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INTERNATIONAL JOURNAL Of ACADEMIC RESEARCH Vol. 3. No. 3. May, 2011, I Part
CARBON DIOXIDE ABSORPTION INTO
AQUEOUS POTASSIUM CARBONATE PROMOTED WITH
METHYLDIETHANOLAMINE (MDEA)
L. Pudjiastuti*, A.Altway, N.Soewarno, Kuswandi
Department of Chemical Engineering, Faculty of Industrial Technology,
Institut Teknologi Sepuluh Nopember, Jl. Raya ITS Keputih, Sukolilo Surabaya (INDONESIA)
*Corresponding author: lily_pudji@chem-eng.its.ac.id
ABSTRACT
This paper presents kinetic data and absorption rate for aqueous K2CO3 promoted with MDEA. Kinetics of the
absorption of CO2 into 30 wt% K2CO3 promoted with MDEA were investigated at 303, 313, 323K by using a wetted-
wall column apparatus. Three system of which 30 wt % K2CO3 with 1,2 and 3 wt% boric acid were studied. The
addition of 1,2, and 3 wt%
MDEA to 30 wt% K2CO3 system results in a significant enhancement of CO2 absorption
rates. Two kinetic models were proposed in this work. The first model, based on second-order reaction rate
constant measurement, give the average deviation (ARD) of 6.11%. While the second model, based on pseudo
first-order reaction rate constant measurement, gives ARD of 14%. The first kinetic model is found to be more
satisfactory in representing the CO2 absorption into K2CO3+ MDEA + H2O systems
Keywords: absorption, CO2 removal, kinetics, promoter, MDEA
1. INTRODUCTION
Many commercial processes for removal of carbon dioxide (CO2) from acid gases have used aqueous
potassium carbonate (K2CO3) promoted with amines. Removal of acid gases, e.g. CO2, by using reactive
absorption with aqueous alkonalamine or K2CO3 solution is an important industrial operation. A wide variety of
amines such as MEA, DEA, MDEA have been used industrially for a number of years [1]. The advantage of using
alkanolamine solvent is its high reaction rate with carbon dioxide. Several investigators have explored the reaction
rate of carbon dioxide is un-promoted, promoted and blended aqueous amines solution ([2] [8]). A problem with
the use of alkanolamines for carbon dioxide removal is that they degrade as a result of long exposure or repeated
use. Several attempts have been made to use alternative more stable solvent having high enough reaction rate
with carbon dioxide for example amino acid salts [9].
The absorption of CO2 with K2CO3 solvent has gained widespread and has been accepted for removal of CO2
from the natural and synthetic gas stream due to its stability, low cost and low energy requirement for solvent
regeneration. However, the reaction rate between carbon dioxide with K2CO3 is lower than the reaction rate with
amines solution ([10], [11]). The most important improvement is the discovery that small amounts of certain organic
or inorganic additives can enhance the absorption rate to a large extent. During the past several years, various
additives have been suggested for increasing the efficiency of K2CO3 scrubbing processes. Several researchers
have shown that the application of piperazine/amines-promoted K2CO3 could accelerate the absorption process
[11]. However, many promoters are not stable at stripper conditions. There is some information available regarding
the absorption of carbon dioxide using aqueous solution of K2CO3 promoted with MDEA ([8]-[12]). but the published
information is not so detailed. However, there is too little information available in the literature regarding the effect
of MDEA on the performance of the industrial column for carbon dioxide absorption by potassium carbonat
solution.. The detailed kinetics of the reaction is essential for the process design and simulation of CO2 absorption
in MDEA promoted K2CO3 solvent.
This work focuses on expanding the investigation of promoted K2CO3 using MDEA. The main purpose of this
work is to investigate the effect of MDEA on the reaction rate constant of CO2 absorption into aqueous K2CO3
solution using a laboratory wetted wall column. Experimental kinetic data were collected and a simplified model
used to interpret the results.
2. MATERIALS AND METHODS
Reaction system
The basic reaction for K2CO3 solution and CO2 is represented by following overall reaction:
C0
2
+K
2
C0
3
+ E
2
0 2KEC0
3
(1)
Since K2CO3 and potassium bicarbonate are both strong electrolytes, it may be assumed that the metal is
present only in the form K
+
ions, and reaction (1) can be more realistically represented in the ionics terms as
( )
+ +
3 2 2 3
2HCO aq CO O H CO (2)
B a k u , A z e r b a i j a n | 89
INTERNATIONAL JOURNAL Of ACADEMIC RESEARCH Vol. 3. No. 3. May, 2011, I Part
The reaction is usually described in term of two parallel, reversible reactions.
( )
+
3 2
HCO OH aq CO (3)
O H CO OH HCO
2
2
3 3
+ +
(4)
Since the reaction with hydroxide is the rate-limiting step, the forward reaction rate is represented as a second
order rate expression.
| || |
2
2
CO OH k r
OH
CO
= (5)
This reaction, though important to the solution equilibrium, is generally much slower than aqueous amines,
limiting its application in processes requiring a high percentage of removal. It is often advantageous to add a
promoter to increase the absorption rate. The energy required to reverse the reaction is typically less than that
required for amine solvents.
The rate equation for the reaction of carbon dioxide with unpromoted hot K2CO3 is ([4],[13])
| | | | | | ( )
e OH OH
CO CO OH k r
2 2
=
(6)
The carbonate-bicarbonate system is buffer solution; hence the concentration of OH
-
ion in the solution near
the surface of the liquid is not significantly affected by the absorption of CO2. In this case, carbon dioxide
undergoes a pseudo-first-order reaction and Eq. (6) can be rewritten as ([4],[14])
| | | |
e OH
CO CO k r
2 2 1
= (7)
When a small amount of MDEA is added to the K2CO3 solution, the absorption rate process will be increasing
with reaction mechanisms as follows [11]:
C0
2
+ HEA+ E
2
0 HEAE
+
+EC0
3
-
(8)
HEAE
+
+0E
-
HEA +E
2
0 (9)
EC0
3
-
+0E
-
C0
3
2-
+ E
2
0 (10)
In the high temperature as process in industry , the rate reaction (9) significantly inscreasing, The rate
determination step (9). With the same approach with this reaction (7) is pseudo-first order.
Where k is the overall apparent first-order rate constant and is defined as [13],[15].
k = (k
0H
|0E
-
] +k
MLA
|HEA]) (11)
The rate constant has been measured by Astarita [11],
log k
0H
- = 1S,6SS
2895
1
u,u8 I (12)
In this event, the K2CO3 content of the solution must be properly adjusted to compensate for that consumed
by reaction with the added MDEA.
The main role played by buffer solution, when MDEA is present, is that of creating a medium in which the salt
can dissociate and then the catalytic activity may be exploited. The rate equation for the catalyzed reaction, which
is always first-order with respect to carbon dioxide, can be written in the following way [3]:
r
pomotc
= k
pomotc
|C0
2
] (13)
r
pomotc
= k
MLA
|HEA] (14)
Using the same approach for deriving Eq (6), gives the following pseudo-first-order rate equation of carbon
dioxide with activated potassium in liquid phase:
r = (k
MLA
|HEA])(|C0
2
] |C0
2
]
c
) (15)
Eqs.(6) and (15) lead to overall pseudo-first-order rate equation of CO2 with activated K2CO3:
r = (k
MLA
|0E
-
] +k
MLA
|HEA])(|C0
2
] |C0
2
]
c
) (16)
Where k is the overall apparent first-order rate constant and is defined as [13],
k = (k
0H
|0E
-
] +k
MLA
|HEA]) (17)
The rate constant has been measured by [4]
logk
0H
- = 1S.6SS
2895
1
u.u8I (18)
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INTERNATIONAL JOURNAL Of ACADEMIC RESEARCH Vol. 3. No. 3. May, 2011, I Part
Wetted Wall Column (WWC)
WWC is equipment commonly used to study the kinetics of gas-liquid reaction. The liquid flow in the wwc is
usually maintained in laminar pattern. In this case the gas-liquid contact time is determined as follows,
s
u
h
t =
(19)
Where
2
2
g
u
s
=
(20)
and
3
3
gW
Q
sol
=
(21)
The total rate of absorption into the film is related to ) (t Q by
dh
q Q(t)
=
t
(22)
The absorption rate is usually measured experimentally. Then, equation (19) can be used to determine the
value of pseudo first-order reaction rate constant of reversible reaction using the experimental absorption rate data.
( ) ' C C Q
1 Ae Ai
k D t
A
= (23)
Where
'
'
1
1
k D He k
C k D P k
C
A G
Ae A A G
Ai
+
+
=
(24)
] [CO K
] [HCO K
- 2
3 1
2 -
3 2
=
Ae
C (25)
The gas film mass transfer coefficient in the WWC was determined as in [14] using SO2 absorption into 0.1 M
NaOH. The results of the experiments are correlated as in equation (26)
85 , 0
Re 075 , 1 |
.
|
\
|
=
h
d
Sc sh (26)
Where
d u
= Re
(27)
2
DCO
Sc
=
(28)
The gas film transfer coefficient can be found from the following definition of the Sherwood number
2
/
CO g
D h RTk Sh = (29)
Experimental procedure
The WWC depicted in Fig.1 and 2, was used as the gas-liquid contactor throughout the kinetic data and
absorption rate measurement. The contactor is the same equipment as used in the work of [6],[9], and [15]. The
stainless steel, 9.3-cm in height and 1.3 cm in outside diameter, is a tube extending from the liquid feed line into
the column. The liquid is pumped through the inside of the tube, overflows, and is evenly distributed across the
outer surface of the tube. Gas enters near the base of the column, counter-currently contacting the fluid as it flows
up to the gas outlet. The liquid flow rate was varied in the range 5-10 cm
3
/s. The gas flow rate is 100 cm
3
/s . The
CO2 absorption rate was measured from the difference in inlet and outlet CO2 composition in the gas as
determined using by Orsat apparatus.
C : Heater
P1 : Promoted K2CO3
pump.
P2 : Water-pump.
R1 : Liquid rotameter.
R2 : Gas rotameter.
T1 : Waterbath
T2 : Promoted K2CO3
tank.
T3 : Overflow tank.
T4 : CO2 tank
T5 : Sample tank.
T :Thermocouple
V1 : Liquid Valve
V2 : CO2 Valve
V3 :Valve ( by pass )
B a k u , A z e r b a i j a n | 91
INTERNATIONAL JOURNAL Of ACADEMIC RESEARCH Vol. 3. No. 3. May, 2011, I Part
Fig.1. Experimental Apparatus
Fig.2. Wetted Wall Column
3. RESULTS AND DISCUSSION
Absorption Rates
The absorption experiments for CO2 into 30wt% K2CO3 solution with the addition of MDEA were carried out
over the concentration range 0,0840,252 mol.l
-1
. The experiments were carried out over the temperature range of
303K-323K. All experiments were performed under atmospheric pressure with partial pressure of CO2 near
atmospheric pressure. Table 1 are the rate of CO2 absorption as measured in the WWC, where sol-1 is the addition
of MDEA 1wt% to 30wt% K2CO3; sol-2 is the addition of MDEA 2 wt% and sol-3 is the addition of MDEA 3 wt%.
The effect temperature on rate of CO2 absorption is shown in Fig. 3, 4, and 5. It can be seen from that figures, that
the avarage CO2 absorption rate increase by factor of 1.152 as temperature increases from 303K to 323K . This
indicate, reaction rate of CO2 increase by increasing temperature.
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INTERNATIONAL JOURNAL Of ACADEMIC RESEARCH Vol. 3. No. 3. May, 2011, I Part
Table 1. Experimental result of absorption rate
T v.10
6
t (s)
q.10
8
(kmol/s)
K m
3
/s
sol-1 sol-2 sol-3
303
5 0.817 7.88635 8.8504511 16.53553
6.667 0.675 9.80985 10.764579 17.61736
8.333 0.581 10.76458 12.660169 18.23836
10 0.515 12.6011 14.537488 19.45352
313
5 0.817 9.80985 10.80985 17.31978
6.667 0.675 10.76458 11.714675 18.23836
8.333 0.581 11.71467 13.601096 19.15256
10 0.515 13.6011 15.469378 20.06242
323
5 0.817 10.76458 11.714675 18.23836
6.667 0.675 12.66017 13.460169 19.15256
8.333 0.581 13.6011 14.537488 19.45256
10 0.515 15.46938 16.396799 20.96797
Fig.3. CO2 absorption rate in sol-1 Fig.4. CO2 absorption rate in sol-2
Fig.5. CO2 aborption rate in sol-3 Fig.6. CO2 aborption rate at Tsol=303
4
6
8
10
12
14
16
18
20
4 6 8 10 12
q
.
1
0
8
(
k
m
o
l
/
s
)
V.106 (m3/s)
Tsol-1 303K
Tsol-1 313K
Tsol-1 323K
6
8
10
12
14
16
18
4 6 8 10 12
q
.
1
0
8
(
k
m
o
l
/
s
)
V.106 (m3/s)
Tsol-2 303K
Tsol-2 313K
Tsol-2 323K
10
12
14
16
18
20
22
4 6 8 10 12
q
.
1
0
8
(
k
m
o
l
/
s
)
V.106 (m3/s)
Tsol-3 303K
Tsol-3 313K
Tsol-3 323K
4
6
8
10
12
14
16
18
20
22
4 6 8 10 12
q
.
1
0
8
(
k
m
o
l
/
s
)
V.106 (m3/s)
sol-1
sol-2
sol-3
B a k u , A z e r b a i j a n | 93
INTERNATIONAL JOURNAL Of ACADEMIC RESEARCH Vol. 3. No. 3. May, 2011, I Part
The CO2 absorption rate in various solutions is plotted in Figs.6, 7,and 8. Increasing the MDEA
concentration from 1wt% to 3wt% affects the CO2 absorption rate enhancement by factor of 1.631. The avarage
CO2 absorption rate increase by factor of 0.375 with increasing volumentric rate from 5 m
3
/s to 10 m
3
/s.
Fig.7. CO2 aborption rate at Tsol=303 Fig.8. CO2 aborption rate at Tsol=303
Kinetics of CO2 Absorption with K2CO3+MDEA
CO2 reaction with aqueous solution of K2CO3:
C0
2
+ 0E
-
EC0
3
-
(28)
C0
3
=
+E
+
EC0
3
-
(29)
C0
2
+ E
2
0 E
+
+EC0
3
-
(30)
C0
3
=
+E
2
0 EC0
3
-
+ 0E
-
(31)
Both reactions (28) and (30) are slow and rate determining [18]. Reaction rate constant (k1) for the equation
(28) is shown in Table 2. Reaction rate constant for CO2 absorption into MDEA promoted K2CO3 solution was
determined experimentally in this work, and is shown in Table 3 and 4.
Table 2. Reaction rate constant equation (28)
Temperature, K k1(m
3
/kmol.s) Reff
303 12170
[1] 313 24560
323 36950
Table 3 shows the reaction rate constant for equation (30) as measured in the WWC.
Table 3. Experiment result of reaction rate constant equation (30)
Table 4. Experimental result of reaction rate constant
Solution
k1' . 10
-4
( 1/s ) k2
'
. 10
-4
( 1/s )
303 K 313 K 323 K 303 K 313 K 323 K
Sol-1 0.85 6.93 38.7 0.85 6.93 38.7
Sol-2 2.54 17.3 94.5 2.53 17.3 94.5
Sol-3 7.36 50.1 235 7.35 50.1 235
Reaction rate constant (k2) is affected by temperature solution and concentration of MDEA. Addition of MDEA
into solution, increases reaction rate constant siqnificantly.
The reaction rate constant (k2) for various temperature are plotted in Fig. 9 and are fitted by the following
Arrhenius equation (Model-1):
4
9
14
19
4 6 8 10 12
q
.
1
0
8
(
k
m
o
l
/
s
)
V.106 (m3/s)
sol-1
sol-2
sol-3
4
9
14
19
4 6 8 10 12
q
.
1
0
8
(
k
m
o
l
/
s
)
V.106 (m3/s)
sol-1
sol-2
sol-3
Solution
k2. 10
-5
( m
3
/kmol.s )
303 K 313 K 323 K
Sol-1 1.019 3.013 8.748
Sol-2 4.123 10.29 29.83
Sol-3 15.34 37.46 93.27
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INTERNATIONAL JOURNAL Of ACADEMIC RESEARCH Vol. 3. No. 3. May, 2011, I Part
(32)
Fig. 9. Reaction rate constant in various temperature
Equation (32) indicated that addition MDEA decreases the activation energy, so that increases k2. The ARD of
k2 from equation (32) and experimental data is shown in Table 5.
Fig. 10. Reaction rate constant in various temperature
Table 5. Average deviation of eq.(32)
T [MDEA]
k'2
(experiment)
k'2 (eq.32) Deviation
(K) (kmol/m
3
) (m
3
/kmol.s) (m
3
/kmol.s)
303 0.08403 101933.800 105643.7333 3.64%
313 0.08403 301352.047 317918.0502 5.50%
323 0.08403 874860.896 893634.4802 2.15%
303 0.16807 412330.862 393943.1957 4.46%
313 0.16807 1029650.558 1136693.542 10.40%
323 0.16807 2983256.394 3071547.384 2.96%
303 0.25210 1534172.899 1469005.653 4.25%
313 0.25210 3746755.258 4064167.504 8.47%
323 0.25210 9327484.900 10557340.33 13.19%
ARD = 6.11%
10000
100000
1000000
10000000
300 303 306 309 312 315 318 321 324
k
2
(
m
3
/
k
m
o
l
.
s
)
T (K)
sol-1
sol-2
sol-3
1,00E+03
1,00E+04
1,00E+05
1,00E+06
1,00E+07
300 305 310 315 320 325
k
2
'
(
1
/
s
)
T(K)
sol-1
sol-2
sol-3
|
|
.
|
\
|
=
RT
MDEA] [ 3.946,10 - 9.019,10 -
exp 10 , 00 . 1 k
7 7
20
MDEA
B a k u , A z e r b a i j a n | 95
INTERNATIONAL JOURNAL Of ACADEMIC RESEARCH Vol. 3. No. 3. May, 2011, I Part
From Table 5, ARD of the second-order rate constant of reaction with promotor is 6.11%. This reaction rate
model is found to be satisfactory in representing the CO2 absorption into K2CO3+MDEA+H2O systems.
The reaction rate constant (k2MDEA) for various temperature are plotted in Fig. 10 and are fitted by the following
Arrhenius equation (model-2):
(33)
Reaction rate constant (k2
\
|
=
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INTERNATIONAL JOURNAL Of ACADEMIC RESEARCH Vol. 3. No. 3. May, 2011, I Part
The first kinetic model is found to be more satisfactory in representing the CO2 absorption into K2CO3+MDEA+H2O
systems.
Nomenclature
d
DCO2
h
k1
k1MDEA
k1
k2,MDEA
k2,MDEA
kg
Q
q
r
u
us
v
V
: Diameter of WWC, m
: Diffusivity of CO2, m
2
/s
: Height of WWC, m
: Rate constant of overall-reaction, 1/s
: Rate constant of overall-reaction with
MDEA, 1/s
: Second-order rate constant of
reaction, m
3
/ kmol.s
: Second-order rate constant of reaction
with MDEA, m
3
/ kmol.s
: k2,MDEA x [ MDEA] ,1/s.
: Gas phase mass transfer coeficient,
kmol/ m
2
.s
: Quantity of gas absorbed by unit area
in time of contact t, kmol/m
2
: absorption rate (kmol/s)
: Rate of reaction, kmol/(m
3
.s)
:: contact time, s
: Distribution of velocity in film, m/s
: Velocity in film surface , m/s.
: Liquid flow rate, m
3
/s.
: Volume of liquid, m
3
: Thickness of liquid film,m
Acknowledgements
The authors wish to acknowledge the financial support of Guru Besar research grant administered by the
Department of Research and Social Services, ITS Surabaya, Indonesia.
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