CHEMICAL ENGINEERING SERIES 1

CRYSTALLIZATION

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. There are 5 basic methods of generating
supersaturation

(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

 CHEMICAL ENGINEERING SERIES 3
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

 CHEMICAL ENGINEERING SERIES 4
CRYSTALLIZATION

(1) CUBIC SYSTEM – 3 equal axes at right angles to each other

(2) TETRAGONAL – 3 axes at right angles to each other, one axis longer than the other 2
(3) ORTHOROMBIC – 3 axes at right angles to each other, all of different lengths
(4) 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

 CHEMICAL ENGINEERING SERIES 5
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
 CHEMICAL ENGINEERING SERIES 6
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 = mass of the cooling water
XF = 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
Over-all material Balance: liquor
F=L+ C X C = mass of solute (salt) in the srystals per mass of crystals
h F = enthalpy of the feed solution
Solute Balance: h L = enthalpy of the mother liquor
X F F=X L L+ X C C
hC = enthalpy of the crystals
q water = heat absorbed by the cooling water
Enthalpy Balance:
hf F=hL L+h c C+ q q crystals = heat loss by the crystals
C pF = specific heat of the feed solution
Heat Balance: C p H O = specific heat of cooling water
2

q water=qcrystals H C = heat of crystallization

q crystals=F C pF ( t F −t L ) +C H C U = over-all heat transfer coefficient
q water=W C p H O ( t 2−t 1) A = heat transfer area
t F = temperature of the feed solution
2

Heat Transfer Equation t L = temperature of the mother liquor

q=UA ∆ T lm t 1 = inlet temperature of cooling water
t 2 = outlet temperature of cooling water

[ ]
( t F −t 2 ) −( t L −t1 )
q=UA
t F −t 2
ln
t L−t 1
 CHEMICAL ENGINEERING SERIES 7
CRYSTALLIZATION

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:
F = mass of the feed solution
L = mass of the mother liquor, usually saturated solution
C = mass of the crystals
W = mass of the cooling water
V = mass of the evaporated solvent
XF = 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 liquor
Over-all material Balance: X C = mass of solute (salt) in the srystals per mass of
F=L+ C+V crystals
h F = enthalpy of the feed solution
Solute Balance: h L = enthalpy of the mother liquor
X F F=X L L+ X C C hC = enthalpy of the crystals
hV = enthalpy of the vapor
Solvent Balance:
q water = heat absorbed by the cooling water
( 1− X F ) F=V + ( 1−X L) L+( 1− X C ) C
q crystals = heat loss by the crystals
Enthalpy Balance: C pF = specific heat of the feed solution
hf F=hV V + hL L+ hc C+ q C p H O = specific heat of cooling water
2

H C = heat of crystallization
Heat Balance: λV = latent heat of vaporization
q water=qcrystals U = over-all heat transfer coefficient
q crystals=F C pF ( t F −t L ) +C H C −V λV A = heat transfer area
q water=W C p H O ( t 2−t 1)
2
t F = temperature of the feed solution
 CHEMICAL ENGINEERING SERIES 8
CRYSTALLIZATION

t L = temperature of the mother liquor

t 1 = inlet temperature of cooling water
t 2 = outlet temperature of cooling water

SUPERSATURATION BY ADIABATIC EVAPORATION OF SOLVENT

where:
F = mass of the feed solution
L = mass of the mother liquor, usually saturated solution
C = mass of the crystals
W = mass of the cooling water
V = mass of the evaporated solvent
XF = 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 liquor
X C = mass of solute (salt) in the srystals per mass of
Over-all material Balance: crystals
F=L+ C+V h F = enthalpy of the feed solution
h L = enthalpy of the mother liquor
Solute Balance: hC = enthalpy of the crystals
X F F=X L L+ X C C hV = enthalpy of the vapor
H C = heat of crystallization
Solvent Balance: t F = temperature of the feed solution
( 1− X F ) F=V + ( 1−X L ) L+ ( 1− X C ) C t L = temperature of the mother liquor
t 1 = inlet temperature of cooling water
Enthalpy Balance:
hf F=hV V + hL L+ hc C t 2 = outlet temperature of cooling water

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

LP =LS + ∆ L
D P =DS + ∆ D
Where:
LP ∨D P = characteristic particle dimension of the product
 CHEMICAL ENGINEERING SERIES 9
CRYSTALLIZATION

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=aρ D P3=aρ ( DS + ∆ D )3
W S =aρ D S3
WS 3
W P= 3 ( D S +∆ D )
DS
DS + ∆ D 3
W P=W S
DS ( ) 3

W P=W S ( [ ])
DS + D P−D S
DS
3
DP
W P=W S ( )
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 3
∫ d W P= ∫
0 0
( 1+
DS )
d WS

WS 3
∆D
W P= ∫
0
( 1+
DS
d WS
)
C=W P−W S
 CHEMICAL ENGINEERING SERIES 10
CRYSTALLIZATION

PROBLEM # 01:
A 20 weight % solution of Na2SO4 at
200°F is pumped continuously to a
vacuum crystallizer from which the
magma is pumped at 60°F. What is
the composition of this magma, and
what percentage of Na2SO4 in the
feed is recovered as Na2SO4·10H2O
crystals after this magma is
centrifuged?
SOLUTION:

Basis: 100 lb feed

From table 2-122 (CHE HB), solubility of Na2SO4·10H2O

T,°C 10 15 20
g/100 g H2O 9.0 19.4 40.8

Consider over-all material balance:

F=C+ L
L=100−C eqn 1
Consider solute balance:
X F F=X C C+ X L L
M Na SO 142 lb Na2 SO 4
X C= 2
= 4
=0.4410
M Na SO ∙10 H O 322
2 4 2
lb Na2 SO 4 ∙10 H 2 O
At 60°F, solubility is 21.7778 g per 100 g water
21.7778 lb Na2 SO 4
X L= =0.1788
100+21.7778 lb liquor
lb Na 2 SO 4 lb Na 2 SO 4 lb Na 2 SO 4
(
0.20
lb feed ) (
( 100 lb feed )= 0.1788
lbliquor ) (
( L ) + 0.4410 )
lb Na 2 SO 4 ∙ 10 H 2 O
(C)

20=0.1788 L+0.4410 C eqn2

Substitute 1 in 2
20=0.1788 ( 100−C )+ 0.4410C
C=8.0854 lb crystals
L=100−8.0854
L=91.9146 lb
Magma composition:
8.0854
C= x 100=8 .0854
100
91.9146
L= x 100=91 .9146
100
 CHEMICAL ENGINEERING SERIES 11
CRYSTALLIZATION

% Recovery:
lb Na2 SO 4

recovery =
XCC
x 100=
( 0.4410
lb Na2 SO4 ∙10 H 2 O )
( 8.0854 lb Na2 SO4 ∙10 H 2 O )
x 100
XF F lb Na2 SO4
( 0.20
lb feed )
( 100 lb feed )
recovery =17 . 83 ANSWER

PROBLEM # 02:
A solution of 32.5% MgSO4 originally
at 150°F is to be crystallized in a
vacuum adiabatic crystallizer to give
a product containing 4,000 lb/h of
MgSO4·7H2O crystals from 10,000
lb/h of feed. The solution boiling
point rise is estimated at 10°F.
Determine the product temperature,
pressure and weight ratio of mother
liquor to crystalline product.
SOLUTION:

Consider over-all material balance:

F=V + L+C
V =10,000−L−4,000
V =6,000−L⟶ equation 1
Consider solute balance:
x F F=x C C + x L L
M Mg SO 120.38 lb Mg SO 4
x C= 4
= =0.4884
M Mg SO ∙ 7 H O 246.49
4 2
lb Mg SO 4 ∙7 H 2 O
lb Mg SO4 lb Mg SO 4
( 0.325
lbfeed )( 10,000
lb feed
h )
=X L ( L )+ 0.4884 (
lb Mg SO 4 ∙ 7 H 2 O
4,000
lb
h )( )
x L L=1,296.4 ⟶ equation 2

Consider enthalpy balance:

hf F=hV V + hL L+ hc C

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
 CHEMICAL ENGINEERING SERIES 12
CRYSTALLIZATION

3. Solve for “L” using equation 2

4. Solve for “V” using equation 1
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 60°F

From figure 27-3 (Unit Operations by McCabe and Smith 7 th edition)
lb Mg SO 4
x L =0.245
lb liquor
Substitute to equation 2
1,296.4
L= =5,291.43 lb
0.245
Substitute to equation 1
V =6,000−5,291.43=708.57 lb

From figure 27-4 (Unit Operations by McCabe and Smith, 7th edition)
BTU
h F at 150 ° F∧32.5 Mg SO 4 =−10
lb
BTU
hC at 60 ° F∧48.84 Mg SO 4 =−158
lb
BTU
h L at 60 ° F∧24.5 Mg SO 4=−50
lb
Temperature of vapor is 60 – 10 = 50°F
hV =H V +C P x BPE
BTU
From steam table at 50°F, H V =1,083.3
lb
hV =1,083.3
BTU
lb
+ 0.45
[(
BTU
lb ∙° F )
( 10 ° F )
]
BTU
hV =1,087.8
lb

hf F=hV V + hL L+ hc C
(−10 )( 10,000 ) =( 1087.8 ) (V )+ (−50 )( 5,291.43 ) + (−158 ) ( 4,000 )
V =732.28 lb
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 50°F
 CHEMICAL ENGINEERING SERIES 13
CRYSTALLIZATION

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
0°C, 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 0°C

From table 2-120 (CHE HB), solubility at 0°C:

5 g Na 2 SO 4 ∙10 H 2 O
100 g H 2 O

MT Na2 SO 4 1 1 MTmol Na2 SO 4 1 MTmol Na 2 SO 4 ∙10 H 2 O 32

mass Na2 SO4 ∙10 H 2 O=30,000 x x x x
yr 0.95 142 MT Na2 SO 4 1 MTmol Na2 SO 4 M

1 yr
mass Na2 SO4 ∙10 H 2 O=71,608.60 MT x
300 days

238.6953 MT
mass Na2 SO4 ∙10 H 2 O=
day

238.6953 MT Na2 SO 4 ∙ 10 H 2 O 105 MT feed

F= x
day 5 MT Na 2 SO 4 ∙ 10 H 2 O

MT
F=5 , 012. 60 ANSWER
day
 CHEMICAL ENGINEERING SERIES 14
CRYSTALLIZATION

PROBLEM # 04 :
1,200 lb of barium nitrate are dissolved in
sufficient water to form a saturated solution at
90°C. Assuming that 5% of the weight of the
original solution is lost through evaporation,
calculate the crop of the crystals obtained when
cooled to 20°C. solubility data of barium nitrate
at 90°C = 30.6 lb/100 lb water; at 20°C = 9.2
lb/100 lb water

CHE BP July 1968

SOLUTION:

lb Ba ( NO 3 )2 100lb water lb Ba ( NO 3 )2
x F =0.306 x =0.2343
lbwater ( 100+30.6 ) lb feed lb feed
x F F=1,200 lb Ba ( NO 3 )2
lb feed
F=1,200lb Ba ( N O3 )2 x
0.2343 lb Ba ( N O3 )2
F=5,121.5686lb
lb Ba ( NO3 )2 100 lb water lb Ba ( NO 3 )2
x L =0.092 x =0.0842
lb water (100+ 9.2 ) lb liquor lbliquor

Consider over-all material balance around the crystallizer

F=V + L+C
V =0.05 F
L=0.95 ( 5,121.5686 )−C
L=4,865.4902−C ⟶ equation 1

Consider Ba(NO3)2 balance

 CHEMICAL ENGINEERING SERIES 15
CRYSTALLIZATION

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 ( 4,865.4902−C ) +C

1,200−[ ( 0.0842 ) ( 4,865.4902 ) ]

C=
0.9158

C=862 .9894 lb ANSWER

PROBLEM # 05:

A Swenson-Walker crystallizer is to be used to

produce 1 ton/h of copperas (FeSO4·7H2O)
crystals. The saturated solution enters the
crystallizer at 120°F. The slurry leaving the
crystallizer will be at 80°F. Cooling water
enters the crystallizer jacket at 60°F and
leaves at 70°F. It may be assumed that the U
for the crystallizer is 35 BTU/h·°F·ft 2. 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/lb·°F; heat of solution= 4400 cal/gmol
copperas; solubility at 120°F = 140 parts
copperas/100 parts excess water; solubility at
80°F = 74 parts copperas/100 parts excess
water

SOLUTION:

Consider over-all material balance:

F=L+ C
L=F−2,000 ⟶ equation1
Consider copperas (FeSO4·7H2O) balance:
x F F=x C C + x L L
x C =1.0
 CHEMICAL ENGINEERING SERIES 16
CRYSTALLIZATION

74 lb Fe SO 4 ∙ 7 H 2 O 100 lb H 2 O lb Fe SO 4 ∙7 H 2 O
x L= x =0.4253
100 lb H 2 O 174 lb liquor lb liquor
140 lb Fe SO 4 ∙7 H 2 O 100 lb H 2 O lb Fe SO 4 ∙7 H 2 O
xF = 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 F−4,702.5629 ⟶ equation2

Equate1 and 2
F−2,000=1.3715 F−4,702.5629
lb
F=7,274.73
h
lb
L=5,274.73
h
Consider heat balance:
q water=qcrystals
q crystals=F C pF ( t F −t L ) +C H C

[ ( )]
BTU
1
[(
q crystals= 7,274.73
lb
h
0.70
BTU
)(
lb∙ ° F ) ](
( 120−80 ) ° F + 2,000
lb
h
4,400
cal
)x
gmol
gmol 277.85 g
x
lb
0.55556
cal
g
BTU
q crystals=260,701.1615
h

q water=W C p H O ( t 2−t 1)
2

BTU
260,701.1615
h
W=
BTU
( 1.0
lb∙ ° F )
( 70−60 ) ° F
3
lb 1 ft 7.481 gal 1h
W =26,070.1162 x x 3
x
h 62.335 lb ft 60 min

gal
W =52 . 14 ANSWER
min

q=UA ∆ T lm
( t F−t 2 ) −( t L −t1 )
∆ T lm=
t F −t 2
ln
t L −t 1
(120−70 )− ( 80−60 )
∆ T lm=
120−70
ln
80−60
∆ T lm=32.7407 ° F
 CHEMICAL ENGINEERING SERIES 17
CRYSTALLIZATION

BTU
260,701.1615
h
A=
( 35 h ∙BTU
ft ∙° F )
2
( 32.7407 ° F )

A=227.5029 ft 2

1 ft lengt h 1 unit
¿ of units=227.5029 ft 2 x x
3.5 ft 2 10 ft

¿ of units=6 .5 ≈ 7 units ANSWER

PROBLEM # 06:
Crystals of Na2CO3·10H2O are dropped into a saturated solution of Na 2CO3 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:

Assume 100 g of Na2CO3·10H2O added into the saturated solution

124 g Na 2 CO3 ∙ H 2 O
wt Na2 CO 3 ∙ H 2 O=100 g Na 2 CO 3 ∙ 10 H 2 O x
286 g Na2 CO3 ∙10 H 2 O
wt Na2 CO 3 ∙ H 2 O=43.3566 g

106 g Na2 CO3

wt Na2 CO 3=100 g Na2 CO3 ∙10 H 2 O x
286 g Na2 CO 3 ∙ 10 H 2 O
wt Na2 CO 3=37.0629 g

180 g H 2 O
wt H 2 O=100 g Na 2 CO3 ∙10 H 2 O x
286 g Na2 CO3 ∙ 10 H 2 O
wt H 2 O=62.9371 g
 CHEMICAL ENGINEERING SERIES 18
CRYSTALLIZATION

X
Na2 CO 3 ∈satd solnat 100° C= x 100=31.2
X +62.9371
X =28.5412 g

wt Na2 CO 3 precipitated=37.0629−28.5412=8.5217 g

124 g Na 2 CO 3 ∙ H 2 O
wt Na2 CO 3 ∙ H 2 O precipitated=8.5217 g Na 2 CO 3 x
106 g Na 2 CO 3
wt Na2 CO 3 ∙ H 2 O precipitated=9.9688 g

9.9688
Na 2 CO 3 ∙ H 2 O precipitated= x 100
43.3566

Na 2 CO 3 ∙ H 2 O precipitated =22. 99 ANSWER

PROBLEM # 07:

A solution of MgSO4 at 220°F containing 43 g

MgSO4 per 100 g H2O is fed into a cooling
crystallizer operating at 50°F. If the solution
leaving the crystallizer is saturated, what is the
rate at which the solution must be fed to the
crystallizer to produce one ton of MgSO 4·7H2O
per hour?

SOLUTION:

Consider over-all material balance:

F=L+ C
L=F−1 ⟶ equation1
Consider MgSO4 balance

x F F=x L L+ x C C
 CHEMICAL ENGINEERING SERIES 19
CRYSTALLIZATION

43 ton MgSO4 100 ton H 2 O ton Mg SO 4

xF = x =0.3007
100 ton H 2 O ( 100+43 ) ton feed ton feed
120.38 ton MgSO 4 ton MgSO 4
x C= =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, 7 th edition), at 50°F
ton MgSO4
x L =0.23
tonliquor
( 0.3007 ) ( F )=( 0.23 ) ( L )+ ( 0.4884 ) ( 1 )
L=1.3074 F−2.1235 ⟶ equation2

Equate 1 and 2

F−1=1.3074 F−2.1235

ton
F=3 .65 ANSWER
h

PROBLEM # 08:

The solubility of sodium bicarbonate in water

is 9.6 g per 100 g water at 20°C and 16.4 g
per 100 g water at 60°C. If a saturated
solution of NaHCO3 at 60°C is cooled to 20°C,
what is the percentage of the dissolved salt
that crystallizes out?

SOLUTION:

Basis: 100 kg feed

Consider over-all material balance:

F=L+ C
L=100−C ⟶ equation1
Consider NaHCO3 balance
x F F=x L L+ x C C
 CHEMICAL ENGINEERING SERIES 20
CRYSTALLIZATION

16.4 kg NaHCO3 100 kg H 2 O kg NaH CO 3

xF = x =0.1409
100 kg H 2 O ( 100+ 16.4 ) kg feed kg feed
x C =1.0
9.6 kg NaHCO 3 100 kg H 2 O kg NaH CO 3
xL= x =0.0876
100 kg H 2 O ( 100+9.6 ) kg liquor kg liquor

( 0.1409 ) ( 100 )=( 0.0876 )( L ) + ( C )( 1 )

L=160.8447−11.4155 C ⟶ equation 2

Equate 1 and 2

100−C=160.8447−11.4155 C
C=5.8417 kg

C
NaHCO 3 crystallized= x 100
xF F

5.8417 kg
NaHCO 3 crystallized= x 100
( 0.1409 ) ( 100 kg )

NaHCO 3 crystallized=41 . 46 ANSWER

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 Na 2SO4 per 100
g H2O.

SOLUTION:
 CHEMICAL ENGINEERING SERIES 21
CRYSTALLIZATION

Basis: 1 L feed
1.077 kg
F=1 L x =1.077 kg
L
Consider over-all material balance:
F=V + L+C
L=1.077−V −C ⟶ equation 1

x C C=0.80 x F F

x F F=( 1.077 kg feed ) ( 8.4100kgkgNafeedSO )=0.0905 kg Na SO

2 4
2 4

x C C=( 0.80 ) ( 0.0905 kg Na2 SO 4 )=0.0724 kg Na2 SO 4

M Na SO 142 kg Na 2 SO 4
x C= 2 4
= =0.4410
M Na SO ∙ 10 H O 322
2 4 2
kg Na2 SO 4 ∙ 10 H 2 O
0.0724 kg Na 2 SO 4
C= =0.1642 kg
kg Na 2 SO 4
0.4410
kg Na 2 SO 4 ∙ 10 H 2 O

1
Substitute to equation
L=1.077−V −0.1642
L=0.9128−V ⟶ equation 2

Consider Na2SO4 balance

x F F=x L L+ x C C
19.4 kg Na 2 SO 4 100 kg H 2 O kg Na2 SO 4
xL= 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

Substitute to equation 2
0.1114=0.9128−V
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
the following:
a) The yield of crystals if the solution is
cooled to 290K, where the solubility is 8.6
 CHEMICAL ENGINEERING SERIES 22
CRYSTALLIZATION

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

Source: Transport Processes and Unit

Operations (Geankoplis)

SOLUTION:

a) If solution is cooled to 290K

Consider over-all material balance:

F=V + L+C
L=100−V −C
L=100−V −C
If water evaporated is 10% of the original water present
V =0.10 ( 1−x F ) F
30.6 kg Ba ( NO 3) 2 100 kg H 2 O kg Ba ( NO 3 )2
xF = x =0.2343
100 kg H 2 O ( 100+30.6 ) kg feed kg feed
V =0.10 ( 1−0.2343 ) (100 kg )
V =7.657 kg
L=100−7.657−C
L=92.343−C ⟶ equation 1
Consider Ba(NO3)2 balance
x F F=x L L+ x C C
8.6 kg Ba ( NO 3 )2 100 kg H 2 O kg Ba ( NO 3 )2
xL= x =0.0792
100 kg H 2 O ( 100+8.6 ) kg liquor kg liquor
x C =1.0

( 0.2343 ) ( 100 )=( 0.0792 ) ( L ) + ( 1.0 ) ( C )

L=295.8333−12.6263C ⟶ equation 2

Equate 1 and 2
92.343−C=295.8333−12.6263 C
C=17 .5026 kg ANSWER

b) If solution is cooled to 283 K

Consider over-all material balance:

F=V + L+C
L=100−V −C
L=100−V −C
If water evaporated is 10% of the original water present
 CHEMICAL ENGINEERING SERIES 23
CRYSTALLIZATION

V =0.10 ( 1−x F ) F
30.6 kg Ba ( NO 3) 2 100 kg H 2 O kg Ba ( NO 3 )2
xF = x =0.2343
100 kg H 2 O ( 100+30.6 ) kg feed kg feed
V =0.10 ( 1−0.2343 ) (100 kg )
V =7.657 kg
L=100−7.657−C
L=92.343−C ⟶ equation 1
Consider Ba(NO3)2 balance
x F F=x L L+ x C C
7.0 kg Ba ( NO3 ) 2 100 kg H 2 O kg Ba ( NO 3 )2
xL= x =0.0654
100 kg H 2 O (100+ 7 ) kg liquor kg liquor
x C =1.0

( 0.2343 ) ( 100 )=( 0.0654 ) ( L ) + ( 1.0 )( C )

L=358.2569−15.2905C ⟶ equation 2

Equate 1 and 2
92.343−C=358.2569−15.2905 C

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
 CHEMICAL ENGINEERING SERIES 24
CRYSTALLIZATION

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)

Consider over-all material balance:

F=L+ C
100 kg soln
F=1,000 kg KCl x =2,857.14 kg feed
35 kg KCl
L=2,857.14−C ⟶ equation 1
Consider KCl balance
x F F=x L L+ x C C
kg KCl
x L =0.254
kg liquor
x C =1.0
1,000=( 0.254 ) ( L )+ (1.0 )( C )
L=3,937−3.937 C ⟶ equation 2

Equate 1 and 2
2,857.14−C=3,937−3.937 C

C=367 . 67 kg ANSWER

H 2 O∈feed=100− KCl=100−35=65
wt H 2 O
H 2 O∈feed= x 100
wt feed
65 kg H 2 O
wt H 2 O=( 2,857.14 kg feed ) (
100 kg feed )
wt H 2 O=1 ,857 . 14 kg ANSWER

d) Crystallization with evaporation

 CHEMICAL ENGINEERING SERIES 25
CRYSTALLIZATION

Consider over-all material balance:

F=V + L+C
V =0.05 ( 1,857.14 kg )
V =92.8571kg
L=2,857.14−92.8571−C
L=2,764.2829−C ⟶ 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=3,937−3.937 C ⟶ equation 4

Equate 3 and 4
2,764.2829−C=3,937−3.937 C
C=399 .29 kg ANSWER

PROBLEM # 12:
The solubility of sodium sulfate is 40 parts
Na2SO4 per 100 parts of water at 30°C, and
 CHEMICAL ENGINEERING SERIES 26
CRYSTALLIZATION

13.5 parts at 15°C. The latent heat of

crystallization (liberated when crystals form) is
18,000 g-cal per gmol Na2SO4. Glauber’s salt
(Na2SO4·10H2O) is to be made in a Swenson-
Walker crystallizer by cooling a solution,
saturated at 30°C, to 15°C. Cooling water
enters at 10°C and leaves at 20°C. The over-
all heat transfer coefficient in the crystallizer is
25 BTU/h·ft2·°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

Source: Unit Operations (Brown)

SOLUTION:

Consider over-all material balance:

F=L+ C
L=F−1 ⟶ equation1
Consider Na2SO4 balance
x F F=x L L+ x C C
40 ton Na2 SO 4 100 ton H 2 O ton Na2 SO 4
xF = x =0.2857
100ton H 2 O ( 100+ 40 ) tonfeed tonfeed
13.5 ton Na2 SO 4 100 ton H 2 O ton Na2 SO 4
xL= x =0.1189
100 ton H 2 O ( 100+13.5 ) ton liquor ton liquor
142 ton Na2 SO 4 ton Na2 SO 4
x C= =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 F−3.709⟶ equation 2

Equate 1 and 2
F−1=2.4029 F−3.709
ton
F=1.931
h

Consider heat balance:

q crystal=F C P ( t F−t C ) +C H C
( m C P )Na SO + ( mC P ) H O
C P= 2 4 2

F
 CHEMICAL ENGINEERING SERIES 27
CRYSTALLIZATION

From Table 2-194 (CHE HB 8th edition)

cal BTU
C PNa SO4 =32.8 =0.231
2
° C ∙mol lb∙ ° F
C P=
[ ( 0.2857 ) ( 0.231 ) + ( 0.7143 ) ( 1.000 ) ] =0.7803 BTU
1 lb ∙° F

[(
q crystal= 1.931
ton 2,000 lb
h
x
ton
0.7803
BTU
lb∙° F )(
(30−15 ) ° C x
1.8 ° F
)
°C
+ 1
h
x
] [(
ton 2,000 lb lbmol 454 gm
ton
x
322lb
x
lbmo
BTU
q crystal=282,656.8961
h

q=UA ∆ T lm
( t F−t 2 ) −( t L −t1 )
∆ T lm=
t F −t 2
ln
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
( 86−68 )−( 59−50 )
∆ T lm= =12.9842° F
86−68
ln
59−50

BTU
262,656.8961
h
A=
( 25 h ∙BTU
ft ∙° F )
2
( 12.9842 ° F )

A=870.7718 ft 2
1 ft lengt h 1 unit
¿ of units=880.7718 ft 2 x x
3 ft 2
10 ft lengt h

¿ of units=29. 03 ≈ 30 units ANSWER

 CHEMICAL ENGINEERING SERIES 28
CRYSTALLIZATION

PROBLEM # 13:
A continuous adiabatic vacuum crystallizer is
to be used for the production of MgSO 4·7H2O
crystals from 20,000 lb/h of solution containing
0.300 weight fraction MgSO4. The solution
enters the crystallizer at 160°F. The
crystallizer is to be operated so that the
mixture of mother liquor and crystals leaving
the crystallizer contains 6,000 lb/h of
MgSO4·7H2O crystals. The estimated boiling
point elevation of the solution in the
crystallizer is 10°F. How many pounds of
water are vaporized per hour?

Source: Unit Operations (Brown)

SOLUTION:

Consider over-all material balance:

F=V + L+C
L=20,000−6,000−V
L=14,000−V ⟶ equation 1

Consider MgSO4 balance

x F F=x L L+ x C C
lb Mg SO 4
x F =0.3000
lb feed
120 lb Mg SO 4 lb Mg SO 4
x C= =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 )
3,073.2
L= ⟶ equation2
xL

Consider enthalpy balance:

hf F=hV V + hL L+ hc C

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 2
4. Solve for “V” using equation 1
5. Check if assumed temperature is correct by conducting enthalpy balance
 CHEMICAL ENGINEERING SERIES 29
CRYSTALLIZATION

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 60°F

From figure 27-3 (Unit Operations by McCabe and Smith 7 th edition)
lb Mg SO 4
x L =0.245
lb liquor
Substitute to equation 2
3,073.2
L= =12,543.67lb
0.245
Substitute to equation 1
V =14,000−12,543.67=1,456.33 lb

From figure 27-4 (Unit Operations by McCabe and Smith, 7th edition)
BTU
h F at 160 ° F∧30 Mg SO 4=5
lb
BTU
hC at 60 ° F∧48.78 Mg SO 4 =−158
lb
BTU
h L at 60 ° F∧24.5 Mg SO 4=−50
lb
Temperature of vapor is 60 – 10 = 50°F
hV =H V +C P x BPE
BTU
From steam table at 50°F, H V =1,083.3
lb
hV =1,083.3
BTU
lb
+ 0.45
[(
BTU
lb ∙° F )
( 10 ° F )
]
BTU
hV =1,087.8
lb

hf F=hV V + hL L+ hc C
( 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.

lb lb
V =1 , 539 .97 ∨1, 456 .33 ANSWER
h h
 CHEMICAL ENGINEERING SERIES 30
CRYSTALLIZATION

PROBLEM # 14:
Crystals of CaCl2·6H2O 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 100°F
and receives 250 BTU/lb of feed from the
external heater. Products are withdrawn
from the crystallizer at 40°F.
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
CaCl2·6H2O 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 CaCl2·6H2O

0°C 59.5 lb/100 lb H2O

10°C 65 lb/100 lb H2O
20°C 74.5 lb/100 lb H2O
30°C 102 lb/100 lb H2O
At 100°F (37.8°C), solubility is (by extrapolation), 123.45 lb/100 lb H 2O
At 40°F (4.4°C), 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 λV

From table 2-194, specific heat of CaCl2, cal/K·mol

C P=16.9+ 0.00386T
where T is in K
At 100°F (310.93 K)
BTU
1
cal 1mol lb∙ ° F BTU
C P=18.1 x x =0.1632
mol ∙ K 110.9g cal lb∙ ° F
1
g ∙° F
At 40°F (277.59 K)
 CHEMICAL ENGINEERING SERIES 31
CRYSTALLIZATION

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
0.1632+0.1620 BTU
Ć P= =0.1626
2 lb ∙ ° F

For the feed

BTU BTU

C P=
( ) (
( 0.35 lbCa Cl2 ) 0.1626 lb CaCl ∙ ° F + ( 0.55 lb H 2 O ) 1 lb H O ∙° F
2 2
)
( 0.35+0.55 ) lb feed
BTU
C P=0.6743
lb∙ ° F

From table 2-224 (CHE HB 8 th edition), heat of solution of CaCl 2·6H2O = -4,100 cal/mol;
in the absence of data on heat of crystallization, heat of solution can be used instead but
of opposite sign
cal cal BTU
H C =4,100 =18.73 =33.71
mol g lb

From the steam table, at 40°F, λ=1,070.9 BTU / lb

( 250 ) ( 1 )=( 1 ) ( 0.6743 ) (100−40 )+ ( 33.71 )( C )−( 1,070.9 ) ( V )

V =0.0315 C−0.1957 ⟶ equation 1

Consider over-all material balance:

F=V + L+C
L=1−V −C ⟶ equation 2

Substitute 1 in 2
L=1− ( 0.0315C−0.1994 )−C
L=0.8006−1.0315 C ⟶ equation3

Consider solute (CaCl2·6H2O) balance, inert soluble-free

x F F=x L L+ x C C
lbCaCl 2 ∙ 6 H 2 O
218.9
35lb CaCl2 1lbmol CaCl2 ∙ 6 H 2 O lbmol CaCl 2 ∙ 6 H 2 O
xF = x x =0.7676
(35+ 55 ) lb feed lbmol CaCl2 lbCaCl2
110.9
lbmol CaCl2
61.92lbCaCl 2 ∙ 6 H 2 O 100 lb H 2 O
xL= x =0.3824
100lb H 2 O ( 100+61.92 ) lb liquor
x C =1
 CHEMICAL ENGINEERING SERIES 32
CRYSTALLIZATION

( 0.7676 ) ( 1 )=( 0.3824 ) ( L ) + ( 1 ) ( C )

L=2.0073−2.6151C ⟶ equation 4

Equate 3 and 4
0.8006−1.0315C=2.0073−2.6151C
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)
61.92 lbCaCl2 ∙ 6 H 2 O 100 lb H 2 O
wt CaCl2 ∙6 H 2 O∈liquor=0.0146 lb liquor x x
100 lb H 2 O ( 100+61.92 ) lbliquor
wt CaCl2 ∙6 H 2 O∈liquor=0.0056 lb
wt H 2 O∈liquor=0.0146−0.0056=0.0090 lb

lb %
CaCl2·6H2O 0.0056 4.89
H2O 0.0090 7.85
inerts 0.1000 87.26
0.1146 100.00

For the crystals leaving the centrifuge:

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

lb
CaCl2·6H2O
crystallized 0.7620
from liquor 0.0762 x 0.0489 0.0037 0.7657

H2O 0.0762 x 0.0785 0.0060 0.0060

inerts 0.0762 x 0.8726 0.0665 0.0665
0.8382

In the dryer, assume all free water has been removed

Composition of dried crystals

lb %
CaCl2·6H2O 0.7657 92.01
inerts 0.0665 7.99
0.8322 100.00

Purity=92 .01 ANSWER

 CHEMICAL ENGINEERING SERIES 33
CRYSTALLIZATION

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 57°C to 10°C. Lactose
crystallizes with one molecule of water of
crystallization. The specific heat of the lactose
solution is 3470 J/kg·°C. 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 10°C 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
10 kg H 2 O
wt H 2 O∈ feed=2,500 kg feed x =1,388.89 kg
( 10+ 8 ) kg feed
V =0.01 ( 1,388.89 kg ) =13.89 kg
L=2,500−13.89−C
L=2,486.11−C ⟶ equation 1
Consider lactose balance
x F F=x L L+ x C C
8 kg kg C 12 H 22 O11
xF = =0.4444
10+ 8 kg feed
1.5 kg C12 H 22 O11
xL= =0.1304
10+ 1.5 kg liquor
MC H O 342 kg C 12 H 22 O11
x C= 12
= 22
=0.95
11

M C H O ∙ H O 360
12 22 11 2
kg crystal
 CHEMICAL ENGINEERING SERIES 34
CRYSTALLIZATION

( 0.4444 )( 2,500 ) =( 0.1304 ) ( L ) + ( 0.95 ) ( C )

L=8,519.9386−7.2853C ⟶ equation2

Equate 1 and 2
2,486.11−C=8,519.9386−7.2853 C
C=959.99 kg
L=1,526.12 kg

Consider heat balance:

q crystals=F C P ( t F −t L ) +C H C −V λ V
At 10°C (50°F),
BTU kJ
λ=1,065.2 =2,472.47
lb kg
kJ kmol kJ
H C =15,500 x =43.06
kmol 360 kg kg

[ (
q crystals= ( 2,500 kg ) 3.47
3
kJ
kg ∙° C ) ][ (
(57−10 ) ° C + ( 959.99 kg ) 43.06 )]
kJ
kg [ (
− (13.89 kg ) 2,472.47
kJ
kg )]
q crystals=414.7196 x 10 kJ

qT =414.7196 x 103 kJ + 4 x 10 4 kJ
3
qT =454 . 72 x 10 kJ ANSWER
 CHEMICAL ENGINEERING SERIES 35
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.

Crystallization is to be done in a Swenson-Walker crystallizer. This is to be supplied with water at

10°C, and sufficient cooling water is to be used to ensure that the exit water will not be over 20°C.
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 2·h·°F is expected.

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.

SOLUTION:

Basis: 2,000 lb/h (1 ton/h) of sal soda

Consider over-all material balance of the system

 CHEMICAL ENGINEERING SERIES 36
CRYSTALLIZATION

W + F=V +C
V =W +F−2,000⟶ equation 1
Consider Na2CO3 balance around the system
x F F=x C C
x F =1.0
M Na CO 106 lb Na 2 CO3
x C= 2 3
==0.3706
M Na CO ∙ 10 H O 286
2 3 2
lb Na 2 CO 3 ∙ 10 H 2 O
lb Na 2 CO3 lb Na2 CO 3 ∙ 10 H 2 O

F=
( 0.3706
lb Na 2 CO 3 ∙ 10 H 2 O
2,000 )( h )
lb Na 2 CO 3
1.0
lb soda as h
lb
F=741. 2 ANSWER
h

1
Substitute to equation
V =W + 741.2−2,000
V =W −1,258.8 ⟶ equation2
Consider solute (Na2CO3) balance around the dryer
x D D=x C C
106 lb Na CO 14.2lb Na CO

xD =
( 2 3
)
( 0.90lb Na2 CO 3 ∙ 10 H 2 O ) 286 lb Na CO ∙10 H O + ( 0.10lb L )
2 3 2
( 2 3

( 100+14.2 ) lb L )
1lb D
lb Na 2 CO3
x D =0.3460
lb D

lb Na 2 CO 3 lb Na2 CO3 ∙ 10 H 2 O

D=
( 0.3706
lb Na 2 CO3 ∙10 H 2 O
2,000 )(
h )
lb Na 2 CO3
0.3460
lb D
lb
D=2,142.20
h
Consider over-all material balance around the dryer
D=V +C
V =2,142.20−2,000
lb
V =142.20
h
2
Substitute to equation
142.20=W −1,258.8
lb
W =1 , 401 ANSWER
h
Consider solute (Na2CO3) balance around the dissolver
 CHEMICAL ENGINEERING SERIES 37
CRYSTALLIZATION

x F F+ x R R=x A A
lb Na2 CO 3
x A=0.30
lb A
14.2lb Na 2 CO3 lb Na2 CO 3
xR = =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
lb
R=560.8
h
lb
A=2,973.0
h
Consider heat balance around the crystallizer
q crystals= A C P ( t A −t B ) + C ' H C
lb lb
C' =0.90 D=0.90 2,142.20 ( h )
=1,928.0
h
BTU
1
cal mol lb BTU
H C =25,000 x x =157.34
mol 286 g cal lb
0.55556
g

[(
q crystals= 2,973.0
lb
h )(
0.85
BTU
lb ∙ ° F )
( 45−15 ) ° C x
1.8 ° F
°C ] [(
+ 1,928.0
lb
h)(157.34
BTU
lb )]
BTU
q crystals=439,812.22
h

q=UA ∆ T lm
( t A −t 2 )−( t B −t1 )
∆ T lm=
t A−t 2
ln
t B −t 1
[( 45−20 )−( 15−10 ) ] ° C x 1.8° C° F
∆ T lm=
45−20
ln
15−10
∆ T lm=22.37 ° F
 CHEMICAL ENGINEERING SERIES 38
CRYSTALLIZATION

BTU
439,812.22
h
A=
( 35 h ∙BTU
ft ∙° F )
2
( 22.37 ° F )

A=561.74 ft 2
2 1 ft lengt h 1 unit
¿ of units=561.74 ft x x
3 ft 2 10 ft

¿ of units=18 . 7 ≈ 19 units ANSWER

Refrigeration capacity:
BTU tonrefrigeration
RC=439,812.22 x
h BTU
12,000
h

RC=36 . 65 tons ANSWER

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:

WP WS 3
∆D
∫ d W P=∫
0 0
( 1+
DS )
d WS

From table 19-6 (CHE HB 8th edition)

D P =mes h 14=1.19 mm(sieve opening)
DS =mes h 20=0.841 mm( sieve opening)
∆ D= DP −D S
∆ D=1.19−0.841=0.349 mm
W W
0.349 3
P S

∫ d W P=∫ 1+ 0.841 d W S
0 0
( )
W P=2.833 W S ⟶ equation 1
 CHEMICAL ENGINEERING SERIES 39
CRYSTALLIZATION

W P=C+ W S
W P=2,000+W S ⟶ equation2
Equate 1 and 2
2.833 W S =2,000+W S
lb
W S =1 , 091. 11 ANSWER
h
Consider Na2S2O3 balance:
x F F=x L L+ x C C
lb Na2 S 2 O3
x F =0.565
lb feed
83 lb Na 2 S2 O3 lb Na2 S 2 O 3
xL= =0.4536
(100+ 83 ) lbliquor lb liquor
M Na S O 158 lb Na2 S2 O 3
x C= 2
= 2 3
=0.6371
M Na S O ∙ 5 H O 248
2 2 3 2
lb Na2 S 2 O3 ∙5 H 2 O
( 0.565 ) ( F ) =( 0.4536 ) ( L )+ ( 0.6371 )( 2,000 )
L=1.2456 F−2,809.08 ⟶ equation3
Consider over-all material balance
F=L+ C
L=F−2,000 ⟶ equation 4
Equate 3 and 4
1.2456 F−2,809.08=F−2000
lb
F=3 ,294 .31 ANSWER
h

PROBLEM # 18:

A Swenson-Walker crystallizer is fed with a saturated solution of magnesium sulfate at 110°F.

The solution and its crystalline crop are cooled to 40°F. 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

Consider over-all material balance
F=L+ C
L=100−C ⟶ equation1
Consider MgSO4 balance
x F F=x L L+ x C C
From figure 27-3 (Unit Operation 7th edition, McCabe and Smith) at 110°F
lb MgS O4
x F =0.32
lb feed
From figure 27-3 (Unit Operations 7th edition, McCabe and Smith) at 40°F
 CHEMICAL ENGINEERING SERIES 40
CRYSTALLIZATION

lb MgS O4
x L =0.21
lbliquor
M MgS O 120.38 lbMgSO 4
x C= 4
= =0.4884
M MgS O ∙7 H O 246.49
4 2
lb MgS O 4 ∙ 7 H 2 O
( 0.32 ) ( 100 )=( 0.21 ) ( L ) + ( 0.4884 ) ( C )
L=152.38−2.3257 C ⟶ equation2
Equate 1 and 2
100−C=152.38−2.3257 C
C=39.51lb
1 lb seeds
W S =100 lb feed x =1lb
100lb feed
W P=C+ W S =39.51+1=40.51lb
WP WS
∆D 3
∫ d W P=∫ 1+
0 0
3
( DS )
d WS

W P=
[ ]
DP
DS
WS
From table 19-6 (CHE HB 8th edition)
D S =mes h 80=0.177 mm(sieve opening)

D P =( 0.177 mm )
D P =0.6079 mm
√
3 40.51lb

1 lb

From table 19-6 (CHE HB 8th edition)

MESH ¿24 MESH ANSWER

PROBLEM # 19:

Trisodium phosphate is to be recovered as Na 3PO4·12H2O from a 35 weight % solution originally

at 190°F 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/lb·°F.
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:
 CHEMICAL ENGINEERING SERIES 41
CRYSTALLIZATION

WP WS 3
∆D
∫ d W P=∫ 1+
0 0
DS ( d WS
)
d W S =W S d ϕ S
1
∆D 3
W P=W S∫
0
( 1+
DS
d ϕS
)
WP 1 ∆D 3
=∫ 1+
WS 0 DS ( d ϕS
) 1
WP ∆D 3
let , m= =∫ 1+
WS 0 DS
d ϕS
3
( )
∆D
Δ m= 1+ ( DS
Δ ϕS )
Where: Δ ϕ S = fractional weight range

Solve for required m :

W 7,000 lb
mreqd = P = =14
W S 500 lb

This problem can be solved by trial and error

1. Assume value of ΔD
∆D 3
2. Solve for 1+
DS( )
for each size range, use the mean D́ S for each size range

3. Solve for Δ m
4. Get the total Δ m
5. If ∑ Δ m=m reqd , then assumed Δ D is correct; if not, redo another trial

TRIAL 1: Assume Δ D=0.004∈¿

3 3
ΔD ΔD
D́ S Δ ϕS
( 1+
D́S ) (
Δ m= Δ ϕ S 1+
D́ S )
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
1.00 14.4201
Since % error is less than 5%, assumed value can be considered
 CHEMICAL ENGINEERING SERIES 42
CRYSTALLIZATION

For particle size distribution:

D P =Δ D+ D S
Δm
wt=100 Δ ϕS = 3
x 100
ΔD
( 1+
D́ S )
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

Consider over-all material balance:

F=L+ C
lb
C=W P−W S=7,000−500=6,500
h
lb
L=20,000−6,500=13,500
h

Consider Na3PO4 balance:

x F F=x L L+ x C C
M Na PO 164 lb Na3 PO 4
x C= 3 4
= =0.4316
M Na PO ∙12 H O 380
3 4 2
lb Na 3 PO 4 ∙12 H 2 O
( 0.35 ) ( 20,000 )=( x L ) ( 13,500 ) + ( 0.4316 )( 6,500 )

lb Na3 PO 4
x L =0.3107
lb soln
lb Na3 PO 4 lb soln
x L =0.3107 x
lb soln ( 1−0.3107 ) lb H 2 O
lb Na3 PO 4
x L =0.4507
lb H 2 O

From table 2-120 (CHE HB 8th edition)

50°C 43 lb/100 lb H2O

60°C 55 lb/100 lb H2O
 CHEMICAL ENGINEERING SERIES 43
CRYSTALLIZATION

T =51.725° C ≈ 125.11 ° F ANSWER

Cooling Duty:

Consider heat balance:

q=F C P ( t F −t P ) +C H C

[(
q= 20,000
lb
h)(
0.8
BTU
lb∙ ° F ) ] [(
( 190−125.11 ) ° F + 6,500
lb
)(
h
27,500
BTU lbmol
x
lbmol 380 lb )]
BTU
q=1,508,634.74 ANSWER
h
 CHEMICAL ENGINEERING SERIES 44
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:

For a saturated solution utilizing 100 kg water as solvent:

1. Mole of CaCl2 required

6.7 gmol CaCl2 1 kmol CaCl2
nCaCl =100 kg H 2 O x x
2
kg H 2 O 1,000 gmol CaCl2
nCaCl =0.67 kmol
2

2. Weight of CaCl2 required

110.994 kg CaCl2
W CaCl =0.67 kg CaCl 2 x
2
kmol CaCl2
W CaCl =74.36 kg
2

3. Mole of CaCl2·6H2O required

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

4. Weight CaCl2·6H2O required

218.994 kg CaCl2 ∙ 6 H 2 O
W CaCl ∙ 6 H O =0.67 kmol CaCl2 ∙6 H 2 O x
2 2
kmol CaCl2 ∙ 6 H 2 O
W CaCl ∙ 6 H O =146.72kg
2 2

5. Composition of the solution in terms of CaCl 2·6H2O

W CaCl ∙ 6 H O =146.72kg
2 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−( 146.72−74.36 ) kg=27.64 kg

2

6. Amount of CaCl2·6H2O required for every 100 kg free water (net of water of hydration)

146.72kg CaCl 2 ∙ 6 H 2 O
W CaCl ∙ 6 H O =100 kg free H 2 O x
2 2
27.64 kg free H 2 O
W CaCl ∙ 6 H
2 2 O =530. 82 kg ANSWER