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

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

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

Types of Solubility Curve

 CHEMICAL ENGINEERING SERIES 5
CRYSTALLIZATION

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
and indicates different “hydrates” or water of 100
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 30

of 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

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:

L
F XL
XF hL where:
hf tL 𝐹 = mass of the feed solution
tF 𝐿 = mass of the mother liquor, usually saturated solution
W 𝐶 = mass of the crystals
W
t1 C
t2 𝑊 = mass of the cooling water
XC
𝑋𝐹 = mass solute (salt) in the feed solution per mass of feed solution
hC
tC
𝑋𝐿 = mass of solute (salt) in the mother liquor per mass of mother liquor
𝑋𝐶 = mass of solute (salt) in the srystals per mass of crystals
Over-all material Balance: ℎ 𝐹 = enthalpy of the feed solution
ℎ 𝐿 = enthalpy of the mother liquor
𝐹 = 𝐿+𝐶
ℎ 𝐶 = enthalpy of the crystals
Solute Balance: 𝑞𝑤𝑎𝑡𝑒𝑟 = heat absorbed by the cooling water
𝑞𝑐𝑟𝑦𝑠𝑡𝑎𝑙𝑠 = heat loss by the crystals
𝑋𝐹 𝐹 = 𝑋𝐿 𝐿 + 𝑋𝐶 𝐶
𝐶𝑝𝐹 = specific heat of the feed solution
Enthalpy Balance: 𝐶𝑝𝐻2𝑂 = specific heat of cooling water
ℎ𝑓 𝐹 = ℎ 𝐿 𝐿 + ℎ 𝑐𝐶 + 𝑞 𝐻𝐶 = heat of crystallization
𝑈 = over-all heat transfer coefficient
Heat Balance: 𝐴 = heat transfer area
𝑞𝑤𝑎𝑡𝑒𝑟 = 𝑞𝑐𝑟𝑦𝑠𝑡𝑎𝑙𝑠 𝑡𝐹 = temperature of the feed solution
𝑞𝑐𝑟𝑦𝑠𝑡𝑎𝑙𝑠 = 𝐹𝐶𝑝𝐹 (𝑡𝐹 − 𝑡𝐿 ) + 𝐶𝐻𝐶 𝑡𝐿 = temperature of the mother liquor
𝑞𝑤𝑎𝑡𝑒𝑟 = 𝑊𝐶𝑝 𝐻2 𝑂 (𝑡2 − 𝑡1 ) 𝑡1 = inlet temperature of cooling water
𝑡2 = outlet temperature of cooling water
Heat Transfer Equation
𝑞 = 𝑈𝐴∆𝑇𝑙𝑚
( 𝑡𝐹 − 𝑡2 ) − (𝑡𝐿 − 𝑡1 )
𝑞 = 𝑈𝐴 [ 𝑡 − 𝑡2 ]
ln 𝐹
𝑡𝐿 − 𝑡1
 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 𝐹 = mass of the feed solution
F XL 𝐿 = mass of the mother liquor, usually saturated solution
XF hL 𝐶 = mass of the crystals
hf tL 𝑊 = mass of the cooling water
tF 𝑉 = mass of the evaporated solvent
W 𝑋𝐹 = mass solute (salt) in the feed solution per mass of feed
W
t1 C solution
t2
XC 𝑋𝐿 = mass of solute (salt) in the mother liquor per mass of
hC
mother liquor
tC
𝑋𝐶 = mass of solute (salt) in the srystals per mass of crystals
Over-all material Balance:
ℎ 𝐹 = enthalpy of the feed solution
𝐹 = 𝐿+𝐶 +𝑉 ℎ 𝐿 = enthalpy of the mother liquor
ℎ 𝐶 = enthalpy of the crystals
Solute Balance:
ℎ 𝑉 = enthalpy of the vapor
𝑋𝐹 𝐹 = 𝑋𝐿 𝐿 + 𝑋𝐶 𝐶 𝑞𝑤𝑎𝑡𝑒𝑟 = heat absorbed by the cooling water
𝑞𝑐𝑟𝑦𝑠𝑡𝑎𝑙𝑠 = heat loss by the crystals
Solvent Balance:
(1 − 𝑋𝐹 )𝐹 = 𝑉 + (1 − 𝑋𝐿 )𝐿 + (1 − 𝑋𝐶 )𝐶 𝐶𝑝𝐹 = specific heat of the feed solution
𝐶𝑝𝐻2𝑂 = specific heat of cooling water
Enthalpy Balance: 𝐻𝐶 = heat of crystallization
ℎ𝑓 𝐹 = ℎ 𝑉 𝑉 + ℎ 𝐿 𝐿 + ℎ 𝑐𝐶 + 𝑞 𝜆𝑉 = latent heat of vaporization
𝑈 = over-all heat transfer coefficient
Heat Balance: 𝐴 = heat transfer area
𝑞𝑤𝑎𝑡𝑒𝑟 = 𝑞𝑐𝑟𝑦𝑠𝑡𝑎𝑙𝑠 𝑡𝐹 = temperature of the feed solution
𝑞𝑐𝑟𝑦𝑠𝑡𝑎𝑙𝑠 = 𝐹𝐶𝑝𝐹 (𝑡𝐹 − 𝑡𝐿 ) + 𝐶𝐻𝐶 − 𝑉𝜆𝑉 𝑡𝐿 = temperature of the mother liquor
𝑞𝑤𝑎𝑡𝑒𝑟 = 𝑊𝐶𝑝 𝐻2 𝑂 (𝑡2 − 𝑡1 ) 𝑡1 = inlet temperature of cooling water
𝑡2 = outlet temperature of cooling water
 CHEMICAL ENGINEERING SERIES 8
CRYSTALLIZATION

SUPERSATURATION BY ADIABATIC EVAPORATION OF SOLVENT

V where:
hV 𝐹 = mass of the feed solution
𝐿 = mass of the mother liquor, usually saturated solution
F 𝐶 = mass of the crystals
XF 𝑊 = mass of the cooling water
hf
𝑉 = mass of the evaporated solvent
L 𝑋𝐹 = mass solute (salt) in the feed solution per mass of feed
XL
M hL solution
𝑋𝐿 = mass of solute (salt) in the mother liquor per mass of
C mother liquor
XC
hC 𝑋𝐶 = mass of solute (salt) in the srystals per mass of crystals
ℎ 𝐹 = enthalpy of the feed solution
Over-all material Balance: ℎ 𝐿 = enthalpy of the mother liquor
𝐹 = 𝐿+𝐶 +𝑉 ℎ 𝐶 = enthalpy of the crystals
ℎ 𝑉 = enthalpy of the vapor
Solute Balance: 𝐻𝐶 = heat of crystallization
𝑋𝐹 𝐹 = 𝑋𝐿 𝐿 + 𝑋𝐶 𝐶 𝑡𝐹 = temperature of the feed solution
𝑡𝐿 = temperature of the mother liquor
Solvent Balance: 𝑡1 = inlet temperature of cooling water
(1 − 𝑋𝐹 )𝐹 = 𝑉 + (1 − 𝑋𝐿 )𝐿 + (1 − 𝑋𝐶 )𝐶 𝑡2 = outlet temperature of cooling water

Enthalpy Balance:
ℎ𝑓 𝐹 = ℎ 𝑉 𝑉 + ℎ 𝐿 𝐿 + ℎ 𝑐𝐶

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
𝐷𝑃 = 𝐷𝑆 + ∆𝐷
Where:
𝐿𝑃 𝑜𝑟 𝐷𝑃 = characteristic particle dimension of the product
𝐿𝑆 𝑜𝑟 𝐷𝑆 = characteristic particle dimension of the seed
∆𝐿 𝑜𝑟 ∆𝐷 = 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

𝑊𝑃 = 𝑎𝜌𝐷𝑃 3 = 𝑎𝜌 (𝐷𝑆 + ∆𝐷) 3

𝑊𝑆 = 𝑎𝜌𝐷𝑆 3
𝑊𝑆
𝑊𝑃 = (𝐷𝑆 + ∆𝐷) 3
𝐷𝑆 3
𝐷𝑆 + ∆𝐷 3
𝑊𝑃 = 𝑊𝑆 ( )
𝐷𝑆
3
𝐷𝑆 + [𝐷𝑃 − 𝐷𝑆]
𝑊𝑃 = 𝑊𝑆 ( )
𝐷𝑆
𝐷𝑃 3
𝑊𝑃 = 𝑊𝑆 ( )
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
∫ 𝑑𝑊𝑃 = ∫ (1 + ) 𝑑𝑊𝑆
0 0 𝐷𝑆
𝑊𝑆
∆𝐷 3
𝑊𝑃 = ∫ (1 + ) 𝑑𝑊𝑆
0 𝐷𝑆

𝐶 = 𝑊𝑃 − 𝑊𝑆

PROBLEM # 01:
 CHEMICAL ENGINEERING SERIES 10
CRYSTALLIZATION

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

𝐹 = 𝐶 +𝐿
𝐿 = 100 − 𝐶 𝑒𝑞𝑛 1
Consider solute balance:
𝑋𝐹 𝐹 = 𝑋𝐶 𝐶 + 𝑋𝐿 𝐿
𝑀𝑁𝑎 2𝑆𝑂4 142 𝑙𝑏 𝑁𝑎2 𝑆𝑂4
𝑋𝐶 = = = 0.4410
𝑀𝑁𝑎2𝑆𝑂4∙10𝐻2 𝑂 322 𝑙𝑏 𝑁𝑎2 𝑆𝑂4 ∙ 10𝐻2 𝑂
At 60°F, solubility is 21.7778 g per 100 g water
21.7778 𝑙𝑏 𝑁𝑎2 𝑆𝑂4
𝑋𝐿 = = 0.1788
100 + 21.7778 𝑙𝑏 𝑙𝑖𝑞𝑢𝑜𝑟
𝑙𝑏 𝑁𝑎2 𝑆𝑂4 𝑙𝑏 𝑁𝑎2 𝑆𝑂4 𝑙𝑏 𝑁𝑎2 𝑆𝑂4
(0.20 ) (100 𝑙𝑏 𝑓𝑒𝑒𝑑 ) = (0.1788 ) (𝐿 ) + (0.4410 ) (𝐶 )
𝑙𝑏 𝑓𝑒𝑒𝑑 𝑙𝑏 𝑙𝑖𝑞𝑢𝑜𝑟 𝑙𝑏 𝑁𝑎2 𝑆𝑂4 ∙ 10𝐻2 𝑂
20 = 0.1788 𝐿 + 0.4410 𝐶 𝑒𝑞𝑛 2
Substitute 1 in 2
20 = 0.1788 (100 − 𝐶 ) + 0.4410 𝐶
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
% Recovery:
𝑙𝑏 𝑁𝑎2 𝑆𝑂4
𝑋𝐶 𝐶 (0.4410 ) (8.0854𝑙𝑏 𝑁𝑎2 𝑆𝑂4 ∙ 10𝐻2 𝑂)
𝑙𝑏 𝑁𝑎2 𝑆𝑂4 ∙ 10𝐻 2 𝑂
% 𝑟𝑒𝑐𝑜𝑣𝑒𝑟𝑦 = 𝑥 100 = 𝑥100
𝑋𝐹 𝐹 𝑙𝑏 𝑁𝑎2 𝑆𝑂4 (
(0.20 ) 100 𝑙𝑏 𝑓𝑒𝑒𝑑 )
𝑙𝑏 𝑓𝑒𝑒𝑑
% 𝒓𝒆𝒄𝒐𝒗𝒆𝒓𝒚 = 𝟏𝟕. 𝟖𝟑 % 𝐴𝑁𝑆𝑊𝐸𝑅
 CHEMICAL ENGINEERING SERIES 11
CRYSTALLIZATION

PROBLEM # 02: MgSO4 solution V

A solution of 32.5% MgSO4 F = 10,000 lb/h
originally at 150°F is to be xF = 0.325
crystallized in a vacuum adiabatic tF = 150°F
crystallizer to give a produc t
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:

𝐹 = 𝑉+𝐿+𝐶
𝑉 = 10,000 − 𝐿 − 4,000
𝑉 = 6,000 − 𝐿 ⟶ 𝑒𝑞𝑢𝑎𝑡𝑖𝑜𝑛 1
Consider solute balance:
𝑥 𝐹 𝐹 = 𝑥 𝐶𝐶 + 𝑥 𝐿 𝐿
𝑀𝑀𝑔 𝑆𝑂4 120 .38 𝑙𝑏 𝑀𝑔𝑆𝑂4
𝑥𝐶 = = = 0.4884
𝑀𝑀𝑔 𝑆𝑂4∙7𝐻2 𝑂 246 .49 𝑙𝑏 𝑀𝑔𝑆𝑂4 ∙ 7𝐻2 𝑂
𝑙𝑏 𝑀𝑔𝑆𝑂4 𝑙𝑏 𝑓𝑒𝑒𝑑 𝑙𝑏 𝑀𝑔𝑆𝑂4 𝑙𝑏
(0.325 ) (10,000 ) = 𝑋𝐿 (𝐿 ) + (0.4884 ) (4,000 )
𝑙𝑏 𝑓𝑒𝑒𝑑 ℎ 𝑙𝑏 𝑀𝑔𝑆𝑂4 ∙ 7𝐻2 𝑂 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 CRYSTALLIZA TION 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
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
 CHEMICAL ENGINEERING SERIES 12
CRYSTALLIZATION

TRIAL 1: Assume temperature of the solution at 60°F

From figure 27-3 (Unit Operations by McCabe and Smith 7th edition)
𝑙𝑏 𝑀𝑔𝑆𝑂4
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, 7 th edition)

𝐵𝑇𝑈
ℎ𝐹 𝑎𝑡 150°𝐹 𝑎𝑛𝑑 32.5% 𝑀𝑔𝑆𝑂4 = −10
𝑙𝑏
𝐵𝑇𝑈
ℎ𝐶 𝑎𝑡 60°𝐹 𝑎𝑛𝑑 48.84% 𝑀𝑔𝑆𝑂4 = −158
𝑙𝑏
𝐵𝑇𝑈
ℎ𝐿 𝑎𝑡 60°𝐹 𝑎𝑛𝑑 24.5% 𝑀𝑔𝑆𝑂4 = −50
𝑙𝑏
Temperature of vapor is 60 – 10 = 50°F
ℎ𝑉 = 𝐻𝑉 + 𝐶𝑃 𝑥 𝐵𝑃𝐸
𝐵𝑇𝑈
From steam table at 50°F, 𝐻𝑉 = 1,083.3
𝑙𝑏
𝐵𝑇𝑈 𝐵𝑇𝑈
ℎ𝑉 = 1,083.3 + [(0.45 ) (10°𝐹 ) ]
𝑙𝑏 𝑙𝑏 ∙ °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
𝑷 = 𝟎. 𝟏𝟕𝟖𝟎𝟑 𝒑𝒔𝒊 𝐴𝑁𝑆𝑊𝐸𝑅

Ratio of mother liquor to crystalline product

𝐿 5,291.43
=
𝐶 4,000

𝑳
= 𝟏. 𝟑𝟐 𝐴𝑁𝑆𝑊𝐸𝑅
𝑪
 CHEMICAL ENGINEERING SERIES 13
CRYSTALLIZATION

PROBLEM # 03 :

A plant produces 30,000 MT of anhydrous

sulfate annually by crystallizing sulfate brine F
CALCINATION CRYSTALLIZATION
at 0°C, yields of 95% and 90% in the
crystallization and calcinations operations T=0C
YIELD = 90%
are obtained respectively. How many metric YIELD = 95%
tons of liquor are fed to the crystallizer daily?
P
Note: 300 working days per year 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:

5 𝑔 𝑁𝑎2 𝑆𝑂4 ∙ 10𝐻2 𝑂
100 𝑔 𝐻2 𝑂

𝑚𝑎𝑠𝑠 𝑁𝑎2 𝑆𝑂4 ∙ 10𝐻2 𝑂

𝑀𝑇 𝑁𝑎2 𝑆𝑂4 1 1 𝑀𝑇𝑚𝑜𝑙 𝑁𝑎2 𝑆𝑂4 1 𝑀𝑇𝑚𝑜𝑙𝑁𝑎2 𝑆𝑂4 ∙ 10𝐻2 𝑂 322 𝑀𝑇𝑁𝑎2 𝑆𝑂4 ∙ 10𝐻2 𝑂
= 30,000 𝑥 𝑥 𝑥 𝑥
𝑦𝑟 0.95 142 𝑀𝑇𝑁𝑎2 𝑆𝑂4 1 𝑀𝑇𝑚𝑜𝑙 𝑁𝑎2 𝑆𝑂4 𝑀𝑇𝑚𝑜𝑙 𝑁𝑎2 𝑆𝑂4 ∙ 10𝐻2 𝑂

1 𝑦𝑟
𝑚𝑎𝑠𝑠 𝑁𝑎2 𝑆𝑂4 ∙ 10𝐻2 𝑂 = 71,608.60 𝑀𝑇 𝑥
300 𝑑𝑎𝑦𝑠

238.6953𝑀𝑇
𝑚𝑎𝑠𝑠 𝑁𝑎2 𝑆𝑂4 ∙ 10𝐻2 𝑂 =
𝑑𝑎𝑦

238.6953𝑀𝑇 𝑁𝑎2 𝑆𝑂4 ∙ 10𝐻2 𝑂 105 𝑀𝑇 𝑓𝑒𝑒𝑑

𝐹= 𝑥
𝑑𝑎𝑦 5 𝑀𝑇 𝑁𝑎2 𝑆𝑂4 ∙ 10𝐻2 𝑂

𝑴𝑻
𝑭 = 𝟓, 𝟎𝟏𝟐. 𝟔𝟎 𝐴𝑁𝑆𝑊𝐸𝑅
𝒅𝒂𝒚
 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 T = 90 C
barium nitrate at 90°C = 30.6 lb/100 lb water; L
at 20°C = 9.2 lb/100 lb water T = 20 C

CHE BP July 1968

SOLUTION:

𝑙𝑏 𝐵𝑎 (𝑁𝑂3 ) 2 100 𝑙𝑏 𝑤𝑎𝑡𝑒𝑟 𝑙𝑏 𝐵𝑎( 𝑁𝑂3 ) 2

𝑥 𝐹 = 0.306 𝑥 = 0.2343
𝑙𝑏 𝑤𝑎𝑡𝑒𝑟 (100 + 30.6) 𝑙𝑏 𝑓𝑒𝑒𝑑 𝑙𝑏 𝑓𝑒𝑒𝑑
𝑥 𝐹 𝐹 = 1,200 𝑙𝑏 𝐵𝑎( 𝑁𝑂3 )2
𝑙𝑏 𝑓𝑒𝑒𝑑
𝐹 = 1,200 𝑙𝑏 𝐵𝑎(𝑁 𝑂3 ) 2 𝑥
0.2343 𝑙𝑏 𝐵𝑎(𝑁 𝑂3 ) 2
𝐹 = 5,121.5686 𝑙𝑏
𝑙𝑏 𝐵𝑎 (𝑁𝑂3 )2 100 𝑙𝑏 𝑤𝑎𝑡𝑒𝑟 𝑙𝑏 𝐵𝑎( 𝑁𝑂3 ) 2
𝑥 𝐿 = 0.092 𝑥 = 0.0842
𝑙𝑏 𝑤𝑎𝑡𝑒𝑟 (100 + 9.2) 𝑙𝑏 𝑙𝑖𝑞𝑢𝑜𝑟 𝑙𝑏 𝑙𝑖𝑞𝑢𝑜𝑟

Consider over-all material balance around the crystallizer

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

Consider Ba(NO3)2 balance

𝑥 𝐹 𝐹 = 𝑥 𝐿 𝐿 + 𝑥 𝐶𝐶
1,200 = (0.0842)(𝐿 ) + (1.0)(𝐶 )
1,200 = 0.0842𝐿 + 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

 CHEMICAL ENGINEERING SERIES 15
CRYSTALLIZATION

PROBLEM # 05:

A Swenson-Walker crystallizer is to be used

to produce 1 ton/h of copperas L
(FeSO4·7H2O) crystals. The saturated tL = 80 F
F
solution enters the crystallizer at 120°F. The SWENSON-WALKER
tF = 120 F
CRYSTALLIZER
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 W
C, 1 ton/h
t2 = 70 F Fe2SO4·7H2O
that the U for the crystallizer is 35 t1 = 60 F
tC = 80 F
BTU/h·°F·ft 2. There are 3.5 ft 2 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 ⟶ 𝑒𝑞𝑢𝑎𝑡𝑖𝑜𝑛 1

Consider copperas (FeSO4·7H2O) balance:

𝑥 𝐹 𝐹 = 𝑥 𝐶𝐶 + 𝑥 𝐿 𝐿
𝑥 𝐶 = 1.0
74 𝑙𝑏 𝐹𝑒𝑆𝑂4 ∙ 7𝐻2 𝑂 100 𝑙𝑏 𝐻2 𝑂 𝑙𝑏 𝐹𝑒𝑆𝑂4 ∙ 7𝐻2 𝑂
𝑥𝐿 = 𝑥 = 0.4253
100 𝑙𝑏 𝐻2 𝑂 174 𝑙𝑏 𝑙𝑖𝑞𝑢𝑜𝑟 𝑙𝑏 𝑙𝑖𝑞𝑢𝑜𝑟
140 𝑙𝑏 𝐹𝑒𝑆𝑂4 ∙ 7𝐻2 𝑂 100 𝑙𝑏 𝐻2 𝑂 𝑙𝑏 𝐹𝑒𝑆𝑂4 ∙ 7𝐻2 𝑂
𝑥𝐹 = 𝑥 = 0.5833
100 𝑙𝑏 𝐻2 𝑂 240 𝑙𝑏 𝑓𝑒𝑒𝑑 𝑙𝑏 𝑓𝑒𝑒𝑑
(0.5833) (𝐹 ) = (1.0)(2,000) + (0.4253)(𝐿 )
𝐿 = 1.3715𝐹 − 4,702.5629 ⟶ 𝑒𝑞𝑢𝑎𝑡𝑖𝑜𝑛 2

Equate 1 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:

𝑞𝑤𝑎𝑡𝑒𝑟 = 𝑞𝑐𝑟𝑦𝑠𝑡𝑎𝑙𝑠
𝑞𝑐𝑟𝑦𝑠𝑡𝑎𝑙𝑠 = 𝐹𝐶𝑝𝐹 (𝑡𝐹 − 𝑡𝐿 ) + 𝐶𝐻𝐶
 CHEMICAL ENGINEERING SERIES 16
CRYSTALLIZATION

𝑙𝑏 𝐵𝑇𝑈
𝑞𝑐𝑟𝑦𝑠𝑡𝑎𝑙𝑠 = [(7,274.73 ) (0.70 ) (120 − 80) °𝐹 ]
ℎ 𝑙𝑏 ∙ °𝐹
𝐵𝑇𝑈
𝑙𝑏 𝑐𝑎𝑙 𝑔𝑚𝑜𝑙 1
𝑙𝑏
+ [(2,000 ) ( 4,400 𝑥 𝑥 )]
ℎ 𝑔𝑚𝑜𝑙 277 .85 𝑔 0.55556 𝑐𝑎𝑙
𝑔
𝐵𝑇𝑈
𝑞𝑐𝑟𝑦𝑠𝑡𝑎𝑙𝑠 = 260,701.1615
ℎ

𝑞𝑤𝑎𝑡𝑒𝑟 = 𝑊𝐶𝑝 𝐻2𝑂 ( 𝑡2 − 𝑡1 )

𝐵𝑇𝑈
260,701.1615
ℎ
𝑊=
𝐵𝑇𝑈 (
(1.0 ) 70 − 60) °𝐹
𝑙𝑏 ∙ °𝐹
𝑙𝑏 1 𝑓𝑡 3 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∆𝑇𝑙𝑚
(𝑡𝐹 − 𝑡2 ) − ( 𝑡𝐿 − 𝑡1 )
∆𝑇𝑙𝑚 = 𝑡 − 𝑡2
ln 𝐹
𝑡𝐿 − 𝑡1
(120 − 70) − (80 − 60)
∆𝑇𝑙𝑚 =
120 − 70
ln
80 − 60
∆𝑇𝑙𝑚 = 32.7407°𝐹

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

𝐴 = 227.5029 𝑓𝑡 2

1 𝑓𝑡 𝑙𝑒𝑛𝑔𝑡ℎ 1 𝑢𝑛𝑖𝑡
# 𝑜𝑓 𝑢𝑛𝑖𝑡𝑠 = 227.5029 𝑓𝑡 2 𝑥 𝑥
3.5 𝑓𝑡 2 10 𝑓𝑡

# 𝒐𝒇 𝒖𝒏𝒊𝒕𝒔 = 𝟔. 𝟓 ≈ 𝟕 𝒖𝒏𝒊𝒕𝒔 𝐴𝑁𝑆𝑊𝐸𝑅

 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

124 𝑔 𝑁𝑎2 𝐶𝑂3 ∙ 𝐻2 𝑂
𝑤𝑡 𝑁𝑎2 𝐶𝑂3 ∙ 𝐻2 𝑂 = 100 𝑔𝑁𝑎2 𝐶𝑂3 ∙ 10𝐻2 𝑂 𝑥
286 𝑔 𝑁𝑎2 𝐶𝑂3 ∙ 10𝐻2 𝑂
𝑤𝑡 𝑁𝑎2 𝐶𝑂3 ∙ 𝐻2 𝑂 = 43.3566 𝑔

106 𝑔 𝑁𝑎2 𝐶𝑂3

𝑤𝑡 𝑁𝑎2 𝐶𝑂3 = 100 𝑔𝑁𝑎2 𝐶𝑂3 ∙ 10𝐻2 𝑂 𝑥
286 𝑔 𝑁𝑎2 𝐶𝑂3 ∙ 10𝐻2 𝑂
𝑤𝑡 𝑁𝑎2 𝐶𝑂3 = 37.0629 𝑔

180 𝑔 𝐻2 𝑂
𝑤𝑡 𝐻2 𝑂 = 100 𝑔𝑁𝑎2 𝐶𝑂3 ∙ 10𝐻2 𝑂 𝑥
286 𝑔 𝑁𝑎2 𝐶𝑂3 ∙ 10𝐻2 𝑂
𝑤𝑡 𝐻2 𝑂 = 62.9371 𝑔

𝑋
% 𝑁𝑎2 𝐶𝑂3 𝑖𝑛 𝑠𝑎𝑡𝑑 𝑠𝑜𝑙𝑛 𝑎𝑡 100°𝐶 = 𝑥 100 = 31.2
𝑋 + 62.9371
𝑋 = 28.5412 𝑔

𝑤𝑡 𝑁𝑎2 𝐶𝑂3 𝑝𝑟𝑒𝑐𝑖𝑝𝑖𝑡𝑎𝑡𝑒𝑑 = 37.0629 − 28.5412 = 8.5217 𝑔

124 𝑔 𝑁𝑎2 𝐶𝑂3 ∙ 𝐻2 𝑂

𝑤𝑡 𝑁𝑎2 𝐶𝑂3 ∙ 𝐻2 𝑂 𝑝𝑟𝑒𝑐𝑖𝑝𝑖𝑡𝑎𝑡𝑒𝑑 = 8.5217 𝑔𝑁𝑎2 𝐶𝑂3 𝑥
106 𝑔 𝑁𝑎2 𝐶𝑂3
𝑤𝑡 𝑁𝑎2 𝐶𝑂3 ∙ 𝐻2 𝑂 𝑝𝑟𝑒𝑐𝑖𝑝𝑖𝑡𝑎𝑡𝑒𝑑 = 9.9688 𝑔

9.9688
% 𝑁𝑎2 𝐶𝑂3 ∙ 𝐻2 𝑂 𝑝𝑟𝑒𝑐𝑖𝑝𝑖𝑡𝑎𝑡𝑒𝑑 = 𝑥 100
43.3566

% 𝑵𝒂𝟐 𝑪𝑶 𝟑 ∙ 𝑯𝟐 𝑶 𝒑𝒓𝒆𝒄𝒊𝒑𝒊𝒕𝒂𝒕𝒆𝒅 = 𝟐𝟐. 𝟗𝟗 % 𝐴𝑁𝑆𝑊𝐸𝑅

 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 C, 1 ton/h
MgSO4·7H2O
the crystallizer to produce one ton of tC = 50 F

MgSO4·7H2O per hour?

SOLUTION:

Consider over-all material balance:

𝐹 = 𝐿+𝐶
𝐿 = 𝐹 − 1 ⟶ 𝑒𝑞𝑢𝑎𝑡𝑖𝑜𝑛 1

Consider MgSO4 balance

𝑥 𝐹 𝐹 = 𝑥 𝐿 𝐿 + 𝑥 𝐶𝐶
43 𝑡𝑜𝑛 𝑀𝑔𝑆𝑂4 100 𝑡𝑜𝑛 𝐻2 𝑂 𝑡𝑜𝑛 𝑀𝑔𝑆𝑂4
𝑥𝐹 = 𝑥 = 0.3007
100 𝑡𝑜𝑛 𝐻2 𝑂 ( )
100 + 43 𝑡𝑜𝑛 𝑓𝑒𝑒𝑑 𝑡𝑜𝑛 𝑓𝑒𝑒𝑑
120 .38 𝑡𝑜𝑛 𝑀𝑔𝑆𝑂4 𝑡𝑜𝑛 𝑀𝑔𝑆𝑂4
𝑥𝐶 = = 0.4884
246.49 𝑡𝑜𝑛 𝑀𝑔𝑆𝑂4 ∙ 7𝐻2 𝑂 𝑡𝑜𝑛 𝑀𝑔𝑆𝑂4 ∙ 7𝐻2 𝑂

From table 27-3 (Unit Operations by McCabe and Smith, 7 th edition), at 50°F
𝑡𝑜𝑛 𝑀𝑔𝑆𝑂4
𝑥 𝐿 = 0.23
𝑡𝑜𝑛 𝑙𝑖𝑞𝑢𝑜𝑟
(0.3007) (𝐹 ) = (0.23)(𝐿 ) + (0.4884) (1)
𝐿 = 1.3074𝐹 − 2.1235 ⟶ 𝑒𝑞𝑢𝑎𝑡𝑖𝑜𝑛 2

Equate 1 and 2

𝐹 − 1 = 1.3074 𝐹 − 2.1235

𝒕𝒐𝒏
𝑭 = 𝟑. 𝟔𝟓 𝐴𝑁𝑆𝑊𝐸𝑅
𝒉
 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 C,
dissolved salt that crystallizes out? 9.6 g NaHCO3
per 100 g H2O
tC = 20 F

SOLUTION:

Basis: 100 kg feed

Consider over-all material balance:

𝐹 = 𝐿+𝐶
𝐿 = 100 − 𝐶 ⟶ 𝑒𝑞𝑢𝑎𝑡𝑖𝑜𝑛 1

Consider NaHCO3 balance

𝑥 𝐹 𝐹 = 𝑥 𝐿 𝐿 + 𝑥 𝐶𝐶

16.4 𝑘𝑔 𝑁𝑎𝐻𝐶𝑂3 100 𝑘𝑔 𝐻2 𝑂 𝑘𝑔 𝑁𝑎𝐻𝐶𝑂3

𝑥𝐹 = 𝑥 = 0.1409
100 𝑘𝑔 𝐻2 𝑂 (100 + 16.4) 𝑘𝑔 𝑓𝑒𝑒𝑑 𝑘𝑔 𝑓𝑒𝑒𝑑
𝑥 𝐶 = 1.0
9.6 𝑘𝑔 𝑁𝑎𝐻𝐶𝑂3 100 𝑘𝑔 𝐻2 𝑂 𝑘𝑔 𝑁𝑎𝐻𝐶𝑂3
𝑥𝐿 = 𝑥 = 0.0876
100 𝑘𝑔 𝐻2 𝑂 (100 + 9.6) 𝑘𝑔 𝑙𝑖𝑞𝑢𝑜𝑟 𝑘𝑔 𝑙𝑖𝑞𝑢𝑜𝑟

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

𝐿 = 160.8447 − 11.4155𝐶 ⟶ 𝑒𝑞𝑢𝑎𝑡𝑖𝑜𝑛 2

Equate 1 and 2

100 − 𝐶 = 160.8447 − 11.4155𝐶

𝐶 = 5.8417 𝑘𝑔

𝐶
% 𝑁𝑎𝐻𝐶𝑂3 𝑐𝑟𝑦𝑠𝑡𝑎𝑙𝑙𝑖𝑧𝑒𝑑 = 𝑥 100
𝑥𝐹 𝐹

5.8417 𝑘𝑔
% 𝑁𝑎𝐻𝐶𝑂3 𝑐𝑟𝑦𝑠𝑡𝑎𝑙𝑙𝑖𝑧𝑒𝑑 = 𝑥 100
(0.1409) (100 𝑘𝑔)

% 𝑵𝒂𝑯𝑪𝑶 𝟑 𝒄𝒓𝒚𝒔𝒕𝒂𝒍𝒍𝒊𝒛𝒆𝒅 = 𝟒𝟏. 𝟒𝟔 % 𝐴𝑁𝑆𝑊𝐸𝑅

 CHEMICAL ENGINEERING SERIES 20
CRYSTALLIZATION

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

C,
tC = 20 C

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:

Basis: 1 L feed
1.077 𝑘𝑔
𝐹 = 1𝐿 𝑥 = 1.077 𝑘𝑔
𝐿

Consider over-all material balance:

𝐹 = 𝑉+𝐿+𝐶
𝐿 = 1.077 − 𝑉 − 𝐶 ⟶ 𝑒𝑞𝑢𝑎𝑡𝑖𝑜𝑛 1

𝑥 𝐶 𝐶 = 0.80𝑥 𝐹 𝐹
8.4 𝑘𝑔 𝑁𝑎2 𝑆𝑂4
𝑥 𝐹 𝐹 = (1.077 𝑘𝑔 𝑓𝑒𝑒𝑑 ) ( ) = 0.0905 𝑘𝑔 𝑁𝑎2 𝑆𝑂4
100 𝑘𝑔 𝑓𝑒𝑒𝑑
𝑥 𝐶 𝐶 = (0.80)(0.0905 𝑘𝑔 𝑁𝑎2 𝑆𝑂4 ) = 0.0724 𝑘𝑔 𝑁𝑎2 𝑆𝑂4
𝑀𝑁𝑎 2𝑆𝑂4 142 𝑘𝑔 𝑁𝑎2 𝑆𝑂4
𝑥𝐶 = = = 0.4410
𝑀𝑁𝑎2𝑆𝑂4∙10𝐻2 𝑂 322 𝑘𝑔 𝑁𝑎2 𝑆𝑂4 ∙ 10𝐻2 𝑂
0.0724 𝑘𝑔 𝑁𝑎2 𝑆𝑂4
𝐶= = 0.1642 𝑘𝑔
𝑘𝑔 𝑁𝑎2 𝑆𝑂4
0.4410
𝑘𝑔 𝑁𝑎2 𝑆𝑂4 ∙ 10𝐻2 𝑂

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

Consider Na2SO4 balance

𝑥 𝐹 𝐹 = 𝑥 𝐿 𝐿 + 𝑥 𝐶𝐶
19.4 𝑘𝑔 𝑁𝑎2 𝑆𝑂4 100 𝑘𝑔 𝐻2 𝑂 𝑘𝑔 𝑁𝑎2 𝑆𝑂4
𝑥𝐿 = 𝑥 = 0.1625
100 𝑘𝑔 𝐻2 𝑂 ( )
100 + 19.4 𝑘𝑔 𝑙𝑖𝑞𝑢𝑜𝑟 𝑘𝑔 𝑙𝑖𝑞𝑢𝑜𝑟

0.0905 = (0.1625) (𝐿 ) + 0.0724

𝐿 = 0.1114 𝑘𝑔
 CHEMICAL ENGINEERING SERIES 21
CRYSTALLIZATION

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(NO 3)2/100
kg H2O and goes to a crystallizer where the
solution is cooled and Ba(NO3)2 crystallizes.
V
On cooling, 10% of the original water present
evaporates. For a feed solution of 100 kg L
F
total, calculate 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
C
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

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( 𝑁𝑂3 )2 100 𝑘𝑔 𝐻2 𝑂 𝑘𝑔 𝐵𝑎 (𝑁𝑂3 )2
𝑥𝐹 = 𝑥 = 0.2343
100 𝑘𝑔 𝐻2 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 𝐶𝐶
8.6 𝑘𝑔 𝐵𝑎 (𝑁𝑂3 )2 100 𝑘𝑔 𝐻2 𝑂 𝑘𝑔 𝐵𝑎 (𝑁𝑂3 ) 2
𝑥𝐿 = 𝑥 = 0.0792
100 𝑘𝑔 𝐻2 𝑂 (100 + 8.6)𝑘𝑔 𝑙𝑖𝑞𝑢𝑜𝑟 𝑘𝑔 𝑙𝑖𝑞𝑢𝑜𝑟
𝑥 𝐶 = 1.0

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

 CHEMICAL ENGINEERING SERIES 22
CRYSTALLIZATION

𝐿 = 295.8333 − 12.6263 𝐶 ⟶ 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
𝑉 = 0.10(1 − 𝑥 𝐹 )𝐹
30.6 𝑘𝑔 𝐵𝑎( 𝑁𝑂3 )2 100 𝑘𝑔 𝐻2 𝑂 𝑘𝑔 𝐵𝑎 (𝑁𝑂3 )2
𝑥𝐹 = 𝑥 = 0.2343
100 𝑘𝑔 𝐻2 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 𝐶𝐶
7.0 𝑘𝑔 𝐵𝑎 (𝑁𝑂3 )2 100 𝑘𝑔 𝐻2 𝑂 𝑘𝑔 𝐵𝑎( 𝑁𝑂3 ) 2
𝑥𝐿 = 𝑥 = 0.0654
100 𝑘𝑔 𝐻2 𝑂 (100 + 7) 𝑘𝑔 𝑙𝑖𝑞𝑢𝑜𝑟 𝑘𝑔 𝑙𝑖𝑞𝑢𝑜𝑟
𝑥 𝐶 = 1.0

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

𝐿 = 358.2569 − 15.2905 𝐶 ⟶ 𝑒𝑞𝑢𝑎𝑡𝑖𝑜𝑛 2

Equate 1 and 2
92.343 − 𝐶 = 358 .2569 − 15.2905 𝐶

𝑪 = 𝟏𝟖. 𝟔𝟎𝟕𝟕 𝒌𝒈 𝐴𝑁𝑆𝑊𝐸𝑅

 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
V
in 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:

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 𝐶𝐶
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

% 𝐻2 𝑂 𝑖𝑛 𝑓𝑒𝑒𝑑 = 100 − %𝐾𝐶𝑙 = 100 − 35 = 65%

 CHEMICAL ENGINEERING SERIES 24
CRYSTALLIZATION

𝑤𝑡 𝐻2 𝑂
% 𝐻2 𝑂 𝑖𝑛 𝑓𝑒𝑒𝑑 = 𝑥 100
𝑤𝑡 𝑓𝑒𝑒𝑑
65 𝑘𝑔 𝐻2 𝑂
𝑤𝑡 𝐻2 𝑂 = (2,857.14 𝑘𝑔 𝑓𝑒𝑒𝑑 ) ( )
100 𝑘𝑔 𝑓𝑒𝑒𝑑
𝒘𝒕 𝑯𝟐 𝑶 = 𝟏, 𝟖𝟓𝟕. 𝟏𝟒 𝒌𝒈 𝐴𝑁𝑆𝑊𝐸𝑅

d) Crystallization with evaporation

Consider over-all material balance:

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

Consider KCl balance

𝑥 𝐹 𝐹 = 𝑥 𝐿 𝐿 + 𝑥 𝐶𝐶
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
 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)
L
is 18,000 g-cal per gmol Na2SO4. Glauber’s tL = 15 C
F
salt (Na2SO4·10H2O) is to be made in a tF = 30 C
SWENSON-WALKER
CRYSTALLIZER
Swenson-Walker crystallizer by cooling a
solution, saturated at 30°C, to 15°C. Cooling
C, 1 ton/h
water enters at 10°C and leaves at 20°C. W
t2 = 20 C Na2SO4·10H2O
t1 = 10 C
The over-all heat transfer coefficient in the tC = 15 C

crystallizer is 25 BTU/h·ft 2·°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 ⟶ 𝑒𝑞𝑢𝑎𝑡𝑖𝑜𝑛 1

Consider Na2SO4 balance

𝑥 𝐹 𝐹 = 𝑥 𝐿 𝐿 + 𝑥 𝐶𝐶
40 𝑡𝑜𝑛 𝑁𝑎2 𝑆𝑂4 100 𝑡𝑜𝑛 𝐻2 𝑂 𝑡𝑜𝑛 𝑁𝑎2 𝑆𝑂4
𝑥𝐹 = 𝑥 = 0.2857
100 𝑡𝑜𝑛 𝐻2 𝑂 ( )
100 + 40 𝑡𝑜𝑛 𝑓𝑒𝑒𝑑 𝑡𝑜𝑛 𝑓𝑒𝑒𝑑
13.5 𝑡𝑜𝑛 𝑁𝑎2 𝑆𝑂4 100 𝑡𝑜𝑛 𝐻2 𝑂 𝑡𝑜𝑛 𝑁𝑎2 𝑆𝑂4
𝑥𝐿 = 𝑥 = 0.1189
100 𝑡𝑜𝑛 𝐻2 𝑂 (100 + 13.5) 𝑡𝑜𝑛 𝑙𝑖𝑞𝑢𝑜𝑟 𝑡𝑜𝑛 𝑙𝑖𝑞𝑢𝑜𝑟
142 𝑡𝑜𝑛 𝑁𝑎2 𝑆𝑂4 𝑡𝑜𝑛 𝑁𝑎2 𝑆𝑂4
𝑥𝐶 = = 0.4410
322 𝑡𝑜𝑛 𝑁𝑎2 𝑆𝑂4 ∙ 10𝐻2 𝑂 𝑡𝑜𝑛 𝑁𝑎2 𝑆𝑂4 ∙ 10𝐻2 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
 CHEMICAL ENGINEERING SERIES 26
CRYSTALLIZATION

Consider heat balance:

𝑞𝑐𝑟𝑦𝑠𝑡𝑎𝑙 = 𝐹𝐶𝑃 (𝑡𝐹 − 𝑡𝐶 ) + 𝐶𝐻𝐶
(𝑚𝐶𝑃 )𝑁𝑎 𝑆𝑂 + (𝑚𝐶𝑃 )𝐻 𝑂
2 4 2
𝐶𝑃 =
𝐹
From Table 2-194 (CHE HB 8th edition)
𝑐𝑎𝑙 𝐵𝑇𝑈
𝐶𝑃 𝑁𝑎 𝑆𝑂 = 32.8 = 0.231
2 4 °𝐶 ∙ 𝑚𝑜𝑙 𝑙𝑏 ∙ °𝐹
[(0.2857) (0.231) + (0.7143) (1.000)] 𝐵𝑇𝑈
𝐶𝑃 = = 0.7803
1 𝑙𝑏 ∙ °𝐹

𝑡𝑜𝑛 2,000 𝑙𝑏 𝐵𝑇𝑈 1.8°𝐹

𝑞𝑐𝑟𝑦𝑠𝑡𝑎𝑙 = [(1.931 𝑥 ) (0.7803 ) (30 − 15) °𝐶 𝑥 ]
ℎ 𝑡𝑜𝑛 𝑙𝑏 ∙ °𝐹 °𝐶
𝑡𝑜𝑛 2,000 𝑙𝑏 𝑙𝑏𝑚𝑜𝑙 454 𝑔𝑚𝑜𝑙 18000 𝑐𝑎𝑙 𝐵𝑇𝑈
+ [(1 𝑥 𝑥 𝑥 )( 𝑥 )]
ℎ 𝑡𝑜𝑛 322 𝑙𝑏 𝑙𝑏𝑚𝑜𝑙 𝑔𝑚𝑜𝑙 252.16 𝑐𝑎𝑙
𝐵𝑇𝑈
𝑞𝑐𝑟𝑦𝑠𝑡𝑎𝑙 = 282 ,656.8961
ℎ

𝑞 = 𝑈𝐴∆𝑇𝑙𝑚
(𝑡𝐹 − 𝑡2 ) − ( 𝑡𝐿 − 𝑡1 )
∆𝑇𝑙𝑚 = 𝑡 − 𝑡2
ln 𝐹
𝑡𝐿 − 𝑡1
𝑡𝐹 = 30°𝐶 = 86°𝐹
𝑡𝐿 = 15°𝐶 = 59°𝐹
𝑡1 = 10°𝐶 = 50°𝐹
𝑡2 = 20°𝐶 = 68°𝐹
(86 − 68) − (59 − 50)
∆𝑇𝑙𝑚 = = 12.9842°𝐹
86 − 68
ln
59 − 50

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

𝐴 = 870.7718𝑓𝑡 2
1 𝑓𝑡 𝑙𝑒𝑛𝑔𝑡ℎ 1 𝑢𝑛𝑖𝑡
# 𝑜𝑓 𝑢𝑛𝑖𝑡𝑠 = 880.7718 𝑓𝑡 2 𝑥 𝑥
3 𝑓𝑡 2 10 𝑓𝑡 𝑙𝑒𝑛𝑔𝑡ℎ

# 𝒐𝒇 𝒖𝒏𝒊𝒕𝒔 = 𝟐𝟗. 𝟎𝟑 ≈ 𝟑𝟎 𝒖𝒏𝒊𝒕𝒔 𝐴𝑁𝑆𝑊𝐸𝑅

 CHEMICAL ENGINEERING SERIES 27
CRYSTALLIZATION

PROBLEM # 13:
A continuous adiabatic vacuum crystallizer is
to be used for the production of MgSO 4·7H2 O
V
crystals from 20,000 lb/h of solution
containing 0.300 weight fraction MgSO 4. 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:

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 𝐶𝐶
𝑙𝑏 𝑀𝑔𝑆𝑂4
𝑥 𝐹 = 0.3000
𝑙𝑏 𝑓𝑒𝑒𝑑
120 𝑙𝑏 𝑀𝑔𝑆𝑂4 𝑙𝑏 𝑀𝑔𝑆𝑂4
𝑥𝐶 = = 0.4878
246 𝑙𝑏 𝑀𝑔𝑆𝑂4 ∙ 7𝐻2 𝑂 𝑙𝑏 𝑀𝑔𝑆𝑂4 ∙ 7𝐻2 𝑂
(0.30)(20,000) = ( 𝑥 𝐿)(𝐿 ) + (0.4878) (6,000)
3,073.2
𝐿= ⟶ 𝑒𝑞𝑢𝑎𝑡𝑖𝑜𝑛 2
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 CRYSTALLIZA TION IS UNKNOWN AND ENTHALPIES ARE DEPENDENT
ON TEMPERATURE
 CHEMICAL ENGINEERING SERIES 28
CRYSTALLIZATION

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
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 7th edition)
𝑙𝑏 𝑀𝑔𝑆𝑂4
𝑥 𝐿 = 0.245
𝑙𝑏 𝑙𝑖𝑞𝑢𝑜𝑟
Substitute to equation 2
3,073.2
𝐿= = 12,543.67 𝑙𝑏
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, 7 th edition)

𝐵𝑇𝑈
ℎ𝐹 𝑎𝑡 160°𝐹 𝑎𝑛𝑑 30% 𝑀𝑔𝑆𝑂4 = 5
𝑙𝑏
𝐵𝑇𝑈
ℎ𝐶 𝑎𝑡 60°𝐹 𝑎𝑛𝑑 48.78% 𝑀𝑔𝑆𝑂4 = −158
𝑙𝑏
𝐵𝑇𝑈
ℎ𝐿 𝑎𝑡 60°𝐹 𝑎𝑛𝑑 24.5% 𝑀𝑔𝑆𝑂4 = −50
𝑙𝑏

Temperature of vapor is 60 – 10 = 50°F

ℎ𝑉 = 𝐻𝑉 + 𝐶𝑃 𝑥 𝐵𝑃𝐸
𝐵𝑇𝑈
From steam table at 50°F, 𝐻𝑉 = 1,083.3
𝑙𝑏
𝐵𝑇𝑈 𝐵𝑇𝑈
ℎ𝑉 = 1,083.3 + [(0.45 ) (10°𝐹 ) ]
𝑙𝑏 𝑙𝑏 ∙ °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 𝒐𝒓 𝟏, 𝟒𝟓𝟔. 𝟑𝟑 𝐴𝑁𝑆𝑊𝐸𝑅
𝒉 𝒉
 CHEMICAL ENGINEERING SERIES 29
CRYSTALLIZATION

PROBLEM # 14:
Crystals of CaCl2·6H2O are to be obtained
from a solution of 35 weight % CaCl 2, 10
V
weight % inert soluble impurity, and 55
weight % water in an Oslo crystallizer.
The solution is fed to the crystallizer at M (magma)
F C
100°F and receives 250 BTU/lb of feed CaCl2 = 35% Inert
OSLO CRYSTALLIZER
from the external heater. Products are Inert = 10% L
H2O = 55% tF = 40 F
withdrawn 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 C’’ DRYER
CaCl2·6H2O
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 CaCl 2·6H2O
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 H2O
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 = 𝐹𝐶𝑃 (𝑡𝐹 − 𝑡𝐿 ) + 𝐶𝐻𝐶 − 𝑉𝜆 𝑉

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

𝐶𝑃 = 16.9 + 0.00386𝑇
where T is in K
At 100°F (310.93 K)
 CHEMICAL ENGINEERING SERIES 30
CRYSTALLIZATION

𝐵𝑇𝑈
𝑐𝑎𝑙 1 𝑚𝑜𝑙 1 𝐵𝑇𝑈
𝑙𝑏 ∙ °𝐹
𝐶𝑃 = 18.1 𝑥 𝑥 = 0.1632
𝑚𝑜𝑙 · 𝐾 110.9 𝑔 𝑐𝑎𝑙 𝑙𝑏 ∙ °𝐹
1
𝑔 ∙ °𝐹
At 40°F (277.59 K)
𝐵𝑇𝑈
𝑐𝑎𝑙 1 𝑚𝑜𝑙 1 𝐵𝑇𝑈
𝑙𝑏 ∙ °𝐹
𝐶𝑃 = 17.97 𝑥 𝑥 = 0.1620
𝑚𝑜𝑙 · 𝐾 110.9 𝑔 𝑐𝑎𝑙 𝑙𝑏 ∙ °𝐹
1
𝑔 ∙ °𝐹
0.1632 + 0.1620 𝐵𝑇𝑈
𝐶̅𝑃 = = 0.1626
2 𝑙𝑏 ∙ °𝐹

For the feed

(0.35 𝑙𝑏 𝐶𝑎𝐶𝑙 2 ) (0.1626 𝐵𝑇𝑈 𝐵𝑇𝑈
) + (0.55 𝑙𝑏 𝐻2 𝑂) (1 )
𝑙𝑏 𝐶𝑎𝐶𝑙 2 ∙ °𝐹 𝑙𝑏 𝐻2 𝑂 ∙ °𝐹
𝐶𝑃 =
(0.35 + 0.55) 𝑙𝑏 𝑓𝑒𝑒𝑑
𝐵𝑇𝑈
𝐶𝑃 = 0.6743
𝑙𝑏 ∙ °𝐹

From table 2-224 (CHE HB 8th 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
𝐻𝐶 = 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 = 0.0315𝐶 − 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 − 1.0315𝐶 ⟶ 𝑒𝑞𝑢𝑎𝑡𝑖𝑜𝑛 3

Consider solute (CaCl 2·6H2O) balance, inert soluble-free

𝑥 𝐹 𝐹 = 𝑥 𝐿 𝐿 + 𝑥 𝐶𝐶
𝑙𝑏 𝐶𝑎𝐶𝑙 2 ∙ 6𝐻2 𝑂
35 𝑙𝑏 𝐶𝑎𝐶𝑙 2 1 𝑙𝑏𝑚𝑜𝑙 𝐶𝑎𝐶𝑙 2 ∙ 6𝐻2 𝑂 218 .9 𝑙𝑏𝑚𝑜𝑙 𝐶𝑎𝐶𝑙 2 ∙ 6𝐻2 𝑂
𝑥𝐹 = 𝑥 𝑥 = 0.7676
(35 + 55) 𝑙𝑏 𝑓𝑒𝑒𝑑 𝑙𝑏𝑚𝑜𝑙 𝐶𝑎𝐶𝑙 2 𝑙𝑏 𝐶𝑎𝐶𝑙 2
110.9
𝑙𝑏𝑚𝑜𝑙 𝐶𝑎𝐶𝑙 2
 CHEMICAL ENGINEERING SERIES 31
CRYSTALLIZATION

61.92 𝑙𝑏 𝐶𝑎𝐶𝑙 2 ∙ 6𝐻2 𝑂 100 𝑙𝑏 𝐻2 𝑂

𝑥𝐿 = 𝑥 = 0.3824
100 𝑙𝑏 𝐻2 𝑂 (100 + 61.92) 𝑙𝑏 𝑙𝑖𝑞𝑢𝑜𝑟
𝑥𝐶 = 1
(0.7676) (1) = (0.3824 )(𝐿 ) + (1)(𝐶 )
𝐿 = 2.0073 − 2.6151𝐶 ⟶ 𝑒𝑞𝑢𝑎𝑡𝑖𝑜𝑛 4

Equate 3 and 4
0.8006 − 1.0315 𝐶 = 2.0073 − 2.6151 𝐶
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 𝑙𝑏 𝐶𝑎𝐶𝑙 2 ∙ 6𝐻2 𝑂 100 𝑙𝑏 𝐻2 𝑂
𝑤𝑡 𝐶𝑎𝐶𝑙 2 ∙ 6𝐻2 𝑂 𝑖𝑛 𝑙𝑖𝑞𝑢𝑜𝑟 = 0.0146 𝑙𝑏 𝑙𝑖𝑞𝑢𝑜𝑟 𝑥 𝑥
100 𝑙𝑏 𝐻2 𝑂 (100 + 61.92) 𝑙𝑏 𝑙𝑖𝑞𝑢𝑜𝑟
𝑤𝑡 𝐶𝑎𝐶𝑙 2 ∙ 6𝐻2 𝑂 𝑖𝑛 𝑙𝑖𝑞𝑢𝑜𝑟 = 0.0056 𝑙𝑏
𝑤𝑡 𝐻2 𝑂 𝑖𝑛 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:

0.1 𝑙𝑏 𝑙𝑖𝑞𝑢𝑜𝑟
𝑤𝑡 𝑙𝑖𝑞𝑢𝑜𝑟 𝑎𝑑ℎ𝑒𝑟𝑒𝑑 𝑖𝑛 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 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 lactose 2,500 kg
OSLO CRYSTALLIZER
solution is 3470 J/kg·°C. The heat of solution 8 g lactose per 10 g
water
for lactose monohydrate is -15,500 kJ/kmol. tF = 57 C
C
tC = 10 C
The molecular weight of lactose monohydrat e L
1.5 g lactose
is 360 and the solubility of lactose at 10°C is per 10 g water
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 104 kJ. Calculate the heat to be
removed in the cooling process.

SOLUTION:

Consider over-all material balance

𝐹 = 𝐿+𝑉+𝐶
10 𝑘𝑔 𝐻2 𝑂
𝑤𝑡 𝐻2 𝑂 𝑖𝑛 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 𝐶𝐶
8 𝑘𝑔 𝑘𝑔 𝐶12 𝐻22 𝑂11
𝑥𝐹 = = 0.4444
10 + 8 𝑘𝑔 𝑓𝑒𝑒𝑑
1.5 𝑘𝑔 𝐶12 𝐻22 𝑂11
𝑥𝐿 = = 0.1304
10 + 1.5 𝑘𝑔 𝑙𝑖𝑞𝑢𝑜𝑟
𝑀𝐶12𝐻22𝑂11 342 𝑘𝑔 𝐶12 𝐻22 𝑂11
𝑥𝐶 = = = 0.95
𝑀𝐶12𝐻22𝑂11∙𝐻2 𝑂 360 𝑘𝑔 𝑐𝑟𝑦𝑠𝑡𝑎𝑙
(0.4444) (2,500) = (0.1304 )(𝐿 ) + (0.95)(𝐶 )
𝐿 = 8,519.9386 − 7.2853 𝐶 ⟶ 𝑒𝑞𝑢𝑎𝑡𝑖𝑜𝑛 2
 CHEMICAL ENGINEERING SERIES 33
CRYSTALLIZATION

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

Consider heat balance:

𝑞𝑐𝑟𝑦𝑠𝑡𝑎𝑙𝑠 = 𝐹𝐶𝑃 (𝑡𝐹 − 𝑡𝐿 ) + 𝐶𝐻𝐶 − 𝑉𝜆 𝑉
At 10°C (50°F),
𝐵𝑇𝑈 𝑘𝐽
𝜆 = 1,065.2 = 2,472.47
𝑙𝑏 𝑘𝑔
𝑘𝐽 𝑘𝑚𝑜𝑙 𝑘𝐽
𝐻𝐶 = 15,500 𝑥 = 43.06
𝑘𝑚𝑜𝑙 360 𝑘𝑔 𝑘𝑔
𝑘𝐽 𝑘𝐽
𝑞𝑐𝑟𝑦𝑠𝑡𝑎𝑙𝑠 = [(2,500 𝑘𝑔) (3.47 ) (57 − 10) °𝐶 ] + [(959 .99 𝑘𝑔) (43 .06 )]
𝑘𝑔 ∙ °𝐶 𝑘𝑔
𝑘𝐽
− [(13.89 𝑘𝑔) (2,472.47 )]
𝑘𝑔
𝑞𝑐𝑟𝑦𝑠𝑡𝑎𝑙𝑠 = 414.7196 𝑥 103 𝑘𝐽

𝑞𝑇 = 414.7196 𝑥 103 𝑘𝐽 + 4 𝑥 104 𝑘𝐽

𝒒𝑻 = 𝟒𝟓𝟒. 𝟕𝟐 𝒙 𝟏𝟎𝟑 𝒌𝑱 𝐴𝑁𝑆𝑊𝐸𝑅

 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.
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.

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

𝑊+𝐹= 𝑉+𝐶
 CHEMICAL ENGINEERING SERIES 35
CRYSTALLIZATION

𝑉 = 𝑊 + 𝐹 − 2,000 ⟶ 𝑒𝑞𝑢𝑎𝑡𝑖𝑜𝑛 1
Consider Na2CO3 balance around the system
𝑥 𝐹 𝐹 = 𝑥 𝐶𝐶
𝑥 𝐹 = 1.0
𝑀𝑁𝑎 2𝐶𝑂3 106 𝑙𝑏 𝑁𝑎2 𝐶𝑂3
𝑥𝐶 = = = 0.3706
𝑀𝑁𝑎2𝐶𝑂3∙10𝐻2𝑂 286 𝑙𝑏 𝑁𝑎2 𝐶𝑂3 ∙ 10𝐻2 𝑂
(0.3706 𝑙𝑏 𝑁𝑎 2 𝐶𝑂3 ) (2,000 𝑙𝑏 𝑁𝑎 2 𝐶𝑂3 ∙ 10𝐻2 𝑂 )
𝑙𝑏 𝑁𝑎2 𝐶𝑂3 ∙ 10𝐻2 𝑂 ℎ
𝐹=
𝑙𝑏 𝑁𝑎2 𝐶𝑂3
1.0
𝑙𝑏 𝑠𝑜𝑑𝑎 𝑎𝑠ℎ
𝒍𝒃
𝑭 = 𝟕𝟒𝟏. 𝟐 𝐴𝑁𝑆𝑊𝐸𝑅
𝒉

Substitute to equation 1
𝑉 = 𝑊 + 741.2 − 2,000
𝑉 = 𝑊 − 1,258.8 ⟶ 𝑒𝑞𝑢𝑎𝑡𝑖𝑜𝑛 2

Consider solute (Na2CO3) balance around the dryer

𝑥 𝐷𝐷 = 𝑥 𝐶𝐶
(0.90 𝑙𝑏𝑁𝑎2 𝐶𝑂3 ∙ 10𝐻2 𝑂) ( 106 𝑙𝑏 𝑁𝑎2 𝐶𝑂3 14.2 𝑙𝑏 𝑁𝑎2 𝐶𝑂3
) + (0.10 𝑙𝑏 𝐿 ) ( )
286 𝑙𝑏 𝑁𝑎2 𝐶𝑂3 ∙ 10𝐻2 𝑂 (100 + 14.2)𝑙𝑏 𝐿
𝑥𝐷 =
1 𝑙𝑏 𝐷
𝑙𝑏 𝑁𝑎2 𝐶𝑂3
𝑥 𝐷 = 0.3460
𝑙𝑏 𝐷

(0.3706 𝑙𝑏 𝑁𝑎2 𝐶𝑂3 ) (2,000 𝑙𝑏 𝑁𝑎2 𝐶𝑂3 ∙ 10𝐻2 𝑂)

𝑙𝑏 𝑁𝑎2 𝐶𝑂3 ∙ 10𝐻2 𝑂 ℎ
𝐷=
𝑙𝑏 𝑁𝑎2 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
Substitute to equation 2
142.20 = 𝑊 − 1,258.8
𝒍𝒃
𝑾 = 𝟏, 𝟒𝟎𝟏 𝐴𝑁𝑆𝑊𝐸𝑅
𝒉

Consider solute (Na2CO3) balance around the dissolver

𝑥 𝐹 𝐹 + 𝑥 𝑅 𝑅 = 𝑥𝐴 𝐴
𝑙𝑏 𝑁𝑎2 𝐶𝑂3
𝑥𝐴 = 0.30
𝑙𝑏 𝐴
14.2 𝑙𝑏 𝑁𝑎2 𝐶𝑂3 𝑙𝑏 𝑁𝑎2 𝐶𝑂3
𝑥𝑅 = = 0.1243
(100 + 14.2)𝑙𝑏 𝑅 𝑙𝑏 𝑅
(1.0)(741.2) + (0.1243) (𝑅) = (0.30)(𝐴)
𝐴 = 2,470.67 + 0.4143𝑅 ⟶ 𝑒𝑞𝑢𝑎𝑡𝑖𝑜𝑛 3
 CHEMICAL ENGINEERING SERIES 36
CRYSTALLIZATION

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 + 0.4143𝑅 = 2,142.2 + 𝑅
𝑙𝑏
𝑅 = 560.8
ℎ
𝑙𝑏
𝐴 = 2,973.0
ℎ

Consider heat balance around the crystallizer

𝑞𝑐𝑟𝑦𝑠𝑡𝑎𝑙𝑠 = 𝐴𝐶𝑃 (𝑡𝐴 − 𝑡𝐵 ) + 𝐶′𝐻𝐶
𝑙𝑏 𝑙𝑏
𝐶 ′ = 0.90𝐷 = 0.90 (2,142.20 ) = 1,928.0
ℎ ℎ
𝐵𝑇𝑈
𝑐𝑎𝑙 𝑚𝑜𝑙 1 𝐵𝑇𝑈
𝑙𝑏
𝐻𝐶 = 25,000 𝑥 𝑥 = 157.34
𝑚𝑜𝑙 286 𝑔 0.55556 𝑐𝑎𝑙 𝑙𝑏
𝑔
𝑙𝑏 𝐵𝑇𝑈 1.8°𝐹 𝑙𝑏 𝐵𝑇𝑈
𝑞𝑐𝑟𝑦𝑠𝑡𝑎𝑙𝑠 = [(2,973.0 ) (0.85 ) (45 − 15) °𝐶 𝑥 ] + [(1,928.0 ) (157.34 )]
ℎ 𝑙𝑏 ∙ °𝐹 °𝐶 ℎ 𝑙𝑏
𝐵𝑇𝑈
𝑞𝑐𝑟𝑦𝑠𝑡𝑎𝑙𝑠 = 439,812.22
ℎ

𝑞 = 𝑈𝐴∆𝑇𝑙𝑚
(𝑡𝐴 − 𝑡2 ) − (𝑡𝐵 − 𝑡1 )
∆𝑇𝑙𝑚 = 𝑡 − 𝑡2
ln 𝐴
𝑡𝐵 − 𝑡1
[(45 − 20) − (15 − 10)] °𝐶 𝑥 1.8°𝐹
°𝐶
∆𝑇𝑙𝑚 =
45 − 20
ln
15 − 10
∆𝑇𝑙𝑚 = 22.37°𝐹
𝐵𝑇𝑈
439,812.22
ℎ
𝐴=
𝐵𝑇𝑈
(35 ) (22.37°𝐹 )
ℎ ∙ 𝑓𝑡 2 ∙ °𝐹
𝐴 = 561.74 𝑓𝑡 2
1 𝑓𝑡 𝑙𝑒𝑛𝑔𝑡ℎ 1 𝑢𝑛𝑖𝑡
# 𝑜𝑓 𝑢𝑛𝑖𝑡𝑠 = 561.74 𝑓𝑡 2 𝑥 𝑥
3 𝑓𝑡 2 10 𝑓𝑡

# 𝒐𝒇 𝒖𝒏𝒊𝒕𝒔 = 𝟏𝟖. 𝟕 ≈ 𝟏𝟗 𝒖𝒏𝒊𝒕𝒔 𝐴𝑁𝑆𝑊𝐸𝑅

Refrigeration capacity:
 CHEMICAL ENGINEERING SERIES 37
CRYSTALLIZATION

𝐵𝑇𝑈 𝑡𝑜𝑛 𝑟𝑒𝑓𝑟𝑖𝑔𝑒𝑟𝑎𝑡𝑖𝑜𝑛

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
∫ 𝑑𝑊𝑃 = ∫ (1 + ) 𝑑𝑊𝑆
0 0 𝐷𝑆
From table 19-6 (CHE HB 8th edition)
𝐷𝑃 = 𝑚𝑒𝑠ℎ 14 = 1.19 𝑚𝑚 (𝑠𝑖𝑒𝑣𝑒 𝑜𝑝𝑒𝑛𝑖𝑛𝑔)
𝐷𝑆 = 𝑚𝑒𝑠ℎ 20 = 0.841 𝑚𝑚 (𝑠𝑖𝑒𝑣𝑒 𝑜𝑝𝑒𝑛𝑖𝑛𝑔)
∆𝐷 = 𝐷𝑃 − 𝐷𝑆
∆𝐷 = 1.19 − 0.841 = 0.349 𝑚𝑚
𝑊𝑃 𝑊𝑆
0.349 3
∫ 𝑑𝑊𝑃 = ∫ (1 + ) 𝑑𝑊𝑆
0 0 0.841
𝑊𝑃 = 2.833 𝑊𝑆 ⟶ 𝑒𝑞𝑢𝑎𝑡𝑖𝑜𝑛 1

𝑊𝑃 = 𝐶 + 𝑊𝑆
𝑊𝑃 = 2,000 + 𝑊𝑆 ⟶ 𝑒𝑞𝑢𝑎𝑡𝑖𝑜𝑛 2
Equate 1 and 2
2.833𝑊𝑆 = 2,000 + 𝑊𝑆
𝒍𝒃
𝑾𝑺 = 𝟏, 𝟎𝟗𝟏. 𝟏𝟏 𝐴𝑁𝑆𝑊𝐸𝑅
𝒉

Consider Na2S2O3 balance:

𝑥 𝐹 𝐹 = 𝑥 𝐿 𝐿 + 𝑥 𝐶𝐶
𝑙𝑏 𝑁𝑎2 𝑆2 𝑂3
𝑥 𝐹 = 0.565
𝑙𝑏 𝑓𝑒𝑒𝑑
83 𝑙𝑏 𝑁𝑎2 𝑆2 𝑂3 𝑙𝑏 𝑁𝑎2 𝑆2 𝑂3
𝑥𝐿 = = 0.4536
(100 + 83) 𝑙𝑏 𝑙𝑖𝑞𝑢𝑜𝑟 𝑙𝑏 𝑙𝑖𝑞𝑢𝑜𝑟
𝑀𝑁𝑎 2𝑆2𝑂3 158 𝑙𝑏 𝑁𝑎2 𝑆2 𝑂3
𝑥𝐶 = = = 0.6371
𝑀𝑁𝑎2𝑆2𝑂3∙5𝐻2 𝑂 248 𝑙𝑏 𝑁𝑎2 𝑆2 𝑂3 ∙ 5𝐻2 𝑂
 CHEMICAL ENGINEERING SERIES 38
CRYSTALLIZATION

(0.565)(𝐹 ) = (0.4536 )(𝐿 ) + (0.6371 )(2,000)

𝐿 = 1.2456𝐹 − 2,809.08 ⟶ 𝑒𝑞𝑢𝑎𝑡𝑖𝑜𝑛 3

Consider over-all material balance

𝐹 = 𝐿+𝐶
𝐿 = 𝐹 − 2,000 ⟶ 𝑒𝑞𝑢𝑎𝑡𝑖𝑜𝑛 4
Equate 3 and 4
1.2456𝐹 − 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 ⟶ 𝑒𝑞𝑢𝑎𝑡𝑖𝑜𝑛 1
Consider MgSO4 balance
𝑥 𝐹 𝐹 = 𝑥 𝐿 𝐿 + 𝑥 𝐶𝐶
From figure 27-3 (Unit Operation 7th edition, McCabe and Smith) at 110°F
𝑙𝑏 𝑀𝑔𝑆𝑂4
𝑥 𝐹 = 0.32
𝑙𝑏 𝑓𝑒𝑒𝑑
From figure 27-3 (Unit Operations 7th edition, McCabe and Smith) at 40°F
𝑙𝑏 𝑀𝑔𝑆𝑂4
𝑥 𝐿 = 0.21
𝑙𝑏 𝑙𝑖𝑞𝑢𝑜𝑟
𝑀𝑀𝑔𝑆 𝑂4 120 .38 𝑙𝑏𝑀𝑔𝑆 𝑂4
𝑥𝐶 = = = 0.4884
𝑀𝑀𝑔𝑆 𝑂4∙7𝐻2 𝑂 246 .49 𝑙𝑏 𝑀𝑔𝑆𝑂4 ∙ 7𝐻2 𝑂
(0.32)(100 ) = (0.21)(𝐿 ) + (0.4884) (𝐶 )
𝐿 = 152.38 − 2.3257𝐶 ⟶ 𝑒𝑞𝑢𝑎𝑡𝑖𝑜𝑛 2
Equate 1 and 2
100 − 𝐶 = 152.38 − 2.3257 𝐶
𝐶 = 39.51 𝑙𝑏
1 𝑙𝑏 𝑠𝑒𝑒𝑑𝑠
𝑊𝑆 = 100 𝑙𝑏 𝑓𝑒𝑒𝑑 𝑥 = 1 𝑙𝑏
100 𝑙𝑏 𝑓𝑒𝑒𝑑
𝑊𝑃 = 𝐶 + 𝑊𝑆 = 39.51 + 1 = 40.51 𝑙𝑏
𝑊𝑃 𝑊𝑆
∆𝐷 3
∫ 𝑑𝑊𝑃 = ∫ (1 + ) 𝑑𝑊𝑆
0 0 𝐷𝑆
𝐷𝑃 3
𝑊𝑃 = [ ] 𝑊𝑆
𝐷𝑆
From table 19-6 (CHE HB 8th edition)
 CHEMICAL ENGINEERING SERIES 39
CRYSTALLIZATION

𝐷𝑆 = 𝑚𝑒𝑠ℎ 80 = 0.177 𝑚𝑚 (𝑠𝑖𝑒𝑣𝑒 𝑜𝑝𝑒𝑛𝑖𝑛𝑔)

3 40.51 𝑙𝑏
𝐷𝑃 = (0.177 𝑚𝑚) √
1 𝑙𝑏
𝐷𝑃 = 0.6079 𝑚𝑚

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

𝑴𝑬𝑺𝑯 𝑺𝑰𝒁𝑬 = 𝟐𝟒 𝑴𝑬𝑺𝑯 𝐴𝑁𝑆𝑊𝐸𝑅

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:

𝑊𝑃 𝑊𝑆 3
∆𝐷
∫ 𝑑𝑊𝑃 = ∫ (1 + ) 𝑑𝑊𝑆
0 0 𝐷𝑆
𝑑𝑊𝑆 = 𝑊𝑆 𝑑𝜙𝑆
1
∆𝐷 3
𝑊𝑃 = 𝑊𝑆 ∫ (1+ ) 𝑑𝜙𝑆
0 𝐷𝑆
𝑊𝑃 1
∆𝐷 3
= ∫ (1 + ) 𝑑𝜙𝑆
𝑊𝑆 0 𝐷𝑆
𝑊𝑃 1
∆𝐷 3
𝑙𝑒𝑡, 𝑚 = = ∫ (1 + ) 𝑑𝜙𝑆
𝑊𝑆 0 𝐷𝑆
3
∆𝐷
Δ𝑚 = (1 + ) Δ𝜙𝑆
𝐷𝑆
Where: Δ𝜙𝑆 = fractional weight range

Solve for required 𝑚:

𝑊𝑃 7,000 𝑙𝑏
𝑚𝑟𝑒𝑞𝑑 = = = 14
𝑊𝑆 500 𝑙𝑏

This problem can be solved by trial and error

1. Assume value of Δ𝐷
 CHEMICAL ENGINEERING SERIES 40
CRYSTALLIZATION

∆𝐷 3
2. Solve for (1 + ̅𝑆 for each size range
) for each size range, use the mean 𝐷
𝐷𝑆
3. Solve for Δ𝑚
4. Get the total Δ𝑚
5. If ∑ Δ𝑚 = 𝑚𝑟𝑒𝑞𝑑 , then assumed Δ𝐷 is correct; if not, redo another trial

TRIAL 1: Assume Δ𝐷 = 0.004 𝑖𝑛

3 3
Δ𝐷 Δ𝐷
̅𝑆
𝐷 Δ𝜙𝑆 (1 + ) Δ𝑚 = Δ𝜙𝑆 (1 + )
̅𝑆
𝐷 ̅𝑆
𝐷

0.0150 𝑖𝑛 0.10 2.0322 0.2032

0.0075𝑖𝑛 0.20 3.6050 0.7210
0.0038 𝑖𝑛 0.40 8.6483 3.4593
0.0018 𝑖𝑛 0.30 33.4554 10.0366
1.00 14.4201
Since % error is less than 5%, assumed value can be considered

For particle size distribution:

𝐷𝑃 = Δ𝐷 + 𝐷𝑆
Δ𝑚
% 𝑤𝑡 = 100Δ𝜙𝑆 = 3 𝑥 100
Δ𝐷
(1 + )
̅𝑆
𝐷

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 = 𝑊𝑃 − 𝑊𝑆 = 7,000 − 500 = 6,500
ℎ
𝑙𝑏
𝐿 = 20,000 − 6,500 = 13,500
ℎ
 CHEMICAL ENGINEERING SERIES 41
CRYSTALLIZATION

Consider Na3PO4 balance:

𝑥 𝐹 𝐹 = 𝑥 𝐿 𝐿 + 𝑥 𝐶𝐶
𝑀𝑁𝑎 3𝑃𝑂4 164 𝑙𝑏 𝑁𝑎3 𝑃𝑂4
𝑥𝐶 = = = 0.4316
𝑀𝑁𝑎3𝑃𝑂4∙12𝐻2 𝑂 380 𝑙𝑏 𝑁𝑎3 𝑃𝑂4 ∙ 12𝐻2 𝑂
(0.35)(20,000) = ( 𝑥 𝐿)(13,500) + (0.4316 )(6,500)

𝑙𝑏 𝑁𝑎3 𝑃𝑂4
𝑥 𝐿 = 0.3107
𝑙𝑏 𝑠𝑜𝑙𝑛
𝑙𝑏 𝑁𝑎3 𝑃𝑂4 𝑙𝑏 𝑠𝑜𝑙𝑛
𝑥 𝐿 = 0.3107 𝑥
𝑙𝑏 𝑠𝑜𝑙𝑛 (1 − 0.3107) 𝑙𝑏 𝐻2 𝑂
𝑙𝑏 𝑁𝑎3 𝑃𝑂4
𝑥 𝐿 = 0.4507
𝑙𝑏 𝐻2 𝑂

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

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

𝑻 = 𝟓𝟏. 𝟕𝟐𝟓°𝑪 ≈ 𝟏𝟐𝟓. 𝟏𝟏°𝑭 𝐴𝑁𝑆𝑊𝐸𝑅

Cooling Duty:

Consider heat balance:

𝑞 = 𝐹𝐶𝑃 (𝑡𝐹 − 𝑡𝑃 ) + 𝐶𝐻𝐶
𝑙𝑏 𝐵𝑇𝑈 𝑙𝑏 𝐵𝑇𝑈 𝑙𝑏𝑚𝑜𝑙
𝑞 = [(20,000 ) (0.8 ) (190 − 125.11) °𝐹 ] + [(6,500 ) (27,500 𝑥 )]
ℎ 𝑙𝑏 ∙ °𝐹 ℎ 𝑙𝑏𝑚𝑜𝑙 380 𝑙𝑏

𝑩𝑻𝑼
𝒒 = 𝟏, 𝟓𝟎𝟖, 𝟔𝟑𝟒. 𝟕𝟒 𝐴𝑁𝑆𝑊𝐸𝑅
𝒉
 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 CaCl 2 at 20°C is 6.7 gmol anhydrous salt (CaCl 2) per kg of water.

SOLUTION:

For a saturated solution utilizing 100 kg water as solvent:

1. Mole of CaCl2 required

6.7 𝑔𝑚𝑜𝑙 𝐶𝑎𝐶𝑙 2 1 𝑘𝑚𝑜𝑙 𝐶𝑎𝐶𝑙 2
𝑛𝐶𝑎 𝐶𝑙2 = 100 𝑘𝑔 𝐻2 𝑂 𝑥 𝑥
𝑘𝑔 𝐻2 𝑂 1,000 𝑔𝑚𝑜𝑙 𝐶𝑎𝐶𝑙 2
𝑛𝐶𝑎 𝐶𝑙2 = 0.67 𝑘𝑚𝑜𝑙

2. Weight of CaCl2 required

110.994 𝑘𝑔 𝐶𝑎𝐶𝑙 2
𝑊𝐶𝑎 𝐶𝑙2 = 0.67 𝑘𝑔 𝐶𝑎𝐶𝑙 2 𝑥
𝑘𝑚𝑜𝑙 𝐶𝑎𝐶𝑙 2
𝑊𝐶𝑎 𝐶𝑙2 = 74.36 𝑘𝑔

3. Mole of CaCl2·6H2O required

1 𝑘𝑚𝑜𝑙 𝐶𝑎𝐶𝑙 2 ∙ 6𝐻2 𝑂
𝑛 𝐶𝑎𝐶𝑙2 ∙6𝐻2 𝑂 = 0.67 𝑘𝑚𝑜𝑙 𝐶𝑎𝐶𝑙 2 𝑥
𝑘𝑚𝑜𝑙 𝐶𝑎𝐶𝑙 2
𝑛 𝐶𝑎𝐶𝑙2 ∙6𝐻2 𝑂 = 0.67 𝑘𝑚𝑜𝑙

4. Weight CaCl2·6H2O required

218 .994 𝑘𝑔 𝐶𝑎𝐶𝑙 2 ∙ 6𝐻2 𝑂
𝑊𝐶𝑎𝐶𝑙2 ∙6𝐻2 𝑂 = 0.67 𝑘𝑚𝑜𝑙 𝐶𝑎𝐶𝑙 2 ∙ 6𝐻2 𝑂 𝑥
𝑘𝑚𝑜𝑙 𝐶𝑎𝐶𝑙 2 ∙ 6𝐻2 𝑂
𝑊𝐶𝑎𝐶𝑙2 ∙6𝐻2 𝑂 = 146.72 𝑘𝑔

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

𝑊𝐶𝑎𝐶𝑙2 ∙6𝐻2 𝑂 = 146.72 𝑘𝑔

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

𝑊𝑓𝑟𝑒𝑒 𝐻2 𝑂 = 100 𝑘𝑔 − (146 .72 − 74.36) 𝑘𝑔 = 27.64 𝑘𝑔

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

146.72 𝑘𝑔 𝐶𝑎𝐶𝑙 2 ∙ 6𝐻2 𝑂

𝑊𝐶𝑎𝐶𝑙2 ∙6𝐻2 𝑂 = 100 𝑘𝑔 𝑓𝑟𝑒𝑒 𝐻2 𝑂 𝑥
27.64 𝑘𝑔 𝑓𝑟𝑒𝑒 𝐻2 𝑂
𝑾𝑪𝒂𝑪𝒍𝟐∙𝟔𝑯𝟐 𝑶 = 𝟓𝟑𝟎. 𝟖𝟐 𝒌𝒈 𝐴𝑁𝑆𝑊𝐸𝑅