Energy Fuels 2010, 24, 213–219 : DOI:10.

1021/ef900564x
Published on Web 07/28/2009

Reduction of Energy Requirement of CO2 Desorption by Adding Acid into

CO2-Loaded Solvent†
Bo Feng,* Min Du, Timothy James Dennis, Kim Anthony, and Marc Jarrod Perumal
School of Mechanical and Mining Engineering, The University of Queensland, St Lucia, Qld 4072, Australia

Received June 2, 2009. Revised Manuscript Received July 19, 2009

The effect of the addition of weak acids into CO2-loaded solvents or rich solvents on the energy
requirement of CO2 desorption was investigated experimentally. The commercially available CO2 solvent
monoethanolamine (MEA) was used to absorb different amounts of CO2. Subsequently, a few weak acids
such as suberic acid, phthalic acid, and oxalic acid were added into the solvents to study the effect of acid
amount on the rate of CO2 release. It was found that CO2 could be released much faster and in much larger
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quantity with the addition of weak acids while the other desorption conditions were maintained the same.
The amount of CO2 released was found to be proportional to the amount of acid added. Acid addition
could be potentially used to reduce the energy requirement for CO2 desorption from solvent.
Downloaded via UNIV OF STRATHCLYDE on July 3, 2024 at 08:01:47 (UTC).

1. Introduction The solvent technology has been investigated exten-

The current CO2 capture methods can be classified into
three categories: precombustion, postcombustion and oxy-
fuel,1 which are under various development stages. So far the
only technology that is commercially available is the solvent
technology, which is in the postcombustion category.
† (see Figure 1). In spite of a mature technology, the solvent
Presented at the 2009 Sino-Australian Symposium on Advanced Coal
and Biomass Utilisation Technologies.
*To whom correspondence should be addressed. Telephone: þ61 7
3346 9193. Fax: þ61 7 3365 4799. E-mail: b.feng@uq.edu.au.
(1) Beck, R. A.; Hoag, K. J. Energy 1997, 22 (2/3), 115–120.
(2) Al-Baghli, N. A.; Pruess, S. A.; Yesavage, V. F.; Selim, M. S. Fluid
Phase Equilib. 2001, 185, 31–34.
(3) Alie, C.; Backham, L.; Croiset, E.; Douglas, P. L. Energy Conver-
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(4) Barreau, A; Blanchon le Bouhelec, E; Habchi Tounsi, K. N.;
Mougin, P; Lecomte, F. Oil Gas Sci. Technol. - Rev. IFP 2006, 61 (3),
345–361.
(5) Bavbek, O; Alper, E. G. Turk J Chem 1999, 23, 293–300.
(6) Chakravarti, S; Gupta, A; Hunek, B. Advanced Technology for
the Capture of Carbon Dioxide from Flue Gases. In First National
Conference on Carbon Sequestration, Washington, DC, 2001, 1-10.
(7) Chiu, L; Li, M. J. Chem. Eng. Data 1999, 44 (6), 1396–1401.
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(13) Eimer, D.; Sjøvoll, M.; Eldrup, N.; Heyn, R.; Juliussen, O.;
McLarney, M.; Swang, O. New thinking in CO2 removal. Nordic
Symposium; Oct 2003.
(14) Kohl, A; Nielsen, R. Gas Purification, 5 ed.; Gulf Publishing
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(17) Ramachandran, N; Aboudheir, A; Idem, R; Tontiwachwuthikul,
P. Ind. Eng. Chem. Res. 2006, 45 (8), 2608–2616.
(18) Rochelle, G. T. Oxidative Degradation of Monoethanolamine. In
First National Conference on Carbon Sequestration, Washington, DC, 2001.
(19) Strazisar, B. R.; Anderson, R. R.; White, C. M. Energy Fuels
2003, 17 (4), 1034–1039.
(20) Svendsen, H. F.; Hoff, K. A.; Poplsteinova, J.; da Silva, E. F.
Absorption as a Method for CO2 Capture. In Second Nordic Minisym-
posium on Carbon Dioxide Capture and Storage, Goteborg, 2001, 24-29.
sively.2-24 Briefly, carbon dioxide is captured first in an
absorption column (at 40-60 °C) using physical or chemical
solvent. The CO2-saturated solvent (or rich solvent) is subse-
quently pumped to a desorption tower (or stripper) to release
CO2 and regenerate the solvent (at 100-150 °C). The fresh
solvent is then sent back to the absorption tower for reuse
technology faces three major limitations:6,14,16
• Solvent degradation. A significant practical problem
in the operation of a solvent absorption system is sol-
vent losses due to degradation. The degradation of
amine-based solvents typically occurs in three different
ways.18,19 The flue gas stream generally contains
5-10% O2, which induces a series of oxidation reactions
between the solvent and the O2, resulting in the forma-
tion of unwanted products. Oxidative degradation
occurs in the presence of metal ions such as iron or
copper, which act as catalysts to the process. The
oxidation of the solvent produces organic acids and
NH3, which occurs most heavily in the aqueous loaded
solvent mixture built up at the bottom of the absorption
column. Another form of solvent degradation is caused
by a reaction of the solvent with the CO2 molecules in
what is called carbamate polymerization. Finally the
solvent is also susceptible to thermal degradation result-
ing in changes to the chemical composition when sub-
jected to temperatures higher than roughly 200 °C.
• Corrosion. The conventional solvent absorption system
is contained within columns made from carbon steel
and, as such, is very susceptible to corrosion. Corrosion
occurs through standard oxidization of the iron in the
steel and results in uniform deterioration of the material
(21) Thuy, L. T.; Weiland, R. H. Ind. Eng. Chem. Fundam. 1976, 15
(4), 286–293.
(22) Tomcej, R. A.; Otto, F. D. AIChE J. 1989, 50 (5), 861–864.
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(24) Weiland, R. H.; Rawal, M; Rice, R. G. AIChE J. 1982, 28 (6),
963–973.

r 2009 American Chemical Society 213 pubs.acs.org/EF

Energy Fuels 2010, 24, 213–219 : DOI:10.1021/ef900564x
Figure 1. pH swing process in conventional solvent absorption system.13
over all surface areas. Corrosion occurs naturally, how-
ever in this system corrosion rates are increased by
higher solvent concentration, higher acid gas loading,
higher operating temperatures, and a higher pH. Re-
search has shown that it is not the amines themselves
that increase the rate of corrosion, however it is the free
acid gas that is released from the amines.9
• High regeneration energy. The chemical absorption
process is hindered by several factors that limit the
process efficiency and ease of operation. The main
limitation arises from the need to use a solvent with
high reaction energy to extract the dilute carbon dioxide
in the flue gas stream. The unavoidable flipside to this is
that same amount of energy is needed to put back into
the system in regeneration at significant cost to the
operator. The amount of energy required for regenera-
tion accounts for roughly 70-80% of the total operat-
ing cost of the system. The large amount of low-grade
heat is supplied to the system via the regeneration steam
cycle and partially conserved through use of heat ex-
change where possible. The practicality of the process is
often limited to facilities that can easily supply bulk
amounts of low-grade heat, such as power plants. The
high regenerative energy requirement and associated
high operating cost is the single greatest barrier to
chemical absorption being a widespread and effective
CO2 capture solution.
A range of work is ongoing to address the above limitations,
for example new solvents are being developed to reduce
degradation and corrosion.6,8 A new method, that is, pH
swing method,13 has also been proposed to reduce the energy
requirement of regeneration. This work intends to evaluate
the effectiveness of the pH swing method in energy savings.
The principal feature of the pH swing process is the addition
of a pH control agent or acid to the system to lower the pH
of the solution to be regenerated in order to reduce the amount
of energy needed compared to conventional methods.13
The integration of the pH swing process to the conven-
tional solvent absorption system (as shown in Figure 1)
involves the addition of the pH control agent to the saturated
solvent-CO2 mixture in transit from the bottom of the
214
Feng et al.
absorption prior to regeneration. It is expected that the pH
control agent will dissolve in the solution with the temperature
increase and will remain dissolved in the solvent until being
passed through the heat exchanger on return to absorption.
Removal of the pH control agent from the system flow can be
achieved by a drop in temperature and drop in solubility,
bringing about crystallization from out of the solvent before
returning to the absorption column.
The idea of reducing the energy requirement to regenerate
the CO2 capture solvent by reducing the pH is a relatively new
theory and, as such, there is no specific information available
from previous research. The most relevant link to current
developments in pH swing is the sodium citrate and sodium
adipate processes10-12 used for SO2 extraction from flue gas
streams in a near identical fashion to CO2 extraction.
The sodium citrate process operates like a conventional
system with selective absorption of SO2 taking place through
flue gas contact with an aqueous solvent followed by an
energy input in the form of steam to regenerate the solvent
and liberate the SO2. The SO2 is extracted with the steam and
separated through condensation of the water vapor to leave
the pure SO2 ready for storage. The process offers many
advantages to industrial applications for flue gas desulfuriza-
tion, which is an important environmental requirement in
light of the contribution of SO2 to acid rain. The sodium
citrate process offers several advantages, including a high gas
loading capacity and low solvent oxidation losses, however
these attributes are beset by the high energy requirement of the
system, used to produce the steam. The large energy require-
ment presents itself as a significant cost item in the sodium
citrate method.
The sodium adipate process10 is a modification of the
sodium citrate process that is able to achieve a significant
decrease in energy usage through the introduction of adipic
acid to the system. The sodium adipate process operates
in the same way as the sodium citrate process but in-
volves the addition of adipic acid to the SO2-loaded solvent
solution prior to steam stripping. The lowering of the pH
in this solution results in a significant saving in steam re-
quired for regeneration while maintaining all of the inherent
advantages of the sodium citrate processes. The relatively
low cost of the adipic acid (C6H10O4) together with the
Energy Fuels 2010, 24, 213–219 : DOI:10.1021/ef900564x
savings in energy from the reduced steam requirement found
experimentally mean that this modification is economically
beneficial.
Apparently, in order to evaluate the feasibility of the pH
swing method for CO2 capture, the following questions need
to be answered:
• Are there any acids that can reduce the regeneration
energy significantly?
• Can the acids be recovered easily?
• Would the residue acids in the solvent affect the absorp-
tion performance largely?
As the initial step of the pH swing method project, this work
attempts to answer the first question, that is, whether we can
find any acids that can reduce the regeneration energy require-
ment for CO2 desorption. A few weak acids were selected and
tested for the effect on the regeneration energy requirement of
a conventional CO2 solvent.
2. Experimental Section
The experimental steps are as follows. First of all, typical
solvents of different concentrations were prepared. Subsequently
the solvents were subject to CO2 absorption. Third, selected acids
were added into the solvents, and the energy consumed for CO2
desorption for the solvents was then obtained and compared with
the case when no acid was added.
2.1. Solvent Selection. The chemical solvents commercially
available by order were alkanolamines: monoethanolamine
(MEA), diethanolamine (DEA), and methyldiethanolamine
(MDEA). There are currently solvent absorption facilities in
three power stations in the U.S and six other heavy industries
worldwide that all use MEA as the chemical solvent.6 It is
apparent from this that MEA is the industry standard, making
it the most suitable solvent to experiment with. There is far more
research literature related to the properties of MEA than any
other solvents as well, therefore MEA was selected as the
solvent. MEA is a good solvent to use also because of its high
absorption performance and high regenerative energy require-
ment. These properties allow for the most effective absorption
and will serve to highlight the regenerative energy savings.
2.2. pH Control Agents. Three weak acids selected in this work
were suberic acid (C6H12(COOH)2), phthalic acid (C6H4-
(COOH)2), and oxalic acid (HOOC-COOH). The selection
criterion is based on the properties of adipic acid, in particular,
the wide pH buffering capacity, the steep solubility, and the
monetary cost. The three acids were selected because they are
dicarboxylic acids similar in chemical structure to adipic acid.
The basic structure of dicarboxylic acids is HOOC-R-
COOH where R consists of a hydrocarbon chain of varying
length. In solution the acid dissociates through ionization of
the carboxyl groups on either end of the molecule in the form
HOOC-R-COOH f HOOC-R-COO- þ Hþ. Ionization of
the second carboxyl group occurs less readily than the first.
The steep solubility curve is a key requirement for the pH
swing process so that the acid can be effectively removed
through crystallization by a drop in temperature. The three
acids exhibit the desired solubility over the operating tempera-
tures of the solvent absorption process. At the high tempera-
tures the acids are highly soluble in solution. However this
solubility drops steeply with decreasing temperature, so that at
the low temperatures of the process the acids are far less soluble
and precipitate out as crystals.
The final criterion, which is important from a commercializa-
tion stand point, is the price and availability of the acids. All
three acids are relatively inexpensive and are available by order
in small quantities; however, a detailed cost analysis for bulk
supply is required to confirm the financial viability on an
industry scale.
215
Feng et al.
2.3. Absorption Stage. The purpose of the absorption experi-
mentation stage was to prepare a large volume of sufficiently
CO2-loaded solvent solution to then be divided up into samples
and individually used in regeneration.
The first step in the absorption experimental process was the
calculating and measuring 160 mL of solvent solution based on
the solvent concentration selected, either 1.1 M (30 wt %) or
2 M. The volumes of MEA and distilled water were measured
and poured into an absorption unit flask, and the whole
absorption system was flushed with nitrogen until the CO2
concentration reached zero. A mixture of CO2 and nitrogen
(CO2 concentration of 20 000 ppm) was then introduced, and the
concentration of CO2 was monitored continuously until the
concentration reached 20 000 ppm. The amount of CO2 ab-
sorbed by the solvent was calculated based on the CO2 concen-
tration profile. Three solvents were prepared with different CO2
loadings at room temperature (25 °C).
2.4. Regeneration Stage. Experimentation was conducted
prior to the regeneration experimentation regarding the beha-
vior of the three acids when mixed with the loaded solvent
solution. It was noted that while suberic acid and phthalic acid
showed little reaction and dissolved in the solution readily,
oxalic acid produced a violent reaction when mixed with the
solution, which involved violent fizzing, generation of heat, and
the release of a sweet smelling gas, inferred to be an ester. The
instability of the oxalic reaction justified the discontinuance of
regeneration experimentation using that acid.
The regeneration experiments were carried out using both
concentrations of solvent solutions in 15 mL samples by heating
the samples from room temperature to 95 °C, first with control
runs with no acid added and then with suberic (2, 4, or 6 g and
0.5, 1, 2, 3, 4, or 6 g) and phthalic acid (2, 4, or 6 g) of varied
amounts.
The first step of experimentation was to pipet out a 15 mL
volume of the loaded solvent and transfer it to the regenera-
tion unit. The required amount of acid was then weighed out
and added to the solvent solution, and the regeneration unit
was sealed. Once the regeneration unit was sealed and connected
in with the rest of the apparatus, nitrogen gas was passed
through the system to bring the CO2 concentration readings
to a minimum level as a reference point. When the CO2 level
had dropped to the reference point, the regeneration unit was
submerged into an oil bath controlled at 95 °C. The regenera-
tion unit was left for a period of time in the oil bath while the
CO2 levels from the outflow and temperature were monitored.
At the end of the period of time given to regeneration, the
CO2 and temperature data logging was stopped and the nitro-
gen flow was closed off. At this point the regeneration unit was
opened up and, while still in the oil bath maintaining the
solution at 95 °C, the pH of the solution was measured
using a pH meter. The regeneration unit containing the partially
regenerated solvent was then cooled and the volume of the
solution inside was measured.
The time period for the experiments was kept at 10 or 20 min.
Randomly selected experiments were repeated, and it was
found the difference was within 10%. The reported results
are the average values in the case multiple tests were run
under the same conditions.
3. Results and Discussion
3.1. Absorption Results. The following observations were
noted during absorption experimentation:
• Heat is released when water is mixed with MEA.
• Solution increases in viscosity with absorption.
• Solution changes color and texture with greater absorp-
tion; Small bubbles are evident throughout solution.
• If left over longer periods of time, the loaded solvent
solution changes color to deep yellow/amber.
Energy Fuels 2010, 24, 213–219 : DOI:10.1021/ef900564x Feng et al.

Table 1. Volume of CO2 Absorbed into Solution in Samples 1-3 Table 3. Regeneration of Sample 2
volume of moles of mass of acid start volume finish volume finish N2 flow
CO2 CO2 acid (g) (mL) (mL) pH reading
MEA total absorbed in absorbed
none 0 15 10.5 9 150
sample concen- volume absorption solution in
suberic 2 15 11.5 8.66 150
ID tration (mL) time (min) (mL) solution
suberic 4 15 13 8.44 150
sample 1 2M 160 125 5872.4 0.2622 suberic 6 15 14.5 8 150
sample 2 1.12 M 160 90 3312.8 0.1479 phthalic 2 15 12.2 8.7 150
sample 3 2M 160 170 6725.9 0.3003 phthalic 4 15 12 8.6 150
phthalic 6 15 14 7.8 150
Table 2. Regeneration of Sample 1
mass of acid start volume finish volume finish N2 flow Table 4. Regeneration of Sample 3
acid (g) (mL) (mL) pH reading
mass of acid start volume finish volume finish N2 flow
none 0 15 8 10.45 150 acid (g) (mL) (mL) pH reading
suberic 2 15 10 9.1 150
suberic 4 15 11 8.75 150 none 0 15 10.5 9 160
suberic 6 15 12 8.28 150 suberic 0.5 15 11.5 8.9 160
none 0 15 8.5 9.48 150 suberic 1 15 12 8.85 160
phthalic 2 15 15 8.9 150 suberic 2 15 13.5 8.7 130
phthalic 4 15 10.5 8.7 150 suberic 3 15 12 8.5 160
phthalic 6 15 11.5 8.6 150 suberic 4 15 14.5 8.37 160
suberic 6 15 15 8 160
The observations were consistent with the previous
work,20-22 indicating the reaction between CO2 and MEA.
Three samples were produced with different MEA con-
centrations and CO2 loadings, as listed in Table 1.
It can be noted that the volume of CO2 absorbed into the
solution is consistent with the molar fraction of the solvent
MEA in solution and the amount of time given to the
absorption process. The calculation of moles of gas is under
the assumption that CO2 is an ideal gas. This data can be
used to determine the amount of CO2 contained within each
15 mL sample used in regeneration and compared to the
amount released in each experiment to find the regeneration
efficiency.
3.2. Regeneration Results. The three CO2-loaded solvent
samples were divided into 15 mL samples and tested for
regeneration. The following observations were noted during
regeneration experimentation:
• A significant amount of heat was released by the solu-
tion from the addition of the acid.
• There is an instant release of CO2 from the solution
corresponding to the heat release from the addition of Figure 2. Desorption of CO2 from sample 1 (2 M MEA).
the acid.
• Solution increases in viscosity throughout regeneration. absorbed CO2, was calculated based on the above results and
• Solution changes color to deep amber throughout re- is shown in Figure 8.
generation. It can be seen clearly from the figure that:
• Acid appeared to be fully dissolved at higher operating • The regeneration efficiency increases with the increase
temperatures. of acid amount in the solvent, for both acids and three
• Appeared to be some crystallization of acid on cooling samples. For sample 1, the increase is more than 400%
of the solution after regeneration. with 6 g of suberic acid added.
• The amount of water was reduced during regeneration. • It appears that suberic acid is more effective than
phthalic acid when the same amount of acid is added.
The major results are shown in Tables 2-4 and Figures 2-6.
• It appears that the regeneration efficiency is higher for
It can be observed immediately that there is an increase
the solvent with lower CO2 loading, if we compare
in CO2 output with an increase of acid in the solution, or a
sample 1 with sample 3.
decrease of pH level in the solution. The apparent trend
shows in all cases except for 6 g of suberic acid in sample 2. The mechanism of the effect of acid addition on the
It was also noticed the each experiment resulted in increase of regeneration efficiency is most likely to be
an almost identical temperature curve for the regenera- attributable to the shift of the overall reaction between
tion process, as shown in Figure 7. There appeared only CO2 and the solvent toward the release of CO2 as discussed
to be a slight difference in the maximum temperature below, though no detailed quantitative work has been con-
achieved by the control samples and the samples containing ducted to confirm this.
the acid. The predominant reversible reactions that take place in the
3.3. Regeneration Efficiency. The regeneration efficiency, aqueous solvent solution to absorb the CO2 using MEA are
defined as the ratio of the amount of desorbed CO2 to that of as follows:2,21
216
Energy Fuels 2010, 24, 213–219 : DOI:10.1021/ef900564x Feng et al.

Figure 3. Desorption of CO2 from sample 1 (2 M MEA). Figure 5. CO2 desorption from sample 2 (1.12 M MEA).

Figure 6. CO2 desorption from sample 3 (2 M MEA).

Figure 4. Desorption of CO2 from sample 2 (1.12 M MEA).

Deprotonization of the MEA molecule to form a stable

carbamate ion.
CO2 þ RNH2 f Hþ þ RNHCOO - ð1Þ
Further deprotonization to form another stable ion
RNHCOO - þ RNH2 f RNH3 þ þ RNCOO2 - ð2Þ
Reaction of carbamate ion with water molecule
RNHCOO - þ H2 O f H3 Oþ þ RNCOO2 - ð3Þ
Formation of carbonate ion from the reaction of carbon
dioxide with water
CO2 þ H2 O f Hþ þ HCO3 - ð4Þ
The overall affect of these reactions is the formation of
carbamate and carbonate ions from reactions with CO2 with
the release of heat. All of these reactions are reversible, and
the reverse reactions are activated with the addition of heat Figure 7. Temperature variation of solvent during regeneration.
into the system in the regeneration process.
When an acid is added into a solution, dissociation occurs equilibrium of reactions 1, 3, and 4. In all of these reactions,
to produce hydrogen ions (Hþ), the concentration of which the equilibrium shift brought about by the Hþ concentra-
is measured on the pH scale. The addition of an acid to tion increase favors the reverse reactions that take place to
this system of reactions has the effect of increasing the release the CO2 molecules. In effect, the addition of the acid
concentration of Hþ ions and causing a disturbance to the shifts the equilibrium to provide a driving forcing for the
217
Energy Fuels 2010, 24, 213–219 : DOI:10.1021/ef900564x
Figure 8. Regeneration efficiency, that is, the ratio of the amount of
CO2 desorbed to that of absorbed CO2, as a function of acid amount
in the solvent.
regeneration reactions, and this in turn reduces the energy
barrier to initiate these reactions.
The regeneration efficiency is lower than 40% in most of
the tests. This is not unexpected because the energy transfer
in the experiment is mainly through conduction, which is a
slow process. In a practical system, heat will be transferred
mainly through convection and mass transfer, and thus the
regeneration efficiency should be much higher within the
same time period.
3.4. Energy Efficiency. The total energy absorbed by each
solvent and the corresponding energy efficiency that is
defined as the ratio of the energy used for CO2 desorption
(heat of reaction) to the total energy absorbed by the sample
per mole of CO2 released are calculated.
The total energy absorbed by the solution in the regenera-
tion process can be calculated from summing the energy
components in the solution that are the sensible heat of
solution, the heat of reaction, the latent heat of vaporization
of water, and the latent heat of vaporization of solvent, that is,
total energy ¼ heat of reaction
þ latent heat of vaporization of water
þ latent heat of vaporization of solvent
þ sensible heat of solution
Subsequently, the energy efficiency is calculated as,
heat of reaction
energy efficiency ¼
total energy
The sensible heat is the heat required to raise the rich
CO2-solvent mixture to the right temperature for stripping
to take place. The sensible heat term is calculated using the
heat capacity of the solution and the temperature increase
observed in the experimentation. From available specific heat
capacity curves for the two different molar concentrations of
solution 2 and 1.12 M7,23 and the experimental temperature
data, the sensible heat can be calculated. Because all of the
experiments were subject to the same temperature increase,
the only difference affecting the sensible heat term is the molar
composition of the solvent solution.
The heat of reaction is the heat absorbed in the endo-
thermic reverse reactions to those that have taken place
218
Feng et al.
in absorption. The heat of reaction is the energy transferred
into the chemical reactions for the regeneration and release of
the CO2 molecules. The heat of reaction term can be calcu-
lated from available data relating to the chemical energy
requirement per unit volume of CO2. This heat of reaction
term can be multiplied by the volume of CO2 calculated for
each experiment. The heat of reaction term was found from
research literature to be 65 KJ/mol.24
In the regeneration process a significant amount of heat is
transferred into heating water into steam. The latent heat of
vaporization is the amount of heat required to produce the
steam, the amount of which will vary depending on the
concentration of the solvent mixture, for example, 30 wt %
MEA will have a smaller latent heat of vaporization than
10 wt % MEA. The latent heat of vaporization can be
calculated from the standard heat of vaporization value for
water given as 2.26 KJ/g and the amount of water vaporized
in each experiment. Because of the high boiling point of
MEA at roughly 170 °C and the fact that the regeneration
temperature only reached 90 °C, the assumption can be made
that the volume loss in solution over regeneration is solely
water. It would be expected that a very small amount of
solvent would be vaporized; however, it is not practically
possible to determine the volume fraction of the solvent and
the water in the solution loss.
In a similar way, the latent heat of vaporization of solvent
is heat absorbed in the vaporizing of usually a very small
amount of the solvent. While this is unintentional in the
regeneration process, it can be presumed that a small fraction
of the liquid solvent changes phase to gas.
The total energy transferred into the solvent solution in the
regeneration process is calculated by summing each of these
terms together for each experiment sample. From this total
energy input value and data for the corresponding molar
volume of CO2 released, the energy required per mole of CO2,
and the energy efficiency, can be found for each sample. The
detailed calculation results are shown in Table 5. It can be seen
that the major energy consumption is in heat of vaporization,
and the addition of acid reduces this term significantly.
The effect of the type and the amount of added acid on the
experimental sample’s total energy and energy efficiency is
shown in Figure 9. It can be observed that:
• There is a general trend that the total energy consump-
tion decreases with the increase of acid amount for both
suberic acid and phthalic acid, whereas the energy
efficiency increases with the increase of acid amount.
For sample 3, the decrease in energy consumption is
more than 1400% with 6 g of suberic acid added.
• The suberic acid is more effective in reducing the energy
consumption, or the energy efficiency is higher for
suberic acid, compared with phthalic acid.
• The energy consumption is very high, with an average
value of 3 MJ/mol CO2. This value is significantly higher
than the reported value for the energy requirement for
CO2 desorption from solvent, about 80 KJ/mol CO2.
A detailed analysis of the energy consumption items
reveals that most of the energy is consumed to generate
steam in our experimental system (Table 5). It is ex-
pected that the figure will be much smaller when steam is
used directly to heat up the solvent.
• The energy efficiency is found to be low, less than 10%
in most of the cases. This is again due to that most of the
input energy is used to generate steam rather than for the
desorption reaction. It is expected that the energy
Energy Fuels 2010, 24, 213–219 : DOI:10.1021/ef900564x Feng et al.

Table 5. Energy Consumption during Regeneration of Solvent Samples

heat of reaction heat of vaporization sensible heat released CO2 energy cons.
acid mass of acid (g) energy term (KJ) energy term (KJ) energy (KJ) total energy (KJ) (mmoles) (MJ/mol CO2)

Sample 1
none 0 0.17 15.82 3.59 19.58 2.62 7.48
Suberic 2 0.44 11.30 3.59 15.33 6.81 2.25
Suberic 4 0.48 9.04 3.59 13.11 7.31 1.79
Suberic 6 0.67 6.78 3.59 11.04 10.36 1.07
Phthalic 2 0.35 13.56 3.59 17.50 5.32 3.29
Phthalic 4 0.24 10.17 3.59 14.00 3.64 3.84
Phthalic 6 0.34 7.91 3.59 11.84 5.27 2.25
Sample 2
none 0 0.09 10.17 3.83 14.09 1.39 10.12
Suberic 2 0.19 7.91 3.83 11.93 2.86 4.17
Suberic 4 0.29 4.52 3.83 8.64 4.47 1.94
Suberic 6 0.20 1.13 3.83 5.17 3.14 1.65
Phthalic 2 0.16 6.33 3.83 10.32 2.43 4.24
Phthalic 4 0.17 6.78 3.83 10.78 2.57 4.19
Phthalic 6 0.20 4.52 3.83 8.56 3.14 2.72
Sample 3
none 0 0.11 10.17 3.59 13.87 1.65 8.39
Suberic 0.5 0.13 7.91 3.59 11.63 2.08 5.60
Suberic 1 0.22 6.78 3.59 10.59 3.37 3.15
Suberic 2 0.18 5.65 3.59 9.42 2.73 3.44
Suberic 3 0.28 6.78 3.59 10.64 4.24 2.51
Suberic 4 0.34 1.13 3.59 5.06 5.20 0.97
Suberic 6 0.50 0.00 3.59 4.09 7.66 0.53

that the heat transfer rate is quite different from that in

practical systems, as discussed before. This causes both the
regeneration efficiency and the energy efficiency to be much
lower than the expected values in practical systems. How-
ever, the results reported here do show without a doubt that
acid addition has a pronounced effect on the regeneration
and energy efficiency. Therefore, further work is being
conducted to investigate in more detail the pHS method,
including testing of more acids to identify the most suitable
one, crystallization of the acids, chemistry of pH swing, effect
of pH swing on corrosion, economics of the method, and
application of the method for other solvents, etc. It should
also be pointed out that the addition of acid might have less
effect on CO2 desorption in a practical system than it was
shown here because of the uncertainties discussed above.
Further work is needed to test relatively larger systems that
represent practical conditions.

Figure 9. Effect of acid type and amount on total energy consump-
tion and energy efficiency.
efficiency will be much faster in practical systems in
which the heat transfer rate is higher.
4. Conclusions
The concept of utilizing a swing in pH in the solvent
absorption process for CO2 capture was investigated. The
experimental results proved to substantiate the theory of pH
swing and proved that the concept was indeed valid. The
experimental evidence showed that a significant energy saving
could be achieved through a swing in pH in the solution in the
regeneration process. Experimentation that was carried out
was able to achieve a maximum energy efficiency increase of
1400%, in terms of KJ of energy per mole of CO2 released,
relative to the conventional process.
The increase in energy efficiency was contributed to by the
increase in volume of CO2 release and the decrease in heat
energy consumption. The decrease in heat energy consump-
tion was primarily due to a drop in water vaporization. It is
considered beneficial to continue the investigation of the pH
swing method in more detail.

3.5. Discussion. A few uncertainties exist in the preliminary Acknowledgment. The financial support of the University of
experiments conducted in this work. The main uncertainty is Queensland is gratefully acknowledged.
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