Mass Transfer - Ii: Crystallization

Mass Transfer – II
Crystallization
Ashwini Kumar Sharma

Department of Chemical and Biochemical Engineering
Indian Institute of Technology Patna
Email: [email protected]
Refs.
[1] B. K. Dutta, Principles of mass transfer and separation processes, PHI Learning Pvt Ltd, 2017
1
Introduction
 Variety of finished solid products from chemical process

industries: sugar, salt, NaHPO4, (NH4)2SO4, Citric acid,
etc.
 Often comes in the form of crystals
 A crystal is a solid composed of atoms, ions, or molecules

arranged in a pattern that is periodic in three dimensions.
 The smallest part with the specific pattern ≡ Unit cell
 The unit cell is repeated by translation in 3 dimensions ≡

creates the whole crystal
Ashwini Kumar Sharma (IIT Patna) Mass Transfer-II 2

The unit cell
 Crystals are usually presented in terms of their unit

cell.

Crystal lattice
 Mathematical description of the arrangement of the particles
 Unit cell is defined by the lattice points
 Lattice constants: a, b, c, α, β, γ

Crystallization
 A process by which a chemical is converted from a

liquid solution into a solid crystalline state
 Acts as both a separation and purification step
 The impurities present in a soln are mostly discarded

when crystals are formed
 Crystalline materials have a high degree of purity

even when obtained from a relatively impure solution
 Solution crystallization vs melt crystallization (e.g.

xylene isomers)

Purification with crystallization
https://byjus.com/chemistry/crystallization/
Sugar manufacturing

Mechanism
 Solid undergoes dissolution until

Solution concn < the solubility of the solid {= f(T)}
 Conversely, if the solution concn > the solubility, it is

a supersaturated soln
 Increase the concn of the substance in the liquid

solution or decrease the temperature of the solution
-> saturation
 Supersaturation: Can be created and maintained

Solubility
 Solubility = f (T)
 Solubility = f (size)
𝐶𝑠,𝑟 2𝜎𝑀𝑤
ln =
𝐶𝑠,∞ 𝑅𝑇𝜌𝑐 𝑟
𝐶𝑠,𝑟 = solubility of a particle of radius r
𝐶𝑠,∞ = the solubility of the solid of a plane surface (or
consisting of large particles)
𝜌𝑐 = density of the particle
𝜎 = solid-liquid interfacial tension
*For size smaller than 1000 nm in size

*Higher surface energy per unit mass

Mechanism continued…
 The level of supersaturation attainable depends on

– The particular system
– Impurities (e.g. sugar solution)
– Agitation
– Rate of achieving supersaturation
 Two types of possible formation

– In a supersaturated soln, spontaneous formation and growth of
tiny crystals: nuclei
– If a nucleus or a seed crystal is added to a supersaturated soln,
it grows in size
 Transport of the solute from the bulk of the solution to the

crystal surface
 Magma: the suspension or slurry containing the crystals
 Mother liquor: The solution remaining after the removal of

crystals

Concentration with crystallization
 Partial removal of the solvent from a solution
 E.g. concentration of fruit juice by cooling and

removing the crystals of ice
 Why not evaporation?
 Other alternatives?

Purification with recrystallization
 Common in production of fine chemicals
 Improving the purity of a solid by dissolution and

recrystallization

Solid-liquid phase equilibrium
Supersolubility
curve
Solubility curve


 Eutectic point
 Complete solidification of the solution
 The region below CED: Solid mixtures of benzene and

naphthalene
 The product of crystallization is determined by the

state of the solution on the phase diagram

Nucleation
 Formation of tiny new crystals
 Inadequately understood phenomenon (Arrangement

of molecules from random distribution in a soln into
the regular crystal lattice)

Primary nucleation
 Formation of new crystals independent of the

presence of other crystals
– Homogeneous: In the absence of foreign particles
– Heterogeneous: Formation of the crystals on tiny
foreign particles or on the surface of crystallizer
 Experimental observations
– Probability of a requisite no. of molecules forming
clusters and then ordered arrangement: might be called
a crystal of submicroscopic size
– Solubility of the crystals of the size of this initial
crystal lattice unit

Primary nucleation
 Theoretical rate of homogeneous nucleation
 A’=a statistical measure of the rate of formation of

embryos the reach the critical size
 Exact value is not known, ~1025 nuclei/cm3.s
 Vm = volume of a substance / mol
 σ = solid-liquid interfacial tension; value is uncertain,
~0.08-0.1 J/m2
 K = Boltzmann constant

Secondary nucleation
 Induced by the presence of crystals of the same

substance
 Fracture and attrition

– Impeller
– Between two crystals
 Contact Nucleation
– More nuclei than the first two modes
 Sheer Nucleation

 Factors affecting
– Degree of supersaturation, s
– Intensity of agitation, w
– Impeller material
– Density of the suspension (mass of crystals per unit
volume of the suspension), MT
– Temperature

 To be controlled for the reduction of fines in the

final product
 Steps taken
– Adjustment of the speed of the stirrer tip
– Clearance b/w the impeller tip and the wall
– Reduction in suspension density (of the suspended
crystals)
– Maintaining a lower level of supersaturation
– Coating the impeller with soft material

Crystal growth

Crystal size distribution
 The process of crystallization gives a product in

acceptable and granular form
 Important quality parameter of a crystalline product

is the crystal size distribution
– Market acceptance
– Down-stream processing of crystals
 Development of crystallization processes represents

a complex and challenging issue, requiring
simultaneous control of various product properties,
including purity, crystal size and shape, and molecular
level solid structure.

Crystallization equipment
 Tank with natural cooling

– Inefficient
– No control of size range of crystals
– Formation of large crystals
 Provision of agitation
– Batch crystallization
– Most economical
• For small quantity of production
• Size range pf product is not of importance

Batch crystallization
 Fine chemicals,
Feed solution is pumped into the vessel
pharmaceuticals, specialty
chemicals The necessary supersaturation is created
Seed crystals are added; their growth takes

 Capacity 100 kg – 15 tons place
a day Level of supersaturation has to be maintained

throughout the operation. How?
 Challenges: Product crystals are harvested
– Multimodal size distribution

– Due to secondary nucleation
– Narrow size distribution
– If little or no nucleation
– Reduce the rate of nucleation

Batch crystallizer
 Assumption
– No nucleation
– ‘N’ Seed crystals are fed of uniform size, Ls
– Constant level of supersaturation, s = (C-Cs)/Cs
– Constant growth rate, G
 If it is a evaporative crystallizer, determine the rate
of evaporation (dV/dt) in order to maintain a constant
level of supersaturation
 If it is a cooling crystallizer, determine the rate of
cooling (dT/dt) in order to maintain a constant level
of supersaturation

Mass balance
Rate of change of mass of the crystals = rate of change

of mass of solute in the solution
𝑑𝑀 𝑑 𝑀𝑤 𝐶𝑉
= − (1)
𝑑𝑡 𝑑𝑡
Where M is the total mass of the crystals,
Mw is the mol wt of the solute,
C is the conc of the solute in the solution (mol/volume),
V is the volume of the solution.
The total mass of the crystals can be written as

𝑀 = 𝑁ϕ𝑣 𝐿3 𝜌𝑐 (2)
Thus, eqn. 1 becomes
𝑑𝐿 𝑑 𝑀𝑤 𝐶𝑉
3𝑁ϕ𝑣 𝐿 2
𝜌𝑐 = − (3)
𝑑𝑡 𝑑𝑡

Mass balance contd…
Now we know that dL/dt = G and L = Ls+Gt, we can write

𝐿𝑠 +𝐺𝑡 2 𝐺 𝑑 𝑀𝑤 𝐶𝑉
3
3𝑁ϕ𝑣 𝜌𝑐 𝐿𝑠 =− (4)
𝐿3𝑠 𝑑𝑡
Or
𝐺𝑡 2 𝐺 𝑑 𝑀𝑤 𝐶𝑉
3𝑀𝑠 1 + =− (5)
𝐿𝑠 𝐿𝑠 𝑑𝑡
where 𝑀𝑠 = 𝑁ϕ𝑣 𝜌𝑐 𝐿3𝑠 is the mass of the seed crystals.
Note that the variable on the LHS, i.e., Ms, G and Ls are
constant, not function of time.

Evaporative crystallizer
 Continuous evaporation of the solvent from

the solution to maintain supersaturation
 Volume of the solution decreases with time
 Evaporation can be assumed to occur at a
constant temperature; T is fixed so is Cs.
 To maintain a constant level of
supersaturation {s = (C-Cs)/Cs},
concentration of the solute in the solution
has to be maintained constant.
 Eq. 5 can be written as
2
𝑑𝑉 3𝑀𝑠 𝐺𝑡 𝐺
=− 1+
𝑑𝑡 𝑀𝑤 𝐶 𝐿𝑠 𝐿𝑠
 The above equation can be used to
determine the evaporation program of a
batch crystallizer.

Cooling crystallizer
 Temperature of the solution is

continuous lowered to maintain
supersaturation.
 Volume of the solution remains almost
constant.
 Since T is varied, Cs also varies.
 To maintain a constant level of
supersaturation {s = (C-Cs)/Cs}, C also
has to be varied.
 Eq. 5 can be written as
𝑑𝐶 3𝑀𝑠 𝐺𝑡 2 𝐺
= − 1 + (6)
𝑑𝑡 𝑉𝑀𝑤 𝐿𝑠 𝐿𝑠

Cooling crystallizer
 For simplicity, let us consider

𝐶𝑠 = 𝑎 + 𝑏𝑇
 Since s = (C-Cs)/Cs, we can write
𝐶 = 𝑠 + 1 𝐶𝑠
or
𝑑𝐶 𝑑𝐶𝑠
= 𝑠+1
𝑑𝑡 𝑑𝑡
or
𝑑𝐶 𝑑𝑇
= 𝑠+1 𝑏
𝑑𝑡 𝑑𝑡
 If C and Cs are mass conc., we can rewrite eqn 6 as
2
𝑑𝑇 3𝑀𝑠 𝐺𝑡 𝐺
=− 1+
𝑑𝑡 𝑉𝑀𝑤 𝑠 + 1 𝑏 𝐿𝑠 𝐿𝑠
 The above equation can be used to determine the cooling
program of a batch crystallizer.

Example
 KCl crystals of 1.1 mm size are to be produced at a rate of 800

kg per batch in an evaporative crystallizer. The crystallizer is
operated at 40oC under vacuum at a constant level of
supersaturation of 5%. The seed size is 80 μm and the crystal
growth rate is constant at 3x10-8 m/s. A maximum slurry density
of 150 kg crystals/m3 is allowed.
 Determine
1. The crystallizer volume if it is filled 70% at the start.
2. The mass of the seeds used
3. The batch time
4. The evaporation profile
5. Initial and final evaporation rate
 Data required: The solubility of KCl at 40oC is 400 kg/m3,
density of the KCl solution can be assumed to be constant at
1300 kg/m3, density of the crystals is 1990 kg/m3, crystal shape
factor is 1.0.

Continuous crystallization

Forced-circulation (evaporative) crystallizer
 Sugar, salt
 (NH4)2SO4, citric acid

Draft-tube-baffle crystallizer

Circulating liquor crystallizer
 Oslo evaporative crystallizer

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Mass Transfer – II

Ashwini Kumar Sharma

 Variety of finished solid products from chemical process

 Often comes in the form of crystals

 A crystal is a solid composed of atoms, ions, or molecules

 The smallest part with the specific pattern ≡ Unit cell

 The unit cell is repeated by translation in 3 dimensions ≡

Ashwini Kumar Sharma (IIT Patna) Mass Transfer-II 2

 Crystals are usually presented in terms of their unit

Ashwini Kumar Sharma (IIT Patna) Mass Transfer-II 3

Ashwini Kumar Sharma (IIT Patna) Mass Transfer-II 4

 A process by which a chemical is converted from a

 Acts as both a separation and purification step

 The impurities present in a soln are mostly discarded

 Crystalline materials have a high degree of purity

 Solution crystallization vs melt crystallization (e.g.

Ashwini Kumar Sharma (IIT Patna) Mass Transfer-II 5

Ashwini Kumar Sharma (IIT Patna) Mass Transfer-II 7

 Solid undergoes dissolution until

 Conversely, if the solution concn > the solubility, it is

 Increase the concn of the substance in the liquid

 Supersaturation: Can be created and maintained

Ashwini Kumar Sharma (IIT Patna) Mass Transfer-II 8

*For size smaller than 1000 nm in size

Ashwini Kumar Sharma (IIT Patna) Mass Transfer-II 9

 The level of supersaturation attainable depends on

 Two types of possible formation

 Transport of the solute from the bulk of the solution to the

 Magma: the suspension or slurry containing the crystals

 Mother liquor: The solution remaining after the removal of

Ashwini Kumar Sharma (IIT Patna) Mass Transfer-II 10

 Partial removal of the solvent from a solution

 E.g. concentration of fruit juice by cooling and

 Why not evaporation?

Ashwini Kumar Sharma (IIT Patna) Mass Transfer-II 11

 Common in production of fine chemicals

 Improving the purity of a solid by dissolution and

Ashwini Kumar Sharma (IIT Patna) Mass Transfer-II 12

Ashwini Kumar Sharma (IIT Patna) Mass Transfer-II 13

Ashwini Kumar Sharma (IIT Patna) Mass Transfer-II 14

 Complete solidification of the solution

 The region below CED: Solid mixtures of benzene and

 The product of crystallization is determined by the

Ashwini Kumar Sharma (IIT Patna) Mass Transfer-II 15

 Formation of tiny new crystals

 Inadequately understood phenomenon (Arrangement

Ashwini Kumar Sharma (IIT Patna) Mass Transfer-II 16

 Formation of new crystals independent of the

Ashwini Kumar Sharma (IIT Patna) Mass Transfer-II 17

 Theoretical rate of homogeneous nucleation

 A’=a statistical measure of the rate of formation of

Ashwini Kumar Sharma (IIT Patna) Mass Transfer-II 18

 Induced by the presence of crystals of the same

 Fracture and attrition

Ashwini Kumar Sharma (IIT Patna) Mass Transfer-II 19

Ashwini Kumar Sharma (IIT Patna) Mass Transfer-II 20

 To be controlled for the reduction of fines in the

Ashwini Kumar Sharma (IIT Patna) Mass Transfer-II 21