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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. 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
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

WATER
SOLUTION

CRYSTALS

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

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) 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
CHEMICAL ENGINEERING SERIES 5
CRYSTALLIZATION

Types of Solubility Curve


300

Solubility, gram per 100 gram water


250

200
(1) TYPE I: Solubility increases with temperature
150
and there are no hydrates or water of
crystallization 100

50

0
0 20 40 60 80 100
Temperature, °C

250

Solubility, gram per 100 gram water


200

150

(2) TYPE II: Solubility increases with temperature 100


but curve is marked with extreme flatness
50

0
0 20 40 60 80 100
Temperature, °C
Solubility of NaCl (CHE HB 8th edition)

250
Solubility, gram per 100 gram water

200

(3) TYPE III: Solubility increasing fairly rapid with 150


temperature but is characterized by “breaks” Na2HPO4·7H2O Na2HPO4·2H2O
Na2HPO4
100
and indicates different “hydrates” or water of Na2HPO4·12H2O
crystallization 50

0
0 20 40 60 80 100
Temperature, °C
Solubility of Na2HPO4 (CHE HB 8th edition)
60
Solubility, gram per 100 gram water

50

40
(4) TYPE IV: Unusual Curve; Solubility increases Na2CO3·H2O

at a certain transition point while the solubility of 30

the hydrate decreases as temperature 20


Na2CO3·10H2O
increases 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
CHEMICAL ENGINEERING SERIES 6
CRYSTALLIZATION

Pan Crystallizers

Batch operation; seldom used in modern practice, except in small scale operations, because they are
wasteful of floor space and of labor; usually give a low quality product

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
F XL
XF hL where:
hf tL = mass of the feed solution
tF = mass of the mother liquor, usually saturated solution
W = mass of the crystals
W
t1 C
t2 = mass of the cooling water
XC
= mass solute (salt) in the feed solution per mass of feed solution
hC
tC = mass of solute (salt) in the mother liquor per mass of mother liquor
= mass of solute (salt) in the srystals per mass of crystals
= enthalpy of the feed solution
Over-all material Balance:
= enthalpy of the mother liquor
= enthalpy of the crystals
= heat absorbed by the cooling water
Solute Balance:
= heat loss by the crystals
= specific heat of the feed solution
Enthalpy Balance: = specific heat of cooling water
= heat of crystallization
= over-all heat transfer coefficient
Heat Balance: = heat transfer area
= temperature of the feed solution
( ) = temperature of the mother liquor
( ) = inlet temperature of cooling water
= outlet temperature of cooling water
Heat Transfer Equation

( ) ( )
[ ]
CHEMICAL ENGINEERING SERIES 7
CRYSTALLIZATION

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 where:
hV L = mass of the feed solution
F XL = mass of the mother liquor, usually saturated solution
XF hL = mass of the crystals
hf tL = mass of the cooling water
tF = mass of the evaporated solvent
W = mass solute (salt) in the feed solution per mass of feed
W
t1 C solution
t2
XC
= mass of solute (salt) in the mother liquor per mass of
hC
mother liquor
tC
= mass of solute (salt) in the srystals per mass of crystals
Over-all material Balance: = enthalpy of the feed solution
= enthalpy of the mother liquor
= enthalpy of the crystals
Solute Balance:
= enthalpy of the vapor
= heat absorbed by the cooling water
= heat loss by the crystals
Solvent Balance:
( ) ( ) ( ) = specific heat of the feed solution
= specific heat of cooling water
Enthalpy Balance: = heat of crystallization
= latent heat of vaporization
= over-all heat transfer coefficient
Heat Balance: = heat transfer area
= temperature of the feed solution
( ) = temperature of the mother liquor
( ) = inlet temperature of cooling water
= outlet temperature of cooling water
CHEMICAL ENGINEERING SERIES 8
CRYSTALLIZATION

SUPERSATURATION BY ADIABATIC EVAPORATION OF SOLVENT

V where:
hV
= mass of the feed solution
= mass of the mother liquor, usually saturated solution
F = mass of the crystals
XF = mass of the cooling water
hf
= mass of the evaporated solvent
L = mass solute (salt) in the feed solution per mass of feed
XL
M hL solution
= mass of solute (salt) in the mother liquor per mass of
C
XC
mother liquor
hC = mass of solute (salt) in the srystals per mass of crystals
= enthalpy of the feed solution
Over-all material Balance: = enthalpy of the mother liquor
= enthalpy of the crystals
= enthalpy of the vapor
Solute Balance: = heat of crystallization
= temperature of the feed solution
= temperature of the mother liquor
Solvent Balance: = inlet temperature of cooling water
( ) ( ) ( ) = outlet temperature of cooling water

Enthalpy Balance:

CRYSTALLIZATION BY SEEDING

ΔL Law of Crystals

 States that if all crystals in magma grow in a supersaturation field and at the same temperature and if
all crystal grow from birth at a rate governed by the supersaturation, then all crystals are not only
invariant but also have the same growth rate that is independent of size

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

Where:
= characteristic particle dimension of the product
= characteristic particle dimension of the seed
= change in size of crystals and is constant throughout the range of size present
CHEMICAL ENGINEERING SERIES 9
CRYSTALLIZATION

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

( )

( )

( )

[ ]
( )

( )

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

∫ ∫ ( )

∫ ( )
CHEMICAL ENGINEERING SERIES 10
CRYSTALLIZATION

PROBLEM # 01: Na2SO4 solution


xF = 0.20
A 20 weight % solution of Na2SO4 at tF = 200°F
200°F is pumped continuously to a
vacuum crystallizer from which the
magma is pumped at 60°F. What is Na2SO4 ·10H2O
the composition of this magma, and Magma, M
C
tM = 60°F
what percentage of Na2SO4 in the
feed is recovered as Na2SO4·10H2O
crystals after this magma is
centrifuged? L
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:

Consider solute balance:

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

( )( ) ( )( ) ( )( )

Substitute in
( )

Magma composition:

% Recovery:
( )( )

( )( )
CHEMICAL ENGINEERING SERIES 11
CRYSTALLIZATION

PROBLEM # 02: MgSO4 solution V


F = 10,000 lb/h
A solution of 32.5% MgSO4 originally
xF = 0.325
at 150°F is to be crystallized in a tF = 150°F
vacuum adiabatic crystallizer to give
a product containing 4,000 lb/h of
MgSO4·7H2O crystals from 10,000 MgSO4 ·7H2O
lb/h of feed. The solution boiling C = 4,000 lb/h
point rise is estimated at 10°F.
Determine the product temperature,
pressure and weight ratio of mother
liquor to crystalline product. L
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 60°F


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 = 50°F

From steam table at 50°F,

[( )( )]

( )( ) ( )( ) ( )( ) ( )( )

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

Product temperature

Operating Pressure
From steam table for vapor temperature of 50°F

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 F
CALCINATION CRYSTALLIZATION
0°C, yields of 95% and 90% in the
crystallization and calcinations operations are T=0C
YIELD = 90%
obtained respectively. How many metric tons YIELD = 95%
of liquor are fed to the crystallizer daily? Note:
300 working days per year P
Na2SO4
30,000 MT/yr
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:


CHEMICAL ENGINEERING SERIES 14
CRYSTALLIZATION

PROBLEM # 04 :
1,200 lb of barium nitrate are dissolved in
V
sufficient water to form a saturated solution at
90°C. Assuming that 5% of the weight of the
C
original solution is lost through evaporation, F
T = 20 C
1,200 lb BaNO3
calculate the crop of the crystals obtained CRYSTALLIZER
when cooled to 20°C. solubility data of barium T = 90 C
nitrate at 90°C = 30.6 lb/100 lb water; at 20°C = L
9.2 lb/100 lb water T = 20 C

CHE BP July 1968


SOLUTION:

( ) ( )
( )
( )

( )
( )

( ) ( )
( )

Consider over-all material balance around the crystallizer

( )

Consider Ba(NO3)2 balance

( )( ) ( )( )

Substitute in

( )

[( )( )]
CHEMICAL ENGINEERING SERIES 15
CRYSTALLIZATION

PROBLEM # 05:

A Swenson-Walker crystallizer is to be used


to produce 1 ton/h of copperas (FeSO4·7H2O) L
crystals. The saturated solution enters the tL = 80 F
F
crystallizer at 120°F. The slurry leaving the SWENSON-WALKER
tF = 120 F
CRYSTALLIZER
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 W
C, 1 ton/h
2 t2 = 70 F Fe2SO4·7H2O
for the crystallizer is 35 BTU/h·°F·ft . There t1 = 60 F
tC = 80 F
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/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:

Consider copperas (FeSO4·7H2O) balance:

( )( ) ( )( ) ( )( )

Equate and

Consider heat balance:

( )
CHEMICAL ENGINEERING SERIES 16
CRYSTALLIZATION

[( )( )( ) ]

[( )( )]

( )

( )( )

( ) ( )

( ) ( )

( )( )
CHEMICAL ENGINEERING SERIES 17
CRYSTALLIZATION

PROBLEM # 06:
Crystals of Na2CO3·10H2O are dropped into a saturated solution of Na2CO3 in water at 100°C.
What percent of the Na2CO3 in the Na2CO3·H2O is recovered in the precipitated solid? The
precipitated solid is Na2CO3·H2O. Data at 100°C: the saturated solution is 31.2% Na 2CO3;
molecular weight of Na2CO3 is 106

SOLUTION:

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


CHEMICAL ENGINEERING SERIES 18
CRYSTALLIZATION

PROBLEM # 07:

A solution of MgSO4 at 220°F containing 43 g L


F
MgSO4 per 100 g H2O is fed into a cooling tF = 220 F
tL = 50 F

crystallizer operating at 50°F. If the solution 43 g MgSO4/100 g H2O


COOLING CRYSTALLIZER
leaving the crystallizer is saturated, what is the
rate at which the solution must be fed to the C, 1 ton/h
MgSO4·7H2O
crystallizer to produce one ton of MgSO4·7H2O tC = 50 F

per hour?

SOLUTION:

Consider over-all material balance:

Consider MgSO4 balance

( )

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

( )( ) ( )( ) ( )( )

Equate and
CHEMICAL ENGINEERING SERIES 19
CRYSTALLIZATION

PROBLEM # 08:

F L
The solubility of sodium bicarbonate in water tF = 60 F tL = 20 F
is 9.6 g per 100 g water at 20°C and 16.4 g 16.4 g
NaHCO3 /100 g
per 100 g water at 60°C. If a saturated H2O
COOLING CRYSTALLIZER
solution of NaHCO3 at 60°C is cooled to 20°C,
what is the percentage of the dissolved salt C,
that crystallizes out? 9.6 g NaHCO3
per 100 g H2O
tC = 20 F

SOLUTION:

Basis: 100 kg feed

Consider over-all material balance:

Consider NaHCO3 balance

( )

( )

( )( ) ( )( ) ( )( )

Equate and

( )( )

V
L
F tL = 20 C
tF = 20 C
8.4% Na2SO4
CRYSTALLIZER

C,
tC = 20 C
CHEMICAL ENGINEERING SERIES 20
CRYSTALLIZATION

PROBLEM # 09:

Glauber’s salt is made by crystallization from a water solution at 20°C. The aqueous solution at
20°C contains 8.4% sodium sulfate. How many grams of water must be evaporated from a liter of
such solution whose specific gravity is 1.077 so that when the residue solution after evaporation
is cooled to 20°C, there will be crystallized out 80% of the original sodium sulfate as Glauber’s
salt. The solubility of sodium sulfate in equilibrium with the decahydrate is 19.4 g Na2SO4 per 100
g H2O.

SOLUTION:

Basis: 1 L feed

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, V
10% of the original water present evaporates.
For a feed solution of 100 kg total, calculate L
F
the following: 30.6 kg Ba(NO3)2/100 kg H2O
CRYSTALLIZER
a) The yield of crystals if the solution is
cooled to 290K, where the solubility is 8.6
C
kg Ba(NO3)2/100 kg total water
b) The yield if cooled instead to 283K, where
the solubility is 7 kg Ba(NO 3)2/100 kg total
water

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
V
water. The solution is cooled to 293 K, at
L
which temperature its solubility is 25.4 wt %. F
293K
1,000 kg KCl
a) What are the weight of water required for 363K
CRYSTALLIZER
the solution and the weight of KCl crystals
obtained?
C
b) What is the weight of crystals obtained if 293K
5% of the original water evaporates on
cooling?

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

( )( )
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 30°C, and
13.5 parts at 15°C. The latent heat of
crystallization (liberated when crystals form) is
L
18,000 g-cal per gmol Na2SO4. Glauber’s salt tL = 15 C
F
(Na2SO4·10H2O) is to be made in a Swenson- tF = 30 C
SWENSON-WALKER
CRYSTALLIZER
Walker crystallizer by cooling a solution,
saturated at 30°C, to 15°C. Cooling water
C, 1 ton/h
enters at 10°C and leaves at 20°C. The over- W
t2 = 20 C Na2SO4·10H2O
t1 = 10 C
all heat transfer coefficient in the crystallizer is tC = 15 C
2
25 BTU/h·ft ·°F and each foot of crystallizer
has 3 sq ft of cooling surface. How many 10-ft
units of crystallizer will be required to produce
1 ton/h of Glauber’s Salt

Source: Unit Operations (Brown)

SOLUTION:

Consider over-all material balance:

Consider Na2SO4 balance

( )

( )

( )

Equate and
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 MgSO4·7H2O
V
crystals from 20,000 lb/h of solution containing
0.300 weight fraction MgSO4. The solution
enters the crystallizer at 160°F. The C = 6,000 lb/h
F, 20,000 lb/h
crystallizer is to be operated so that the xF = 0.3000 ADIABATIC VACUUM
MgSO4·7H2O
mixture of mother liquor and crystals leaving tF = 160 F CRYSTALLIZER
the crystallizer contains 6,000 lb/h of
MgSO4·7H2O crystals. The estimated boiling L
point elevation of the solution in the BPE = 10 F
crystallizer is 10°F. How many pounds of
water are vaporized per hour?

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 60°F


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 = 50°F

From steam table at 50°F,

[( )( )]

( )( ) ( )( ) ( )( ) ( )( )

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


CHEMICAL ENGINEERING SERIES 29
CRYSTALLIZATION

PROBLEM # 14:
Crystals of CaCl2·6H2O are to be obtained
from a solution of 35 weight % CaCl2, 10
V
weight % inert soluble impurity, and 55
weight % water in an Oslo crystallizer. The
solution is fed to the crystallizer at 100°F M (magma)
F C
and receives 250 BTU/lb of feed from the CaCl2 = 35% Inert
OSLO CRYSTALLIZER
external heater. Products are withdrawn Inert = 10% L
H2O = 55% tF = 40 F
from the crystallizer at 40°F. tF = 100 F
a) What are the products from the
crystallizer? L
CENTRIFUGE
b) The magma is centrifuged to a moisture
content of 0.1 lb of liquid per lb of
CaCl2·6H2O crystals and then dried in a
conveyor drier. What is the purity of the
final dried crystalline product? C’’ DRYER
CaCl2·6H2O
nd
Source: Principles of Unit Operations 2
edition (Foust, et al)

SOLUTION:

Basis: 1 lb of inert soluble-free feed


th
from table 2-120 (CHE HB 8 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


( )

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

where T is in K
At 100°F (310.93 K)

At 40°F (277.59 K)

̅
CHEMICAL ENGINEERING SERIES 30
CRYSTALLIZATION

For the feed


( )( ) ( )( )
( )

th
From table 2-224 (CHE HB 8 edition), heat of solution of CaCl2·6H2O = -4,100 cal/mol;
in the absence of data on heat of crystallization, heat of solution can be used instead but
of opposite sign

From the steam table, at 40°F,

( )( ) ( )( )( ) ( )( ) ( )( )

Consider over-all material balance:

Substitute in
( )

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

( )

( )

( )( ) ( )( ) ( )( )

Equate and

( )
( )
CHEMICAL ENGINEERING SERIES 31
CRYSTALLIZATION

Composition of the liquor (including the inert soluble)

( )

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:

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
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
V
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 F
crystallization. The specific heat of the 2,500 kg
OSLO CRYSTALLIZER
lactose solution is 3470 J/kg·°C. The heat of 8 g lactose per 10 g
water
solution for lactose monohydrate is -15,500 tF = 57 C
C
tC = 10 C
kJ/kmol. The molecular weight of lactose L
1.5 g lactose
monohydrate is 360 and the solubility of per 10 g water
lactose at 10°C 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.

SOLUTION:

Consider over-all material balance

( )
( )

Consider lactose balance

( )( ) ( )( ) ( )( )

Equate and
CHEMICAL ENGINEERING SERIES 33
CRYSTALLIZATION

Consider heat balance:


( )
At 10°C (50°F),

[( )( )( ) ] [( )( )]

[( )( )]
CHEMICAL ENGINEERING SERIES 34
CRYSTALLIZATION

PROBLEM # 16:
Sal soda (Na2CO3·10H2O) is to be made by dissolving soda ash in a mixture of mother liquor and
water to form a 30% solution by weight at 45°C and then cooling to 15°C. The wet crystals
removed from the mother liquor consist of 90% sal soda and 10% mother liquor by weight. The
mother liquor is to be dried on the crystals as additional sal soda. The remainder of the mother
liquor is to be returned to the dissolving tanks. At 15°C, the solubility of Na 2CO3 is 14.2 parts per
100 parts water.

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.
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 ·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.

F (Soda Ash)

W (Water)
V

A B D
DISSOLVER CRYSTALLIZER FILTER DRYER
45C 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 Na2S2O3·5H2O is to be crystallized per hour by cooling a solution containing 56.5%
Na2S2O3 to 30°C in a Swenson-Walker crystallizer. Evaporation is negligible. The product is to
be sized closely to approximately 14 mesh. Seed crystals closely sized to 20 mesh are
introduced with the solution as it enters the crystallizer. How many tons of seed crystals and how
many tons of solutions are required per hour? At 30°C, solubility of Na 2S2O3 is 83 parts per 100
parts water
Source: Unit Operations (Brown, et al)

SOLUTION:

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

∫ ∫ ( )

Equate and

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 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

Consider MgSO4 balance

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

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

( )( ) ( )( ) ( )( )

Equate and

∫ ∫ ( )

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

( )√

th
From table 19-6 (CHE HB 8 edition)
CHEMICAL ENGINEERING SERIES 39
CRYSTALLIZATION

PROBLEM # 19:

Trisodium phosphate is to be recovered as Na3PO4·12H2O 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:

∫ ∫ ( )

∫ ( )

∫ ( )

∫ ( )

( )

Where: = fractional weight range

Solve for required :

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 Wt % Size Range, in Wt %

Consider over-all material balance:

Consider Na3PO4 balance:

( )( ) ( )( ) ( )( )
CHEMICAL ENGINEERING SERIES 41
CRYSTALLIZATION

( )

th
From table 2-120 (CHE HB 8 edition)
50°C 43 lb/100 lb H2O
60°C 55 lb/100 lb H2O

Cooling Duty:

Consider heat balance:


( )

[( )( )( ) ] [( )( )]
CHEMICAL ENGINEERING SERIES 42
CRYSTALLIZATION

PROBLEM # 20:

How much CaCl2·6H2O must be dissolved in 100 kg of water at 20°C to form a saturated
solution? The solubility of CaCl2 at 20°C is 6.7 gmol anhydrous salt (CaCl2) per kg of water.

SOLUTION:

For a saturated solution utilizing 100 kg water as solvent:

1. Mole of CaCl2 required

2. Weight of CaCl2 required

3. Mole of CaCl2·6H2O required

4. Weight CaCl2·6H2O required

5. Composition of the solution in terms of CaCl2·6H2O

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

( )

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