Absorption

Definitions

Absorption is a unit operation in which one or more

selected components, the solute or solutes, are removed
from a gas mixture (solute + carrier gas), by contacting it
with a nonvolatile liquid stream, called solvent.

Since the carrier gas is assumed to be insoluble in the

solvent, only the solute "moves" to the solvent.
Mass transfer of solute to the solvent is due to its
greater affinity towards the liquid phase compared with
the gas phase. The transport of the solute requires that
the two phases are in contact for a certain contact-time.
The affinity can have physical or chemical nature. In the
latter case a reaction is present between solute and
solvent termed as chemical absorption..

 An example of this is the removal of CO2 or H2S removal by

NaOH through reversible reaction.
An irreversible reaction occurs when using MEA
(monoethanolamine) instead of NaOH.

In the case of irreversible reactions, the resulting solvent must

be disposed of, whereas in reversible reactions, the solvent
can be regenerated. Therefore, reversible reactions are often
preferred.
In physical absorption only physical interactions are present
between solute and solvent.
An example is the transport of acetone from an air stream to
a water stream. The acetone dissolves into the water while
the air passes out

Process description
A gas and liquid stream are put in contact in a
counter current configuration

The gas enters the column at its bottom with a

solute concentration yn+1 and a flow rate of G
The liquid enters the column at its top, flowing by
gravity through the column. L is the flow rate and
x0 is its initial solute concentration
The two streams exchange matter during the
contact along the whole length of the column and
leave the column at the opposite side.
In absorption process, the solute moves from the
gas to the liquid stream

The gas leaves the column at its top with a concentration

of y1 different from the initial concentration yn+1
G y1

L x0

The liquid enters the column at its top with an initial

composition of x0 leaving at the bottom with composition
xn

Stage 1

Since the two streams exchange solute, in absorption

process, y1<<yn+1 and xn>>x0, since the solute moves from
the gas to the liquid stream

Stage i

Stage n

G yn+1

L xn

The mass transfer and the change in the composition of

the two stream take place step by step during their
contact along the column.
The column can be seen as a cascade of separated steps
called stages going from 1 to n

The thermodynamic conditions of the column (temperature T and

pressure p) determine the mass transfer for a certain system and have
an effect on the equilibrium in between the two streams.

When mass transfer takes place, a certain amount of energy is

generally involved. If this energy is significant, the temperature of the

liquid or gas stream changes. The process is not isothermal anymore,
making the modeling of the operation much more complicated.
Fortunately, in most of the cases, we can neglect the temperature

change effect, allowing us to design a simpler process.

Solvent Selection
A solvent is selected based on the following criteria:
Absorption Capacity
For a given degree of separation, the required amount of solvent depends
on the absorption capacity of the solvent. High capacity means that the

amount of required solvent is low and vice versa.

When the solvent reacts with the solute (chemical absorption), the
capacity of absorption is high, but this reaction must be reversible
(under certain conditions such as at an elevated temperature).

Otherwise the solvent cannot be regenerated (refer to plant

regenerations operation).

b) Selectivity

The 'selectivity' is an important factor when the process deals with the
separation of one or more components from a mixture of gases.
Only when the solvent has more affinity for the components to be
separated, the process can be successful.

c) The solvent regeneration process

Since the solvent is usually recycled, regeneration of it should be taken
into account: the relative easy of regeneration may determine the

selection of the solvent.

In the case of an absorption column. A gas stream has been purified with a
suitable solvent.

But what will be about the polluted solvent? besides how expensive
would the absorption operation be if "fresh and cleaned" solvent is to be
used always?
An appropriate approach to this would be regeneration of the liquid
solvent and recycle it to the absorption column.

This is done by a stripping operation. Therefore, most of the time an

absorption operation often is couples with a stripping counterpart.

Different plant configurations are possible depending on the nature and

difficulty of the solvent regeneration.

 Thermodynamic aspects (desorption temperature or

decomposition temperature of the solvent), solvent volatility, and

chemical/physical aspects like corrosiveness, viscosity, toxicity, as

well as costs, are taken into account when choosing the solvent for
a specific absorption process keeping regeneration in mind.
When solvent volatility is very low, i.e. solvent is not present in the
gas stream, a simple regeneration process by heating is adequate.
The system looks then very simple.

Assumptions
To approach the study of the absorption/stripping operation, a certain
number of assumptions are needed in order to simplify the design
and easily understand the basics concepts:

 In reality, most of the time, the above assumptions about gas

and liquid streams are true.
However different options can be considered for the solute,
the equilibrium, and the temperature, i.e. multicomponent,

nonlinear equilibrium, nonisothermal operation.

In every section, a table shows the assumptions valid for the

case study taken under consideration

The liquid-vapor equilibrium

Linear Equilibrium

Typically in an absorption or stripping

problem the solute, which has to be

removed, is present in the liquid or in gas

phase at very low concentration (<1%). The
Henry's law is therefore used to represent
the equilibrium correlation for a solute A
between the gas and the liquid phase.

yA = m xA where m = H/Ptotal

In the x-y composition diagram the

equilibrium correlation is represented as
follows

Non-linear Equilibrium

In the range of concentration when

Henry's law can not be applied
anymore (xA>1%), the relationship in
between y and x is not linear but more
in general a curve, expressed as:

yA = f(xA)
which in the same mole fraction
composition diagram will give a curve:

Mole ratios vs. mole fractions in the equilibrium representation

Besides the mole fraction, there are others ways to express

the gas and the liquid composition. In some cases it can be
more useful to express it with the mole ratios:

 Mole fractions and mole ratios are linked with the

following relationships:
mole fraction = f (mole ratio)

mole ratio = f (mole fraction)

 If the equilibrium is a straight line y=mx in the mole fraction plan

x-y , it will be a curve Y=f(X) in the mole ratios plan X-Y:

However in most of the cases, we are in the condition of infinite

dilution of the solute (very low concentration). In this case the
following simplification can be done:

xiXi; yiYi
which allows us to assume a linear equilibrium in the (x-y) or (X-Y)
plan.

This is of a key importance to simplify the application

of the McCabe-Thiele graphical methods for the
design of an absorption or a stripping process.

Single Stage
During the absorption operation, the gas phase and the liquid
phase must be in contact.

The solute contained in G transfers to the liquid phase L. The

concentration in the gas decreases while the concentration in
the liquid increases.
The pairs of points (concentration of solute in the gas and
liquid phases) at each moment constitute the operating line.

Mass transfer ends when equilibrium is reached. Graphically, it means

that the operating line crosses the equilibrium line. The driving force for
absorption can be qualitatively seen as the distance between the
equilibrium and operating line. Therefore, when the two lines cross, the
driving force is zero.

Calculation for Single Stage

Mass balance :

L0 + G2 = L1 + G1
Mass balance for component A:

Calculation for Single Stage Equilibrium

In gas-liquid system, solute A in the gas phase G along
with inert air and in the liquid phase L with inert water
Since component A can be redistributed into G and L, the
balance of A can be written as:

Where L= moles of inert water and G = moles of inert air

 To solve the above equation, the relation between

yA1 and XA1 is given by Henrys Law
yA1 = m xA1 where m = H/Ptotal

Example
A gas mixture at 1.0 atm pressure containing air and CO2 is
contacted in a single stage mixer continuously with pure water
at 293K. The two exit gas and liquid streams reach equilibrium.
The inlet gas flow rate is 100 kg mol/h with a mole fraction of

CO2 of yA2 = 0.20. The liquid flow rate entering is 300 kg mol/h.
Calculate the amount and compositions of the two outlet phase
assuming that

water does not vaporise to gas. The Henry

constant, H, for CO2 at 293K is 1420 atm/mol fraction.

ANSWER: xA1 = 1.41 x 10-4

yA1 = 0.20

Multiple Stages
Multiple ideal stages in different configurations.
The assumptions remain the same as in the ideal equilibrium stage
case.
As discussed before, the main characteristic of an ideal stage is that
the gas and liquid going out of it are at equilibrium, this means that

point (x1, y1) in the x-y-diagram is on the equilibrium curve. The

solvent cannot take more solute.
Depending on the disposition of the liquid and gas streams there are
three possible configurations:

 Co-current cascade

Cross-current cascade

Counter-current cascade

 Comparison
To compare the different configurations, co-, crossand counter-current, the fraction of absorption is
used.

Co-current cascade configuration

When the gas flow is parallel to the solvent flow in a cascade
of ideal stages, only the first stage is effective.
The solvent flow is at equilibrium with the gas at the outlet.
This means that the concentration of solute in the solvent is
maximal and, at the same conditions of temperature and

pressure, the absorption operation cannot be more

effective.
There is no driving force at equilibrium.

A cascade of single stages, all of them at the same conditions, is

then equivalent to one single stage.

Cross-current cascade configuration

n this case the solvent stream is divided in n streams before

entering the n stages of the cascade. The solvent flows in crosscurrent configuration to the gas flow.
At every stage the solvent that comes in is fresh. The solvent
coming out is at equilibrium with the gas stream and is not driven

to another stage but collected and mixed with the other solvent
outlets.
That way, the performance of the operation is improved in
respect to a single stage or to a co-current cascade.

Each step has a different operating line, since the conditions

of the concentration in the gas change. The slope of the
operating line is constant, since we consider variations on the
gas flow not being significant and the amount of solvent is
kept constant.

Counter-current cascade
configuration
In that configuration the gas flows in the opposite direction
to the solvent. The gas, rich on pollutant at the entrance, is
put in contact with the solvent already charged of pollutant
(outlet). On the contrary, on the other bottom, the gas now
poor on pollutant is put in contact with the clean solvent.
This is the characteristic of any counter-current process,
and is convenient because the driving force is nearly
constant along the cascade (the operation). On the diagram
the driving force is represented qualitatively by the
distance between the equilibrium and the operating lines.

Overall Mass balance

Let's consider an absorption case. In the most typical configuration the
gas and the liquid enter and leave the column at opposite ends (counter-

current configuration).
The gas enters from the bottom with flow rate G1 and contains a certain
amount of solute yn+1

The liquid enters from the top with flow rate L0 and can contain also some
solute with composition x0
The two streams come in contact during their passage through the column,
exchanging matter.
The gas leaves at the top with flow rate G2 but contains still a certain
amount of solute y1.
The liquid leaves at the bottom with flow rate L1 and it contain now solute
with composition xn.

The overall mass balance around the column:

The amount of solute entering the column, with both gas and
liquid streams, must be equal to the amount of solute leaving the

column with both streams.

This can be written as:

L x0 + G yn+1 = L xn + G y1

Mass balance at stage i

For convention, we use the composition of a stream

leaving the stage with a index, which is the same as the
name of the stage. For the generic stage i, it is then
(refer to the figure):
Composition of the gas entering stage i: yi+1
Composition of the liquid entering stage i: xi-1
Composition of the gas leaving stage i: yi
Composition of the liquid leaving stage i: xi
Same as the overall material balance, mass balance
around stage i must be fulfilled.
Mass balance around the section going from stage 1
and stage i is then:

L0 x0 + Gi+1 yi+1 = Lixi + G1 y1

 which solved for yi+1 gives:

Mass balances allow us to relate stream flow rates and

compositions of the two streams exchanging matter
along with the external known compositions with the
internal unknown compositions. For this reason, mass
balances are a powerful tool for process design purposes.

Operating line
The operating line is the points of compositions (xi, yi+1), where xi and yi+1 are
respectively the compositions of liquid and gas stream exchanging matter

in the generic stage i, as shown in the figure below:

(xi, yi+1) are correlated by the mass balance at the stage (i+1):

In the x-y diagram this correlation can be represented by a straight line

with slope L/G and it is known as operating line.

 In general the ratio L/G is not constant since during the

process the solute moves from one phase to another, hence
modifying the flow rates of both the liquid and the gas phase.

However in the condition of infinite dilution of the solute

(very low concentration), the amount of absorbed solute is so
small that its passage from one stream to the other doesn't
impact significantly the flow rates of the two involved
streams.

 Therefore the liquid and gas flow rates can be considered

constant and the equation is represented in the x-y plan
as a straight line:

 The equilibrium and operating lines are constructed as follows:

Example
It is desired to absorb 90% of the acetone in a gas containing 1 mol% of

acetone in air in a counter current stage tower. The total inlet gas to the
tower is 30.0 kg mol/h and the total inlet pure water flow to be used to
absorb acetone is 90.0 kg mol water/h The process is to operate

isothermally at 300K and a total pressure of 101.3kPa. The equilibrium

relation for the acetone in the gas-liquid is yA = 2.53xA. Determine the
theoretical stages required for this separation.

ANSWER: About 5.2 stages

Additional information:
Read ABS3500-2