SEPARATION PROCESSES

Gas Absorption

2
 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.

• 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

3
• 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.

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 Conditions of Equilibrium between Liquid and Gas

• 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

5
• 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
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• 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.
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Mechanism of Absorption

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 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:

9
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

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• 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

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 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

12
• Since the film thickness is rarely known,
equation is usually rewritten as

• In equation, kL is the liquid-film transfer

coefficient. For dilute concentrations:

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Packed Towers for Gas Absorption
 Absorption …… Packed Tower

 Cylindrical column or tower

 Gas and liquid inlet

 Distribution space and Distributors

 Gas and Liquid outlets

 Tower packing

 Packing support

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 Absorption …… Packed Tower

 Weak Liquor

 Strong Liquor

 Rich gas

 Dilute or lean gas

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17
 Characteristics of tower packings

• Large surface area

• Uniform flow of the gas and the liquid
• Void volume
• Mechanical strength
• Fouling resistance

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 Types of Packing
 Dumped or Random Packing

 Structured or Ordered Packing

 Grid

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 First generation random packings

These are mostly packed

randomly; stacked packings
are used in only a few cases

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Second generation random packings

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Third generation random packings

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Structured Packings

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Structured Packings

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• The size of packing used influences the height and diameter of a
column, the pressure drop and cost of packing.

• Generally, as the packing size is increased, the cost per unit volume
of packing and the pressure drop per unit height of packing are
reduced, and the mass transfer efficiency is reduced.

• Reduced mass transfer efficiency results in a taller column being

needed, so that the overall column cost is not always reduced by
increasing the packing size.

• Normally, in a column in which the packing is randomly arranged, the

packing size should not exceed one-eighth of the column diameter.

• Above this size, liquid distribution, and hence the mass transfer
efficiency, deteriorates rapidly
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 Packing Support and Gas Distributor

Support plate or grid has three functions

1. It supports the weight of the packing and the liquid

held up in the packing during operation

2. It allows the gas to flow through it and to get

distributed.

3. It allows the liquid to leave the bed.

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 Types of Support Grid

• Gas injection grid

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 Types of Support Grid
Grid Support
• Free area of 95% is attainable
• Suitable for clean liquids and large diameter columns
• Handle moderate to large vapor rates

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 Liquid Distributors
• At the top of the packed bed a liquid distributor of suitable
design provides for the uniform irrigation of the packing
which is necessary for satisfactory operation.

• Uniform liquid flow is essential if the best use is to be made of

the packing and, if the tower is high, re-distributing plates are
necessary.

• A “hold-down” plate is often placed at the top of a packed

column to minimize movement and breakage of the packing
caused by surges in flowrates.

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A simple orifice type which gives very fine distribution though it
must be correctly sized for a particular duty and should not be
used where there is any risk of the holes plugging.

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The notched chimney type of distributor, which has a good range
of flexibility for the medium and upper flowrates, and is not
prone to blockage

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The notched trough distributor which is specially suitable for the
larger sizes of tower, and, because of its large free area, it is also
suitable for the higher gas rates

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• The perforated ring type of distributor for use with absorption columns
where high gas rates and relatively small liquid rates are encountered.
• This type is especially suitable where pressure loss must be minimized.
For the larger size of tower, where installation through manholes is
necessary, it may be made up in flanged sections.

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 GENERAL DESIGN CONSIDERATIONS
Absorber design or analysis requires consideration of the following factors:

1. Entering gas (liquid) flow rate, composition, T, and P

2. Desired degree of recovery of one or more solutes
3. Choice of absorbent
4. Operating P and T, and allowable gas pressure drop
5. Minimum absorbent flow rate and actual absorbent flow rate
6. Heat effects and need for cooling (heating)
7. Number of equilibrium stages and stage efficiency
8. Type of absorber equipment (trays or packing)
9. Need for redistributors if packing is used
10.Height of absorber
11.Diameter of absorber
 Choice of Absorbent
The ideal absorbent should have

1. a high solubility for the solute(s)

2. a low volatility to reduce loss
3. stability and inertness
4. low corrosiveness
5. low viscosity and high diffusivity
6. low foaming proclivities
7. low toxicity and flammability
8. availability, if possible, within the process
9. a low cost.
Rate of Absorption
 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:

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These conditions may be illustrated graphically as in Figure,

where ABF is the equilibrium curve for the soluble

component A.

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40
 Overall coefficients

• In order to obtain a direct measurement of the values of kL and kG

the measurement of the concentration at the interface would be
necessary. These values can only be obtained in very special
circumstances, and it has been found of considerable value to use
two overall coefficients KG and KL defined by:

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Relation between film and overall
coefficients

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43
Rates of absorption in terms of mole
fractions

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ABSORPTION ASSOCIATED WITH
CHEMICAL REACTION
• In the absorption of carbon dioxide by caustic soda, the
carbon dioxide reacts directly with the caustic soda and
the process of mass transfer is thus made much more
complicated.

• Again, when carbon dioxide is absorbed in an

ethanolamine solution, there is direct chemical reaction
between the amine and the gas.

• In such processes the conditions in the gas phase are

similar to those already discussed, though in the liquid
phase there is a liquid film followed by a reaction zone.

46
• Considered a case in which chemical reaction is irreversible and of
the type in which a solute gas A is absorbed from a mixture by a
substance B in the liquid phase.

• As the gas approaches the liquid interface, it dissolves and reacts at

once with B.

• The new product AB, thus formed, diffuses towards the main body
of the liquid.

• The concentration of B at the interface falls; this results in diffusion

of B from the bulk of the liquid phase to the interface.

• Since the chemical reaction is rapid, B is removed very quickly so

that it is necessary for gas A to diffuse through part of the liquid
film before meeting B. 47
• There is thus a zone of reaction between A and
B which moves away from the gas-liquid
interface, taking up some position towards the
bulk of the liquid.

• The final position of this reaction zone will be

such that the rate of diffusion of A from the
interface is equal to the rate of diffusion of B
from the main body of the liquid.
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ABSORPTION ASSOCIATED WITH
CHEMICAL REACTION

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50
• For transfer in the gas phase

• In the liquid phase

• The effect of the chemical reaction is to

accelerate the removal of A from the
interface, and supposing that it is now r times
as great then

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• The concentration profile through the liquid film of thickness zL
is represented by a straight line such that kL = DL/zL.

• In b, component A is removed by chemical reaction, so that the

concentration profile is curved.

• The dotted line gives the concentration profile if, for the same
rate of absorption, A were removed only by diffusion.

• The effective diffusion path is 1/r times the total film thickness
zL.

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53
• Figure 12.12 illustrates three conditions:

(a) If k2 is very small, r=1, and conditions are those of physical

absorption.

(b) If k2 is very large, r=CBL/iCAi , and the rate of the process

is determined by the transport of B towards the phase
boundary.

(c) At moderate values of k2, r=(jDLCBL)1/2/kL, and the rate of the

process is determined by the rate of the chemical reaction.

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Capacity of Packed Towers
 Capacity of Packed towers
• Figure illustrates the conditions that occur during the steady
operation of a countercurrent gas–liquid absorption tower.

• It is convenient to express the concentration of the streams in terms

of moles of solute gas per mole of inert gas in the gas phase, and as
moles of solute gas per mole of solute free liquid in the liquid
phase.

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 • On this basis the general equation, for mass transfer

Can be written as:

The actual area of interface between the two phases is not known, and the term a is
introduced as the interfacial area per unit volume of the column

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Height of column based on conditions in the
gas film

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59
 Height of column based on conditions in liquid film

• A similar analysis may be made in terms of the liquid film.

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61
Height based on overall coefficients

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 The operating line and graphical integration for the
height of a column

• Taking a material balance on the solute from the bottom of the

column to any plane where the mole ratios are Y and X gives for
unit area of cross-section:

• This is the equation of a straight line of slope Lm/Gm, which

passes through the point (X1, Y1). It may be seen by making a
material balance over the whole column that the same line passes
through the point (X2, Y2). This line, known as the operating line,
represents the conditions at any point in the column.
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64
• The equilibrium curve is represented by the line FR, and the
operating line is given by AB, A corresponding to the
concentrations at the bottom of the column and B to those at
the top of the column.

• D represents the condition of the bulk of the liquid and gas at

any point in the column, and has coordinates X and Y .

• Then, if the gas film is controlling the process, Yi equals Ye,

and is given by a point F on the equilibrium curve, with
coordinates X and Yi . The driving force causing transfer is
then given by the distance DF.

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• It is therefore possible to evaluate the expression:

by selecting values of Y , reading off from the Figure the

corresponding values of Yi, and thus calculating 1/(Yi − Y). It
may be noted that, for gas absorption, Y > Yi and Yi − Y and dY in
the integral are both negative.

• If the liquid film controls the process, Xi equals Xe and the driving force
Xi − X is given in Figure 12.19 by the line DR. The evaluation of the
integral:

may be effected in the same way as for the gas film.

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 The Transfer Unit

• The group (dy/ye − y), has been defined by CHILTON and

COLBURN as the number of overall gas transfer units NOG.

• The application of this group to the countercurrent conditions

in the absorption tower is now considered.

• Over a small height dZ, the partial pressure of the diffusing

component A will change by an amount dPAG. Then the moles
of A transferred are given by:

(change in mole fraction) × (total moles of gas)

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The number of overall gas transfer units NOG is an integrated value of
the change in composition per unit driving force, and therefore
represents the difficulty of the separation.

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69
• Thus, equation 12.77 may lead to the use of an integral which
is difficult to evaluate graphically because of the very steep
slope of the curve.

• In these circumstances, the new form of the integral is much

more readily evaluated. Equation 12.77 may be written as:

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• In this analysis, it is assumed that the total number of moles of
gas and liquid remain the same. This is true in absorption only
when a small change in concentration takes place.

• With distillation, the total number of moles of gas and liquid

does remain more nearly constant so that no difficulty then
arises
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 Special case when equilibrium curve is a
straight line

• If over the range of concentrations considered the

equilibrium curve is a straight line, it is permissible to
use a mean value of the driving force over the
column.

• For dilute concentrations, over a small height dZ of

column, the absorption is given by:

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73
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• It is of interest to note from Figure 12.20, that, as long as the ratio kL/kG remains
constant (that is, if the slope of DE is constant), then the ratio of DQ, the driving
force through the gas phase, divided by DF, the driving force assuming all the
resistance to be in the gas phase, will be a constant.

• Thus, the use of the driving force DF is satisfactory even if the resistance does not
lie wholly in the gas phase. The coefficient kG on this basis is not an accurate value
for the gas-film coefficient, although is proportional to it. It follows that, if the
equilibrium curve is straight, either the gas-film or the liquid-film coefficient may be
used.

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The importance of liquid and gas flowrates and the slope of
the equilibrium curve
• For a packed tower operating with dilute concentrations, since x X1
and y Y1, then:

where, as before, x and y are the mole fractions of solute in the liquid and gas
phases, and Gm and Lm are the gas and liquid molar flowrates per unit area on a
solute free basis.

• A material balance between the top and some plane where the
mole fractions are x, y gives:

• If the entering solvent is free from solute, then x2 = 0 and:

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• But the number of overall transfer units is given by:

• For dilute concentrations, Henry’s law holds and ye = mx.

Therefore:

COLBURN has shown that this equation may usefully be plotted as shown in
Figure 12.23 which is taken from his paper.
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• In this plot the number of transfer units NOG is shown for values
of y1/y2 using m(Gm/Lm) as a parameter and it may be seen that
the greater m(Gm/Lm) the greater is the value of NOG for a given
ratio of y1/y2.

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Fluid flow in Packed Columns

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Bed Pressure drop and Phenomena of
Loading and Flooding

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ROSE and YOUNG correlated their experimental
pressure drop data for Raschig rings by the following
equation

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• Another approach is that of MORRIS and JACKSON who
arranged experimental data for a wide range of ring and grid
packings in a graphical form convenient for the calculation of
the number of velocity heads N lost per unit height of
packing. N is substituted in the equation:

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Generalized Pressure drop correlation

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85
86
 Liquid distribution

• Provision of a packing with a high surface area per

unit volume may not result in good contacting of gas
and liquid unless the liquid is distributed uniformly
over the surface of the packing.

• The effective wetted area decreases as the liquid rate

is decreased and, for a given packing, there is a
minimum liquid rate for effective use of the surface
area of the packing
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• A useful measure of the effectiveness of wetting of the
available area is the wetting rate LW defined as:

• Thus the wetting rate is analogous to the volumetric

liquid rate per unit length of circumference in a
wetted-wall column in which the liquid flows down the
surface of a cylinder.
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• A Nomograph which relates liquid rate, tower diameter and
packing size is given in Figure 4.19. The wetting rate LW may be
obtained as an absolute value from the inner right-hand axis
or as wetting fraction from the outer scale

• A value of wetting fraction exceeding unity on that scale

indicates that the packing is satisfactorily wet.

• It should be noted that many organic liquids have favorable

wetting properties and wetting may be effective at much
lower rates, though materials such as plastics and polished
stainless steel are difficult to wet.

• Figure 4.19 does, however, represent the best available data

on the subject of wetting.
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93
 Hold-up
• In many industrial applications of packed columns, it is
desirable to know the volumetric hold-up of the liquid phase
in the column.
• For gas–liquid systems the hold-up of liquid HW for conditions
below the loading point has been found to vary approximately
as the 0.6 power of the liquid rate, and for rings and saddles
this is given approximately by:

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 Economic design of packed columns
• In designing industrial scale packed columns a balance must
be made between the capital cost of the column and ancillary
equipment on the one side, and the running costs on the
other.

• Generally, reducing the diameter of the column will reduce

the capital cost though increase the cost of pumping the gas
through the column due to the increased pressure drop.

• In selecting a gas velocity, and hence the column cross-

sectional area, it is necessary to check that the liquid rate is
above the minimum wetting rate, as discussed in the previous
section
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• Selection of the appropriate packing will help in achieving the
minimum wetting rate.

• The loading condition should also be calculated to ensure that

the column would not be operating above this condition.

• For columns operating at high pressures, the capital cost of

the column shell becomes much more significant and it may
be more economic to operate at gas velocities above the
loading condition.

• MORRIS and JACKSON suggest a gas velocity about 75–80

percent of the flooding velocity for normal systems, and less
than 40 per cent of the flooding rate if foaming is likely to
occur.
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Effect of Pressure
Temperature Variations