Gas-liquid absorption

CL 321
Kaustubh Rane

1
 Intro
• Absorption: Transfer from gas to liquid

• Stripping: Transfer from liquid to gas

• Equipment for absorption:

• Based on the dispersed phase
• Gas dispersed
• Liquid dispersed
• Based on the type of contact
• Tray column: Stage-wise contact
• Packed column: Continuous contact
• Generally, there are three components

• Liquid-vapour equilibrium: Gibb’s phase rule

• 𝐹 =𝐶−𝑃+2=3
• 𝑇, 𝑃 and mole fraction of component being transferred
2
 Liquid-vapor equilibrium: Raoult’s law

• Relates the composition of the condensable component in the liquid

and vapour phases

• 𝑦𝐴 : Composition in vapour
• 𝑥𝐴 : Composition in liquid
• 𝑦𝐴 ∗ 𝑃𝑇 = 𝑥𝐴 𝑝𝐴∗

• Ideal solution:
• Δ𝑆𝑚𝑖𝑥 = 0
• Δ𝑉𝑚𝑖𝑥 = 0
• Δ𝐻𝑚𝑖𝑥 = 0

• No additional parameter required

3
 Liquid-vapor equilibrium: Henry’s law

• Relates the composition of the dissolved component in liquid and

vapour phases

• 𝑦𝐵 : Composition in vapour
• 𝑥𝐵 : Composition in liquid
• 𝑦𝐵 ∗ 𝑃𝑇 = 𝑥𝐵 𝐻𝐵
• 𝐻𝐵 : Henry’s law constant for 𝐵 (solvent dependent)

• Valid when:
• Non-ideal solution
• 𝑥𝐵 → 0 (𝐵 should not dissociate, ionize or react in liquid phase)
• Applied for less soluble gases

• 𝐻 can be obtained from the Perry’s handbook

4
 Raoult’s law vs. Henry’s law

Raoult’s law Henry’s law

• Ideal vapour phase • Ideal vapour phase

• Ideal solution • Non-ideal solution

• High conc. Of species • Low conc. of species

• Solution containing species of • Solution may contain species of

similar characteristics dissimilar characteristics

• Fails above moderate pressures • Fails at high pressures

• Requires vapour pressure • Requires Henry’s constant

5
 Equilibrium line and operating line
• 𝐺1 , 𝐺2 : Total molar flow-rate of gas
𝑮𝟐 , 𝒚𝟐 𝑳𝟐 , 𝒙𝟐
• 𝐿1 , 𝐿2 : Total molar flow-rate of liquid

• 𝑦1 , 𝑦2 : Mole fractions in bulk gas

• 𝑥1 , 𝑥2 : Mole fractions in bulk liquid

𝒚𝟏
𝑮𝟏 , 𝒚𝟏 𝑳𝟏 , 𝒙𝟏

𝒚𝟐

6
𝒙𝟐 𝒙𝟏
 Equilibrium line and operating line
• 𝐺𝑠 :Molar flow-rate of non-diffusing gas

𝑮𝒔 , 𝒀𝟐 𝑳𝒔 , 𝑿𝟐 • 𝐿𝑠 : Molar flow-rate of non-volatile liquid

𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑑𝑖𝑓𝑓𝑢𝑠𝑖𝑛𝑔 𝑐𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡 𝑖𝑛 𝑔𝑎𝑠

• 𝑌1 , 𝑌2 :
𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑛𝑜𝑛−𝑑𝑖𝑓𝑓𝑢𝑠𝑖𝑛𝑔 𝑐𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡 𝑖𝑛 𝑔𝑎𝑠

𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑑𝑖𝑓𝑓𝑢𝑠𝑖𝑛𝑔 𝑐𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡 𝑖𝑛 𝑙𝑖𝑞𝑢𝑖𝑑

• 𝑋1 , 𝑋2 :
𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑛𝑜𝑛−𝑑𝑖𝑓𝑓𝑢𝑠𝑖𝑛𝑔 𝑐𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡 𝑖𝑛 𝑙𝑖𝑞𝑢𝑖𝑑

𝒀𝟏

𝑮𝒔 , 𝒀𝟏 𝑳𝒔 , 𝑿𝟏
𝒀𝟐

7
𝑿𝟐 𝑿𝟏
 Equilibrium line and operating line
𝑦
𝑌=
𝑮𝟐 , 𝒚𝟐 𝑳𝟐 , 𝒙𝟐 1−𝑦
𝑮𝒔 , 𝒀𝟐 𝑳𝒔 , 𝑿𝟐
𝑥
𝑋=
1−𝑥

𝐺
𝐺𝑠 = 𝐺 1 − 𝑦 =
1+𝑌

𝐿
𝐿𝑠 = 𝐿 1 − 𝑥 =
1+𝑋

𝑮𝒔 , 𝒀𝟏 𝑳𝒔 , 𝑿𝟏
Material balance on the section of column
𝑮𝟏 , 𝒚𝟏 𝑳𝟏 , 𝒙𝟏
𝐿𝑠
𝑌1 − 𝑌 = (𝑋1 − 𝑋)
𝐺𝑠 8
 Equilibrium line and operating line

𝑮𝒔 , 𝒀𝟐 𝑳𝒔 , 𝑿𝟐 𝒀𝟏

𝑳𝒔
𝑮𝒔

𝒀𝟐 𝑳𝒔
𝑮𝒔 𝒎𝒊𝒏

𝑮𝒔 , 𝒀𝟏 𝑳𝒔 , 𝑿𝟏 𝑿𝟐 𝑿𝟏 𝑿𝒎𝒂𝒙
• Generally, 𝐺𝑠 , 𝑋2 , 𝑌1 , 𝑌2 are fixed

• 𝐿𝑠 can be controlled
• Minimum 𝐿𝑠 ≡ Operating line touches the equilibrium line 9
 Significance in design

• Minimum slope ≡ Maximum liquid concentration

• However liquid flow-rate is low

• The height of column is high

• Taller columns are expensive to build

• 𝐿𝑠 ≈ 1.2 − 2.0 times the minimum flow-rate

10
 Calculating the liquid flow-rate

Vapor pressure of benzene: 100𝑚𝑚𝐻𝑔 at 26𝑜 𝐶 and 2400 𝑚𝑚𝐻𝑔 at

120𝑜 𝐶
11
Adapted from “Mass transfer operations” by Treyball
 Cascade and ideal stages

𝑮𝒔 , 𝒀𝟎 𝑳𝒔 , 𝑿𝟎
𝒀𝒊 𝑿𝒊−𝟏 • Ideal stage: A part of the
𝒊=𝟏 process where effluents
𝒊=𝟐 are in equilibrium
𝒊=𝟑 𝒊𝒕𝒉 stage
• Cascade ≡ series of
stages
𝒀𝒊+𝟏 𝑿𝒊
𝒊=𝒏
• Countercurrent flow of
𝑮𝒔 , 𝒀𝒃 𝑳𝒔 , 𝑿𝒃 liquid and vapour

12
 Stages and height of column
• Height proportional to the stages

• Useful in designing both stage-wise and differential contact absorbers

• Stage-wise contact: One plate ≡ One stage

• Differential contact: HETP (height equivalent of theoretical plate)

• In reality, No. of real plates > No. of ideal stages

𝒀𝒊 𝑿𝒊−𝟏
𝑁𝑒𝑞
• Overall column efficiency:
𝑁𝑎𝑐𝑡𝑢𝑎𝑙

𝒊𝒕𝒉 stage
• Stage efficiency (Murphree efficiency)
𝑌𝑖+1 −𝑌𝑖
• Vapor side: ∗
𝑌𝑖+1 −𝑌𝑖
𝒀𝒊+𝟏 𝑿𝒊
13
 Estimating the number of ideal stages
• Given: Inlet concentrations, liquid and gas flow-rates and
equilibrium curve
𝒀𝟏 𝑿𝟎
𝒀𝒃

Stage 1

𝒀𝟐 𝑿𝟏

𝒀𝟐
𝒀𝟐 𝑿𝟏

𝒀𝟎 = 𝒀𝟏
Stage 2
𝑿𝟎 𝑿 𝑿𝟐 𝑿𝒃
𝟏

𝒀𝟑 𝑿𝟐
14
 Slopes of equilibrium and operating lines
• Assuming 𝑦 ≪ 1 and 𝑥 ≪ 1

• 𝑌 ≈ 𝑦 and 𝑋 ≈ 𝑥

• 𝐺𝑠 = 𝐺 1 − 𝑦 ≈ 𝐺 and 𝐿𝑠 = 𝐿(1 − 𝑥) ≈ 𝐿

𝐿
• Slope of operating ling ≈
𝐺

• Assuming Henry’s law because dilute solution ⇒ Equilibrium curve is

straight

𝐻
• Slope of equilibrium line 𝑚 ≈
𝑃𝑡

𝐿 𝑠𝑙𝑜𝑝𝑒 𝑜𝑓 𝑜𝑝𝑒𝑟𝑎𝑡𝑖𝑛𝑔 𝑙𝑖𝑛𝑒

• 𝐴= = (Absorption factor)
𝐺𝑚 𝑠𝑙𝑜𝑝𝑒 𝑜𝑓 𝑒𝑞𝑢𝑖𝑙𝑖𝑏𝑟𝑖𝑢𝑚 𝑙𝑖𝑛𝑒
• 𝑆 = 1/𝐴 (Stripping factor) 15
 Analytical solution
• For 𝐴 = 1
𝑦𝑁𝑝 − 𝑦1
𝐴𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑠𝑒𝑝𝑎𝑟𝑎𝑡𝑖𝑜𝑛
𝑁𝑝 = =
𝑦1 − 𝑚𝑥𝑜 𝐷𝑟𝑖𝑣𝑖𝑛𝑔 𝑓𝑜𝑟𝑐𝑒

• For 𝐴 ≠ 1
• For absorber
1 1 𝑦𝑁𝑝 +1 − 𝑚𝑥𝑜
ln 𝐴 + 1 − 𝐴 𝑦1 − 𝑚𝑥𝑜
𝑁𝑝 =
ln 𝐴

• For stripper
1 1 𝑥𝑜 − 𝑦𝑁𝑝 +1 /𝑚
ln + 1 −
𝑆 𝑆 𝑥𝑁𝑝 − 𝑦𝑁𝑝 +1 /𝑚
𝑁𝑝 =
ln 𝑆
16
 Slopes of equilibrium and operating lines

𝑨=𝟏 𝑨<𝟏
𝒀𝒃 𝒀𝒃

𝒀𝟎 = 𝒀𝟏 𝒀𝟎 = 𝒀𝟏

𝑿𝟎 𝑿𝒃 𝑿𝟎 𝑿𝒃

𝒀𝒊+𝟏 − 𝒀𝒊 = constant 𝒀𝒊+𝟏 − 𝒀𝒊 = decreases

𝑬𝒐 = 𝑬𝑴𝑮 𝑬𝒐 > 𝑬𝑴𝑮

No limit on degree of separation Separation limited by

17
equilibrium curve
 Slopes of equilibrium and operating lines
𝑨>𝟏
𝒀𝒃

• Large 𝐴 ⇒ Large 𝐿

• Large 𝐿 ⇒ Dilute outlet solution

𝒀𝟎 = 𝒀𝟏

𝑿𝟎 𝑿𝒃

𝒀𝒊+𝟏 − 𝒀𝒊 = increasing

𝑬𝒐 < 𝑬𝑴𝑮

18
No limit on degree of separation
 Overall and stage efficiencies
𝑌𝑖+1 −𝑌𝑖
• Murphree efficiency: 𝐸𝑀𝐺 =
𝑌𝑖+1 −𝑌𝑖∗
𝑨<𝟏
𝑁𝑒𝑞
• Overall efficiency: 𝐸𝑜 =
𝑁𝑎𝑐𝑡𝑢𝑎𝑙

𝑨=𝟏
𝑬𝑴𝑮 < 𝑬𝒐
= 𝟎. 𝟓

𝑨>𝟏

𝑬𝒐 = 𝑬𝑴𝑮
= 𝟎. 𝟓
𝑬𝑴𝑮 > 𝑬𝒐
= 𝟎. 𝟓 19
 Determination of 𝐸𝑀𝐺 or 𝐸𝑜
1
ln 1 + 𝐸𝑀𝐺 −1
𝐴
𝐸𝑜 =
1
ln
𝐴

• Drickamer and Bradford correlation:

• 𝐸𝑜 = 19.2 − 57.8 log(𝜇𝐿 )
• 𝐸𝑜 (%) and 𝜇𝐿 (1.6 𝑡𝑜 2 𝑐𝑝)

• O’Connell correlation for 𝐸𝑜

• Considers the Henry’s law constant of the absorbed component

• Van Winkle’s correlation for 𝐸𝑀𝐺

• Considers the design features of the tray

Self-study 20
 Examples
20.3 A column with eight plates and an estimated plate efficiency of 75% is
used to remove a component from a dilute gas by absorption in water. By what
𝐿
factor must the ratio exceed the slope of the equilibrium line to achieve the
𝐺
95% removal of component A

20.4 If the ammonia absorber has 2% ammonia in the inlet gas and no
ammonia in the incoming water, what fraction of ammonia could be absorbed
with an absorption factor of 0.9 and 𝑁 = 5 or 𝑁 = 10

20.1 Calculate the number of ideal stages for the absorption column with
following input and output conditions:
Acetone in entering gas: 25 mol%
Acetone in entering oil: 1.5 mol %
Acetone in bottoms liquor, 8 mol%
Acetone absorbed 90%

Equilibrium relationship: 𝑦𝑒 = 1.9𝑥𝑒

21
Adapted from “Unit Operations in Chemical Engineering” by McCabe, Smith and Harriott
 Examples

Carbon disulphide 𝐶𝑆2 used as a solvent in a chemical plant, is evaporated from

the product in a drier into an inert gas (essentially 𝑁2 ) in order to avoid an
explosion hazard, The vapour-𝑁2 mix is to be scrubbed with absorbent
hydrocarbon oil (𝑀𝑊 = 180), which will be subsequently steam-stripped to
remove 𝐶𝑆2 . The 𝐶𝑆2 − 𝑁2 mixture has a partial pressure of 𝐶𝑆2 equal to 500
mmHg at 24𝑜 𝐶 and is blown into the absorber at essentially standard
atmospheric pressure at the expected rate of 0.4𝑚3 /𝑠. The vapour stripped of
all 𝐶𝑆2 . Solutions of oil and 𝐶𝑆2 , follow Raoult’s law. The vapour pressure of
𝐶𝑆2 at 24𝑜 𝐶 = 346𝑚𝑚 𝐻𝑔. Assuming isothermal operation

1. Determine the minimum liquid/gas ratio

2. Determine the kg of oil entering the absorber per hour for a liquid/gas ratio
of 1.5 times the minimum
3. Determine the number of theoretical trays required

22
Adapted from tutorial in Autmn 2010 of CL 303
 Point efficiency and Murphree efficiency
𝑙𝑜𝑐𝑎𝑙
𝑌𝑖+1 −𝑦𝑖𝑙𝑜𝑐𝑎𝑙
• Point efficiency 𝐸𝐺 = 𝑙𝑜𝑐𝑎𝑙
𝑦𝑖+1 −𝑦𝑖∗𝑙𝑜𝑐𝑎𝑙

• 𝑎 ≡ Interfacial area per unit volume

• ℎ ≡ height of the liquid on the tray

• 𝐾𝑦 ≡ Overall mass-transfer coefficient

• 𝑠 ≡ Cross-sectional area of the tray

• Material balance on the small element of the tray

𝐺𝑑𝑦 = 𝑠 𝑎𝑑ℎ 𝐾𝑦 (𝑦 − 𝑦𝑖∗𝑙𝑜𝑐𝑎𝑙 )

• Integrating over the entire tray:

𝐸𝐺 = 1 − 𝑒 −𝐾𝑦 𝑎𝑠ℎ/𝐺
23
 Point efficiency and Murphree efficiency
• When the liquid is mixed well with gas: 𝐸𝐺 = 𝐸𝑀𝐺

• When liquid is not mixed with gas at all: 𝐸𝑀𝐺 > 𝐸𝐺

𝐿 𝐸𝐺 𝑚𝐺
𝐸𝑀𝐺 = 𝑒 𝐿 −1
𝑚𝐺

• If the situation is between two extremes:

𝐸𝑀𝐺 1 − 𝑒 −(𝜂+𝑃𝑒) 𝑒𝜂 − 1
= +
𝐸𝐺 𝜂 + 𝑃𝑒 𝜂
𝜂 + 𝑃𝑒 1 + 𝜂 1+
𝜂 𝜂 + 𝑃𝑒

0.5
𝑃𝑒 4𝑚𝐺𝐸𝑂𝐺
𝜂= 1+
2 𝐿𝑃𝑒

𝑧2
𝑃𝑒 = 24
 Absorption in continuous contact equipment

• From ideal number of stages:

𝐿 = 𝐻𝐸𝑇𝑃 × 𝑁𝑖𝑑𝑒𝑎𝑙

• Empirical and does not explicitly relate the packing characteristics to the
HETP

• Tray column: Not all points on the operating line are really acheived

• Packed column: All points on the operating line are achieved

𝐿 = 𝐻𝑡𝐺 𝑁𝑡𝐺 = 𝐻𝑡𝐿 𝑁𝑡𝐿 = 𝐻𝑡𝑂𝐺 𝑁𝑡𝑂𝐺 = 𝐻𝑡𝑂𝐿 𝑁𝑡𝑂𝐿

• 𝑁𝑡𝐺 or 𝑁𝑡𝐿 ≡ Number of transfer units

• 𝐻𝑡𝐺 or 𝐻𝑡𝐿 ≡ Height equivalent of transfer unit

25
 Absorption in continuous contact equipment
• 𝑁𝑡𝑂𝐺 : Measure of the effectiveness of the separation

• 𝐻𝑡𝑂𝐺 : Height of the transfer unit

𝑦𝑏
𝑑𝑦
𝑁𝑡𝑂𝐺 = න
(1 − 𝑦)(𝑦 − 𝑦 ∗ )
𝑦𝑜

𝐿
𝐻𝑡𝑂𝐺 =
𝐾𝑦 𝑆𝑎

• For dilute gases and when Henry’s law is applied:

1 1 1 𝑦𝑏 − 𝑚𝑥𝑏
𝑁𝑡𝑂𝐺 = ln + 1 −
1 𝐴 𝐴 𝑦𝑜 − 𝑚𝑥𝑜
1−
𝐴

26
 Examples

1. 90% of the 𝑆𝑂2 is to be removed from a flue gas stream using a packed
tower that is 0.7𝑚 in diameter. The tower has an HTU, based on the gas-phase
resistance, of 0.26𝑚. For the absorbing liquid, 𝑦 = 8.4𝑥. The liquid enters
without containing 𝑆𝑂2 . If the flow of the liquid is adjusted such that the
driving force 𝑦 − 𝑦 ∗ is constant, how tall a tower will be needed?
Adapted from the remedial examination of 2012 of CL 303

27
Adapted from tutorial in Autmn 2010 of CL 303
 Equipment for absorption: Tray columns

http://encyclopedia.che.engin.umich.edu
28
Adapted from “Mass transfer operations” by Treyball
 Trays: Type of vapour-inlets
Bubble-cap trays

Wermac.org

Sieve trays

Godrej process equipment Godrej process equipment 29

 Trays: Other components
Direction of flow

Weirs and downspouts

• Cross-flow is cheapest

• Reverse flow or radial flow may

be used for large diameters

• Downspouts permit separation of

gas from liquid

Adapted from “Mass transfer operations”

by Treyball
• Downspouts should dip into the
30
liquid on the tray below
 Tray columns: Design considerations

• The shell can be made of suitable material to avoid corrosion. Mostly, metal

• The towers are cylindrical to reduce costs

• The plates are made of metal

• Tray spacing should prevent flooding or entrainment

• The tower diameter is governed by the liquid and gas flow-rates

• Relationships are empirical

31
 Tray columns: Operation

• Dumping: Liquid leaks through

sieves and does not reach the
downspouts

• Weeping: Liquid leaks through the

sieves

• Flooding: Liquid fills the space

between the plates

• Priming: Foam fills the region

between trays

• Excessive entrainment: Gas caries the liquid droplets to the next tray

• Coming: Gas pushes the liquid away from the sieves

Adapted from “Mass transfer operations” by Treyball 32
 Typical values used for the design of tray columns

• At flooding, the velocity of gas is given by:

0.5
𝜌𝐿 − 𝜌𝐺
𝑉𝐹 = 𝐶𝐹
𝜌𝐺

• Cross-sectional area is such that

• 𝑉 = 0.8 − 0.85𝑉𝐹 (for non-foaming liquids)
• 𝑉 < 0.75𝑉𝐹 (for foaming liquids)

• For a sieve plate column:

1 𝜎 0.2
𝐶𝐹 = 𝛼 log 0.5 +𝛽
𝜌𝐺 0.020
𝐿𝑏 /𝐺𝑏
𝜌𝐿

• The liquid depth on tray is between 50 and 100 mm

33
Adapted from “Mass transfer operations” by Treyball 34
Adapted from “Mass transfer operations” by Treyball 35
 Typical values used for the design of tray columns
• Pressure drop for the gas:
Δ𝑝 = Δ𝑝𝑑𝑟𝑦−𝑝𝑙𝑎𝑡𝑒 + Δ𝑝𝑙𝑖𝑞𝑢𝑖𝑑 + Δ𝑝𝑟𝑒𝑠

• Δ𝑝𝑑𝑟𝑦−𝑝𝑙𝑎𝑡𝑒 : Due to gas flowing through the perforations

• Δ𝑝𝑙𝑖𝑞𝑢𝑖𝑑 : Due to the hydraulic head

• Δ𝑝𝑟𝑒𝑠 : Overcoming the liquid surface tension

36
Example

37
 Equipment for absorption: Packed columns

• Packing enhances the contact between

liquid and gas

• Liquid distributor to spread the liquid

throughout the cross-section

• Size of the packings < 1/8 column

diameter

38
Adapted from “Mass transfer operations” by Treyball
 Packing characteristics

• Enable good contact between liquid and gas.

• Empty space should be large to allow the passage of liquid and gas

• Resistance to corrosion by fluids

• Installation should be easier and low cost

• Two types:
• Random packings

• Regular packings

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 Random packings

Regular packings

Adapted from “Mass transfer operations” by

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Exportersindia.com Treyball
 Comparison between random and regular packings

Random packing Regular packing

• Less channeling • More channeling

• Higher pressure drop • Less pressure drop

• Less expensive • More expensive

• Less efficiency • More efficiency

• Units of sizes ranging between 2.5 • Few inches thick.

to 5cm

• Dumped in the column • Stacked inside the column

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 Operation: Loading and flooding points

• Δ𝑃: Gas pressure-drop

• Increases with liquid flow-rate

because of less space

• Dry packing has slope of ~1.8

• Slope increases after 𝐴 due to

liquid hold-up (loading point)

• Flooding point (Point B):

• Gas bubbles in liquid at top
Adapted from “Mass transfer operations” by Treyball • Liquid fills the gas
• Slugs of foams

Optimum gas velocity: Between loading and flooding point

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 Operation: Flooding points

𝐶𝑗 depends on the type and dimensions of packing

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Self-study
 Typical values used for the design of packed column

• Absorbers are designed for gas-pressure drops of 200 – 400 Pa/m

• Atmospheric pressure fractionators for 400 to 600 Pa/m

• Vacuum stills for 8 to 40 Pa/m

• Diameters are governed by the flow-rates at the bottom of the column

• For dry packing, with gas flow-rates greater than 0.7 𝑘𝑔/𝑚2 𝑠

Δ𝑝 𝐶𝐷 𝐺 ′2
=
𝑧 𝜌𝐺

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 When to use tray columns?

• When liquid cooling is required

• When liquid flow-rate is low relative to that of gas

• When side streams are to be removed

• When frequent cleaning is required

When to use tray columns?

• When low gas pressure-drops are required

• When low liquid holdup is required

• When system shows tendency to foam

• Less costly for corrosive systems

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 Example

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Adapted from “Mass transfer operations” by Treyball