SEPARATION PROCESS II

(BTK3263)

CHAPTER 3
CRYSTALLISATION
 TOPIC OUTCOMES

❖ Ability to solve simple mass balance

❖ Ability to determine the amount of energy involved in
crystallization
❖ Ability to determine the growth rate of crystal
❖ Ability to explain factor that affects crystallization
process
WHY CRYSTALLIZED?
 HOW CRYSTAL FORMED?

Crystallization cannot occur without

SUPERSATURATION.

FIVE (5) basic methods of generating supersaturation

(1)EVAPORATION–by evaporating a portion of the

solvent
(2)COOLING–by cooling a solution through indirect
heat exchange
(3)VACUUM COOLING–by flashing of feed solution
adiabatically to a lower temperature and inducing
crystallization by simultaneous cooling and
evaporation of the solvent
(4)REACTION–by chemical reaction with a third
substance
INTRODUCTION TO CRYSTALLIZATION

1) Crystallization is also a solid-liquid separation process in

which mass transfer occurs from the liquid solution to a pure
solid crystalline phase
2) The solution is concentrated and usually cooled until the
solute concentration becomes greater than its solubility at that
temperature (supersaturation) --> the solute comes out of the
solution forming crystals of approximately pure solute
3) Consists of 2 stages:
i) formation of small particles (nuclei)
ii) growth of the nuclei
 Crystallization Theory

Nucleation theory
•Nucleation is number of new particles formed per unit time per unit volume
of mother liquor

Solubility and crystal size

•Solubility refers to the ability for a given substance, the solute, to dissolve in a
solvent. It is measured in terms of the maximum amount of solute dissolved in a
solvent at equilibrium. The resulting solution is called a saturated solution.
•Smaller crystal is better
•Solubility of small crystal better
 NUCLEATION
Primary @ Homogeneous nucleation
•High supersaturation and no agitation
•Result of random fluctuations of molecules in
homogeneous solution

Secondary @ Contact nucleation

•Formation of nuclei occurs in the collision between
crystals
•Formation of nuclei due to interference of the
contacting agent (walls of a container or agitator
blades)
FACTORS AFFECTING
CRYSTAL GROWTH
1. Cooling rate (temperature control)
2. Existence of other component
3. Solvent types
4. Time
5. Nucleation rate
6. Mixing rate

OUTCOME FOR
CONSIDERATIONS
FOR YIELD, PURITY,
SHAPE and SIZE OF
CRYSTAL
SUPERSATURATION & CRYSTAL
FORMATION

CLICK ON/COPY THE LINK BELOW FOR LECTURE ON THE CRYSTALLIZATION

PROCESS.

https://www.youtube.com/watch?v=SHu_P-YRNuQ&t=281s
 Types of Crystal
Geometry
Crystal is a solid composed of atoms, ions, or molecules which are arranged in
an orderly and repetitive manner. It is a highly organised type of matter. The
atoms, ions or molecules are located in 3D arrays or space lattices.

Crystals appear as polyhedrons having flat faces and sharp corners. The relative
sizes of the faces and edges of different crystals of the same material may
different greatly. However, the angles between the corresponding faces of all
crystals of the same material are equal and are characteristic of that particular
material. Therefore, crystals are classified on the basis of these interfacial angles.
7 classes of crystals,
• Cubical system
• Tetragonal system
• Orthorhombic system
• Hexagonal system
• Monoclinic system
• Triclinic system
• Trigonal system
 Equilibrium solubility in
Crystallization

•In crystallization,
equilibrium is attained when
the solution or mother liquor
is saturated
•In general, the solubilities of
most salts increase slightly or Please insert figure 12.11-
markedly with temperature 1 (Geankoplis, page 739)
•E.g : Solubility curve for
sodium thiosulfate
 NUCLEATION THEORIES
🙑 Primary/homogeneous nucleation

•result of rapid fluctuations on a molecular scale in a

homogeneous phase

•particulars or solutes form clusters

🙑 Heterogenous nucleation

-Mixed nucleation

🙑Secondary/ contact nucleation

•most effective method of nucleation

•occurs when crystals collide with each

other, with the impellers in mixing or

the walls of the pipe or container

YIELD, HEAT & MASS BALANCES IN
CRYSTALLIZATION

 The yield of crystals can be calculated by knowing:

• initial concentration of solute
• final temperature

• the solubility at this temperature

 simple material (solute and water) balances are made to
obtain yield
EXAMPLE 3: YIELD OF A
CRYSTALLIZATION
A salt solution weighing 10 000 kg with 30 wt % Na2CO3 is
cooled to 293 K (20oC) . The salt crystallizes as the
decahydrate. What will be the yield of Na2CO3. 10H2O
crystals if the solubility is 21.5 kg anhydrous Na2CO3/100 kg
of water assuming that:
a) no water is evaporated
b) 3% of the total weight of the solution is lost by evaporation
of water in cooling
c) 10% of water is evaporated
Solution:
Molecular weights of :
Na2CO3 = 106.0
10H2O = 180.2
Na2CO3. 10H2O = 286.2
 Process Flow for Crystallization in
Example 1
Solution:
W kg H2O

10 000 kg solution S kg solution

Cooler and
30 % Na2CO3 crystallizer 21.5 kg Na2CO3/ 100 kg
H2O

C kg crystals, Na2CO3.10
H2O
Solution:
For part (a) , make a material balance around the dashed-line
box for water, where W=0.
Inlet=Outlet

Material balance for Na2CO3 ,

Solving simultaneously;
C = 6370 kg of Na2CO3.10H2O crystals
S = 3630 kg solution
Solution:
For part (b) , W=0.03(10 000) = 300 kg H2O

Also, using the Na2CO3 balance equation;

Solving simultaneously,
C = 6630 kg of Na2CO3.10H2O crystals
S = 3070 kg solution
GIVEN THE HEAT OF SOLUTIONS FOR THE
MGSO4 IS -91.2 KJ/KMOL. (MW = 120.37)
What is Heat of Crystallization?
The heat of crystallization or enthalpy of
crystallization is the energy that changes during the
crystallization of a substance. Crystallization may occur as
either a natural process or as an artificial process. In the
solid phase of a substance, the molecules or atoms are
highly organized into a crystalline structure. We call this a
crystal structure.
 HEAT EFFECTS AND HEAT
BALANCES IN CRYSTALLIZATION

❖When a compound whose solubility increases as the

temperature increases dissolves , there is an absorption of heat ,
called the heat of solution.

❖ An evaluation of heat accurse when the compound dissolves

whose solubility does not change with temperature , there is no
heat evolution on dissolution .

❖In crystallization the opposite of dissolution occurs . At

equilibrium the heat of crystallization is equal to the negative of
the heat of solution at the same concentration in solution .

❖With many materials this heat of dilution is small compared

with the heat of solution , and this approximation is reasonably
accurate.
SEE EXAMPLE 12.11-2
❖The most satisfactory method for the calculating heat effects
during a crystallization process is to use the enthalpy-
concentration chart for the solution and various solid phases
which are present for the system.

❖Few charts are available for some materials and systems.

❖The enthalpy H1 is kJ for the total feed , the enthalpy H2 of

the final mixture of crystals and another liquor at the final
temperature is also read off the chart.

❖If some evaporation accurse , the enthalpy Hv of the water

vapor is obtained from the steam tables. Then the total heat
absorbed q in kJ is

q = (H2 + Hv) – H1

If q is positive ……. Heat must be added to the system

If q is negative ……. Heat must be given off the system
MASS BALANCE

F=C+S+W
FxF = CxC + SxS

HEAT BALANCE

Fhf + Q = CHc + Shs + VHv  with evaporative

Fhf + Q = CHc + Shs  no evaporation

EXAMPLE :Crystallization of Ba(NO3)2

A hot solution of Ba(NO3)2 from an evaporator contains

30.6 kg Ba(NO3)2 / 100 kg H2O and goes to a
crystallizer where the solution is cooled and
Ba(NO3)2 crystallizes. On cooling, 10% of the
original water present evaporates. For a feed
solution of 100 kg total, calculate the following:
a) The yield of crystals if the solution is cooled to
290 K (17oC), where the solubility is 8.6 kg
Ba(NO3)2/ 100 kg total water

b) The yield if cooled instead to 283 K, where the

solubility is 7.0 kg Ba(NO3)2/ 100 kg total water
 Rate of crystal growth ΔL Law
❖The rate of growth of a crystal face is a distance move per unit time in a
direction that is perpendicular to the face. Crystal growth is layer-by-layer
process.

❖Particle size distribution of crystal and since growth can occur only at the outer
face of the crystal , the solute material must be transported to that face from the
bulk of the solution .

❖The solute molecules reach the face by diffusion through the liquid phase. The
usual mass transfer coefficient ky applies in this case.

❖The equation for mass transfer of solute A from the bulk solution of
supersaturation concentration yA , mole fraction of A, to the surface where the
concentration is y’A is

Where ky is the mass transfer coefficient in kg mol/s.m2

 Where ks is a surface –reaction coefficient in kg mol/s.m2

Where K is the overall mass transfer coefficient.

NOTE
1- when the mass transfer coefficient ky is very large , the surface
reaction is controlling and 1/ky is negligible .
2- when the mass transfer coefficient is very small , diffusional
resistance is controlling .
The ΔL law for crystal growth :

❖It was shown that all crystals that are geometrically similar and of
the same material in the same grow at the same time .

❖Growth is measured as the increase in the length ΔL , in mm .

❖Mathematically the law of crystal growth can be written as:

ΔL/Δt = G
Where
Δt = time in h and growth rate G is a constant in mm/h
❖ Particle size distribution of crystal

❖An important factor in the design of any crystallizer is the size

of the crystal formed or the size distribution of the crystals.
❖One of the standard methods in the size distribution estimation
is by using the sieve analysis technique .(please see appendix
A.5-3.)

❖The common parameter used to characterize the size

distribution is the coefficient of variation CV

CV = 100*[(PD16% - PD84%)/2PD50%]
Where:
PD16%= particle diameter at 16% retained

❖By giving the coefficient of variation and mean particle

diameter , a description of the particle size distribution is
obtained if the line is approximately straight between 90 and
10% .
Model for mixed suspension-mixed product
removal crystallizer
❖One of the most important types of the models used in the
crystallization is what is called (mixed suspension-mixed product
removal crystallizer , (MSMPR).

❖To analyze the data from a crystallizer , an overall theory must

consider combining the effects of nucleation rate , growth rate , and
material balance.

❖Randolph and larson derived such model. They plotted the total
cumulative number of crystals N per unit volume of suspension
(usually 1L) of the size L and smaller versus the size L as in Fig 12.12-
2
The slope dN/dL of this line is denied as a crystal population
density n:

n= dN/dL
Where n is the number of crystals /(L.mm).

❖This population density is obtained experimentally by screen

analysis of the total crystal content of a given volume
❖Each sieve fraction by weight is obtained by collection between
two closely spaced and adjacent screens. Then
Lav = (L1+L2)/2
L1 & L2= the openings in mm in the two adjacent screens
❖Population material balance:
Average particle size and nucleation rate
❖Prediction of cumulative weight fraction
obtained
 EXAMPLE 12.12-1 Growth of nucleation rates in
MSMPR crystallizer

Calculate the population density and nucleation growth rates for

crystal samples of urea from screen analysis . The slurry density (g of
crystals) is 450g/liter , the crystal shape factor a is 1.00 , the crystal
density is 1.335 g/cm3 , and the resistance time τ is 3.38 h . The
screening analysis from reference B5 is as follows :
Solution

1.The data above are tabulated in table 12.12-1 using data from appendix A.5-3.

2.The value of L is the screen opening

3.For the 14-20 mesh portion , Lav = (1.168+0.833) /2 = 1.001 mm

ΔL = 1.168 – 0.833 = 0.335 mm

4.For Lav = 1.001 mm using equation (12.12.8) ,

vp = aLav3 = 1.00(1.001)3 = 1.003 mm3/particle

5.The mass particle = ρ.vp = 1.335*10-3(1.003) = 1.339*10-3 G

6.The total mass crystals = (450 g/L)(0.044 wt.fr)

7.Using equation (12.12-9) to calculate n for the 14-20 mesh size range,
n= (ΔN/ ΔL) = (450g/L)(wt frac)/(ρa(Lav)3. ΔL)
= 4.414 * 104 number of crystals /L.mm
8. Then ln n = ln 4.414*104 = 10.695

9. For the 20-28 mesh size range , Lav = 0.711/mm , and ΔL =

0.244 , then

n = ((450*0.144)/(1.335*10-3 *1.00*(0.711)3*0.244))
= 5.535*105

Then ln n = 13.224

10. The ln n is plotted versus L in figure 12.12-3 . The equation of

this line is equation 12.12-14 , where the slope is (-9.12) and
intercept = 19.79
11. The slope -9.12 = -1/Gτ = -1/(G)(3.38) . Hence , G= 0.03244
mm/h .

12. The intercept ln no=19.79. Hence , no = 3.933*108. from

equation 12.12-18 . The nucleation rate Bo is

Bo = Gon = 0.03244(3.933*108) = 1.27 * 107 nuclei/h.L

The average size is , from equation 12.12-15 , La = 3.67Gτ =

3.67(0.03244)(3.38) = 0.402 mm

The predominant size , from equation 12.12-16 , is Ld = 3.00 Gτ

= 3.00(0.03244)(3.38) = 0.329 mm
In order to produce crystal of NiCl 2.6H2O, water has to be removed from the solution during the
crystallization process. The flowrate of the feed solution is 7 500 kg (50 °C) contain 50% of solid. In the
crystallizer, solution is cooled to 20 °C while 20% of the initial water content is removed to create the
supersaturation condition. The solubility of the salt is 30.5 kg NiCl 2 /100 kg total water in the mother

liquor. The average heat capacity of the feed solution is given as function, c p (kJ/kg °C) = 2.134 + 1.27x,

where x is the solid composition. The heat of solution is given as -21.13 kJ/kg of NiCl 2.6H2O. The
molecular weight of elements is given [Ni:250.87, Cl:35.5, O: 16, H=1]. Table 1 represent the data for the
above production, showing the listing from screen analysis of crystals.
Table 1: Screen Analysis for the NiCl 2 production

Mesh Wt %
-12, +16 6.5
-16, +25 19.5
-25, +30 26.3
-30, +50 31.5
-50, +60 8.5
-60, +100 5.2
-100 2.5
a) Calculate the yield of crystals, C, water, W and the solution, S in kg.
[8 Marks]
[CO1, PO1, C3]
b) Determine the heat requirement and operational based (requirement for
cooling/ heating and insulations) for the crystallizer in (KW).
[14 Marks]
[CO2, PO2, C4]

c) The slurry density is given as 2968 g/L, the crystal density, ρ is 3.65 g/cm3, the
residence time is 8.63 h while the shape factor, a is given as 0.74. Determine the
population density, nucleation rate and the average size of the crystals using
MSMPR.
[14 Marks]
[CO2, PO2, C4]
 Equipment for
crystallization
• Crystallization equipment can be classified
according to
• Method used to bring supersaturation
• Supersaturation produced from cooling the solution with
negligible evaporation
• Tank and batch type crystallizers
• Solubility curves decrease markedly with temperature
• Supersaturation produced by evaporation of solvent with little
or no cooling
• Evaporator crystallizers
• Solubility curve changes little with temperature
• Supersaturation by combined cooling and evaporation in an
adiabatic evaporators
• adiabatic evaporator-vacuum crystallizers
• Hot solution is introduced into a vacuum, solvent evaporates and
the solution is cooled adiabatically
 5 TYPES OF COMMON
CRYSTALLIZER
EQUIPMENT
1) MIXED-SUSPENSION, MIXED PRODUCT REMOVAL (MSMPR)
CRYSTALLIZERS.
• Also sometimes called circulating magna crystallizers, this type of
equipment circulates the growing crystals through the zone of the
crystallizer where the supersaturation conditions are generated. This may
be accompanied by mixed- or classified-product removal, and with or
without destruction of fines.

2) CIRCULATING LIQUOR/CLASSIFIED- SUSPENSION CRYSTALLIZERS.

• In this type, only the liquor or a weak slurry is circulated, while the bulk of
the growing crystals are not circulated. Supersaturation is imparted to the
liquor in one part of the equipment, whereupon this liquor is circulated to
another area where it relieves the supersaturation on growing crystals. This
type of crystallizer is also available with or without fines destruction
capabilities. The units are usually identified as Krystal- or Oslo-type
crystallizers.
 3) SCRAPED-SURFACE CRYSTALLIZERS.
• Crystallization is induced by indirect heat exchange with a
cooling medium at the heat-transfer surface, which is
continuously scraped and agitated to minimize fouling. This
type of equipment employs vertical tanks with scrapers or
horizontal pipes

4) TANK CRYSTALLIZERS.
• Crystallization is produced by cooling the feed solution in either
static or agitated tanks by natural convection and radiation, by
surface cooling through coils or a jacket, programmed
evaporative cooling, reaction or antisolvent methods.
Types of crystalliser
 FORCE
CIRCULATION
(FC)
CRYSTALLIZER
• Utilizes the MSMPR model
Types of crystalliser
Forced circulation Crystallizer Draft Tube Baffle (DTB)
Crystallizer
Smaller Crystal (0.5 -1.0 mm) Larger Crystal (> 2 mm)
Prevent Secondary Nucleation by
reducing mechanical contact
High shear stress Higher quality energy saving
Simplicity and easy fabrication
Small capacity production Large production
Reduce energy consumption
 VIDEO : Forced Circulation Crystallizer
https://www.youtube.com/watch?v=7cNHecFHHT4
VIDEO: Draft Tube Baffle (DTB) Crystallizer
https://www.youtube.com/watch?v=42BA1GWIWic
QUIZ 1

A solution consisting of 30 wt% MgSO4 and 70% water is

cooled to 60oF. During cooling 5% of the total water in the
system evaporates. How many kilograms of crystals are
obtained per 1000 kg of the original mixture? Cp of solution
is assumed at 3.51 kJ/kg and heat of solution is given as
20.31 kJ/kg mol. Also calculate the heat requirement (q) for
the process.