Topic Outline

 Introduction
 Gas – Liquid Equilibrium
 Mass Transfer between Phases
 Unit operation for Absorption:
a) Packed tower
b) Plate Column
Introduction
 Absorption – occur when the two contacting phases
are a gas and a liquid.
 In gas absorption, solutes are absorbed from the gas
phase into the liquid phase.
 Absorption does not destroy the gases, it simply
transfers the contaminated gas from the gaseous
state to the liquid state.
“Gas absorption is a process in which a gas mixture is
in placed in contact with a liquid for the purpose of
preferential dissolving of one or more components
of the gas mixture”
Air, H2, NO, HCl → water
Introduction
 Used to separate gas mixtures; remove impurities,
contaminants, pollutants, or catalyst poisons from a
gas; or recover valuable chemicals.
Stripping or desorption: The reverse of absorption
- A liquid mixture is contacted with a gas to selectively
remove components by mass transfer from the
…………. to the …………
- Example: removal of H2S from sour crude oil
 Absorption VS Adsorption
A gas mixture is contacted with a liquid (absorbent or
solvent) to selectively dissolve one or more components
(solutes or absorbate) by mass transfer from the gas to
the liquid
Adsorption is the adhesion of atoms, ions, biomolecules
or molecules of gas, liquid, or dissolved solids to a
surface
Adsorption is the process through which a substance,
originally present in one phase, is removed from that
phase by accumulation at the interface between that
phase and a separate (solid) phase.
Coupling of Absorber and Stripper
Introduction
Example:
1. NH3 is removed from oven gas by water
2. Benzene, toluene are removed from natural gas using
hydrocarbon oil
3. Absorbing SO2 from the flue gases by absorption in
alkaline solutions
4. CO2, H2S are removed from natural gas using water
solutions of alkaline salts
5. Hydrogenation of edible oils in food industry- hydrogen
gas is bubbled into oil and absorbed.
6. Absorbing dimethyl sulfide from the food processing
industry
Absorption Systems – Physical
 Examples:
CO2 and water Acetylene and acetic acid
CO and water NH3 and acetone
H2S and water Ethane and carbon disulfide
NH3 and water N2 and methyl acetate
NO2 and water NO and ethanol

 Physical absorption relies on the solubility of a particular gas in a liquid.

 This solubility is often quite low; consequently, a relatively large amount of

liquid solvent is needed to obtain the required separation.

 This liquid solvent containing the solute is typically regenerated by heating

or stripping to drive the solute back out.

 Because of the low solubility and large solvent amounts required in

physical absorption, chemical absorption is also used…
Absorption Systems – Chemical
 Chemical absorption relies on reaction of a particular gas with
a reagent in a liquid.
 Examples:
CO2 / H2S and aqueous ethanolamines
CO2 / H2S and aqueous hydroxides
CO and aqueous Cu ammonium salt
SO2 and aqueous dimethyl aniline
HCN and aqueous NaOH
HCl / HF and aqueos NaOH
 This absorption can often be quite high; consequently, a
smaller amount of liquid solvent/reagent is needed to obtain
the required separation.
 However, the reagent may be relatively expensive, and it is
often desirable to regenerate when possible.
Gas-Liquid Equilibrium
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
The solubility of any gas is influenced by the temperature
(Van’t Hoff’s law)
Solubility
The concentration of dissolved gas in the liquid: gas solubility at
the prevailing temperature and pressure

Fig 8.1 Solubilities of gas in water

Thermodynamics of the process:
binary systems
Imagine a system where we have a binary mixture of
two components A and B, one (A) is volatile and the
second one (B) is a non-volatile solvent.
P, T
The mixture coexists with an equilibrium gas of almost
pure volatile component, which has pressure P. So if we
place a piston on the top of the system, exerting pressure
P, the system will be in equilibrium.

The concentration of the volatile component A in

solvent B is called solubility of A in B at P, T. This
characteristics can be measured for a range of binary
systems under different P,T conditions.

In general solubility decreases with temperature. it is

natural to guess that if we heat the system up, the energy
supplied in the system will be used to evaporate more of
the volatile component A.
Thermodynamics of the process:
Multicomponent mixture
• Now we deal with a jar where a number of components is
dissolved in the solvent and also forms and equilibrium gas
mixture.
• Each component can be characterized with it’s own solubility P, T
under these conditions (composition, P, T).
• In general these solubilities (and other properties of the
systems) must be described using methods of multicomponent
phase equilibria (or measured experimentally).
• In many cases the system can be described with simplified
relations
• If ideal gas is in equilibrium with ideal mixture we can apply
the following expression to find partial pressures of the
components:
pi* = Pxi
•If ideal gas is in equilibrium with non-ideal mixture, Henry’s
law applies

pi* = H (T ) xi
Ideal liquid solutions
Four significant characteristics of ideal solutions, all interrelated:
1. The average intermolecular forces of attraction and repulsion in the
solution are unchanged on mixing the constituents
2. The volume of the solution varies linearly with composition.
3. There is neither absorption nor evolution of heat in mixing the
constituents. For gas dissolving in liquids, however, this criterion should
not include the heat of condensation of the gas to the liquid state.
4. The total vapor pressure of the solution varies linearly with composition
expressed as mole fractions

Raoult’s law: when the gas mixture in equilibrium with an ideal liquid
solution, the partial pressure p* of a solute gas A equals the product of its
vapour pressure p at the same temperatue and its mole fraction in the solution x
Nonideal liquid solutions
Raoult’s cannot apply to calculate partial presure of solute gas

Herry’s law:
 The equilibrium relation between p *A in the gas phase and xA can be expressed by a
straight line Henry’s Law equation at low concentration:
pi* = H (T ) xi
Where H = Henry’s law constant (mol frac gas/ mol frac liquid)

 Apply Clapeyron and Dalton theory,

pA
yA =
Pt

*
p H
y* = = x = mx
Pt Pt

Where m=contant
Absorption: General design considerations
1. Entering gas composition flow rate, temperature and pressure Design
2. Desired degree of separation objective
3. Choice of solvent:
- High gas solubility Thermophysical
characteristics
- Low volatility
- Low corrosiveness
- Low cost
- Low viscosity
- Non-toxic, non-explosive Basic design
4. Minimum solvent flow rate -> actual solvent flow rate elements
5. Number of equilibrium stages
6. Heat/cooling requirements Technical
specifications
7. Type of absorber
8. Geometrical parameters of the system/economy
Mass Transfer Between Phases
Two-Film Theory
 In absorption, solute from gas phase must diffuse into liquid phase.
 The rate of diffusion in both phases affect the overall rate of mass
transfer.
 Assumption in Two-Film Theory:
a) equilibrium is assumed at the interface
b) the resistance to mass transfer in the two phases are added
to get an overall resistance.
 Nomenclature:
ky = mass-transfer coefficient in gas phase
kx = mass-transfer coefficient in liquid phase
Ky = Overall mass-transfer coefficient in gas phase
Kx = Overall mass-transfer coefficient in liquid phase
a = interfacial area per unit volume
 The rate of absorption per unit
volume of packed column is given
by any of the following equations:

where y and x refer to the mole fraction

of the component being absorbed.
The overall coefficient:

 Where m = the local slope of the equilibrium curve.

 In Eq. (18.12),
= the resistance of mass transfer in the gas
film.

= the resistance of mass transfer in the

liquid film
The liquid film resistance control the rate of absorption
 when kya = kxa and m > 1.0.
 This means that any change in kxa has a nearly proportional
effect on both Kya and Kxa on the rate of absorption,
 whereas a change in kya has little effect.

The gas film resistance control the rate of absorption

 when kya = kxa and m << 1.0 (very small)
 Solubility of the gas is very high
 Such as absorption of HCl in water and absorption of NH3 in
water
 Physical absorption VS Chemical absorption

Fig. Concentration profile for

absorbed component A

Fig. Concentration profile for

absortion with chemical reaction
Coulson and Richardson_Chemical Engineering Volume 2
Principles of Absorption
Material Balances:
a) Countercurrent flow
b) Cocurrent flow
Limiting gas-liquid ratio
Calculation ideal tray/real trays
Calculation of tower height
Number of transfer unit
Material Balances, Countercurrent flow
Gas tream:

G: total mol/(area of tower cross ection)(time)

y: mol fraction of solute A
p: partial pressure
Y: mole ratio
Gs: insoluble gas (nondiffusing) mol /(area)(time)

Liquid stream :

L: total mol/(area of tower cross ection)(time)

x: mol fraction of solute A
X: mole ratio
Ls: nonvolatile solvent; mol /(area)(time)
Material Balances, Countercurrent flow
Gas tream: Liquid stream :

A solute balance about the lower part of the tower

Rearrange Eq. (8.9) gives operating-line equation:

Material Balances, Countercurrent flow
Material Balances, Countercurrent flow

For an absorber (mass transfer from gas to liquid) the operating line
always lies about the equilibrium-solubility curve
For a stripper (mass transfer from liquid to gas) the operating line
always lies below the equilibrium-solubility curve
Material Balances, Countercurrent flow
Operating-line equation base on mole fraction or partials pressure

(mole fraction of A in G)

y equilibrium line

yb
The driving
force for
mass transfer
ya

Figure 8.6 Operating line in mol fractions

xa xn xb x*b x
(mole fraction of A in L)
Limiting gas-liquid ratio
Minimum liquid – gas ratio, absorption
Material Balances, Cocurrent flow
Gas tream:

G: total mol/(area of tower cross ection)(time)

y: mol fraction of solute A
p: partial pressure
Y: mole ratio
Gs: insoluble gas (nondiffusing) mol /(area)(time)

Liquid stream :

L: total mol/(area of tower cross ection)(time)

x: mol fraction of solute A
X: mole ratio
Ls: nonvolatile solvent; mol /(area)(time)
Material Balances, Cocurrent flow
Mass balance about the tower
L1  G1 = L2  G2
A solute balance about the tower
L1x1 + G1y1 = L2x2 + G2y2
or L1x1 - L2x2 = G2y2 - G1y1
x1
Ls = L1 (1 - x1 )  L1 x1 = Ls = Ls X 1
1 - x1

Ls ( X 1 - X 2 ) = Gs (Y2 - Y1 )

Ls ( X 1 - X ) = Gs (Y - Y1 )
Material Balances, Cocurrent flow

Ls ( X 1 - X ) = Gs (Y - Y1 )
Countercurrent multistage operation
Countercurrent multistage operation

The step marked on the operating diagram therefore represents this ideal tray.
The nearer the operating line to the equilibrium curve, the more steps will be required
Two curves touch at any point corresponding to a minimum Ls/Gs ratio, the number
of steps will be infinite
Real tray and Tray efficiency
Real tray and Tray efficiency
 The ammonia in the air (20oC, 1 atm) was absorbed by pure water (20oC) in
the packed tower with cocurrent flow. The flow of gas inlet is 41,6m3/h.
If the concentration of ammonia was reduced from 3,52% to 1,26%
(volumetric), the water rate of 1,37 times the minimum is to be used.
Find :
a) The minimun rate Ls/Gs ?
b) The flow rate of water has been used?
c) Concentration of amonia in water?
d) Repeat the calculaton if countercurrent flow had been used and
the flow rate of water is 34 kg/h, let’s solve the question a and c?

equilibrium data at 20oC, 1 atm are

X, kmolNH3 / kmol water 0,0164 0,0252 0,0349 0,0455 0,0722

Y, kmol NH3 / kmol air 0,021 0,032 0,042 0,053 0,080

 The ammonia in the air (20oC, 1 atm) was absorbed by pure water
(20oC) in the packed tower with countercurrent flow. The flow of
gas inlet is 41,6m3/h. If the concentration of ammonia was reduced
from 3,52% to 1,26% (volumetric), the water rate of 1,37 times
the minimum is to be used. Find :
a) The minimun rate Ls/Gs ?
b) The flow rate of water has been used?
c) Concentration of amonia in water?

equilibrium data at 20oC, 1 atm are

X, kmolNH3 / kmol water 0,0164 0,0252 0,0349 0,0455 0,0722

Y, kmol NH3 / kmol air 0,021 0,032 0,042 0,053 0,080

Equipment for Absorption and Stripping
Unit Operation 1: PACKED TOWER
 A common apparatus used in gas absorption is the packed
tower as shown in Figure below
 The device consist of:
a) cylindrical column or tower
b) gas inlet and distributing space at the bottom
c) liquid inlet and distributor at the top
d) gas & liquid outlets at the top & bottom, respectively
e) tower packing – supported mass of inert solid shapes
PACKED TOWER
• The liquid inlet - pure solvent or weak liquor
- is distributed over the top of packing by the
distributor
- uniformly wets the surfaces of the packings
• The distributor - is a set of perforated pipes (Fig. 18.1)
- a spray nozzles in a large towers
• The gas inlet - enter the distributing space below the packing
- flow upward in the packing countercurrent to the
flow of the liquid
PACKINGS
• The packing - provides a large area of contact between the liquid
and gas
- encourage intimates contact between the phases
• 3 principal types: dumped packings, stacked packings and
structured/ordered packings.
• Made from: plastic, metal or ceramic
 Structured Packing

Ceramic Intalox Saddle Packing

Pressure Drop & Limiting Flow rates
 Figure 18.4 shows typical data for the pressure drop in a
packed tower.
 Pressure drop is due to fluid friction
 The graph is plotted on logarithmic coordinates for ΔP (inches
H20/ft packing) versus the gas flow rate, Gy (lb/ft2.h)
Loading & Flooding Point
• Point K is the loading point
• Point L is the flooding point for
the given liquid flow.
• Loading point is a point where
liquid hold up starts to increase
and caused a change in the slope
of the pressure drop
• Flooding point is a point where
the gas velocity will result in all
packing to be wetted at this
point, the contact area between
gas and liquid will be
maximized.
PLATE COLUMN (TRAYED TOWER)
 Plate Column absorbers distribute a contacting liquid over
plates situated one above the other.
 The contacting liquid flows downward through the column
from one plate to the other in a stepwise fashion.
 The inlet gas rises through each plate through openings in the
plate and comes into contact with the liquid.
 Usually, a layer of foam and froth is formed above each plate
resulting from the mixing of liquid and gas.
 The gas not absorbed rises through the foam layer to the next
plate for another stage of absorption.
 Plate column absorbers result in a high removal efficiency
since there are multiple stages of contact between liquid and
gas.
Unit operation 2: PLATE COLUMN (TRAYED
TOWER)
PLATE or TRAY type
Chi tiết mâm

Mâm xuyên lỗ
Chi tiết mâm

Mâm chóp
Chi tiết mâm

Mâm van
 Gờ chảy tràn

 Gờ chảy tràn có tác dụng duy trì mực chất lỏng trên mâm
 Plate columns have certain advantages over packed bed
towers:
a) plate columns can handle high gas flow rates
accompanied by a low liquid flowrate with little chance
of flooding.
b) little chance for channeling inside of a plate column
compared to a packed bed tower.
c) sediment build-up often can be easily removed in plate
column absorbers (packed bed towers are harder to
clean).
 However, plate columns are usually more expensive
than packed bed towers.
 The advantages of plate columns are usually not
justified in small operations where a packed bed
tower will suffice.
 Countinuous-contact Equipment
Packed tower: the liquid and gas A compositions change continuously
with height of packing
Height equivalent to an Equilibrium Stage (theoretical plate) :
The required height of packing = (HETP)x(quantity of plate)
HETP: the height equivalent to a theoretical tray or plate
HETP must be an experimentally determined quantity characteristic for
each parking
Depend on:
-Type and size of the parking
-Flow rates of each fluid
 Countinuous-contact Equipment
Z: the packed volume, volume per unit tower cross section, or height of
tower
Gas phase

HtG: height of gas transfer unit ; NtG: number of gas transfer unit:

Liquid phase

HtL: height of liquid transfer unit ; NtL: number of liquid transfer unit:
 Countinuous-contact Equipment
Overall coefficients and Transfer unit

HtOG: the height of an overall gas transfer unit ;

NtOG: number of overall gas transfer units:
 Countinuous-contact Equipment
Overall coefficients and Transfer unit
Principal mass-transfer resistance lies within the liquid
 Countinuous-contact Equipment
Overall heights of Transfer units
The Minimum and Design Liquid- Gas Ratio
The minimum rate is highly
undesirable. At this point
driving force is almost 0.
Hence it would take an
infinetely tall absorber to
accomplish the desired
separation
As a general operating
principle an absorber is
typically designed to operate
at liquid rates which are 30
to 70 % greater than
minimum rate.
Tower Diameter and Pressure Drop
per Unit Tower Height
 For a given packing and liquid flow rate in an
absorption tower variation in the gas velocity
has a significant effect on the pressure drop
 As the gas velocity is increased, the liquid
tends to be retarded in its downward flow,
giving rise to term liquid holdup (LH)
 A LH increases, the free cross-sectional area
for gas flow decreases and pressure drop per
unit height increases.
 Problems with High Gas Velocity
 Channeling: the gas or liquid flow is much greater
at some points than at others
 Loading: the liquid flow is reduced due to the
increased gas flow; liquid is held in the void space
between packing
 •Flooding: the liquid stops flowing altogether and
collects in the top of the column due to very high
gas flow
 TO AVOID this condition experience dictates
operating at gas velocities which are 40 to 70 % of
those which causing flooding
Flood Point
 The relationship between DP/Z and other
important tower variables-liquid and gas rates,
liquid and gas stream densities and viscosities,
and type of packing has been extensively studied
on an experimental basis.
 A widely accepted correlation among these
parameters can be seen in below figure
 Where G' and L': superficial gas and liquid mass
flow rate defined as actual flow rates divided by
the empty cross-sectional area of the tower.
 (G ' ) 2 F L0.1
g c (  L - G ) G

G’:gas mass flux (lb/s-

ft2)
F:packing factor (ft2/ft3)
L:liquid viscosity, cp
gc: proportıonality
constant, 32.17 ft-
lb/s2-lbf
L:liquid density, lb/ft3
L’/G’√(G/L-G)
G:gas density, lb/ft3 L’: liquid mass flux (lb/s-ft2)
In Cooper and Alley’s book, Figure 13.6 can be used. Note that in Figure 13.6 Gx
and Gy are liquid and gas flux (lg/s-ft2), respectively. In our notation G’ and L’
correspond to G and Gy
 Packing Factor F
 The top line in the figure represents the
general flooding condition for many
packings. The flooding condition however
has been found to vary as a function of the
packing factor F (dimensionless packing
factor tabulated below)
 Recent studies showed that when F is in the
range of 10 to 60, the pressure drop can be
expressed by:
DPflood = 0.115F0.7
Packing Data
 Determining Tower Diameter
First abscissa value is calculated
(L'/G')(pG/(pL-pG))0.5

Where this value intercepts the flooding line on

Figure A, move horizontally to the left and read
the value of the ordinate:
(G')2F(L)0.1/gc(pL-pG)pG

Calculate the G’ and take 30 to 70% of it to prevent

flooding

Tower crossectional area: A = G/G‘

Evaluate the tower diameter

Determining Expected Pressure Drop per Unit
Height of Tower
 First calculate actual G’ and L’ and then
calculate the abscissa and the ordinate for
use in Figure 13.6
 From those values the intersection on the
figure defines the pressure drop per foot
of packed height

Another emprical correlation found in the

litrature for the DP in packing when
operating below the load point is
DP/Z = 10-8m[10nL’/L](G’2/G) m and n are
packing constants see Table 6.2
Determining Tower Diameter and Expected Pressure
Drop per Unit Height of Tower
Example
A tray towers is to be designed to remove 95% of the ammonia
from a gaseous mixture of 8 percent ammonia and 92% air, by
volume. The flow rate of the gas mixture entering the tower at
25 oC and 1 atm is 40 kmoles/hr. Water containing no ammonia
is to be the solvent. The velocity of gas in tower is 0.5 m/s.
Determine

 1. The gas-phase flow rates for the solute and carrier gas.
 2. The mole ratios of the gas and liquid phases at inlet and
outlet and the required water rate (2 times the minimum
water had been used).
 [Link] gas and liquid rates for carrier gas, solute gas, total
gas, liquid solvent, solute in liquid, and total liquid
 4. The tower diameter.
 5. The real tray and the heigh of this tower.
Example
Determine composition of the liquid at the exit (X1)
(Inlet liquid concentration since pure water is used is x2=X2=0)
Use equilibrium data for ammonia-air-water mixtures which are given
below for 68 F and 14,7 psia. :
X 0.0206 0.0310 0.0407 0.0502 0.0735 0.0962
Y 0.0158 0.024 0.0329 0.0418 0.0660 0.0920

In order to determine composition of liquid at the exit, we need to

calculate the minimum solvent flow rate first.
By plotting X vrs Y at the equilibrium, we can evaluate the
minimum solvent and then operating solvent rate.
 Determination of an Absorption
Tower Height
Height of a packed tower = f(the overall resistance to mass
transfer between the gas and liquid phases, the average driving
force and interfacial area)
Consider a differential height of the absorber dZ. In height dZ,
the rate of mass transfer of species A

N A A ( adZ ) = d ( G m y ) = Ad ( G ' y )

a: interfacial area available to mass transfer per unit volume of

the packing
A: cross-sectional area of the tower
Tower Height
N A A(adz) = d(Gm y) = Ad(G ' y)

K y a ( y AG - y *A ) dz = d ( G m ' y)
G m ' dy Gm'y
dZ = *
=
K ya( y - y ) K G aP ( y - y * )

The equation can be also written for liquid resistance

part.
Tower Height
Gm ' y Gm ' y
dZ = *
=
K y a( y - y ) K G aP(y - y* )

To solve the above equation we can determine the overall

value of Kya (Kga) based on experimental “pilot plant”
operated with a certain packing and gas/liquid rate.
The right side of the equation can be integrated from
the knowledge of the operating line and equilibrium
line chracteristics.
This method can be modified to deal with the “height of
a transfer unit” and “the number of transfer units” by
modifiying the equation somewhat
 Tower Height
G m ' dy G m ' dy
dZ = *
=
K ya( y - y ) K G aP ( y - y * )

To solve the above equation we can determine the overall

value of Kya (Kga) based on experimental “pilot plant”
operated with a certain packing and gas/liquid rate.
The right side of the equation can be integrated from
the knowledge of the operating line and equilibrium
line chracteristics.
This method can be modified to deal with the “height of
a transfer unit” and “the number of transfer units” by
modifiying the equation somewhat
 Tower Height
The equation can be expressed in terms of height of
transfer unit (HTU ) and number of transfer units :

G 'm y1 dy
Z=
K OG aP yZ ( y - y *)

HTU or NTU or
Hoy Noy

HTU is reaonably constant through the absorber and has

unit of length. NTU is dimensionless. 81
 x1, y1
For dilute gas
streams, transfer
unit equation can
be simplified:
x1, y1*

G 'm y1 dy xZ, yZ
Z=
K OG aP y Z ( y - y *)
xZ, yZ*

Z=
G 'm
´
y1 - yz
; DyLM =
( y1 - y1) ( z
*
- y - y z)
*

KOG aP DyLM æ y - y* ö
ln ç 1 1* ÷
è yz - yz ø
2016/4/7 Aerosol & Particulate Research Lab 82