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Chemical Engineering Operations

Gas Absorption

Dr. Anand V. Patwardhan


Professor of Chemical Engineering
Institute of Chemical Technology
Nathalal M. Parekh Road
Matunga (East), Mumbai−400019

Email: anand@udct.org; avpuict@gmail.com, avpiitkgp@gmail.com


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GAS ABSORPTION
• The gas from coke ovens is washed with water to remove NH3
and again with an oil to remove C6H6 and C6H5−CH3 vapours
(physical).
• H2S is removed from coke oven gas or from natural
hydrocarbon gases by washing it with various alkaline
solutions in which it is absorbed (with chemical reaction).
• Valuable solvent vapours carried by a gas stream can be
recovered for reuse by washing the gas with an appropriate
solvent for the vapours (with or without chemical reaction).
These operations require mass transfer of a substance from gas
stream to the liquid. When the mass transfer occurs in the
opposite direction, it is called “stripping”.

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Equilibrium Solubility of Gases in Liquids (Two Component
Systems): If a quantity of a single gas and a relatively nonvolatile
solvent are brought to equilibrium, the resulting concentration of
dissolved gas in the liquid is said to be the gas solubility at the
given P and T. At any fixed T, the solubility increases with
pressure.
B A
↑ SO2, 10 C
0
NH , 30 0C
3

pA ↑
NH3, 10 0C
D
E C HCl, 10 0C
xA →
Solubilities of gases in water
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ƒ High equilibrium partial pressure of a gas at a given liquid
concentration (curve B): relatively insoluble gas,
ƒ Low equilibrium partial pressure of a gas at a given liquid
concentration (curve C): relatively soluble gas

Solubility = f (T), as described by van’t Hoff’s law of mobile


equilibrium, ⇒ “If the T of a system at equilibrium is raised, the
change will occur in such a way as to absorb the heat”.

ƒ Generally, (not always), the solution of a gas results in an


evolution of heat, ⇒ the solubility of a gas decreases with
increasing T.
ƒ Exceptionally, the solubility of many low molecular weight gases
such as H2, O2, N2, CH4, in water increases with increased T
above 100 0C, obviously at pressures > 1atmosphere.
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Multicomponent Systems

Ideal Solutions
• If a mixture of gases is brought into contact with a liquid, under
certain conditions, the equilibrium solubilities of each gas will
be independent of the others, provided, the equilibrium is
described in terms of the partial pressures in the gas mixture.
• If all, except one, components of the gas mixture are very
slightly soluble, their concentrations in the liquid will be so
small that they cannot influence the solubility of the relatively
soluble component.
• For example, absorption of NH3–air mixture into water,
provided that the Y-axis is taken to be the partial pressure of
NH3 in the mixture.

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• Even if many components of the gas mixture are significantly
soluble, then the ideal solution assumption will be applicable
only if the solute gases are indifferent to the nature of liquid
and indifferent to each other.
• For example, a mixture of C3H8 and C4H10 dissolved in
higher hydrocarbon solvent.

Non−Ideal Solutions
• For example, the solubility of NH3 in water is influenced by
the presence of methylamine, and hence the resulting
solution of these two gases in water is non−ideal.
• The solubility of a gas is also influenced by the presence of a
nonvolatile solute in the solvent, such as a salt, hence these
solutions are also non−ideal.

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Ideal Liquid Solutions
When the liquid phase is ideal, the equilibrium partial pressure of a
gas from the solution can be calculated theoretically. The
characteristics of ideal solutions are:
ƒ The average intermolecular forces of attraction and repulsion in
the solution are unchanged on mixing the components.
ƒ The volume of the solution varies linearly with composition.
ƒ No heat of mixing is involved.
ƒ The total vapour pressure of the solution varies linearly with
composition expressed as mole fractions.

When the gas mixture (in equilibrium with an ideal liquid solution)
also follows the ideal gas law, the equilibrium partial pressure
p*A of a solute gas A is equal to the product of its vapour
pressure pV (at the same temperature) and its mole fraction in
the solution xA. This is Raoult's law, given by,
p*A = pV xA
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Nonideal Liquid Solutions
In this case, the equilibrium partial pressure p*A of a solute gas A
is proportional to product of total pressure pT and its mole fraction
in the solution xA. This is Henry's law.
p*A ∝ pT xA
Therefore p*A = m pT xA
p*
Or, y* = A = m x
p A
T
ƒ Henry’s law: modest liquid concentration range, (m = constant)
ƒ Under other conditions, m = f(xA), that is “m is NOT constant”,
and hence needs to be found out accordingly.
ƒ The deviations from Henry’s law may be due to chemical
interaction with the liquid or electrolytic dissociation (for
example, NH3 + water system), or nonideality in the gas phase.

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Choice of Solvent for Absorption

ƒ If absorption is involved for production of a specific product, then


the solvent is automatically specified by the nature of the product.
ƒ If the purpose is to remove some constituent from the gas, some
choice is usually available. In that case, following considerations
are involved:

1. Gas solubility: should be high.


Generally solvents having similar chemical nature as that of solute
will have good solubility. A chemical reaction of solvent (or a
component in the solvent) will result in high gas absorption
rates, but if the solvent is to be recovered for reuse, the reaction
must be reversible. For example:
ƒ H2S absorption in alkanolamines (reversible)
ƒ H2S absorption in alkali (irreversible)
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2. Volatility: low vapour pressure because the gas leaving absorption
equipment is usually saturated with the solvent and this will amount to
the loss.
If necessary, a second, less volatile liquid can be used to recover
the evaporated portion of the first. For example, in the case of
hydrocarbon absorbers, where relatively volatile solvent oil is used in the
main absorption operation (due to good solubility criteria), the evaporated
solvent is recovered from the vent gas by absorption in nonvolatile oil.
3. Corrosiveness: The MOC required for the equipment should not be
uncommon or very expensive.
4. Viscosity: Low viscosity is preferred for higher liquid side mass transfer
coefficients, better flooding characteristics of absorption columns, low
pressure drops on pumping, and better heat transfer characteristics.
5. Other considerations: AS FAR AS POSSIBLE, It should be nontoxic,
nonflammable, chemically stable, and having low freezing point.

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One Component Transferred, Material Balances
(Countercurrent Flow)
L2 mole/(time).(area)
LS, x2, X2 G2, GS, y2, Y2, pA2

L, LS, x, X G, GS, y, Y, pA

Flow quantities for an


absorber or stripper

L1, LS, x1, X1 G1, GS, y1, Y1, pA1


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y p
Y= = A
For GAS stream: 1− y p − p
T A
G
G = G (1 − y ) =
S 1+ Y
For LIQUID stream: x
X=
1− x
L
L = L (1 − x ) =
S 1+ X
The solute (A) balance across the envelope is given by:

GS (Y1 – Y) = LS (X1 – X)

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Operating line, Operating line
Slope = LS/GS for absorber and
Y1 BOTTOM stripper
ABSORBER
P (X,Y) • For an absorber (mass transfer
Y2 TOP from gas to liquid), the
M operating line always lies
TOP
Y2 STRIPPER above the equilibrium curve.
• For a stripper (mass transfer
Y1 BOTTOM from liquid to gas), the
operating line always lies
below the equilibrium curve.
X2 X1 X1 X2

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If the equation of operating line is expressed in terms of mole
fractions (instead of mole ratios), then,
⎛ y y ⎞ ⎛ p p ⎞ ⎛ x x ⎞
G ⎜ 1 − ⎟ = G ⎜ A1 − A ⎟ = L ⎜ 1 − ⎟
S ⎜1− y 1− y ⎟ S ⎜ p −p p −p ⎟ S ⎜1− x 1− x ⎟
⎝ 1 ⎠ ⎝ T A1 T A ⎠ ⎝ 1 ⎠
When written for a plate column, the equation is modified as
follows:
GS (YNP+1 – Y1) = LS (XNP – X0)

Minimum Liquid−to−Gas Ratio for Absorbers:


In absorbers design, the quantity of gas to be treated G (or GS),
the terminal gas concentrations Y1 and Y2, and the composition
of the entering liquid X2 are generally fixed by the process
requirements, but the quantity of liquid to be used is a matter of
choice, and X1 varies accordingly.

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Minimum liquid−to−gas
ratio for absorption

Y1 E F M
Slope = LS/GS
ƒ Operating line must pass
P through point D(X2,Y2), and
must end at the ordinate Y1.
Slope = LS(min)/GS ƒ If such a quantity of liquid is
Y2 used to give line DE, the
D
exit liquid will have
X2 X1 X1(max) composition X1.

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ƒ If still lesser quantity of liquid is used, the exit liquid
composition will be higher, say at point F, but absorption is
more difficult. Hence the number of contacts between gas
and liquid phase must be more, and the absorber must be taller
accordingly.
ƒ The minimum liquid rate, which can be used for a given duty,
is given by line DM that is tangent to the equilibrium curve
at P. At P, the diffusion driving force is zero, the required
contact time is infinite and this gives rise to an infinitely tall
absorption tower.
ƒ The above principles also apply to strippers, where an
operating line touching anywhere the equilibrium
curve represents a maximum ratio of liquid to gas and
a maximum exit gas concentration.
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G1 GS y1 Y1
L0 LS x0 X0
Y1
1 X1
Y2
2 Countercurrent Multistage
X2 Operation
3 Y3
X3 (One component Transferred)
Y4

NP−2
YNP−2 Tray / Plate Absorber
XNP−2
NP−1 YNP−1
XNP−1
YNP
NP XNP
GNP+1 GS yNP+1 YNP+1

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ƒ The number of ideal stages required to bring about a
given change in composition of the liquid or the gas,
for either absorbers or strippers, can be determined
graphically.
ƒ The nearer the operating line to the equilibrium curve,
the more steps will be required and if the two curves
touch at any point, it corresponds to (LS/GS)min ratio,
and the number of steps will be infinite.
ƒ The construction for strippers is the same, except, that
the operating line will be below the equilibrium
curve.

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CONTINUOUS CONTACT EQUIPMENT
In a packed or spray tower, the liquid and gas compositions
change continuously with height.

Height Equivalent to an Equilibrium Stage (Theoretical


Plate):
ƒ This methods ignores the differences between stagewise and
continuous contact.
ƒ The number of theoretical trays required for a given change in
concentration is computed by the graphical (or numerical)
methods.
ƒ This is then multiplied by a quantity called “height equivalent
to a theoretical plate (HETP)” to give the required height of
the packing or the empty column.
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Absorption of one component
Consider a packed tower as shown in the following figure:

LS L2 x2 X2 GS G2 y2 Y2

LG Packed Tower:
x y Design method based on
dz Z individual mass
transfer coefficients

LS L1 x1 X1 GS G1 y1 Y1

ƒ The flow rates (G and L) are taken on the basis of Unit Cross
Sectional Area, that is, mol/[(area)(time)]
ƒ The specific interfacial area of contact between gas and liquid,
a, is on the basis of Unit Packed Volume., that is m2/m3 20
ƒ The flow rate of solute = G y mol/[(area)(time)]
ƒ Change in solute flow rate over differential section = − d(G y)
ƒ Packed volume in the differential section for unit cross
sectional area of the column = (1) (dz)
ƒ Interfacial Area in differential section = (a) (1) (dz)
ƒ NA = local flux of solute
ƒ ky = individual gas-phase (gas-side) mass transfer coefficient
ƒ Therefore, mass transfer rate of solute = (a) (dz) NA
ƒ Mass balance over the differential section of packed column:
(a) (dz) NA = − d(G y) = − G dy − y dG
ƒ However, the carrier gas is not soluble, hence,
Change in the total gas flow rate = Solute mass transfer rate
⇒ − dG = (a) (dz) NA
⇒ (a) (dz) NA = − G dy + y (a) (dz) NA 21
⇒(a) (dz) ky (y − yi) = − G dy + y (a) (dz) ky (y − yi)
ƒ Rearranging,
(a) (dz) NA (1 − y) = − G dy
ƒ Integrating within appropriate limits,
Z y y
2 G dy 1 G dy
Z = ∫ dz = − ∫ = ∫
0 ( )
y k y a (1 − y ) y − yi
1 (
y k y a (1 − y ) y − yi
2 )
ƒ Integration is slightly complicated because the
Interfacial Concentration yi is NOT explicitly known.
ƒ Graphical construction is used to generate the
Integrand, then the integration is executed.
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ƒ Draw an Operating Line from material balance,
⎛ y y ⎞ ⎛ x x ⎞
G ⎜ 1 − ⎟ = L ⎜ 1 − ⎟
S ⎜ 1- y 1- y ⎟ S ⎜ 1- x 1- x ⎟
⎝ 1 ⎠ ⎝ 1 ⎠
ƒ Take any point (x,y) on Operating Line.
ƒ Using values of kx and ky (OR kxa and kya), draw a line of
slope = −kx/ky from the point (x,y) to meet point (xi, yi) on the
Equilibrium Curve. Thus, yi is known for a given y.
ƒ The line joining above 2 points: Tie Line (why ?).
ƒ Repeat the above procedure for several points: to obtain a set
of (y, yi) in the range [y2 ≤ y ≤ y1].
ƒ The assumption: kx/ky (or kxa/kya) is constant. If it is NOT,
then it is obtained from various published correlations.
ƒ Calculate G [= Gs (1+y)] at each point. Gs is already known
from the given feed gas flow rate.
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ƒ Evaluate the Integrand graphically or numerically.
ƒ Similarly the Height of Packing can be obtained using other
types of Individual Mass Transfer Coefficients, namely, kx,
kG, kL, KY, KX).
x
1 L dx
Z = ∫
x
2 x (
k a (1 − x ) x − x
i )
y
1 G dy
= ∫
y
2 G T (
k a P (1 − y ) y − y
i )
x
1 G dy
= ∫
x
2
k a ( C)
L average ( (
1 − x) x − x
i )

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Design Method Based on Height of A Transfer Unit
ƒ Recall the previous equation for Z and rewrite as,

Z =
y
1 ( )
G y
iB LM
dy

( )
y k y a y iB
2 LM
(
(1 - y ) y - yi )
y
1 G (1 - y ) dy
= i LM

(
y k y a ( 1 - y )i LM ( 1 - y ) y - y i
2
)
where y ( iB )LM = Log Mean value of yB = (1 - y A )i LM
(1 - yi ) - (1 - y ) ... dropping the subscript A from y
=
1- y )
( )
ln
( i
A

(1 - y )
Note: B is the CARRIER GAS, hence NON-DIFFUSING
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G
ƒ The quantity k a 1 − y remains fairly constant over the
y
( ) i LM

packed section although the total gas flow rate G, varies. This
quantity is called “height of a transfer unit (based on gas-
side), denoted by Htg. Taking Htg out of the integral sign,
y y
G 1 ( 1 − y )i LM dy 1 ( 1 − y )i LM dy
Z = ∫ = H
tg ∫ 1 − y y − y
k a (1 − y )
y 2 (
i LM y ( 1 − y ) y − y i ) y (
2 (
) )
i

ƒ The Integral = “number of transfer units (gas-side), Ntg”.


ƒ Therefore, the packed height = Z = Htg Ntg
ƒ The height of a transfer unit and the number of transfer
units can be defined similarly when any other kind of mass
transfer coefficient is used.

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Height of the packed column based on liquid-side mass
transfer coefficient
x
L 1 ( 1 − x )i LM dy
Z = H N = ∫
tl tl k a (1 − x )
x (
i LM x ( 1 − x ) xi − x
2 )

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Use of GAS-SIDE and LIQUID-SIDE mass transfer coefficients for
the case “diffusion of A through non-diffusing B”
D P P −p
N = AB T ln T AL ... for Gas Phase
A RTL P −p
T A0
1− y D P
⇒ N = F ln Ai where F = AB T
A G 1− y G RTL
A
1− x
Similarly, N = F ln A ... for Liquid Phase
A L 1− x
Ai
F F F a F a
1− y ⎡ 1− x ⎤ L G ⎡ 1− x ⎤ L G
⇒ Ai = ⎢ A⎥ =⎢ A⎥
1− y 1− x ⎥ ⎢⎣ 1 − x Ai ⎥⎦
A ⎣⎢ Ai ⎦

Note: for any value of (xA,yA) on Operating curve, a curve of yAi versus
xAi is plotted to determine the intersection with Equilibrium curve.
This gives local yA and yAi for use in the Equation for Z.
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y
2 G dy
Z=− ∫
y ⎡ 1-y ⎤
1 F a ( 1 − y ) ln ⎢ Ai ⎥
G ⎢⎣ 1-y A ⎥⎦

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y
2 G dy
Z=− ∫
y ⎡ 1-y ⎤
1 F a ( 1 − y ) ln ⎢ Ai ⎥
G ⎢⎣ 1-y A ⎥⎦
Alternative method:
ƒ Since yA – yAi = (1 – yAi) – (1 – yA), the Numerator of the
above equation can be multiplied by the R.H.S. and L.H.S.,
respectively. This gives:
1
y G ⎡1 − y ⎤ dy
⎣ A ⎦ iM
Z= ∫
(
y FG a 1 − y A
2
) (1 - y Ai )
where, (1 – yA)iM = log-mean of (1 – yAi) and (1 – yA)
y ⎡1 − y ⎤ dy
1 ⎣ A ⎦ iM G G
⇒Z= ∫ H where H = =
y
2 (
tG 1 − y
A )( 1- y
Ai) tG F a k a ⎡1 − y ⎤
G y ⎣ A ⎦ iM

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Numerical problems (HOME ASSIGNMENTS)
(1)
ƒ In an experimental agitated contactor, pure CO2 is being absorbed in
water at 25 0C and 2 atm.
ƒ Water is pumped into the contactor @ 1 litre/minute and the carbonated
water leaves the vessel continuously so that a constant volume is
maintained in the contactor.
ƒ The outlet water contains 2.3 gm CO2/litre.
ƒ The specific interfacial area (a) of gas−liquid contact is 80 m2/m3 of the
gas−liquid dispersion (volume of the gas−liquid dispersion is 8 litre).
The liquid phase can be assumed to be well mixed.
ƒ The solubility of CO2 in water can be calculated using Henry’s law.
ƒ At 25 0C, the Henry’s law constant for CO2 is 1640 atm/mol fraction
ƒ Diffusivity of CO2 in water is 1.92 × 10−9 m2/s.
Calculate the thickness of the liquid film if the film theory is applicable.

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Numerical problems (HOME ASSIGNMENTS)
(2)
ƒ The solute A is absorbed from a gas (G) in a liquid (L) in a
countercurrent packed tower.
ƒ Given:
9 Feed gas rate = 35 kmol/h, 10 mol% A, 90 mol% carrier;
9 Liquid rate at the top (solute-free) = 40 kmol/h
9 Equilibrium relation: Y = 1.1 X (Y is the concentration in the gas
phase in the mole ratio unit).
9 The overall driving force at the top (gas phase basis)
= (ΔY)TOP = 0.00555.
What is the driving force at the bottom of the tower ?

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Numerical problems (HOME ASSIGNMENTS)
(3)
ƒ In a certain equipment used for the absorption of SO2 from air by water,
at one section, the gas and liquid phase concentrations of the solute are
10 mol% and 4 mass% respectively.
ƒ The solution density is 990.831 kg/m3.
ƒ At the given temperature (40 0C) and pressure (10 atm), the distribution
of SO2 between air and water can be approximately described by the
equation: pA = 25 xA, where pA is the partial pressure of SO2 in the gas
phase in atm.
ƒ The individual mass transfer coefficients are:
9 kx = 10 kmol/[(h)(m2)(Δx)]
9 ky = 8 kmol/[(h)(m2)(Δy)]
Calculate: (i) overall coefficient, KG in kmol/[(h)(m2)(Δp mmHg)]
(ii) xAi and yAi at the gas− liquid interface

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