~kmkd

~nghraimg Scimcc Vol. 1. pp. 479A82

Perpmon Press Ltd.. 1981. Printed in Great Britain

REACTION

OF CO2 WITH ETHANOLAMINES:

FROM GAS-ABSORPTION
S. S. LADDHA

Department

KINETICS

and P. V. DANCKWERTS*

of Chemical Engineering, University of Cambridge, Pembroke St., Cambridge CB2 3RA, England

(Accepted 2 October 1980)

Abstraci-C~ at very low pressure was absorbed in a stirred cell into aqueous solutions of MEA and DEA. The
rates of absorption were determined from the fall in pressure. The results were analysed on the assumption (for
which experimental support is given) that the solubilities and diilusivities of CO2 in these solutions bear a constant
proportionalitv to those of N,O, which have been measured. The results for MEA at 25C agree very closely with
those of Hikita et al.[lj, determined by a rapid-mixing thermal method. The results for DEA appear to support a
reaction mechanism proposed by Danckwerts[l3],
the reaction tending to he second-order in amine at low
concentrations and fi&<rder at l&h concentrations.

INTRODUCIION

et PI.[ 11, using a rapid-mixing

thermal method,
showed that the reaction
between
CO, and monoethanolamine (MEA) in aqueous solution
Hikita

amine (D$D, - l/2) and was comfortably satisfied in all

our experiments.
Under these circumstances
the rate of
absorption of CO2 per unit area, R, is given by
R = pSd/(DJL(AW

CO, + 2RNH+
appeared
(Am):

to be first-order

RNCOZ-

+ RNHs

in the amine

concentration

r,,, = k&O&Am)
(rM being the homogeneous
the corresponding
reaction
appeared to be second-order:

(1)

(2)

reaction-rate
of CO3 while
of diethanolamine
(DEA)

rD = kj(CO&Am)=.

where

DA is the diffusivity

where p is the partial pressure of CO*, S its solubility,

(Am) the concentration
of amine, k. a rate-coefficient
which may be a function of (Am)-e.g.
k,(Am) for DEA
according to Hikita et al.[lJ-and
k,&OH-)
the contribution made to the reaction rate by the hydroxyl ions,
whcih is small and can be calculated with sufficient
precision @Ka is 9.50 for MEA and 8.92 for DEA at
2X [5]; kOH is 8322 llmol s [6]). It is easily shown that in
a sealed absorber with a gas space of volume V, CO2
being absorbed into a liquid surface of area A

(6)
where RG is the gas-constant
and T the absolute temperature.
In the case of a gas such as N20 which does not react
with the amine the quantity kLS, where kL and S are the
mass-transfer
coefficient
and the solubility,
can be
determined in a similar way:
kLS=&(+).
In order to calculate /3 from (6) it is necessary to
estimate D,p for CO,. Laddha et al. [33 have shown that
the solubilities of CO1 and NzO bear a constant ratio
(1.37) to one another in water and in aqueous solutions of
a number of alcohols (mol fraction up to 0.06) and thus
there is every reason to suppose this ratio to hold in
solutions of MEA and DEA. For similar reasons one
might expect the diffusivities of the two gases in solution
to exhibit a constant ratio.
Now, if the stirrer in the stirred cell brings about some

(4)

of CO2 and Da that of the

*Author to whom correspondence

should be addressed.
479

CBS Vd. 36. No. M

(5)

(3)

Hikita d nl.[2] also absorbed CO, at 1 atm into laminar

jets of MEA and DEA solutions and in order to reconcile
the homogeneous
kinetics with the observed rates of
absorption
had to make assumptions about the solubilities of CO* in solutions of MEA and DEA which
appear to be anomalous[3].
In the experiments
discussed below we absorbed CO*
at an initial partial pressure of about 10ml atm into a pool
of amine solution in a stirred cell similar to that described by Danckwerts
and Alper(41, in which a fourbladed stirrer wiped the surface of the liquid. The rate
of rotation was 70rpm. The low partial pressure of CO2
resulted in a low absorption rate, so that the depletion of
amine at the surface was negligible. The condition for the
concentration
to be uniform is
R @; k,(A~W~D,ID,d

+ k&OH-)])

S. S. LADDHAand P. V. DANCKWERTS

480

kind of surface-renewal the ratios of the values of krS

for CO2 and N20 at a given stirring-speed will be the
same as the ratios of Sd/o[7]. The values of SVD for
CO* and NzO in water at 25C are well-established [g-l l]
and the ratio is 1.43. Our measurements in the stirred cell
showed that the ratio of kLS in water was 1.43 and
furthermore that the ratio was within 3% of 1.43 in a
variety of solutions of alcohols (see Table 1). We also did
some experiments in a laminar jet at 25C which showed
that the ratio of SVD was equal to 1.43 to within 4% for
aqueous solutions of glycerol and glycol (m.f. 0.06).
Since S and D have been measured for NZO in solutions of MEA and DEA[!&ll] it seems highly probable
that values of SVR for CO2 can be assigned by multiplying those for N20 by the factor 1.43. Prof. Sada has
been kind enough to communicate the actual values of
SqD for NzO measured in a laminar-jet apparatus. If
those for DEA are plotted against the concentration a
point of inflection occurs in the range 2.5-3.5 M. There is
no corresponding feature in the curves of solubility or
viscosity. We therefore have some reservation about
applying the analogy with CO? in our experiment at
2.88 M. This point is discussed below.

two vessels were then isolated from the pump and one
another. At this stage the pressure on each side of the
micromanometer was the saturated water-vapour pressure and the deflection was zero. A small amount of CO2
(-0.02atm)
was admitted to the stirred cell and the
stirrers were started. The chart was started when the
pressure of the CO, was about 0.01 atm. The pressure
was recorded over lO-l35 s. The experiment could be
repeated by allowing the deflection to fall to zero and
admitting more CO2 (the CO2 absorbed was very much
less than the amine in the liquid).
The record could conveniently be analysed by reading
from the chart the time B required for the pressure of CO?
to fall by a factor 4: -d In p/dt = In de.
In order to measure kL the stirred vessel was purged
with the appropriate gas at atmospheric pressure and
then isolated. The difference, Ap, between the pressure
in the vessel and the atmosphere at time B was recorded,
Since Ap was much less than the pressure of the gas, p,
-d In pldr = Ap/pfL The back-pressure of the dissolved
gas was negligible.
All experiments were done at 25C with a stirrer speed
of 70 rpm.
The experimental results are shown in Tables 1 and 2.

EXPERIMENTAL
DISCUSSIONOF RESULW

The stirred vessel (9.2 cm i.d.) was similar to that

described by Danckwerts and Alper[4] except that the
stirrer was driven by a small electric motor enclosed in
the gas-space so that a shaft passing through a gland was
not necessary and the system could be positively sealed.
Another internal motor drove a gas stirrer and it was
found that above a certain speed gas-side resistance
ceased to decrease and was presumably negligible.
The surface area, A, of the liquid was determined by
geometrical considerations. The volume, V, of the gas in
the vessel and its associated connections was measured
by evacuating it, connecting it to another vessel of
known volume containing air at atmospheric pressure
and measuring the resultant pressure.
The apparatus consisted of the absorber and a
reference vessel containing a little of the solution under
investigation. The pressure difference between these two
vessels could be recorded on a chart by a micromanometer. A fixed volume (500 cm3) of the solution was
put into the stirred cell and the whole system made
vacuum-tight, evacuated and held under vacuum until
bubbles of air ceased to be evolved by the liquid. The
Table 1. Comparative values

nole
Praction

values of /3 (eqn 6) as inferred from the pressure

measurements are given in Table 2 and in Fig. 1 log /3 =
log k,(Am) is plotted against log (Am). As regards MEA,
the extrapolation of the homogeneous results-of Hikita et
al. [I] agrees extradordinarily well with OUTfindings, establishing that the reaction is indeed second-order in the
amine concentration and that the method for estimating
SD,, for CO, in the amine solutions is correct (and that
therefore the figures given by Hikita et a[.(21 for the
solubilities are incorrect). Furthermore, it has been
shown[ll] that the diffusivities of N20 in solutions of
amine cannot be correlated by expressions of the form
&A = const, The same is presumably true for C02.
As regards DEA, Danckwerts[12] suggested that the
reaction mechanism of CO2 with amine might be
CO2 -t &NH 2
R,NH+CO,- + &NH 7

(the nomenclature

R,NH+CO,-

(8)

RzNCO,- + &NH,+

(9)

is changed here) leading to a homo-

of kLS for CO*and NZO in various solutions at 25C

v = 637 cm3
Partial preseure of gas, p = 1 atm
SD1"t.Z

The

A = 61)cm2
a = 1.43 (kLSINzO

104<l/p)cAp/Ar).s-1

lo*

(kLNC02

CLS,m*l/cm2.atm.s

co2

NzO

N2O

water

1.00

2.31

1.62

6.44

6.60

1.00

Glycol

0.06

1.70

1.16

6.92

2.72

0.98

Glycerol

0.06

1.12

Cl.76

4.66

3.0s

0.97

Diethyleneelycol

0.06

I.27

0.90

6.17

3.66

1.01

Reaction of CO, with ethanolamines: kinetics from gas-absorption

481

Table 2. Reaction rates of CO?

Amine

10

(Am)
mOl/l

PK.4

DEA

S JD

103<-din

rno1fom2atm.sf

pldt)

ka(Aml+k,,l,CO1~-~

koH(O1l-)

6 i kg<Am)

s-1

s-1

s-1

s-1

0.49

1.47

19.29

2853

33

2820

0.73

1.46

22.99

4109

40

YO61

0.98

1.411

25.96

5385

46

5339

1.21

1.43

29.35

6980

51

6929

1.46

1.39

32.93

9300

67

9253

1.71

1.36

32.66

9666

61

9495

O.Li6

1.92

4.32

16

163

0.67

1.41

5.70

18

253

0.66

1.39

6.40

19

332

0.765

1.38

7.3l1

21

4U8

0.99

1.35

8.71

23

667

1.50

1.29

11.22

29

1225

1.98

1.2u

12.83

2.66

(1.11,

14.20

33

17111

40

<2671)

MEA/~
/

Fig. 1.
geneous rate of reaction
rD

k.(CO&Am)

= :co2)(tm)
+A
k2

SW4

where k, = kzkdk_z.
If this were so a plot of (Am)/kJAm)

the value of s~/D

=(Am)/g
against l/(Am) should be a straight line of slope l/k, and
intercept Ilk,. Such a plot is shown for DEA in Fii. 2.
Linear regression analysis leads to

(Am)_ (AmI
---_-_---+
k.(Am)
B

1410

I
12OO(Am)

Ill)

((Am) in mol/l) with a coefficient of confidence of 0.99.

about

As explained above, we have some reservations

in 2.88 M DEA (inferred rate-constants shown by crosses in Fiis. 1 and 2). This value of /3
does not correlate very well with the others shown in
Fig. 2 and has not been taken into account in the analysis
leading to eqn (11). If it were it would lead to a more
pronounced falling-off to the second-order reaction at
higher concentrations, without appreciably affecting the
inferred value of k3. Since the two terms on the righthand side of eqn (1 I) are of comparable magnitude the
results iend very strong support to eqn (10). The thirdorder coefficient 4

has a value of 12OC1(moi/l)-~s-,

S. S.

482

LADDHA
and P. V.

compared with the value of 1253 found by Hikita et

al.[l], a difference of only 5%. The value of kz is found

to be 14101/mol s, much less than that for MEA (5868),
as might be expected from the lower basic strength of
DEA and the fact that the approach of a CO, molecule to
the nitrogen atom is hindered, in the case of DEA, by
two rather than one-(CHZ)OH groups (no doubt with
hydrogen-bonded water molecules).
There is, however, one important discrepancy between
our results and those of Hikita et al. [I], namely that they
found the reaction to be third-order when the amine
concentration was as high as 0.72 M whereas we found
that third-order kinetics were not attained (although
fairly closely approached) at concentrations as low as
0.5 M. Very recently Alvarez-Fuster et a/.[121 have
reported experiments on the rate of absorption of CO2
into amine solutions in a wetted-wall column which
suggest that the kinetics of the reaction reported by
Hikita et al. [l] are correct, both as to order of reaction
and rate-constants, for MEA and DEA, third-order
kinetics being maintained in the latter case up to 0.8 M.
We have information from the British Gas Corporation
(private communication) that experiments with a stopped-flow apparatus indicate that the reaction between
CO2 and DEA is first-order in the concentration of amine
in the range 0.01-0.03 M. The kinetics of the CO,DEA
reaction still admit room for speculation.
Acknowledgement-This
Research Council.

work was supported by the Science

NOTATION

surface area of absorbing liquid, cm*

concentration of amine, mol/l

(Am3
D

diffusivity of dissolved gas, cm2/s

DA dzusivity of dissolved C02, cm%

DB diffusivity of amine in solution, cm2js

DANCKWERTS

mass-transfer coefficient for dissolved

gas, cm/s
rate-constants defined by eqns (Q-o-(O)
partial pressure of CO*, atm
differential pressure at time t
specific rate of absorption of CO*.
mol/cm2 s
gas constant, cm3 atm/mol K
rates of reaction of CO* in MEA and
DEA solutions, molll s

solubility of gas, mol/cm3atm (pp. of

gas)
temperature, K
volume of gas iu absorber, cm
k,(Am)

(eqn 6), s-

time elapsed for decrease in pressure

by factor 4, s
RlWERENCE3

[1] Hikita H., Asai S., Ishikawa 1. and Honda M., Chem. Engng
J 1977117
_.
__. __
[2] Hikita H.. Asai S., Katsu Y. and Ikuno S.. A.LCh.E.J. 1979
2s 3.
131Laddha S. S., Diaz M. and Danckwerts P. V.. Chem. Engng
sci. 1981 36 226.
[41

Danckwerts P. V. and Alper E., Tmns. Inst. Chum. Engrs

197553 74.

fS] Perrin D. D., Dissocicltion Constanfs of Organic Bases in

Aauwus Sol&on, Butterworths. London 1%5.
[aI P&sent B. R. W., Pearson L. and Roughton F. J. W., Trans.
Famday Sot. 1956 52 1512.
171 Danckwerta P. V.. Ind. Enema Chem. 195143

1460.

i8j Yasunishi A. and kushida $.;I. C&m. Engng Data 197924

11.
[91 Sada E. and Kito S.. Kaanku K&?aku 1972 36 218.
[iOj Sada E., Kumazawa H.-and Buit M. A., L Gem. Engng
Data 197722 11.
[Ill Sada E., Kumazawa H. and Butt M. A., J. Chem. Engng
Data 197823 161.
[121 Alvarez-Fuster C.. Midoux N., Laurent A. and Charpentier
J. C., Chem. Engng Sci. 1980 35 1717.