Lecture presentation outline

Equilibrium Studies & Staged Contacts

Gas absorption-definition
Basic principle of absorption
Types of absorption
Industrial application of absorption
Single –stage Equilibrium

1
Equilibrium Studies &
Staged Contacts

2
Introduction
Most of the substances that occur in the chemical and biological processes occur in a mixture,
contaminated.
The components in the mixture could be in the; gas, liquid or solid phase. Therefore to remove
components from the mixture, it is important that one phase is contacted with another.

The phases can be; gas-liquid, gas-solid, liquid-liquid or liquid-solid.

By choosing the right conditions and phases, one phase can be enriched while the other is
depleted.

3
Separation Processes
Absorption (gas – liquid) ✓
Distillation (vapor – liquid)✓
Liquid-liquid extraction (liquid – liquid) ✓
Leaching/extraction (solid – liquid)
Membrane processing (semi-permeable)
Crystallization (liquid – solid)
Adsorption (gas/liquid – solid)
Ion exchange

4
Processing methods
Single Stage: the 2 phases can be mixed together in a vessel and then separated
Multiple-stage process: Phases are mixed in one stage, separated, and then brought into contact
again

❖Both methods can be carried out batchwise or continuously

5
Gas absorption-definition
Gas absorption is the transfer (separation) between gas and liquid system. That
is a solute or solutes A is/are absorbed from the gas phase into the liquid state.
This process is achieved through molecular and turbulent diffusion or mass
transfer of the solute A.
The solute A is transferred through a stagnant non-diffusing gas B into a
stagnant liquid C.
The species transferred to the liquid phase are referred to solutes or absorbates

6
 In absorption, Liquid phase is called the solvent,
In stripping, the vapour or gas is called the stripping agent

Figure 1: Typical absorption-stripping process with recycle of solvent: (a) absorber, (b)
stripper

7
Absorption cont.….
Absorption therefore;
➢Occurs between gas and liquid
➢Solutes are absorbed from the gas phase into the liquid phase
➢Absorption does not destroy the gases; it simply transfers the gas to the
liquid state
Assumption
The gas phase is non-volatile, this means that non of the liquid becomes
part of the gas phase. Mass transfer is therefore from the gas to the liquid

8
Stripping
➢Stripping or Desorption is the opposite of absorption (removing of
the solute from the liquid.
➢The component absorbed into the liquid is vaporised into gas phase
Assumption
➢The vapour or gas phase is non soluble in the liquid phase. That is it
not absorbed in the liquid phase, hence no mass transfer from the
liquid phase to the vapour phase

9
Uses of absorption
✓To separate gas mixtures
✓To remove impurities from gases
✓To recover valuable chemicals.

10
Industrial application of absorption
✓Use in refineries to separate gas components (desulphurisation) by removing; CO2, H2S, COS
✓Natural gas upgrading by removing; CO2, H2S, N2 and RSH
✓Use to control the emissions of pollutants to the atmosphere, retaining polluting substances
such as sulphur, chlorinated and fluorinated compounds;
✓The control is based on the elimination of sulphur dioxide from combustion gases with aqueous
solutions of sodium hydroxyl and the elimination of nitrogenous oxide with solutions of oxidizing
agents.
✓Recovery of gaseous stream products for production purposes

11
Equipment for absorption

Figure 2: Example of absorption equipment

12
Equilibrium in absorption and stripping
Assumptions
The carrier gas is insoluble
The solvent is non volatile
The system is isobaric; constant pressure and isothermal (constant
temperature).
Analysing using Gibbs phase-rule law

13
Phase rule and equilibrium
When systems are in equilibrium no mass transfer
When not in equilibrium mass transfer is proportional to driving force
Variables affecting the equilibrium of a solute are temperature, pressure, and concentration
The equilibrium between two phases in a given situation is restricted by the phase rule:
F=C–P+2
❖F - number of variants or degrees of freedom
❖C - number of total components in the two phases
❖P - number of phases at equilibrium

14
Example; CO2-air-water system
F=C–P+2
F= (3 -2+2)
C = 3 (carrier gas, solvent and solute)
P = 2 (gas and liquid)
F = 3 (degree of freedom)
So if temperature and pressure are set, then 1 variable can be set arbitrarily
Then if xA in the liquid phase is set, yA or pA in the gas phase is automatically determined
➢This is determined using the Henry’s law

15
Henry’s law
The equilibrium relation between the ρA in the gas phase and xA can be expressed by a straight
line Henry’s law of equation at low concentrations

Where, H is the Henry’s law constant in atm/mole fraction for the given system
If both sides are divided by total pressure P in atm

Where, H′ is the Henry’s law constant in mole frac gas/mole frac liquid and is equal to H/P
Note that H′ depends on total pressure, whereas H does not

16
Gas-liquid equilibrium data
Consider that an amount of gaseous SO2, air and water are put into a closed container and
mixed at constant temperature until equilibrium
Samples of gas and liquid are removed and analysed for pA (SO2 in gas) and xA (SO2) in liquid

Fig. 3 Equilibrium plot for So2 –water system at 293 K (20 °C)
17
 Single –stage Equilibrium cont.

Fig. 4 Equilibrium plot for So2 –water system at 293 K (20 °C)

18
Example: Dissolved oxygen concentration
in water
What will be the concentration of oxygen dissolved in water at 298 K when the solution is in
equilibrium with air at 1 atm total pressure? The Henry’s law constant is 4.38 ×104atm/mol
fraction.
Solution: The partial pressure pA of oxygen (A) in air is 0.21 atm.
0.21 = HxA = 4.38 ×104 xA
Solving, xA = 4.80 ×10–6 mol fraction. This means that 4.80 ×10–6mol O2 is dissolved in 1.0 mol
water plus oxygen

19
Co-current and Counter-current Gas
Absorption

Figure 4: Co-current and counter current flows in absoprtion

20
COUNTER-CURRENT GAS ABSORPTION
The gas is introduced from the bottom while the liquid is introduced from the top.

As we gradually move up the column, the gas component (A) is continuously transferred from
the gas phase to the liquid phase.

Moving up the column, there’s a decrease in total gas flowrate and a decrease in concentration
of A in the gas phase.

Moving down the column, there’s an increase in total liquid flowrate and an increase in
concentration of A in the liquid phase

21
 Single –stage Equilibrium contact

Fig 5. Single stage equilibrium process

22
Single –stage Equilibrium contact cont.
In the single stage, two different phases are brought into intimate contact with each other and
are then separated. As the phases make contact, mixing occurs and the various components
diffuse and redistribute.
If the mixing is long enough, the components gets to a point of equilibrium in the two phases
after separation
Thus, two entering phases of known amounts and compositions, liquid (L0) and gas (V2), enter
the stage; mixing and equilibration occur; and the two exit streams, L1 and V1, leave in
equilibrium with each other.

23
Material balance on a single stage
Making a total mass balance
Total mass/mole balance:
Lo = entering liquid (Kg)
L1 = exit liquid (Kg)
V2 = entering gas (Kg)
V1 = exit gas (Kg)
M = total (Kg)
Assuming that three components, A, B, and C, are present in the streams and making a
balance on A and C (B is not required)

24
 Mass balance contd.
Assuming that three components A, B and C are present in the streams. Equation
for B is not needed since xA +xB + xc = 1.

Where,
xA = mass fraction of A in L stream
yA = mole fraction of A in V stream
xAM = mass fraction of A in M

25
 Single –stage Equilibrium for Gas –Liquid System contd.
▪In the gas-liquid system, the solute A is in the gas phase V, along with inert air B
and in the liquid phase L, along with inert water C.
▪Air is insoluble in the water phase and water does not vaporize to the gas phase.
▪The gas phase is a binary A-B and the liquid phase is a binary A-C.
A balance on A can be written as:

where L′ is moles inert water C and V′ is moles inert air B. Both L′ and V′ are constant
and usually known

26
Single –stage Equilibrium for Gas –Liquid System contd.
To solve, the relation between yA1 and xA1 in equilibrium is given by Henry’s law

H’ = Henry’s law constant

Also,
L’ = L (1 –xA)
V’ = V (1 –yA)

27
Example: equilibrium stage contact for
CO2-air water
A gas mixture at 1.0 atm pressure abs containing air and CO2 in a single-stage mixer is in
continuous contact with pure water at 293 K. The two exit streams of gas and liquid reach
equilibrium. The inlet gas flow rate is 100 kg mol/h, with a mole fraction of CO2 of yA2= 0.20. The
liquid flow rate entering is 300 kg mol water/h. Calculate the amounts and compositions of the
two outlet phases. Assume that water does not vaporize to the gas phase.
Solution:

28
Counter-current multiple-contact stages

Figure 6: countercurrent multiple stage

▪ Component A is being exchanged between the V and L streams.
▪ The V stream is composed mainly of component B and the L stream of component C.
▪ Components B and C may or may not be somewhat miscible in each other

29
Material balance
Making a total overall mass balance on all stages

Note: any two streams leaving a stage are at equilibrium with each other

Making an overall component balance on A, B, or C. But we take a component balance on A

30
▪ Figure 7: counter-current multiple stage

▪ Making a total balance over the first n stages:

▪ Making a component balance over the first n stages:

▪ Solving for yn+1:

▪ This is an important material-balance equation, often called an operating line. From the equation, V1, y1, xo
and Lo are usually given or determined.

31
 Counter-current contact with immiscible
streams
▪ Assume the system has three components (A, B, and
C).
▪ A = Solute (desired component been transferred)

▪ B = Inert air (carrier gas for A)

▪ C = Solvent (liquid in which component A is

absorbed).
▪ The gas stream V contains components A and B
with no C, and the solvent stream L contains A
and C with no B
▪ The two streams L and V are immiscible in each
other, with only A being transferred

Figure 7: Number of stages in a counter-current multiple-stage contact

32
Graphical number of stages
From figure 7, the composition of the two streams leaving each stage are in equilibrium to each
other.
Therefore, to calculate the number of stages that will bring about reduction of yN+1 to y1 , a graph
is needed.
Again, from figure 7, at stage 1: y1 and xo are on the operating line and the vapour y1 leaving is in
equilibrium with the liquid x1. At that point, both compositions are said to be in equilibrium.
Then y2 and x1 are on the operating line and y2 and x2 are in equilibrium, this continuous for the
other stages until the final stage (n) is reached.

33
EXAMPLE: Absorption of Acetone in a
Countercurrent Stage Tower
It is desired to absorb 90% of the acetone in a gas containing 1.0 mol % acetone
in air in a countercurrent stage tower. The total inlet gas flow to the tower is
30.0 kg mol/h, and the total inlet pure water flow to be used to absorb the
acetone is 90 kg mol H2O/h. 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 the
gas–liquid is yA = 2.53xA. Determine the number of theoretical stages required
for this separation.
Solution:

34
▪ When the equilibrium line and operating lines are straight, analytical equations may be used:
▪ N stages:
▪ n stages:
▪ Rearranging :
▪ N stages:
▪ n stages:

▪ Equating:

35
Since molar flows are constant, Ln =LN =L. Also, Vn+1= VN+1 =V, costant.
The previous equation

Becomes:

▪ Since yn+1 and xn+1 are in equilibrium and the equilibrium line is straight, yn+1 =
mxn+1 and
yN+1 = mxN+1
▪ Substituting mxn+1 for yn+1 and calling A = L/mV:
where A is an absorption factor and is constant
▪ Thus:

▪ Becomes:

36
▪ This equation is a linear first-order difference equation
▪ The term A is often called the absorption factor and S the stripping factor, where S
= 1/A
▪ The final derived equation is seen on the next slide.

37
For transfer of solute A from phase V to L (absorption)

When A = 1

38
For transfer of solute A from phase L to V (stripping)

When A = 1

39
Repeat the example below using the Kremser analytical equations to calculate the
number of stages

It is desired to absorb 90% of the acetone in a gas containing 1.0 mol

% acetone in air in a countercurrent stage tower. The total inlet gas
flow to the tower is 30.0 kg mol/h, and the total inlet pure water flow to
be used to absorb the acetone is 90 kg mol H2O/h. 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 the gas–liquid is yA =
2.53xA. Determine the number of theoretical stages required for this
separation.

40