Article

pubs.acs.org/IECR

Facile Method for Determination of Amine Speciation in CO2 Capture

Solutions
Naser S. Matin, Joseph E. Remias, James K. Neathery, and Kunlei Liu*
Center for Applied Energy Research, University of Kentucky, Lexington, Kentucky 40511, United States
*
S Supporting Information

ABSTRACT: A simple and quantitatively reliable method for determination of amine speciation is introduced. The method
employs three experimental methods that should be readily accessible. The results for CO2 loaded aqueous solutions of 30 wt %
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monoethanolamine (MEA) are used for demonstration of the method and show promising agreement with the more
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complicated spectroscopic methods reported in the literature. The measurements were done at ambient temperature and
atmospheric pressure, since theoretical calculations and experimental data from the open literature revealed no considerable
difference in speciation at different temperatures. The procedure is based on acid and base titration of the CO2 loaded amine
solution along with the determination of total CO2 loading. The quantitative results for the different species concentration in the
example MEA solution is in agreement with other available spectroscopic methods, mainly NMR, particularly for the free amine,
carbamate, and protonated amine concentrations. Aspen Plus was also used for further assessment of the experimental data.

■ INTRODUCTION
Removal of acidic gases, particularly CO2, is a very important
operation from an industrial and environmental point of view.
Primary, secondary, and tertiary amines and their blends have
found widespread application in the absorption and removal of
carbon dioxide from process gases.1,2 In the designing of
absorption or desorption columns for a CO2 capture process by
amine or other reactive solvents, the precise knowledge of the
reaction chemistry is crucial. In this regard, having an accurate
determination of liquid phase species concentration is critical in
CO2 absorption processes modeling vapor−liquid equilibria
data. The contribution of the protonated amine, carbamate, and
bicarbonate formed in amine solvents to, for example, the CO2
heat of absorption makes their quantities critical for
thermodynamic understanding.3 Furthermore, providing a
good estimation of the free amine concentration is important
for mass transfer study of the CO2 absorption process, where
the free amine concentration explicitly appears in the liquid film
mass transfer coefficient.4 Finally, with good understanding of
the above concepts it is possible to better design new solvents
and blends.
Various thermodynamic models, mainly based on activity
coefficients, have been proposed for the CO2−H2O−alkanol-
amine systems.5−7 However, many of the models employ
computational models, which are not readily accessible or
require parameters not necessarily available for all solvents,
making experimental methods of merit.5 Furthermore, reliable
experimental values for species concentration in the liquid
phase can improve the thermodynamic models. The activity
coefficient models and their parameters can be better evaluated
by the available amine speciation data.3
The NMR approach for speciation study of alkanolamine
solutions containing dissolved CO2 is one of the basic methods
for this purpose.8−10 As it was discussed by Böttinger et al., the
quantification study in NMR spectroscopy is easier than optical
spectroscopy or gas chromatography because no calibration is
necessary.9 They used the combination of proton and carbon
NMR to study speciation in monoethanolamine (MEA)−
H2O−CO2 and diethanolamine (DEA)−H2O−CO2 solutions
at a wide CO2 loading range and temperatures between 20 and
80 °C. Of course, as noted, due to the fast proton transfer
between molecular and protonated amine, only the sum of their
concentrations can be observed. Furthermore, the NMR
method is time-consuming and requires expensive equipment.
Jakobsen et al. applied the same technique in the experimental
part of their work to study species distribution in 2-[(2-
aminoethyl)amino]-ethanol (AEEA)−H2O−CO2 system.10
Fourier transform infrared spectroscopy (FTIR) was also
used for the speciation study of CO2 absorbed into aqueous
alkanolamines by Jackson et al.11 Their work was not
quantitative, but they assigned the major peaks corresponding
to a few important species in the liquid phase for MEA−CO2
and 2-amino-2-methyl-1-propanol (AMP)−CO2 system. On
the other hand Derks et al. recently applied the FTIR technique
to quantitative measurements of speciation in CO2 loaded
aqueous solutions of N-methyldiethanolamine (MDEA).12 For
performing the analysis, they initially prepared calibration
curves for the species under study. Souchon et al. employed in
situ Raman spectroscopy for the quantitative determination of
the species distribution in alkanolamines (MEA, DEA, and
MDEA)−H2O−CO2 systems at equilibrium at 40 °C.13 A gas
chromatography technique also has been proposed.14
A titration method for the concentration measurement of
different species in AMP−H2O−CO2 and DEA−H2O−CO2
was used by Haji-Sulaiaman et al.15 They employed a strong
base (i.e., NaOH) to titrate the solution, followed by solving
the equilibrium equations simultaneously to determine solution
Received: February 3, 2012
Revised: April 20, 2012
Accepted: April 27, 2012
Published: April 27, 2012

© 2012 American Chemical Society 6613 dx.doi.org/10.1021/ie300230k | Ind. Eng. Chem. Res. 2012, 51, 6613−6618
Industrial & Engineering Chemistry Research
speciation. Their approach is simple and reliable but still
requires solving the simultaneous system of equations and
requires the necessary thermodynamic parameters, which may
not be available for all amines.
In this work, a new method based on the total alkalinity
measurements (acid titration), strong base titration, and CO2
loading of the solution was developed to calculate the different
species concentrations in the MEA (monoethanolamine)−
H2O−CO2 system. The method has several advantages in that
it is fast, repeatable, and employs methods that are typically
available in any laboratory studying CO 2 absorption.
Furthermore, the approach does not require the knowledge
of any thermodynamic parameters to determine speciation. The
developed system is compared to experimentally determined
values obtained using NMR for the same solution and to an
Aspen Plus equilibrium model for MEA. Good agreement was
found between the three methods.
■ EXPERIMENTAL SECTION
The aqueous solutions of 30 wt % MEA with different CO2
loadings were prepared and used for all experiments by
contacting the aqueous MEA solution with a CO2 containing
gas stream for different time periods. From each sample, five
pieces of data were collected: pH, density, CO2 loading, total
alkalinity, and base titration. The pH was measured at ambient
temperature using a temperature corrected probe and 2 point
calibration. The density was measured by dispensing 1 mL of
solution (calibrated pipet to water) in quadruplicate and
determining the mass.
The CO2 solution loading was measured by an adaptation of
a total inorganic carbon method previously described.16 In this
method, phosphoric acid liberates the dissolved CO2 in amine
solutions. The CO2 gas is stripped out with a nitrogen carrier
gas and is directed to a HORIBA CO2 analyzer (VIA-510). The
area under the curve is integrated, and CO2 concentration is
determined using a calibration curve from a known analytical
standard of potassium carbonate. Approximately 1 mL of
sample (mass determined) was injected into the phosphoric
acid reactor yielding CO2 concentration in mol CO2/kg sln.
The HORIBA CO2 analyzer was calibrated with a certified
CO2/N2 gas mixture (PurityPlus, 14.00% CO2) each day. The
uncertainty was checked with a known analytical standard prior
and after each set of unknowns with the allowable discrepancy
in CO2 measurement (|(expected − measured)/expected| ×
100) set at less than ±2% absolute. The standard deviation for
repeated measurements was ±2.7%.
Total alkalinity measurements were conducted using a
Metrohm Titrando 836 and a standard equivalence point
determination method, (with accuracy of ±0.003 in pH, and
standard deviation at ±3.6% in end point measurements).
Having the consumed acid volume at the final equivalence
point (typically two were observed, see Figure S.1, Supporting
Information) and its molarity, the following equation is used for
alkalinity determination (and also base titration) of sample
solution. A typical total alkalinity titration curve is shown in
Figure S.1, Supporting Information.
nMv
Total alkalinity (moleCO2 /kg sln) =
wsample (1)
Where M, n, v, and wsample are molarity of acid, number of
proton per acid molecule, volume of acid was used during
titration (mL), and sample mass (g), respectively. A nominal
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0.1 M sulfuric acid solution was utilized here with sample size
selected to require a minimum of 10 mL of titrant to minimize
volumetric delivery error.
For the base titrations, the dynamic equivalence titration
(DET) method incorporated in the Metrohm Titrando 836
software was used as previously described.15 The method was
validated by adding known amounts of potassium bicarbonate
to 30 wt % MEA solutions and titrating using the method. A
nominally 0.1 M sodium hydroxide solution was used for the
base titrations with sample size selected to require a minimum
of 10 mL of titrant. The base titrations were performed at
ambient temperature. For the base titration, eq 1 can be used
with M, n, v as the base molarity, number of hydroxide ions per
base molecule, and volume of base (in mL) used for titration,
respectively. (see Figure S.2, Supporting Information for typical
DET titration curve)
■ RESULTS AND DISCUSSION
Background. Liquid bulk concentrations of chemical
species and the partial pressure of solutes in the gas phase
are required for all calculations including kinetic analysis and
system simulation. Therefore, the independent chemical
reactions, which produce or consume stable species in the
bulk phase, and phase equilibrium equations have to be known
for the system under study. Having such information makes it
possible to calculate the desired quantities mentioned above.
The following reactions may occur when CO2 absorbs into
and reacts with aqueous primary and secondary amines.17
Ionization of water:
2H 2O ↔ OH− + H3O+ (2)
Dissociation of dissolved CO2 through carbonic acid:
CO2 + 2H 2O ↔ HCO3− + H3O+ (3)
Dissociation of bicarbonate:
HCO3− + H 2O ↔ CO32 − + H3O+ (4)
Carbamate reversion to bicarbonate (hydrolysis reaction):
RNHCOO− + H 2O ↔ RNH 2 + HCO−3 (5)
Dissociation of protonated amine:
RNH3+ + H 2O ↔ RNH 2 + H3O+ (6)
Considering the above reactions, the potential species
concentrations in question are OH−, H3O+, HCO3−, CO2,
CO 3 − , RNH 3 + , RNH 2 (unreacted free amine), and
RNHCOO−. One approach to finding the concentrations of
the above-mentioned species is solving eight of the equations
below simultaneously. The chemical reaction equilibriums, the
mass and charge balances in the aqueous phase, and the phase
equilibrium between CO2 in the gas and aqueous phase give
enough (eqs 7−15) to perform the calculations.17
Amine balance:
[RNH 2]f + [RNH3+] + [RNHCOO−] = [RNH 2]t (7)
Carbon balance:
[CO2 ] + [HCO3−] + [CO32 −] + [RNHCOO−]
= α[RNH 2]t (8)
Charge balance:
dx.doi.org/10.1021/ie300230k | Ind. Eng. Chem. Res. 2012, 51, 6613−6618
Industrial & Engineering Chemistry Research Article

Table 1. Equilibrium Constants18,19,a

A B C D
K1, (mol/dm3)2 132.89888 −13445.9 −22.4773 0
K2, (mol/dm3) 231.465439 −12092.1 −36.7816 0
K3, (mol/dm3) 216.050446 −12431.7 −35.4819 0
K4, (mol/dm3) −0.52135 −2545.53 0 0
K5, (mol/dm3) −3.038325 −7008.357 0 −0.0031348
a
ln (K) = A + B/T + C ln(T) + DT, where T is in Kelvin.

[RNH3+] + [H3O+] CO2 + RNH 2 + H 2O ↔ H3O+ + RNHCOO− (17)

= [HCO3−] + [OH−] + 2[CO32 −] + [RNHCOO−]
Independent equilibrium constants:
K1 = [OH−][H3O+]
K 2 = [HCO3−][H3O+]/[CO2 ]
K3 = [CO32 −][H3O + ]/[HCO3−]
K4 = [RNH 2][HCO3−]/[RNHCOO−]
Therefore, it can be assumed that, during titration for total
(9) alkalinity, the free amine also includes all of the carbamate in
the solution. Considering the pH for carbonated alkanolamine
solutions, which are generally between 8 to 10, and the
dissociation constant (pK2) of dissolved CO2 through carbonic
(10)
acid at ambient temperature is ∼6.0 (see Table 1); it is a
plausible approximation that the bicarbonate−carbon dioxide
(11)
equilibrium, eq 3 is shifted toward the formation of bicarbonate.
Thus, the concentration of free CO2 is generally very low.15
(12) The alternative form of eq 8, considering carbon balance, gives
(13) [CO2 ]t = [CO2 ]f + [HCO3−] + [CO32 −]

K 5 = [RNH 2][H3O + ]/[RNH3+] + [RNHCOO−] (8-a)

(14)
PCO2 = He × [CO2 ] (15)
Where [RNH2]f, [RNH2]t, α, and He are unreacted free amine
and total amine concentrations, carbon loading, and Henry’s
constant. The equilibrium constants are given in Table 1.
Using eqs 2−15 is the approach applied to thermodynamic
modeling of CO2 loaded solutions (alkanolamines) to calculate
each species concentration in the liquid and gas phase, and it is
necessary to solve and optimize the system of nonlinear
equations over the experimental solubility data. In the next
section, a simple and reliable titration method is introduced to
obtain the speciation data in alkanolamine solutions based on
the mass and charge balance without the need for equilibrium
constants.
Method Description. For total alkalinity measurement, the
reactions 3, 4, and 6 can take place with approximate pK values
of 7, 11, and 10, respectively (see Table 1). Therefore,
considering the pK of the mentioned reactions, with addition of
proton (acid) the bicarbonate ion and protonated amine
formation take place at approximately pH ≅ 6 (pH of 7.3 in
experiments), that is, the first equivalence point. Further
addition of acid results in the bicarbonate ion converting to
CO2 through eq 3 at pH ≅ 4 (pH of 4.4 in experiments), that
is, the second equivalence point. Depending on the amine
protonation equilibrium constant of various alkanolamines, the
pH versus acid volume graph might display three equivalence
points, that is, a large difference in equilibrium constants of eqs
4 and 6, but the pattern and interpretation remain the same.
The total alkalinity of the solution can be calculated using an
acid titration, as follows:
Alka t = [RNH 2]f + [HCO3−] + 2[CO32 −]
−
+ [RNHCOO ] (16)
The addition of the acid (proton) in alkalinity measurement
causes protonation of the carbamate to produce free amine and
CO2 through the reverse reaction
6615
Therefore, from eq 16, 8-a, and discussion followed by eq 17,
the following equation can be reached,
Alka t = {[RNH 2]f + [RNHCOO−]} + 2[CO2 ]t
− [HCO3−] − [RNHCOO−] (16-a)
which is simplified as follows,
Alka t = [RNH 2]f + 2[CO2 ]t − [HCO3−] (16-b)
Considering eq 4, at basic conditions, the following equilibrium
reaction can be considered between bicarbonate and carbonate
ions
CO32 − + H 2O ↔ HCO3− + OH− (4-a)
Using the dissociation constant for bicarbonate to carbonate
ion and proton at room temperature (pK3 ≅ 10.3), and the
water dissociation constant (pKw ≅14), the equilibrium
constant for eq 4-a can be expressed as
K3‐a = K w /K3 = [HCO3−][OH−]/[CO32 −] ≅ 10−3
(18)
Considering eq 18, the basicity determines the bicarbonate/
carbonate ratio in the solution. Therefore, it can be inferred at
the mentioned solution’s pH (8 ≤ pH ≤ 10) that
10 ≤ [HCO3−]/[CO32 −] ≤ 1000
So, for most CO2 loading ranges considered and particularly at
the loadings above 0.25 molCO2/molamine, the concentration of
CO32− compared to HCO3− is very low, and it can be discarded
from the eq 8 or 8-a. Therefore, the simplified form of the eq 8-
a is
[CO2 ]t = [HCO3−] + [RNHCOO−] (8-b)
where [CO2]t was determined experimentally using the above-
described method.
Moving from the alkalinity measurements, as the acid
titration gives the free amine concentration, the dynamic
dx.doi.org/10.1021/ie300230k | Ind. Eng. Chem. Res. 2012, 51, 6613−6618
Industrial & Engineering Chemistry Research
titration of the amine solution with a strong base yields the
concentration of bicarbonate, protonated amine and free
CO2,15 so that the following balanced equation can be written
[Base] = [RNH3+] + [HCO3−] + [CO2 ]f (19)
with the same reasoning for eqs 16 to 16-a and 8-a to 8-b,
[Base] = [RNH3+] + [HCO3−] (19-a)
Considering the charge balance equation (eq 9) and the
assumption that the concentrations of H3O+, OH−, and CO32−
species are negligible compared to other species (i.e., pH ≅ 9),
then the charge balance can be written as follows,
[RNH3+] = [HCO3−] + [RNHCOO−] (9-a)
Then, from eq 8-b and the simplified charge balance (eq 9-a),
the following useful equation can be derived:
[Base] = [CO2 ]t + [HCO3−] (19-b)
Therefore, titration of a sample solution with strong base (e.g.,
NaOH) and using eq 19-b gives bicarbonate concentration.
Then, applying eqs 19-a and 8-b the protonated amine and
carbamate concentrations can be calculated, respectively. Using
the above, along with the alkalinity measurements (acid
titration), total inorganic carbon content of the solution and
using eq 16-b the free amine concentration can be determined.
Table S.1 (Supporting Information) shows the experimental
values for the concentration of the different species in MEA
solution with different CO2 loading. As it can be seen from
Table S.1 (Supporting Information), in terms of the carbamate,
protonated amine, and free amine, the agreement is good. In
the case of bicarbonate concentration, the values determined in
this work generally give higher values compared to the work
done by Jakobsen et al., which is discussed later in this section.8
Table S.2 (Supporting Information) displays the uncertainty in
this work compared to literature values.
Aspen Model Verification. For further verification of the
experimental method, Aspen Plus with the ENRTL-RK activity
coefficient model was chosen to compare the results. Figure 1
Figure 1. Experimental pH from this work compared to the Aspen
Plus predicted values, at 21 °C temperature.
shows the comparison of the experimental pH compared with
AspenPlus ENRTL-RK model predicted values for the same
MEA solution at different CO2 loadings. The model parameters
in the Aspen Plus data bank were selected from recent work
done by Zhang et al.20 As it can be seen in Figure 1 at the
working range for CO2 capture (i.e., CO2 loading of higher than
0.1 up to 0.5), the experimental pH values are in good
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agreement with the Aspen Plus predicted values. The pH is
defined as the activity of the proton in the solution. On the
other hand, the single ion activity coefficients are related to the
activity coefficient of the neutral electrolyte (i.e., γ+γ− = γN2).21
Therefore, as it can be deduced from the fundamental
equations for ionic species activity in the electrolyte systems,
and as it has also been mentioned in the literature that the
single ion activity cannot be measured experimentally using pH
and compared to predicted activity coefficient models for high
ionic strength solutions.22 However, Chan et al. displayed that
the pH measurement using a glass electrode even at high ionic
strength comparing to the Pitzer model for single ion activity
coefficient of hydrogen ion is in the acceptable range of error
(generally less than 1.4%).23
Speciation Comparisons. Figure 2 displays the speciation
measured by the method developed in this work compared to
Figure 2. MEA speciation as a function of carbon loading: this work at
21 °C, blank symbols; Jakobsen et al.,8 filled symbols; and Aspen Plus,
dotted and filled lines at 20 °C.
the Aspen Plus prediction and literature.8 The agreement
between data produced in this work using total carbon and
HCO3− analytical measurement with the data from Jakobsen et
al.8 and the Aspen Plus prediction are fairly good. As can be
seen at the intermediate CO2 loading (i.e., 0.3 to 0.45) the
predicted values for the total bicarbonate and carbonate
concentration reveals slightly different values. At increased
CO2 loading, 0.45 molCO2/molMEA, the predicted values for the
three different sources come closer. The bicarbonate
concentration determined in this work is higher than the data
from Jakobsen et al.,8 particularly in the range of 0.3 to 0.45
CO2 loading. However, as it is discussed by Jakobsen et al.,8
their data shows the average uncertainties of 10.1% and 11.7%
and the maximum uncertainties were 29.2% and 34.4% for data
at 20 and 40 °C, respectively, in electroneutrality. They also
pointed out that because of the sensitivity of their results to the
calibration method used, for the species with fractions <10%,
such as bicarbonate ion at low CO2 loadings, the quantitative
values are not valid.
As explained in the previous section, some approximations
were made for the method in this work. At low CO2 loading
(i.e. <0.3), the concentration of either carbonate or bicarbonate
are very low. Therefore, at the CO2 loadings in the range 0−
0.3, in fact, ignoring one of them (i.e. carbonate) and
incorporating its portion for the bicarbonate concentration
does not affect the general trend of the speciation for four
dx.doi.org/10.1021/ie300230k | Ind. Eng. Chem. Res. 2012, 51, 6613−6618
Industrial & Engineering Chemistry Research
major species concentrations in the solution including
bicarbonate (which is actually close to zero in this range),
free amine, protonated amine, and carbamate. At the CO2
loading between 0.3 to about 0.45, the bicarbonate to carbonate
concentration ratio rises from 2 to 10. This ratio might not be
high enough, so discarding the carbonate and/or incorporating
its portion in the solution as the bicarbonate mainly does not
affect the bicarbonate concentration in the general speciation
profile. With the above description and considering Figure 2, at
the CO2 loading higher than 0.45, ignoring the carbonate
concentration compared to the other species is completely
reasonable.
Figure 3 shows that the CO2 loading has a strong effect on
speciation. As can be seen from Figure 3, and discussed in detail
Figure 3. MEA speciation at 21 °C, this work, blank symbols;
Böttinger et al.,9 filled symbols, temperature 20 °C.
by Böttinger et al.,9 the species distribution of MEA−H2O−
CO2 shows that at low loadings practically all carbon dioxide is
chemically bound as carbamate. The carbamate concentration
increases linearly with carbon dioxide loading. With increasing
carbon dioxide loading, the concentration of protonated amine
increases while the unprotonated free amine concentration
decreases. This trend is almost linear up to a loading of about
0.5 molCO2/molMEA. At a loading of about 0.5 molCO2/molMEA,
the mole fraction of molecular amine has dropped to almost
zero. The amine is now either protonated or has reacted to
carbamate. With further increasing carbon dioxide loading, the
concentration of the protonated amine continues to rise, but
this can only occur at the expense of the carbamate, so that its
concentration begins to drop. The carbon dioxide now released
from the carbamate reacts to bicarbonate.
In fact, in the reported experimental values for the MEA
speciation data by NMR spectroscopy, generally up to the CO2
loading of about 0.4 (depending on the amine concentration),
the carbonate and bicarbonate mole fraction are close or equal
to zero.9 The values for the bicarbonate concentrations
determined in this work has at least an order of magnitude
difference with the reported experimental values mentioned in
the Figures 2 and 3 and Table S.1 in the Supporting
Information, despite the acceptable prediction for free amine
and protonated and carbamate concentration at the normal
CO2 loading. Regardless, Aspen over predicts the bicarbonate
concentration based on the ENRTL-RK model beyond even
the values obtained in this work. The same over prediction by
extended UNIQUAC was mentioned by Faramarzi et al.24 Of
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course, as it has been discussed by them, the mass balance in
the reported values for MEA speciation by NMR spectroscopy
displays considerable deviation at 40 °C temperature (about
30% AAD).9 The speciation data reported by Böttinger et al.9
did not include the free amine and protonated amine
concentration separately. Figure 3 shows the comparison of
the carbamate and total free amine plus protonated amine
concentrations determined in this work with data from
Böttinger et al. showing good agreement.9
Since the experimental speciation was conducted at room
temperature, while CO2 absorption conditions are typically
above this temperature, it was of interest how much
temperature affects speciation. As can be deduced from the
speciation data obtained by Jakobsen et al.8 at 20 and 40 °C
and mentioned in other published works,8,9,25 temperature has
a minimal effect on speciation. So, the same trends for the
amine speciation can be applied to typical absorption
temperatures. In terms of temperature effect, AspenPlus also
quantitatively shows no different patterns for speciation.
Therefore, based on this work and the literature, it can be
inferred that the speciation patterns has “no” or “very low”
temperature dependency.
Difference in Free Amine When Not Considering
Bicarbonate. Considering eq 16-b, the bicarbonate concen-
tration in the solution will affect the free amine concentration
in solution. Figure 4 shows the effects of bicarbonate
Figure 4. Calculated free amine (MEA) concentration with and
without considering the bicarbonate concentration term in eq 16-a at
21 °C.
concentration in free amine concentration in the solution as a
function of CO2 loading using speciation in comparison to a
simple approximation where each CO2 reacts with 2 amines. As
it is obvious from Figure 4, the bicarbonate portion in the total
alkalinity of the solution is increased with CO2 loading. While
at lean loading the impact is small, the difference at rich loading
is substantial. For example, considering a loading of 0.4 molCO2/
molMEA, a 29% increase in the amount of free amine is
calculated.
■
CONCLUSIONS
The versatile and quantitatively reliable method for amine
speciation determination is introduced. The procedure utilizes
two commonly used analytical methods for CO2 capture
dx.doi.org/10.1021/ie300230k | Ind. Eng. Chem. Res. 2012, 51, 6613−6618
Industrial & Engineering Chemistry Research
solvents total alkalinity and total CO2 loading. Another titration
using strong base is used for bicarbonate concentration
allowing for speciation to be determined. The quantitative
results for the different species concentration in MEA solution
is in good agreement with other available spectroscopic
methods, mainly NMR, particularly for the free amine,
carbamate, and protonated amine concentrations. The
AspenPlus predicted speciation also compared favorably with
the experimental data to further assess the data.
■
*
ASSOCIATED CONTENT
S Supporting Information
Additional tables and figures. This material is available free of
charge via the Internet at http://pubs.acs.org.
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: kunlei.liu@uky.edu .
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
The authors acknowledge the Carbon Management Research
Group (CMRG) members, including Big Rivers Electric
Corporation, Duke Energy, East Kentucky Power Cooperative
(EKPC), Electric Power Research Institute (EPRI), Illinois
Clean Coal Institute (ICCI), Kentucky Department of Energy
Development and Independence (KY-DEDI), Kentucky Power
(AEP), and LG&E and KU Energy, for their financial support.
■
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