HEAT AND MASS TRANSFER

CRYSTALLIZATION

1. Definition

Crystallization, which involves simultaneous heat and mass transfer, is basically a solid-
liquid separation process where solids are formed from a homogeneous phase upon
reaching supersaturation.

A crystal is a highly organized array of atoms, molecules, or ions arranged in three-

dimensional space lattices.

2. Common Methods of Reaching Supersaturation

Cooling achieved near a heat-transfer surface

Solvent evaporation achieved near a heat-transfer surface
Drowning addition of non-solvent, which decreases the solubility of
the solid
Chemical reaction decreases the solubility of the dissolved solute, leading to
supersaturation

3. Solubility Curves

Solubility refers to the maximum amount of solute that a given amount of solvent
dissolves at a particular temperature. Solubility curves are diagrams that give the
solubility of a particular solute in a given solvent at different temperatures. Some of
these figures even show points at which crystals form with the corresponding enthalpy.
The latter are specifically called enthalpy-concentration diagrams.

Some of the diagrams are given in the following sources.

Fig. 18-56 (Perrys CHE Handbook, 7th Ed.) Solubility of MgSO4.xH2O in water
at 1 atm
Fig. 12.11-1 (Geankoplis, 4th Ed.) Solubility of Na2S2O3 in water at 1 atm
Fig. 19.27 (Foust et al., 2nd Ed.) Solubility of Na2SO4 in water at 1atm
Fig. 19.28 (Foust et al., 2nd Ed.) Enthalpy-concentration diagram for the
Na2SO4 - H2O system at 1 atm
Fig. 19.29 (Foust et al., 2nd Ed.) Enthalpy concentration diagram for the CaCl2 -
H2O system at 1 atm

The figure below is an example of a solubility curve.

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DS-L x.H2O

CS-L x.2H2O

Solubility, BS-L x.3H2O

wt X/wt solution

AS-L x.4H2O

AL BL CL DL

Temperature
Figure 1. Example of a solubility curve

Note: AL, BL, CL, and DL are regions where only solution is present.
AS-L is the region where x.4H2O crystals coexist with saturated solution.
BS-L is the region where x.3H2O crystals coexist with saturated solution.
CS-L is the region where x.2H2O crystals coexist with saturated solution.
DS-L is the region where x.H2O crystals coexist with saturated solution.

4. Progress Of Crystallization

Metastable
zone
4 3 2
1

5
1 Feed location unsaturated
2 Solution cools to saturation
concentration 3 Enter metastable zone, nucleation begins
6 4 Rapid nucleation
undersaturate 5 Concentration decreases with crystal growth
d 6 Crystal growth during main cooling cycle
7 7 Exit location supersaturated

Saturation
curve

temperature

Figure 2. Progress of crystallization

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5. Crystallization Equipment

5.1 Classification according to the method by which supersaturation is achieved

5.1.1 Evaporative crystallizers

In evaporative crystallizers conditions are approximately isothermal, and

supersaturation is achieved as a result of the removal of the solvent. Evaporative
crystallization is normally used in applications where the solubility shows little
variation with temperature.

5.1.2 Cooling crystallizers

In cooling crystallizers, supersaturation results from lowering the temperature of the

solution, which can be effected by sensible heat exchange or by evaporative cooling.
In the later case, there is a small solvent loss.

5.2 Classification according to mode of operation

5.2.1 Batch crystallizers

5.2.1.1 Open tank crystallizers

These are the simplest and cheapest type.

These can be used as an evaporative crystallizer, where the
liquor is generally heated by means of steam coils or from jacket.
These can also be used as a cooling crystallizer, where the
solvent is evaporated until the concentration has reached the required value,
and cooling is then effected by transfer of sensible heat to the surroundings
and evaporation at the free surface.
Crystals form on the surface of the coils and seriously
impede the heat transfer.

5.2.1.2 Salting evaporators

These are calandria type evaporators with relatively short

wide tubes and a large downcomer, designed so that the crystals do not
cause obstruction.
The solution is concentrated and then withdrawn, using either
a salt box or a barometric leg.

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The mother liquor, which is separated from crystals, is

recycled and mixed with the feed, and evaporation is continued until the
concentration of impurities in the solution becomes excessive.
Salting evaporators may be operated at atmospheric or
reduced pressure, the latter being essential for the formation of many
hydrated crystals.

5.2.1.3 Evaporative crystallizers

Crystallizers employing evaporative cooling often operate

under vacuum.
Hot feed is introduced into the equipment, which is maintained
at low pressure. This results to flash evaporation of the solution, which
produces rapid cooling accompanied by a small increase in concentration.
Vacuum crystallization is frequently used in the sugar industry.
The amount of evaporation taking place during vacuum
operation may be estimated by making a heat balance as given in the next
section (Section 6).

5.2.2 Continuous crystallizers

5.2.2.1 Linear type

5.2.2.1.1 Swenson-Walker crystallizer

Swenson-Walker crystallizer is basically a long open trough about 0.6

m across. It is divided into a number of sections, which can be
independently cooled with water in an external jacket to possibly
control the rate of cooling throughout.

This equipment is suitable only when supersaturation can be effected

by cooling alone, and fairly uniform crystals are produced though
some breakage is caused by the scraper.

Typically for Swenson-Walker crystallizer, the area available is 1 m 2

per m length.

5.2.2.1.2 Wuff-Bock crystallizer

Wuff-Bock crystallizer has similar characteristics to the Swenson-

Walker crystallizer; however, it relies on air cooling and gives more
uniformly-sized crystals.

5.2.2.1.3 Double-pipe cooler crystallizer

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This is a linear type cooler crystallizer in which the heat transfer

medium flows through an annular jacket. The solution passes through
the narrow space between the heat transfer surface and the shaft of the
mutator which carries scraper blades.

5.2.2.2 Stirred type

5.2.2.2.1 Oslo (or Krystal) crystallizer

This equipment combines evaporation and crystallization. The unit is

particularly used for production of large-sized uniform crystals.
Consisting essentially of a forced-circulation evaporator equipped with
external heater with salt filter and particle-size classifier, Oslo
crystallizer is the only one of crystallizers described that effects any
classification in the crystals formed.

6. Material Balance and Energy Balance

Consider the schematic diagram of a generalized crystallization process given below.

Evaporated solvent, V kg/h

crystallizer

Feed solution, F kg/h

Product magma, M kg/h

Figure 3. Generalized crystallization process

The material and energy balances are based on the assumption that the operation is
steady-state with liquid feed (F) and product magma (M). The latter contains the crystals
and saturated solution (usually referred to as the mother liquor) characteristic of the
crystallizer content.

The theoretical yield is based on material and energy balances.

Solute material balance:

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Ma Mh Ma
Fx C F 1 x F V C S'
F Mh Mh (1)

Total balance:

F VM VCS (2)

where: C = mass of crystals in the product magma per unit time

Ma = molecular weight of anhydrous salt or crystal
Mh = molecular weight of hydrated crystal
xF = mass fraction of anhydrous solute in feed
S = solubility of the anhydrous solute at product temperature
= expressed as a weight ratio of anhydrous salt to solvent
F = total mass of feed solution per unit time
V = evaporation rate in mass of solvent per unit time
S = mass of saturated solution produced per unit time
M = total mass of product magma produced per unit time
= mass of crystals formed + saturated solution

Energy balance:

HF HC q HL H V (3)

where: q = total heat absorbed in the crystallization/evaporation process

HF = total enthalpy of entering solution at TF, which is read off
enthalpy-concentration diagram
HM = total enthalpy of the crystals and saturated solution in the
product magma at the final temperature, TL
HV = total enthalpy of the vapor
HC = total heat of crystallization
= positive if crystallization is exothermic
= evaluated as the negative of the heat of solution

Heat balance in vacuum operation:

V V H F H L H C (4)

where: V = latent heat of vaporization of the solvent

HF HL = sensible heat drop

Sample Problem 1

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A 3000-kg aqueous solution, which consists of 20% by mass Na 2SO4, is cooled from
60oC to 10oC in an agitated mild steel vessel of mass 500 kg. At 10 oC the stable
crystalline phase is Na2SO410H2O. The mean heat capacity of the solution is 3.6 kJ /
kgK. During cooling, 2.5% by mass water is lost by evaporation. Estimate the yield of
crystals formed and the heat removed.

Additional data:
Specific heat of steel 500 J / kgK
Concentration of saturated solution of
Na2SO4 at 10oC 8.17% by mass Na2SO4
Heat of solution of Na2SO410H2O -78,500 kJ / kmol

Sample Problem 2

A solution containing 23% by mass of Na 3PO4 is cooled from 313 K to 298 K in a

Swenson-Walker crystallizer to form crystals of Na 3PO412H2O. The solubility of
Na3PO4 at 298 K is 15.5 kg / 100 kg water, and the required flow of crystals is 0.063 kg/s.
The mean heat capacity of the solution is 3.2 kJ / kgK and the heat of crystallization is
146.5 kJ/kg. If cooling water enters and leaves at 288 and 293 K, respectively, and the
overall heat transfer coefficient is 0.14 kW / m2K, what length of crystallizer is required?

7. The L Law

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

L = Gt (5)

In other words, the growth rate, G, is not a function of crystal size, L. In the preceding
equation, t refers to time.

8. Crystallizer Design

8.1 Crystal Size Distribution (CSD)

It is usually desired that large crystals that are easily filterable and relatively pure are
produced. Therefore, crystallization is operated to maximize crystal growth and restrict
nucleation.

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Product CSD is based on kinetics and nucleation growth of crystals. If, in the first place,
it is assumed that nucleation does not occur (i.e. the number of crystals is constant) and
that the initial CSD is not known, a rough estimation of CSD can be calculated. The
McCabe L law (described previously) is commonly used to calculate the final CSD if
initial CSD in known.

Calculation of CSD for a seeded crystallizer

L P L S L (6)

where: LP = characteristic crystal product dimension

LS = characteristic crystal seed dimension
L = change in dimension; constant throughout the range of sizes
present

Relationship between seed mass (mS) and product mass (mP)

m P ' L3P L S L
3
(7)
m S ' L 3
S (8)

Combining (8) and (7):

3
L
m P m S 1
L S
(9)

where: = shape factor (different from the usual shape factor)

= particle density

For the entire crystal mass:

mP mS 3

L
0 dm P 0 L S dm s m P
1
(10)

Sample Problem 3

A solute that forms cubic crystals is to be precipitated from solution at a rate of 10,000 kg
of solid (dry basis) per hour using 1,000 kg/h of seed crystals. If no nucleation occurs
and the seed crystals have the following size distribution, determine the product CSD.

Tyler Sieve Mesh Weight Fraction Retained

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-48 +65 0.16

-65 +100 0.32
-100 +150 0.44
-150 +200 0.05
-200 +270 0.03

8.2 Mixed-Suspension-Mixed-Product Removal (MSMPR) Model

MSMPR is an idealized crystallizer model, which is a basis for identifying the kinetic
parameters and showing how knowledge of them can be applied to calculate the
performance of such crystallizer.

Assumptions of the MSMPR Model

Steady-state
Crystallizer contains a mixed-suspension magma at all times, with no product
classification
Uniform supersaturation exists throughout the magma at all times
L law of crystal growth applies
No size-classified withdrawal system
No crystals in the feed
Mother liquor in the product magma is saturated (equilibrium)
No crystal breakage into finite particle size
Effluent composition is the same as in the vessel

8.2.1 Crystal population-density function (n)

The method described in Figure 4 permits the calculation of n for each fraction collected
in the screen analysis with an average size of Lav mm.

In the graph, N refers to the cumulative number of crystals per liter and L refers to the
crystal size in mm.

The parameter n can be estimated as:

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dN N
n
dL L
(11)

dN
N n
dL

L
Figure 4. Graphical determination of population-density (n) of crystals

8.2.2 Population material balance

Assumptions:

In t time, nL crystals are withdrawn.

The effluent composition in the outflow is Q L/h, which is the same as that in the
crystallizer of volume V.

n L Q t

n L V (12)

Recall the L law (equation 5). If G is in mm/h, combining equation 5 and 12 gives

n Q L

n VG (13)
As both L and n approach 0, and integrating,

n L
dn 1
0 n G 0 dL
n (14)
L
n n 0 exp
G (15)

where = V/Q, which is the total retention time or holding time (in hours) in the
crystallizer.

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References:

COULSON, J. M., RICHARDSON, J. F., BACKHURST, J. R., and HARKER, J. H.:

Chemical Engineering Volume 2 (Pergamon, Oxford, 1991)

FOUST, A. S., WENZEL, L. A., CLUMP, C. W., MAUS, L. and ANDERSEN, L. B.:
Principles of Unit Operations, 2nd ed. (John Wiley & Sons, Inc., New York, 1980).

GEANKOPLIS, C. J.: Transport Processes and Separation Process Principles, 4 th ed.

(Prentice Hall PTR, New Jersey, 2003).

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