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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:

(2) formation of solid particles from a liquid melt

(3) formation of solid crystals from a solution

(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

(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

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

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

(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

(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

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

300

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

200

150

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

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

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

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

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

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

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

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:

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

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

Substitute in

( )

Magma composition:

% Recovery:

( )( )

( )( )

CHEMICAL ENGINEERING SERIES 11

CRYSTALLIZATION

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:

( )( ) ( ) ( )( )

THE PROBLEM CAN BE SOLVED BY TRIAL AND ERROR SINCE TEMPERATURE OF THE

SOLUTION AFTER CRYSTALLIZATION IS UNKNOWN AND ENTHALPIES ARE DEPENDENT

ON TEMPERATURE

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

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)

[( )( )]

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

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

CHEMICAL ENGINEERING SERIES 13

CRYSTALLIZATION

PROBLEM # 03 :

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

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

SOLUTION:

( ) ( )

( )

( )

( )

( )

( ) ( )

( )

( )

( )( ) ( )( )

Substitute in

( )

[( )( )]

CHEMICAL ENGINEERING SERIES 15

CRYSTALLIZATION

PROBLEM # 05:

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:

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

Equate and

( )

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:

CHEMICAL ENGINEERING SERIES 18

CRYSTALLIZATION

PROBLEM # 07:

F

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

tL = 50 F

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:

( )

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:

( )

( )

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

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

( )( )

( )( )

Substitute to equation

( )

( )( )

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

Operations (Geankoplis)

SOLUTION:

( )

( ) ( )

( )

( )( )

( ) ( )

( )

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

Equate and

CHEMICAL ENGINEERING SERIES 22

CRYSTALLIZATION

( )

( ) ( )

( )

( )( )

( ) ( )

( )

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

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?

Operations (Geankoplis)

SOLUTION:

( )( ) ( )( )

Equate and

( )( )

CHEMICAL ENGINEERING SERIES 24

CRYSTALLIZATION

( )

( )( ) ( )( )

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

SOLUTION:

( )

( )

( )

Equate and

CHEMICAL ENGINEERING SERIES 26

CRYSTALLIZATION

( )

( ) ( )

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?

SOLUTION:

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

THE PROBLEM CAN BE SOLVED BY TRIAL AND ERROR SINCE TEMPERATURE OF THE

SOLUTION AFTER CRYSTALLIZATION IS UNKNOWN AND ENTHALPIES ARE DEPENDENT

ON TEMPERATURE

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

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)

[( )( )]

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

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:

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

( )

where T is in K

At 100°F (310.93 K)

At 40°F (277.59 K)

̅

CHEMICAL ENGINEERING SERIES 30

CRYSTALLIZATION

( )( ) ( )( )

( )

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

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

Substitute in

( )

( )

( )

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

Equate and

( )

( )

CHEMICAL ENGINEERING SERIES 31

CRYSTALLIZATION

( )

lb %

CaCl2·6H2O 0.0056 4.89

H2O 0.0090 7.85

inerts 0.1000 87.26

0.1146 100.00

lb

CaCl2·6H2O

crystallized 0.7620

from liquor 0.0762 x 0.0489 0.0037 0.7657

inerts 0.0762 x 0.8726 0.0665 0.0665

0.8382

lb %

CaCl2·6H2O 0.7657 92.01

inerts 0.0665 7.99

0.8322 100.00

CHEMICAL ENGINEERING SERIES 32

CRYSTALLIZATION

PROBLEM # 15:

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:

( )

( )

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

Equate and

CHEMICAL ENGINEERING SERIES 33

CRYSTALLIZATION

( )

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.

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:

( )( )

CHEMICAL ENGINEERING SERIES 35

CRYSTALLIZATION

Substitute to equation

( )( ) ( )( )

( )

( )( )

Substitute to equation

( )

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

CHEMICAL ENGINEERING SERIES 36

CRYSTALLIZATION

Equate and

( )

( )

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

( ) ( )

[( ) ( )]

( )( )

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

( )

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

Equate and

CHEMICAL ENGINEERING SERIES 38

CRYSTALLIZATION

PROBLEM # 18:

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:

Consider over-all material 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:

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:

∫ ∫ ( )

∫ ( )

∫ ( )

∫ ( )

( )

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

̅ ( ) ( )

̅ ̅

( ̅ )

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

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:

( )

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

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:

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)