EKC 217 : Mass Transfer

Gas Absorption

Sub -Topics
• Definition of Absorption and Desorption
• Equipments used for Absorption
• Contact between Liquid and Gas
• Equilibrium Solubility of Gases in Liquids
• Ideal Liquid Solutions
• Roult’s & Henry’s Law
• Choice of Solvent for Absorption
• One Component Transferred : Material Balances
• Equilibrium and Operating Line
• Minimum Liquid-Gas Ratio for Absorbers
• Pressure drop
• Height of Absorber
• Diameter of Absorbers

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 Definition
• In absorption (gas absorption, gas scrubbing, gas washing), a gas
mixture is contacted with a liquid (absorbent or solvent) to
selectively dissolve one or more components by mass transfer from
the gas to the liquid.
• The components transferred to the liquid are referred to as solutes
or absorbate.
• The species of interest in the gas mixture may be all components,
only the component(s) not transferred, or only the component(s)
transferred.
• Example: Removal of ammonia from a mixture of ammonia and air
by means of liquid water.
• In gas absorption, a substance is transfer from the gas stream to the
liquid. When mass transfer occurs in the opposite direction, from the
liquid to the gas, the process is known as stripping or desorption.
• Absorbers are often couple with strippers to permit regeneration (or
recovery) and recycling of the absorbent.
• Since stripping is not perfect, the recycled absorbent may contain
the solute.
• Since the principles of both absorption and desoprtion is basically
the same, we will study both together but concentration will be given
to absorption.

Equipment for
Absorption
• Since absorption involves the
transference of a component
from the gas phase to the liquid
phase, thus a suitable equipment
for the process must be able to
provide an intimate contact
between the two phases.
• The equipment used includes
tray towers (plate columns),
packed columns, spray towers,
bubble columns and centrifugal
contactors as shown
schematically in Fig. 1.
• However, the 2 most developed
techniques are tray towers and
packed columns.

Fig. 1: Industrial equipment for absorption and

stripping; (a) tray towers, (b) packed columns,
(c) spray towers, (d) bubble columns and (e)
centrifugal contactors.
(e)

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 Tray (Plate) Towers
• 3 types of tray towers often used are Sieve Tray, Valve Tray
and Bubble-Cap Tray.
• Sieve Tray as shown in Fig. 2 is the most commonly used.
• In the sieve tray, vapor bubbles
up through simple holes in the
tray through the flowing liquid. Wap/Gas
Hole sizes range from 3 to 12
mm in diameter.
Penurun
• The liquid is held on the tray
surface and prevented from Cecair
flowing down through the holes
by the kinetic energy of the gas
vapor.
• The depth of liquid on the tray
is maintained by an overflow,
outlet weir. The overflow liquid
flows into the downspout to the Fig. 2 : Sieve Tray
next tray below.
5

• A modification of the sieve tray is the valve tray shown in Fig. 3(a).
It consists of an opening in the tray and a lift-valve cover with
guides to keep the cover properly positioned over the opening.
• This provide variable open area which is varied by the vapor flow
inhibiting leakage of liquid down the opening at low flow rates.
Hence, this tray can operate over a wider range of flow rates, with
cost 20% higher than sieve tray.
• Bubble-cap trays have been used over 100 years, but since 1950,
they have been superseded by sieve or valve trays because their
cost is almost double of sieve tray.
• As shown in Fig. 3(b), a bubble-cap
tray has bubble caps that consists of
a fixed cap mounted over and above
a riser. The vapor flows up through
the tray opening into the riser, turns
around, and passes out through the
slots of the cap into the liquid.
Fig. 3: Tray with (a) Valve cap and (b) bubble-cap

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 Packed Tower
• Fig. 4 shows a packed tower commonly used for absorption.
• The packed section is filled with a mass of inert solid shapes (tower packing)
held by a support.
• The inlet liquid, which may be pure solvent or a dilute solution of solute in the
solvent and which is called the weak liquor, is distributed over the top of the
packing by the distributor.
•The solute containing gas, or rich gas enters
the tower from the space below the packing
and flows upward through the spaces
between in the packing counter current to
the flow of liquid.
• The packing provides a large area of
contact between liquid and gas.
• The solute in the rich gas is absorbed by the
fresh liquid entering the tower, and dilute or
lean gas leaves the top.
• The liquid is enriched in solute as it flows
down the tower, and concentrated liquid,
called strong liquor, leaves from the bottom.
Fig. 4 : Packed Tower

Tower Packings
• 3 principle types of tower packings; those dumped at random; those that
must be stacked by hand and those known as structured or ordered
packings.
• Dumped packings consist of units 6 to 75 mm in major dimension while
stacked packings consist of units 50 to 200 mm. Stacked packings are
now days rarely used.
• Dumped tower packings are made
of cheap, inert materials such as
clay, porcelain or various plastic.
Thin-walled metal rings of steel or
aluminum are sometimes used.
• High void spaces and large
passages for the fluids are
achieved by making the packings
irregular or hollow, so that they
interlock into open structures with Fig. 5 : Common tower packings (a) Raschig
rings, (b) metal Pall ring, (c) plastic Pall ring, (d)
a porosity or void fraction of 60%
Berl saddle, (e) ceramic Intalox saddle, (f)
to 90%. Common dumped plastic Super Intalox saddle and (g) metal
packings are shown in Fig. 5. Intalox saddle

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 • Fig. 6 shows a common structured packings. Mostly, they are
made of sheets of perforated corrugated metal, with adjacent
sheets arranged so that liquid spreads over their surfaces while
vapor flows through channels formed by the corrugations.
• The channels are set at an angle of 45 oC with the horizontal; the
angles alternates in direction in successive layers. Each layer is a
few inches thick.

• Various proprietary
packings differ in the size
and arrangement of the
corrugations and the
treatment of the packing
Vapor
surfaces.
Vapor
• The porosity ranges from
0.93 to 0.97. Fig. 6 : Typical structured packing

Contact between Liquid and Gas

• The requirement of good contact between liquid and gas is the hardest to
meet, especially in large tower. Ideally, the liquid, once distributed over
the top of the packing, flows in thin films over all the packing surface all
the way down the tower.
• However, actually, the films tend to grow thicker in some places and
thinner in others, so that liquid collects into small rivulets and flows along
localized paths through the packing.
• Especially at low liquid rates, much of the packing surface may be dry or,
at best, covered by a stagnant film of liquid. This effect is known as
channeling and it is the chief reason for the poor performance at large
packed towers.
• Channeling is severe in towers filled with stacked packing, which is the
main reason they are not much used. It is less severe in dumped
packings. In towers of moderate size, channeling can be minimized by
having the diameter of the tower at least 8 times the packing diameter. If
the ratio is less than that, the liquid tends to flow out of the packing and
down the walls of the column.
• Even in small towers filled with packings that meet this requirement,
however, liquid distribution and channeling have a major effect on
column performance. In big tower, liquid re-distributor is required for
every 5 to 10 m in the tower.
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 Equilibrium Solubility of Gases in Liquids
• The rate at which a gaseous constituent of a mixture will dissolve in an
absorbent liquid depends upon the departure from equilibrium which exists
and therefore it is necessary to consider the equilibrium characteristic of
gas-liquid systems.
• If a quantity of a single gas and a relatively nonvolatile liquid are brought to
equilibrium in a close container at a constant pressure and temperature, the
resulting concentration of the dissolved gas in the liquid is said to be the gas
solubility at the prevailing temperature and pressure.
• At fixed temperature, the solubility concentration will increase with pressure.
How about the other way around?
• In most cases, the solubility of a gas decreases with increasing temperature.
On the other hand, the solubility of many low-molecular-weight gases such
as hydrogen, oxygen, nitrogen and methane in water increases with
increase temperature above about 100 oC.
• Different gasses and liquids yield separate solubility curves which must
ordinarily be determined experimentally for each system.

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Ideal and Non-ideal Liquid Solutions

• When the liquid phase can be considered ideal, the equilibrium partial pressure
of a gas from the solution can be computed without resort to experimental
determination.
• There are 4 significant characteristic of an ideal solutions. What are they?
• In reality there are no ideal solutions, and actual mixtures only approach
ideality as a limit. Ideality would require that the molecules of the constituents
be similar in size, structure and chemical nature and the nearest approach to
such a condition is perhaps exemplified by solutions of optical isomers of
organic compounds. Practically, however, many solutions are so nearly ideal
that for engineering purposes, they can be considered so.
• When the gas mixture in equilibrium with an ideal solution that also follows the
ideal gas law, the partial pressure of a solute gas A (pA) equals the product of
its vapor pressure at that same temperature (p*A) multiple its mole fraction in
the solution (xA). This is known as the Raoult’s Law:
• PA = PA* ´ x A (1)
• For liquid solutions which are not ideal, Eq. (1) will give highly incorrect results.
Thus, for non-ideal solutions, an alternative equation can be used for a small
concentration range. The equation is known as Henry’s Law whereby KH is the
Henry constant:
• PA = K H ´ x A (2)

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 Choice of Solvent for Absorption
• Gas solubility. The gas solubility should be high, thus increasing
the rate of absorption and decreasing the quantity of solvent
required.
• Volatility. The solvent should have a low vapor pressure since the
gas leaving an absorption operation is ordinarily saturated with the
solvent.
• Corrosiveness. The materials of construction required for the
equipment should not be unusual or expensive.
• Cost. The solvent should be in-expensive, so that losses are not
costly and should be readily available.
• Viscosity. Low viscosity is preferred for reasons of rapid
absorption rates, improved flooding characteristic in absorption
towers, low pressure drops on pumping and good heat-transfer
characteristic.
• Miscellaneous. The solvent if possible should be non-toxic, non-
flammable, and chemically stable and should have low freezing
point.

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G2
Liquid Flow
GS Material Balance (One Component Transferred)
L2
LS Y2
X2 y2 • Fig. 7 shows a countercurrent tower (packed/spray/tray) for absorption.
x2 p2 • The gas stream at any point in the tower consists of G total mol / (area
of tower cross section) (time), made up of diffusing solute A
represented by y, p or Y and nondiffusing, essentially insoluble gas GS.
• The variables used above are:
L G G = Total gas stream [mol / (area of tower cross section) (time)]
LS GS
y = Mole fraction of solute A in the gas phase
XA YA
xA yA p = Partial pressure of solute A in the gas phase
P
Y = Mole ratio of solute A in the gas phase
GS = Insoluble gas [mol / (area of tower cross section) (time)]

• The relationship between these variables are :

L1 G1
y p
LS GS Y= = (3)
X1 1 - y PT - p
Y1
x1 y1
p1 G
G S = G(1 - y) = (4)
Gas Flow 1+ Y
Fig. 7

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 G2
Liquid Flow
GS Material Balance (One Component Transferred)
L2
LS Y2
X2 y2 • Still using the same Fig.7.
x2 p2 • Similarly, the liquid stream at any point in the tower consists of L total
mol / (area of tower cross section) (time), made up of diffusing solute A
represented by x or X and essentially nonvolatile solvent LS.
• The variables used above are:
L G
L = Total liquid stream [mol / (area of tower cross section) (time)]
LS GS
x = Mole fraction of soluble gas in the liquid phase
XA YA
xA yA X = Mole ratio of soluble gas in the liquid phase
P
LS = Nonvolatile solvent [mol / (area of tower cross section) (time)]

• The relationship between these variables are :

x
X= (5)
1- x
L1 G1
L
LS GS LS = L(1 - x) = (6)
1+ X
X1 Y1
x1 y1 • Since the nonvolatile solvent (LS) and the insoluble gas (GS) are
p1
essentially unchanged in quantity as they pass through the tower, it is
Gas Flow convenient to express the material balance in terms of these variables.
Fig. 7

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Material Balance (One Component Transferred)

• Referring to Fig. 7, a material balance for solute A from the dotted line to the bottom of the tower can
be written as :

G S (Y1 - Y) = LS (X1 - X) (7)

• Eq. (7) is a straight line (operating line) on X & Y coordinates, of slope LS/GS which passes through
points (X1,Y1) and (X2,Y2).
• Eq. (7) is known as the operating line that indicates the relation between the liquid and gas
concentration at any level in the tower, as at point P (shown in Fig. 7 & 8).
• The equilibrium solubility data for the solute gas in the solvent liquid can also be plotted in terms of
these concentration units on the same diagram, as represented by curve MN. Each point on this
curve represents the gas concentration in equilibrium with the corresponding liquid at its local
concentration and temperature.
• For an absorber (mass transfer from gas to liquid) the operating line always lies above the
equilibrium-solubility curve, while for a stripper (mass transfer from liquid to gas) the line is always
below as shown in Fig. 8 (a) and (b).
• The operating line is straight only when plotted in terms of the mole-ratio units. In terms of mole
fractions or partial pressures, the line is curved, as shown in Fig. 9 for an absorber. The equation of
the line is then:

æ y y ö æ p1 p ö æ x1 x ö (8)
G S çç 1 - ÷÷ = G S ç ÷ ç ÷
ç P - p - P - p ÷ = LS ç 1 - x - 1 - x ÷
è 1 - y1 1 - y ø è T 1 T ø è 1 ø

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 Fig. 8 : Operating Line
for (a) absorber and
(b) stripper

Fig. 9 : Operating line

in mole fractions

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Minimum Liquid-Gas Ratio for Absorbers

• In the design of absorbers, the quantity of gas to be treated (G atau GS), the terminal
concentrations Y1 & Y2, and the composition of the entering liquid (X2) are ordinarily fixed by
the process requirements.
• However, the quantity of liquid (solvent) to be used is subject to choice.
• Refer to Fig. 10(a). The operating line must pass through point D and must end at the ordinate
Y1. If such a quantity of liquid is used to give operating line DE, the exit liquid will have the
composition X1.
• If less liquid is used, the exit-liquid composition will clearly be greater, as at point F, but since
the driving forces for diffusion are less, the absorption is more difficult. The time of contact
between gas and liquid must then be greater and the absorber must be correspondingly taller.

Fig. 10 : Minimum liquid-gas

ratio for absorption

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 Minimum Liquid-Gas Ratio for Absorbers
• The minimum liquid which can be used corresponds to the operating line DM, which has the greatest
slope for any line touching the equilibrium curve and as tangent to the curve at P. At P, the diffusional
driving force is zero, the required time for contact for the concentration change desired is infinite, and
an infinitely tall tower results. This then represents the limiting liquid-gas ratio.
• The equilibrium curve is frequently concave upward, as shown in Fig. 10(b), and the minimum liquid-
gas ratio then corresponds to an exit liquid concentration in equilibrium with the entering gas.
• These principles also apply to strippers, where an operating line which anywhere touches the
equilibrium curve re-presents a maximum ratio of liquid to gas and a maximum exit-gas
concentration.
Example 1
A coal gas is to be freed of its light oil by scrubbing with wash oil as an absorbent and the light
oil recovered by stripping the resulting solution with steam. The circumstances are as follows:
Absorber. Gas in, 0.25 m3/s at 26oC and Pt = 1.07 ´ 105 N/m2 containing 2.0% (volume) of light
oil vapors. The light oil will be assumed to be entirely benzene, and a 95% removal is required.
The wash oil is to enter at 26oC containing 0.005 mole fraction benzene, and has an average
molecular weight 260. An oil circulation rate of 1.5 times the minimum is to be used. Wash oil-
benzene solution are ideal. The temperature will be constant at 26 oC.
Stripper. The solution from the absorber is to be treated to 120 oC and will enter the stripper at
1 std atm pressure. Stripping steam will be at standard atmospheric pressure, superheated to
122 oC. The debenzolized oil, 0.005 mole fraction benzene, is to be cooled to 26 oC and
returned to the absorber. A steam rate of 1.5 times the minimum is to be used. The temperature
will be constant at 122 oC.
Compute the oil-circulation rate and the steam rate required.

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Pressure Drop & Limiting Flow Rates

• Fig. 11 shows typical data for pressure drop in a packed bed.
• The pressure drop per unit packing depth comes from fluid friction.
• When the packing is dry, the line so obtained is straight and has a slope of about 1.8. the
pressure drop therefore increases with the 1.8 power of the velocity.
• If the packing is irrigated with a
constant flow of liquid, the
relationship between pressure drop
and the gas flow rate initially
follows a line parallel to that for dry
packing. The pressure drop is
greater than that in dry packing,
because the liquid in the tower
reduces the space available for gas
flow. The void fraction, however,
does not change with gas flow.
• At moderate gas velocities, the line
for irrigated packing gradually
becomes steeper, because the gas
now impedes the downflowing
liquid and the liquid holdup
increases with gas rate.
Fig. 11 : Pressure drop in a packed tower for air-water
system with 1-in Intalox saddles

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 Pressure Drop & Limiting Flow Rates
• The point at which the liquid holdup starts to increase, as judged by a change in the
slope of the pressure drop line, is called the loading point. However, as is evident
from Fig. 11, it is not easy to get an accurate value for the loading point.
• With still further increase in gas velocity, the pressure drop rises even more rapidly
and the lines becomes almost vertical when the pressure drop is about 2 to 3 in. of
water per foot of packing.
• In local regions of the column, the liquid becomes the continuous phase and the
flooding point has been reached. Higher gas flows can be used temporarily, but then
liquid rapidly accumulates and the entire column may fill with liquid.
• The gas velocity in an operating packed column must obviously be lower than the
flooding velocity. However, as flooding is approached, most of or all the packing
surface is wetted, maximizing the contact area between gas and liquid. Thus, the
designer must choose a velocity far enough from the flooding velocity to ensure safe
operation but not so low as to require a much larger column.
• Packed towers may also be designed on the basis of a definite pressure drop per
unit height of packing.

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Pressure Drop & Limiting Flow Rates

• A widely used correlation for
estimating pressure drops in
dumped packings is given in Fig.
12 where Gx and Gy are in unit
lb/ft2.s, rX and rY are in unit
lb/ft3, Fp is the packing factor
(dimensionless), n is the
kinematic viscosity of the liquid
in centistokes and CS is the
capacity factor.
• The capacity factor (CS) can
correlated with the superficial
velocity (uo) in feet per second
as shown in the equation below:

ry
CS = u o (9) Fig. 12 : A generalized pressure drop correlation
rx - ry

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 Diameter for Tray Columns
• For a given liquid flow rate in tray columns, a maximum vapor flow rate
exists, in which beyond that value, column flooding occurs because of
backup of liquid in the downcomer. This condition, if sustained, leads to
carryout of liquid with the overhead vapor leaving the column.
• In another words, downcomer flooding takes place when liquid backup is
caused by downcomers of inadequate cross-sectional area, Ad. However,
this phenomena rarely occurs if downcomer cross-sectional area is at least
10% of total column cross-sectional area and if tray spacing is at least 24
inch.
• The usual design limit is entrainment flooding, which is caused by excessive
carry-up of liquid by vapor entrainment to the tray above. Entrainment of
liquid is due to carry up of suspended droplets by rising vapor or throw up of
liquid particles by vapor jets formed at tray perforations, valves or bubble-
cap slots.
• Tray/Column diameter is determined generally to avoid flooding.
• Column diameter is calculated at both top and bottom of the column, with the
larger of the two diameters used for the entire column. Because of the need
for internal access to columns with trays, a packed column is generally used
if the calculated diameter is less than 2 ft.

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• Usually, before determining the column diameter, tray spacing must be specified. As
spacing is increased, column height is increased but column diameter is reduced. A
spacing of 24 inch which provides ease of maintenance, is optimum for a wide range
of operations.
• One of the methods use to calculate tray diameter required is using Eq. (10):
• é 4 G MG ù
0.5

DT = ê ú (10)
ë f U f π (1 - A d /A ) ρ G û
where:
DT = Tray diameter (m)
G = Mole flowrate of the gas stream (kmol/s)
MG = Molecular weight of the components in the gas stream (kg/kmol)
f = Fraction of flooding (dimensionless)
Uf = Flooding velocity (m/s)
Ad = Cross-sectional area of downcomer (m2)
A = Total column cross-sectional area (m2)
rG = Density of the gas stream (kg/m3)

• Ad/A can be determine using Eq. (11) below:

•

(11)

24
 where:
FLV = Liquid Vapor Factor (dimensionless) which is calculated using Eq. (12)

FLV = (L M L / G M G ) (ρ G / ρ L ) 0.5
(12)
where:
L = Mole flowrate of the liquid stream (kmol/s)
ML = Molecular weight of the components in the liquid stream (kg/kmol)
rL = Density of the liquid stream (kg/m3)

• On the other hand Uf can be calculated using Eq. (13) below:

• æρ -ρ ö
0.5

U f = C çç L G ÷÷ (13)
è ρG ø
where:
C = Capacity parameter (ft/s) which can be determine using Eq. (14):
C = FST FF FHA CF
(14)
where:
s factor (dimensionless) = ( /20)0.2 ; s = surface tension of liquid
FST = Surface tension s
(dyne/cm)
FF = Foaming factor (dimensionless)
FHA = Ratio of vapor hole area to tray active area factor (dimensionless)
CF = Capacity parameter factor (ft/s). This value can be determine from the Entrainment
Flooding Capacity Plot given in Fig. 13

25

Example 2
A tower packed with 1-in ceramic ‘Intalox
Saddle’ is to be built to treat 25,000 ft3 (708 m3)
of entering gas per hour. The ammonia content
of the entering gas is 2% (volume). Ammonia-
free water is used as absorbent. The
temperature of the netering gas and the water
is 68oF (20oC); the pressure is 1 atm. The ratio
of liquid flow to gas flow is 1.25 lb liquid per lb
of gas. If the design pressure drop is 0.5 inci
H2O per foot of packing, what should be the
mass velocity of the gas and the diameter of
the tower. The packing factor can be taken as Fig. 13 : Entrainment Flooding Capacity in a
92 and kinematic viscosity at 20oC is 1.0 cSt. Tray Tower

Example 3
You are required to remove 90% of the acetone in a gas stream containing 1 mol% acetone in air
using a counter current absorption tower. The total flowrate of gas stream to the tower 30 kg-
mol/h and the total flowrate of pure water that will be used to absorb the acetone is 90 kg-mol/h.
The operation will occur at isothermal condiation at 300 K and at101.3 kPa pressure. The
equilibrium relationship between acetone in gas-liquid is y = 2.53x. Determine the number of
theoretical stages required for the separation process above using the graphical method.

Example 4
Repeat Example 3 by using the calculation method (Kremser Equation)

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