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CHAPTER 3:

ABSORPTION
PROCESS
LEARNING OUTCOMES

Explain gas absorption and (desorption), and the


method of contacting between gas-liquid phase.

Explain the choice of solvents in gas absorption

Derive the operating line equation for counter-


current operation and understand the graphical
representation.

Use graphical method to determine the number of


theoretical trays required for separation
INTRODUCTION
Absorption, or gas absorption, is a unit
operation used in the chemical
industry to separate gases by washing
or scrubbing a gas mixture with a
suitable liquid.
DEFINITION:
Mass transfer of the component of the gas from
the gas phase to the liquid phase.

Gas mixture is contacted with a liquid for the


purposes of preferentially dissolving one/more
components of gas and to provide a solution of
them in the liquid.

Gas mixture = inert gas + solute.


Solute = transferred component.
Purpose Of Absorption

To obtain or remove the DESIRED


component of Vapor Mixture with the usage
of a LIQUID SOLVENT based on
SOLUBILITY characteristic of the
component towards the Liquid Solvent.
EXAMPLE:
NH3 that is diffusing from an gaseous air-NH3 mixture into liquid phase water.

 Liquid  Gas   Liquid  Gas


Solvent    A  B    B  solvent    A 
       
Nonvolatile Component to be
eg: water Carrier & insoluble removed
e.g: air+ NH3 e.g: NH3

Ammonia - desired component


Air – unwanted component
Result : To absorb ammonia, water is used as a solvent & air free of ammonia
Example of applications
 Removal of ammonia, benzene and
toluene from coke gas
 Removal of SO2 from stack gas
 Removal of CO2 from synthesis gas
 Air pollution control, the various oxides
of nitrogen can be removed by
absorption with water, sulphuric acid,
and organic solutions
 Table
below showed representative
commercial absorption applications:
GAS ABSORPTION OPERATION
Two methods of contacting the gas and liquid :
Counter-current operation
Co-current operation

Counter-current Co-current
Application of Packed Absorption Tower

Most common type of absorption tower


High flowrate of liquid solvent
Based on diagram:
Air-mixture enter at the bottom
Liquid solvent enter via liquid distributor(3)
Packed section (2) : air-mixture contact liquid
Air will rise up
Liquid+gas at the bottom
Liquid solvent will recycle to fully utilize
Some of the liquid solvent will be remove for further treatment
to obtain desired comp.
Make-up stream : to add some more liq solvent if some amount
is lost by vapourization or not much left at the bottom since
some has already being withdrawn.
PLATE COLUMN ABSORPTION TOWER
Suitable for low flowrate of liquid solvent

Based on diagram :
Air-mixture enter at the bottom.
Liquid solvent enter at the top and flow downward by
gravity
Solvent will flow across each tray and flows down the
tray below
Type of column : bubble tray or sieve tray
Type of flow : counter-currrent most popular
SOLVENT PROPERTIES
Gas solubility

Miscellaneous Volatility

SOLVENT

Viscosity Corrosiveness

Cost
Gas solubility
Solute gas should be high solubility into solvent
thus increase the rate of absorption and decrease
the quantity of solvent required.

Volatility
Solvent non volatile.
Have low vapor pressure to reduce loss of solvent
in the gas leaving an absorption column.

Corrosiveness
Material of construction should not be unusual or
expensive.
Cost
Solvent should be inexpensive, losses are not
costly and should be readily available.

Viscosity
Low viscosity to increase absorption rate, improved
flooding characteristics in absorption tower, low
pressure drop on pumping and good heat transfer
characteristics.

Others
Solvent should be nontoxic, nonflammable and
chemically stable and have low freezing point.
►gas-phase pollutant is brought into
close contact with the liquid to
facilitate diffusion across the gas-liquid
interface.
►gaseous pollutant diffuse through a
thin boundary layer on the gas side of
the interface (gas film) and a thin
boundary layer on the liquid side of the
interface (liquid film.).
►Once the pollutant enters the liquid
phase, it can simply dissolve, or it can
react with other chemicals also in the
liquid.
►Once the pollutant in the liquid phase
has reached its solubility limit, there is no
net transfer of pollutant across the gas-
liquid interface.
►At this point, equilibrium has been
reached whereby the amount of
gaseous pollutant that continues to
dissolve equals the amount coming out
of solution and reentering the gas
phase.
►Henry's law can be used to determine
the solubility limit of absorption.
GAS-LIQUID EQUILIBRIUM
PA  H . X A
When the solution is non-ideal, Raoult's Law cannot be applied.
For non-ideal solution, use Henry's Law which states that:

p A  H .x A
yA  H xA '

Where,
pA = partial pressure of component A .
H = Henry’s law constant (pressure/mol fraction).
y H x '
H’ = Henry’s law constant (molAfrac.gas/mol frac.liquid)
A
= H/P(dimensionless).
xA = mole fraction of component A in liquid.
yA = mole fraction of component A in gas = pA/P.
P = total pressure (atm).
In Figure 10.2-1, the data follow Henry’s Law up to a concentration xA of
about 0.005, where H=29.6atm/mol frac. In general, up to a total
pressure of about 5 atm, the value of H is independent of P.
EXAMPLE 1

• What will be the concentration of oxygen dissolved in


water at 298K when the solution is in equilibrium with air
at 1 atm total pressure? Given partial pressure of
oxygen in air is 0.21 atm and the Henry’s Law constant
is 4.38 X 104 atm/mol fraction.
SOLUTION…
• The partial pressure pA of oxygen (A) in air is 0.21atm.
• Apply Henry’s Law;
• pA=HxA
• 0.21atm=(4.38 X 104 atm/mol frac )(xA)
• xA=4.795 X 10-6 mol frac
• It means that 4.795 X 10-6 mol oxygen is dissolved in 1.0
mol water plus oxygen.
SINGLE-STAGE EQUILIBRIUM
CONTACT FOR GAS-LIQUID SYSTEM

• Assuming 3 components A,B and C are present in


the streams, making balance on A & C
• No need to do balance for B because:
• xA + xB + xC = 1.0
• The mass fraction of A in L stream is xA and V stream is yA.
• The mass fraction of A in M stream is xAM.

• Since the component A is the only component that


redistribute between the two phases, a balance on A
can be written as:

Where L’ = moles inert water C Constant and


V’ = moles inert air B usually known
EXAMPLE 2
• A gas mixture at 1.0 atm pressure abs 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 mole/hr, with a
mole fraction of CO2 of yA2=0.20. The liquid flow rate entering
is 300 kg mole water/hr. Make a balance on CO2(A) and
calculate the amounts and compositions of the two outlet
phases. Assume that the water does not vaporize to the gas
phase.
SOLUTION:

The inert water flow is L’=L0=300 kg mole/hr


The inert air flow V’=V(1-yA)
Hence, V’=V2(1-yA2)=100(1-0.20)=80 kg mole/hr
Then, substitute into this equation:

Eq 2
Balance on CO2
CONT…
• From properties table, Henry’s law constant,
• H=0.142 X 104 atm/mole.frac.
• Then, H’=H/P=(0.142 X 104 atm/mole.frac)/1atm
• =0.142 X 104 mole frac gas/mole frac liq
• Substituting in Henry’s law equation,
• yA1=0.142 X 104 xA1 ------------Eq 2
• Solve simultaneously
• xA1=1.41 X 10-4
• yA1=0.20
CONT…

*Since the liquid solution is so dilute, L0≈L1


COUNTER-CURRENT MULTIPLE
CONTACT STAGES

Overall balance on all stages;

• VN+1 is mole/hr entering


• LN is mole/hr leaving
• M is total flow
Overall component balance on A,B or C;

• x and y are mole fraction


• The flows are in mass flowrate or mole
flowrate
Total balance over the first n
stages;

Component balance over the first n


stages;

Rearrange the equation to get yn+1;


• Equilibrium line relates the compositions of two streams
leaving a stage in equilibrium which each other.

• To determine the number of ideal stages required to


bring about a given separation or reduction of the
concentration of A from yN+1 to y1, the calculation is
often done graphically.
• Starting at stage 1, y1 and x0 are on the operating line.
• The vapor y1 leaving is in equilibrium with the leaving x1
and both composition are on the equilibrium line.
• Then, y2 and x1 are on the operating line and y2 is
equilibrium in x2, and so on.
• Each stage is represented by a step drawn in the figure.
• The steps are continued on the graph until yN+1 is
reached.
• Alternatively, we can start at yN+1 and draw the steps
going to y1.
EXAMPLE 3
• It is desired to absorb 90% of the acetone in the gas
containing 1.0 mol% acetone in air in counter-current
stage tower. The total inlet gas flow to the tower is 30 kg
mol/hr, and total inlet pure water flow to be used to
absorb the acetone is 90 kg mol H20/hr. The process is to
operate isothermally at 300 K and a total pressure of
101.3 kPa. The equilibrium relation for the acetone (A) in
gas-liquid is yA=2.53xA. Determine number of theoretical
stages required for this separation.
SOLUTION…
• Given:
• yAN+1=0.01
• xA0=0
• VN+1=30 kg mol/hr
• L0=90 kg mol/hr
• Making acetone material balance;
• Amout of entering acetone: yAN+1VN+1=0.01(30)=0.30 kg
mol/hr
• Entering air:
(1-yAN+1)VN+1=(1-0.01)(30)=29.7 kg mol air/hr
• Acetone leaving in V1= 0.1(0.30) =0.03 kg mol/hr
• Acetone leaving in LN = 0.9(0.30) =0.27 kg mol/hr
• V1 = 29.7+0.03= 29.73 kg mol (air+acetone)/hr
• yA1 =0.03/29.73 =0.00101
• LN = 90+0.27=90.27 kg mol (water+acetone)/hr
• xAN =0.27/90.27=0.003
• *Since the flow of liquid varies only slightly from L0=90
and LN=90.27 at the outlet and V from 30 to 29.73, the
slope Ln/Vn+1 of operating line is constant.
• Apply this equation;

Slope of the graph

5.2 theoretical stages


ANALYTICAL EQUATIONS FOR
COUNTERCURRENT STAGE CONTACT
• Can be applied if satisfied these 2 conditions:

• When the flow rates V and L in a


countercurrent process are essentially
constant, operating line becomes straight.

• If the equilibrium line is also a straight line.


V1 L0
y1 x0

VN+1 LN
yN+1 xN

*A refers to absorption factor


MASS TRANSFER BETWEEN PHASES

CONCENTRATION PROFILES IN INTERPHASE MASS TRANSFER


 Solute A diffuse from bulk gas phase G to the liquid
phase L, must pass through (phase G, interphase,
phase L) in series.
 Must have concentration gradient.
 The average or bulk conc. of A in gas phase in mole
fraction unit is yAG where yAG=pA/P and in the bulk
liquid phase in mole fraction units is xAL.
 Conc. in bulk gas phase yAG decreases to yAi at
interphase.
 Liquid conc. start at xAi falls to xAL.
 Since no resistance in the interphase, yAi and xAi are
in equilibrium.
MASS TRANSFER USING FILM MASS-
TRANSFER COEFFICIENTS AND
INTERPHASE CONCENTRATION

Equimolar
counterdiffusion
2 main cases:
Diffusion of A
through
stagnant B
CASE 1: EQUIMOLAR
COUNTERDIFFUSION
• Point P represents the bulk phase composition yAG and xAL of
two phases.
• Point M is the interface concentrations yAi and xAi.
• For A diffusing from gas to liquid and B is
equimolarcounterdiffusion;
• NA=k’y(yAG-yAi)=k’x(xAi-xAL)
• Where k’y=gas phase mass transfer coefficient in
kgmol/s.m2.mol frac
• k’x=liquid phase mass transfer coefficient in
kgmol/s.m2.mol frac
𝑘′𝑥 𝑦𝐴𝐺 −𝑦𝐴𝑖
• − ′ =
𝑘 𝑦 𝑥𝐴𝐿 −𝑥𝐴𝑖
• Where (yAG-yAi) is gas phase driving force
• (xAL-xAi) is liquid phase driving force
𝑘′𝑥
• − ′ is slope of PM line
𝑘 𝑦
CASE 2: DIFFUSION OF
A THROUGH STAGNANT B
 Point P represents the bulk phase composition yAG
and xAL of two phases.
 Point M is the interface concentrations yAi and xAi.
 NA=ky(yAG-yAi)=kx(xAi-xAL)

 Rearrange Eq 1 &Eq 2;
𝑘′𝑦 𝑘′𝑥
 𝑘𝑦 = , 𝑘𝑥 =
(1−𝑦𝐴)𝑖𝑀 (1−𝑥𝐴)𝑖𝑀
−𝑘 ′ 𝑥/ 1−𝑥𝐴 𝑖𝑀
 is slope of PM line
𝑘 ′ 𝑦/ 1−𝑦𝐴 𝑖𝑀
1−𝑦𝐴𝑖 −(1−𝑦𝐴𝐺)
 Where (1-yA)iM = 1−𝑦𝐴𝑖
ln[1−𝑦𝐴𝐺]

1−𝑥𝐴𝐿 −(1−𝑥𝐴𝑖)
 (1-xA)iM= 1−𝑥
ln[ 1−𝑥𝐴𝐿]
𝐴𝑖

𝑘′ 𝑘′𝑥
 Then, NA= 𝑦
𝑦𝐴𝐺 − 𝑦𝐴𝑖 = 𝑥𝐴𝑖 − 𝑥𝐴𝐿
1−𝑦𝐴 𝑖𝑀
1−𝑥𝐴 𝑖𝑀
−𝑘 ′ 𝑥/ 1−𝑥𝐴 𝑖𝑀 𝑦𝐴𝐺 −𝑦𝐴𝑖
 =
𝑘 ′ 𝑦/ 1−𝑦𝐴 𝑖𝑀 𝑥𝐴𝐿−𝑥𝐴𝑖
 When A is diffusing through stagnant B and the
solutions are dilute,
 (1-yA)iM and (1-xA)iM ≈ 1

 To get the slope (Eq 4), a trial and error method is


needed.
 1st trial: (1-yA)iM and (1-xA)iMare assumed to be 1.0
 Then, get slope using Eq 4 and yAi and xAi
 2nd trial: These values of yAi and xAiare used to
calculate new slope to get new yAi and xAi
 This is repeated until the interface compositions do
not change. Three trials are usually sufficient.
OVERALL MASS TRANSFER
COEFFICIENTS AND DRIVING FORCES
• Film or single phase mass transfer coefficient k’y and
k’x or ky and kx are often difficult to measure
experimentally.
• Thus, overall mass transfer coefficients K’y and K’x are
measured based on the gas or liquid phase.
• NA=K’y(yAG-y*A) and NA=K’x(x*A-xAL)
• Where;
• K’y is overall gas phase driving force in kgmol/s.m2.mol
frac
• y*A is value that would be in equilibrium with xAL
• K’x is overall liquid phase driving force in
kgmol/s.m2.mol frac
• x*A is value that would be in equilibrium with yAG
EQUIMOLAR COUNTER DIFFUSION
AND/OR DIFFUSION IN DILUTE SOLUTIONS
• NA=k’y(yAG-yAi)=k’x(xAi-xAL)
• yAG-y*A=(yAG-yAi)+(yAi-y*A)
• Between point

E and M, the slope m’ can be given as:
𝑦𝐴𝑖−𝑦 𝐴
• m’=
𝑥𝐴𝑖−𝑥𝐴𝐿
• Rearrange equation,
• yAG-y*A=(yAG-yAi)+m’(xAi-xAL)
• Rearrange equation to canceling out NA,
1 1 𝑚′
• = +
𝐾′ 𝑦 𝑘′𝑦 𝑘′𝑥

Gas film resistance


Total resistance Liquid film resistance
• In similar manner,
• x*A-xAL=(x*A-x*Ai)+(xAi-xAL)
• Between point D and M, the slope m’’ can be given
as:
𝑦𝐴𝐺 −𝑦𝐴𝑖
• m’’= ∗
𝑥 𝐴−𝑥𝐴𝑖
• Rearrange equation to canceling out NA,
1 1 1
• = +
𝐾′𝑥 𝑚′′ 𝑘′𝑦 𝑘′𝑥

• When m’ value is quite small, m’/k’xis very small.


1 1
• So, ≈ and yAG-y*A≈yAG-yAi
𝐾′𝑦 𝑘 ′𝑦
• When m’’ is very large, 1/(m’’k’y) becomes small.
1 1
• So, ′ ≈ ′ and xAi≈x*A
𝐾 𝑥 𝑘 𝑥
DIFFUSION OF A THROUGH
STAGNANT OR NONDIFFUSING B
𝑘′𝑦 𝑘′𝑥
• NA= 𝑦𝐴𝐺 − 𝑦𝐴𝑖 = 𝑥𝐴𝑖 − 𝑥𝐴𝐿
1−𝑦𝐴 𝑖𝑀
1−𝑥𝐴 𝑖𝑀
 yAG-y*A=(yAG-yAi)+m’(xAi-xAL)
 We must define the equations for the flux
using overall coefficients as follows:
𝐾′ 𝑦 ∗ 𝐾′ 𝑥 ∗
 NA=[ ∗ ] 𝑦𝐴𝐺 − 𝑦 𝐴 =[ 1−𝑥𝐴 ∗ ] 𝑥 𝐴 − 𝑥𝐴𝐿
1−𝑦𝐴 𝑀 𝑀
𝐾′ 𝑦 𝐾′ 𝑥
 Ky=[ ∗ ] , Kx=[ ∗ ]
1−𝑦𝐴 𝑀 1−𝑥𝐴 𝑀
 Rearrange equation to canceling out NA
1 1 𝑚′

𝐾′ 𝑦
= +
𝑘 ′ 𝑦/ 1−𝑦𝐴 𝑖𝑀 𝑘 ′ 𝑥/ 1−𝑥𝐴 𝑖𝑀
1−𝑦𝐴 ∗𝑀
1−𝑦∗𝐴 −(1−𝑦𝐴𝐺)
 Where; (1-yA)*M= 1−𝑦∗
ln[1−𝑦𝐴𝐺
𝐴]

 Similarly for K’x,


1 1 1
 𝐾′ 𝑥
= +
𝑚′′𝑘 ′ 𝑦/ 1−𝑦𝐴 𝑖𝑀 𝑘 ′ 𝑥/ 1−𝑥𝐴 𝑖𝑀
1−𝑥𝐴 ∗𝑀
1−𝑥𝐴𝐿 −(1−𝑥∗𝐴)
 Where; (1-xA)*M= 1−𝑥
ln[1−𝑥∗𝐴𝐿 ]
𝐴
DESIGN OF PLATE ABSORPTION
TOWERS
• A plate (tray) absorption tower has the same process
flow diagram as counter current multiple stage process.

Overall material balance on component A

A balance around the dashed-line box

Material balance in absorption tray or plate


tower
EXAMPLE: ABSORPTION
OF SO2 IN A TRAY TOWER
A tray tower is to be designed to absorb SO2 from an air stream
by using pure water at 293 K (680F). The entering gas contains
20 mol% SO2 and that leaving 2 mol% at a total pressure of
101.3 kPa. The inert air flow rate is 150 kg air/hr.m2, and the
entering water flow rate is 6000 kg water/hr.m2. Assuming an
overall tray efficiency of 25%, how many theoretical trays and
actual trays are needed? Assume that the tower operates at
293K (200C). Molecular weight of air and water is 29 kg/kmol
and 18 kg/kmol respectively. The equilibrium curve is plotted
using data for SO2-Water System in Appendix.
SOLUTION…
V1=? L0=6000
y1=0.02 X0=0 (pure water)

T=293K (200C)
P=1 atm

VN+1=150 LN=?
yN+1=0.2 xN=?
• Calculate the molar flow rates
150 kg inert air/hr.m2
• V’ = ൘29 kg/kmol
=5.18 kmol inert air/hr.m2

6000 kg inert water/hr.m2


• L’ = ൘18 kg/kmol
=333 kmol inert water/hr.m2
Substituting in material balance,
0 0.20 𝑥 0.02
333( )+5.18( )=333( 𝑁 )+5.18( )
1−0 1−0.20 1−𝑥𝑁 1−0.02
𝑥𝑁 =0.00355
From graph, 2.4 trays
Efficiency=25%=0.25
The actual no of tray
is=2.4/0.25=9.6 trays
SIMPLIFIED DESIGN METHODS FOR
ABSORPTION OF DILUTE GAS
MIXTURES IN PACKED TOWERS
• The concentration can be considered dilute when
mole fraction gas (y) and liquid (x) are less than 10%
which is 0.1

1−𝑦 𝑖𝑀 1−𝑦 ∗𝑀 1−𝑥 𝑖𝑀 1−𝑥 ∗𝑀


• Thus, , , , ≈ 1.0
(1−𝑦) (1−𝑦) (1−𝑥) (1−𝑥)

• Since the solution dilute, operating line will be straight.


LENGTH OR HEIGHT OF THE ABSOPRTION COLUMN
1−𝑦 𝑖𝑀 1−𝑦 ∗𝑀 1−𝑥 𝑖𝑀 1−𝑥 ∗𝑀
 Because , , , ≈ 1,
(1−𝑦) (1−𝑦) (1−𝑥) (1−𝑥)
substitute back to z, length or height
equation will get:
 Where S is the cross sectional area of the tower in
m2
 The left side is the kg mol absorbed/s.m2
 The right side is rate equation for mass transfer
 Vav=(V1+V2)/2 and Lav=(L1+L2)/2
𝑉′ 𝑉′
 V1= and V2= , L’≈L1≈L2≈Lav
1−𝑦1 1−𝑦2
Material balance in absorption packed tower
STEPS TO CALCULATE HEIGHT,Z FOR
PACKED ABSORPTION TOWER
• Plot the operating line (just need two coordinates [x1,y1]
as P1 and [x2,y2] as P2.------straight line
• Calculate Vav and Lav
• Plot equilibrium line (data refer to Appendix)
• k’ya and k’xa will be given
• If use K’ya is used, have to find y1* and y2* while if K’xa is
used, have to find x1* and x2*. Usually, you have to find
the K’ya or K’xa using the equation.
Find slope, PM1Trial 1 to get the value of yi1 and xi1
• 1st trial, use

• 2nd trial, get yi1 and xi1 from 1st trial and insert into this
equation to get the value of (1-y)iM and (1-x)iM

• Then, find PM1Trial 2 using this equation


 Stop the iteration when value for last trial of slope is
approximately same with the previous slope. Then
will get the final value of yi1 and xi1.
 Next, find the PM2Trial 1 and get value of yi2 and xi2
using this equation

 If the PM2Trial 1 value is almost same with the PM1Trial


2(or last trial), stop the iteration and get the value yi2
and xi2 from graph.
 Calculate the log mean driving force (y-yi)M using this
equation if k’ya is used

 If K’ya is used, find the log mean driving force using this
equation

 If using the liquid coefficient which is k’xa and K’xa, use


the appropriate driving force equation.
 Lastly, calculate height, z using this equation relate to
which gas coefficient used.
SIMPLIFIED METHOD:DESIGN OF PACKED
TOWERS USING TRANSFER UNITS
• Useful design method of packed towers is the use of the
transfer unit concept.
• For the case of A diffusing through stagnant and non-
diffusing B:

 The height of the packed tower is then:


In term of film coefficient
H= height of
transfer unit
N – number of
Liq transfer unit
Gas
phase phase

In term of Overall film coefficient


 The height of the packed tower :

In term of
film
coefficient

In term of
Overall film
coefficient
Where:
In term of film coefficient

In term of overall film coefficient


• When the solution are dilute with concentration below
10%:
• the term (1-y)iM/(1-y),(1-x)iM/(1-x),(1-y)*M/(1-y) and (1-
x)*M/(1-x) can be taken outside the integral & average
values used.
• Often they are quite close to 1 & can be dropped out.
Operating line and interphase compositions in a packed tower
for absorption of dilute gases

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