Revision Lectr online clases

separation Processes

• Prepared by:Ms.Ammarah Batool

Separation Processes - An Introduction

6
 What is Separation process

Separation process is a method to achieve any phenomenon that

converts a mixture of chemical substance into two or more distinct
product mixtures, which may be referred to as mixture, at least one
of which is enriched in one or more of the mixture's constituents.
Role of separation processes in Chemical Industry:

1. Isolating valuable chemicals from mixtures,

2. Removing impurities from raw materials,
3. Purification of products,
4. Environmental Protection by removing contaminants and pollutants
from effluent stream
Chemical Process

Raw
Products
materials

9
Industrial Examples

10
Mass Transfer Operations

12
Mass Transfer Operations – classification

 On the basis of phase involved

 On the basis of separation principle

 On the basis of contact type

 On the basis of nature of transfer
 On the basis of nature of contact

14
On the basis of phases involved ……

 S–S  L–S  G–S

 S–L  L–L  G–L

 S–G  L–G  G–G

15
On the basis of separation principle ……

 By phase creation

 By phase addition
 By barrier
 By solid agent

 By external forces

16
Separation Operations – classification

17
Phase Creation Technique
• The most common separation technique, shown in Figure (a), creates a second phase,
immiscible with the feed phase, by energy (heat and/or shaft-work) transfer or by pressure
reduction.

• Common operations of this type are distillation, which involves the transfer of species
between vapor and liquid phases, exploiting differences in volatility (e.g., vapor pressure
or boiling point) among the species; and crystallization, which exploits differences in
melting point.

18
Phase Addition Technique
• A second technique, shown in Figure (b), adds another fluid phase, which
selectively absorbs, extracts, or strips certain species from the feed.

• The most common operations of this type are liquid–liquid extraction, where the
feed is liquid and a second, immiscible liquid phase is added; and absorption,
where the feed is vapor, and a liquid of low volatility is added. In both cases,
species solubilities are significantly different in the added phase.

19
Barrier Separation Technique
• Less common, but of growing importance, is the use of a barrier
(shown in Figure c), usually a polymer membrane, which involves a
gas or liquid feed and exploits differences in species permeability
through the barrier.

20
Solid Agent Separation
• Also of growing importance are techniques that involve contacting a vapor
or liquid feed with a solid agent, as shown in Figure d.

• Most commonly, the agent consists of particles that are porous to achieve
a high surface area, and differences in species absorbability are exploited.

12/22/2020 Adeem Ghaffar Rana 21

Gradient Separations
• Finally, external fields (centrifugal, thermal, electrical, flow, etc.), shown in
Figure e, are applied in specialized cases to liquid or gas feeds, with
electrophoresis being especially useful for separating proteins by
exploiting differences in electric charge and diffusivity.

12/22/2020 Adeem Ghaffar Rana 22

 Example
For each of the following binary mixtures, a separation operation is
suggested. Explain why the operation will or will not be successful.

a) Separation of air into oxygen-rich and nitrogen-rich products by

distillation.
b) Separation of m-xylene from p-xylene by distillation.
c) Separation of benzene and cyclohexane by distillation.
d) Separation of isopropyl alcohol and water by distillation.
• a) The normal boiling points of O2 (183C) and N2 (195.8C) are
sufficiently different that they can be separated by distillation, but
elevated pressure and cryogenic temperatures are required. At
moderate to low production rates, they are usually separated at lower
cost by either adsorption or gas permeation through a membrane.
• (b) The close normal boiling points of m-xylene (139.3C) and pxylene
(138.5C) make separation by distillation impractical. However, their
widely different melting points of 47.4C for m-xylene and 13.2C for p-
xylene make crystallization the separation method of choice.
• The normal boiling points of benzene (80.1C) and cyclohexane (80.7C) preclude a practical separation by
distillation. Their melting points are also close, at 5.5C for benzene and 6.5C for cyclohexane, making
crystallization also impractical. The method of choice is to use distillation in the presence of phenol (normal
boiling point of 181.4C), which reduces the volatility of benzene, allowing nearly pure cyclohexane to be obtained.
The other product, a mixture of benzene and phenol, is readily separated in a subsequent distillation operation.
• (d) The normal boiling points of isopropyl alcohol (82.3C) and water (100.0C) seem to indicate that they could be
separated by distillation. However, they cannot be separated in this manner because they form a minimum-boiling
azeotrope at 80.4C and 1 atm of 31.7 mol% water and 68.3 mol% isopropanol. A feasible separation method is to
distill the mixture in the presence of benzene, using a two-operation process. The first step produces almost pure
isopropyl alcohol and a heterogeneous azeotrope of the three components. The azeotrope is separated into two
phases, with the benzene-rich phase recycled to the first step and the water-rich phase sent to a second step,
where almost pure water is produced by distillation, with the other product recycled to the first step.
• (e) Penicillin has a melting point of 97C, but decomposes before reaching the normal boiling point. Thus, it would
seem that it could be isolated from water by evaporation of the water. However, penicillin and most other
antibiotics are heat-sensitive, so a near-ambient temperature must be maintained. Thus, water evaporation would
have to take place at impractical, high vacuum conditions. A practical separation method is liquid liquid extraction
of the penicillin with n-butyl acetate or n-amyl acetate.
The extent of separation possible depends on the exploitation of
differences in molecular, thermodynamic, and transport properties of
the species. Properties of importance are:
Separation Operations Based on Phase Creation or
Addition

27
28
29
30
Separation Operations Based on a Barrier

31
32
Separation Operations Based on a Solid Agent

33
34
Separation Operations by Applied field or Gradient

35
On the basis of contact…..

 Direct contact of Immiscible phases

 Indirect contact of miscible phases

36
On the basis of nature of transfer…..

 Interphase mass transfer operations

 Intraphase mass transfer operations

37
On the basis of nature of contact…..

 Stage-wise contact
 Continuous contact

38
Selection of Feasible Separation Processes

39
40
Example
Propylene and propane are among the light hydrocarbons produced
by cracking heavy petroleum fractions. Propane is valuable as a fuel
and in liquefied natural gas (LPG), and as a feedstock for producing
propylene and ethylene. Propylene is used to make acrylonitrile for
synthetic rubber, isopropyl alcohol, cumene, propylene oxide, and
polypropylene. Although propylene and propane have close boiling
points, they are traditionally separated by distillation. From Figure
1.16, it is seen that a large number of stages is needed and that the
reflux and boilup flows are large. Accordingly, attention has been
given to replacement of distillation with a more economical and less
energy-intensive process. Based on the factors in Table 1.12, the
characteristics in Table 1.13, and the list of species properties given
at the end of section 1.2, propose alternatives to Figure 1.16.

41
42
43
SEPARATION PROCESSES
 Difference b/W distillation vs Absorption

I. The essential difference between distillation and absorption is that in the

former the vapour has to be produced in each stage by partial vaporization of
the liquid which is therefore at its boiling point, whereas in absorption the
liquid is well below its boiling point.

II. In distillation there is a diffusion of molecules in both directions, so that for an

ideal system equimolecular counter diffusion takes place, though in absorption
gas molecules are diffusing into the liquid, with negligible transfer in the reverse
direction.

III. In general, the ratio of the liquid to the gas flowrate is considerably greater in
absorption than in distillation with the result that layout of the trays is different
in the two cases. Furthermore, with the higher liquid rates in absorption,
packed columns are much more commonly used.
 Absorption Introduction
The removal of one or more selected components from a mixture of gases by absorption
into a suitable liquid is the second major operation of chemical engineering that is based on
interphase mass transfer controlled largely by rates of diffusion.
Examples
Acetone can be recovered from an acetone–air mixture by passing the gas stream into
water in which the acetone dissolves while the air passes out. Similarly same phenomena
occurs in ammonia-air mixture.

When oxides of nitrogen are absorbed in water to give nitric acid, however, or when
carbon dioxide is absorbed in a solution of sodium hydroxide, a chemical reaction
occurs, the nature of which influences the actual rate of absorption. Absorption
processes are therefore conveniently divided into two groups, those in which the
process is solely physical and those where a chemical reaction isoccurring.
46
• In considering the design of equipment to achieve gas
absorption, the main requirement is that the gas should be
brought into intimate contact with the liquid, and the
effectiveness of the equipment will largely be determined by
the success with which it promotes contact between the two
phases.

• In absorption, the feed is a gas introduced at the bottom of the

column, and the solvent is fed to the top, as a liquid; the
absorbed gas and solvent leave at the bottom, and the
unabsorbed components leave as gas from the top.

47
Conditions of Equilibrium between Liquid and Gas

• When two phases are brought into contact they eventually reach equilibrium. Thus, water in
contact with air evaporates until the air is saturated with water vapour, and the air is absorbed by
the water until it becomes saturated with the individual gases.

• In any mixture of gases, the degree to which each gas is absorbed is determined by its partial
pressure. At a given temperature and concentration, each dissolved gas exerts a definite partial
pressure.

• Three types of gases may be considered from this aspect—

a very soluble one
a moderately soluble one
a slightly soluble one

48
• It may be seen that a slightly soluble gas requires a much higher
partial pressure of the gas in contact with the liquid to give a solution
of a given concentration.
• Conversely, with a very soluble gas a given concentration in the liquid
phase is obtained with a lower partial pressure in the vapor phase
49
• For dilute concentrations of most gases, and over a wide
range for some gases, the equilibrium relationship is given by
Henry’s law

where:
PA is the partial pressure of the component A in the gas
phase
CA is the concentration of the component in the liquid
H is Henry’s constant.
50
Mechanism of Absorption

51
Diffusion through a stagnant gas
• The process of absorption may be regarded as the diffusion of a soluble gas A into
a liquid.
• The molecules of A have to diffuse through a stagnant gas film and then through
a stagnant liquid film before entering the main bulk of liquid.
• The absorption of a gas consisting of a soluble component A and an insoluble
component B is a problem of mass transfer through a stationary gas to which
Stefan’s law applies:

52
Integrating over the whole thickness zG of the film, and
representing concentrations at each side of the interface by
suffixes 1 and 2:

Since CT = P/RT, where R is the gas constant, T the absolute

temperature, and P the total pressure. For an ideal gas,
then

54
• Writing PBM as the log mean of the partial pressures
PB1 and PB2, then:

• Hence the rate of absorption of A per unit time per unit area is
given by

55
• In the great majority of industrial processes the film thickness is not
known, so that the rate equation of immediate use is
kG is known as the gas-film transfer coefficient for absorption and is a
direct measure of the rate of absorption per unit area of interface with
a driving force of unit partial pressure difference
Diffusion in the liquid phase
• The rate of diffusion in liquids is much slower than in gases, and
mixtures of liquids may take a long time to reach equilibrium
unless agitated
• Whilst there is at present no theoretical basis for the rate of
diffusion in liquids comparable with the kinetic theory for gases,
the basic equation is taken as similar to that for gases, or for
dilute concentrations

57
• Since the film thickness is rarely known, equation is
usually rewritten as

• In equation, kL is the liquid-film transfer coefficient.

For dilute concentrations:

58
Rate of absorption
• In a steady-state process of absorption, the rate of transfer of
material through the gas film will be the same as that through
the liquid film, and the general equation for mass transfer of a
component A may be written as

 where PAG is the partial pressure in the bulk of the gas, CAL is
the concentration in the bulk of the liquid, and PAi and CAi are
the values of concentration at the interface where equilibrium
conditions are assumed to exist. Therefore:

59
These conditions may be illustrated graphically as in Figure,

where ABF is the equilibrium curve for the soluble

component A.

60
61
Relation between film and overall
coefficients

62
63
Rates of absorption in terms of mole
fractions

64
Factors influencing the transfer coefficient
• The influence of the solubility of the gas on the shape of the equilibrium curve, and the effect on
the film and overall coefficients, may be seen by considering three cases in turn—very soluble,
almost insoluble, and moderately soluble gases.
SEPARATION PROCESSES
 Difference b/W distillation vs Absorption

I. The essential difference between distillation and absorption is that in the

former the vapour has to be produced in each stage by partial vaporization of
the liquid which is therefore at its boiling point, whereas in absorption the
liquid is well below its boiling point.

II. In distillation there is a diffusion of molecules in both directions, so that for an

ideal system equimolecular counter diffusion takes place, though in absorption
gas molecules are diffusing into the liquid, with negligible transfer in the reverse
direction.

III. In general, the ratio of the liquid to the gas flowrate is considerably greater in
absorption than in distillation with the result that layout of the trays is different
in the two cases. Furthermore, with the higher liquid rates in absorption,
packed columns are much more commonly used.
 Absorption Introduction
The removal of one or more selected components from a mixture of gases by absorption
into a suitable liquid is the second major operation of chemical engineering that is based on
interphase mass transfer controlled largely by rates of diffusion.
Examples
Acetone can be recovered from an acetone–air mixture by passing the gas stream into
water in which the acetone dissolves while the air passes out. Similarly same phenomena
occurs in ammonia-air mixture.

When oxides of nitrogen are absorbed in water to give nitric acid, however, or when
carbon dioxide is absorbed in a solution of sodium hydroxide, a chemical reaction
occurs, the nature of which influences the actual rate of absorption. Absorption
processes are therefore conveniently divided into two groups, those in which the
process is solely physical and those where a chemical reaction isoccurring.
75
• In considering the design of equipment to achieve gas
absorption, the main requirement is that the gas should be
brought into intimate contact with the liquid, and the
effectiveness of the equipment will largely be determined by
the success with which it promotes contact between the two
phases.

• In absorption, the feed is a gas introduced at the bottom of the

column, and the solvent is fed to the top, as a liquid; the
absorbed gas and solvent leave at the bottom, and the
unabsorbed components leave as gas from the top.

76
Conditions of Equilibrium between Liquid and Gas

• When two phases are brought into contact they eventually reach equilibrium. Thus, water in
contact with air evaporates until the air is saturated with water vapour, and the air is absorbed by
the water until it becomes saturated with the individual gases.

• In any mixture of gases, the degree to which each gas is absorbed is determined by its partial
pressure. At a given temperature and concentration, each dissolved gas exerts a definite partial
pressure.

• Three types of gases may be considered from this aspect—

a very soluble one
a moderately soluble one
a slightly soluble one

77
• It may be seen that a slightly soluble gas requires a much higher
partial pressure of the gas in contact with the liquid to give a solution
of a given concentration.
• Conversely, with a very soluble gas a given concentration in the liquid
phase is obtained with a lower partial pressure in the vapor phase
78
• For dilute concentrations of most gases, and over a wide
range for some gases, the equilibrium relationship is given by
Henry’s law

where:
PA is the partial pressure of the component A in the gas
phase
CA is the concentration of the component in the liquid
H is Henry’s constant.
79
Mechanism of Absorption

80
Diffusion through a stagnant gas
• The process of absorption may be regarded as the diffusion of a soluble gas A into
a liquid.
• The molecules of A have to diffuse through a stagnant gas film and then through
a stagnant liquid film before entering the main bulk of liquid.
• The absorption of a gas consisting of a soluble component A and an insoluble
component B is a problem of mass transfer through a stationary gas to which
Stefan’s law applies:

81
Integrating over the whole thickness zG of the film, and
representing concentrations at each side of the interface by
suffixes 1 and 2:

Since CT = P/RT, where R is the gas constant, T the absolute

temperature, and P the total pressure. For an ideal gas,
then

83
• Writing PBM as the log mean of the partial pressures
PB1 and PB2, then:

• Hence the rate of absorption of A per unit time per unit area is
given by

84
• In the great majority of industrial processes the film thickness is not
known, so that the rate equation of immediate use is
kG is known as the gas-film transfer coefficient for absorption and is a
direct measure of the rate of absorption per unit area of interface with
a driving force of unit partial pressure difference
Diffusion in the liquid phase
• The rate of diffusion in liquids is much slower than in gases, and
mixtures of liquids may take a long time to reach equilibrium
unless agitated
• Whilst there is at present no theoretical basis for the rate of
diffusion in liquids comparable with the kinetic theory for gases,
the basic equation is taken as similar to that for gases, or for
dilute concentrations

86
• Since the film thickness is rarely known, equation is
usually rewritten as

• In equation, kL is the liquid-film transfer coefficient.

For dilute concentrations:

87
Rate of absorption
• In a steady-state process of absorption, the rate of transfer of
material through the gas film will be the same as that through
the liquid film, and the general equation for mass transfer of a
component A may be written as

 where PAG is the partial pressure in the bulk of the gas, CAL is
the concentration in the bulk of the liquid, and PAi and CAi are
the values of concentration at the interface where equilibrium
conditions are assumed to exist. Therefore:

88
These conditions may be illustrated graphically as in Figure,

where ABF is the equilibrium curve for the soluble

component A.

89
90
Relation between film and overall
coefficients

91
92
Rates of absorption in terms of mole
fractions

93
Factors influencing the transfer coefficient
• The influence of the solubility of the gas on the shape of the equilibrium curve, and the effect on
the film and overall coefficients, may be seen by considering three cases in turn—very soluble,
almost insoluble, and moderately soluble gases.
 LECTURE NO. 4

Counter-current multi-stage absorption (Tray absorber)

In tray absorption tower, multi-stage contact between gas and liquid takes
place. In each tray, the liquid is brought into intimate contact of gas and
equilibrium is reached thus making an ideal stage. In ideal stage, average
composition of liquid leaving the tray is in equilibrium with liquid leaving that
tray. The most important step in design of tray absorber is the determination
of number of trays. The schematic of tray tower is presented in figure 4.7.
The liquid enters from top of the column whereas gas is added from the
bottom.
It is desired to absorb 95% of acetone by water from a mixture of acetone and nitrogen containing
1.5% of the component in a countercurrent tray tower. Total gas input is 30 kmol/hr and water
enters the tower at a rate of 90 kmol/hr. The tower operates at 27ºC and 1 atm. The equilibrium
relation is Y=2.53X. Determine the number of ideal stages necessary for the separation using (a)
graphical method
 LECTURE NO. 4

Counter-current multi-stage absorption (Tray absorber)

In tray absorption tower, multi-stage contact between gas and liquid takes
place. In each tray, the liquid is brought into intimate contact of gas and
equilibrium is reached thus making an ideal stage. In ideal stage, average
composition of liquid leaving the tray is in equilibrium with liquid leaving that
tray. The most important step in design of tray absorber is the determination
of number of trays. The schematic of tray tower is presented in figure 4.7.
The liquid enters from top of the column whereas gas is added from the
bottom.
It is desired to absorb 95% of acetone by water from a mixture of acetone and nitrogen containing
1.5% of the component in a countercurrent tray tower. Total gas input is 30 kmol/hr and water
enters the tower at a rate of 90 kmol/hr. The tower operates at 27ºC and 1 atm. The equilibrium
relation is Y=2.53X. Determine the number of ideal stages necessary for the separation using (a)
graphical method
The following parameters should be known for the determination of “number of
stages”
(1) Gas feed rate
(2) Concentration of gas at inlet and outlet of the tower
(3) Minimum liquid rate; actual liquid rate is 1.2 to 2 times the minimum liquid
rate.
(4) Equilibrium data for construction of equilibrium curve Now, the number of
theoretic stages can be obtained graphically or algebraically.
The following parameters should be known for the determination of “number of
stages”
(1) Gas feed rate
(2) Concentration of gas at inlet and outlet of the tower
(3) Minimum liquid rate; actual liquid rate is 1.2 to 2 times the minimum liquid
rate.
(4) Equilibrium data for construction of equilibrium curve Now, the number of
theoretic stages can be obtained graphically or algebraically.
Algebraic Determination of Number of Ideal Stages

If both operating line and equilibrium lines are straight, number of ideal
stages can be calculated algebraically.
Let solute transfers from gas to liquid (Absorption) Equilibrium line, Y=αX
Example Problem 4.2. It is desired to absorb 95% of acetone by water from a mixture of acetone
and nitrogen containing 1.5% of the component in a countercurrent tray tower. Total gas input is 30
kmol/hr and water enters the tower at a rate of 90 kmol/hr. The tower operates at 27ºC and 1 atm.
The equilibrium relation is Y=2.53X. Determine the number of ideal stages necessary for the
separation using (b) Kremser analysis method.
Choice Of Solvent for Absorption

If the principal purpose of the absorption operation is to produce a

specific solution, as in the manufacture of hydrochloric acid, for
example, the solvent is specified by the nature of the product, i.e.
water is to be the solvent. If the principal purpose is to remove some
components (e.g. impurities) from the gas, some choice is frequently
possible. The factors to be considered are:
GAS SOLUBILITY :
The gas solubility should be high, thus increasing the rate of absorption and decreasing the
quantity of solvent required. Solvent with a chemical nature similar to the solute to be absorbed
will provide good solubility.
VOLATALITY :
The solvent should have a low vapour pressure to reduce loss of solvent in the gas leaving an
absorption column.
CORROSIVENESS :
Use of non corrosive material reduce the material cost of the equipment as wwell as
maintenance cost.
COST :
The materials of construction required for the equipment should not be unusual or expensive.
VISCOSITY :
Low viscosity is preferred for reasons of rapid absorption rates, improved flooding characteristics
in packed column, low pressure drops on pumping, and good heat transfer characteristics.
The solvent should be non-toxic, non-flammable and chemically stable.
Design of single stage counter-current flow
absorption tower (packed tower)
• Two common gas absorption equipments are packed tower and plate
tower. Other absorption equipments are, namely, spray column, agitated
contactor, venture scrubber, etc. The gas and the liquid phases come in
contact in several discrete stages. Thus, a stage wise contact is there in a
plate column. But in packed tower, the up-flowing gas remains in
contact with down-flowing liquid throughout the packing, at every point
of the tower. Therefore, packed tower is known as “continuous
differential contact equipment It is different from the stage-wise
distillation column. In the stage distillation column the equilibrium in
each stage will vary not in a continuous fashion whereas in the packed
column the equilibrium is changed point wise in each axial location.
Steps for the design of packed tower

(A) Selection of solvent

(B) Selection of packing
(C) Calculation of minimum solvent flow rate as well as actual solvent flow rate
(D) Column diameter
(E) Height of column
(F) Design of solvent distributors and redistributors (if needed)
(G) Design of gas distributor, packing support, shell, nozzles, column support

(a) Equilibrium data; (b) gas and liquid flow rates; (c) solute concentration in two
terminals; (d) individual and overall volumetric mass transfer coefficients should be
known for the design of a packed absorption tower.
Steps for the design of packed tower

(A) Selection of solvent

(B) Selection of packing
(C) Calculation of minimum solvent flow rate as well as actual solvent flow rate
(D) Column diameter
(E) Height of column
(F) Design of solvent distributors and redistributors (if needed)
(G) Design of gas distributor, packing support, shell, nozzles, column support

(a) Equilibrium data; (b) gas and liquid flow rates; (c) solute concentration in two
terminals; (d) individual and overall volumetric mass transfer coefficients should be
known for the design of a packed absorption tower.
Packing Materials:
Packing materials are utilized to provide large interfacial area of contact
between two phases. These are made from either of ceramics, metals or
plastics. A number of packing materials with various size, shape and
performance are available. These are classified into three types, namely,
dumped or random, structured and grid. The packing materials have
following characteristics:
(a) Cost: The cost of the packing materials should be very low.
(b) Surface area: A large interfacial area of contact is always recommended. In
that case, pressure drop will be more.
(c) Void volume: A high void volume is needed to maintain low pressure
drop.
• (d) Fouling resistance: Packing materials should not trap suspended
solids present in liquid. Bigger packing materials generally give low
fouling resistance.
(e) Mechanical strength: Good mechanical strength is desired for
choosing packing materials as this will not break or deform during filling
or operation.
(f) Uniform flow of streams: Stack of packing materials should have
uniform void spaces through which both the streams (gas and liquid)
can flow uniformly. Non-uniform flow of streams leads to stagnant
liquid pool which in turn gives low mass transfer.