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Chemical En#inetrin# Science, Vol. 47, No. 2, pp.

381-390,
Printed in Great Britain.

1992

ooo-2509pz
$5.00 + 0.00
0 1991 Rrgamon Pres plc

COz ABSORPTION
BY NaOH, MONOETHANOLAMINE
2-AMINO-2-METHYL-l-PROPANOL
SOLUTIONS
PACKED
COLUMN+
PAITOON

TONTIWACHWUTHIKUL,

AXEL

MEISENZ

AND
IN A

and C. JIM LIM

Chemical Engineering Department, The University of British Columbia, Vancouver, BC, Canada
V6T 1W5
(First received16 August 1990; accepted for publication in revised form 4 June 1991)
concentration and temperature measurements are reported for the absorptionof CO1
monocthanolamine (MEA) and 2-amino-2-methyl-l-propanol
(AMP)
solutions. An absorber (0.1 m i.d. packed with 12.7 mm Berl Saddles up to heights of 6.55 m) was used which
operated in countercurrent mode and near ambient conditions. The measurements
for the CO,-NaOH and
CO,-MEA systemsare comparedwith predictionsfrom a mathematicalmodel and gave generally good
agreement, except at high CO2 loadings of MEA solutions. Compared with MEA, AMP was found to have
superior CO, absorption capacities and inferior mass transfer rates.
Abatcae-Detailed

from air into aqueous NaOH,

INTRODUCTION

Gas absorption with chemical reaction is widely used


in the chemical and petroleum industries. Although
the operation has been studied for many years, most
process &signs are still based on experience or rule
of the thpmb (Maddox, 1983; Decoursey, 1985). This
is due to the scarcity of fundamental design data (e.g.
mass transfer coefficients, interfacial area, reaction
kinetics, physicochemical
properties) and/or the lack
of confidence in the design methods themselves. Furthermore, exact design methods are often complicated
and require extensive computations.
Design procedures for physical absorption
in
packed columns have been improved substantially in
recent ye&. Treybal (1969) developed a method for
steady state, adiabatic absorption and stripping involving single solute systems. The procedure properly
accounts for the heats of absorption, solvent evaporation and condensation
as well as heat and mass
transfer resistances in both phases. The method was
successfully tested by Raal and Khurana (1973) using
the
air-ammonia-water
system.
Feintuch
and
Treybal (1978) subsequently extended the work to
multicomponent
systems. Experimental
verification
was provided by Kelly et al. (1984) for the physical
absorption of acid gases from coal gas using methanol
as the absorbent.
Rigorous
theories for absorption
with chemical
reaction were well documented by Astarita (1967) and
Danckwerts
(1970). Their efforts were primarily
directed towards developing expressions for the local
mass transfer coefficients. By contrast, little emphasis
was placed on devising design methods. A new set of
design equations for isothermal gas absorption with
chemical reaction was recently developed by Joshi
et al. (1981). However, assuming adiabatic conditions

would have been more realistic because heat losses are


generally small in industrial absorbers (Treybal, 1969;
Pandya, 1983).
A rigorous design .,proeedure for adiabatic
gas
absorption with chemical reaction was first described
by Pandya (1983). The procedure
was based on
Treybals (1969) concepts for adiabatic, physical gas
absorption
and Danckwerts (1970) work on isothermal gas absorption
with chemical
reaction.
Pandyas
procedure
accounted
for the heats of
absorption
and reaction, solvent evaporation
and
condensation, chemical reactions in the liquid phase
as well as heat and mass transfer resistances in both
phases. DeLeye and Froment (1986) used a similar
procedure and presented some numerical results for
commercial
processes; comparisons
with industrial
data were however not given. Recently, Sanyal et al.
(1988) used a similar approach to model Benfield
absorbers in which CO2 is removed with hot carbonate solutions. Although good agreement between the
predictions and field data was claimed, only two sets
of absorber inlet and outlet data were presented.
The present paper has two principal objectives:
(i) to provide comprehensive
experimental data (i.e.
concentrations
and temperature profiles along the
column) for CO, absorption from air into aqueous
NaOH, monoethanolamine
(MEA) and 2-amino-2methyl-l-propanol
(AMP) solutions; (ii) to compare
the experimental results with the predictions from a
computer
model
based on Pandyas
work. The
CO,-NaOH
and C02-MEA
systems could
be
modeled exactly since the necessary fundamental data
have been published previously. Rigorous modeling of
the CO,-AMP
system is still not possible since insufficient fundamental data have been reported.
MATHEMATICALMODEL

Qhis is an extended version of a paper presented at the

3&h CSChE Conference,Edmonton,Alberta,October 1988.


*Authorto whom correspondenceshould be addressed.
301

The present mathematical


model is based on
Pandyas procedure (1983) since it is rigorous and
based on the widely accepted concepts proposed by

382

PAIT~~N TONTIWACEWLJTHIKULet ol.

Treybal (1969) and Danckwerts (1970). A five-component system is considered which comprises an inert
carrier gas (I), and acid gas (A), an inert liquid solvent
(S), a reactant (B) in the liquid and a reaction product
(C). The overall chemical reaction in the liquid phase
is given by
A + bB = C.

(1)

The major assumptions of the present model are:


the reaction is fast and takes place only in the liquid
film; heat and mass transfer resistances for the inert
liquid solvent (S) in the liquid phase are negligible; the
interfacial area is the same for heat and mass transfer;
axial dispersion is negligible. The principal model
equations are only presented in summary form.
Overall differential material balance:
G, dY, = (L/b)dC,

(2)

where
Y, = y,/(l
Liquid-side

- y,)dz.

mass transfer:

(L/b)dC,

= S~;U,(C,.~

- C,)dz

(3)

where 3 denotes the enhancement factor.


Gas-side mass transfer:
GI d Y, = ko, A a,POI,

- yA, *) dz

GrdY, = k,,sOYys - YS,,)~.

(4)
(5)

Interfacial equilibrium:
C A.i = HPy,,,.

(6)

Heat balance for liquid phase:


LG,,dT

tent of the exit gas are in equilibrium ivith the entering


lean absorbent. This assumption is valid in most cases
as suggested by Pandya (1983). By using this assumption, the composition of the rich absorbent leaving the
bottom of the absorber can be determined from
material and energy balances. There are several
methods for numerically solving two-point boundary
value problems. The so-called shooting method
(Fox, 1957; Sanyal et al., 1988) was selected for this
work because it is robust and relatively easy to program and has been used successfully earlier (Treybal,
1969; Pandya, 1983; Kelly et al., 1984; Sanyal et al.,
1988).
A FORTRAN
program was developed to solve eqs
(2)-(g). The numerical method used is similar to that
employed by Treybal (1969), Pandya (1983). Kelly
et al. (1984) and Sanyal et al. (1988). Due to the
implicit relationships between the material and energy
balances, an iterative procedure was adopted to determine the interfacial compositions, temperature and
transfer rates in each element of absorber of height dz.
For the systems considered in this work, CA was
negligible and y,,i was derived from the equilibrium
water vapor pressure of the solution. The temperature
and concentration gradients are then combined with
material and energy balances to calculate the compositions and temperatures of both phases in the next
higher element in the absorber. The total height of the
absorber was obtained by summing the differential
heights until the conditions at the top of the absorber
were satisfied. A simplified flow chart for the program
is shown in Fig. 1.
Various parameters (e.g. mass transfer coefficients,
solubility. reaction rate constant, etc.) are needed

Start cakutaitona

at the bottom of abaorbor

= G[ ~Wk,I]dT,
+ G,H,dY,

where j denotes component

- GrH,dY,

(7)

A, S or I.

Heat balance for gas phase:


t

GI[

?Y,C~,J]dTo

= &a&&o

- T,)dz-

(8)

To determine the packing height for a given absorption duty, the above equations must be solved simultaneously. Since the equations are coupled and highly
nonlinear, analytical solutions are impossible and
numerical methods must be used.
In designing absorbers operating in countercurrent
mode, the temperatures and compositions of the lean
absorbent and raw feed gas are generally given while
only the CO, concentration of the exit gas is specified.
The temperature and moisture content of the exit gas
are not usually known. As a result, a two-point
boundary value problem arises. A good initial assumption is that the temperature and moisture con-

ComDute
heat

and mass transfer

t
assumed interfacial
conditions

Assume new
interfaclal
conditions

Yes

Fig. 1. Simplified flow chart of the major calculation steps


used in the present computer model.

CO2 absorptionby solutions in a packedcolumn

before the model equations can be evaluated. These


parameters may be obtained from experimental measurements or correlations. Great care has to be exercised because there are considerable discrepancies
between reported data (Kelly et al., 1984; Raal and
Khurana, 1973) and they can strongly affbct the
results.
Although several correlations are available for
estimating k, and a, (Shulman et a!., 195kOnda et al.,
1968; Puranik and Vogelpohl, 1974), the expressions
proposed by Onda et al. were chosen because they
were found to be very satisfactory by Kelly et al.
(1984) and Sanyal et al. (1988). The liquid mass transfer coefficients were estimated from Chos (1988) expression for Berl Saddles. The heat transfer coefficients were calculated by invoking the analogy between heat and mass transfer and using the correlation suggested by Pandya (1983). The total heat of
absorption, which is the sum of the heat of solution
and the heat of reaction, were taken from Danckwerts
(1970) and Kohl and Riesenfeld (1985) for the
CO,-NaOH and CO,-MEA systems, respectively.
One of the most difficult and important aspects of
modeling absorption with chemical reaction is the
determination
of the enhancement
factor 9.
Danckwerts (1970) defined the latter as the ratio of the
mass transfer coefficient for absorption with chemical
reaction (kL) to the mass transfer coefficient for purely
physical absorption (k!). In contrast with k:, which is
fairly constant, k, and 3 change significantly along
the column.
The general determination of X requires the solution of a set of partial differential equations governing
the simultaneous diflusional mass transfer and
chemical reactions in the liquid film. There are no
general analytical solutions. The CO,-NaOH
and
C02-MEA
reactions are second-order (Astarita,
1967; Danckwerts, 1970) and approximate solutions
have been proposed by van Krevelen and Hoftijzer
(1948), Porter (1966), Decoursey (1974) and Wellek et
al. (1978). Although the latter authors found the equations derived by van Krevelen and Hoftijxer (1948) to
be most accurate, they require an iterative procedure
to determine 4. The explicit equation presented by
Wellek et al. (1978), which deviates by less than 3%
from the most accurate solution, was therefore
adopted here:
4 = 1 + { 1 + [(Hm - 1)/(X1 - 1)]-35}11.=

(9)

where
Y1 = m/tanh(&)

(IO)

M = (DAk, CB)/ki2

(11)

3,

= 1 + (43 CBW~,

CA,).

(12)

The reaction rate constant for the CO,-NaOH


system was recently correlated by Pohorecki and
Moniuk (1988) for the temperatures and ionic
strengths (I,) of practical interest:

log@,,

383

NaOH) = 11.895 - 2382/T


+ 0.221 z, - 0.016Zf.

(13)

For the CO,-MEA system, Blauwhoff et al. (1984)


expressed the second-order reaction rate constant by
log(k,,

MEA) = 10.99 - 2152/T.

(14)

The Henrys constant for COs in NaOH solutions


was obtained from
log @Y/z&,) =

-&I,.

(15)

where K, denotes the sum of the contributions due to


ions in the liquid phase [as reported by Danckwerts
(1970)] and I?, denotes the Henrys constant of CO2
in water (Pohrecki and Moniuk, 1988):
log (II,) = 9.1229 - 0.059044 T + 7.8857 x lo- T2.
(145)

For the CO,-MEA


that

system, Hikita et al. (1979) found

log(H/H,,,) = 0.3(MEA)/[l

- rc(MEA)] - &I,

(17)
where
K = 1/[1.2850 - O.OOl(T- 314.5513)2].
The diffusivities for the CO,-NaOH
-and
CO,-MEA
systems were taken from Danckwerts
(1970) and Thomas and Furzer (1962). The effect of
temperature on di8usivity was calculated by using the
equation suggested by Reid et al. (1987):
B,(Tz)/B,tTi)

= C(T, - T,)/(T, -

T,H

(18)

where T, represents the critical temperature of the


solvent. The index n is related to the heat of vaporization of the solvent and has a value of 3 for the
present systems.
The data for other parameters such as density,
viscosity, specific heat, etc. were taken from Edwards
(1984), Kohl and Riesenfeld (1985), and the Dow Gas
Conditioning Fact Book (1962).
EXPERIMENTAL

EQUIPMENT

AND

PBOCEDURE

equipment used to obtain the experimental data was similar to that descriw
earlier
(Tontiwachwuthikul et al., 1989). The absorption column (7.2 m high and 0.1 m i.d.) was made of acrylic
plastic and packed with 12.7 mm (l/2) ceramic Berl
Saddles. The column consisted of six sections (each
1.2 m high) with redistributors inserted between sections. The packing height of each section was about
1.1 m. In order to vary the effective packing height, the
gas could be introduced at different locations between
sections.
The gas and liquid phases were sampled at the
section inlets and outlets by means of probes consisting of 1OOmm long, IS-gauge needles fitted with
9 !mm o.d. and 9 mm high teflon cups. To sample the
gas phase, the cups were positioned so that their open
ends faced into the direction of the gas flow. The
The

384

PAIT~NTONTIWACHWIJIHIKUL~C

needle outlets were connected to an infrared gas


analyzer by nylon tubes. For liquid sampling, the
open endi of the cups pointed into the direction of the
liquid flow and the needles were connected to 50 ml
syringes.
Before each run, the feed solution of the desired
composition was prepared and stored in a 200 1 tank.
The latter capacity was sufficient for at least 90 min of
operation. All chemicals used were commercial grade
and provided by Van Water and Roger Co. of
Vancouver, BC.
The liquid, air and CO, flow rates were measured
by rotameters and all fluids were. preheated in a
constant temperature bath. The gas mixture, which
was introduced into the column at the desired height,
flowed upwards and counter-currently to the liquid
solution which was introduced into the top of the
tower. The solution leaving the absorber bottom was
discarded or regenerated.
Steady state was usually reached within 30 to
40 min and could be determined from the constancy
of the temperature measurements along the column
and the CO, outlet concentration. After reaching
steady state, the exact gas .concentrations and temperatures were measured along the column. Liquid
samples were also collected and subsequently analyzed.
The concentration of CO, in the gas phase was
measured with an infrared gas analyzer (Model 3OOD,
Nova
Analytical
Systems, Hamilton,
Ont.). Its
accuracy was + 2% of the full scale reading. Before
each run, the analyzer was calibrated with standard
C02-N2
mixtures provided
by Matheson
Inc.,
Vancouver, BC.
The analytical technique described by Bassett et al.
(1979) was used to determine the compqsition of
NaOH
solutions. The total alkali (carbonate and
hydroxide) content was determined by titration with
standard 1 N HCl using a methyl orange indicator.
To determine the hydroxide content, the carbonate
ions were precipitated with excess barium chloride
before titrating the solution with standard 1 N HCl
and using phenolphthalein as the indicator. The carbonate content was subsequently determined from the
difference in the titration readings.
In case of amine solutions, the total amine concentration was found by titration with standard 1 N HCl
to the methyl orange end point. The CO, content in
the liquid sample was determined by the AOAC
method
(Horwitz,
1975). The
latter
involved
acidifying the sample with 2 N HCl and collecting the
released CO, in a precision burette.
The following
operating conditions were used:
superficial gas flow rate 11.1 td 14.8 mol/m3 s; superficial liquid flow rate 9.5 to 13.5 m3/m2 h; feed CO,
concentration 11.5 to 19.5%; total absorbent concentration 1.2 to 3.8 kmol/m; CO2 loading in the liquid
feed 0.00 to 0.371 mol CO,/mol absorbent; liquid feed
temperature 14 to 20C; total pressure 103.15 kPa.
The column was operated at 30 to 75% of flooding
which is typical for gas absorbers.

al.
RRSULTSANDDISCUSSION

The experimental results from 30 runs are summarized in Tables l-3. The data are presented in
detail to enable comparisons with predictions of our
model as well as models which might be developed by
others in future. The present data differ from previously reported measurements because the latter
were usually obtained with short columns (typically
1-2 m high) and only inlet and outlet conditions were
recorded. Furthermore, the present concentration and
temperature changes are considerable and column
data for CO2 absorption into AMP
solutions are
reported for the first time.
Typical plots of experimental and predicted gas
concentrations, liquid compositions and temperatures
along the column are shown in Figs 2 and 3 for the
CO,-NaOH
and CO,-MEA
systems, respectively.
The agreement between the results is generally very
good thereby confirming the validity of the mathematical model. It should be noted that these results
represent the first detailed experimental verification of
the fundamental design procedures for absorbers with
chemical reaction.
As seen from Figs 2 and 3, the gas and liquid
temperature profiles differ significantly near the column bottom where the entering gas is rapidly heated
by the descending liquid. Higher up the column, the
gas and liquid temperatures reach a maximum and
then become very similar. Figures 2 and 3 also show
that the enhancement factors vary considerably along
the column, with the greatest changes occurring in the
lower sections. The assumption of a constant enhancement is therefore not generally justifiable. For
instance, in the case run T9 (Fig. 2), 9 increases from
approximately 20 at the column bottom to 80 at the
column top. This means that the absorption rate with
chemical reaction is 20 to 80 times higher than without chemical reaction.
The importance of accurately knowing the enhancement factor is underscored by Fig. 4 which
shows results for the CO,-MEA
system. The difference between the experimental and predicted CO2
profiles (solid line) is significant even though the
values at the column inlet and outlet are in good
agreement. One reason for the discrepancy may be
due to bicarbonate formation, which becomes irnportant as the CO2 loading approaches 0.5 mol of CO2
per mole of MEA and which was not taken into
account in the present model. Another reason may be
the effect of ionic strength on the reaction rate constant which was not included in eq. 14 since it is not
known. Since both the reaction mechanism and the
rate constant influence the enhancement factor, it is
not surprising that good agreement was not obtained
at high CO, loadings. The calculations were then
repeated for just the top five sections of the absorber
and using the experimentally determined composition
of the gas phase leaving the sixth section (which is the
same as the composition of the gas phase entering the
f&h section). Under these conditions, the solution

Tl

Liquidtemperature
(C)e
z-O.OOm
1 = 1.05m
z= 2.15q
z= 3.25m
z= 4.35m
z=5.45m
z= 6.55m

Mass balance(X)

i = 5.45m
z= 6.55m

15.0
17.0
20.0
23.0

t 1.54

-..

-.._.-.

16.0
21.5
26.5
29.0
-

t 1.91

- 0.37
16.0
20.0
25.0
29.0
-

1.02
0.59
0.19
0.01
-

62.2

A::
0.31
0.05
-

73.1

7.7
12.3
16.5
18.2
-

4.4
7.8
11.8
14.6
-

14.8
13.5
1.2

14.8
13.5
1.2

T3

T2

75.6

OIj- wn;mtration (kmol/m3)e


0.75
iz IIO5m
0.61
d=215m
0.42
1 = 3.25q
0.18
z= 4.35q

CO, removal(%)

z= 5.45m
z= 6.55m

Air flow (mol/m*s)


14.8
Liquidflow (m/mh)
13.5
NaOH feed(kmol/m3)
1.2
Gy z?g;centration
(%) 8
2.3
z= 1105m
4.0
z= 2.15m
6.3
8.9
z= 3.25m
z= 4.35m

Run(#)

18.0
19.0
20.5
24.0
26.0

--__

+ 3.06

0.80
0.71
0.55
0.32
0.10
-

89.4

fY
-

1.0
2.2
4.2

14.8
13.5
1.2

T4

^_I.

16.5
19.0
23.0
26.5
27.0
-

- 1.24

0.86
0.66
0.39
0.13
0.01
-

78.4

2.9
5.3
8.5
11.2
12.3
-

14.8
13.5
1.2

TS

- .----

16.0
18.0
21.0
26.0
27.5
-

- 3.76

1.03
0.88
0.62
0.30
0.07
-

86.8

1.9
3.7
6.7
10.1
125
-

14.8
13.5
1.2

T6

--

14.5
17.0
23.0
35.0
37.0
-

- 1.78

2.000
1.800
1.425
0.720
0.137

93.0

1.25
295
6.15
11.20
15.45
-

14.8
9.5
20

T7

2500
2275
1.800
0.950
0.180
-

92.5

1.70
3.50
7.05
1285
18.70
-

14.8
9.5
2.5

T8

_-

14.0
17.0
23.5
39.0
42.0
-

- 2.23

Table 1. Experimental
resultsfor the CO,-NaOH system

--

15.0
17.0
22.0
29.0
35.0
-

- 5.69

2000
1.900
1.625
1.075
0.413

95.5

1.75
3.60
6.65
10.90
15.20

1.00
2.65
5.80
11.55
18.45
-

15.0
17.0
20.0
26.0
30.0
-

t 1.50

1.500
1.350
1.060
0.625
0.243

90.0

14.8
13.5
2.0

TlO

14.8
13.5
2.0

T9

20.0
20.0
21.0
23.5
28.0
35.0
37.5

t 1.20

(KY
(1:270)
0.930
0.470
0.080

1.530

100.0

x
12:o
15.5

0.0
0.5
1.2

14.8
13.5
2.0

Tll

21.0
21.0
22.0
23.0
26.0
33.0
39.0

+ 1.42

1.90
1.90
1.90
1.75
1.60
1.15
0.48

100.0

0.0
0.0
0.5
1.4
3.7
a.2
15.4

14.8
13.5
2.0

T12

Liquidtemperature
(C)r
z= 0.00 m
z= 1.05m
z= 2.15m
I= 3.25m
z= 4.35m
2= 5.45m
z= 6.55m

Mass balance(%)

z= 0.00m
z=l.OSm
z= 2.15m
z= 3.25m
2= 4.35m
z= 5.45m
z= 6.55m

19.0
19.0
19.5
20.0
23.0
29.0
34.0

+ 2.36

(Kg
(0.012)
0.025
0.078
0.200
0.362

100.0

CO1 loading
(mol CO,/mol MEA)@

CO, removal(%)

200

MEA feed(kmol/m3)

::::
8.3
15.3

13.5

Liquidflow (m3/m2h)

0.0
0.0
0.4

14.8

Air Row(mol/m2s)

Gas CO, concentration(%)s


2= 0.00
m
z= 1.05m
z= 215 m
z= 3.25m
z= 4.35m
z= 5.45m
z= 6.55m

T13

Run (#)

13.5
203

13.5
2.00

19.0
20.0
21.0
220
28.0
33.0
34.0

t 0.09

0.118
(0.125)
0.140
(0.198)
0.295
0.400
0.480

loo.0

19.0
19.0
19.0
21.0
25.0
35.0
37.5

- 0.34

(z&
0.013
(O.@w
0.140
0.302
0.415

100.0

0.0
0.0
0.6
21
6.5
13.6
19.5

14.8

14.8

0.0
0.6
1.4
4.0
8.4
12.8
15.6

T15

T14

m.0

21.0
22.0
26.0
32.0
36.0
z
33.0
41.0
39.0

20.0

+ 0.89

0.237
(0.237)
0.243
0.255
0_296
0.350
0.428

100.0

zt
0:8
2.0
5.3
10.2
15.6

3.80

13.5

14.8

T17

19.0
19.0

- 231

0.255
0.425
0.500

0.090

0.038

WJW

0.000

100.0

z
1:3
3.9
8.9
13.8
15.5

2.08

9.5

14.8

T16

20.0
27.0
36.0
43.0
42.0
41.0
36.0

- 0.94

O.ooO
0.150
0.362
0.482
(0.530)
0.538
0.558

85.4

3.3
1.9
14.0
17.2
18.4
18.8
19.1

2.00

9.5

14.8

T18

Table 2 Experimental
resultsfor the Cot-MEA system

19.0
19.0
19.0
19.0
20.0
24.0
30.0

+ 4.58

(0.002)
0.005
0.032
0.108
0.265

10.0

0.0
0.0
0.1
0.2
1.4
4.8
11.5

2.00

13.5

14.8

T19

19.0
20.0
22.0
32.0
47.0
57.0
48.0

- 3.14

0.000
0.010
0.070
0.190
(0.366)
0.474
0.514

100.0

0.0
0.6
2.8
1.1
14.2
17.7
19.2

2.55

9.5

14.8

T20

19.0
19.0
19.0
21.0
26.0
33.5
31.5

- 1.19

;:g
O.ooO
0.030
0.142
0.325
0.488

100.0

0.0
0.0
0.1
1.2
6.0
13.2
19.1

2.00

9.5

11.1

T21

19.0
19.0
19.0
21.0
29.0
45.0
41.0

t 0.92

0.033
0.125
0.292
0.443

ZE
O.ooO

100.0

0.0
0.0
0.1
1.2
5.3
12.8
19.1

3.00

9.5

14.8

T22

- 4.24
15.0
16.0
17.0
19.0
23.0
-

Liquid temperature (C)@


z=O.OOm
i = &OSm
i =2.15m
z= 3.25m
I= 4.35m
z= 5.45m
z=6.55m

0.000
0.058
0.131
0.212
0.285
-

Mass balance (%)

co, loading
(mol COJmol AMP)@
z= 0.00m
z= 1.05m
z= 2.15m
z= 3.25m
i = 4.35m
z= 5.45m
z= 6.55m

15.0
17.0
19.0
21.0
21.0

+ 1.52

0.147
0.202
0.258
0.317
0.387
-

46.6

15.0
17.0
18.0
21.0
23.0
24.5
24.5

- 1.53

0.152
0.215
0.211
0.341
0.3%
0.442
0.464

51.8

10.10
11.80
13.40
15.15
16.70
17.80
18.90

8.90
10.50
12.20
13.85
15.45
-

6.80
8.60
10.70
13.30
15.25

60.4

2.0

9.5

14.8

T25

2.0

9.5

14.8

T24

2.0

CO, removal (%)

9.5

Liquid flow (m3/mzh)

14.8

Air flow (mol/m2s)

AMP concentration
(kmoVm3)
Gas CO, concentration (%)e
z= 0.00
m
z= 1.05m
z= 2.15m
z= 3.25m
z= 4.35m
z= 5.45m
z= 6.55m

T23

Run (#)

15.0
17.0
20.0
23.0
26.5
28.0
29.0

- 4.31

0.022
0.083
0.149
0.223
0.303
0.358
0.411

63.6

1.70
9.55
11.55
13.70
15.70
17.35
18.65

2.0

9.5

14.8

T26

15.0
16.5
19.0
21.0
24.5
26.0
28.0

- 9.31

0.021
0.058
0.113
0.174
0.254
0.323
0.383

81.1

4.25
6.15
8.40
11.20
14.15
16.95
19.00

2.0

9.5

11.1

T21

Table 3. Experimental results for the AMP-CO, system

15.0
16.0
18.0
19.0
20.0
21.0
21.0

- 9.67

0.371
0.417
0.449
0.484
0.536
0.550
0.583

35.5

13.25
14.55
15.65
16.75
17.7s
18.40
19.15

2.0

9.5

14.8

T28

14.0
16.0
18.0
20.0
22.5
24.0
26.0

f 3.61

0.038
(0.079)
(0.119)
(0.173)
(0.251)
(0.316)
0.385

73.0

5.95
7.65
9.50
11.70
14.70
17.05
19.00

2.0

13.5

14.8

T29

15.0
16.0
17.0
19.0
21.0
23.0
25.0

11.60

0.029
0.045
0.078
0.122
0.182
0.233
0.300

88.4

2.65
4.00
6.00
8.70
12.25
15.85
19.00

2.0

13.5

11.1

T30

388

PAITOON
20

TONTIWACBWUTHIKIJL

et al.

loon
2

( b)

3
tbl

Distsnc* lrom tho

4
bottom

I m1

(cl
Fig. 2. Predicted (lines) and experimental (points) results for
the CO,-NaOH
system
(run T9): (a) CO, concentration
profiles, (b) temperature profiles for the liquid (solid line) and
gas phases (dotted line), (c) enhancement factor.

Fig. 3. Predicted (lines) and experimental (points) results for


the CO,-MEA
system (run T22): (a) CO, concentration
pro&s, (b) temperature profiles for the liquid (solid line) and
gas phases (dotted line), (c) enhancement factor.

Fig. 4. Concentration of CO, in the gas phase for run T16.


Open circles representexperimental
measurements; the solid
line and dotted line denote the predicted values using a
column consisting of 6 and 5 sections, respectively. (In both
cases, the distance is measured from a point located at the
bottom of the sixth section.)

Fig. 5. Comparison of absorber performance using NaOH


(run T7: circles), MEA (run T16: triangles) and AMP (run
T23: crosses). The lines represent smoothed experimental
values and not model predictions.

The effect of solvent type on CO, absorption is


by Figs S and 6. There is almost no
difference in column performance when using NaOH
or MEA under the conditions of run T7 and T16 as
shown by Fig. 5. The latter also indicates that the
column performance is better and hence the absorpdemonstrated

ranged from 0.00 mol COz/mol MEA in the


liquid entering the top of the absorber to 0.425 mol
CO,/mol
MEA in the liquid leaving the bottom
section (i.e. the fifth) of the absorber. As shown by the

loadings

dotted

line

in Fig.

4, the agreement

predicted and experimental


very good.

values

between

becomes

the

at once

tion rates are much higher for MEA


than AMP.
It
should however he noted that in runs T16 and T23 the
solution loading stayed below approximately
0.5 mol

389

CO, absorption by solutions in a packed column

SJ
0

Disionce

from

cohmn

bottom

Henrys law constant, kmol/m3 kPa


heat transfer coefficient, kJ/s m2 K
heat of absorption and reaction, kJ/kmol
heat of vaporization of solvent S, kJ/kmol
inert carrier gas
enhancement factor
ionic strength, kmol/m3
reaction rate constant, m3/kmol s
physical
gas mass transfer coefficient,
kmol/m2 s kPa
physical liquid mass transfer coefficient, m/s
liquid flow rate, m3/m2 s
dimensiodess
film conversion parameter

[ml

Fig. 6. Comparison of absorber performance at high CO2


loadings using MEA (run Tl8: triangles) and AMP (run T28:
circles). The solid lines represent smoothed experimental
values and not model predictions.

of CO, per mole of amine. When the loadings increased above this value, the concentration profiles
crossed and AMP became more effective than MEA.
This phenomenon is clearly demonstrated by Fig. 6,
which corresponds to run T18 and T28. The choice of
absorbent is therefore not only dependent on absorption rate but also absorption capacity.

CONCLUSIONS

The following principal conclusions may be drawn


from the present work:

(1) Good

agreement was found between the experimental measurements and model predictions
for the CO,-NaOH
and CO,-MEA
systems
except at loadings exceeding about 0.5 mol of
CO* per mole of MEA.
(2) Model validation should be based on concentration and temperature profiles and not just
the conditions at the absorber top and bottom.
(3) The enhancement factor varies significantly
along the absorption column and must he accurately known for reliable modeling.
(4) Compared with MEA, AMP has a higher CO,
absorption capacity and lower absorption rate.
AMP is therefore well suited for treating gases
rich in COz.
Acknowledgement-The
financial support of the Natural
Sciences and Engineering Research Council of Canada is
gratefully acknowledged.
NOTATION

interfacial area per unit volume of packing,


m2/m3
concentration of component j in the liquid,
kmol/m3
heat capacity of component j in the gas,
kJ/kmol K
heat capacity of solution, kJ/m3 K
diffusivity of component j, m2/s
molar gas flow rate of component
I,
kmol/m+

cs= eq. (1111


total pressure, kPa
temperature, K
mole ratio of component j, kmolj/kmol I
mole fraction of component j, kmol j/m01
total height of packing, m
vertical distance from bottom of packing, m
vertical distance from top of packing (z = 2
- 2). m
Subscripts
A

absorbed compound

reagent in liquid

G
i

gas
interface
generalized component j
liquid
water

i
L
W

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