Separation Processes

Crystallization
 Crystallisation is an operation in which solid particles are formed
from a liquid solution.
 It is a solid-liquid operation used to separate a solute from its
solution in the form of crystals.
 In this operation, mass is transferred from the liquid phase
(solution) to a pure solid crystalline phase.
 Crystallisation is an important operation in the chemical industry as
the number of commercial products have to be in the form of
crystals.
 Crystallization gives almost pure product in the form of crystals of a
desired size ranging from relatively impure solutions in a single
processing step.
 From the energy point of view, crystallisation requires much less
energy for separation as compared to other purification methods
(e.g., distillation).
 It may be carried out at relatively low temperatures and on a scale
ranging from a few grams to thousands of tons per day.
Crystal
Crystal
Crystal
Crystallization
 Crystallisation usually involves :
 (i) concentration of solution (by evaporating a part of the
solvent) and/or
 (ii) cooling of solution until the concentration of solute
becomes higher than its solubility at the prevailing
temperature.
 (iii) Addition of third component (antisolvent)
 The solute then comes out of the solution (i.e., precipitates) in the
form of pure crystals.
 The performance of crystallisation process is evaluated in terms of
size, shape, structure, yield and purity of crystals.
 So in commercial crystallisation, the size and shape of crystals are
as important as the yield and purity of crystals.
Crystallization
Crystallization
 Solubility : The solubility of a solute in a given solvent is the concentration of
the solute in a saturated solution at a given temperature.
 The solubility of the solute in a given solvent is different at different
temperatures and it forms the basis of crystallisation by cooling.
 Saturation :
 Consider a process of dissolving copper sulphate in water (solvent) at a
given temperature. Initially, when some amount of copper sulphate is
added, all of it goes in the solution (i.e., it dissolves in water). Additional
amount can be dissolved further till a stage comes when no more copper
sulphate can be dissolved in a given amount (i.e. a fixed amount) of the
solvent. At this stage, the solution is called a saturated solution.
 A saturated solution is defined as the one which is in equilibrium with an
excess of solid solute at a given temperature.
 Supersaturation : It is the quantity of solute present in a solution (in which
crystals are growing) compared with the quantity of solute that is in
equilibrium with the solution (i.e., the equilibrium solubility at the temperature
under consideration).

 Solubility Curves : A graphical relationship between the solubility of a solute

and temperature is termed as the solubility curve.
Crystallization
Problem: A solution of sodium nitrate in water contains 48 % NaNO3 by weight at 313
K (40o C) temperature. Calculate the percentage yield of NaNO3 crystals that may be
obtained when the temperature is reduced to 283 K (10o C). Also, calculate the quantity
of NaNO3 crystals obtained from 100 kg of the solution.
Solubility of NaNO3 in water at 283 K (10o C) is 80.18 kg NaNO3 per 100 kg water.

Amount of NaNO3 = 48% by wt

Amount of water in 100 kg = 52 kg
Amount of NaNO3 = 48 kg
100 kg water = 80.18 kg NaNo3
52 kg water = 41.69 kg NaNO3
NaNO3 crystallized = 48-41.69 = 6.31 kg
% Crystallized out = 6.31/48 *100 = 13.14%
Solid liquid Phase equilibrium
diagram:
Solid liquid Phase equilibrium
diagram:
Crystallization
Population balance equation:
• A population balance on any system is concerned with keeping
track of numbers of entities whose presence or occurrence may
dictate the behavior of the system under study.
• Since the behavior of individual entities may depend on variables
associated with their environment, the population balance
equation may be mutually coupled with balance equations in the
environmental variables.
• Dispersed phase systems are more difficult to describe than bulk
phase systems.
• Crystal size distribution is analytically or empirically
representation of number of particles of any size.
• If n(L) population density function; i.e n(L) is the number of
particles of size L then
represents particle in (L1 –L2)
represents total number of particles.
• Empirical distribution function: normal distribution function, log-
normal distribution function etc.
Average particle size:
Average particle size:
Moments of size distribution
MSMPR crystallizer
MSMPR: Mixed suspension mixed product removal
 Mass of 1
Mesh No Mass (g) Opening Average ΔL crystal (kg) N n/m ln (n)
12 28.5 1.41 1.3 0.22 1.29184E-06 22061.62 1.003E+08 18.42348 0.0013
14 29.2 1.19 1.0155 0.349 6.15768E-07 47420.46 1.359E+08 18.72725 0.001016
20 37.5 0.841 0.718 0.246 2.17646E-07 172298.1 7.004E+08 20.36716 0.000718
28 27 0.595 0.5075 0.175 7.68574E-08 351300.1 2.007E+09 21.42012 0.000508
35 24.7 0.42 0.3585 0.123 2.70922E-08 911700.4 7.412E+09 22.72639 0.000359
48 3.1 0.297 0.1485 0.297 1.92556E-09 1609923 5.421E+09 22.41348 0.000149
Consider a batch crystallizer operated with constant
supersaturation (s)
𝐶−𝐶𝑠
𝑠=
𝐶𝑠
This can be achieved by:
Maintaining C constant.
Varying Cs (i.e temperature) such that ratio remains same.
This is possible by two types of crystallizer:
Evaporative crystallizer
Cooling crystallizer.
If s is kept constant then growth rate will remain constant..!
 𝐺
𝑑𝑧 = 𝑑𝑡
𝐿𝑠
First we find out density of solvent assuming volumes of solute and solvent are additive

1 m3 of solution = 1300 kg solution = 400 kg solute + 900 kg solvent

1 m3 of solution = 0.2 m3 of solute + x m3 of solvent
X = 0.8 m3 hence density of solvent = 1125 kg/m3
 5.333+ 1.6 = 6.933

6.933/0.7 = 9.90 m3
Steps:
1) Material Balance
2) Find Volume of crystallizer
3) Sizing
4) Heat balance and heat exchanger design
Crystal layer thickness:
Plane wall Cylindrical wall
Solubility of MgSO4 in water is dependent on temperature and is given by following
relation.
C=0.468T + 26.76,
where T is in 0C and C is solubility in kg MgSO4/ 100 kg Water
1200 kg of MgSO4 is dissolved in water at higher temperature 76 0C to obtain its
saturated solution. After cooling given solution to final temperature of 34 0C,
heptahydrated salt of MgSO4 is obtained. Calculate the yield of MgSO4·7H2O crystals
assuming 10 % of the water is lost by evaporation during cooling.
Crystals of average size 1.1 mm have to be produced in a batch evaporative crystallizer
at a rate of 600 kg per batch. The solubility is given as Cs = 275 kg/m3 solvent. Density
of crystals 1750 kg/m3. Shape factor 0.9, maximum allowable growth rate = 0.06
μm/sec, seed size = 65 μm. Average density of solution 1150 kg/m3, maximum
allowable suspension density = 180 kg/m3 solution.
Determine (a) batch time and (b) initial and final evaporation rates.