Crystallization

References:
Unit Operations of Chemical Engineering, chapter 27
McCabe W.L., Smith J., & Harriot P. (2005)
McGraw-Hill
Coulson & Richardson's Chemical Engineering
Volume 2 - Particle Technology and Separation Processes, chapter 15
Richardson J.F., Harker J.H., Backhurst J.R. (2002)
Elsevier
 Program

Chemical and food plants, processes, and utilities

Extraction (liquid-liquid, solid-liquid)
Adsorption
Crystallization
Separation
Other batch processes for food/pharmaceutical
Hygienic cleaning
Refrigeration cycles
General approach to the design of unit
operations

Thermodynamics

Heat & Mass

Transfer

Design
Crystallization
Definition
Crystallization
Definition

Formation of solid particles within a

homogeneous phase
• Solids from vapor
• Solidification from liquid melt
• Crystallization from liquid solution
Definition
Definition

Separation and purification process to produce a wide

variety of materials in the fine chemical, food, and
pharmaceutical industries.
Definition

Separation and purification process to produce a wide

variety of materials in the fine chemical, food, and
pharmaceutical industries.
Definition

Mass is transferred from a liquid solution, whose

composition is generally mixed, to a pure solid crystal.
Definition

Mass is transferred from a liquid solution, whose

composition is generally mixed, to a pure solid crystal.
Definition

Soluble components are removed from solution by

making the solution supersaturated, and to crystallize
out excess solute in pure form.
Definition

Soluble components are removed from solution by

making the solution supersaturated, and to crystallize
out excess solute in pure form.
Definition
Definition

Equilibrium is established between the crystals and the

surrounding solution, the mother liquor.
Definition

Equilibrium is established between the crystals and the

surrounding solution, the mother liquor.
Definition

Equilibrium is established between the crystals and the

surrounding solution, the mother liquor.
Definition
Definition

The two-phase mixture of mother liquor and crystals of

all sizes is called magma.
Examples
Examples
Sucrose
(Sugar cane or beet)
Examples
Sucrose Other sugars
(Sugar cane or beet) (glucose, lactose)
Examples
Sucrose Other sugars Food additives
(Sugar cane or beet) (glucose, lactose) (salt)
Examples
Sucrose Other sugars Food additives
(Sugar cane or beet) (glucose, lactose) (salt)

Drugs
Examples
Sucrose Other sugars Food additives
(Sugar cane or beet) (glucose, lactose) (salt)

Drugs Foodstuff
(Chocolate)
Examples
Sucrose Other sugars Food additives
(Sugar cane or beet) (glucose, lactose) (salt)

Drugs Foodstuff Foodstuff

(Chocolate) (ice cream, margarine)
Examples
Crystallization
Definition

Objectives of industrial crystallization

• Good yields
• High purity
• Crystal size range
• Crystal appearance
Crystallization
Definition

Purity of product
• A well-formed crystal is nearly pure
• However it retains mother liquor on the
surface when collected
• When mother liquor of low purity is dried on
the product, contamination results
• Much of the retained liquor is separated by
filtration or centrifuging
Exercise

CuSO4·5H2O is obtained from a solution where CuSO4·H2O is

dissolved until supersaturation conditions. The solution
contains also 3.5 % of a soluble impurity.
The crystals, obtained in a crystallization process where
equilibrium between crystals and mother liquor is attained at
25 °C, when recovered from the crystallizer carry 10 % of their
dry weight as adhering mother liquor. The crystals are then
dried to zero free water (CuSO4·5H2O).
Verify if the percentage of impurity in the product respects the
product specification of < 0.6% wt.
The CuSO4·5H2O solubility at 25 °C is 40 g per 100 g of free H2O.
Driving force

Soluble components are removed from solution by

making the solution supersaturated, and to crystallize
out excess solute in pure form.
Driving force

Temperature Concentration

Salting out Chemical reaction

Soluble components are removed from solution by

making the solution supersaturated, and to crystallize
out excess solute in pure form.
Driving force

Temperature Concentration

Salting out Chemical reaction

Soluble components are removed from solution by

making the solution supersaturated, and to crystallize
out excess solute in pure form.
Driving force

Temperature Concentration

Salting out Chemical reaction

Soluble components are removed from solution by

making the solution supersaturated, and to crystallize
out excess solute in pure form.
Driving force

Temperature Concentration

Salting out Chemical reaction

Soluble components are removed from solution by

making the solution supersaturated, and to crystallize
out excess solute in pure form.
Driving force

Temperature Concentration

Salting out Chemical reaction

Soluble components are removed from solution by

making the solution supersaturated, and to crystallize
out excess solute in pure form.
Driving force

Temperature Concentration

Salting out (Precipitation)

Soluble components are removed from solution by

making the solution supersaturated, and to crystallize
out excess solute in pure form.
Crystal Size and Shape

Crystals are regular in shape.

Space lattices:
cubic, hexagonal, trigonal, tetragonal, orthorhombic,
monoclinic, and triclinic.
Crystal Size and Shape

Crystals are regular in shape.

Space lattices:
cubic, hexagonal, trigonal, tetragonal, orthorhombic,
monoclinic, and triclinic.
Crystal Size and Shape

Angle of repose Rate of dissolution

Invariant Crystal
Invariant Crystal
Crystal Size and Shape

Ratio of the total surface area of a crystal sp to the crystal

volume vp
𝑠𝑝 6
=
𝑣𝑝 Φ𝑠 𝐷𝑝
where s is the sphericity.
Crystal Size and Shape

Ratio of the total surface area of a crystal sp to the crystal

volume vp
𝑠𝑝 6
=
𝑣𝑝 Φ𝑠 𝐷𝑝
where s is the sphericity.

If the characteristic length L of a crystal is defined as s·Dp

6𝑣𝑝
𝐿 = Φ𝑠 𝐷𝑝 =
𝑠𝑝
For geometric solids:
L is close to the size determined by screening
Typical crystallization layout (pilot)
Typical crystallization layout (pilot)
Typical crystallization layout (pilot)
Equilibrium
Equilibrium

Once crystallization is concluded, equilibrium is reached

between the crystals of pure solute and the residual
mother liquor.
Equilibrium

The equilibrium relationship for bulk crystals is the

solubility curve
Solubility curve

water

1-component systems
Solubility curve

water

1-component systems
Solubility curve

polymorphic
substances

1-component systems
Solubility curve

polymorphic
substances

1-component systems
Solubility curve

polymorphic
substances

1-component systems
Solubility curve

polymorphic
substances

1-component systems
Solubility curve

polymorphic
substances

1-component systems
Solubility curve

polymorphic
substances

1-component systems
Solubility curve

Slow heating

polymorphic
substances

1-component systems
Solubility curve

Rapid heating

polymorphic
substances

1-component systems
Solubility curve

polymorphic
substances

1-component systems
Solubility curve

polymorphic
substances

1-component systems
Solubility curve

polymorphic
substances

1-component systems
Solubility curve

2-component systems
Solubility curve

2-component systems
Solubility curve

Effect of pressure is
usually negligible
Data can be shown on a
2-D T–conc plot

2-component systems
Solubility curve

2-component systems
Solubility curve

2-component systems
Solubility curve

2-component systems
Solubility curve

2-component systems
Solubility curve

2-component systems
Solubility curve

2-component systems
Solubility curve

2-component systems
Solubility curve

2-component systems
Solubility curve

2-component systems
Solubility curve

2-component systems
Solubility curve

2-component systems
Solubility curve

2-component systems
Solubility curve

2-component systems
Solubility curve

2-component systems
Solubility curve

2-component systems
Solubility curve

3-component systems
Solubility curve

3-component systems
Solubility curve

3-component systems
Solubility curve

3-component systems
Solubility curve

3-component systems
Solubility curve

3-component systems
Solubility curve

3-component systems
Solubility curve

3-component systems
Solubility curve

3-component systems
Solubility curve

3-component systems
Solubility curve

3-component systems
Solubility curve
Solubility curve
Exercise

A solution of MgSO4 containing 43 g of solid per 100 g of water

is cooled to 60 °F.
During cooling, 5% of the total water in the system evaporates.
How many kilograms of crystals are obtained per kilogram of
original mixture?
Solubility curve
Solubility curve
Solubility curve

In the food industry, the

solvent is generally water.
• Solubility is a function of
temperature.
• Pressure has very little
effect on solubility.
Solubility curve
Phenomenology of crystallization
Phenomenology of crystallization
Phenomenology of crystallization

Crystals are grown from solutions with concentrations

higher than the saturation level in the solubility curves.
Phenomenology of crystallization
Phenomenology of crystallization

Spontaneous
nucleation
Phenomenology of crystallization

Slow
crystallization
Phenomenology of crystallization

Crystal
dissolution
Phenomenology of crystallization

In many industrial
crystallization
processes, the crystals
and mother liquor are
in contact long enough
to reach equilibrium
Phenomenology of crystallization
Phenomenology of crystallization

The driving force for crystals grow

The concentration excess (supersaturation) of the
solution above the equilibrium (saturation) level.
Phenomenology of crystallization

The resistances for crystals grow

• The mass transfer within the solution
• The energy needed at the crystal surface for
incoming molecules to orient themselves to the
crystal lattice.
Heat of crystallization

During the crystallization process, heat must be

removed
• Sensible heat to cool the solution
• Heat of crystallization
• Heat of vaporization
(in case evaporation is used to achieve the
supersaturation)
Heat of crystallization

During the crystallization process, heat must be

removed
• Sensible heat to cool the solution
• Heat of crystallization
• Heat of vaporization
(in case evaporation is used to achieve the
supersaturation)
Heat of crystallization

Heat of crystallization =
Heat of solution + Heat of dilution
Heat of crystallization

Heat of crystallization =
Heat of solution + Heat of dilution
Heat of crystallization

Heat of crystallization ≈ Heat of solution

Heat of crystallization

Heat of crystallization ≈ Heat of solution

For most food materials > 0

Heat of crystallization
Heat of crystallization
Heat of crystallization
Crystallization process

Once nucleii are formed, either spontaneously or by

seeding, the crystals will continue to grow as long as
supersaturation persists.
Crystallization process

Temperature
Degree of
supersaturation

Interfacial tension
between the solute
and the solvent
Crystallization process

Consideration #1
Crystallization process

Consideration #1
If supersaturation low, nucleus formation is not
encouraged but the available nucleii will continue to
grow and large crystals will result.
Crystallization process

Consideration #2
Crystallization process

Consideration #2
If supersaturation is high, there may be further
nucleation and so the growth of existing crystals
will not be so great.
Crystallization process

Therefore:
Crystallization process

Therefore:
Slow cooling at low level of supersaturation
 Large crystals
Crystallization process

Therefore:
Slow cooling at low level of supersaturation
 Large crystals
Fast cooling  Small crystals
Crystallization process

Consideration #3
Crystallization process

Consideration #3
Nucleation rate is also increased by agitation
Crystallization process
Crystallization process

State of supersaturation
Crystallization process

State of supersaturation
Labile: spontaneous (primary) nucleation occurs
Crystallization process

State of supersaturation
Labile: spontaneous (primary) nucleation occurs
Metastable: No spontaneous nucleation
Crystallization process

The width of the metastable zone can be expressed as a

temperature difference, ΔT related to the corresponding
concentration difference, Δc by the point slope of the
solubility curve, dc∗/dT
Crystallization process

*
dc
c  T
dT
Crystallization process
Crystallization process

Rate of generation
of supersaturation

Presence of crystals Degree of

or impurities agitation
Crystallization process
Crystallization process
Crystallization process
Crystallization process
Crystallization process
Crystallization process
Crystallization process
Crystallization process

Nucleation
Temperature
Growth
(°C) No crystal-solid Crystal-solid
contact contact

Good growth
Ts – 1 Contact
No nucleation
nucleation
Ts – 4 Veiled growth

Ts – 8 Splintering &
Splintering &
Dendritic, attrition
attrition
spikewise, of colliding
from splinters
brooming crystals
Ts – 16 growth Heterogeneous
Nucleation
Crystallization process

Nucleation
Temperature
Growth
(°C) No crystal-solid Crystal-solid
contact contact

Good growth
Ts – 1 Contact
No nucleation
nucleation
Ts – 4 Veiled growth

Ts – 8 Splintering &
Splintering &
Dendritic, attrition
attrition
spikewise, of colliding
from splinters
brooming crystals
Ts – 16 growth Heterogeneous
Nucleation
Crystallization process

Nucleation
Temperature
Growth
(°C) No crystal-solid Crystal-solid
contact contact

Good growth
Ts – 1 Contact
No nucleation
nucleation
Ts – 4 Veiled growth

Ts – 8 Splintering &
Splintering &
Dendritic, attrition
attrition
spikewise, of colliding
from splinters
brooming crystals
Ts – 16 growth Heterogeneous
Nucleation
Crystallization process

Nucleation
Temperature
Growth
(°C) No crystal-solid Crystal-solid
contact contact

Good growth
Ts – 1 Contact
No nucleation
nucleation
Ts – 4 Veiled growth

Ts – 8 Splintering &
Splintering &
Dendritic, attrition
attrition
spikewise, of colliding
from splinters
brooming crystals
Ts – 16 growth Heterogeneous
Nucleation
Crystallization process

Nucleation
Temperature
Growth
(°C) No crystal-solid Crystal-solid
contact contact

Good growth
Ts – 1 Contact
No nucleation
nucleation
Ts – 4 Veiled growth

Ts – 8 Splintering &
Splintering &
Dendritic, attrition
attrition
spikewise, of colliding
from splinters
brooming crystals
Ts – 16 growth Heterogeneous
Nucleation
Crystallization process

Nucleation
Temperature
Growth
(°C) No crystal-solid Crystal-solid
contact contact

Good growth
Ts – 1 Contact
No nucleation
nucleation
Ts – 4 Veiled growth

Ts – 8 Splintering &
Splintering &
Dendritic, attrition
attrition
spikewise, of colliding
from splinters
brooming crystals
Ts – 16 growth Heterogeneous
Nucleation
Crystallization process

Nucleation
Temperature
Growth
(°C) No crystal-solid Crystal-solid
contact contact

Good growth
Ts – 1 Contact
No nucleation
nucleation
Ts – 4 Veiled growth

Ts – 8 Splintering &
Splintering &
Dendritic, attrition
attrition
spikewise, of colliding
from splinters
brooming crystals
Ts – 16 growth Heterogeneous
Nucleation
Crystal nucleation
Crystal nucleation

Nucleation is the creation of crystalline bodies within a

supersaturated fluid.
Crystal nucleation

Nucleation is the creation of crystalline bodies within a

supersaturated fluid.
Nuclei may be generated by many different mechanisms.
Crystal nucleation

Nucleation is the creation of crystalline bodies within a

supersaturated fluid.
Nuclei may be generated by many different mechanisms.

• Primary nucleation – in the absence of crystals

Crystal nucleation

Nucleation is the creation of crystalline bodies within a

supersaturated fluid.
Nuclei may be generated by many different mechanisms.

• Primary nucleation – in the absence of crystals

• Secondary nucleation – in the presence of crystals.
Crystal nucleation

Nucleation is the creation of crystalline bodies within a

supersaturated fluid.
Nuclei may be generated by many different mechanisms.

• Primary nucleation – in the absence of crystals

• Secondary nucleation – in the presence of crystals.
• Spurious nucleation – attrition/initial breeding/needle
breeding
Primary nucleation
Primary nucleation

In general homogeneous nucleation.

Primary nucleation

In general homogeneous nucleation.

Primary nucleation

In general homogeneous nucleation.

Cluster Embryo Nucleus

Primary nucleation

In general homogeneous nucleation.

Cluster Embryo Nucleus

Unstable equilibrium
Crystal size and solubility

The solubility of a substance is related to its particle size

Crystal size and solubility

4VM 
ln  
ni RTL
α = C/Cs = (Cs+ΔC)/Cs = 1+ΔC/Cs = 1+S
α: ratio of concentrations of supersaturated and saturated
solutions
VM: molar volume of crystals,
σ: interfacial tension of the crystallisation surface in contact
with its solution
ni: moles of ions formed from one mole of electrolyte.
Crystal size and solubility

cr 2 M
ln * 
c ni RT s r

cr: solubility of particles of radius r,

ρs: density of the solid,
M: relative molecular mass of the solute in solution,
σ: interfacial tension of the crystallisation surface in contact
with its solution
ni: moles of ions formed from one mole of electrolyte.
Crystal size and solubility

cr 2 M
ln * 
Ostwald ripening c ni RT s r
• A small crystal can be in equilibrium with a
supersaturated solution
cr: •solubility
If largeofcrystals
particles are
of radius r, in the solution, the
present
ρs: density of the
smaller solid, will dissolve and the larger one
crystal
M: relative molecular mass of the solute in solution,
will grow
σ: interfacial tension of the crystallisation surface in contact
with its solution
ni: moles of ions formed from one mole of electrolyte.
Rate of homogeneous nucleation
Rate of homogeneous nucleation

4 3
G  4 r   2
r Gv
3

ΔG: overall excess free energy associated with the formation

of the crystalline body
σ: interfacial tension between the crystal and its surrounding
supersaturated fluid
ΔGv: free energy change per unit volume associated with the
phase change
Rate of homogeneous nucleation

4 3
G  4 r  
2
r Gv
3
Rate of homogeneous nucleation

4 3
G  4 r   2
r Gv
3
Surface
contribution >0
Rate of homogeneous nucleation

4 3
G  4 r   2
r Gv
3
Surface Volume
contribution >0 contribution <0
Rate of homogeneous nucleation

4 3
G  4 r   2
r Gv
3
Surface Volume
contribution >0 contribution <0
Rate of homogeneous nucleation

4 3
G  4 r   2
r Gv
3
Surface Volume
contribution >0 contribution <0

Any crystal smaller than the critical nucleus size rc is

unstable and tends to dissolve.
Rate of homogeneous nucleation

4 3
G  4 r   2
r Gv
3
Surface Volume
contribution >0 contribution <0

Any crystal smaller than the critical nucleus size rc is

unstable and tends to dissolve.
Any crystal larger than rc is stable and tends to grow.
Rate of homogeneous nucleation

4VM  4 3
ln   G  4 r  
2
r Gv
ni RTL 3
Rate of homogeneous nucleation

4VM  4 3
ln   G  4 r   2
r Gv
ni RTL 3

 16  VM N a 
3 2
B  C exp  
0

2 
 3 ni RT  ln   
2 3

C: frequency factor,
Na: Avogadro constant, 6.022·1023 molecules/g mol,
R: gas constant, 8,3143·107 ergs/g mol K,
Rate of homogeneous nucleation

4VM  4 3
ln   G  4 r   2
r Gv
ni RTL 3

 16  VM N a 
3 2
B  C exp  
0

2 
 3 ni RT  ln   
2 3

C: frequency factor,
Na: Avogadro constant, 6.022·1023 molecules/g mol,
R: gas constant, 8,3143·107 ergs/g mol K,
Rate of homogeneous nucleation

4VM  4 3
ln   G  4 r   2
r Gv
ni RTL 3

 16  VM N a 
3 2
B  C exp  
0

2 
25 3
≈10 nuclei/cm s  3 ni
2
 RT 3
ln   

C: frequency factor,
Na: Avogadro constant, 6.022·1023 molecules/g mol,
R: gas constant, 8,3143·107 ergs/g mol K,
Rate of homogeneous nucleation

4VM  4 3
ln   G  4 r   2
r Gv
ni RTL 3

 16  VM N a 
3 2
B  C exp  
0

2 
 3 ni RT  ln   
2 3

C: frequency factor,
Na: Avogadro constant, 6.022·1023 molecules/g mol,
R: gas constant, 8,3143·107 ergs/g mol K,
Rate of homogeneous nucleation

4VM  4 3
ln   G  4 r   2
r Gv
ni RTL 3

 16  VM N a 
3 2
B  C exp  
0

2 
 3 ni RT  ln   
2 3

C: frequency factor,
Na: Avogadro constant, 6.022·1023 molecules/g mol,
R: gas constant, 8,3143·107 ergs/g mol K,
Rate of homogeneous nucleation

4VM  4 3
ln   G  4 r   2
r Gv
ni RTL 3

 16  VM N a 
3 2
B  C exp  
0

2 
 3 ni RT  ln   
2 3

≈100 ergs/cm2
C: frequency factor,
Na: Avogadro constant, 6.022·1023 molecules/g mol,
R: gas constant, 8,3143·107 ergs/g mol K,
Rate of homogeneous nucleation

4VM  4 3
ln   G  4 r   2
r Gv
ni RTL 3

 16  VM N a 
3 2
B  C exp  
0

2 
 3 ni RT  ln   
2 3

≈100 ergs/cm2
C: frequency factor,
Na: Avogadro constant, 6.022·1023 molecules/g mol,
R: gas constant, 8,3143·107 ergs/g mol K,
Primary nucleation

In general homogeneous nucleation.

Primary nucleation

In general homogeneous nucleation.

Heterogeneous if initiated by foreign substances.

Primary nucleation

In general homogeneous nucleation.

Heterogeneous if initiated by foreign substances.

In industrial crystallization, most primary nucleation is

heterogeneous, induced by foreign solid particles present
in working solutions.
Rate of heterogeneous nucleation

 16  a VM N a 
3 2
B  10 exp 
0 25
3 2 

 3 ni RT  S 
2

σa: apparent interfacial tension,

s: α-1, based on the approximation ln α = α-1
Rate of heterogeneous nucleation

 16  a VM N a 
3 2
B  10 exp 
0 25
3 2 

 3 ni RT  S 
2

≈2-3 ergs/cm2

σa: apparent interfacial tension,

S: α-1, based on the approximation ln α = α-1
Rate of heterogeneous nucleation

 16  3
V
2
Na 
B  10 exp 
0 25 a M
3 2 

 3 ni RT  S 
2
Exercise

Assuming the rate of heterogeneous nucleation of KCl is

consistent with an apparent interfacial tension of 2.5
ergs/cm2, determine the nucleation rate as a function of
S at a temperature of 300 K.
Exercise

Assuming the rate of heterogeneous nucleation of KCl is

consistent with an apparent interfacial tension of 2.5
ergs/cm2, determine the nucleation rate as a function of
S at a temperature of 300 K.

What would be the size of a nucleus in equilibrium with a

supersaturation of 0.009?
Rate of primary nucleation [industrial]
Rate of primary nucleation [industrial]

B  k N c 
n

kn: nucleation constant

n: empirical factor
Rate of secondary nucleation [industrial]
Rate of secondary nucleation [industrial]
Formation of nuclei attributable to the influence of
existing macroscopic crystals in the magma
Rate of secondary nucleation [industrial]
Formation of nuclei attributable to the influence of
existing macroscopic crystals in the magma

• Fluid-shear nucleation
Rate of secondary nucleation [industrial]
Formation of nuclei attributable to the influence of
existing macroscopic crystals in the magma

• Fluid-shear nucleation
• Contact secondary nucleation between the existing
crystals
Rate of secondary nucleation [industrial]
Formation of nuclei attributable to the influence of
existing macroscopic crystals in the magma

• Fluid-shear nucleation
• Contact secondary nucleation between the existing
crystals
• Contact secondary nucleation between crystals and the
internal parts of the crystallizer
Rate of secondary nucleation [industrial]
Formation of nuclei attributable to the influence of
existing macroscopic crystals in the magma

• Fluid-shear nucleation
• Contact secondary nucleation between the existing
crystals
• Contact secondary nucleation between crystals and the
internal parts of the crystallizer
• Contact secondary nucleation between crystals and the
mechanical agitator
Rate of secondary nucleation [industrial]
Formation of nuclei attributable to the influence of
existing macroscopic crystals in the magma
Rate of secondary nucleation [industrial]
Formation of nuclei attributable to the influence of
existing macroscopic crystals in the magma

B  kb  N c 
j l b
m

B: rate of secondary nucleation or birthrate,

kb: birthrate constant,
ρm: slurry concentration or magma density,
N: a term accounting for the intensity of agitation in the
system (i.e. rotational speed of an impeller).
The exponents j, l, and b vary according to the operating
conditions.
Rate of crystal growth
Rate of crystal growth
Once nucleii have been formed, the limiting step is the rate
of crystals growth
Rate of crystal growth
Once nucleii have been formed, the limiting step is the rate of
crystals growth

• Diffusion of the solute through the solvent to the

surface of the crystal
Rate of crystal growth
Once nucleii have been formed, the limiting step is the rate of
crystals growth

• Diffusion of the solute through the solvent to the

surface of the crystal

 K d Ac  ci 
dw
dt
Rate of crystal growth
Once nucleii have been formed, the limiting step is the rate of
crystals growth

• Diffusion of the solute through the solvent to the

surface of the crystal

 K d Ac  ci 
dw
dt
• Rate of reaction at the crystal face, when solute
molecules rearrange themselves into the crystal lattice
Rate of crystal growth
Once nucleii have been formed, the limiting step is the rate of
crystals growth

• Diffusion of the solute through the solvent to the

surface of the crystal

 K d Ac  ci 
dw
dt
• Rate of reaction at the crystal face, when solute
molecules rearrange themselves into the crystal lattice

 k s Aci  cs 
dw
dt
Rate of crystal growth
Once nucleii have been formed, the limiting step is the rate of
crystals growth

 K d Ac  ci   k s Aci  cs 
dw dw
dt dt

dw: increase in weight of crystals in time dt,

A: surface area of the crystals,
c: solute concentration of the bulk solution,
ci: solute concentration at the crystal/solution interface,
cs: concentration of the saturated solution,
Kd: mass transfer coefficient to the interface
ks: rate constant for the surface reaction
Rate of crystal growth
Once nucleii have been formed, the limiting step is the rate of
crystals growth

 K d Ac  ci   k s Aci  cs 
dw dw
dt dt

dw: increase in weight of crystals in time dt,

A: surface area of the crystals,
c: solute concentration of the bulk solution,
ci: solute concentration at the crystal/solution interface,
cs: concentration of the saturated solution,
Kd: mass transfer coefficient to the interface
ks: rate constant for the surface reaction
Rate of crystal growth
Once nucleii have been formed, the limiting step is the rate of
crystals growth

 K d Ac  ci   k s Aci  cs 
dw dw
dt dt

 KAc  cs 
dw
dt
Rate of crystal growth
Once nucleii have been formed, the limiting step is the rate of
crystals growth

 K d Ac  ci   k s Aci  cs 
dw dw
dt dt

 KAc  cs 
dw
dt
1
 1 1
K    
 K d ks 
Rate of crystal growth
Once nucleii have been formed, the limiting step is the rate of
crystals growth

 K d Ac  ci   k s Aci  cs 
dw dw
dt dt

dL K c  cs 

dt s
dL: increase in growth of the side of crystals in time dt,
s: density of the crystals
Rate of crystal growth
Rate of crystal growth
Rate of crystal growth
Rate of crystal growth

At low temperatures:
Diffusion has relatively little effect on the growth rate.
Rate of crystal growth

At low temperatures:
Diffusion has relatively little effect on the growth rate.

At higher temperatures:
Diffusion becomes much more important
Rate of crystal growth

At low temperatures:
Diffusion has relatively little effect on the growth rate.

At higher temperatures:
Diffusion becomes much more important
Diffusion energies ≈ growth energies
Rate of crystal growth

At low temperatures:
Diffusion has relatively little effect on the growth rate.

At higher temperatures:
Diffusion becomes much more important
Diffusion energies ≈ growth energies

Impurities in the solution retard crystal growth

Rate of crystal growth

The rate of crystal growth may be expressed as:

Rate of crystal growth

The rate of crystal growth may be expressed as:

• overall mass deposition rate, RG [kg/m2 s]
Rate of crystal growth

The rate of crystal growth may be expressed as:

• overall mass deposition rate, RG [kg/m2 s]
• overall linear growth rate, Gd = dL/dt [m/s]
Rate of crystal growth

The rate of crystal growth may be expressed as:

• overall mass deposition rate, RG [kg/m2 s]
• overall linear growth rate, Gd = dL/dt [m/s]
• mean linear velocity, u′ = dr/dt [m/s]
Rate of crystal growth

The rate of crystal growth may be expressed as:

• overall mass deposition rate, RG [kg/m2 s]
• overall linear growth rate, Gd = dL/dt [m/s]
• mean linear velocity, u′ = dr/dt [m/s]

dL
3 
1 dm dt 6  dr 6  u '
RG  K G c 
s
  
A dt   dt 
Rate of crystal growth

The rate of crystal growth may be expressed as:

• overall mass deposition rate, RG [kg/m2 s]
• overall linear growth rate, Gd = dL/dt [m/s]
• mean linear velocity, u′ = dr/dt [m/s]

dL
3 
1 dm dt 6  dr 6  u '
RG  K G c 
s
  
A dt   dt 

ρ: density of the crystal,

φ and ψ: volume and surface shape factors related to particle
mass m and surface area A
Rate of crystal growth

The rate of crystal growth may be expressed as:

• overall mass deposition rate, RG [kg/m2 s]
• overall linear growth rate, Gd = dL/dt [m/s]
• mean linear velocity, u′ = dr/dt [m/s]

dL
3 
1 dm dt 6  dr 6  u '
RG  K G c 
s
  
A dt   dt 

m   L A   L2
 Rate of crystal growth

Mean linear growth

velocity u′ (= 0.5 Gd )
for crystals 0.5–1 mm
growing in the presence
of other crystals
Crystallization equipment
Crystallization equipment
Crystallization equipment

1.
Supersaturated
solution
Crystallization equipment

1.
Supersaturated
solution
Crystallization equipment

1.
Supersaturated
solution

2.
Contact of
crystals with
supersaturated
liquid
Crystallization equipment

1.
Supersaturated
solution

2.
Contact of
crystals with
supersaturated
liquid
• Circulating-liquid
method
• Circulating-magma
method
Crystallization equipment

Circulating-liquid method
Crystallization equipment

Circulating-magma method
Crystallization equipment

1.
Supersaturated
solution

2.
Contact of
crystals with
supersaturated
liquid
Crystallization equipment

1.
Supersaturated
solution

2.
Contact of
crystals with
supersaturated
liquid
Crystallization equipment

1.
Supersaturated
solution

2.
Contact of
crystals with
3.
supersaturated
Crystal
liquid
separation
Crystallization equipment

1.
Supersaturated
solution

2.
Contact of
crystals with
3.
supersaturated
Crystal
liquid
separation • Size-classification devices
• Thoroughly mixed solution
• Devices to segregate and remove
fine particles
Crystallization equipment

1.
Supersaturated
solution

2.
Contact of
crystals with
3.
supersaturated
Crystal
liquid
separation
Crystallization equipment

1.
Supersaturated 4.
solution Agitation

2.
Contact of
crystals with
3.
supersaturated
Crystal
liquid
separation
Crystallization equipment

1.
Supersaturated 4.
solution Agitation
• To improve growth rate
• To prevent segregation
• To keep crystals in suspension 2.
Contact of
crystals with
3.
supersaturated
Crystal
liquid
separation
Cooling crystallizers
Cooling crystallizers
Cooling crystallizers
Cooling crystallizers
Cooling crystallizers
Cooling crystallizers
Cooling crystallizers
Cooling crystallizers

Example:
The cylindrical, scraped surface heat exchanger, used for
plasticizing margarine and cooking fat, and for
crystallizing ice cream.
Cooling crystallizers

Example:
The cylindrical, scraped surface heat exchanger, used for
plasticizing margarine and cooking fat, and for
crystallizing ice cream.
Double-pipe heat exchanger fitted with an internal scraper.
Cooling crystallizers

Example:
The cylindrical, scraped surface heat exchanger, used for
plasticizing margarine and cooking fat, and for
crystallizing ice cream.
Double-pipe heat exchanger fitted with an internal scraper.
Cooling crystallizers

Example:
The cylindrical, scraped surface heat exchanger, used for
plasticizing margarine and cooking fat, and for
crystallizing ice cream.
Double-pipe heat exchanger fitted with an internal scraper.
Cooling crystallizers

Example:
The cylindrical, scraped surface heat exchanger, used for
plasticizing margarine and cooking fat, and for
crystallizing ice cream.
Double-pipe heat exchanger fitted with an internal scraper.
Cooling crystallizers

Example:
The cylindrical, scraped surface heat exchanger, used for
plasticizing margarine and cooking fat, and for
crystallizing ice cream.
Double-pipe heat exchanger fitted with an internal scraper.
Cooling crystallizers

Margarine
Cooling crystallizers

Ice cream
Exercise

A solution containing 23 % wt of sodium phosphate is

cooled from 313 to 298 K in a 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 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 K, what length of crystallizer is required?
Cooling crystallizers
Cooling crystallizers

Krystal crystallizer
Cooling crystallizers

Krystal crystallizer
Evaporative crystallizers
Evaporative crystallizers
Common in the sugar and salt industries.
They are generally of the Calandria type.
Evaporative crystallizers
Common in the sugar and salt industries.
They are generally of the Calandria type.
Evaporative crystallizers
Common in the sugar and salt industries.
They are generally of the Calandria type.
Evaporative crystallizers
Common in the sugar and salt industries.
They are generally of the Calandria type.
Evaporative crystallizers
Common in the sugar and salt industries.
They are generally of the Calandria type.
Evaporative crystallizers
Common in the sugar and salt industries.
They are generally of the Calandria type.
Evaporative crystallizers
Common in the sugar and salt industries.
They are generally of the Calandria type.
Evaporative crystallizers

Multiple-effect evaporator-crystallizers
Sugar refining
Evaporative crystallizers

Multiple-effect evaporator-crystallizers
Sugar refining

Usually operated under reduced pressure

Evaporative crystallizers

Multiple-effect evaporator-crystallizers
Sugar refining

Usually operated under reduced pressure to:

• aid solvent removal,
Evaporative crystallizers

Multiple-effect evaporator-crystallizers
Sugar refining

Usually operated under reduced pressure to:

• aid solvent removal,
• minimize heat consumption,
Evaporative crystallizers

Multiple-effect evaporator-crystallizers
Sugar refining

Usually operated under reduced pressure to:

• aid solvent removal,
• minimize heat consumption,
• decrease the operating temperature of the solution.
Evaporative crystallizers

Multiple-effect evaporator-crystallizers
Sugar refining

Usually operated under reduced pressure to:

• aid solvent removal,
• minimize heat consumption,
• decrease the operating temperature of the solution.
 Reduced-pressure evaporating crystallizers
Stage-equilibrium crystallization

When the first crystals have been separated, the

temperature and concentration of mother liquor can be
changed to establish a new equilibrium and a new
harvest of crystals.

The limit to successive crystallizations is the build up of

impurities in the mother liquor, which makes both
crystallization and crystal separation slow and difficult.

This is also the reason why multiple crystallizations are

used, with the purest and best crystals coming from the
early stages.
Stage-equilibrium crystallization

Example: manufacture of sugar

• The concentration of the solution is increased and then
seed crystals are added.
• The temperature is controlled until the crystal nucleii
added have grown to the desired size, then the crystals
are separated from the residual liquor by centrifuging.
• The liquor is returned to a crystallizing evaporator,
concentrated again to produce supersaturation,
seeded, for a further crop of crystals of desired size.
• The final mother liquor [molasses] can be held
indefinitely without producing any crystallization of
sugar.
Stage-equilibrium crystallization
Exercise

Multiple stage sugar crystallization by evaporation

The conditions in a series of sugar evaporators are:
• I evaporator: Tliquor = 85°C, inlet concentration = 65%, weight
of entering liquor 5000 kg/h, concentration at seeding = 82%.
• II evaporator: Tliquor = 73°C, concentration at seeding = 84%.
• III evaporator: Tliquor = 60°C, concentration at seeding = 86%.
• IV evaporator: Tliquor = 51°C, concentration at seeding 89%.

 Calculate the yield of sugar in each evaporator and the

concentration of sucrose in the mother liquor leaving the
final evaporator.
 Calculate the amount of steam generated for each stage,
and assess the possibility to use it for driving the
evaporation process in the following stage.
Exercise
Vacuum crystallizers
Vacuum crystallizers

Control of crystal size through careful manipulation of

vacuum and feed.
Vacuum crystallizers

Batch crystallization
• The evaporator first concentrates the solute solution
• When seeding commences, the vacuum is increased
• This increase causes further evaporation of water, which
cools the solution and the crystals grow
• Fresh saturated solution is added and evaporation
continued until the crystals reach the desired size.
Vacuum crystallizers
Vacuum crystallizers
Supersaturation is achieved
by simultaneous evaporation
and adiabatic cooling of the
feedstock.
Vacuum crystallizers
Supersaturation is achieved
by simultaneous evaporation
and adiabatic cooling of the
feedstock.
Vacuum crystallizers
Supersaturation is achieved
by simultaneous evaporation
and adiabatic cooling of the
feedstock.
Vacuum crystallizers
Vacuum crystallizers
Under the low
pressure existing in
the unit, the effect of
static head on the
boiling point is
important.
Vacuum crystallizers
Under the low
pressure existing in
the unit, the effect of
static head on the
boiling point is
important.
Admission of the feed
at a point where it
does not flash enables
a better control of
nucleation.
Vacuum crystallizers
Under the low
pressure existing in
the unit, the effect of
static head on the
boiling point is
important.
Admission of the feed
at a point where it
does not flash enables
a better control of
nucleation.
Vacuum crystallizers
Under the low
pressure existing in
the unit, the effect of
static head on the
boiling point is
important.
Admission of the feed
at a point where it
does not flash enables
a better control of
nucleation.
Forced-circulation crystallizers
Forced-circulation crystallizers
Swenson crystallizer
Forced-circulation crystallizers
Swenson crystallizer
Reduced
pressure
Forced-circulation crystallizers
Swenson crystallizer
Reduced
pressure
Forced-circulation crystallizers
Swenson crystallizer
Reduced
pressure
Forced-circulation crystallizers
Swenson crystallizer
Reduced
pressure
Fluidized-bed crystallizers
Fluidized-bed crystallizers

Oslo crystallizer
Fluidized-bed crystallizers

Oslo crystallizer
Fluidized-bed crystallizers

Oslo crystallizer
Fluidized-bed crystallizers

Oslo crystallizer
Fluidized-bed crystallizers

Oslo crystallizer
Fluidized-bed crystallizers

Oslo crystallizer
Draught-tube agitated vacuum crystallizers
Draught-tube agitated vacuum crystallizers

Swenson draught-tube-baffled (DTB) vacuum unit

Draught-tube agitated vacuum crystallizers

Swenson draught-tube-baffled (DTB) vacuum unit

Draught-tube agitated vacuum crystallizers

Swenson draught-tube-baffled (DTB) vacuum unit

Draught-tube agitated vacuum crystallizers

TS - 1

Swenson draught-tube-baffled (DTB) vacuum unit

Draught-tube agitated vacuum crystallizers

TS - 1

Swenson draught-tube-baffled (DTB) vacuum unit

Draught-tube agitated vacuum crystallizers

TS - 1

Swenson draught-tube-baffled (DTB) vacuum unit

Draught-tube agitated vacuum crystallizers

Standard-Messo turbulence vacuum unit

Draught-tube agitated vacuum crystallizers

Standard-Messo turbulence vacuum unit

Draught-tube agitated vacuum crystallizers

Standard-Messo turbulence vacuum unit

Draught-tube agitated vacuum crystallizers

Standard-Messo turbulence vacuum unit

Draught-tube agitated vacuum crystallizers

Standard-Messo turbulence vacuum unit

Draught-tube agitated vacuum crystallizers

Standard-Messo turbulence vacuum unit

Controlled crystallization
Controlled crystallization
Rapid cooling−unseeded
Controlled crystallization
Slow cooling−seeded
Crystallization from melts
A melt is a liquid or a liquid mixture at a temperature near
its freezing point
Melt crystallization is the process of separating the
components of a liquid mixture by cooling until
crystallized solid is deposited from the liquid phase.
Where the crystallization process is used to separate, or
partially separate, the components, the composition of the
crystallized solid will differ from that of the liquid mixture
from which it is deposited.
• Gradual deposition of a crystalline layer on a chilled
surface in a static or laminar flowing melt,
• Fast generation of discrete crystals in the body of an
agitated vessel.
Crystallizer design – Population balance
Crystallizer design – Population balance

Growth and nucleation interact in a crystallizer:

Both contribute to the final crystal size distribution (CSD)
of the product.
Crystallizer design – Population balance

Growth and nucleation interact in a crystallizer:

Both contribute to the final crystal size distribution (CSD)
of the product.
Crystallizer design – Population balance

MSMPR idealized case

Mixed-Suspension, Mixed-Product Removal crystallizer
• Steady state operation
• At all times, mixed-suspension of magma, without
product classification
• At all times, supersaturation exists throughout the
magma
• The ΔL law of crystal growth applies
• No size-classified withdrawal system is used
• No crystals in the feed
• The mother liquor in the product magma is saturated
• No crystal breakage into finite particles
Crystallizer design – Population balance

MSMPR idealized case

Mixed-Suspension, Mixed-Product Removal crystallizer
• Steady state operation
• At all times, mixed-suspension of magma, without
product classification
• At all times, supersaturation exists throughout the
magma
• The ΔL law of crystal growth applies
• No size-classified withdrawal system is used
Lfeed
• No crystals in the  Gd t
• The mother liquor in the product magma is saturated
• No crystal breakage into finite particles
Crystallizer design – Population balance
Crystallizer design – Population balance

Population density
Assume that a distribution function of the cumulative
number of crystals in the magma (number per unit
volume of mother liquor) is a function of L, the crystal size.
Crystallizer design – Population balance

Population density
Assume that a distribution function of the cumulative
number of crystals in the magma (number per unit
volume of mother liquor) is a function of L, the crystal size.
N is the number of crystals of size L and smaller in the
magma.
At L=0, N=0;
At L=LT (the size of largest crystal), N=NT (the total number
of crystals)
Crystallizer design – Population balance

Population density
Assume that a distribution function of the cumulative
number of crystals in the magma (number per unit
volume of mother liquor) is a function of L, the crystal size.
N is the number of crystals of size L and smaller in the
magma.
At L=0, N=0;
At L=LT (the size of largest crystal), N=NT (the total number
of crystals)
n' is the population density (number of crystals per unit
size per unit volume of the system)
Crystallizer design – Population balance

d  N V  1 dN
n'  
dL V dL

V by assumption is constant.
The function n'=f(L) has a maximum value n° where L=0,
and is zero where L=LT.
Crystallizer design – Population balance

d  N V  1 dN
n'  
dL V dL
Crystallizer design – Population balance

d  N V  1 dN
n'  
dL V dL
Crystallizer design – Population balance

Honey
Crystallizer design – Population balance

Ice cream
Crystallizer design – Population balance
Crystallizer design – Population balance

t
Crystallizer design – Population balance

Need of a relation between population density n' and L

Crystallizer design – Population balance

In the MSMPR model, each crystal of length L has the

same age tm

L  Gd tm
Crystallizer design – Population balance

Consider the n'dL crystals between sizes L and L+dL.

Of the n'dL crystals per unit volume of liquid, Δn'dL are

withdrawn as product during time Δt.
Crystallizer design – Population balance

Consider the n'dL crystals between sizes L and L+dL.

Of the n'dL crystals per unit volume of liquid, Δn'dL are

withdrawn as product during time Δt.
If Q is the volumetric flow rate of liquid and Vc is the
total volume of liquid in the crystallizer:

n' dL n' Qt

  
n' dL n' Vc
Crystallizer design – Population balance

The time interval Δt is also a period in the live of each

crystal, which grows:

L  Gd t
Crystallizer design – Population balance

n' Qt
L  Gd t  
n' Vc

n' Q n'
 
L Gd Vc
Crystallizer design – Population balance

n' Qt
L  Gd t  
n' Vc

n' Q n'
 
L Gd Vc

dn' Q n'
 
dL Gd Vc
Crystallizer design – Population balance

Vc

Q

dn' 1
  dL
n' Gd 
Crystallizer design – Population balance

Vc

Q

dn' 1
  dL
n' Gd 
Integration

n dn' 1 L
n0 n'   Gd  
0
dL
Crystallizer design – Population balance

Vc

Q

dn' 1
  dL
n' Gd 
Integration

n L
ln 
n' Gd 
Crystallizer design – Population balance

Vc

Q

dn' 1
  dL
n' Gd 
Integration

n° is the population
n L
density at L=0: ln 
n° = nuclei n' Gd 
Crystallizer design – Population balance

The quantity L/Gd·τ is the dimentionless length z

z
n'  ne
Crystallizer design – Population balance

In crystallization design, using the population balance

and the MSMPR mode, 3 parameters must be evaluated:
• The retention time τ
• The growth rate Gd
• The nucleus density n°
Crystallizer design – Population balance

In crystallization design, using the population balance

and the MSMPR mode, 3 parameters must be evaluated:
• The retention time τ
• The growth rate Gd
• The nucleus density n°
Crystallizer design – Population balance

In crystallization design, using the population balance

and the MSMPR mode, 3 parameters must be evaluated:
• The retention time τ Designer
• The growth rate Gd
• The nucleus density n°
Crystallizer design – Population balance

In crystallization design, using the population balance

and the MSMPR mode, 3 parameters must be evaluated:
• The retention time τ Designer
• The growth rate Gd
• The nucleus density n°
Crystallizer design – Population balance

In crystallization design, using the population balance

and the MSMPR mode, 3 parameters must be evaluated:
• The retention time τ Designer
• The growth rate Gd
Plant engineering
• The nucleus density n°
Action of the impeller
Circulating pump
Nucleating and growth
characteristics
Crystallizer design – Population balance

z
n'  ne
Crystallizer design – Population balance

z
n'  ne
Moment equations:

z

j
n' z dz
j  0


j
n' z dz
0
Crystallizer design – Population balance

z
n'  ne
Moment equations:

0  1  e z

1  1  1  z e z

 1 2  z
 2  1  1  z  z e
 2 
 1 2 1 3  z
 3  1  1  z  z  z e
 2 6 
Crystallizer design – Population balance

z
n'  ne
Moment equations:

number 0  1  e z

length 1  1  1  z e z

 1 2  z
area  2  1  1  z  z e
 2 
 1 2 1 3  z
mass  3  1  1  z  z  z e
 2 6 
Crystallizer design – Population balance

dN  dL dN 
lim  lim 
L 0 dt

L 0 dt dL

Crystallizer design – Population balance

 dL   dN 
B  lim  lim 
  L0 dL 
L 0 dt
Crystallizer design – Population balance

 dN 
B  Gd lim 

L 0 dL

Crystallizer design – Population balance

B  Gd n
Crystallizer design – Population balance

Correlation between nucleation rate B° and zero-size

particle density n°:

B  Gd n
Crystallizer design – Population balance
Crystallizer design – Population balance

L

Gd 
n'  ne
Crystallizer design – Population balance

L

Gd 
n'  ne
Crystallizer design – Population balance
[empirical]

B  k1c b

Gd  k 2 c s

B  k3Gd
i

B  Gd n
i 1
n  k 4G d
Crystallizer design – Population balance

i 1
n  k 4G
d
Crystallizer design – Population balance

i 1
n  k 4G
d
Crystallizer design – Population balance

The number of crystals nc per unit volume of the system:

 
nc   n' dL  nGd  e dz z
0 0

nc  nGd
Crystallizer design – Population balance

The mass of crystals per unit volume of the system,

the magma density cs:

 3 
cs   m n dL   nGd   3 z
z e dz
0 0

cs  6 nGd 
4

α: volume shape factor defined by α = volume/L3

ρ: crystal density
Crystallizer design – Population balance

The number of crystals per unit mass:

nc nGd 1
 
cs 6 nGd 4
6 Gd 
3
Crystallizer design – Population balance

The peak of the mass distribution,

the dominant size Lpr of the CSD:

L pr  3Gd
Crystallizer design – Population balance

The peak of the mass distribution,

the dominant size Lpr of the CSD:

L pr  3Gd

Lpr can be related to the crystallization kinetics

i 1 i  3 
L pr  
Crystallizer design – Population balance

The peak of the mass distribution,

the dominant size Lpr of the CSD:

L pr  3Gd

Lpr can be related to the crystallization kinetics

i 1 i  3 
L pr  
Crystallizer design – Population balance

The peak of the mass distribution,

the dominant size Lpr of the CSD:

L pr  3Gd

Lpr can be related to the crystallization kinetics

i 1 i  3 
L pr  
Crystallizer design – Population balance

The peak of the mass distribution,

the dominant size Lpr of the CSD:

L pr  3Gd

nc 9

cs 2  L pr
3
Crystallizer design – Population balance

The nucleation rate must be just sufficient to generate

one nucleus for each crystal in the product.
If C is the mass production rate of crystals, the required
nucleation, in number per unit time and volume of
mother liquor, is:

C nc
B 
csVc
Crystallizer design – Population balance

The nucleation rate must be just sufficient to generate

one nucleus for each crystal in the product.
If C is the mass production rate of crystals, the required
nucleation, in number per unit time and volume of
mother liquor, is:

C nc C
B  
csVc 6   Gd  Vc
3
Crystallizer design – Population balance

The nucleation rate must be just sufficient to generate

one nucleus for each crystal in the product.
If C is the mass production rate of crystals, the required
nucleation, in number per unit time and volume of
mother liquor, is:

C nc C 9C
B   
csVc 6   Gd  Vc 2   Vc L pr
3 3
Crystallizer design – Population balance

Contact nucleation
• The total generation of nuclei is proportional to the
sum of the nucleation from all crystals of all sizes each
time they pass through the impeller
• The driving potential is the supersaturation, which is
proportional to the growth rate Gd
• The energy imparted to a crustal of size L and mass ρL3
is that necessary to accelerate the particle from the
speed of the folwing magma to the speed of the tip of
the impeller
• The area of contact is proportional to L2
Crystallizer design – Population balance

Contact nucleation

2
 Gd 
u
B  K N nGd T 5

tT0

KN: dimensional constant

uT : tip speed of the impeller
tT0: turnover time