Gas Absorption

During commercial ammonia production, a gas containing about 18% (dry basis) CO2
is generated. This CO2 is to be removed to low levels because it is poisonous to iron
oxide based ammonia synthesis catalyst. How is CO2 removed?
Natural gas is reformed by steam (you will learn more about this in Chemical
Processes course during the next sem=1.5/ester) to make synthesis gas, a mixture
of CO and H2. As sourced from reservoirs, natural gas contains H2S up to few
percent (~3%). H2S is poison to natural gas reforming catalyst; hence it should be
removed to vanishing levels. How is H2S removal accomplished?
Flue gas generated in thermal power plants contains SO2, which is generated due to
oxidation of sulphur in coal. Air pollution control regulations demand that SO2 is
removed before releasing it to the atmosphere. How is flue gas desulphurization
done?
Natural gas described above also contains moisture, which should be separated
before the first step of its processing. How is natural gas dehydrated?
In sulphuric acid production, S and SO2 are oxidized with air. This air should be
supplied bone-dry (no moisture). How is air dehydrated?
...
More examples like above can be cited. In all of the above processes, the gas in
question is contacted with a liquid into which moisture/CO2/H2S are absorbed. If the
concentration of the gas to be removed is high, 10-50%, a non-reactive liquid could be
used. Such liquids are physical solvents. If the gas concentration is low, processes with
physical solvents is not feasible. Hence liquids which react with absorbing gas are used.
Such liquids are called chemical solvents.
If concentration of H2S is high, it can be dissolved in physical solvents such as ethylene
glycol or propylene carbonate. If its concentration is low, chemical solvents such as
monoethanol amine or diethanol amine are used. The liquids after absorbing the gases
are often heated to remove the dissolved gas. Thus, the regenerated liquid could be
used again.
We will start discussion on physical solvents even though gas absorption in chemical
solvents is twenty times more popular than in physical solvents. The latter is covered
after discussion on simultaneous mass transfer and chemical reaction.
Our aim is to design towers that accomplish gas absorption, that is, to remove the
undesirable gas components to low levels. Design involves finding the diameter and
height of the towers.
Gas absorption takes place in packed towers, as shown below. A gas mixture enters the
bottom of the tower and a liquid is passed into the tower from the top. As the liquid
moves down it mops up gas component(s) from the gas moving upward. Typically, the
tower is filled with some packing material to enhance interfacial area between the liquid
and the gas to promote mass transfer rates.

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Some of the packings commonly used in chemical industry are also shown below. They
are characterized by their nominal size. The smaller the nominal size the more the
surface area they offer per unit volume of the tower.

Absorption tower
(from google.com)

Berl Saddles
Raschig Rings

Intalox saddles

Pall Ring

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Hy-Pak Ring

Nutter Ring

Different packings used in chemical industry

Diameter(from
of absorption
towers
google.com)
An experiment is performed with a packed tower containing Intalox saddles. A gas is being
blown from the bottom and a liquid is passed into the tower from the top. Pressure is
measured at the bottom and top of the tower. The gas flow rate is raised gradually while
maintaining a constant liquid flow rate. The recorded pressure drop across the tower is
plotted against gas flow rate below. The different curves represent different liquid flow rates.
The below plot is taken from the website of manufacturer of the packing material, Intalox
saddles. http://www.koch-glitsch.com/Document%20Library/KGIMTP.pdf

Liq in

Gas in

Gas blows
out liq

NO Liq out

FLOODING

Liq in

Gas out
LOADING

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Gas in

Liq out

x-axis is gas flow rate multiplied with square root of its density, y-axis is pressure drop in
inches of water column per foot of the tower (milli bar per meter of the tower).
At low gas velocities, gas channels flows through regions near the walls, usually the void
pace is more there. This flow is not desirable because it does not lead to good gas-liquid
contact, a requirement for high mass transfer rates. This channelling could be observed
experimentally.
As the gas flow is raised gradually, the pressure drop across the tower also increases
forcing the gas to flow through entire tower instead of only through the peripheral areas. The
pressure drop curve shows a change in curvature, a situation referred to as LOADING. The
entire tower is now occupied with gas and liquid with intimate contact between them
promoting interfacial mass transfer.
Beyond loading point, further increase in gas flow, causes drastic rise in pressure drop. In
fact, pressure drop becomes highly sensitive to gas flow. This situation is commonly called
FLOODING where the entire tower if filled with liquid and the gas splashes liquid out of the
tower from the top.
Absorption towers cannot be operated at gas and liquid flows that lead to channelling and
flooding. It is usually operated at 50-80% flooding velocities where the entire tower is
occupied by gas and liquid and rapid mass transfer occurs between them. Sometimes, the
towers are operated so that a specified pressure drop per their unit length is achieved. This
is about 0.6-0.9 inch water column per foot of tower (that is, about 500-750

2
).

The

operating velocities so determined help us calculate the diameter of the tower. The diameter
of the towers is determined by using empirical graphs such as shown below. It is not
possible describe two phase flow in a packed tower accurately; hence empirical relations are
used.

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Image taken from google.com

x-axis is dimensionless. It can be written as

1
2
2
1
2
2

It is square root of ratio of kinetic energy of the liquid to that of the gas. Note that the and
are liquid and mass fluxes, expressed as lb/(ft2 s). y-axis is not dimensionless; it is
dimensional. is lb/(ft2 s); the densities are given in pounds per cubic foot; the viscosity, ,
of the liquid is expressed in centipoises; is 32.2; and the packing factor is inversely
proportional to the packings size. Values of F are listed in Table below. Be careful about
the units when using the graph.

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Height of absorption towers for dilute systems

Absorption towers are designed for the task of removing a component(s) of a gas mixture
present at a known level (could be high or low) to a desirable level (could be few percentage
or ppm). Lets call this component as solute. Gas and liquid flows are known;
concentrations of the solute in inlet and outlet gas streams and inlet liquid stream are given.
Our aim is to find the height of the tower to accomplish the task for a given packing. The
foregoing analysis is for dilute systems; that is, the concentration of solute in inlet gas is low.
Once you understand the derivation for dilute systems, concentration systems can be
analyzed easily.
Since concentrations are changing along the height of the tower, we start by drawing a
differential element in the tower as shown below.

Packing is usually
represented like this

For a control volume extending from the bottom of the tower to the top of the differential
element, , write mole balance for the absorbing component. Draw the control volume first
and then the balance equation. ), is gas flux in units of mole/(cm2 s) or similar units, is
liquid flux in same units as .

This equation is often called operating line, the first key equation in our design. We will use
it frequently while studying distillation.
Extend the top boundary of the control volume to the top of the column to obtain the
following overall mole balance for the solute.

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Now, the concentrations of the solute in the gas and liquid phases at equilibrium are related
as = , where is related to Henrys law. This is second key equation. You need to
be at a bit careful here.Type equation here.
Under what conditions is the above equilibrium relation valid? (When is linear relationship
expected?)

The third and last key equation is obtained by writing a mole balance of the solute across the
differential element:

solute
=
accumulation

solute flow in
solute lost

minus
by absorption
solute flow out

Write the above balance description as an equation. Use overall mass transfer coefficient
for solute absorption, is area available for unit volume of the tower (usually this area is
supplied by manufacturers of packings), is gas flux in units of mole/(cm2 s) or similar units,
is liquid flux in same units as .

Rearrange the third key equation and integrate to find height of the tower. Use the first and
second key equations to obtain integrand in one variable. Do the integration below.

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The final result for height of the tower is:

=

Or
=

The above equation is derived for absorbing a solute from a gas mixture into a liquid. A
similar analysis can be done for stripping a solute from a liquid mixture into a gas. The
above analysis can be extended to concentrated solutions also.

The first term on LHS in the above equation,

has units of length and is called Height of a

Transfer Unit or HTU. HTU signifies rate of mass transfer; the higher the mass transfer rate,
the lower is HTU and thus height of tower.
The term in square brackets,

, called Number of Transfer Units or NTU.

NTU indicates difficulty of separation. The higher the NTU the more difficult is the
separation.
Whats the relation between NTU and Henrys law constant, ?

Would NTU be high or low if more solute is removed?

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Difficulty of separation can be thought about from two angles: low solubility and extent of
separation.

Find the height of a packed tower that uses air to strip H2S out of water stream containing
only 0.2% H2S. In this design, the liquid flow is 58 kg/s, the liquid out contains only 0.017
mol% H2S, the air enters with 9.3% H2S, the entire tower operates at 25 oC. The tower
diameter and the packing are 50-cm and 1.0-cm Raschig rings, respectively, and the air flow
should be 50% of the value at flooding. The value of is 0.23 sec-1 and the Henrys law

constant 2 is 1,440.
2

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A process gas containing 4% chlorine (average molecular weight 30) is being scrubbed at a
rate of 14 kg/min in a packed tower 60-cm in diameter with dilute aqueous solution of sodium
carbonate flowing at a rate of 850 kg/min. 94% chlorine is removed. The Henrys law

constant 2 for this case is 94; the temperature is constant at 10 oC and the
2
pressure is 1500 mm Hg and the packing has a surface area of 82 m2/m3. If the overall
mass transfer coefficient is 2 x 10-6 gmol/(s cm2), find the height of the tower.

Mention three reasons for the exiting gas to have >6% of chlorine entering the tower.
1.
2.
3.

Calculate heights for 95% and 96% removal of chlorine. What is your conclusion regarding
the height of tower and percentage removal?

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How can more chlorine be removed in the existing tower? What are the consequences of
making changes for absorbing more chlorine?

Design of towers in which concentrated vapours (>20% of solute) follows the same lines as
design of dilute vapour.

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An absorption tower is being designed to remove ammonia from air containing only 3% of
that gas. The air leaves the tower with 0.3% ammonia. The liquid which absorbs ammonia
is free of that gas as it enters the tower. A schematic of the tower is shown below.
Equilibrium between ammonia in air and water is represented as = 0.85.
, =0

, = 0.003

, = 0.03

Write mole balance of ammonia over the control volume extending from the bottom of the
tower to the top of the differential element shown above. This is equation of operating line.

Draw equilibrium line and operating line on the same plot.

Recall that Number of Transfer Units (NTU ) is

. Shade the region representing

NTU on the plot.

What happens to NTU and, thus the height of the tower, if the ratio L/G is reduced?
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Could you identify a limit for this ratio? Whats the significance of this limit?

Write an equation for this limit for absorption of ammonia in terms of

and .

If H2S is to be removed from natural gas by absorbing it in water, what is (L/G)min? Henrys
law for H2S in water is = 545. This removal is one of the first steps in the commercial
production of ammonia and methanol.

SO2 is another gas with high value of m. This gas is present in flue gas emanating from
power plants and also in exit gas of sulphuric acid plants. Its concentration in air is to be
regulated to prevent acid rain.
Two experiments are performed for dissolution of sulphur dioxide (SO2): one in water and
another in dilute aqueous solution of NaOH as shown in Figures below. It is known that the
dissolution of SO2 in pure water is controlled by liquid phase. Table below shows the results
ratio of fluxes at several [NaOH].

[NaOH], mol/L
0.0
0.01
0.1
0.5
2.0

Flux of SO2 with NaOH

Flux of SO2 without NaOH
1
1.4
4.5
16
16

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It is known that SO2 reacts irreversibly with NaOH according to:

SO2 + 2NaOH

Na2SO3 + H2O

Mixture of SO2 in air

Mixture of SO2 in air

Pure water initially;

water is well-mixed
A

Dilute aqueous
solution of NaOH;
solution is wellmixed

Results similar to those shown in above Table are also obtained for other reacting systems.
Such systems are more common in chemical industry than systems where physical
absorption of solutes occurs. H2S is absorbed in aqueous solutions of ethanol amines; CO2
is absorbed in aqueous solutions of ethanol amines and carbonate solutions. SO2 is
removed from flue gas through the use of reactive solvents etc.
What do we want to study for such systems? (Hint: write an equation for mass flux of SO2
and then answer the question)

Mass Transfer with Chemical Reaction

Chemical reactions improve liquid-side mass transfer co-efficient. We will invoke two-film
theory to study the effect of reactions on mass transfer. Research into these effects began
in late 1950s, flourished in 1960s and tapered down later. For this course we will look at a
couple of limiting cases; these provide us an insight into the effects and those who get
involved in reactive systems later in professional life can study them in detail.

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Mass transfer with instantaneous and irreversible second-order chemical reaction

Analysis of the effect of chemical reaction is one utility of two-film theory for mass transfer.
When the reaction between dissolved gas and a liquid component is instantaneous, they
cannot exist. This statement is shown below in the liquid film.

c2 = c2L
Reaction
c1i

front

c1=0
=
=0

=
Liquid film

It is hypothesized that there exists a reaction front within the liquid film such that to the right
side of the front, no dissolved gas exists and to the left side of the front no reacting
component of the liquid does not exist. For the reaction,

Species
Species
+
1
2

Species
3

The diffusive flux of species 1 to the reaction front must equal the diffusive flux of species 2,
adjusted by the stoichiometric factor, .
Diffusive flux of species 1 to the front is: 1 = ________________________________
Diffusive flux of species 2 to the front is: 2 = ________________________________
How are the two fluxes related? (For every one mole of species 1 diffusing to the front, how
many moles of species 2 have to diffuse to the front?)

Eliminate and write an equation for 1 as a factor multiplied by

c1i

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1 =

The factor is the new mass transfer coefficient. Recall that that the mass transfer coefficient
without chemical reaction, = , we have

The RHS is also called the enhancement factor. The reaction kinetics do not alter the
enhancement factor because reactions are instantaneous and the system is limited by how
fast the species diffuse to the front. Enhancement factors can be derived for penetration and
surface renewal theories as well. They usually do not bring any new insights into the effects
of reaction on mass transfer.

Derive an overall mass transfer coefficient for absorption of SO2 in dilute aqueous solutions
of NaOH. Reaction between these two species is instantaneous.

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________________________________________________________________________
Below discussion is not included in your portion
Industrial Gas Treating
The common gases that are removed by reactive liquids are hydrogen sulphide
(H2S), carbon dioxide (CO2) and sulphur dioxide (SO2). H2S is present in small quantities in
natural gas and for reasons discussed earlier, physical solvents are not feasible. CO2 is to
be removed in the manufacture of ammonia to vanishing levels. SO2 is produced during
burning of fuels containing sulphur. More than 90% removal of this gas is desired.
All of the above gases have low solubility in general solvents such as water.
Pressurizing them to improve the absorption rates is not economically viable. If
concentration of these gases is high (20% is a good number), physical solvents can be used.
As the concentration gets lower, physical solvents cannot be used.
We will study removal of H2S by reactive liquids. This is discussed in the textbook in
detail.
Reactive liquids, amines in the case of H2S, alter the equilibrium line also. When
amines are added to water, H2S reacts with them according to:
2

+ + and =

+
2

This is a reversible reaction for which we didnt discuss the enhancement in mass transfer.
It is given in the text book but not derived there, too.
At pH greater than 10, most of H2S exists as HS- in water. It is expected that the
concentration of hydrogen sulphide in water is proportional to its concentration in the gas:

2 = 2 =

is Henrys law constant and is total concentration in the liquid. It can be shown that
2 =

Where is total amine concentration such that = + + .

The plot below shows that the reaction of H2S with amines conforms to instantaneous
regime:
with reaction

=1+
without reaction
2 2

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H2S flux

15
10
5
0
0

0.5

1.5

Amine concentration, mol/liters

We need to use these equations in conjunction with mass balance equation to find the
height of the tower. Interested students should read the text book for description on
absorption of CO2.

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Key Points on Gas Absorption/Stripping

The main gases that are absorbed in chemical processes are H2S and CO2. Of
course, a myriad other gases such mercaptans, water vapour are also absorbed.
Towers that operate for gas absorption/stripping are filled with packing material to
enhance interfacial area between gas and liquid phases.
The packing materials lead to higher pressure drop across the towers; this drop is
dependent on the type of packing and its size. The smaller the packing of certain
type, the higher is the pressure drop.
At a certain liquid flow, low gas flows lead to channelling where the mixing of liquid
and gases is far from perfect. This condition is undesirable. At higher flows,
pressure drop rises and the tower gets loaded with gas and liquid with good contact
between them. At still higher flows, the tower is floodedpressure drop rises
drastically, liquid is splashed out of the column. This condition too is undesirable.
Diameter of the tower is determined by fluid mechanics. The procedure is empirical
resulting from experience of many engineers over many years. Be careful about this
procedure. The only thing difficult about the procedure is the units. Solve a few
problems to become familiar with the units and the procedure.
Diameter of the tower is determined either for specified pressure drop across it or for
a specified percentage flooding. This percentage is typically between 50-75%.
Become comfortable about writing design equations for determining height of the
tower for absorption of dilute vapour. Extension too concentrated vapour is not
difficult.
Key equations for finding height of tower: a) operating line, b) equilibrium line (curve)
and c) mass balance in differential element in the tower.
Equations for removing a component from a liquid are along same lines as equations
for gas absorption.
Height of the tower is written as the product of Height of a Transfer Unit () and
Number of Transfer Units (). = ; HTU signifies rate of mass
transfer. A small HTU is a sign of a good tower. NTU shows how easy or difficult is
the separation. High NTU means difficult separation.
Reactions enhance mass transfer coefficients. They also provide increased driving
forces. Thus they improve overall mass transfer rates.
Industrially important systems that fall under mass transfer with chemical reaction
are: absorption of H2S and CO2.
We considered a couple limiting cases for mass transfer with chemical reaction
reactions that are fast and instantaneous.
Design of towers with reactive liquids follows the same lines of design with physical
solvents. Alteration of equilibrium line by the reactive liquids and enhancement of
should be considered, however.

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