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- Sample Problem #4
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Overview

• Introduction

• Absorption and stripping equilibria

• Operating lines for absorption

• Stripping analysis

• Analytical solution: Kremser equation

Introduction

Gas absorption is a mass transfer operation in which a gas mixture is contacted with a liquid to

preferentially absorb one or more of the components of the gas stream. In this case, the liquid solvent

(absorbing liquid) must be added as a separating agent.

In some cases, a solute is removed from a liquid by contacting it with a gas. This operation is the reverse

of gas absorption and is called desorption or gas stripping. Here, the gas stream (stripping agent) must

be added as a separating agent.

Absorption can be either physical or chemical. In physical absorption, the gas is removed because it has

greater solubility in the solvent than other gases. An example is the removal of butane and pentane from

a refinery gas mixture (C4 – C5) with a heavy oil.

In chemical absorption, the gas to be removed reacts with the solvent and remains in solution. An

example is the removal of CO2 or H2S by reaction with NaOH or with monoethanolamine (MEA).

The reaction can be either irreversible (as with NaOH) or reversible (with MEA). For irreversible

reactions, the resulting liquid must be disposed of, whereas in reversible reactions, the solvent can be

regenerated. Thus, reversible reactions are often preferred.

Chemical absorption usually has a much more favorable equilibrium relationship than physical

absorption (solubility of most gases is usually very low) and is, therefore, preferred.

Both absorption and stripping can be operated as equilibrium stage operations with contact of liquid and

vapor.

In both absorption and stripping a separate phase is added as the separating agent.

For absorption and stripping in three component systems, we often assume that

2. Solvent is nonvolatile.

3. The system is isothermal and isobaric.

F = C–P+2

= 3(A, B, and C) – 2(vapor and liquid) + 2

= 3

If we set T and p constant, there is one remaining degree of freedom. The equilibrium data are usually

represented either by plotting solute composition in vapor versus solute composition in liquid or by

giving a Henry’s law constant.

Henry’s law is

PB = HBxB

xB is the mole fraction B in the liquid; and

pB is the partial pressure of B in the vapor.

Henry’s law is valid only at low concentrations of B. Since partial pressure is defined as

pB

yB ≡

p tot

HB

yB = xB

p tot

This will plot as a straight line if HB is constant. If the component is pure, yB = 1 and pB = ptot.

The Henry’s law constants depend upon temperature and usually follow an Arrhenius relationship. Thus,

−E

H = H 0 exp

RT

The McCabe-Thiele diagram is most useful when the operating line is straight. This requires that

• Liquid flow rate/vapor flow rate = constant

2. Operation is isothermal

These two assumptions will guarantee satisfaction of the enthalpy balances. When the gas and liquid

streams are both fairly dilute, the assumptions will probably be satisfied.

We also desire a straight operating line. This will be automatically true if we define

L G=

moles insoluble carrier gas hr

3. Solvent is nonvolatile

4. Carrier gas is insoluble

Assumptions 3 and 4 are often very closely satisfied. The results of these last two assumptions are that

the mass balance for solvent becomes

LN = Li = L0 = L = constant

GN+1 = Gi = G1 = G = constant

Note that we cannot use overall flow rates of gas and liquid in concentrated mixtures because a

significant amount of solute may be absorbed which would change gas and liquid flow rates and give a

curved operating line. For very dilute solutions (< 1% solute), overall flow rates can be used, and mass

or mole fractions can be used for operating equations and equilibria. Since we want to use L = moles

nonvolatile solvent (S)/hr and G = moles insoluble carrier gas (C)/hr, we must define our compositions

in such a way that we can write a mass balance for solute B.

After some manipulation we find that the correct way to define our compositions is as mole ratios.

Define

moles B in gas

Y=

moles pure carrier gas C

moles B in liquid

and X = moles pure solvent S

The mole ratios of Y and X are related to our usual mole fractions by

y x

Y= and X=

1−y 1−x

Note that both Y and X can be greater than 1.0. With mole ratio units, we have

YiG =

=

moles carrier gas hr hr

and

Xi L = =

moles solvent hr hr

Thus we can easily write the steady-state mass balance, input = output, in these units. The mass balance

around the top column using the mass balance envelope is

Yi +1G + X 0 L = X i L + Y1G

or

L L

Yi +1 = X i + Y1 − X 0

G G

L

This is a straight line with slope L G and intercept Y1 − X 0 . It is our operating line for

G

absorption. Thus if we plot ratios Y vs X we have a McCabe-Thiele type of graph.

2. Values of X0, YN+1, Y1 and L G are known. Point (X0, Y1) is on operating line, since it

represents passing streams.

3. Slope is L G . Plot operating line.

4. Starting at stage 1, step off stages: equilibrium, operating, equilibrium, etc.

Note that the operating line is above the equilibrium line, because solute is being transferred from the

gas to the liquid.

Equilibrium data must be converted to ratio units, Y vs X. These values can be greater than 1.0, since

Y = y (1 − y ) and X = x (1 − x ) . The Y = X line has no significance in absorption. As usual the stages

are counted at the equilibrium curve. If the system is not isothermal, the operating line will not be

affected, but the equilibrium line will be. Then the McCabe-Thiele method must be modified to include

changing equilibrium curves.

For very dilute systems we can use mole fractions, since total flows are approximately constant.

A gas stream is 90 mole % N2 and 10 mole % CO2. We wish to absorb the CO2 into water. The inlet

water is pure and is at 5°C. Because of cooling coils, operation can be assumed to be isothermal.

Operation is at 10 atm. If the liquid flow rate is 1.5 times the minimum liquid flow rate, how many

equilibrium stages are required to absorb 92% of the CO2? Choose a basis of 1 mole/hr of entering gas.

Solution

A. We need to find the minimum liquid flow rate, the value of the outlet gas concentration, and the

number of equilibrium stages required.

B. First we need equilibrium data. Since concentrations are fairly high, the problem should be solved in

mole ratios. Thus we need to convert all compositions including equilibrium data to mole ratios.

C. Derive the equilibrium equation from Henry’s law. Convert compositions from mole fractions to

mole ratios. Calculate Y1 by a percent recovery analysis. Plot mole ratio equilibrium data on a YX

diagram, and determine ( L G ) min and hence Lmin. Calculate actual L G , plot operating line, and step

off stages.

D. Equilibrium:

H 876

y= x= x = 87 .6x

p tot 10

Change the equilibrium data to mole ratios with a table as shown below.

x y

x X= y = 87.6x Y=

1−x 1−y

0 0 0 0

0.0001 0.0001 0.00876 0.00884

0.0004 0.0004 0.0350 0.0363

0.0006 0.0006 0.0526 0.0555

0.0008 0.0008 0.0701 0.0754

0.0010 0.0010 0.0876 0.0960

0.0012 0.0012 0.10512 0.1175

Note that x = X in this concentration range, but y ≠ Y. The inlet gas mole ratio is

YN +1 = = = 0.1111

1 − y N+1 0.9 moles N 2

moles N 2

G = (1 mole total gas/hr)(1-yN+1) = 0.9

hr

= 0.008 mole CO2 out

Thus,

Y1 = = = 0.008888

moles N 2 0.9 mole N 2

Operating line:

L L

Yi +1 = X i + Y1 − X 0

G G

(L G ) min is found as the slope of the operating line from point (Y 1,X0) to the intersection with the

equilibrium curve at YN+1.

(L G ) min = 89 .905

moles water

∴ Lmin = (89.905)(0.9) = 80.914

hr

Lactual = 1.5Lmin = 121.37

and ( L G ) actual =134 .86

Plot operating line from (Y1,X0) with this slope. Step off stages on the diagram. Need 4.1 equilibrium

stages.

Frac = = = 0.13

X5 − X 4 0.00108 − 0.00071

E. The overall mass balances are satisfied by the outlet concentrations. The significant figures carried

in this example are excessive compared with the equilibrium data. Thus they shoud be rounded off when

reported. The concentrations used were quite high for Henry’s law. Thus, it would be wise to check the

equilibrium.

F. Note that the gas is considerably greater than the liquid concentration. This situation is common for

physical absorption (solubility is low). Chemical absorption is used to obtain more favorable

equilibrium. The liquid flow rate required for physical absorption is excessive. Thus, in practice, this

type of operation uses chemical absorption.

If we had assumed that total gas and liquid flow rates were constant (dilute solutions), the result would

be in error. An estimate of this error can be obtained by estimating ( L G ) min . The minimum operating

line goes from (y1, x0) = (0.00881, 0) to (yN+1, xequil,N+1). YN+1 = 0.1 and xequil,N+1 = yN+1/87.6 = 0.1/87.6 =

0.0011415.

Then

( L G ) min, dilute = = = 79 .886

x equil ,N +1 − x 0 0.0011415 −1

This is in error by more than 10%.

Stripping analysis

Since stripping is very similar to absorption we expect a similar result. The mass balance for the column

is the same as for absorption and the operating line is still

L L

Yi +1 = X i + Y1 − X 0

G G

For stripping we know X0, XN, YN+1, and L G . Since (XN, YN+1) is a point on the operating line, we can

plot the operating line and step off stages.

Note that the operating line is below the equilibrium curve because solute is transferred from liquid to

gas. A maximum L G ratio can be defined; this corresponds to the minimum amount of stripping gas.

Start from the known point (YN+1, XN) and draw a line to the intersection of X = X0 and the equilibrium

curve. Alternatively, there may be a tangent pinch point. For a stripper, Y1 > YN+1, while the reverse is

true in absorption. Stripping often has large temperature changes, so the method used here may have to

be modified.

Yi − Yi +1

= E MV

Yi* − Yi +1

For dilute systems the more common definition of Murphree vapor efficiency in mole fractions would

be used. Efficiencies for absorption and stripping are often quite low.

Usually the best way to determine efficiencies is to measure them on commercial-scale equipment.

When the solution is quite dilute (say less than 1% solute in both gas and liquid), the total liquid and gas

flow rates will not change significantly since little solute is transferred. Then the entire analysis can be

done with mole or mass fractions and total flow rates. The operating equation is derived by writing a

mass balance around stage I and solving for yi+1. The result is

L L

yi+1 = x i + y1 − x 0

V V

2. Isothermal system

3. Isobaric system

4. Negligible heat of absorption

If one additional assumption is valid, the stage-by-stage problem can be solved analytically. This

additional assumption is:

yi = mx i + b

This assumption is reasonable for very dilute solutions and agrees with Henry’s law if m = HA/ptot and b

= 0.

An analytical solution for absorption is easily derived for a special case where the operating and

equilibrium lines are parallel. Now the distance between operating and equilibrium lines, ∆ y, is

constant. To go from outlet to inlet concentrations with N stages, we have

N ∆y = y N +1 − y1

since each stage causes the same change in vapor composition. ∆ y can be obtained by substracting the

equilibrium equation from the operating equation.

( ∆y ) i = yi+1 − yi = L − m x i + y1 − L x 0 − b

V V

For the special case of parallel operating and equilibrium lines, L V =m and

( ∆y ) = ( ∆y ) i = y1 − L x 0 − b = cons tan t

V

y N +1 − y1

N= L

L for =1

y1 − x 0 − b mV

V

This equation is a special case of the Kremser equation. When this equation is applicable, absorption and

stripping problems can be solved quite simply and accurately without the need for a stage-by-stage

calculation.

For the more general case, ∆ yi varies from stage to stage. The ∆ y values can be determined from

( ∆y ) i = yi+1 − yi = L − m x i + y1 − L x 0 − b

V V

yi − b

xi =

m

Then

( ∆y ) i = L

− 1 yi + yi −

L L

b − x0

mV mV V

L L L

( ∆y ) i+1 = −1yi +1 + yi − b − x0

mV mV V

( ∆y ) i+1 − ( ∆y ) i = L L

−1( yi +1 − yi ) =

−1( ∆y ) i

mV mV

L

( ∆y ) i+1 = ( ∆y ) i

mV

This equation relates the change in vapor composition from stage to stage to (L/mV), which is known as

the absorption factor. If either the operating or equilibrium is curved, this simple relationship no longer

holds and a simple analytical solution does not exist.

The difference between inlet and outlet gas concentrations must be the sum of the ∆ yi values. Thus,

∆ y1 + ∆ y2 + ⋅ ⋅ ⋅ + ∆ yN = yN+1 – y1

L

Applying ( ∆y ) i+1 = ( ∆y ) i

mV

L L

2

L

N −1

∆y1 1 + + + + = y N +1 − y1

mV mV mV

k

(

a 1 − A k +1 )

∑

i =0

aA =

i

(1 − A )

for A< 1

Then

N

L

1−

y N +1 − y1 mV

=

∆y1 L

1−

mV

If L/mV > 1m then divide both sides of this equation by ( L mV ) N−1 and do the summation in terms of

mV/L. The vapor composition y1* is the value that would be in equilibrium with the inlet liquid, x 0.

Thus,

y1* = mx 0 + b

N

L

1−

y N +1 − y1 mV

Removal of ∆ y1 from = gives

∆y1 L

1−

mV

N +1

L L

−

y N +1 − y1 mV mV

=

y1 − y1* L

1−

mV

This equation is one form of the Kremser equation. A large variety of alternative forms can be

developed by algebraic manipulation. For instance, if we add 1.0 to both sides of the previous equation

and rearrange, we have

N +1

L

1−

y N +1 − y1

*

mV

=

y1 − y1* L

1−

mV

mV y N +1 − y1* mV

ln 1 − +

*

L −

1 1 L

y y

N=

L

ln

mV

where L/mV ≠ 1. These last two equations are also known as forms of the Kremser equation.

A variety of forms of the Kremser equation can be developed. Several alternative forms in terms of the

gas-phase composition are

y N +1 − y1 ( L mV ) − ( L mV )

N +1

=

1 − ( L mV )

N +1

y1 − y1*

N

y N +1 − y*N +1 L

=

y1 − y1* mV

N=

[( )(

ln y N +1 − y*N +1 y1 − y1* )]

ln ( L mV )

N=

[( )(

ln y N +1 − y*N+1 y1 − y1* )]

[ (

ln ( y N +1 − y1 ) y*N+1 − y1* )]

where

L x 0 − x *N L

ln 1 − +

mV x N − x N mV

*

N=

ln( mV L )

N=

[( )(

ln x N − x *N x 0 − x *0 )]

ln( mV L )

N=

[( )(

ln x N − x*N x 0 − x *0 )]

[( )

ln x*0 − x*N ( x 0 − x N ) ]

x N − x *N 1 − ( mV L )

=

x 0 − x N 1 − ( mV L ) N +1

*

N

x N − x *N L

=

x 0 − x *0 mV

where

y N+1 − b y1 − b

x *N = and x *0 =

m m

N=−

{[1 − mV L][( y )(

− y1* y1 − y1* + mV L

N +1 )] }

ln[1 + E MV ( mV L − 1) ]

Which form of the Kremser equation to use depends upon the problem statement. When the assumptions

required for the derivation are valid, the Kremser equation has several advantages over the stage-by-

stage calculation procedure. If the number of stages is large, the Kremser equation is much more

convenient to use, and it is easy to program on a computer or calculator. When the number of stages is

specified, the McCabe-Thiele stage-by-stage procedure is trial-and-error, but the use of the Kremser

equation is not. Because calculations can be done faster, the effects of varying y1, x0, L/V, m etc. are

easy to determine. The major disadvantage of the Kremser equation is that it is accurate only for dilute

solutions where L/V is constant, equilibrium is linear, and the system is isothermal.

A plate tower providing six equilibrium stages is employed for stripping ammonia from a waste water

stream by means of countercurrent air at atmospheric pressure and 80°F. Calculate the concentration of

ammonia in the exit water if the inlet liquid concentration is 0.1 mole % ammonia in water, the inlet air

is free of ammonia, and 30 standard cubic feet (scf) of air are fed to the tower per pound of waste water.

Solution

x0 = 0.001 y1

1

p = 1 atm

80°F

x6

y7 = 0.30 ft3

(std.) air/lb water

B. Since the concentrations are quite low we can use the Kremser equation. Equilibrium data are

available in several sources: we find y NH 3 = 1.414 x NH 3 at 80°F.

C. We have to convert flow to molar units. Since we want a concentration of liquid, we will use

x N − x *N 1 − ( mV L )

=

x 0 − x N 1 − ( mV L ) N +1

*

= × ×

L 1 lb water 379 scf air 1 lb mole water

= 1.43 moles air/mole water

mV

x N − x *N 1−

= L

N +1

x 0 − x *N mV

1−

L

Rearranging,

1 − mV L

xN = x0

1 − ( mV L )

N +1

1 − (1.414 )(1.43 )

xN = ( 0.001)

1 − [ (1.414 )(1.43 ) ]

7

E. We can check with a different form of the Kremser equation or by solving the results graphically;

both give the same result. We should also check that the major assumptions of the Kremser equation

(constant flow rates, linear equilibrium, and isothermal) are satisfied. In this dilute system they are.

F. This problem is trial-and-error when it is solved graphically. Also, the Kremser equation is very easy

to set up on a computer or calculator. Thus, when it is applicable, the Kremser equation is very

convenient.

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