American Journal of Oil and Chemical Technologies: Volume 2. Issue 11.

November 2014

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American Journal of Oil and Chemical Technologies

Journal Website: http://www.petrotex.us/2013/02/20/317/
 

Determining the Kinetics of Carbon Dioxide Absorption with Amine

Absorber: (AIT600) in a laboratory pilot plant

Amir Ghalambor Dezfuli1, Behrooz Roozbehani2

1
Department of Chemical Engineering, College of Chemical Engineering, Mahshahr Branch, Islamic Azad University,
Mahshahr, Iran
2
Department of Chemical Engineering, Petroleum University of Technology, Abadan, Iran

Abstract:
In this article the rate of CO2 absorption with using commercial amine solution, AIT600, was measured in a packed-
tower of pilot plant in temperature range 323.15-338.15 K and during a 240 min. The input CO2 and amine
concentration was 13% (v/v) and 30% (w/w) respectively. The value 3.7 (mole CO2/Lit Solution) was absorbed. The
efficiency of carbon dioxide absorption was obtained about 94.21%. The values of rate constant and reaction order were
reported. The activation energy and fixed frequency factor were calculated according to the Arrhenius equation.

Keyword: Kinetics reaction, carbon dioxide, Amine absorption, packed tower

1. Introduction

So far, a variety of methods for separating acid gases from flue gases had been studied; in particular, carbon dioxide
(CO2) which has constituted about 2/3 emissions of greenhouse gases [1]. Regarding to increasing use of fossil fuels and
thus, increasing the level of greenhouse gases in the atmosphere, separating these gases has attracted more attention than
the past [2].The carbon dioxide gas is the main factor affecting on climate changes [3]. So finding an economical
solution for controlling and reducing these gases is essential, especially for the environment. The emissions of this gas
are shown in Table1 [4].

Table 1. CO2 emissions by fuels in selected years (unit: Million tons of CO2)
Year Solid Liquids Gas Total

1950 1070 423 97 1590

1990 2419 2492 1019 5930

2010 3842 3114 1702 8658

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The use of coal as the main fuel has decreased, generally. This means that the amount of CO2 produced from
combustion of the fuel has also decreased [6]. The much of research costs of fossil fuel are concentrated in power plant;
because about 30% of fossil fuels are used in this sector. The total amount of carbon emitted from fossil fuels
combustion in the world, is about 6 billion tons, while 1.8 billion tons of which are due to power plants [7, 8].

In recent decades, several methods for carbon dioxide absorption have been studied. Eric Favre performed a comparison
between CO2 absorption by packed tower and polymeric membranes, and achieved good results about it [9]. So far the
absorption by amine solutions is widely used in various industries. Different alkanolamines can be used; primary
amines, such as monoethanolamine (MEA), secondary amines, such as diethanolamine (DEA) and tertiary amines such
as N-methyldiethanolamine (MDEA). The reaction rate between primary/secondary and CO2 is different with the
reaction rate between tertiary amines and CO2. The reaction between CO2 and primary/secondary amines is significantly
faster than the reaction between CO2 and tertiary amines [5]. As a result of this faster reaction, the absorption tower,
when primary/secondary amines are used, has smaller dimensions than the time in which tertiary amines are used; but,
the capacity of CO2 absorption for them is less than tertiary amines. However, the regeneration energy of tertiary amines
is significantly lower than the primary and secondary amines [10]. Due to high absorption capacity of tertiary amines,
their reactivity with CO2 and high efficiency of energy, viz. primary amines such as MEA, the use of mixed amines
such as N-2-aminoethyl (AEEA) and piperazine (PZ) is (or will be) more than the past [11]. Ma'mun et al. also
presented the physical and chemical reaction equilibria for the CO2-AEEA-H2O system [12]. In another article, the
reaction kinetics of carbon dioxide of flue gases emitted from coal-fired power plant have been studied, by using a small
wetted-wall column in temperature range 10-40˚C [13]. Also the kinetics of polluting carbon dioxide absorption, with
AMP-MEA-H2O, in temperatures 30, 35 and 40˚C, were tested by using an experimental wetted-wall column. With
using of analogy N2O, the solubility and permeability of carbon dioxide have been reported. The results show that
adding a small amount of MEA to AMP, significantly affects the carbon dioxide absorption rate [13].

The absorption of CO2 with 1-hexyl-3-methylimidazolium Glycine [Hmim][Gly] has been studied in temperatures
ranging 298-323 K and atmospheric pressure. The solubility and the permeability of CO2 in absorber solution, and
overall reaction rate constant are reported [14].

In another experimental work, the value of CO2 absorption in an aqueous solution, containing 30 weight % (AMP+PZ)
with different components in 313.2-393.2 K absorption/desorption temperatures and a pressure, up to 460 kPa, was
reported with using Kent-Eisenberg model [15].

In similar case of this article, the experimental pilot plant for post-combustion capture, with a mixed amine solution
contain (AMP), primary diamine1,2-ethanediamine (EDA), different liquid to gas (L/G) ratio and 100 (mbar) partial
pressure of carbon dioxide was tested. The usage of packed tower was similar to a small pilot in industrial plants. The
temperature and concentration profiles have been reported during the experiments [16].

2. Theory

Different ways of measuring the rate include:

1. Average rate method

2. Instantaneous rate method
3. Initial rate method

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In this article, instantaneous rate method has been used for calculating the overall rate and Arrhenius constants [17].

When carbon dioxide reacts with aqueous solution, three following reactions occur, simultaneously:

• Reaction I - with amine (AIT600)

𝐴𝑚 + 𝐶𝑂! + 𝐻! 𝑂 ↔ 𝐻𝐶𝑂! ! + 𝐴𝑚𝐻 ! (1)

• Reaction II – with hydroxide ion

𝐶𝑂! + 𝑂𝐻 ! ↔ 𝐻𝐶𝑂! ! (2)

• Reaction III – with water

𝐶𝑂! + 2𝐻! 𝑂 ↔ 𝐻𝐶𝑂! ! + 𝐻! 𝑂 ! (3)

The overall forward reaction rate constant (kov) is determined by these three reactions, in which the kinetic rate
expression is usually given as follows [18]:

Reaction I:

𝑅!"! = 𝑘!" C!" C!"! = k !!" C!"! (4)

Reaction II:

𝑅!"! = k !" C!"! C!"! = k !!" C!"! (5)

Reaction III:

𝑅!"! = k !! ! C!"! = k !!! ! C!"! (6)

In any mass transfer of over reactions, the overall forward pseudo-first order reaction rate constant is defined as the sum
of these rates, divided by the concentration of carbon dioxide.

𝑘!" = k !!" + k !!" + k !!! ! (7)

The overall reaction rate is calculated by:

r!"! = 𝑘!" [𝐶𝑂! ]! (8)

and the value of kov is calculated by Arrhenius equation:

!!!
𝑘!" = 𝐴! exp  ( ) (9)
!"

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3. Experimental

3.1 Materials

Carbon dioxide cylinders with a purity of 99% were prepared in research center of Abadan petroleum faculty. The
aqueous amine solution AIT600 with distilled water is a specific material with 30 weight % that was purchased by this
center.

3.2 Experimental setup

The experimental pilot includes two absorption desorption towers. After passing through a mixer, the CO2 (from CO2
cylinders) and Air (contain N2 and O2 from compressor) arrived to bottom of the absorption column, continuously. Also,
the amine solution with a continuous stream in a batch system, enters into the top of the absorption column, from
bottom of the desorption column, and then returned to desorption column again, for regeneration. The absorption
column was in atmospheric pressure and desorption column gauge pressure was in 0.5-1 bar. The size of absorption
packed-tower has been selected about 2 m height and 0.2 m diameter, made of stainless steel, and the type of packing is
metal grid. The internal diameters of absorber and stripper columns are 0.15 and 0.10 m, respectively. The input and
output liquid flow to absorption/desorption column, between 100-400 ml/min and the gas flow, between 3-6 m3/hr are
adjustable. The temperature was adjusted to the desired value with an accuracy of ±0.1 ˚C. A schematic view of the
model has been shown in Figure1.

Figure 1. Experimental pilot plant of absorption and desorption of carbon dioxide with amine
solution(AIT600)

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3.3. Experimental Procedure

A series of experiments were conducted over a wide range of temperatures and CO2 concentrations. In the first one, a
maximum absorption conditions were reached by Taguchi experiment design, for 5 parameters. In this experiment, after
optimizing the flow rates (liquid and gas), CO2 percent and absorption/desorption temperatures for maximum
absorption; the part amine solution regeneration (in striper column) will be disabled. The optimum values obtained are
300 ml/min and 4 m3/hr for liquid and gas flow rates, 60-65 ˚C for absorption temperature, 115-120 ˚C for regeneration
and 12-15%(v/v) for CO2. The results have been presented in term of the carbon dioxide concentration during the time,
for calculating reaction rate. The inlet and outlet gas composition could be measured by gas analyzer, with accuracy
0.01%(v/v). Then a mixture of CO2 and air were charged inside the absorption column. This was considered as the
starting point for the reaction. The time of regenerating the amine solution, after kinetics experiments, was 1.5 hr, in
desired temperature. The decrease of CO2 concentration in gas phase, due to CO2 absorption, was recorded by gas
analyzer, during a 240 min period. This data are plotted for the time interval [0,240] min, and fitted to a third degree
polynomial, using the least-square regression. The coefficients of the functions have been shown in Table2. Based on
the fall-in CO2 concentration technique, in gas phase, this measurement method enabled a simple and straightforward
estimation for the absorption rates. Furthermore, there was no necessity to any analysis of liquid phase and the
concentration factor for evaluating the kinetic parameters.

Table 2. The coefficients of the functions using the least-square regression

Temperature ˚C t0 min t1 min t2 min t3 min
50 0.299464 -0.001887 0.000006 -0.00000001
55 0.384955 -0.003153 0.000014 -0.00000003
60 0.486902 -0.003975 0.000017 -0.00000003
65 0.546886 -0.004435 0.000018 -0.00000003
   

4. Results and discussion

4.1. Absorption percent

The absorption percentage of carbon dioxide gas, at different temperatures, is calculated by the Equation (10):

!!"!,!" ! !!"!,!"#
𝑌! = ×100 (10)
!!"!,!"

where y!"!,!" and y!"!,!"# are CO2 percent components in inlet and outlet of absorption column, respectively. These
values are shown in figure 3. In any temperature, the absorption percentage of CO2 reached to about 50%, after 50min.
Because of purity of amine solution, the value of absorption percent was about 92%, at the beginning of the reaction,
and decreased with the time.

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Figure 2. The percent of carbon dioxide absorption in optimization condition* respect to the time (min): a) in
temperature 50˚C; b) in 55˚C; c) in 60˚C; d) in 65 ˚C
 

*. The optimization condition includes 300 (ml/min) for liquid flow rate, 4 (m3/hr) for gas flow rate, 115˚C for amine regeneration temperature and
13% (v/v) for CO2 percent.

Using the obtained values for the CO2 percent components in any moment, the average concentration of CO2 in gas
phase, until reaching the desired time, is calculated by integration. The results are shown in Figure3.

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5  
4.5  
4  
C(50˚)  
3.5  
C  (mol/m3  sol)  

3   C  (55˚)  

2.5   C(60˚)  

2   C(65˚)      
1.5  
1  
0.5  
0  
0   50   100   150   200   250   300  
Time(min)  

Figure 3. The carbon dioxide concentrations (mol/m3.solution) in different temperatures in gas phase, as a function of
time (min)

4.2. Absorption rate

According to obtained information from the (C-t) graph, the instantaneous rate of forward reaction, respect to the time is
measurable. The average rate curve, respect to the time, is shown in figure4. Because of purity of amine solution, the
rate was at highest level, at the beginning of the reaction. This amount reduced by the time and increasing CO2
concentration in liquid phase.

0.04  
0.035  
0.03  
R(mol/m3.min)  

0.025   R  50˚  
0.02   R  55˚  
0.015   R  60˚  
0.01   R  65˚  

0.005  
0  
0   50   100   150   200   250   300  
Time(min)  

Figure 4.The forward reaction rates (mol/m3.min) respect to the time (min) for 50, 55, 60
and 65 ˚C in maximum absorption conditions
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By using natural logarithm function and the values of reaction rates and CO2 concentration, the overall reaction rate
constant and the order of reaction, related to CO2, are measurable. The values of kov, in different temperatures, are
shown in figure5.

0.012  

0.01  

0.008  
kov  (min-­‐1)    

0.006  

0.004  

0.002  

0  
40   45   50   55   60   65   70  
T  (˚C)  

Figure 5. The overall reaction rate constant, as function of CO2 concentration, vs. temperatur (˚C)
In general, the results of the experiments are given in table 3. The constants of reaction rate, the constants of Arrhenius
equation, the order of reaction related to carbon dioxide and also, the reaction activation energy have been reported.

Table 3. The overall rate and arrhenius constants

Constant
k !" (min!! ) n A! E(j)
Temp(k)

323.15 3.1413×10!! 1.43

328.15 5.4573×10!! 2.51

333.15 6.5414×10!! 1.004 199.43×10! 66.677×10!

338.15 10.037×10!! 0.7702

Avg. 6.2942×10!! 1.428

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5. Conclusion

In the experimental pilot, including two absorption/desorption towers, the maximum absorption conditions and kinetics
data have been studied. The results showed that, in gas flow rate 3-4 m3/hr, liquid flow rate 300 ml/min, the absorption
temperature range 60-65 ˚C and desorption temperatures range 115-120 ˚C, the maximum of carbon dioxide absorption
percent is produced. Due to conditions of maximum absorption, the kinetics of CO2 absorption with aqueous amine
(AIT600) has been studied. The overall rate constant and the order of reaction related to carbon dioxide, were obtained
as 6.2942×10!!   min!! and 1.4, respectively. The value of activation energy and frequency factor, due to Arrhenius
equation, were calculated as 66.677×10!  𝑗 and 199.43×10!  𝑚𝑖𝑛!! , respectively. The results showed that the
absorption rate is directly proportional to absorption temperature. For convenience, with respect to obtained fractional
value of order reaction, related to CO2, we can assume these changes to be linear.

The following equations obtained from the constant values of rate and Arrhenius equation

𝑟!"! = 6.2942×10!! [𝐶𝑂! ]!.! (11)

!!!.!""×!"!
𝑘!" = 199.43×10! exp  ( ) (12)
!"

6. References:
[1] S.A. Montzka, E.J. Dlugokencky, J.H. Butler, “Non-CO2 greenhouse gases and climate change”, Nature, vol.
476, no 7358, 43-50, 2011.
[2] T.A. Boden, G. Marland, R.J. Andres, "Global, Regional and National Fosil-Fuel CO2 Emissions", CO2
Information Analysis Center, U.S. Department of Energy, 2010.
[3] Butler J.H., "The NOAA Annual Greenhouse Gas Index(AGGI)", NOAA Earth System Research Lab., av.
From: http://www.esrl.noaa.gov/gmd/aggi, Accessed 24.1.2012.
[4] U.S. Department of Energy, Office of Science, Office of Biological and Environmental Research, Climate and
Environmental Sciences Division av. From: “http://cdiac.ornl.gov/trends/emis/ira.html”, Accessed 01/12/2013, Last
modified 26/09/12.
[5] G.F. Versteeg, L.A.J. Van Dijck, W.P.M. van Swaaij, “On the kinetics between CO2 and alkanolamines both in
aqueous solution: A review”, Chem. Eng. Communication, 1996, 113-158.
[6] J.W. Sun, The natural and social properties of CO2 emission intensity negotiations on climate change: a
arithmetic perspective. Energy Policy 30, 83–85, 2002.
[7] M.H. Martin, S. Meyer, "Greenhouse gas carbon dioxide mitigation", Lewis Publishers, 1999.
[8] Y.F. Diao, X.Y. Zheng, B.S. He, C.H. Chen, X.C. Xu, "Experimental study on capturing CO2 greenhouse gas by
ammonia scrubbing", Energy Conversion and Management 45, 2283-2296, 2004.
[9] E. Favre, "Carbon dioxide recovery from post-combustion processes: Can gas permeation membranes compete
with absorption?" Journal of Membrane Science 294, 50-59, 2007.
[10] J. Carson, K. Marsh, A. Mather, "Enthalpy of solution of carbon dioxide in (water + monoethanolamine,
or diethanolamine, or n-methyldiethanolamine) and (water+ monoethanolamine+ n- methyldiethanolamine) at
T=298.15 K", J. of Chem. Thermodynamics 32, 1285-1296, 2000.
[11] S. Ma’mun, H.F. Svendsen, K.A. Hoff, O. Juliussen, "Selection of new absorbents for carbon dioxide
capture", Energy Convers. Manage. 48, 251–258, 2007.
[12] S. Ma’mun, J.P. Jakobsen, H.F. Svendsen, O. Juliussen, Experimental and modeling study of the
solubility of carbon dioxide in aqueous 30 mass% 2-((2-aminoethyl)amino)ethanol solution, Ind. Eng. Chem. Res.
45, 2505–2512, 2006.
[13] J. Liu, Sh. Wang, G. Qi, B. Zhao, Ch. Chen, "Kinetics of mass transfer of carbon dioxide absorption into
aqueous ammonia", Elsevier J. of Energy Procedia 4, 525-532, 2011.

357  
 
Ghalambor  Dezfuli,  Roozbehani  /American  Journal  of  Oil  and  Chemical  Technologies  11  (2014)  349-­‐358

[14] J. Xiao, Ch. Li, M.H. Li, "Kinetics of absorption of carbon dioxide into aqueous solutions of 2-amino-2-
methyl-1-propanol + monoethanolamine", PERGAMON J. of Chem. Eng. Sci. 55, 161-175, 2000.
[15] H. Guo, Z. Zhou, G. Jing, "Kinetics of carbon dioxide absorption into aqueous[Hmim][Gly] solution",
Int. J. of Greenhouse Gas Control 16, 197-205, 2013.
[16] D. Tong, G.C. Maitland, M.J.P. Trusler, P.S. Fennell, "Solubility of carbon dioxide in aqueous blends of
2-amino-2-methyl-1-propanol and piperazine", Chem. Eng. Sci. 101, 851-864, 2013.
[17] I.V. Habou, H.P. Mangalapally, H. Hasse, "Pilot plant experiments for two amine solvents for post-
combustion carbon dioxide capture", Int. J. of Greenhouse Gas Control 18, 305-314, 2013.
[18] Margaret Robson."An Introduction to Chemical Kinetics", Pub. John Wiley & Sons, Formerly of The
University of St Andrews, UK, 2004.
[19] Nat. Penders, P. Derks, ”Kinetics of absorption of carbon dioxide in aqueous MDEA solution with
carbonic anhydrase at 298 K”, Int. Journal Of Greenhouse Gas Control 9, 385-392, 2012.

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