Absorption operations

Gas absorption is a unit operation in which one or more

soluble components of a gas mixture are dissolved in a
liquid
Stripping is an inverse operations performed when it is
desired to transfer a volatile component from a liquid into a gas
Absorption operations
Examples:

- NH3 is removed from oven gas by water

- CO2, H2S are removed from natural gas using
water solutions of alkaline salts

- Benzene, toluene are removed from natural gas
using hydrocarbon oil
Absorption operations
Equilibrium relations for dilute solutions:
solubility
- The maximum amount of the gas that can be dissolved in
a solvent at specific conditions (T,P) is called solubility
Equilibrium relations for dilute solutions:
Henrys law
A A A
x T H Py p ) ( = =
Henrys law is valid for dilute solutions,
where A does not ionize, dissociate or
react in the liquid phase
For water H [atm/mole fraction]
Equilibrium relations for dilute solutions:
Henrys law
A A A
x T H Py p ) ( = =
Henrys law is valid for dilute solutions,
where A does not ionize, dissociate or
react in the liquid phase
For water H [atm/mole fraction]
Equilibrium relations for dilute solutions:
Solubility data
Absorption: Design considerations
Va, ya
La, xa
Vb, yb
Lb, xb
Plate 1
Plate 2
Plate n
Plate N
L1 x1
V2 y2
L2 x2
V3 y3
Plate 3
L(n-1) x(n-1)
Vn yn
Ln xn
V(n+1) y(n+1)
Absorption: Design considerations
Va, ya
La, xa
Vb, yb
Lb, xb
Plate 1
Plate 2
Plate n
Plate N
L1 x1
V2 y2
L2 x2
V3 y3
Plate 3
L(n-1) x(n-1)
Vn yn
Ln xn
V(n+1) y(n+1)
We create a contour incorporating a
particular number of plates and consider the
Elements inside as a steady state system:

- for this system two mass balance
equations can be written

- Total mass balance



- Component mass balance
a n n a
V L V L + = +
+1
a a n n n n a a
y V x L y V x L + = +
+ + 1 1
1 n
a a a a
n
1 n
n
V
x L y V
x
V
L
1 n
y
+ +
+ =
+
-
Operating line
Absorption: Design considerations
y
x
(mole fraction of A in L)
(mole fraction of A in V)
x
a
x
b
y
a
y
b
equilibrium line
x*
b
1 n
a a a a
n
1 n
n
V
x L y V
x
V
L
1 n
y
+ +
+ =
+
-
Operating line
) (
*
A A
x f y =
P x T H y
A A
/ ) (
*
=
Equilibrium line
Absorption: Design considerations
y
x
(mole fraction of A in L)
(mole fraction of A in V)
x
a
x
b
y
a
y
b
equilibrium line
x*
b
1 +

n e
y y
The driving force for mass transfer
x
n
Absorption: Design considerations
y
x
(mole fraction of A in L)
(mole fraction of A in V)
x
a
x
b
y
a
y
b
equilibrium line
x*
b
McCabe-Thiele graphical
construction
x
n
Absorption: Design considerations
y
x
(mole fraction of A in L)
(mole fraction of A in V)
x
a
x
b
y
a
y
b
equilibrium line
x*
b
McCabe-Thiele graphical
construction
Absorption: Design considerations
Limiting conditions: gas-liquid ratio
1 n
a a a a
n
1 n
n
V
x L y V
x
V
L
1 n
y
+ +
+ =
+
-
In general this is not a straight line because mass is
constantly transferred from phase V to phase L (so
L
a
<L
b
and V
a
<V
b
and L
n
/V
n+1
is not constant)

If we decrease L, y
b
does not change but overall
concentration of A in L increases. We can continue this
process until the operating line crosses the equilibrium
line.

At this point (x*
b
, y
b
) the driving force of mass transfer
y-y* is equal to zero. This means we need infinite number
of stages to reach this separation.

y
x
(mole fraction of A in L)
(mole fraction of A in V)
x
a
x
b
y
a
y
b
equilibrium line
x*
b
Absorption: Design considerations
Limiting conditions: gas-liquid ratio
This condition is called the limiting (L/V)
min
ratio. This is
the lowest flow of solvent possible in the system to achieve
the desired separation, although in an infinite number of
stages.




The actual solvent flow is usually calculated a multiple of
(L/V)min (1.1-1.5 times)
y
x
(mole fraction of A in L)
(mole fraction of A in V)
x
a
x
b
y
a
y
b
equilibrium line
x*
b
b a
a b a b
b
a a a a
b
b
b
b
V L
V V L L
V
x L y V
x
V
L
y
/
) (
-
* *

+ =
+ =
Absorption: Design considerations
Limiting conditions: Gas-liquid ratio; straight operating line
Condition: L, V constant -> L/V constant

This is possible for very dilute (<5% mole fraction) mixtures
so change in total number of moles of each flow is
insignificant

A) Limiting (L/V)
min
value:

y
x
(mole fraction of A in L)
(mole fraction of A in V)
x
a
x
b
y
a
y
b
equilibrium line
x*
b
B) Number of ideal stages: the actual L/V ratio is
calculated as a multiple of the limiting value (f* (L/V)
min
)
this gives a steeper slope of the operating line.

The number of ideal stages can be then constructed using
McCabe-Thiele method.
a b
a b a a
b b
x x
y y
V
L
V
Lx Vy
x
V
L
y

=
|
.
|

\
|
+ =
*
min
*
-
Absorption: Design considerations
Limiting conditions: Gas-liquid ratio; straight operating and equilibrium lines
Condition: L, V constant -> L/V constant, y
e
=mx
e
This is possible for very dilute (<5% mole fraction) mixtures
so change in total number of moles of each flow is
insignificant

and

the region of interest is in the Henrys law regime

A) Limiting (L/V)
min
value:

y
x
(mole fraction of A in L)
(mole fraction of A in V)
x
a
x
b
y
a
y
b
equilibrium line
x*
b
B) Number of ideal stages: can be calculated
analytically
a b
a b
a b
a b
a a
b b
x m y
y y
x x
y y
V
L
V
Lx Vy
x
V
L
y

=
|
.
|

\
|
+ =
/
-
*
min
*
Design of absorbers: simplified cases
To calculate the number of ideal stages lets consider the following:
n n e e
mx y mx y = = mV L A / =
a a n a a n n
y Ay Ay Amx y Ay y + = + =
+
*
1
) ... ( ) ... 1 (
) ... ( ) ... 1 (
) ( ) 1 (
) (
) 1 (
2 * 2
2 * 2
1
2 * 2
* * 2 2 *
2 3
* *
2
N
a
N
a b N
n
a
n
a n
a a
a a a a a a
a a a a a
A A A y A A A y y y
A A A y A A A y y
A A y A A y
y Ay y A A A y y Ay Ay y
Ay A y y Ay Ay y
+ + + + + + + = =
+ + + + + + + =
+ + + =
= + + = + =
+ = + =
+

Define adsorption factor

Then operating line equation becomes
The applying this equation stage by stage:
Design of absorbers: simplified cases
Lets consider the following:
) ... ( ) ... 1 (
) ... ( ) ... 1 (
2 * 2
2 * 2
1
N
a
N
a b N
n
a
n
a n
A A A y A A A y y y
A A A y A A A y y
+ + + + + + + = =
+ + + + + + + =
+
Inside the brackets we have geometric series:
r
r a
s
n
n

=
1
) 1 (
1
( )
A
A
A y
A
A
y y
N
a
N
a b

=
+
1
) 1 (
1
1
*
1
Therefore:
This is Kremser equation
Design of absorbers: simplified cases
Lets consider the following:
) (
* *
* * *
a b b a
a a b a a N b
y y A y y
y Ay Ay y Ay Ay y
=
+ = + =
( )
( )
b a a b a a
N
N
a
N
a b
N
a
N
a b
y y y y A y y A
A A y A y A y
A
A
A y
A
A
y y
+ =
=

=
+
+ +
+
) ( ) (
) ( 1 ) 1 (
1
) 1 (
1
1
* * 1
1 * 1
*
1
From operating line:
V
N
,y
N
=
V
b
,y
b
L
N
,x
N
=
L
b
,x
b
Design of absorbers: simplified cases
From the previous slide:
) (
* *
a b b a
y y A y y =
b a a b a a
N
y y y y A y y A + =
+
) ( ) (
* * 1
;
) ( ) ( ) (
*
*
* * * * 1
a a
b b
N
a b a b a a
N
y y
y y
A
y y A y y A y y A

=
+ =
+
| |
A
y y y y
N
a a b b
ln
) /( ) ( ln
* *

=
Kremser equation: the number of ideal
stages
| |
A
y y y y
N
a a b b
ln
) /( ) ( ln
* *

=
n n e e
mx y mx y = =
Straight equilibrium line
const mV L A = = /
Adsorption factor, straight operating line
The Kremser equation (1930)
y
x
(mole fraction of A in L)
x
a
x
b
equilibrium line
y*
b
y
b
y*
b
y
b
A stream of gas vented from a condenser in an aromatics plant has a flowrate of 200 kmol h
-1
,
a temperature of 25C and a pressure of 5 bar. The composition (mole fractions) is
Hydrogen 0.900
Methane 0.07
Benzene 0.03
It is proposed to recover 98% of the benzene by absorption into an initially pure, non-volatile
hydrocarbon oil using a plate column. Find:

[i] The minimum feed rate kmol h
-1
of the oil for this separation
[ii] The minimum number of theoretical stages required at an oil rate 30.25 kmol h
-1


Additional data:

m is taken as the slope of the X-Y equilibrium line.
Equilibrium data at 25C and 5 bar.
Substance K
i
= y
i
/x
i

Methane 43.0
Benzene 0.132
Absorption: Example
La, xa
Va, ya
Vb, yb
Lb, xb
Some preliminary considerations

The mole fraction of benzene in
V
b
y
b
=0.03.

The goal is to recover 98% of it.

The equilibrium line is a straight line
y
e
=0.132x
e
. This follows from the relative
volatility table provided in the problem
statement. This table essentially says
that benzene is will be essentially all
dissolved in the oiled compared to methane
(and even more so hydrogen). Therefore we
we can consider hydrogen + methane as
inert carrier. Hence the equilibrium line equation

Absorption: Example
y
x
(mole fraction of A in L)
x
a
x
b
y
a
y
b
equilibrium line
x*
b
Lets solve the first part. In the figure on the right
we schematically show the condition for the
minimum feed rate.

We are interested in finding xb, yb and the liquid
flow rate La corresponding to this condition.

Vb=200kmol/h
ye=0.132xe
yb=0.03

therefore
(xb)*=(yb)/0.132=0.03/0.132=0.227

Amount of benzene in Vb is equal to
NVb=yb*Vb=0.03*200=6.0kmol/h

98% of this has to end in Lb (this is our recovery
target). NLb98%*NVb/100=5.88kmol/h

xb=NLb/Lb from this
Lb=NLb/xb=5.88/0.277=25.9kmol/h

La=Lb-NLb => La=25.9-5.88=20.02kmol/h
Absorption: Example
In the second part we need to find the minimum
number of stages given La=30.25 kmol/h

Lb=La+NLb=30.25+5.88=36.13kmol/h

xb=NLb/Lb=0.1627

Va=Vb-NLb=200-5.88=194.12kmol/h

ya=NVa/Va=0.12/194.12=6.18*10
-4


So we have two points on the operating line:

xa=0.0, ya=6.18*10
-4

xb=0.1627 yb=0.03

In addition we can construct an additional point,
(or any number of additional points) by looking at
a mass balance within the column corresponding
to some intermediate stage

La=30.25, xa=0
Va=194.12,
ya=6.18*10
-4
Vb=200, yb=0.03
Lb=36.13,
xb=0.1627
NVb=6
NVa=0.12
NLb=5.88
Absorption: Example
La=32.25, xa=0
Va, ya
Vb=200, yb=0.03
Lb, xb
V
n+1
,y
n+1
L
n
,x
n
Lets for example consider xn=0.1

Then NLn/Ln=0.1 Ln=La+NLn

So NLn=3.36 and Ln=33.6kmol/h

The overall balance is:

La+Vn+1=Ln+Va
30.25+Vn+1=33.6+194.12
Vn+1=197.8

yn+1 can be found from the operating line
equation
1 n
a a a a
n
1 n
n
V
x L y V
x
V
L
1 n
y
+ +
+ =
+
-
yn+1=0.017
Absorption: Example
So we have three points of the operating line
and an equilibrium line (shown on the right).

Graphical McCabe-Thiele construction gives
11 theoretical stages.




An alternative solution could be obtained using
the Kremser equation (based on straight line
assumption for both the equilibrium and operating
lines).

yb*=0.132*(xb)=0.132*0.1627=0.021
ya*=0.132*(xa)=0






So Nmin=11.2

| |
A
y y y y
N
a a b b
ln
) /( ) ( ln
* *

=
27 . 1
0 . 200
13 . 36
12 . 194
25 . 30
132 . 0
1 1 1
= = =
|
.
|

\
|
=
b
b
a
a
Av
V
L
V
L
m V
L
m
A
0
0.005
0.01
0.015
0.02
0.025
0.03
0.035
0.04
0 0.05 0.1 0.15 0.2
x
y
equilibrium
operating
Absorption: Example