Fluids and Solids Transport

Course Code: ENCH3FS

Credit Hours: 160

Section B: Solids Transport

Lecture 7a Crystallization

Lecturer: Dr. S. Fashu

Lecture 7a Outline

 Introduction

 Crystallisation

 Crystal Geometry

 Equilibria and Yield of Crystals

 Nucleation

 Growth of Crystals

 Examples
Introduction
 Crystallization is a solid-fluid separation process whereby crystals form in a
homogeneous fluid. It is exothermic because of formation of highly ordered
structures with strong bonds.

 The crystals may form by precipitating or freezing from a liquid phase or by

deposition from a gas/vapor phase. Types are:

 Precipitation from a solution is termed solution precipitation.

 Freezing crystallization is termed solidification.

 Deposition from vapor is termed desublimation.

 In most chemical engineering industrial applications, solution precipitation is

most widely used.
Common Applications
A number of materials are marketed in form of crystals; crystallization
applications include.

1. The production of sucrose from sugarcane.

2. Freeze concentration of fruit juices (to reduce handling volumes).

3. Purification of sea water by desalination.

4. Recovery of organic salts from aqueous solutions.

Crystallization
 A crystal is a solid in which atoms are
arranged in an orderly and repetitive
array. The figure shows unit cells as
building blocks for crystals.

 Crystallization involves concentration of solution (by evaporating a part of the

solvent and/ cooling of solution until the concentration of solute becomes higher
than its solubility at the prevailing temperature) to precipitate the solute out of
the solution in the form of pure crystals.

 The slurry containing crystals and the solution is called magma and the solution
remaining after removal of crystals is called the mother liquor.

 The whole process involves crystallization, separation of crystals from the

mother liquor, washing of crystals with fresh solvent and drying of moist
crystals.
Benefits of Crystallization
The performance of crystallization process is evaluated in terms of size, shape,
structure, yield and purity of crystals. Below are the benefits of crystallization.
 Produces highly pure solids from impure solutions in a single step.

 Particles of uniform size can be obtained; uniform size is important during

filtration and washing, in reactions and transportation.

 Particles of specified geometry can be produced e.g. cubes, needles, etc.

 The process is easy to scale up.

 Much less energy intensive than comparable techniques like distillation. e.g.
enthalpy of crystallization of water at 273K is 334kJ/kg while enthalpy of
vaporization (important for distillation) at 373K is 2260kJ/kg.

 Can be performed at low temperatures.

Growth of Crystals : Saturation
 In solution crystallisation, equilibrium between solid and liquid is attained
when the solution or mother liquor is saturated i.e. no more solid can dissolve.

 The phase equilibrium data is represented by a solubility curve which shows

solubility as a function of temperature and stable phases under specific
compositions and temperatures.

 Solubility is the mass of solute dissolving per mass of solvent at a given

temperature e.g., the solubility of MgSO4 in water at 293 K (20oC) is 35.5 kg
MgSO4 per 100 kg water.

 A solution that contains more dissolved solid/solute than the equilibrium value is
termed supersaturated. This is the driving force for crystallization and is
expressed as:

∗
where C is the solution concentration and ∗ is the equilibrium
saturation value. This is analogous to superheat of the solution, .
Solubility Curves
Figure. Solubility curves for (1) KNO3, (2) NaCl, and (3) MnSO4.H2O in aqueous
solution. [McCabe, 2005]

Solubility data are plotted

as solubility curves-curves
wherein solubilities are
plotted against temperature.
Solubility Curves
 Most materials follow curves similar to that of KNO3, i.e., their solubility
increases with temperature.

 A few substances follow

curves like that of NaCl
where an increase in
temperature hardly results in
an increase in solubility.

 In the third instance, the

curve of MnSO4.H2O is
referred to as an inverted
solubility curve; here, an
increase in temperature
results in a decrease in
solubility.
 Many inorganic salts can form hydrates, i.e., crystalline chemical compounds with
water, stable in certain temperature ranges e.g. MnSO4.H2O.
 When the solubility of the solute increases with increase in temperature, a
saturated solution becomes supersaturated, i.e., supersaturation is generated by
cooling and temperature reduction e.g. KNO3.

 When the solubility of the

solute is relatively independent
of temperature (as is the case
with common salt (NaCl) in
H2O), supersaturation is
generated by evaporating a
part of the solvent.

 When the solubility of the solute is very high then neither cooling nor
evaporation if effective and supersaturation may be generated by adding a new
substance (a third component) of lower solubility.
Solubility Curves (MgSO4.H2O Phase Diagram)

Conversions

To convert lb to kg
divide by 2.2
MgSO4.H2O Solubility Curve
 The large area at the bottom right of
the diagram represents under-
saturated solutions of MgSO4 in
water.

 The line p-a represents the freezing

points of ice (water) from solutions of
MgSO4.

 Point a is the eutectic, a mechanical

mixture of ice and MgSO4.12H2O that
melt and freezes at a single
temperature lower than melting points
of separate components or any mixture
of them.

 Lines a-b-c-d-q represent the solubility curve of MgSO4 hydrates.

MgSO4.H2O Solubility Curve
 Lines a-b, b-c, c-d and d-q are solubility
curves of MgSO4.12H2O, MgSO4.7H2O,
MgSO4.6H2O and MgSO4. H2O,
respectively.

 The area enclosed by p-a-e represents

mixtures of ice and saturated solution.

 Any solutions that contains <16.5% MgSO4

precipitates ice when the temperature
reaches p-a while any solutions containing
>16.5% MgSO4 precipitates MgSO4 upon
cooling.

 The area enclosed by c-j-h-b represents an equilibrium mixtures of crystalline

MgSO4.7H2O and saturated solution, while d-k-i-c consists of crystals of
MgSO4.6H2O and saturated solution, and q-d-k encloses mixtures of MgSO4.H2O
and saturated solution.
Material Balances of a Crystallizer
 Material balances are used to calculate the yield of crystallization operation
which is the mass of crystals obtained from a given mass of solution.

 Consider the crystallization

process carried out under
steady state conditions and
shown in the figure.
Let:
F be the mass flow rate of feed solution in kg/h
X'F be the weight fraction of anhydrous solute in the feed solution
C be the crystals obtained in kg/h
V be the mass flow rate of evaporated solvent in kg/h
X' be the solubility of the solute at the final temperature of operation expressed as a weight
ratio of anhydrous salt to solvent
M1 be the molecular weight of anhydrous solute salt
M2 be the molecular weight of hydrated salt
L' be the kg/h of solvent in the mother liquor
L be the kg/h of mother liquor leaving the crystallizer
Overall material balance

Material balance of solvent

Solvent in feed = Solvent evaporated + Solvent in mother liquor + Solvent in
hydrated crystals

Rearranging the above equation, we get

Material balance of solute

Solute in feed = Solute as product crystals + Solute in mother liquor

 If the crystals obtained are anhydrous then the above equation takes the following
form:

 If no evaporation takes place and anhydrous salts are crystallized, then

C – kg/h of crystal obtained (anhydrous/hydrated) and is the yield of the process.

Example
A solution consisting of 30%MgSO4 and 70%H2O is cooled to 60oF. During cooling,
5% of the total water in the system evaporates. How many kilograms of crystals are
obtained per 1000kg of the original mixture?
Solution
 Note that the crystals are MgSO4.7H2O and that the concentration of the mother
liquor is 24.5% anhydrous MgSO4 and hence 75.5%H2O.

Basis =1000kg of original mixture

Total amount of H2O=0.7 1000=700kg.

 5% of the total water evaporates:

Evaporation=0.05 700=35kg.

Given MW MgSO4=120.4 and MW MgSO4.7H2O=246.5kg/kmol

 Total mass is conserved,

the total MgSO4.7H2O=1000 0.3(246.5/120.4)=614kg

 The total free water=1000–35–614=351kg.

 Relating MgSO4 and MgSO4.7H2O: in100kg of mother liquor:

 The amount of MgSO4.7H2O=24.5(246.5/120.4)=50.16kg.

 The amount of free water=100–50.16=49.84kg.

 The amount of MgSO4.7H2O in the mother liquor=(50.16/49.84)351=353kg.

 The final crop=614–353=261kg.

Example: A solution of sodium nitrate in water contains 48 % NaNO3 by weight
at 313 K (40oC) temperature. Calculate the percentage yield of NaNO3 crystals that
may be obtained when the temperature is reduced to 283 K (10oC). Also, calculate
the quantity of NaNO3 crystals obtained from 100 kg of the solution.
Data : Solubility of NaNO3 in water at 283 K (10oC) is 80.18 kg NaNO3 per 100 kg
water.
Basis: 100kg feed solution
F=100kg
‘
weight fraction of NaNO3 in the feed
C=yield of crystals (kg of NaNO3 crystals obtained)
.
solubility of NaNO3 at 283K=
kg of solvent in mother liquor
Water (solvent) balance
Solvent in feed=Solvent in mother liquor
NaNO3 balance-(anhydrous salt as crystal)

NaNO3 in feed=NaNO3 obtained as crystals+NaNO3 in mother liquor

Crystal Nucleation and Growth
 We want to understand how crystals form in a supersaturated solution and grow.

 A necessary condition for crystallisation from a solution is that the solution

must be supersaturated.

 The process of crystallisation consists of two major steps:

(i) Nucleation–or nucleus formation

(ii) Crystal growth

 If the solution contains no solid/foreign particles, then nucleation will occur.

 Consider the solubility curve on the following page.

The Ostwald-Miers Diagram

 When a melt is cooled, its temperature drops until its melting point.

 Further cooling brings the melt to the supercooled (metastable) region and
nucleation starts at CD.

 Disturbances or getting to the limit of the supercooled region results in

solidification.
The Ostwald-Miers Diagram

 In the metastable region, formation of new crystals (nucleation) occurs

following some disturbances, e.g., the presence of solid impurities or stirring.

 The rate of nucleation is the number of new particles formed per unit time per
unit volume of magma or solids-free mother liquor.

 If a solution is free of all solid particles (e.g., small seed crystals, small amounts
of impurities, dust, etc.), then nucleus formation must first occur.

 New nuclei may continue to form while the present ones are growing.
Crystal Growth and Nucleation

 A knowledge of the mechanism by which crystals form and grow is required in

the design and operation of equipment used for crystallization. The formation
of a crystal from a solution is a two-step process.

 Supersaturation is the common driving force for nucleation and crystal growth.
Crystals can neither form nor grow unless a solution is supersaturated.

 If initially a large number of nuclei is formed, then the yield of the process
contains many small or tiny crystals and if a few nuclei are initially formed (at
the start), then the yield of the process contains large size crystals.

 Slow cooling results in the formation of a less number of nuclei and hence large
size crystals are formed (as the material deposits on a relatively few nuclei),
whereas rapid cooling results in the formation of a large number of nuclei, giving
the yield containing a large number of tiny crystals.
Nucleation
 Nucleation can be broadly divided into three groups: spurious, primary and
secondary.

(i) Spurious nucleation

 Spurious nucleation occurs at large supersaturations

or accompanies poor magma circulation.

 It is characterised by abnormal needle like growths

from the ends of crystals which tend to grow faster at
the sides.

 The diagram illustrates various growth regimes

from good to spike-wise growth.
Various Growth Regimes [McCabe, 2005]
(ii) Primary nucleation

 Primary nucleation refers to the development of nuclei spontaneously within

the supersaturated zone.

There are two types: homogeneous or heterogeneous.

 Homogeneous nucleation is characterised by the formation of new crystals

within a phase uninfluenced in any way by solids of any sort, including the
walls of the container or the most minute of substances.

 Heterogeneous nucleation occurs when solid particles of foreign substances

influence the nucleation process by catalysing an increase of nucleation rate at
given super-saturation or giving a rate at super-saturation much less than the
equivalent homogeneous rate.
Nucleation Rate

 The rate of nucleation is given by:

Where Bo= rate of nucleation, number/(cm3.s)

Na= Avogadro constant = 6.0222 1023 molecules/gmol

R = gas constant = 8.3143 107 ergs/(gmol.K)

C = frequency factor depending on the rate of formation of embryos reaching

critical sizes
 The above equation can be adapted for the heterogeneous case in which:

Where a= apparent interfacial tension

s = measure of supersaturation
Solubility

 The solubility of a substance is related to its particle size by the Kelvin equation:

Where L = crystal size

= Ratio of concentrations of supersaturated and saturated solutions

VM= molar volume of crystal

=Average interfacial tension between solid and liquid

= Number of ions per molecule of solute (for molecular crystals, = 1)

(iii) Secondary Nucleation

 This refers to the formation of nuclei attributable to the influence of existing

macroscopic crystals in magma. Foreign solid particles reduce the energy
required for nucleation because the nucleus wets the solid surface. There are two
nucleation mechanisms in crystallizers:

 Fluid-shear nucleation in which, given flow of supersaturated solution past the

surface of a growing crystal, shear stresses in the boundary layer sweep away
nuclei that would have been incorporated into the growing crystal and so appear
as new crystals.

 Contact nucleation occurs when crystals collide with each other, with
impellors, or with the walls of the container.

 It is affected by the intensity of agitation and is the most common type of

nucleation in industrial crystallisers.

 It occurs at low super-saturation, where the crystal growth rate is optimum for
good crystals (regular shape and uniform size).
Example: Nucleation

(a) Assuming that the rate of heterogeneous nucleation of potassium chloride is

consistent with an apparent interfacial tension of 2.5ergs/cm2, determine the
nucleation rate as a function of s at a temperature of 300K. The molecular weight of
KCl is 74.56g/mol. The density of the crystal is 1.988g/cm3.

(b) What would be the size of a nucleus in equilibrium with a supersaturation of

0.029 under the conditions of (a)?

Solution
 Molar volume of KCl is MW/density:

 Furthermore, as KCl dissociates into and in solution, The

exponent in the heterogeneous nucleation expression is

.
 Hence is valid for S in the neighborhood of 0.00788
(b) What would be the size of a nucleus in equilibrium with a supersaturation of
0.029 under the conditions of (a)?

 Since the nucleus size (L) appears in the Kelvin equation, we will use that
equation.

 Given that S=0.029 as well as VM, , R and T from the previous example we
have.

 The value of L is consistent with a nucleus containing particles of the order 102 of
approximately 0.3nm diameter.

 High values of , for example 80ergs/cm2, would result in physically impossible

values for since the super saturation would be approximately 150%.