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Indian J ournal of Chemical Technology

Vol. 13, J anuary 2006, pp. 47-52








Quickly design CO
2
amine absorber

Prakash D Vaidya & Vijaykumar V Mahajani*
Chemical Engineering Division, Institute of Chemical Technology, University of Mumbai, Mumbai 400 019, India
Email: vvm@udct.org
Received 21 December 2004; revised received 22 August 2005; accepted 6 October 2005
An integral rate-based model is used to find a quick and reliable estimate of the height of packing in a CO
2
-
alkanolamine absorber. Heat transfer in the gas phase is neglected. Due to the need to arrive at a quick estimate of the height
of packing, this assumption is made. Starting from the bottom, the height of packing required for a small change in solute
mole fraction in a differential section of the tower is calculated. An average of the enhancement factor calculated using film
theory of mass transfer accompanied by chemical reaction for each boundary, is used. These calculations are repeated until
at the top of the tower, the desired solute concentration is reached. The cumulative height gives total height of packing
required. The method is illustrated.
Keywords: CO
2
, Absorption, Alkanolamine
IPC Code: Int. Cl.
7
C01B31/00; B01D15/00

Absorption of CO
2
is of considerable importance in
the manufacture of ammonia. After the shift
converters (high temperature shift, HTS and low
temperature shift, LTS), the synthesis gas contains N
2
,
H
2
, CO
2
and CO at ppm level. In order to reduce load
on methanator, and hydrogen consumption in totality,
it is essential that CO
2
is removed by absorption/
adsorption. The CO
2
absorption is also important in
natural gas and associated gas processing, particularly
after selective desulfurization is done.
The latest generation plants use chemically reactive
absorbent for CO
2
removal. An aqueous solution of
alkanolamine [mainly monoethanolamine (MEA),
diethanolamine (DEA) and methyl diethanolamine
(MDEA) promoted with stronger amines] being the
most popular absorbent, the same is dealt with in the
present study. The simplified methodology presented
is applicable to any system in general.
The process design of an absorber is based on
hydrodynamic and mass transfer considerations. The
hydrodynamics in column involves two phase flow,
namely, gas phase to be treated and liquid phase as an
absorbent. The column hydrodynamics through mass
transfer coefficients k
L
a and k
G
a has significant
influence on process design based on mass transfer
considerations. A detailed discussion on hydro-
dynamic considerations is excluded from the scope of
this work. Here, the aim is to decide the height of
packing or mass transfer device, which is governed by
mass transfer considerations.
The CO
2
-alkanolamine reaction is exothermic.
Typically, in an industrial absorber, the liquid phase
temperature at the top is 50C and at the bottom is
around 70C. So in addition to mass balance, thermal
effects have to be accounted for in process design.
The heat generated in the liquid phase due to chemical
reaction (H
R
) is dissipated in three ways, namely
direct heat transfer between the gas and liquid phase,
saturation of gas phase by vaporization of water and
heat loss to the surroundings. In large-scale industrial
absorbers, the heat loss to the surroundings is
negligible.
In ammonia plant, the reformed gas is at
temperature near to absorption temperature say 50 to
70C after the shift converter followed by heat
exchange in a heat recovery system. The gas is
saturated with water and hence practically very little
water vaporization can take place. More or less the
same is the case with the reformed syn-gas, CO
2
from
ethylene oxide plant and CO
2
gas laden stream from
desulfurization column. The rate of heat transfer to
gas will be very low due to very low heat transfer
coefficient. Therefore, it was thought desirable to get
away with the complicated procedure of solving
simultaneous mass and heat transfer rate expressions.
INDIAN J . CHEM. TECHNOL., J ANUARY 2006


48
A simple practical approach of adiabatic mode (only
liquid phase) of operation is presented here. The heat
liberated due to chemical absorption is thus assumed
to result in the rise of temperature of liquid phase
only.

Process design
The CO
2
-alkanolamine absorber operating in
countercurrent fashion in an adiabatic mode of
operation is shown in Fig. 1. It is assumed that the gas
and liquid phases move in a plug flow manner and
that the operation is isobaric. From a mass balance for
CO
2
over a small section of differential height dZ at
the bottom of the tower, the height of packing is given
by

1
2
A
2
A
a (1- )
y
s
y
G dy
Z
R S y
=

(1)

The volumetric rate of absorption Ra can be expressed
as

R a= k
G
a(P
AG
P
Ai
) (2)
= k
L
a{ (A
i
*) (A
0
) } E = k
L
aH {P
Ai
P
A0
} E
(3)

From Eqs (2) and (3), eliminating unknown (A
i
*),

AG A0
G L
( )
a
(1/ a 1/ a )
P P
R
k k HE

=
+
(4)

(P
AG
P
A0
)=P
T
(y
A
y
A0
) (5)

Let be defined by =(1/ k
G
+ 1/ k
L
H E)
-1
(6)

Substituting in Eq. (4), R a = aP
T
(y
A
y
A0
) (7)

The value of remains practically constant
throughout the length of the column in case of
physical absorption. However, when absorption is
accompanied by a chemical reaction, the rate of
absorption varies along the column height due to
change in the enhancement factor E and hence the
value of is not constant. From Eqs (1) and (7), one
has

1
2
s A
2
T A A0 A
a ( ) (1 )
y
y
G dy
Z
S P y y y
=

(8)

Eq. (8) is the general design equation for calculating
the height of packing. The reaction between CO
2
and
alkanolamine is, in true sense, reversible. This always
results in equilibrium partial pressures of CO
2
, also
known as backpressure. At the tower bottom, the
solute CO
2
exerts equilibrium backpressure. The mole
fraction in gas being very high the difference
(y
A


y
A0
) is almost the same as y
A
. Therefore, the
effect of reversible reaction can be neglected. In other
words reaction is pseudo irreversible. In the control
volume or height under consideration, the change in
mole fraction of CO
2
is assumed such that the
variation in enhancement factor E and hence at the
top and bottom of this control volume is very small.
Therefore, an average value of can be safely used
for finding the height of packing. Eq. (8) then takes
the form

1
2
s A
2
T A A
a (1 )
y
y
G dy
Z
S P y y
=

(9)

On the other hand, at the top of the column, the
solute CO
2
exerts very low but finite backpressure
over the absorbent. Also the mole fraction y
A
of the
gas being absorbed is very small. Therefore, the
difference (y
A
y
A0
) is different from y
A
and hence the
effect of y
AO
(backpressure) is significant. Thus, the
effect of backpressure (equilibrium) becomes
dominant and here, the reversible nature of the
reaction needs to be considered. The value of y
A0
is
taken as the mean value of the equilibrium mole
fractions calculated at the top and bottom of the
control volume. The equation used for the top section
of the tower is

1
2
s A
2
T A A0 A
a ( ) (1 )
y
y
G dy
Z
S P y y y
=

(10)


Fig. 1Countercurrent packed absorption tower

VAIDYA & MAHAJ ANI: QUICKLY DESIGN CO
2
-AMINE ABSORBER


49
The design algorithm
The following rate consideration approach is based
on the film theory of mass transfer. The mole fraction
of CO
2
at inlet depends upon the performance of shift
converters and feedstock (syngas originating from
natural gas, naphtha or coal). The mole fraction of
CO
2
at exit is decided by overall optimization
including downstream methanator. The CO
2
content
in lean and rich amine is decided by energy
requirement in the regenerator and corrosion,
respectively. It is assumed that mole fractions of CO
2

at inlet and exit and gas and liquid flow rates are
known.
As discussed earlier, the heat released is assumed
to be absorbed by the absorbent liquid. The inlet
temperature of absorbent is known. Therefore
temperature, T, at the bottom of the column is fixed
by energy balance. By and large, 20-30C temperature
rise is observed in liquid phase depending upon the
heat of reaction (H
R
) and liquid flow rate. Some
values of heat of reaction are depicted in Table 1.
Thus, terminal temperatures are fixed by adiabatic
mode.
The absorption of CO
2
in alkanolamine under
industrial operating conditions (strength of amine and
temperature) exhibits first order behaviour with
respect to CO
2
and alkanolamine, thus making overall
second order reaction. The enhancement factors under
various conditions of operation are listed in Table 2. It
is further assumed that the pressure drop across the
column is negligible. Therefore, the column operates
at constant pressure.
The logic block diagram for the proposed design
procedure is shown in Fig. 2. The controlled volume,
dV, where CO
2
absorption takes place also needs
consideration. The calculation algorithm starts from
the bottom of the tower (gas inlet and absorbent exit
conditions).
1 The column diameter is obtained via flooding
considerations. Apart from flooding, consideration is
Table 1Heats of reaction for absorption of CO
2
in
alkanolamine solutions
Alkanolamine Exothermic heat of reaction,
kcal kg
-1

MEA 454.5
DEA 359.7
TEA 347.1
DGA 468.3

Kohl and Risenfield
11

Table 2Enhancement factor E under various conditions of
operation
(Reaction: A +w B Products, First order with respect to A and
B and hence overall second order, Reaction takes place in B
phase, Film theory of mass transfer holds true)

Case No. M E
m =1, n =1

1 M =1
or M <3
M <<q

(M +1)

2

3 <<M <<q


M
3 M >>3
M q


E

4 M >5
M >>q

E
i

M =
1/ 2
m 1 n
A mn 0
L
2
( *) ( )
(m+1)
D k A B
k






0 B
A
( )
q=
( *)
B D
w A D


E
i
=1 +q
1/ 2
2
i
2
i i i
M M M
1
4( 1) ( 1) 2( 1)
E
E
E E E

= + +





De Coursey
12




Fig. 2Logic block diagram for proposed design procedure
INDIAN J . CHEM. TECHNOL., J ANUARY 2006


50
also given to possible foaming due to degradation of
alkanolamine.
2 The superficial gas velocity, liquid velocity is
determined and hence the values of k
G
, k
L
and a are
obtained from published data.
3 From an overall mass and energy balance, the
exit temperature of the liquid at the tower bottom can
be obtained.

H
R
=m C
P
dT (11)

4 The value of the enhancement factor E and
hence at the exit can be calculated with the help of
formulae exhibited in Table 2.
5 A value of y
2
, i.e. mole fraction of CO
2
at the
top of the control volume is selected, as per the
situation of the absorption system.
6 The temperature of the liquid stream entering
this control volume is found from an energy balance
(Heat released =Heat gained by absorbent liquid).
7 The free alkanolamine concentration in the
liquid phase entering this control volume is found
from a material balance over this volume.
8 As before, the values of E and at the top of
this control volume are calculated. If the variation in
at the top and bottom is less than 10%, then an
average value of is used to find the height of this
control volume. It is to be noted that accounts for
change in H and E at the boundaries of control
volume. A revised value of y
2
is to be assumed if this
variation is more than 10%.
9 In the bottom section of the tower, absorption
is not sensitive to equilibrium pressure of CO
2
, so Eq.
(9) can be used to find the height of packing.
10 The calculations proceed upward in similar
fashion until the top section of the tower is reached
where CO
2
exerts a finite backpressure over the
absorbent solution.
If (y y
0
)/y <0.9, the backpressure needs to be
considered. The equilibrium condition for CO
2
in
liquid is obtained from the data published by Kent and
Eisenberg
1
. Eq. (10) is then used instead to find the
height of packing.
11 The total packed height is the sum of the
heights of all sections.
This design procedure would enable the process
design engineer to find a quick estimate of the height
of packing. The results obtained from such an
approach can serve as a preliminary estimate for a
more elaborate rigorous design procedure. Such
procedures have earlier been used by various other
researchers
2-7
.

Illustration
This calculation algorithm described above was
used to find the height of packing for a worked
example presented by Danckwerts and Sharma
8
on
absorption of CO
2
in MEA. Here, the adiabatic
approach was adopted.
The relevant data are as follows: Inlet gas
composition: N
2
, 18.7, H
2
, 56.3 and CO
2
, 25.0%;
Pressure 2026.5 kPa; Liquid inlet temperature, 303 K;
Gas flow 0.25 kmol s
-1
; Absorbent 2.5 M MEA
solution, flow rate 0.1 m
3
s
-1
; Carbonation ratio at inlet
and outlet 0.15 and 0.4; CO
2
in treated gas 2 10
-3
%;
and Packing 1 inch Raschig rings.
The gas temperature throughout the length of the
column was assumed to be 303 K. The equilibrium
pressure of CO
2
along the entire length of the column
was negligible when compared with the partial
pressure of CO
2
in the gas.
For the sake of simplicity, the physical properties
of the liquid such as density (1000 kg m
-3
) and
specific heat were assumed to be constant. The diffu-
sivities of the amine and CO
2
in solution at 303 K
were assumed to be 0.7710
-9
and 1.410
-9
m
2
s
-1
,
respectively.

1 The column diameter was assumed to be
known (2.75 m).
2 The effective gas-liquid interfacial area was
assumed to be 140 m
2
/m
3
. The value of k
L
at 303 K
was assumed to be 2.410
-4
m s
-1
. The variation in k
L
along the length of the column could be found using
the relation k
L
D
A
. Also, it was further assumed
that the value of k
G
a at a point where the mass flow
rate of the gas is G (lb h
-1
ft
-2
) is given by

k
G
a=6.8410
-6
(G/360)
0.72
(12)

3 From an overall energy balance, the exit
temperature of the liquid was found to be 316.38 K.
The variation in the temperature of the liquid phase
along the height of the column is shown in Fig. 3.
4 The second order reaction rate constant for
CO
2
-MEA system was found using the following
correlation
9


log
10
k
2
=11.069 (2142.34/T) (13)

5 The temperature coefficient of diffusivity of
amine D
B
in solution was assumed to be the same as
VAIDYA & MAHAJ ANI: QUICKLY DESIGN CO
2
-AMINE ABSORBER


51
that of CO
2
in water. The diffusivity of CO
2
in water
was found using the following correlation given by
Versteeg
10

D
CO
2
, H
2
O
=2.3510
-6
exp (-2119 / T) (14)

6 Further, it was also assumed that the ratio of
diffusivity of CO
2
in 2.5 M MEA to that in pure water
at 298 K was 0.64 and that it remains unchanged
throughout the length of the column. The ionic
strength varies from 0.375 to 1 g ion L
-1
and hence H
varies from 10
-(0.070.375)
=0.94 to 10
-(0.071)
=0.85 times
that in pure water. The solubility of CO
2
in water was
found using the following correlation given by
Versteeg
10


H
CO
2
, H
2
O
=3.5410
-7
exp (2044/T) (15)

7 In the lower part of the column, from a solute
mole fraction of 0.07 to 0.25, the CO
2
-alkanolamine
reaction is instantaneous. Therefore, the height is
independent of the solubility parameter H and instead
varies with k
L
. Although a large amount of solute is
absorbed here (73.9%), this section accounts for only
20% of the total height. The rise in temperature of the
liquid phase is about 10C. However, the change in k
L

in this section is only 11%.
8 The reaction is in the depletion regime from a
solute mole fraction of 0.03 to 0.07.
9 Thereafter, the system is confined to the fast
reaction regime in the upper part of the column up to
a solute mole fraction of 0.03. Here, the height
depends on the term H(D
A
k
2
)
1/2
and is independent
of k
L
. The contribution of this section to the total
height is maximum (73%) while the amount of solute
absorbed in this section is only 12.5%. Here, the
liquid phase temperature increases by around 3C
only. So the variation in H (D
A
k
2
)
1/2
in this section is
only 1%.
10 The total height of packing was found to be
4.5 m, which compared well with the value reported
by Danckwerts and Sharma
8
for isothermal operation
(4.6 m).
From the foregoing results, it can be concluded that
the height of packing in adiabatic operation is
relatively insensitive to changes in k
L
and H(D
A
k
2
)
1/2

with temperature. Instead, the height is more sensitive
to the effective gas-liquid interfacial area. This, in
turn, depends on the type of packing, which is
supplied by the manufacturer, the properties of the
absorbent liquid and the system under consideration.
Therefore, the emphasis should be given on accurate
determination of the interfacial area a for any
particular system, which will enable the design
engineer to find a reliable estimate of the height of
packing for a commercial contactor.
The mass-transfer description by rate-based models
is now increasingly being used in process design of
CO
2
absorbers. These models are implemented into a
commercial simulator (Aspen Custom Modeler is
preferred) to carry out verification and sensitivity
analysis. The simple procedure presented here gives
the design engineer one more option of checking
calculations of the process licensor in quick time,
before using these commercial simulators. Thus,
review of the basic engineering package is facilitated
to make it cost-effective due to savings on
engineering man-hours.

Conclusion
A simplified rate-based approach for finding the
height of packing in a CO
2
-alkanolamine absorber is
presented. As is often the case in industrial packed
absorbers used in ammonia manufacture, the gas
phase heat transfer is neglected. The procedure can be
applied to any gas-liquid reactive absorption by
appropriately confining to the assumptions made here.

Acknowledgement
P D Vaidya wishes to thank University Grants
Commission, New Delhi, Government of India, for
the financial support provided during this study.


Fig. 3Variation in temperature of liquid along the height of the
column

INDIAN J . CHEM. TECHNOL., J ANUARY 2006


52
Nomenclature
a = gas-liquid interfacial area, m
2
m
-3

A = solute gas, CO
2

(A
i
*) = concentration of CO
2
at gas liquid interface
in equilibrium with the liquid, kmol m
-3

(A
0
) = concentration of CO
2
in the bulk of the
liquid, kmol m
-3

B = reactant in liquid phase, MEA
(B
0
) = free amine concentration, kmol m
-3

(CO
2
) = concentration of CO
2
in bulk liquid,
kmol m
-3

C
P
= specific heat of absorbent, kcal kg
-1
K
-1

dV = control volume
D
B
= diffusivity of MEA in 2.5 M MEA solution,
m
2
s
-1

D
A
= diffusivity of CO
2
in 2.5 M MEA solution,
m
2
s
-1

D
CO
2
, H
2
O
= diffusivity of CO
2
in water, m
2
s
-1

E = enhancement factor due to chemical reaction
G = molar flow rate of gas phase, kmol s
-1

G
s
= molar flow rate of inerts, kmol s
-1

G = mass flow rate of gas phase, (lb h
-1
ft
-2
)
H = Henrys law constant, kmol m
-3
kPa
-1

H
CO
2
, H
2
O
= Henrys law constant for CO
2
in water, kmol
m
-3
kPa
-1

H
R
= heat of reaction, kcal s
-1

k
G
= gas side mass transfer coefficient, kmol m
-2

s
-1
kPa
-1
k
L
= true liquid side mass transfer coefficient, m
s
-1

k
2
= reaction rate constant for the CO
2
-MEA
reaction, m
3
kmol
-1
s
-1

m = order with respect to solute gas CO
2

m = mass flow rate of liquid, kg s
-1

n = order with respect to MEA
P
AG
= partial pressure of CO
2
in bulk gas phase,
kPa
P
Ai
= partial pressure of CO
2
at gas-liquid
interface, kPa
P
A0
= equilibrium pressure of CO
2
, kPa

P
T
= total pressure, kPa
P*
CO
2
= equilibrium pressure of CO
2
, kPa
R a = volumetric rate of absorption, kmol m
-3
s
-1

S = cross-sectional area of the column, m
2

T = temperature of liquid phase, K
w = stoichiometric coefficient of reaction
y
A
= mole fraction of CO
2
in the gas phase
y
1
= mole fraction of CO
2
at the bottom of the
control volume
y
2
= mole fraction of CO
2
at the top of the control
volume
y
A0
= mole fraction of CO
2
in the bulk liquid
Z = height of packing, m
= variable defined by Eq. (6)
1,2 = subscripts for values at bottom and top

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