ChE Unit Operations

(Crystallization)
CONTENTS to be COVERED

Intro
Fundamentals
Crystallization from Solutions
Crystallization from Melts
Crystallization from Vapors
Fractional Crystallization
High Pressure Crystallization
Crystallization, one of the oldest of unit operations.
- used to produce vast quantities of materials, including sodium
chloride, sodium and aluminum sulfates and sucrose
(production rates in excess of 108 tons/year on a world basis)

Many organic liquids are purified by crystallization rather than by

distillation. Why?
Enthalpies of crystallization are generally much lower than
enthalpies of vaporization.

Crystallization may be carried out closer to ambient temperature thereby

reducing energy requirements.
Uses of Crystallization

- freeze-concentration of fruit juices

- desalination of sea water
- recovery of valuable materials such as metal salts
from electroplating processes
- production of materials for the electronic
industries
- biotechnological operations such as the
processing of proteins
Crystallization Fundamentals

Crystallization is the solidification of atoms or molecules into a highly

structured form called a crystal.

Crystallization can also refer to the solid-liquid separation and

purification technique in which mass transfer occurs from the liquid
solution to a pure solid crystalline phase.
Crystal Structure Model of NaCl
 Crystal Systems
- Finite possible arrangements of a crystal lattice.

POLYMORPHISM - a property in which a substance can exist in several

crystal forms. Example: silica, binary metal oxides

ISOMORPHISM - when two or more substances possess the same crystalline

form. Example: sulfates and alums
 What are the three polymorphs of calcium carbonate?
calcite (hexagonal), aragonite (tetragonal), and vaterite (trigonal)
PHASE EQUILIBRIA – important in evaluating crystallization operation

 Composition of product
 Degree of supersaturation

IMPORTANT PARAMETERS TO CONSIDER:

 rate of nuclei formation residence time in

 rate of crystal growth crystallizer size/capacity
crystal sizes
mode and degree of agitation
POLYMORPHISM –substance capable of forming one different
crystal
Polymorphic transformations - rapid and reversible
Example:
Enantiotropic (interconvertible) - ammonium nitrate has five
enantiotropic polymorphs over the temperature range
255–398 K.

Monotropic (incapable of transformation)

Example: graphite and carbon - at ambient temperature and

pressure
PHASE EQUILIBRIA
One-Component System

Phase diagram for water

EXERCISE 1 For the
phase diagrams of the enantiotropic forms
α and β of the same substance, find the melting point of the β form.
PHASE EQUILIBRIA
Two-Component System (Binary System)
Factors that affect: T, P, concentration
- Usually shows T, conc. 2-D data plots in phase diagrams

THREE basic types of binary systems:

1) Eutectics
2) Solid solutions
3) Systems with compound formation
Eutectic - mixture of components that has the lowest crystallization
temperature in the system. A fixed composition of individual
components (not a compound).

Lever arm rule

LZ:ZC = mass proportion of solid phase (crystal) to
liquid phase (residual melt)
 Solid Solution System – crystals are an intimate mixture of components A and B.

NOTE: A simple eutectic system may be purified in a single-stage

crystallization operation, whereas a solid-solution system always needs
multistage operation.
 Compound-Forming System – solute and solvent combine to form one or
more different compounds (ex. hydrates in aqueous solutions)

Congruent melting – compound can co- Incongruent melting - tend to stratify on

exist in stable equilibrium with a liquid
phase of the same composition
repeated temperature cycling.
Example. melting of orthoclase(KAlSi3O8)
produces leucite (KAlSi2O6) in addition to a
melt
Other promising hydrates: sodium sulphate
deca-hydrate, sodium acetate tri-hydrate,
and sodium thiosulphate penta-hydrate.
 THREE-COMPONENT SYSTEM
Temp-conc. space
isothermal triangular
model
diagram

Phase equilibria affected by temperature, pressure, and the concentrations of

any two of the three components. Efffect of pressure is usually negligible.

Eutectic formation in the ternary system o-, m- and p-nitrophenol a)

Temperature–concentration space model; b) Projection on a triangular diagram.
(Numerical values represent temperatures in K)
MULTI-COMPONENT SYSTEM

The more components in a system, the more complex are the phase
equilibria and it is more difficult to represent phases graphically.

SOLUBILITY AND SATURATION

Saturated solution - a solution that is in thermodynamic
equilibrium with the solid phase of its solute at a given
temperature.

Supersaturated solution – contains more dissolved solute

than that given by the equilibrium saturation value.
 SAMPLE PROBLEM 1

At 293 K, a supersaturated solution of sucrose contains

2.45 kg sucrose/kg water. If the equilibrium saturation
value is 2.04 kg/kg water, what is the supersaturation
ratio in terms of kg/kg water and kg/kg solution?

The fundamental driving force for crystallization, the true

thermodynamic supersaturation, is the
difference in chemical potential.

ΔG (wrt change in the amount of the component )

T,P, amounts of other components held constant

Components are in equilibrium if their chemical potentials are equal

CRYSTAL SIZE AND SOLUBILITY
Relationship between particle size and solubility first applied to solid–liquid systems
by OSTWALD

where cr is the solubility of particles of radius r, ρs the density of the solid,

M the relative molecular mass of the solute in solution, σ the interfacial
tension of the crystallization surface in contact with its solution and ni the
moles of ions formed from one mole of electrolyte. F

For a non-electrolyte, ni = 1 and for most inorganic salts in water, the

solubility increase is really only significant for particles of less than 1 µm
 SAMPLE PROBLEM 2
Compare the increase in solubility above the normal equilibrium values of 1,
0.1 and 0.01 µm particles of barium sulfate and sucrose at 298 K. The
relevant properties of these materials are:
CRYSTAL YIELD (FROM COOLING)
- can be estimated from the concentration of the initial solution and
the solubility at the final temperature, allowing for any evaporation
and making solute and solvent balances.

where w1 and w2 are the initial and final masses of solvent in the liquor, y is
the yield of crystals, R is the ratio (molecular mass of hydrate/molecular mass
of anhydrous salt) and E is the ratio (mass of solvent evaporated/mass of
solvent in the initial solution)

For the solute,

where c1 and c2 are the initial and final concentrations of the solution
expressed as (mass of anhydrous salt/mass of solvent)
CRYSTAL YIELD

Yield for aqueous solutions is given by,

Applicable to VACUUM or ADIABIATIC cooling

From a heat balance,

λ is the latent heat of evaporation of the solvent (J/kg), q is the heat

of crystallization of the product (J/kg), T1 is the initial temperature of the
solution (K), T2 is the final temperature of the solution (K) and Cp is the
specific heat capacity of the solution (J/kg K).
SAMPLE PROBLEM 3
What is the theoretical yield of crystals which may be obtained by cooling a
solution containing 1000 kg of sodium sulfate (molecular mass = 142
kg/kmol) in 5000 kg water to 283 K? The solubility of sodium sulfate at
283 K is 9 kg anhydrous salt/100 kg water and the deposited crystals will
consist of the deca-hydrate (molecular mass = 322 kg/kmol). It may be
assumed that 2 per cent of the water will be lost by evaporation during
cooling.

SAMPLE PROBLEM 4
CRYSTALLIZATION FROM SOLUTIONS
- By cooling, evaporation, vacuum, reaction and salting out.

Cooling crystallizers (agitated)

 SAMPLE PROBLEM 5
A solution containing 23 per cent by mass of sodium phosphate is cooled from 313
to 298 K in a Swenson-Walker crystallizer to form crystals of Na3PO4.12H2O. The
solubility of Na3PO4 at 298 K is 15.5 kg/100 kg water, and the required product
rate of crystals is 0.063 kg/s. The mean heat capacity of the solution is 3.2 kJ/kg
deg K 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 coefficient of heat transfer
is 140 W/m2 deg K, what length of crystallizer is required?
COOLING CRYSTALLIZERS
Non-agitated vessels
- simplest type of cooling crystallizer; unstirred tank in which a hot
feedstock solution is charged to an open vessel and allowed to
cool, often for several days, by natural convection. Example:
production of NaCl
Agitated vessels
- gives smaller and more uniform crystals and reduces batch times.
Scraped-surface crystallisers
- scraper rotating at 0.8–1.6 Hz, keeps the cooling surfaces clean
and enhances growth of crystals. Example: Swenson-Walker,
Votator and Armstrong crystallizers
Direct-Contact Cooling (with solid, liq uid or gas coolants)
- Advantages: crystal encrustation is avoided and lower cooling loads
- Disadvantages: product contamination and additional cost due to coolant
recovery
EVAPORATING CRYSTALLIZERS
- supersaturation can be achieved by evaporating some of the
solvent
- usually operated under reduced pressure to aid solvent removal,
minimize heat consumption, or decrease the operating
temperature of the solution
Example: common salt, sugar refining

VACUUM CRYSTALLIZERS
- simultaneous evaporation and adiabatic cooling of the feedstock
CONTINUOUS CRYSTALLIZERS
Basic types: forced circulation, fluidized-bed and draft-tube agitated
units

Swenson forced-circulation crystallizer

 BATCH CRYSTALLIZATION
Advantage: can be cleaned thoroughly at the end of each batch, thus
preventing contamination of the next charge with any undesirable
products.
- In certain cases, produce the required crystal form, size distribution or
purity.
- Simplicity of equipment and reduced encrustation on heat-exchanger
surfaces
Disadvantage: Operating costs can be significantly higher compared to
continuous operation.

CONTINUOUS CRYSTALLIZATION
Advantage: built-in flexibility for control of temperature,
supersaturation nucleation, crystal growth, and other parameters
that influence the size distribution of crystals.
Disadvantage: undesired self-seeding may occur after a certain
operating time.
Semi-continuous crystallization processes combine the best features of batch
and continuous operation!
CRYSTALLIZER SELECTION
IMPORTANT CONSIDERATIONS:
1) temperature–solubility relationship for solute and solvent
Examples: if solution produces appreciable amounts of crystals on
cooling – simple cooling or vacuum cooling unit is appropriate
- if solution changes little in composition – evaporating crystallizer is
appropriate.
2) shape, size and size distribution of the product
Example: for large uniform crystals, a controlled suspension unit
fitted with suitable traps for fines, permitting the discharge of a
partially classified product, would be suitable.
3) initial and operating costs, the space available, the type and
size of the product, the characteristics of the feed liquor, the need
for corrosion resistance and so on.