90 2,142.20
lb
lb
=1,928.0
h
h
BTU
cal mol
lb
BTU
H C =25,000
x
x
=157.34
mol 286 g
cal
lb
0.55556
g
1
[(
q crystals= 2,973.0
)(
q crystals=439,812.22
BTU
h
q=UA T lm
T lm=
( t A t 2) ( t B t1 )
ln
T lm =
t At 2
t B t 1
[ ( 4520 )( 1510 ) ] C x 1.8 C F

ln
4520
1510
T lm=22.37 F
439,812.22
A=
35
] [(
lb
BTU
1.8 F
lb
BTU
0.85
( 4515 ) C x
+ 1,928.0
157.34
h
lb F
C
h
lb
BTU
h
BTU
( 22.37 F )
h ft 2 F
A=561.74 ft 2
1 ft lengt h 1 unit
x
10 ft
3 ft 2
of units=18 . 7 19 units ANSWER
)(
)]

CRYSTALLIZATION
Refrigeration capacity:
RC=439,812.22
BTU tonrefrigeration
x
h
BTU
12,000
h
RC=36 . 65 tons ANSWER
PROBLEM # 17:
One ton of Na2S2O35H2O is to be crystallized per hour by cooling a solution containing 56.5%
Na2S2O3 to 30C 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 30C, solubility of Na 2S2O3 is 83 parts per 100
parts water
Source: Unit Operations (Brown, et al)
SOLUTION:
WP
WS
d W P= 1+
0
D 3
dWS
DS
From table 19-6 (CHE HB 8th edition)
D P =mes h 14=1.19 mm(sieve opening)

D S =mes h 20=0.841 mm(sieve opening)
D= DP D S
D=1.190.841=0.349 mm
WP
WS
d W P= 1+
0
0.349
d WS
0.841
W P=2.833 W S equation 1
W P=C+ W S

CRYSTALLIZATION
W P=2,000+W S equation2
Equate
1 and 2
2.833 W S =2,000+W S
W S =1 , 091. 11
lb
ANSWER
h
Consider Na2S2O3 balance:
x F F=x L L+ x C C
x F =0.565
xL=
x C=
lb Na2 S 2 O3
lb feed
83 lb Na 2 S2 O3
lb Na2 S 2 O 3
=0.4536
(100+ 83 ) lb liquor
lb liquor
M Na S O
2
M Na S O 5 H
2
lb Na2 S2 O 3
158
=0.6371
248
lb Na2 S 2 O 3 5 H 2 O
( 0.565 ) ( F )= ( 0.4536 ) ( L ) + ( 0.6371 ) ( 2,000 )

L=1.2456 F2,809.08 equation3
F=L+ C
L=F2,000 equation 4
Equate
3 and 4
1.2456 F2,809.08=F2000
F=3 ,294 .31
lb
ANSWER
h
PROBLEM # 18:
A Swenson-Walker crystallizer is fed with a saturated solution of magnesium sulfate at 110F.
The solution and its crystalline crop are cooled to 40F. The inlet solution contains 1 g of seed
crystals per 100 g of solution. The seeds are 80 mesh. Assuming ideal growth, what is the mesh
size of the crystals leaving with the cooled product? Evaporation may be neglected.
SOLUTION:
Basis: 100 lb feed

CRYSTALLIZATION
F=L+ C
L=100C equation1
x F F=x L L+ x C C
From figure 27-3 (Unit Operation 7th edition, McCabe and Smith) at 110F
x F =0.32
lb MgS O4
lb feed
From figure 27-3 (Unit Operations 7th edition, McCabe and Smith) at 40F
x L =0.21
x C=
lb MgS O4
lbliquor
M MgSO
M MgS O 7 H
4
lbMgS O4
120.38
=0.4884
246.49
lb MgS O4 7 H 2 O
( 0.32 ) (100 )=( 0.21 ) ( L )+ ( 0.4884 ) ( C )

L=152.382.3257 C equation2
Equate
1 and 2
100C=152.382.3257 C
C=39.51lb
W S =100 lb feed x
1 lbseeds
=1lb
100lb feed
W P=C+ W S =39.51+1=40.51lb
WP
WS
d W P=
0
D 3
1+
dWS
DS
[ ]
D
W P= P W S
DS
D S =mes h 80=0.177 mm(sieve opening)

D P =( 0.177 mm )
40.51lb
1 lb
D P =0.6079 mm

CRYSTALLIZATION
MESH 24 MESH ANSWER

PROBLEM # 19:
Trisodium phosphate is to be recovered as Na3PO412H2O from a 35 weight % solution originally
at 190F by cooling and seeding in a Swenson-Walker crystallizer. From 20,000 lb/h feed, 7,000
lb/h of product crystals in addition to the seed crystals are to be obtained. Seed crystals fed at a
rate of 500 lb/h have the following size range:
Weight Range
Size Range, in
10 %
- 0.0200 + 0.0100
20 %
- 0.0100 + 0.0050
40 %
- 0.0050 + 0.0025
30 %
- 0.0025 + 0.0010
Latent heat of crystallization of trisodium phosphate is 27,500 BTU/lbmol. Specific heat for the
trisodium phosphate solution may be taken as 0.8 BTU/lbF.
a) Estimate the product particle size distribution
b) To what temperature must the solution be cooled, and what will be the cooling duty in BTU/h
SOLUTION:
WP
WS
d W P= 1+
0
D 3
dWS
DS
d W S =W S d S
1
D 3
d S
DS
W P=W S 1+
0
WP 1
D 3
= 1+
d S
WS 0
DS
let , m=
WP 1
D 3
= 1+
d S
WS 0
DS
m= 1+
Where:
Solve for required
D
S
DS
S = fractional weight range

m :

CRYSTALLIZATION
mreqd =
W P 7,000 lb
=
=14
W S 500 lb
This problem can be solved by trial and error
1. Assume value of
2. Solve for
3. Solve for
1+
4. Get the total

5. If
D
DS
S
D
for each size range
for each size range, use the mean
m=mreqd
, then assumed
is correct; if not, redo another trial
D=0.004
TRIAL 1: Assume
D
S
D
m= S 1+
S
D
0.0150
0.10
2.0322
0.2032
0.0075
0.20
3.6050
0.7210
0.0038
0.40
8.6483
3.4593
0.0018
0.30
33.4554
10.0366
1+
1.00
Since % error is less than 5%, assumed value can be considered
For particle size distribution:
D P = D+ D S
wt=100 S=
m
D
1+
S
D
x 100
14.4201
D
S
D

CRYSTALLIZATION
SEED CRYSTALS
PRODUCT CRYSTALS
Size Range, in
Wt %
Size Range, in
Wt %
0.0200+ 0.0100
10.00
0.0240+ 0.0140
1.41
0.0100+ 0.0050
20.00
0.0140+ 0.0090
5.00
0.0050+ 0.0025
40.00
0.0090+ 0.0065
23.99
0.0025+ 0.0010
30.00
0.0065+ 0.0050
69.60
100.00
100.00
F=L+ C
C=W PW S=7,000500=6,500
L=20,0006,500=13,500
lb
h
lb
h
Consider Na3PO4 balance:
x F F=x L L+ x C C
x C=
M Na
M Na
PO4
PO4 12 H 2 O
lb Na3 PO 4
164
=0.4316
380
lb Na3 PO 4 12 H 2 O
( 0.35 ) ( 20,000 )=( x L ) ( 13,500 ) + ( 0.4316 ) ( 6,500 )
x L =0.3107
lb Na3 PO 4
lb soln
x L =0.3107
lb Na3 PO 4
lb soln
x
lb soln
( 10.3107 ) lb H 2 O
x L =0.4507
lb Na3 PO 4
lb H 2 O

50C
60C
43 lb/100 lb H2O
55 lb/100 lb H2O

CRYSTALLIZATION
T =51.725 C 125.11 F ANSWER

Cooling Duty:
q=F C P ( t F t P ) +C H C
[(
q= 20,000
] [(
lb
BTU
lb
BTU lbmol
0.8
( 190125.11 ) F + 6,500
27,500
x
h
lb F
h
lbmol 380 lb
)(
q=1,508,634.74
BTU
ANSWER
h
)(
)]

CRYSTALLIZATION
PROBLEM # 20:
How much CaCl26H2O must be dissolved in 100 kg of water at 20C to form a saturated
solution? The solubility of CaCl2 at 20C is 6.7 gmol anhydrous salt (CaCl2) per kg of water.
SOLUTION:
For a saturated solution utilizing 100 kg water as solvent:
1. Mole of CaCl2 required
nCaCl =100 kg H 2 O x
2
6.7 gmol CaCl2

1 kmol CaCl2
x
kg H 2 O
1,000 gmol CaCl 2
nCaCl =0.67 kmol

2
2. Weight of CaCl2 required
W CaCl =0.67 kg CaCl 2 x

2
110.994 kg CaCl2
kmol CaCl2
W CaCl =74.36 kg
2
3. Mole of CaCl26H2O required
nCaCl 6 H O=0.67 kmol CaCl2 x

2
1kmol CaCl2 6 H 2 O
kmol CaCl2
nCaCl 6 H O=0.67 kmol

2
4. Weight CaCl26H2O required
W CaCl 6 H O=0.67 kmol CaCl2 6 H 2 O x

2
218.994 kg CaCl2 6 H 2 O
kmol CaCl2 6 H 2 O
W CaCl 6 H O=146.72 kg
2
5. Composition of the solution in terms of CaCl26H2O
W CaCl 6 H O=146.72 kg
2
Since there should only be total of 100 kg water in the solution, the amount of free water (net
of water of hydration)
W free H O =100 kg( 146.7274.36 ) kg=27.64 kg

2
6. Amount of CaCl26H2O required for every 100 kg free water (net of water of hydration)

CRYSTALLIZATION
W CaCl 6 H O=100 kg free H 2 O x

2
146.72 kg CaCl2 6 H 2 O
27.64 kg free H 2 O
W CaCl 6 H O=530 . 82 kg ANSWER

2

Crystallizat ION: Chemical Engineering Series

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CHEMICAL ENGINEERING SERIES

CHEMICAL ENGINEERING SERIES 2

There are 5 basic methods of generating

(1) EVAPORATION by evaporating a portion of the solvent

Mechanism of Crystallization Process

CHEMICAL ENGINEERING SERIES 3

Important Factors in a Crystallization Process

Types of Crystal Geometry

CHEMICAL ENGINEERING SERIES 4

CUBIC SYSTEM 3 equal axes at right angles to each other

Either tables or curves

Types of Solubility Curve

CHEMICAL ENGINEERING SERIES 5

(1) TYPE I: Solubility increases with temperature

(2) TYPE II: Solubility increases with temperature

(3) TYPE III: Solubility increasing fairly rapid with

(4) TYPE IV: Unusual Curve; Solubility increases

CHEMICAL ENGINEERING SERIES 6

F = mass of the feed solution

= mass of the cooling water

X F = mass solute (salt) in the feed solution per mass of feed

X L = mass of solute (salt) in the mother liquor per mass of mother

X C = mass of solute (salt) in the srystals per mass of crystals

h F = enthalpy of the feed solution

hC = enthalpy of the crystals

Heat Transfer Equation

q water = heat absorbed by the cooling water

= specific heat of cooling water

CHEMICAL ENGINEERING SERIES 7

= over-all heat transfer coefficient

= heat transfer area

t F = temperature of the feed solution

SUPERSATURATION BY EVAPORATION OF SOLVENT

F = mass of the feed solution

= mass of the cooling water

= mass of the evaporated solvent

CHEMICAL ENGINEERING SERIES 8

X F = mass solute (salt) in the feed solution per mass of

X L = mass of solute (salt) in the mother liquor per mass of

X C = mass of solute (salt) in the srystals per mass of

h F = enthalpy of the feed solution

hC = enthalpy of the crystals

= enthalpy of the vapor

q water = heat absorbed by the cooling water

q crystals = heat loss by the crystals

C pF = specific heat of the feed solution

= specific heat of cooling water

= latent heat of vaporization

= over-all heat transfer coefficient

= heat transfer area

t F = temperature of the feed solution

SUPERSATURATION BY ADIABATIC EVAPORATION OF SOLVENT

CHEMICAL ENGINEERING SERIES 9

F = mass of the feed solution

= mass of the cooling water

= mass of the evaporated solvent

X F = mass solute (salt) in the feed solution per mass of

X L = mass of solute (salt) in the mother liquor per mass of

X C = mass of solute (salt) in the srystals per mass of

h F = enthalpy of the feed solution

= enthalpy of the vapor

CHEMICAL ENGINEERING SERIES 10

LP D P = characteristic particle dimension of the product