Environ. Sci. Technol.
2009, 43, 6427–6433
Carbon Dioxide Postcombustion
Capture: A Novel Screening Study of
the Carbon Dioxide Absorption
Performance of 76 Amines
G R A E M E P U X T Y , * ,† R O B E R T R O W L A N D , †
ANDREW ALLPORT,† QI YANG,‡
MARK BOWN,‡ ROBERT BURNS,§
MARCEL MAEDER,§ AND
MOETAZ ATTALLA†
CSIRO Energy Technology, PO Box 330, Newcastle NSW 2300,
Australia, CSIRO Molecular and Health Technologies, Private
Bag 10, Clayton VIC 3169, Australia, and Discipline of
Chemistry, The University of Newcastle, University Drive,
Callaghan NSW 2308, Australia
Downloaded by INST OF CHEMICAL TECHNOLOGY at 02:41:12:443 on May 24, 2019
Received May 7, 2009. Accepted June 24, 2009.
The significant and rapid reduction of greenhouse gas
from https://pubs.acs.org/doi/10.1021/es901376a.
emissions is recognized as necessary to mitigate the potential
climate effects from global warming. The postcombustion
capture (PCC) and storage of carbon dioxide (CO2) produced
from the use of fossil fuels for electricity generation is a key
technology needed to achieve these reductions. The most
mature technology for CO2 capture is reversible chemical
absorption into an aqueous amine solution. In this study the
results from measurements of the CO2 absorption capacity of
aqueous amine solutions for 76 different amines are presented.
Measurements were made using both a novel isothermal
gravimetric analysis (IGA) method and a traditional absorption
apparatus. Seven amines, consisting of one primary, three
secondary, and three tertiary amines, were identified as exhibiting
outstanding absorption capacities. Most have a number of
structural features in common including steric hindrance and
hydroxyl functionality 2 or 3 carbons from the nitrogen. Initial CO2
absorption rate data from the IGA measurements was also
used to indicate relative absorption rates. Most of the outstanding
performers in terms of capacity also showed initial absorption
rates comparable to the industry standard monoethanolamine
(MEA). This indicates, in terms of both absorption capacity and
kinetics, that they are promising candidates for further
investigation.
Introduction
The capture, reversible release, and storage of carbon dioxide
(CO2) from combustion flue gases (postcombustion capture,
PCC) is now recognized by government and industry as a
viable near-term option for greenhouse gas abatement (1, 2).
It is particularly relevant to electricity generation from fossil
fuels (coal, oil, and gas) which accounts for approximately
25% of global CO2 emissions (3) with this figure set to increase
drastically in the next 25 years (4). PCC has a number of
practical advantages over other methods such as oxy-firing
* Corresponding author e-mail: graeme.puxty@csiro.au.
†
CSIRO, Division of Energy Technology.
‡
CSIRO, Division of Molecular and Health Technologies.
§
The University of Newcastle.
10.1021/es901376a CCC: $40.75  2009 American Chemical Society
Published on Web 07/17/2009
to produce a pure CO2 stream and IGCC with precombustion
capture and is of similar economic cost (5). In particular,
PCC can be retro-fitted to existing power stations and
integrated into new ones. Additionally, the parasitic energy
demand of a PCC plant on a power station can be reduced
(at the cost of CO2 removal efficiency) according to electricity
demand if additional electricity output is required from a
power station during times of peak load or optimal electricity
pricing.
Mature technology to separate CO2 from H2 or CH4 and
release it as a pure gas stream already exists in the gas
processing and ammonia production industries (6). Tradi-
tionally, the CO2 is vented or used for enhanced oil recovery,
food manufacture, and chemical production (6). The most
mature and applied technology for the capture and release
of CO2 is cyclic chemical absorption/desorption using an
aqueous amine solution of monoethanolamine (MEA) 30%
w/w. Aqueous solutions of other amines that have better
performance characteristics than MEA are also available as
proprietary formulations from a number of commercial
suppliers (e.g., Fluor, BASF and MHI). The standard chemical
process for PCC by chemical absorption/desorption is shown
in Figure 1. The gas (entering from the bottom) and amine
solution (entering from the top) are contacted at atmospheric
pressure in a counter-current fashion inside a packed
absorber column at low temperature (∼40 °C). The CO2 rich
amine solution is then circulated to the top of a desorption
column which is at high temperature (∼120 °C). At this
temperature the chemical equilibria and CO2 solubility are
shifted such that the absorbed CO2 is released and exits at
the top of the column. The regenerated amine solution is
then circulated back to the absorber column.
The application of PCC to combustion flue gases from
electricity generation poses a number of technical challenges.
The main issue is the energy requirement of the process,
which using current industry standard technology is expected
to reduce the efficiency of a coal fired electricity plant by
∼21% (5). The main energy cost is the heat and steam required
for the desorption column and to pump the absorbing
solution around the system. By increasing the capacity of a
chemical absorbent in terms of the amount of CO2 that can
be absorbed and desorbed per unit mass of solution, this
energy requirement may be more than halved (7).
In this work 76 different amine moeties have been
screened for their ability to absorb CO2. These include
primary, secondary, and tertiary amines; alkanolamines;
polyamines of a mixed or single type; cyclic and aromatic
amines; amino acids; and sterically free and hindered amines.
The screening process involved an initial screening method
using isothermal gravimetric analysis (IGA) to measure CO2
absorption as a mass increase. This method required only
milligrams of material for screening, allowing testing of
amines that were prohibitively expensive or difficult to obtain
in large quantities. The initial rate of CO2 absorption was
also used as an indicator of the kinetic behavior. Many of the
amines that were identified as performing well using this
method were also tested with a more traditional larger scale
CO2 absorption apparatus to validate the initial screening
results and provide a more reliable estimate of the CO2
absorption capacity. The measured CO2 absorption capacity
was compared to the absorption capacity from model
calculations. This allowed identification of a number of
amines showing absorption capacities greater than current
understanding of the CO2 absorption mechanism would
predict. The results of the screening study and modeling
VOL. 43, NO. 16, 2009 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 9 6427
FIGURE 1. The chemical absorption and desorption process for cyclic CO2 capture and release.
were then used to identify the chemical properties of the
amines most relevant to their performance as chemical
absorbents.
Experimental Section
Micro-Scale Isothermal Gravimetric Analysis (IGA). A
Setaram TG-DTA/DSC thermal gravimetric analyzer was used
in isothermal mode at 40 °C to monitor the increase in mass
of an aqueous amine solution when exposed to an atmo-
sphere of 15% CO2 and 85% N2 by volume at ambient pressure.
This CO2 concentration was chosen as it closely resembles
that of a coal fired power station flue gas. The instrument
was setup with two gas stream inputs, one providing a mix
of 15% CO2 and 85% N2 (99.9% purity, BOC Australia) and
the other N2 (>99.99% purity, BOC Australia). Both flows were
controlled using mass flow controllers (Bronkhurst High-
Tech El-Flow) with a total gas flow of 30 mL.min-1 used for
all experiments.
Two separate IGA experiments were performed in order
to determine the total CO2 uptake of the amine test solution.
The first experimental run determined the mass loss due to
evaporation and the second determined the mass increase
of the test solution when exposed to CO2 over the same length
of time. Each experiment was performed on a fresh 100 µL
aliquot of the test solution in a 100 µL alumina crucible
(Setaram). The samples were allowed to reach thermal
equilibrium under N2 for 20 min. Following this, the
experiment was continued under N2 to measure evaporative
loss or the gas flow changed to the CO2-N2 mix to measure
absorption for a period of six hours. The test solutions were
made to an amine concentration of 30% w/w in deionized
water, unless solubility constraints only allowed lower
concentration. All chemicals were purchased from Sigma-
Aldrich and used without further purification. The purity of
all the amines used was in the range 95-99.5% with the
highest purity available always chosen.
For calculations of absorption capacities the mass at time
t from the evaporation run is subtracted from the mass at
time t of the absorption run. This is illustrated in the
Supporting Information (SI). Large figures showing repre-
sentative experimental curves are also given in the SI. The
CO2 absorption capacity is then determined from the
6428 9 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 43, NO. 16, 2009
maximum point on the absorption curve. Total mass loss
due to water evaporation at the point of maximum CO2
absorption was generally 20%, with the rate of evaporation
unaffected by CO2 absorption.
Macro-Scale CO2 Absorption. Many of the amines that
showed promise from the IGA experiments were also tested
in a larger scale absorption apparatus based on that used by
Ma’Mun et al. (8). In this apparatus a mixture of 13% CO2
(99.5% purity, BOC Australia) and 87% N2 (>99.99% purity,
BOC Australia) was delivered using mass-flow controllers
(Bronkhurst High-Tech El-Flow). The gas was passed through
a mixing chamber, humidified to maintain the water balance
and then sparged via a sintered glass frit through a 30% w/w
amine solution in a glass reactor vessel at ambient pressure.
Gas flow rates and solution volumes of 1.7 mL.min-1 and
300 mL or 1.0 mL.min-1 and 20 mL, respectively, were used
depending on the quantity of amine available. The CO2
content of the gas outflow was measured using a Horiba
VS-3001 general purpose gas sampling unit and Horiba VA-
3000 NDIR multigas analyzer. The difference between the
inflow and outflow CO2 concentration was used to determine
the amount of CO2 absorbed. The humidifier and amine
solution were thermostatted to 40 °C by immersion in a
temperature controlled water bath (Techne). A schematic of
this apparatus is shown in the SI.
The experiments were run by initially allowing the
humidifier and reactor containing the amine solution to
thermally equilibrate. During this period the system was
flushed with N2 and calibration of the CO2 analyzer was
completed. The appropriate gas mix was first established
with the gas flow passing through the saturator but bypassing
the reactor and passing directly to the CO2 analyzer. The gas
flow was then switched to pass through the reactor to begin
the experiment. Each experiment was run until the measured
CO2 concentration in the outflow returned to the original
value (typical runs lasted between 30 min and 3 h).
Results and Discussion
The definition of CO2 absorption capacity often used is the
moles of CO2 absorbed per mole of amine in solution (molar
capacity, nCO2/namine). As many of the amines tested were
FIGURE 2. Plot of CO2 absorption capacity from the micro-scale and macro-scale methods for 10 amines (two fall on the same point)
showing the level of agreement between the two methods. The correlation coefficient between the data sets (G) is 0.89.
polyamines, and each amine functional group can contribute,
the molar absorption capacity can be further normalized to
the number of amine functional groups, or N atoms, present
in each molecule (normalized molar capacity, nCO2/nN). In
this manuscript nCO2/nN is used when discussing absorption
capacity to allow a fair comparison of absorption capacity
between poly and mono amines.
Of the 76 amines tested using the microscale IGA method,
24 were then tested using the larger macro-scale apparatus.
These included amines that gave unreliable results using the
IGA method due to excessive evaporation or precipitation,
and validation of the values for amines found to have high
absorption capacities. The results from the IGA method were
validated against literature data and results from the macro-
scale apparatus. Figure 2 shows a plot of the CO2 absorption
capacity determined reliably via both methods for 10 amines.
If results from both methods were available the macro-scale
results were taken as being more reliable as this method is
less influenced by evaporation or precipitation. From five
replicate runs using MEA, both methods achieved an error
of approximately 5% in terms of reproducibility.
Previous modeling results and experimental work (7-14)
has indicated that the capacity of an aqueous amine solution
to chemically absorb CO2 is a function of the pathway via
which CO2 reacts and the basicity of the amine, which can
be expressed using its pKa. Generally, primary and secondary
amines (represented as R1R2NH) can react with dissolved
CO2 to form a carbamic acid (R1R2NCOOH). Depending upon
its acidity, it may then give up a proton to a second amine
molecule forming a carbamate (R1R2NCOO-) according to
an overall stoichiometry of 2 as shown in eq 1. Via this
pathway two moles of amine are consumed per mole of CO2
if the carbamic acid is acidic, which is generally assumed to
be the case. Kinetically and thermodynamically this reaction
pathway is generally favored for primary and secondary
amines (14).
CO2 + R1R2NH h R1R2NCOOH
R1R2NCOO- + H+ h R1R2NCOOH
R1R2NH + H+ h R1R2NH+
2 (1)
A second reaction pathway that also contributes to CO2
absorption is CO2 hydration to form bicarbonate. In this
pathway an amine molecule (represented as R1R2R3N) simply
acts as a proton accepting base, and possibly a catalyst, for
the hydration of CO2 (11, 15). The overall stoichiometry for
this second pathway is given by eq 2. Via this pathway one
mole of amine is consumed per mole of CO2, so in terms of
capacity it is more efficient. For tertiary and some sterically
hindered primary and secondary amines this is the only
pathway contributing to absorption. However, this pathway
is generally less favorable kinetically than carbamate forma-
tion (14).
CO2 + H2O h HCO-
3 + H
+
(2)
R1R2R3N + H+ h R1R2R3NH+
Assuming that either or both pathways can contribute to
absorption for a given amine, the molar absorption capacity
should vary between 0.5 and 1.0 if the reaction is driven to
the products (which is the case if CO2(g) is constantly dosed).
Both pathways depend on the availability of unprotonated
base to accept a proton. Clearly the basic strength or pKa of
a given amine will influence how far both of these reaction
pathways can proceed to the products. Amines that are weak
bases may not achieve the 0.5-1.0 capacity range.
Figure 3 is a plot of the CO2 absorption capacity versus
the amine group pKa. For polyamines it is the pKa of the most
basic amine group. The pKa values were either taken from
literature if available (16) or calculated using the ACD/pKa
8.3 software package (17). The amines have been divided
into four classes: primary amines; secondary amines; tertiary
amines; and polyamines of mixed type (e.g., primary and
secondary amine functionality in the one molecule). Figure
3 also shows model calculations of the capacity as a function
of pKa. This modeling was done by simulating all of the
relevant elementary steps as equilibria according to a
previously published method (7). The dotted line represents
the predicted capacity if only the pathway of eq 1 occurs
with a large stability constant for carbamic acid formation
(K ) 0.1 L mol-1) and a small carbamic acid pKa (pKa ) 4).
The dashed line is the predicted capacity if only the pathway
of eq 2 occurs. The area between the two lines represents
where amines in which both pathways contribute would fall.
The primary and secondary amines in general do not appear
to show a strong correlation with pKa. This is not surprising
as the sensitivity of carbamate formation to pH, and thus
amine pKa, is dependent on the carbamate stability constant
which varies from amine to amine. The tertiary amines do
VOL. 43, NO. 16, 2009 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 9 6429
FIGURE 3. Plot of the absorption capacity versus amine group pKa (most basic amine for polyamines) at 40 °C. MEA is labeled as a
black dot. The seven amines showing outstanding performance are also labeled. The dashed line represents model predictions of
absorption capacity as a function of pKa if only the pathway of eq 1 occurs (with a large stability constant and small pKa for
carbamaic acid) and the dotted line if only the pathway of eq 2 occurs.
show a strong dependence on pKa consistent with bicarbon-
ate formation being the dominant reaction pathway for CO2
absorption. This is because the CO2 hydration reaction is
independent of the amine but is strongly pH dependent due
to the small stability constant for bicarbonate formation.
The mixed amines all contain primary or secondary func-
tionality and also show little correlation with pKa.
Capacity, Poor Performers. A significant number of the
amines fall below the area bounded by the lines of predicted
capacity. From comparing the structures of these amines
two structural features are apparent. Either the amines
contain a carboxylic acid group or are a polyamine. The effect
of both these features on absorption capacity can be easily
rationalized. An acidic functional group such as a carboxylic
acid will act to protonate a basic functional group such as
an amine on dissolution, reducing the ability of the amine
to participate in reactions with CO2. For the case of
polyamines, those that fall below the lines have at least one
amine functional group with a pKa less than 6. These amine
functionalities with low pKa are weak bases and are effectively
spectators that do not contribute to the overall absorption
capacity.
Capacity, Outstanding Performers. Also apparent in
Figure 3 are seven amines that are significantly above (more
than one absorption capacity unit) the area enclosed by the
lines. They are achieving capacities greater than would
be predicted based on their pKa. These seven amines are
made up of one primary, three secondary and three tertiary
monoalkanolamines and their structures, absorption capaci-
ties, and pKas are given in Figure 4. Three of the four primary
and secondary amines have some form of steric hindrance
around the amine functionality according to the definition
of Satori et al. (18) (2-amino-2-methyl-1,2-propanediol,
2-piperidineethanol and 2-piperidinemethanol). This is a
feature recognized as increasing capacity while maintaining
a fast reaction rate. Satori et al. (18) propose that this large
capacity and fast rate occurs through formation of an unstable
carbamate intermediate that hydrolyses to bicarbonate and
protonated amine (overall the same pathway as eq 2). Two
of the secondary and two of the tertiary amines are
heterocycles. Hetercycles such as piperidine and piperazine
are known to have fast reaction rates toward carbamate
formation (19-23). Being secondary amines, they may also
6430 9 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 43, NO. 16, 2009
be good base catalysts of the CO2 hydration reaction (15),
which may help improve their capacity.
The most interesting result is that all of these amines
share a common structural feature, a hydroxyl group within
2 or 3 carbons of the amine functionality. While it is unclear
what the role of this structural feature is, the distance of the
hydroxyl functionality from the amine and the structural
features around it appears crucial. The structures of three
structurally similar series and their capacities highlighting
this are given in Figure 5. For example, 2-piperidineethanol
and 2-piperidinemethanol achieved capacities of ∼1, whereas
3-piperidinemethanol only achieved a capacity of 0.8. This
indicates that the proximity of the hydroxyl group and its
freedom to move are important. One possibility is that a
hydroxyl group the appropriate distance from the amine
functionality, and with the appropriate structural features
surrounding it, is able to form a stable intramolecular
hydrogen bond with the nitrogen to form a five or six member
ring structure. Intramolecular hydrogen bond formation
between amine and hydroxyl groups has been predicted by
simulation (24, 25) and shown experimentally (24, 26, 27)
and was previously suggested by Sharma (23). While this
may decrease the amine pKa, for primary and secondary
amines it may also destabilize carbamate formation and push
the absorption toward the more stoichiometrically efficient
hydration pathway of eq 2. The type of intramolecular
hydrogen bond proposed is illustrated in Figure 6.
A second possible explanation for primary and secondary
amines is that the carbamic acid formed is a weak acid. It
is generally assumed that the pKa of the MEA carbamic acid
is <7 (28) based on values determined for the pKa of
ammonium carbamate (29). This assumption is not neces-
sarily valid as the electron donating ability of the nitrogen
will have a significant impact on the acidity of the carbamate.
Also, a recent 1H NMR study has revealed the pKa of the MEA
carbamate to be 7.55 (30). If the carbamate formed is a weak
acid then the pathway of eq 1 approaches a 1:1 CO2:amine
molar stoichiometry because the carbamate does not depro-
tonate and consume a second amine molecule.
Initial Absorption Rate. A second parameter important
for the performance of the chemical absorption of CO2 is the
rate of CO2 absorption. Chemical absorbents that have high
capacity but poor kinetic performance are unsuitable for
FIGURE 4. Structures of the sevem amines with outstanding performance in terms of absorption capacity. The absorption capacity
achieved and the pKa are given in parentheses.
FIGURE 5. Three different series of structurally similar
alkanolamines showing the influence of the position of the
hydroxyl group on capacity. CO2 absorption capacity and pKa
are given in parentheses.
industrial applications. The gas-liquid contact times required
for good capacity may not be achievable due to cost and
efficiency constraints. In general the reaction pathway to
form a carbamate, eq 1, is faster than the hydration pathway
of eq 2 (14). Thus, primary and secondary amines exhibit
faster CO2 absorption rates than tertiary amines.
The IGA microscale measurements were used to estimate
the initial rate of CO2 absorption. For these measurements
the initial mass increase follows a linear trend. The slope of
this linear region converted to molar capacity nCO2/namine
(i.e., not normalized to the number of amine functional
groups) was used to estimate the rate of CO2 absorption. The
linear region was taken as that where a linear function could
be fitted to the data with a R2 value of greater than 0.995 as
illustrated in Figure 7. This results in an absorption rate in
min-1 that is normalized to the moles of amine in solution.
Due to a lack of mixing, this method is influenced by effects
such as viscosity, so the measured rate does not necessarily
represent the intrinsic reaction kinetics. However, it does
allow a relative comparison of the rate of CO2 absorption of
the tested amines as 30% w/w aqueous solutions.
Figure 8 is a plot of the initial absorption rate versus the
pKa of first protonation for the amines tested. The general
trend is for increasing initial rate with increasing pKa. This
is consistent with the fact that the basic strength of the
amine influences the reaction rate of both reaction
VOL. 43, NO. 16, 2009 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 9 6431

FIGURE 6. Hypothesized hydrogen-bonded structure for primary
and secondary amines leading to decreased pKa but
destabilized carbamate formation resulting in higher than
theoretically predicted CO2 absorption capacity.
pathways in terms of its affinity to react with CO2, catalyze
the hydration of CO2 and accept a proton. The primary,
secondary and mixed amines span approximately the same
range of initial absorption rate values, 6 × 10-3 to 3.6 ×
10-2 min-1, with a couple of outliers. The bulk of the tertiary
amines fall an order of magnitude lower with 1.2 × 10-4
- 3.6 × 10-3 min-1. This is consistent with the different
reaction pathways and trends seen elsewhere (14). The
amines that exhibit the fastest initial absorption rate are
all polyamines with well separated amine functionality in
structurally similar environments (top six: homopiperazine
> meso-2,3-diaminosuccinic acid > piperazine > 1,4,7-
triazacyclononane > spermine > trans-N-hydroxyethyl-
1,4-diaminocyclohexane). Such amines would be expected
to exhibit faster absorption rates due to the simple fact
that statistically the per mole likelihood of CO2 encoun-
FIGURE 7. The IGA microscale curve showing capacity as a function of time for MEA 30% w/w. The black dashed line shows the
linear region used to calculate the initial rate of CO2 absorption.
FIGURE 8. Plot showing the initial absorption rate versus amine group pKa calculated from the IGA microscale data.
6432 9 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 43, NO. 16, 2009
tering amine functionality is increased. It is worth noting
that all of the primary and secondary amines identified as
having an outstanding capacity also had initial absorption
rates no more than 25% slower than MEA. This means
kinetic performance is not likely to exclude them from
potential CO2 capture applications. Also, it has been shown
that the rate of CO2 absorption can be enhanced and high
absorption capacity maintained by adding at low con-
centration an amine that exhibits a fast absorption rate to
an amine solution that exhibits high absorption capacity
(11).
Of the 76 amines tested seven were found to have an
outstanding CO2 absorption capacity compared to modeling
predictions. Of the four primary and secondary amines
showing outstanding absorption capacity, all showed initial
absorption rates similar to MEA. To further evaluate these
amines as new candidate molecules for large scale CO2
capture significant further testing is required. The particular
information required is detailed information on CO2 absorp-
tion rate as a function of temperature, amine concentration
and CO2 loading; the energy requirement of and their capacity
to cyclically capture and release CO2; their resistance to
oxidative and thermal degradation; their corrosiveness; their
resistance to degradation by flue gas impurities (SOx, NOx,
and trace elements); and their toxicity and the toxicity of
degradation products.
The results from this work indicate that there is still
significant scope for improvement in the use of aqueous
amine solutions for CO2 capture by chemical absorption.
However, what is also clear is that there is a lack of
understanding about the chemistry involved. Understanding
how the amines that show outstanding CO2 absorption
capacities do so while maintaining good rates of CO2
absorption is fundamental to achieving an optimal formula-
tion that maximizes efficiency and minimizes cost and
sustainability for PCC on an industrial scale. Existing
understanding of the reaction pathways are unable to account
for these characteristics.
Supporting Information Available
Figures of the experimental apparatus, figures showing
representative results from the microscale method, a table
containing all amines tested and their associated results
and figures of absorption capacity and initial rate versus
pKa with numbering according to the tables. This material
is available free of charge via the Internet at http://
pubs.acs.org.
Literature Cited
(1) IEA. Capturing CO2; IEA Greenhouse Gas R&D Program:
Cheltenham, UK, 2007; p 23.
(2) IPCC. IPCC Special Report on Carbon Dioxide Capture and
Storage. Prepared by Working Group III of the Intergovernmental
Panel on Climate Change; Cambridge University Press: Cam-
bridge, 2005; p 440.
(3) WRI Climate Analysis Indicators Tool. http://www.wri.org/.
(4) CSIRO. The Heat Is On: The Future of Energy in Australia;
Commonwealth Scientific and Industrial Research Organisation:
Canberra, 2006.
(5) Davison, J. Performance and costs of power plants with capture
and storage of CO2. Energy 2007, 32, 1163–1176.
(6) IEA. Prospects for CO2 Capture and Storage; OECD/IEA: Paris,
2004.
(7) McCann, N.; Maeder, M.; Attalla, M. Simulation of enthalpy
and capacity of CO2 absorption by aqueous amine systems.
Ind. Eng. Chem. Res. 2008, 47 (6), 2002–2009.
(8) Ma’mun, S.; Svendsen, H. F.; Hoff, K. A.; Juliussen, O. Selection
of new absorbents for carbon dioxide capture. Energy Convers.
Manage. 2007, 48, 251–258.
(9) Blauwhoff, P. M. M.; Versteeg, G. F.; Swaaij, W. P. M. V. A study
on the reactions between CO2 and alkanolamines in aqueous
solution. Chem. Eng. Sci. 1983, 38 (9), 1411–1429.
(10) Freguia, S.; Rochelle, G. Modelling of CO2 capture by aqueous
ethanolamine. Seperations 200349 (7), 1676–1686.
(11) Savage, D. W.; Satori, G.; Astarita, G. Amines as rate promoters
for carbon dioxide hydrolysis. Faraday Discuss. Chem. Soc. 1984,
77, 17–31.
(12) Tobiesen, F. A.; Svendsen, H. F. Experimental validation of a
rigorous absorber model for CO2 postcombustion capture. AIChE
J. 2007, 53 (4), 846–865.
(13) Tomizaki, K.-y.; Shimizu, S.; Onoda, M.; Fujioka, Y. An acid
dissociation constant (pKa)-based screening of chemical ab-
sorbents that preferably capture and release pressurized carbon
dioxide for greenhouse gas control. Chem. Lett. 2008, 37 (5),
516–517.
(14) Versteeg, G. F.; Dijck, L. A. J. V.; Swaaij, W. P. M. V. On the
kinetics between CO2 and alkanolamines both in aqueous and
non-aqueous solutions. An overview. Chem. Eng. Commun.
1996, 144, 113–158.
(15) Donaldson, T. L.; Nguyen, Y. N. Carbon dioxide reaction kinetics
and transport in aqueous amine membranes. Ind. Eng. Chem.
Fundam. 1980, 19, 260–266.
(16) NIST. NIST Critically Selected Stability Constants of Metal
Complexes; The National Institute of Standards and Technology:
Gaithersburg, MD, 2001.
(17) ACD/I-Lab ACD/pKa 8.3. http://ilab.acdlabs.com/.
(18) Satori, G.; Savage, D. W. Sterically hindered amines for CO2
removal from gases. Ind. Eng. Chem. Fundam. 1983, 22, 239–
249.
(19) Bishnoi, S.; Rochelle, G. T. Absorption of carbon dioxide into
aqueous piperazine: Reaction kinetics, mass transfer and
solubility. Chem. Eng. Sci. 2000, 55, 5531–5543.
(20) Cullinane, J. T.; Rochelle, G. Kinetics of carbon dioxide absorp-
tion into aqueous potassium carbonate and piperazine. Ind.
Eng. Chem. Res. 2006, 45, 2531–2545.
(21) Derks, P. W. J.; Kleingeld, T.; Aken, C. v.; Hogendoorn, J. A.;
Versteeg, G. F. Kinetics of absorption of carbon dioxide in
aqueous piperazine solutions. Chem. Eng. Sci. 2006, 61, 6837–
6854.
(22) Samanta, A.; Bandyopadhyay, S. S. Kinetics and modeling of
carbon dioxide absorption into aqueous solutions of piperazine.
Chem. Eng. Sci. 2007, 62, 7312–7319.
(23) Sharma, M. M. Kinetics of reactions of carbonyl sulphide and
carbon dioxide with amines and catalysis by bronsted bases of
hydrolysis of COS. Trans. Faraday Soc. 1965, 61 (508P), 681–
688.
(24) Cacela, C.; Fausto, R.; Duarte, M. L. A combined matrix-isolation
infrared spectroscopy and MO study of 1-amino-2-propanol.
Vib. Spectrosc. 2001, 26 (1), 113–131.
(25) Goldblum, A.; Deeb, O.; Leow, G. H. Semiempirical Mndo/H
calculations of opiates part 1. Building blocks: Conformations
of piperidine derivatives and the effect of hydrogen bonding.
J. Mol. Struct. (Theochem) 1990, 207, 1–14.
(26) Przeslawska, M.; Melikowa, S. M.; Lipkowski, P.; Koll, A. Gas
phase FT-IR spectra and structure of aminoalcohols with
intramolecular hydrogen bonds. Vib. Spectrosc. 1999, 20 (1),
69–83.
(27) Ribeiro da Silva, M. A. V.; Cabral, J. I. T. A. Standard molar
enthalpies of formation of 1-methyl-2-piperidinemethanol,
1-piperidineethanol, and 2-piperidineethanol. J. Chem. Ther-
modyn. 2006, 38, 1461–1466.
(28) Danckwerts, P. V. The reaction of CO2 with ethanolamine. Chem.
Eng. Sci. 1979, 34, 443–446.
(29) Christensson, F.; Koefoed, H. C. S.; Peterson, A. C.; Rasmussen,
K. Equilibrium constants in the ammonium carbonate-car-
bamate system. The acid dissociation constant of carbamic acid.
Acta Chem. Scand. A 1978, 32, 15–17.
(30) McCann, N.; Phan, D.; Wang, X.; Conway, W.; Burns, R.; Attalla,
M.; Puxty, G.; Maeder, M. Kinetics and mechanism of carbamate
formation from CO2(aq), carbonate species, and monoetha-
nolamine in aqueous solution. J. Phys. Chem. A 2009, 113,
5022–5029.
ES901376A
VOL. 43, NO. 16, 2009 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 9 6433