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CHEMICAL ENGINEERING SERIES

CRYSTALLIZATION
Compilation of Lectures and Solved Problems

CHEMICAL ENGINEERING SERIES 2


CRYSTALLIZATION

CRYSTALLIZATION
Refers to a solid-liquid separation process in which solid particles are formed within a homogenous phase.
It can occur as:
(1) 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

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

CHEMICAL ENGINEERING SERIES 3


CRYSTALLIZATION
Mechanism of Crystallization Process
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
SOLUTION

WATER

CRYSTALS

Solution is concentrated
by evaporating water

The concentrated
solution is cooled until
the concentration
becomes greater than
its solubility at that
temperature

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

CHEMICAL ENGINEERING SERIES 4


CRYSTALLIZATION

Types of Crystal Geometry


(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

CHEMICAL ENGINEERING SERIES 5


CRYSTALLIZATION

(1) TYPE I: Solubility increases with temperature


and there are no hydrates or water of
crystallization

Solubility, gram per 100 gram water

Types of Solubility Curve


300
250
200

150
100
50
0
0

20

40

60

80

100

80

100

(2) TYPE II: Solubility increases with temperature


but curve is marked with extreme flatness

Solubility, gram per 100 gram water

Temperature, C
250
200

150
100
50
0
0

20

40

60

Temperature, C

(3) TYPE III: Solubility increasing fairly rapid with


temperature but is characterized by breaks
and indicates different hydrates or water of
crystallization

Solubility, gram per 100 gram water

Solubility of NaCl (CHE HB 8th edition)

250
200
150
Na2HPO42H2O

Na2HPO47H2O

100

Na2HPO4

Na2HPO412H2O

50
0
0

20

40

60

80

100

(4) TYPE IV: Unusual Curve; Solubility increases


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

Solubility, gram per 100 gram water

Temperature, C
Solubility of Na2HPO4 (CHE HB 8th edition)
60

50
40
Na2CO3H2O

30
20

Na2CO310H2O

10
0
0

20

40

60

80

100

Temperature, C
Solubility of Na2CO3 (CHE HB 8th edition)

SUPERSATURATION BY COOLING
Crystallizers that obtain precipitation by cooling a concentrated hot solution; applicable for substance that
have solubility curve that decreases with temperature; for normal solubility curve which are common for
most substances

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CRYSTALLIZATION
Pan Crystallizers
Batch operation; seldom used in modern practice, except in small scale operations, because they are
wasteful of floor space and of labor; usually give a low quality product
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:
L
XL
hL
tL

F
XF
hf
tF

W
t1

W
t2

C
XC
hC
tC

Over-all material Balance:


Solute Balance:
Enthalpy Balance:
Heat Balance:
(

)
(

Heat Transfer Equation


[

)
]

where:
= mass of the feed solution
= mass of the mother liquor, usually saturated solution
= mass of the crystals
= mass of the cooling water
= mass solute (salt) in the feed solution per mass of feed solution
= mass of solute (salt) in the mother liquor per mass of mother liquor
= mass of solute (salt) in the srystals per mass of crystals
= enthalpy of the feed solution
= enthalpy of the mother liquor
= enthalpy of the crystals
= heat absorbed by the cooling water
= heat loss by the crystals
= specific heat of the feed solution
= specific heat of cooling water
= heat of crystallization
= over-all heat transfer coefficient
= heat transfer area
= temperature of the feed solution
= temperature of the mother liquor
= inlet temperature of cooling water
= outlet temperature of cooling water

CHEMICAL ENGINEERING SERIES 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:
V
hV
F
XF
hf
tF

L
XL
hL
tL

W
t1

W
t2

C
XC
hC
tC

Over-all material Balance:


Solute Balance:
Solvent Balance:
(
)

Enthalpy Balance:
Heat Balance:
(

)
(

where:
= mass of the feed solution
= mass of the mother liquor, usually saturated solution
= mass of the crystals
= mass of the cooling water
= mass of the evaporated solvent
= mass solute (salt) in the feed solution per mass of feed
solution
= mass of solute (salt) in the mother liquor per mass of
mother liquor
= mass of solute (salt) in the srystals per mass of crystals
= enthalpy of the feed solution
= enthalpy of the mother liquor
= enthalpy of the crystals
= enthalpy of the vapor
= heat absorbed by the cooling water
= heat loss by the crystals
= specific heat of the feed solution
= specific heat of cooling water
= heat of crystallization
= latent heat of vaporization
= over-all heat transfer coefficient
= heat transfer area
= temperature of the feed solution
= temperature of the mother liquor
= inlet temperature of cooling water
= outlet temperature of cooling water

CHEMICAL ENGINEERING SERIES 8


CRYSTALLIZATION

SUPERSATURATION BY ADIABATIC EVAPORATION OF SOLVENT


V
hV

F
XF
hf

L
XL
hL

C
XC
hC

Over-all material Balance:


Solute Balance:
Solvent Balance:
(
)

where:
= mass of the feed solution
= mass of the mother liquor, usually saturated solution
= mass of the crystals
= mass of the cooling water
= mass of the evaporated solvent
= mass solute (salt) in the feed solution per mass of feed
solution
= mass of solute (salt) in the mother liquor per mass of
mother liquor
= mass of solute (salt) in the srystals per mass of crystals
= enthalpy of the feed solution
= enthalpy of the mother liquor
= enthalpy of the crystals
= enthalpy of the vapor
= heat of crystallization
= temperature of the feed solution
= temperature of the mother liquor
= inlet temperature of cooling water
= outlet temperature of cooling water

Enthalpy Balance:

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

The relation between seed and product particle sizes may be written as

Where:
= characteristic particle dimension of the product
= characteristic particle dimension of the seed
= change in size of crystals and is constant throughout the range of size present

CHEMICAL ENGINEERING SERIES 9


CRYSTALLIZATION

Since the rate of linear crystal growth is independent of crystal size, the seed and product masses may
be related for
(
(

)
)

)
[

(
(

]
)

All the crystals in the seed have been assumed to be of the same shape, and the shape has been assumed
to be unchanged by the growth process. Through assumption is reasonably closed to the actual conditions
in most cases. For differential parts of the crystal masses, each consisting of crystals of identical
dimensions:

CHEMICAL ENGINEERING SERIES 10


CRYSTALLIZATION
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?

Na2SO4 solution
xF = 0.20
tF = 200F

Na2SO4 10H2O
C

Magma, M
tM = 60F

SOLUTION:
Basis: 100 lb feed
From table 2-122 (CHE HB), solubility of Na2SO410H2O
T,C
10
15
20
g/100 g H2O
9.0
19.4
40.8
Consider over-all material balance:

Consider solute balance:

At 60F, solubility is 21.7778 g per 100 g water

)(

Substitute

)( )

)( )

in
(

Magma composition:

% Recovery:
)(

(
(

)(

)
)

CHEMICAL ENGINEERING SERIES 11


CRYSTALLIZATION

PROBLEM # 02:
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.

MgSO4 solution
F = 10,000 lb/h
xF = 0.325
tF = 150F

MgSO4 7H2O
C = 4,000 lb/h

SOLUTION:
Consider over-all material balance:

Consider solute balance:

)(

( )

)(

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
th
2. From figure 27-3 (Unit Operations by McCabe and Smoth 7 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
th
Smith 7 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

CHEMICAL ENGINEERING SERIES 12


CRYSTALLIZATION
TRIAL 1: Assume temperature of the solution at 60F
th
From figure 27-3 (Unit Operations by McCabe and Smith 7 edition)

Substitute to equation

Substitute to equation

th

From figure 27-4 (Unit Operations by McCabe and Smith, 7 edition)

Temperature of vapor is 60 10 = 50F


From steam table at 50F,
)(

[(

)(

)( )

)]

)(

)(

Since % error is less than 5%, assumed value can be considered correct.
Product temperature

Operating Pressure
From steam table for vapor temperature of 50F

Ratio of mother liquor to crystalline product

CHEMICAL ENGINEERING SERIES 13


CRYSTALLIZATION
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

CALCINATION

YIELD = 90%

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:

CRYSTALLIZATION
T=0C
YIELD = 95%
P
Na2SO4
30,000 MT/yr

CHEMICAL ENGINEERING SERIES 14


CRYSTALLIZATION
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

C
T = 20 C

F
1,200 lb BaNO3

CRYSTALLIZER
T = 90 C
L
T = 20 C

CHE BP July 1968


SOLUTION:
(

)
(
(

Consider Ba(NO3)2 balance

Substitute

)( )

)( )

in
(
[(

)
)(

Consider over-all material balance around the crystallizer

)]

CHEMICAL ENGINEERING SERIES 15


CRYSTALLIZATION
PROBLEM # 05:
A Swenson-Walker crystallizer is to be used
to produce 1 ton/h of copperas (FeSO47H2O)
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
2
for the crystallizer is 35 BTU/hFft . There
2
are 3.5 ft 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:
Consider over-all material balance:

Consider copperas (FeSO47H2O) balance:

Equate

)( )

)(

and

Consider heat balance:


(

)( )

F
tF = 120 F

L
tL = 80 F
SWENSON-WALKER
CRYSTALLIZER

W
t1 = 60 F

t2 = 70 F

C, 1 ton/h
Fe2SO47H2O
tC = 80 F

CHEMICAL ENGINEERING SERIES 16


CRYSTALLIZATION
[(

)(

)(
[(

)(

(
)

)(

)
(

]
)]

)(

CHEMICAL ENGINEERING SERIES 17


CRYSTALLIZATION
PROBLEM # 06:
Crystals of Na2CO310H2O are dropped into a saturated solution of Na2CO3 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

CHEMICAL ENGINEERING SERIES 18


CRYSTALLIZATION
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
rate at which the solution must be fed to the
crystallizer to produce one ton of MgSO47H2O
per hour?

F
tF = 220 F
43 g MgSO4/100 g H2O

L
tL = 50 F

COOLING CRYSTALLIZER

C, 1 ton/h
MgSO47H2O
tC = 50 F

SOLUTION:
Consider over-all material balance:

Consider MgSO4 balance

th

From table 27-3 (Unit Operations by McCabe and Smith, 7 edition), at 50F

Equate

)( )

and

)( )

)( )

CHEMICAL ENGINEERING SERIES 19


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
Consider over-all material balance:

Consider NaHCO3 balance

(
(

)(

Equate

)( )

( )( )

)(

and

V
F
tF = 20 C
8.4% Na2SO4

L
tL = 20 C

CRYSTALLIZER

C,
tC = 20 C

F
tF = 60 F
16.4 g
NaHCO3 /100 g
H2O

L
tL = 20 F
COOLING CRYSTALLIZER

C,
9.6 g NaHCO3
per 100 g H2O
tC = 20 F

CHEMICAL ENGINEERING SERIES 20


CRYSTALLIZATION

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 Na2SO4 per 100
g H2O.
SOLUTION:
Basis: 1 L feed

Consider over-all material balance:

(
(

)(

)(

Substitute to equation

Consider Na2SO4 balance

(
(

)( )

Substitute to equation

CHEMICAL ENGINEERING SERIES 21


CRYSTALLIZATION
PROBLEM # 10:
A hot solution of Ba(NO3)2 from an evaporator
contains 30.6 kg Ba(NO3)2/100 kg H2O and
goes to a crystallizer where the solution is
cooled and Ba(NO3)2 crystallizes. On cooling,
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
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

V
L

F
30.6 kg Ba(NO3)2/100 kg H2O

CRYSTALLIZER

Source:
Transport Processes and Unit
Operations (Geankoplis)

SOLUTION:
a) If solution is cooled to 290K
Consider over-all material balance:

If water evaporated is 10% of the original water present


(
)
(
)
(
)
(
)(
)

Consider Ba(NO3)2 balance


(

(
(

Equate

)(

and

)( )

)( )

CHEMICAL ENGINEERING SERIES 22


CRYSTALLIZATION

b) If solution is cooled to 283 K


Consider over-all material balance:

If water evaporated is 10% of the original water present


(
)
(
)
(
)
(
)(
)

Consider Ba(NO3)2 balance


(

(
(

Equate

)(

and

)( )

)( )

CHEMICAL ENGINEERING SERIES 23


CRYSTALLIZATION

PROBLEM # 11:
A batch of 1,000 kg of KCl is dissolved in
sufficient water to make a saturated solution at
363 K, where the solubility is 35 wt % KCl in
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?

V
F
1,000 kg KCl
363K

Source:
Transport Processes and Unit
Operations (Geankoplis)

SOLUTION:
c) Assume crystallization by cooling (without evaporation)
Consider over-all material balance:

Consider KCl balance

)( )

Equate

)( )

and

)(

L
293K
CRYSTALLIZER

C
293K

CHEMICAL ENGINEERING SERIES 24


CRYSTALLIZATION

d) Crystallization with evaporation


Consider over-all material balance:
(

Consider KCl balance

Equate

)( )

and

)( )

CHEMICAL ENGINEERING SERIES 25


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
2
25 BTU/hft 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 Glaubers Salt
Source: Unit Operations (Brown)

SOLUTION:
Consider over-all material balance:

Consider Na2SO4 balance

)
(

Equate

and

F
tF = 30 C

L
tL = 15 C
SWENSON-WALKER
CRYSTALLIZER

W
t1 = 10 C

t2 = 20 C

C, 1 ton/h
Na2SO410H2O
tC = 15 C

CHEMICAL ENGINEERING SERIES 26


CRYSTALLIZATION
Consider heat balance:
(
)
(
)

)
th

From Table 2-194 (CHE HB 8 edition)

[(

)(

[(

)(

)(

)(
[(

)(

)
)(

)]

]
)]

CHEMICAL ENGINEERING SERIES 27


CRYSTALLIZATION

PROBLEM # 13:
A continuous adiabatic vacuum crystallizer is
to be used for the production of 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?

F, 20,000 lb/h
xF = 0.3000
tF = 160 F

ADIABATIC VACUUM
CRYSTALLIZER

C = 6,000 lb/h
MgSO47H2O

L
BPE = 10 F

Source: Unit Operations (Brown)

SOLUTION:
Consider over-all material balance:

Consider MgSO4 balance

)(

( )( )

)(

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
th
2. From figure 27-3 (Unit Operations by McCabe and Smoth 7 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
th
Smith 7 edition) at the designated temperatures and concentrations

CHEMICAL ENGINEERING SERIES 28


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


th
From figure 27-3 (Unit Operations by McCabe and Smith 7 edition)

Substitute to equation

Substitute to equation

th

From figure 27-4 (Unit Operations by McCabe and Smith, 7 edition)

Temperature of vapor is 60 10 = 50F


From steam table at 50F,
)(

[(

( )(

)( )

)(

)]

)(

Since % error is about 5%, assumed value can be considered correct.

CHEMICAL ENGINEERING SERIES 29


CRYSTALLIZATION

PROBLEM # 14:
Crystals of CaCl26H2O are to be obtained
from a solution of 35 weight % CaCl2, 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 2
edition (Foust, et al)

F
CaCl2 = 35%
Inert = 10%
H2O = 55%
tF = 100 F

OSLO CRYSTALLIZER

M (magma)
C
Inert
L
tF = 40 F

CENTRIFUGE

C
CaCl26H2O

DRYER

nd

SOLUTION:
Basis: 1 lb of inert soluble-free feed
th
from table 2-120 (CHE HB 8 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
(
)
From table 2-194, specific heat of CaCl2, cal/Kmol
where T is in K
At 100F (310.93 K)

At 40F (277.59 K)

CHEMICAL ENGINEERING SERIES 30


CRYSTALLIZATION

For the feed


(

)(

)
(

)(

th

From table 2-224 (CHE HB 8 edition), heat of solution of CaCl26H2O = -4,100 cal/mol;
in the absence of data on heat of crystallization, heat of solution can be used instead but
of opposite sign

From the steam table, at 40F,

)( )

( )(

)(

)( )

Consider over-all material balance:

Substitute
(

in
)

Consider solute (CaCl26H2O) balance, inert soluble-free

(
(

Equate

)( )

)( )

( )( )

and
(
(

)
)

)( )

CHEMICAL ENGINEERING SERIES 31


CRYSTALLIZATION

Composition of the liquor (including the inert soluble)


(

CaCl26H2O
H2O
inerts

lb
0.0056
0.0090
0.1000
0.1146

%
4.89
7.85
87.26
100.00

For the crystals leaving the centrifuge:

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
lb
CaCl26H2O
0.7657
inerts
0.0665
0.8322

%
92.01
7.99
100.00

0.7657
0.0060
0.0665
0.8382

CHEMICAL ENGINEERING SERIES 32


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 57C to 10C. Lactose
crystallizes with one molecule of water of
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
4
heat loss trough the vat walls is 4 x 10 kJ.
Calculate the heat to be removed in the
cooling process.

F
2,500 kg
8 g lactose per 10 g
water
tF = 57 C

L
1.5 g lactose
per 10 g water

SOLUTION:
Consider over-all material balance

(
(

Consider lactose balance

Equate

)(

and

)( )

)( )

OSLO CRYSTALLIZER

C
tC = 10 C

CHEMICAL ENGINEERING SERIES 33


CRYSTALLIZATION

Consider heat balance:


(
)
At 10C (50F),

)(

[(
[(

)(
)(

)
)]

[(

)(

)]

CHEMICAL ENGINEERING SERIES 34


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.
2
The Swenson-walker crystallizer is built in units 10 ft long, containing 3 ft of heating surface per
2
foot of length. An over-all heat transfer coefficient of 35 BTU/ft hF 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.
F (Soda Ash)
W (Water)
V

A
DISSOLVER

CRYSTALLIZER
45C

FILTER

DRYER

15C

R (remainder
mother liquor)
C (Sal Soda)

SOLUTION:
Basis: 2,000 lb/h (1 ton/h) of sal soda
Consider over-all material balance of the system

Consider Na2CO3 balance around the system

)(

CHEMICAL ENGINEERING SERIES 35


CRYSTALLIZATION

Substitute to equation

Consider solute (Na2CO3) balance around the dryer


(

)(

)(

Consider over-all material balance around the dryer

Substitute to equation

Consider solute (Na2CO3) balance around the dissolver

(
(

)(

)
)( )

)( )

Consider over-all material balance around the dissolver

)(

CHEMICAL ENGINEERING SERIES 36


CRYSTALLIZATION
Equate

and

Consider heat balance around the crystallizer


(
)
(

[(

)(

)(

[(

)(

Refrigeration capacity:

)]

[(

)(

)]

CHEMICAL ENGINEERING SERIES 37


CRYSTALLIZATION
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:

)
th

From table 19-6 (CHE HB 8 edition)


(
(

Equate

and

Consider Na2S2O3 balance:

)( )

)( )

Consider over-all material balance

Equate

and

)(

)
)

CHEMICAL ENGINEERING SERIES 38


CRYSTALLIZATION

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
Consider over-all material balance

Consider MgSO4 balance


th

From figure 27-3 (Unit Operation 7 edition, McCabe and Smith) at 110F

th

From figure 27-3 (Unit Operations 7 edition, McCabe and Smith) at 40F

)(

Equate

)( )

and

)( )

]
th

From table 19-6 (CHE HB 8 edition)


(
(

th

From table 19-6 (CHE HB 8 edition)

CHEMICAL ENGINEERING SERIES 39


CRYSTALLIZATION
PROBLEM # 19:
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:

)
(
(

Where:
Solve for required

)
= fractional weight range
:

This problem can be solved by trial and error


1. Assume value of
2. Solve for (

) for each size range, use the mean for each size range

3. Solve for
4. Get the total
5. If

, then assumed

is correct; if not, redo another trial

CHEMICAL ENGINEERING SERIES 40


CRYSTALLIZATION
TRIAL 1: Assume

Since % error is less than 5%, assumed value can be considered


For particle size distribution:

Size Range, in

Size Range, in

Wt %

Consider over-all material balance:

Consider Na3PO4 balance:

)(

( )(

)(

Wt %

CHEMICAL ENGINEERING SERIES 41


CRYSTALLIZATION
(

th

From table 2-120 (CHE HB 8 edition)


50C
60C

43 lb/100 lb H2O
55 lb/100 lb H2O

Cooling Duty:
Consider heat balance:
(
)
[(

)(

)(

[(

)(

)]

CHEMICAL ENGINEERING SERIES 42


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

2. Weight of CaCl2 required

3. Mole of CaCl26H2O required

4. Weight CaCl26H2O required

5. Composition of the solution in terms of CaCl26H2O

Since there should only be total of 100 kg water in the solution, the amount of free water (net
of water of hydration)
(

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