(572d) The Influence of Dissociation Constants on the Kinetics of Carbon Dioxide Absorption in Aqueous Tertiary Amines Solutions Containing Carbonic Anhydrase

Liang, Z., Hunan University
Tontiwachwuthikul, P., Hunan University
Luo, X., Hunan University

American Institute of Chemical Engineers (AIChE)
Annual Meeting

The influence of dissociation constants
on the kinetics of carbon dioxide absorption in aqueous tertiary amines
solutions containing carbonic anhydrase

Bin Liua, Xiao Luoa*, Zhiwu
Lianga,b*, Paitoon

aJoint International Center
for CO2 Capture and Storage (iCCS), Hunan Provincial Key Laboratory
for Cost-effective Utilization of Fossil Fuel Aimed at Reducing CO2
Emissions, College of Chemistry and Chemical Engineering, Hunan University,
Changsha 410082, PR China

bClean Energy Technologies Research
Institute (CETRI), Faculty of Engineering and Applied Science, University of Regina,
Regina, Saskatchewan, S4S 0A2, Canada

Keywords: Tertiary amines; CO2 absorption; carbonic

Author for correspondence: Dr. Zhiwu Liang  E-mail: zwliang@hnu.edu.cn

 Tel: +86-13618481627 and +86-73188573033


The chemical
absorption of CO2 into primary amine and secondary amine, such as
monoethanolamine (MEA), diethanolamine (DEA), is currently the most widely
accepted commercial approach to carbon capture.[1] This solvent is
extremely effective in forming stable carbamates when reacted with CO2,
leading to a very efficient removal of CO2 with a 2:1 reaction
stoichiometry.[2,3] However, regeneration of the carbamate species requires
a large parasitic supply of energy to release the CO2 during
stripping.[1] This high energy requirement accounts for up to 80% of
the operating costs for CO2 capture and recovery.[4] It
is also a highly corrosive substance that readily undergoes degradation in the
presence of oxygen, emitting harmful volatile organic compounds.[5]

Considering the
high absorption heat and high energy consumption during CO2 capture
process, there are a number of tertiary amines such as methyldiethanolamine
(MDEA), dimethylaminoethanol (DMEA), in place of primary and secondary amine
for carbon capture. While many of tertiary amines solvents are able to reduce
the stripping energy requirement, the reaction rate for CO2 sorption
in the absorber is often slow. This means that it is not possible to recover
high purity carbon dioxide within a reasonable column height. Carbonic
anhydrase (CA), a naturally occurring enzyme and very efficient catalyst that
enhances the reversible reaction of CO2 to HCO3-
, was first identified in 1933 in red blood cells and known to catalyze the
conversion of CO2 into bicarbonate (HCO3-) at
extremely high turnover rates, [6−7] which may be useful for
promoting the absorption rates of CO2 from gas streams when these
alternative solvents are used. There is great potential for using CA to hydrate
CO2, especially when it is known that the hydration step is the rate
determining step in the CO2 absorption process. Carbonic anhydrase
is not just a single enzyme form, but a broad group of zinc metallo-proteins
(enzymes) that exists in three genetically unrelated families of isoforms (¦Á, ¦Â
and ¦Ã). Its catalyzed mechanism of CO2 hydration has been introduced
by Lindskog et al. [6-7] and simplified as shown in Figure 1. Penders et al. [8]
has been working on CO2 absorption into amine solutions
catalyzed by human carbonic anhydrase in string cell reactor since 2012. This
work focuses on the study of effect of dissociation constants (pKa) on the
kinetics of carbon dioxide absorption in aqueous tertiary amines solutions
containing carbonic anhydrase at various temperature using stopped-flow
techniques. The examined alkanolamines were (Figure 2): Triethanolamine (TEA), Methyldiethanolamine (MDEA), Dimethylethanolamine
(DMEA), 2-(Diethylamino)ethanol (DEEA), 1-Diethylamino-2-propanol (1DEA-2P), 3-Diethylamino-1-propanol
(3DEA-1P) and 2-(Dimethylamino)isobutanol (2DEA-2M-1P).
The values of pKa of different amine was determined using conventional pH
method as shown in Figure 3
and its final results was presented a function of temperature in Figure 4.

It can be seen from
the results (Figure 5)
that DMEA with a higher pKa value than MDEA and TEA hence showed a higher
reactivity with carbon dioxide in the absence of enzyme. It can also been found
that the reaction rate constant (k0) in amine-CO2-H2O
system was significantly enhanced in the present of BCA, in which the enzyme
activity is higher in TEA solutions. This is because Enzymes often display a
pH-dependent changes in activity, in characterizing the pH dependence of the enzyme
activity, the experimenter often observes a bell-shaped curve in plot of
activity versus pH or s-shaped curves in plots of activity versus pH (either falling
from optimal activity or rising to optimal activity) with an inflection point
at some pH value. This result would provide a
useful information to understand the reaction activity of CO2
absorption into various amines system.

Figure 1. The catalytic
Mechanism of enzyme in aqueous solutions

 Figure 2.
The chemical structure of amines studied in this work

Figure 3. String cell for
determination of amine pKa

Figure 4. The dissociation
constants show as a function of temperature

Figure 5. Comparison of enzymes
activity in different aqueous amine solutions

Acknowledgment: The financial supports from
the National Natural Science Foundation of China (Nos. 21476064 and 21406057), National
Key Technology R&D Program (Nos. 2012BAC26B01 and2014BAC18B04), Innovative
Research Team Development Plan-Ministry of Education of China (No. IRT1238),
and China¡¯s State ¡°Project 985¡± in Hunan University-Novel Technology Research
and Development for CO2 Capture as well as Hunan University to the
Joint International Center for CO2 Capture and Storage (ICCS) is
gratefully acknowledged.


Tontiwachwuthikul P, Idem R, Gelowitz D, Liang ZH,
Supap T, Chan CW, et al. Recent progress and new development of post-combustion
carbon-capture technology using reactive solvents. Carbon Management. 2011; 2:

McCann N, Phan D, Wang X, Conway W, Burns R, Attalla
M, et al. Kinetics and mechanism of carbamate formation from CO2 (aq),
carbonate species, and monoethanolamine in aqueous solution. The Journal of
Physical Chemistry A. 2009; 113: 5022-9.

Yu C-H, Huang C-H, Tan C-S. A Review of CO2 Capture
by Absorption and Adsorption. Aerosol and Air Quality Research. 2012; 12:

Liang ZH, Sanpasertparnich T, Tontiwachwuthikul P,
Gelowitz D, Idem R. Part 1: Design, modeling and simulation of post-combustion
CO2 capture systems using reactive solvents. Carbon Management. 2011; 2:265-88.

Reynolds AJ, Verheyen TV, Adeloju SB, Meuleman E,
Feron P. Towards commercial scale postcombustion capture of CO2 with
monoethanolamine solvent: key considerations for solvent management and

Lindskog S. Structure and mechanism of carbonic
anhydrase. Pharmacology & therapeutics. 1997; 74: 1-20.

Lindskog S, Silverman DN. The catalytic mechanism of
mammalian carbonic anhydrases. The Carbonic Anhydrases: Springer; 2000. p. 175-95.

Penders-van Elk NJMC, Derks PWJ, Fradette S,
Versteeg GF. Kinetics of absorption of carbon dioxide in aqueous MDEA solutions
with carbonic anhydrase at 298 K. International Journal of Greenhouse Gas
Control. 2012; 9: 385-92.