Article

pubs.acs.org/IECR

CO2 Absorption into Aqueous Solutions Containing

3‑Piperidinemethanol: CO2 Mass Transfer, Stopped-Flow Kinetics,
1 13
H/ C NMR, and Vapor−Liquid Equilibrium Investigations
William Conway,*,† Yaser Beyad,‡ Marcel Maeder,§ Robert Burns,§ Paul Feron,† and Graeme Puxty†
†
CSIRO Energy Flagship, Mayfield West, New South Wales 2304, Australia
‡
CSIRO Energy Flagship, Clayton, Victoria 3169, Australia
§
Department of Chemistry, The University of Newcastle, Callaghan, New South Wales 2308, Australia
*
S Supporting Information

ABSTRACT: Global efforts to reduce carbon dioxide emissions stemming from the combustion of fossil fuels have
acknowledged and focused on the implementation of post combustion capture (PCC) technologies utilizing aqueous amine
solvents to fulfill this role. The cyclic diamine solvent piperazine has received significant attention for application as a CO2
capture solvent, predominantly for its rapid reactivity with CO2. A thorough investigation of alternative but simpler cyclic amines
incorporating a single amine group into the cyclic structure may reveal further insight into the superior kinetic performance of
piperazine and the wider applicability of such cyclic solvents for PCC processes. One such example is the cyclic monoamine 3-
piperidinemethanol (3-PM). To facilitate the evaluation of 3-PM as a capture solvent requires knowledge of the fundamental
chemical parameters describing the kinetic and equilibrium of the reactions occurring in solutions containing CO2 and 3-PM.
Additionally, in parallel with the preceding, experimental measurements of CO2 absorption into 3-PM solutions, including mass
transfer and vapor−liquid equilibrium measurements, can be used to validate the CO2 absorption performance in 3-PM solutions
and compared to that of monoethanolamine (MEA) under similar conditions. The present study is focused in two parts on (a)
determination of fundamental kinetic and equilibrium constants via the analysis of stopped-flow kinetic and quantitative
equilibrium measurements via 1H/13C nuclear magnetic resonance (NMR) spectroscopy and (b) experimental measurements of
CO2 absorption into 3-PM solutions via wetted wall column kinetic measurements, vapor−liquid equilibrium measurements, and
corresponding physical property data including densities and viscosities of the amine solutions over a range of concentrations and
CO2 loadings. Fundamental kinetic rate constants describing the reaction of CO2 with 3-PM are significantly faster than MEA at
similar temperatures (3-PM = 32 × 103 M−1 s−1, extrapolated to 40 °C from kinetic data between 15.0 and 35.0 °C; MEA = 13 ×
103 M−1 s−1, 40 °C). Conversely, the equilibrium constants describing the reaction between bicarbonate and amine, often termed
carbamate stability constants, are significantly lower for 3-PM than MEA at similar temperatures. Overall CO2 absorption rates in
3.0 M solutions of 3-PM and MEA, assessed in overall CO2 mass transfer coefficients, are lower in the former case over the entire
range of CO2 loadings from 0.0 to 0.4 mol of CO2 per mol of amine. The reduced absorption rates in the 3-PM solutions can be
attributed to higher solution viscosities and thus corresponding reductions in CO2 diffusion. CO2 absorption and cyclic capacities
in 3.0 M solutions of 3-PM and MEA were found to be significantly higher in the case of 3-PM. The larger CO2 capacities are
attributed to the lower stability 3-PM carbamate and the formation of larger amounts of bicarbonate compared to MEA. Overall,
the larger CO2 absorption capacity, cyclic capacity, and rapid kinetics with CO2 position 3-PM as an attractive CO2 capture
solvent.

1. INTRODUCTION Currently, the most viable and technologically capable

The generation and release of carbon dioxide stemming from
the combustion of fossil fuels for the production of electricity,
and the potential impacts (of these emissions) on the global
climate system, are among the most significant environmental
challenges of the modern era.1 It is generally acknowledged that
the polluting processes contributing to these underlying
emissions must be addressed in order to ensure future threats,
impacts, and disruptions, to the environment and society, are
minimized.2 In response to these issues, a conscious global
research effort is underway targeting methods which are
positioned to contribute to significant and immediate
reductions in the evolution of parasitic greenhouse gas
emissions.
process which can effectively achieve the required and
immediate reductions in CO2 emissions from fossil fuel
power generation is post combustion CO2 capture (PCC)
with subsequent storage of the captured CO2 gas in geological
formations. Alternatively, the capture CO2 gas can be utilized
for the purposes of enhanced oil recovery3 or as feedstock in
the manufacture of high value chemicals.4 An overview of the
current status of PCC technology indicates two common
roadblocks: large capital costs relating to the manufacture of the
Received: August 11, 2014
Revised: September 9, 2014
Accepted: September 22, 2014
Published: September 22, 2014

© 2014 American Chemical Society 16715 dx.doi.org/10.1021/ie503195x | Ind. Eng. Chem. Res. 2014, 53, 16715−16724
Industrial & Engineering Chemistry Research
absorption equipment and large and parasitic energy require-
ment for the PCC process which demands up to ∼30% of the
base-load output of a power station when PCC is deployed
(devoted to the operation of the capture equipment based on a
benchmark technology employing 30% (w/w) monoethanol-
amine solvent). 5−7 Any industrial realization of PCC
technologies will require improvements in the practical design,
size, and operation of current-generation PCC processes. Of
these, the simplest improvements to date have arisen from the
investigation of the chemical solvent. Higher efficiency and
rapid reacting solvents are favored in view of replacing typical
capture solvents such as monoethanolamine (MEA), methyl-
diethanolamine (MDEA), 1-amino-2-methyl-1-propanol
(AMP), ammonia (NH3), and piperazine (PZ).8,9 The latter
example involving PZ, a cyclic diamine, has been extensively
investigated for its rapid reactivity with CO2.10,11 While
kinetically attractive, several limitations are apparent including
low aqueous solubility, limited CO2 capacity at low PZ
concentrations, and issues relating to operation of the solvent
at high concentrations due to precipitation. Despite the
promising kinetic potential of PZ, the preceding issues indicate
that alternatives are required.11,12 In view of the promising
kinetic performance of PZ a selection of alternatives can be
derived from the similar subfamily of “cyclic monoamines”
which incorporate aspects of the parent piperazine structure. In
a recent screening study13 in which a series of 76 amines were
examined for their CO2 absorption rates and absorption
capacities, the cyclic monoamine 3-piperidinemethanol (3-PM)
was identified as an interesting and promising CO2 capture
solvent. 3-PM shares a cyclic structure similar to that of PZ
incorporating a single amine moiety into the ring structure;
however, unlike PZ, a methanol group is additionally attached
to the ring in the case of 3-PM. In view of the large absorption
capacity and CO2 absorption behavior, the preceding work has
been extended here to include a fundamental investigation of
the chemical reactivity in 3-PM solutions and investigations of
CO2 absorption in 3-PM solutions via wetted wall covering a
range of concentrations and CO2 loadings.
1.1. Outline. CO2 absorption into a series of 3-PM
solutions from 0.1 to 3.0 M and CO2 loadings in a 3.0 M 3-
PM solution from 0.0 to 0.4 mol of CO2 per mol of amine have
been investigated using a wetted wall column gas−liquid
contactor at 40 °C. CO2 solubility in a 3.0 M 3-PM solution
from 40 to 80 °C has been investigated using a vapor−liquid
equilibrium apparatus. The fundamental kinetic reactivity of 3-
PM in the absence of physical mass transfer phenomena, and in
equilibrium solutions, has been investigated using rapid
stopped-flow kinetic and 1H/13C NMR spectroscopic equili-
brium measurements, respectively.
1.2. Kinetic/Equilibrium Reaction Set. The absorption of
CO2 in aqueous amine solutions incorporates consecutive
contributions from the physical dissolution of CO2 (gas to
liquid phase) together with chemical reactions occurring in the
liquid phase which act to chemically consume dissolved
CO2(aq). The former process is described and quantified by
the temperature-dependent Henry’s constant in
pCO
HCO2 = 2
= 2.82 × 106e−2044/ T
cCO2 (1)
where HCO2 represents the Henry’s constant for CO2 solubility
in pure water at infinite dilution (kPa M−1), p is the partial
pressure of CO2 in the gas (vapor) phase above the liquid, and
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cCO2 is the dissolved concentration of CO2 in the liquid
(aqueous) phase.14,15
Once dissolved into solution, a series of parallel reactions
ensue between CO2(aq) and water (H2O), hydroxide (OH−),
and amine (R1R2NH where R1 and R2 are typically side groups
made up of carbon/hydrogen/oxygen/sulfur/nitrogen atoms in
the case of primary and secondary amines) to form carbonic
acid (H2CO3), bicarbonate (HCO3−), carbonate (CO32−), and
carbamic acid/carbamate (R1R2NCO2H/R1R2NCO2−), respec-
tively. The kinetic reactions are described in eqs 2−4.
k1
CO2 (aq) + H 2O XooY H 2CO3
k −1 (2)
k2
CO2 (aq) + OH− XooY HCO3−
k −2 (3)
k7
R1R 2NH + CO2 (aq) XooY R1R 2NCO2 H
k −7 (4)
Equilibrium reactions describing the protonation(s) of
chemical species in solution including those of hydroxide
(OH−), carbonate (CO32−), bicarbonate (HCO3−), carbamate
(R1R2NCO2−), and amine (R1R2R3N) are described in eqs
5−9.
K3
CO32 − + H+ ↔ HCO3− (5)
K4
HCO3− + H+ ↔ H 2CO3 (6)
K5
OH− + H+ ↔ H 2O (7)
K6
R1R 2NH + H+ ↔ R1R 2NH 2+ (8)
K8
R1R 2NCO2− + H+ ↔ R1R 2NCO2 H (9)
An alternative pathway leading to the formation of the
carbamate exists for primary and secondary amines via a
reaction with HCO3− as described in
k9
R1R 2NH + HCO−3 XooY R1R 2NCO2− ( +H 2O)
k −9 (10)
The kinetics of this reaction has also been observed by 1H
NMR spectroscopy.16,17 The significantly slower rate of this
reaction in competition with reactions of CO2 with hydroxide
and amine (eqs 3 and 4) was found to have a negligible impact
on the analysis of absorption flux data obtained from
absorption measurements in a wetted wall contactor and
kinetic stopped-flow measurements.18 Thus, the reaction does
not appear in the kinetic model for the analysis of stopped-flow
and wetted wall measurements. However, the equilibrium
constant for the pathway is typically used to describe the
stability of carbamates and appears exclusively in the model for
the analysis of 1H NMR data here.
1.3. Chemical Constant Data and Activity Coefficient
Corrections. Values for the kinetic and equilibrium constants
for the reactions described in eqs 2, 3, and 5−8 were taken
from the literature.19−21 Kinetic constants for the formation of
the carbamic acid in eq 4, and the carbamate stability constant
in eq 10, were regressed from the stopped-flow kinetic and
NMR equilibrium measurements here, respectively. Values for
the protonation constant of the carbamic acid, log K8, eq 9,
were determined in the kinetic analysis using the equilibrium
dx.doi.org/10.1021/ie503195x | Ind. Eng. Chem. Res. 2014, 53, 16715−16724
Industrial & Engineering Chemistry Research
constant data for eq 10, log K9, determined in the independent
1
H NMR analysis, and the equilibrium constants log K1, log K4,
and log K7 (calculated as K7 = k7/k−7) from eqs 2, 6, and 4,
respectively, via microscopic reversibility as K8 = K7K4/K1K9.
Activity coefficient corrections were applied in the
calculations using the Debye−Hückel approximation and a
reduced version of the specific interaction theory (SIT) for
charged species. The former was used in the analysis of
fundamental kinetic and 1H NMR measurement data while the
latter was used in the analysis of wetted wall column and
vapor−liquid equilibrium (VLE) measurements. All calculated
values correspond to standard state conditions at infinite
dilution at zero ionic strength. The Debye−Hückel and SIT
expressions are shown in eqs 11 and 12.
Az i 2 μ
log γi =
1+ μ (11)
Az i 2 μ
log γi =
1 + 1.5ρ−1/2 μ (12)
where γi is the activity coefficient, A = (1.8248 × 10 )/ (eT)3/2
6 concentrations of amine ([3-PM] tot ) and bicarbonate
is the Debye−Hückel law slope, ρ is the density of water (kg
dm−3), μ is the ionic strength (mol dm−3), and zi is the charge
of species i.
2. EXPERIMENTAL SECTION
2.1. Chemicals. High-purity carbon dioxide gas (CO2, BOC
Gases Australia, 99.99% purity), N2 (Coregas, 99.99%),
potassium bicarbonate (KHCO3−, BDH), sodium carbonate
(Na2CO3, BDH), potassium hydrogen phthalate (AJAX),
sodium hydroxide solid (Merck), 3-piperidinemethanol (3-
PM, Suzhou Rovathin Pharmatech), and hydrochloric acid
(AJAX) were all used as obtained. The concentrations of
sodium hydroxide and 3-PM were standardized by potentio-
metric titrations. A stock solution of sodium hydroxide was
initially titrated with potassium hydrogen phthalate (KHP)
standard, and this solution was used to standardize the
concentration of the hydrochloric acid stock solution. A
known amount of the standardized hydrochloric acid solution
was added to the 3-PM solution and back-titrated to high pH
with standardized sodium hydroxide solution. All solutions
were prepared using ultrahigh purity milli-Q water which was
further boiled to remove dissolved CO2 gas.
2.2. 1H/ 13C NMR Spectroscopy. 2.2.1. Acquisition.
Quantitative proton (1H) and carbon (13C) NMR spectra
were acquired on a Bruker Avance Ascend 600 NMR
spectrometer operating at a frequency of 600.213 MHz. Proton
1
H spectra were obtained as the average of 16 scans with a pulse
delay time (D1) of 1 s. Inverse-gated decoupled 13C spectra
were obtained at a pulse angle of 30° (zgig30 pulse program,
Bruker) as the average of 128 scans with a pulse delay time
(D1) of 60 s, corresponding to a value ∼5 times that of the T1
relaxation time of the slowest relaxing carbon (typically
carbamate/HCO 3 − ). Additional one-dimensional (1-D)
DEPT135 13C and two-dimensional (2-D) HSQC spectra
were measured and utilized in the assignment of spectral peaks
corresponding to 3-PM and its carbamate. These spectra are
available in Figures S1 and S2 in the Supporting Information.
TSP (3-(trimethylsilyl)propionic acid-d4, sodium salt) dissolved
in D2O in a sealed glass capillary insert was present in the NMR
tube acting as the external reference and locking agents,
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respectively. The chemical shift of the TSP standard was
assumed constant and unaffected by temperature over the
narrow range of temperatures investigated in the NMR
measurements here. All samples were tightly capped and sealed
with para film tape so as to minimize any loss of CO2 gas from
the samples during equilibration and measurement. The
concentrations were chosen here to ensure the solution
CO2(aq) concentration did not exceed the solubility at normal
pressure. Solutions were thermostated in a temperature
controlled water bath until equilibrium was completely reached
(determined when no further change in the spectrum was
observed). The set point temperature was maintained internally
within the instrument (±1 °C) during the acquisition of
spectra.
2.2.2. Spectral Processing and Peak Integration. 1H and
13
C NMR spectra were processed individually using Bruker
Topspin 3.0.1.b software. A baseline correction (polynomial)
was applied to all spectra prior to the integration of peaks.
Spectral peaks corresponding to amine and carbamate were
integrated in the topspin software, and the total concentrations
of 3-PM and its carbamate calculated from the total
([HCO3−]tot) in the solution. The average integrals of 13C
signals for the aliphatic carbons in 3-PM and its carbamate were
used in the equilibrium analysis of the low concentration
samples at 25.0 °C for comparison to the 1H data.
2.2.3. NMR 3-PM/Na2CO3/HCl Titration Samples. A series
of equilibrium samples were prepared in 5 mm diameter NMR
tubes containing the TSP/D2O capillary insert by dosing
various amounts of a concentrated HCl solution (4.0 M) into
1.5 mL of an equilibrated carbamate solution initially
containing 0.5 M 3-PM and 1.0 M Na2CO3. The series of
additions were designed to cover the approximate range of pH
conditions over which carbamates are typically observed (pH
12−8). A duplicate series of samples containing 1.0 M 3-PM
and 1.8 M Na2CO3 dosed with various volumes of HCl were
prepared and analyzed in parallel.
2.3. Stopped-Flow Kinetics. Fast reaction kinetics were
performed on an Applied Photophysics DX-17 stopped-flow
spectrophotometer equipped with a J&M Tidas MCS 500-3
diode array detector.22 The absorbance changes of acid−base
indicators, corresponding to changes in the pH of the solutions
upon reaction of solutions in the stopped flow, were observed
over the wavelength region from 400 to 700 nm. All solutions
were thermostated and maintained at the set point temperature
((15.0−35.0) ± 0.1 °C) by a circulating Julabo F20 water bath.
The exact temperature of the solution was monitored by a
thermocouple located inside the stopped-flow absorption cell
block.
2.3.1. Reaction of CO2(aq) with 3-PM and Decomposition
of 3-PM Carbamate. First, the formation of 3-PM carbamate
was investigated by reacting equal volumes of a CO2(aq)
solution (4.35 mM), with a series of 3-PM solutions ([3-PM]0
= 1.0−10.0 mM), in the presence of 0.05 mM alizarin red S and
12.5 μM thymol blue indicators, in the stopped flow. Initially,
CO2(aq) solutions were prepared by bubbling a mixed gas
containing CO2 and N2 into a water solution located in a small
sample reservoir above the drive syringe in the stopped flow.
The initial concentration of CO2(aq) in this solution was
determined from the CO2 partial pressure in the gas stream
(adjusted by gas flow controllers), and the corresponding
Henry’s constant for CO2 solubility in water. Ideal behavior and
dx.doi.org/10.1021/ie503195x | Ind. Eng. Chem. Res. 2014, 53, 16715−16724
Industrial & Engineering Chemistry Research
uniform mixing of the gases in the gas stream was assumed
here.
Second, the decomposition of 3-PM carbamate at low pH
conditions was investigated by reacting a preequilibrated
carbamate solution with hydrochloric acid solutions in the
stopped flow. Initially, a carbamate solution containing 0.025 M
3-PM and 0.05 M HCO3− was prepared and equilibrated for 24
hours at the desired temperature. The composition of the
equilibrated carbamate solution was determined quantitatively
using 1H NMR spectroscopy prior to the stopped-flow
measurements. This equilibrated carbamate solution was
further reacted in the stopped flow with a series of hydrochloric
acid solutions to establish the decomposition reaction kinetics.
Absorbance changes of 0.05 mM alizarin red S and 0.025 mM
methyl orange indicators, and subsequently changes in the pH
of the solutions due to the decomposition of 3-PM carbamate,
carbonic acid, and bicarbonate, and protonation of amine, were
monitored.
The preceding series of reactions were repeated over a range
of temperatures from 15.0 to 35.0 °C to establish the
temperature dependence of the reactions. Measurements were
repeated a minimum of four times to accommodate a statistical
analysis of the regressed kinetic and equilibrium parameters
which were compared to the standard deviations produced in
the software. Analysis of the kinetic and equilibrium data was
performed using ReactLab Kinetic and Equilibrium software
packages (www.jplusconsulting.com) and in-house extensions
of the software written in Matlab.
2.4. Wetted Wall Column. Absorption of CO2 into
individual aqueous solutions of 3-PM and MEA was performed
using a wetted wall column gas−liquid contactor at 40 °C.
Briefly, a stainless steel column with an effective height and
diameter of 8.21 cm and 1.27 cm, respectively, was used here.23
CO2 absorption flux, NCO2, into approximately 0.6 L of amine
solution was measured over a range of CO2 partial pressures
spanning 1.0−20.0 kPa. The total liquid flow in the apparatus
was maintained at 121.4 mL·min−1 (2.02 mL·s−1) by a
Masterflex peristaltic pump. The liquid flow was monitored
using a calibrated liquid flow meter. The total gas flow rate in
the system was maintained at 5.0 L min−1, and the desired
composition of the gas (i.e., CO2 partial pressure) established
by variation of Bronkhorst mass flow controllers, calibrated for
CO2 and N2 gases, respectively. The composition of the gas
stream entering and exiting the wetted wall column, expressed
in vol % CO2, was continuously monitored using a Horiba VA-
3000 IR gas analyzer. The former was measured at each CO2
partial pressure while bypassing the wetted wall column with
the gas stream passing directly to the Horiba gas analyzer.
2.4.1. CO2 Absorption Flux (NCO2) and Overall Mass
Transfer Coefficients (KG). The amount of CO2 absorbing into
the amine liquid was determined from the relative amount of
CO2 in the gas stream entering (bottom) and exiting (top) the
wetted wall column. The CO2 absorption flux, expressed as
millimoles of CO2 absorbed per second, per unit area (mmol·
s−1·m−2) of contact between liquid amine and gas, was
determined over a range of CO2 partial pressures in each of
the amine solutions. The preceding procedure was repeated for
each of the amine solutions including those preloaded with
different amounts of CO2.
Overall mass transfer coefficients, denoted here as KG, were
determined from plots of the absorption flux, NCO2, against the
applied driving force, PCO2. The latter was determined as the
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logarithmic mean of the inlet and outlet CO2 partial pressures.
The linear slope of the NCO2 against PCO2 plot is equal to the
overall mass transfer coefficient, KG. The interested reader is
directed to Darde et al.24 and Puxty et al.18 for a comprehensive
description of the relationships between CO2 diffusion and
chemical reaction during absorption of CO2 into an amine
liquid and the mathematical principles of the absorption
processes.
2.5. Density and Viscosity. Density and viscosities of the
amine solutions were determined using a combined Anton Parr
DMA-38 density meter (±0.001 g/mL) and AMVn viscometer,
at each of the required temperatures. Density and viscosity
measurements were repeated in triplicate, and the resulting
value is the average of these repeats. Density and viscosity data
as a function of 3-PM and MEA concentrations from 0.5 to 6.0
M, and in 3.0 M 3-PM and MEA solutions and CO2 loadings
from 0.0 to 0.4 mol CO2/mol amine, are presented in Figures
S3−S6 in the Supporting Information.
2.6. Vapor−Liquid Equilibrium. CO2 solubilities in 3.0 M
solutions of 3-PM and MEA were determined using a Parr VLE
apparatus from 40 to 80 °C.25 The equilibrium distribution of
CO2 between gas and liquid phases in each of the amine
solutions was investigated by sequentially dosing CO2 gas from
a Swagelok CO2 cylinder, into a known volume of amine
solution (100 mL), contained in a sealed and thermostated
glass reaction vessel (Parr). The precise amount of CO2 dosed
into the vessel was determined by variation in mass of the CO2
cylinder before and after dosing, which was suspended from an
analytical balance (Mettler Toledo pb4002-s). Initially, and
prior to CO2 dosing, the vessel was repeatedly charged with
ultrapure N2 gas to ensure all gas impurities were removed from
the gas lines and gas headspace of the vessel. Following the N2
flush, stirring of the amine solution was initiated and
maintained at ∼500 rpm until steady state conditions were
reached as indicated by constant gas pressure reading
(Swagelok S model transducer) and constant temperature
(thermocouple). Total gas phase pressure and temperature in
the reactor were monitored throughout the measurements
following each dosing of CO2, until steady state/equilibrium
was again reached. Once steady, the proceeding CO2 dosing
was initiated. From the total reactor pressure at each steady
state, and CO2 dosing, the total amount of CO2 remaining in
the gas phase, subtracting contributions to the total reactor
pressure from water vapor and initial N2, and the subsequent
CO2 loading in the amine liquid were calculated according to
eqs 13−15
(Pvessel(tot) − PH2O(vap) − PN2)Vgas
nCO2(gas) = Z
RT (13)
nCO2(liquid) = nCO2 (dose) − nCO2(gas) (14)
loading CO × α = nCO2(liquid)/namine
2 (15)
where nCO2(gas) is the moles of CO2 gas, Z is the compressibility
of CO2, Pvessel(tot) is the total pressure as measured inside the
vessel at steady state, PH2O(vap) is the vapor pressure of water,
PN2 is the partial pressure of nitrogen, Vgas is the volume of the
gas phase (total vessel volume−amine liquid volume in m3), R
is the gas constant (8.314 J·(mol·K)−1), T is the temperature
(K), nCO2(dose) is the moles of CO2 dosed, nCO2(liquid) is the moles
of CO2 dissolved into the amine solution, and namine is the
dx.doi.org/10.1021/ie503195x | Ind. Eng. Chem. Res. 2014, 53, 16715−16724
Industrial & Engineering Chemistry Research Article

moles of amine in solution. Given the large molecular weight

k denotes rate constant; K denotes equilibrium constant and is calculated as Ki = ki/k−i. Numbers in parentheses represents standard deviation in the last digit. MEA data included for comparison. bk(T)
ΔS° (J mol−1 K)
and polarity of 3-PM, and the presence of the polar hydroxyl

−40(10)

81(12)
−43(7)

17(1)
group which can participate in hydrogen bonding interactions,
it was assumed that the amine vapor pressure is too low to

van’t Hoffd
provide an observable contribution to the total measured
pressure.

ΔH° (kJ mol−1)

6.3(2) × 10−3
3. RESULTS AND DISCUSSION

−23(3)
−23(2)
−19(3)
3.1. Kinetics. 3.1.1. Stopped-Flow Studies. The complete
series of kinetic measurements, including measurements of

17
carbamate formation and decomposition, were analyzed in a
single global fit at each temperature. The resulting analysis

ΔS⧧ (J mol−1 K)
produced kinetic and equilibrium constants for the reversible

74(8)

112(8)
−47(3)
−4(7)
formation of 3-PM carbamate, k7 and k−7, eq 4, and the
protonation constant of 3-PM carbamate, K8, eq 9, at each

Eyringc
temperature. Corresponding equilibrium constants for the
carbamate pathway in eq 4 were also calculated from the

ΔH⧧ (kJ mol−1)

ratio of the formation and decomposition rate constants as K7 =

73(3)

96(3)
38(1)
61(2)
k7/k−7. Subsequent analysis of the kinetic constants and their
temperature dependencies using the Arrhenius, Eyring, and

Table 1. Kinetic and Thermodynamic Data Describing the Reversible Formation of 3-PM Carbamate/Carbamic Acida
van’t Hoff relationships resulted in standard activation energies,
Ea, enthalpies, ΔH⧧/ΔH°, and entropies, ΔS⧧/ΔS°, of the
reactions, respectively. The calculated kinetic and thermody-

1.15 × 1019
17

5.8× 1010
1.0× 1013
1.17× 10
namic data are presented in Table 1.

A
Arrheniusb
From the data provided in Table 1 all kinetic values were
found to increase with temperature. A comparison of the
kinetic constants, k7, and the equilibrium constant, K7, for 3-PM
76(3)

98(3)
41(8)
63(2)
and MEA reveals consistently larger values for 3-PM at similar
Ea

temperatures. The underlying reason for this trend relates to

the relative basicities of the amines, 3-PM being ∼1.0 unit
4
1.98(5) × 10

= A exp(−Ea/RT). ck(T) = (k′T/h) exp((ΔH⧧ − TΔS⧧)/RT). dK(T) = exp(−(ΔH°/RT) + (ΔS°/R)).

2.4(3) × 102
7.6(4) × 103
1.9(3) × 102
larger than MEA at similar temperatures. We have previously
35.0 °C

investigated the intimate relationships26 between the kinetic

7.06(4)
81(17)

6.6(1)
41(6)
and equilibrium constants of carbamates and the protonation
constant of the amine. It was typically found that amines with
larger protonation constants resulted in large kinetic constants
3

4.9(2) × 103

1.1(1) × 102
8.2(5) × 10

in interactions with CO2. The resulting data for 3-PM here are
25.0 °C

consistent with this trend where the larger protonation constant

7.28(2)

6.4(1)
73(5)

90(8)

54(4)

of 3-PM correspondingly renders it as a faster reacting amine by

promoting stronger interactions with CO2. This is largely due
to the apparent size of the lone electron pair on the nitrogen
3

2.7(1) × 103

1.6(3) × 102
2.6(4) × 10

(amine group) which, in turn, increases the effective

15.0 °C

nucleophilic reactivity of the amine group toward CO2

16.8(2)

7.52(3)

6.3(5)
35(1)

76(5)

molecules. Conversely, the stability of 3-PM carbamate, as

outlined in the equilibrium constants log K9, is substantially
lower than the corresponding MEA carbamate. Molecular
log (K8/M−1)

log (K8/M−1)
s )

k7 (M−1 s−1)
−1

explanations for the reduced carbamate stability in the case of

constant

K7 (M−1)
K7 (M−1)
k−7 (s−1)

k−7 (s−1)

3-PM are complex and may reside from a combination of

−1
k7 (M

electronic and steric contributions, the latter forming the most

probable explanation where weak steric hindrance imposed by
the relatively close proximity of the large and bulky ethanol tail
3-PM

3-PM

3-PM
MEA

MEA

MEA

to the amine group, and thus the carbamate when formed, may
dissociate under particular conditions. Furthermore, it has been
suggested that the formation of intramolecularly hydrogen
RNH 2 + CO2 (aq) XoooY RNHCO2 H

RNHCO2− + H+ ↔ RNHCO2 H

bonded ring structures may contribute to decreased carbamate

stability.16 The Arrhenius activation energy for 3-PM
determined here is significantly larger than the corresponding
k−7

value for MEA and some other aliphatic amines, the values of
k7
reaction

K8

which are typically in the range of 40−65 kJ/mol. Chemical

explanations for the large values are unclear, however activation
energies reported in the literature for the cyclic amines such as
piperdine and pyrrolidine, 75.9 and 79.9 kJ/mol, respectively,
are similarly larger and close to the activation energies reported
here for 3-PM.27
a

16719 dx.doi.org/10.1021/ie503195x | Ind. Eng. Chem. Res. 2014, 53, 16715−16724

Industrial & Engineering Chemistry Research
3.1.2. CO2 Absorption Flux, NCO2, and Overall Mass
Transfer Coefficient(s), KG. Overall mass transfer coefficients
are critical parameters of amines in the assessment of their CO2
absorption performance. Typically, KG values relate directly to
the absorption area and packing requirements for the capture
process. Overall CO2 absorption rates into 3-PM and MEA
solutions over a range of amine concentrations and CO2
loadings from 0.0 to 0.4 mol of CO2 per mol of amine were
investigated here at 40 °C using a wetted wall column.
Although CO2 absorption into MEA solutions has been
extensively investigated, a spread in published data relating to
experimental variations justifies the repeated measurement of
the data here to allow a consistent comparison. Due to the
limited solubility of 3-PM in aqueous solution the upper
concentration was limited to 3.0 M. Similarly, measurements up
to 3.0 M for MEA were completed and data from 3.0 to 5.0 M
were taken from our previous study and used in the
comparisons here. It should be noted that segments of
nonlinearity were observed in the CO2 flux data for 3-PM. In
such cases, only the linear region of the flux curve was
considered in the calculation of KG values.
3.1.2.1. Effect of 3-PM and MEA Concentration(s) on KG
Values. KG data for CO2 absorption into 3-PM and MEA
solutions as a function of amine concentration, at zero CO2
loading, are presented in Figure 1. Despite larger kinetic
Figure 1. Overall mass transfer coeffeicients at 40 °C, KG, in 3-PM and
MEA solutions as a function of amine concentration.
constants for the reaction of CO2(aq) with 3-PM, the
corresponding trend from the stopped-flow data where 3-PM
is reacting significantly faster than MEA is reversed in the KG
data. From Figure 1, CO2 absorption rates were found to be
comparable at low amine concentrations up to 1.0 M; however
the trend in KG increases more rapidly with increasing amine
concentration in the MEA solutions beyond 1.0 M.
Interestingly, a plateau in KG is observed along the sequences
at higher amine concentrations where KG increases only
marginally with progressive increases of the amine concen-
tration above 2.0 and 3.0 M for 3-PM and MEA, respectively.
Concomitant changes in the physical properties of the amine
solutions as the amine concentration is increased are the
dominant causes of the effect. Any significant increases in KG
with increasing amine concentration above the aforementioned
concentrations are counterbalanced by parallel increases of the
solution viscosities which impact diffusion related processes
occurring in the solution. Further consideration should be given
to the preceding trends with respect to the individual amines.
The slower overall CO2 mass transfer in the 3-PM solutions is
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attributable to the fact that the viscosity increases by a larger
extent as the 3-PM concentration is increased, relative to MEA.
This increased viscosity inhibitively acts to lower the diffusion
coefficients of species in the liquid phase which, in turn, offsets
the kinetic benefit of 3-PM and the larger reaction rate constant
in its reaction with CO2. Given the considerable structural
variations between 3-PM and MEA, specifically the large rigid
cyclic ring structure in 3-PM, as opposed to the small free
rotating chain structure of MEA, the observed increases in KG
are easily justified.
It should be emphasized that while it appears the amine
concentration has only a minor impact on KG at higher amine
concentrations (plateau region in Figure 1), considerable
advantages in terms of the overall absorption uptake and
CO2 capacity when operating the solvent at higher amine
concentrations justifies the pursuit of more concentrated amine
solutions.
3.1.2.2. Effect of CO2 Loading on KG in 3.0 M Amine
Solutions. A comparison between the CO2 absorption
performance in 3-PM and MEA solutions, including solutions
over a range of CO2 loadings, was performed here. Selected KG
data for individual 3.0 M solutions of 3-PM and MEA and for
CO2 loadings from 0.0 to 0.4 mol of CO2 per mol of amine are
presented in Figure 2. Overall, CO2 absorption is slower in the
Figure 2. Overall mass transfer coefficients at 40 °C, KG, for 3.0 M
solutions of 3.0 M 3-PM and MEA and for CO2 loadings from 0.0 to
0.4 mol of CO2 per mol of amine.
3-PM solutions over the entire range of CO2 loadings.
Although the KG values decrease with increasing CO2 loading,
consistent with decreasing amounts of the free reactive amine
for reactions with CO2 in solution, the magnitude of the
decrease is reasonably constant and linear with increasing CO2
loading for both 3-PM and MEA. The observed decrease in KG
with increasing CO2 loading is induced by the changing
chemical and physical properties of the solutions with
increasing CO2 loading; first the reduced availability of free
amine and second changes in the physical properties of the
solutions resulting from the increased concentration of ionic
species (carbamate, bicarbonate, carbonate, and protonated
amine) and the ensuing interactions of these species. From a
theoretical perspective, and in order to compete with MEA at
similar concentrations and CO2 loadings, it is possible that the
3-PM solvent could be operated at slightly elevated temper-
atures which may result in a corresponding increase in the CO2
absorption rate. While the prospect of larger KG values at higher
temperatures is attractive, the effect on diffusion and CO2
solubility may, in parallel, impede such efforts. Similar
dx.doi.org/10.1021/ie503195x | Ind. Eng. Chem. Res. 2014, 53, 16715−16724
Industrial & Engineering Chemistry Research
arguments can be made for the operation of MEA at elevated
temperatures; however the penalty to the absorption capacity,
which is lower at higher temperatures, does not justify the
pursuit for greater mass transfer rates. Conversely, given the
larger absorption capacity of 3-PM, it can potentially sustain
such a trade-off between larger KG values and CO2 capacity.
3.1.3. CO2 Mass Transfer Predictions. Experimental
absorption flux and mass transfer data have been predicted
using the kinetic (rate) and equilibrium constants describing
the reaction of CO2 with 3-PM from the independent stopped-
flow kinetic study. A simple extrapolation of the kinetic
constants to 40 °C via the Arrhenius expression was conducted
in the absence of measured values. An in-house software tool
developed in Matlab was used for the prediction of molar CO2
absorption fluxes occurring in the amine film during absorption
based on a comprehensive diffusion and chemical reaction
model.18,28,29 In the absence of measured values, diffusion
coefficients and CO2 solubility in the solutions were calculated
using correlations for these properties and the measured
density and viscosity data.29 Experimental CO2 absorption data
in the 3-PM solutions were predicted with the overall
agreement between the measured and predicted absorption
fluxes assessed in a parity plot as presented in Figure 3.
Figure 3. Parity plot of measured and calculated absorption flux in 3-
PM solutions at 40 °C and zero CO2 loading.
The agreement between measured and model calculated flux
data is satisfactory in the amine solutions, in the absence of
preloaded CO2, over the entire range of 3-PM concentrations.
The average absolute deviation (AAD) over the entire series is
14.3%. Considering the dynamic nature of the experimental
measurements where small variations in the expected CO2
loading of the solution from the mass difference method
translate into significantly large deviations in the modeling
results, and the simple estimations for the film properties (film
thickness, exposure time, and diffusion coefficients) in the
model, the result can be considered satisfactory. Overall, the
Table 2. Equilibrium Constant Data for the Formation of 3-PM Carbamate Determined from the Analysis of 1H NMR
Measurements at 15.0−45.0 °C
reaction constant NMR sample
K9 log (K9/M−1) 1
H high concn
RNH 2 + HCO3− ↔ RNHCO2− (+ H 2O)
1
H low concn
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determination of fundamental chemical constants and their
application to the prediction of realistic absorption flux data are
broadly demonstrated.
3.2. Equilibrium Studies. The equilibrium performance
and CO2 capacity are critical properties in the selection of an
amine solvent which ultimately defines the overall energy
demand of the desorption step. Two approaches are typically
employed for the investigation of equilibrium behavior in amine
solutions; fundamental investigations of chemical equilibrium
constants relating to the formation of carbamates and direct
measurements of CO2 solubility in a batch type reactor. The
former reveals intimate information about the energy related to
the formation (and destruction) of the carbamate (C−N
bonds). Such information is additionally and fundamentally
useful in the selection of novel solvents and in the prediction of
equilibrium species distribution in CO2−amine solutions.
Direct measurements of the equilibrium CO2 absorption
capacity, as a function of increasing CO2 loading, based on
measurements of the equilibrium CO2 partial pressure in the
gas phase behavior, are principally simpler but do not carry
information about the chemical speciation in the solutions. We
have investigated both of these aspects here using 1H/13C
NMR spectroscopy and direct measurements of CO2 solubility
via VLE measurements. The results of these studies are
presented and discussed in the following.
3.2.1. 1H/13C NMR Investigations: Carbamate Stability
Constants. The robust determination of equilibrium constants
describing the formation of carbamates, also commonly termed
carbamate stability constants, ideally requires a series of
measurements covering a range of pH conditions where the
carbamate is present in measurable and quantifiable amounts.
Simpler investigations which involve the extraction and analysis
of liquid samples from equilibrated amine solutions via NMR,
the solutions of which are typically prepared with increasing
amounts of CO2 sparged into the amine solutions, are prone to
significant error. In favor of this approach we have chosen to
perform a series of acid−base titrations of solutions containing
3-PM and Na2CO3, with various amounts of hydrochloric acid,
to establish a series of samples covering the typical range of pH
conditions where the carbamate is present and at a fixed amine
concentration and CO2 loading. This approach allows the
accurate preparation and delivery of both the amine and CO2
(as CO32− initially) to the sample without introducing small but
often significant errors associated with evaporative losses (both
solvent and water) during the CO2 bubbling and liquid
sampling processes and gaseous loss of CO2 from the samples.
In an effort to establish the existence of any underlying
effect(s) of concentration on the resolution and sensitivity of
the NMR technique for the analysis of CO2/amine systems, we
have prepared duplicate series of samples at both low and high
amine and CO32− concentrations, respectively. Additionally,
selected samples have been analyzed in parallel via 13C
measurements at 25.0 °C and the resulting integrals of the
van’t Hoff
ΔH° ΔS°
15.0 °C 25.0 °C 35.0 °C 45.0 °C (kJ mol−1) (J mol−1 K)
0.93(1) 0.84(1) 0.76(1) 0.67(1) −14.8(1) −34(1)
0.95(1) 0.86(1) 0.78(1) 0.71(1) −13.9(5) −30(2)
dx.doi.org/10.1021/ie503195x | Ind. Eng. Chem. Res. 2014, 53, 16715−16724
Industrial & Engineering Chemistry Research
13
C spectra compared to the analysis of the corresponding 1H
spectra. A typical series of 1H and 13C NMR spectra at 25.0 °C
in the equilibrium solutions containing 0.5 M 3-PM and 1.0 M
Na2CO3 in the presence of additional amounts of HCl are
presented in Figures S7 and S8 in the Supporting Information.
Analysis of the concentration data obtained from the
integration of the carbamate and amine peaks in the NMR
spectrum, together with the initial concentrations of the amine
and Na2CO3 in the solutions, were analyzed using an
equilibrium chemical model incorporating reactions 5−10.
The analysis resulted in values for the carbamate stability
constant, K9, at each of the temperatures from 15 to 45 °C.
Selected fits of the concentration data are shown in Figure S9 in
the Supporting Information. The resulting values for K9 at each
of the temperatures, together with corresponding thermody-
namic values determined from subsequent analysis of the
temperature dependencies (of the equilibrium constants) via
the van’t Hoff relationship, are shown in Table 2.
The equilibrium constants and temperature dependences are
similar for the two series of solutions, confirming the effect of
concentration on the determination of equilibrium constants is
minimal here. Integrals determined from the analysis of 13C
data at 25.0 °C are similar to the corresponding 1H data and
were generally within ∼30% of each other. While the difference
between the 1H and 13C results may appear somewhat large,
the discrepancy relates to the sensitivity of the technique to the
13
C signal and relatively low abundance of the 13C isotope
(∼1% of the 12C isotope abundance). Thus, the integration of
small peaks close to the signal baseline is complex and prone to
slightly larger errors. The case is more relevant for amines such
as 3-PM where the carbamate is not present at significant
concentrations despite the use of high amine concentrations
here. However, both 1H and 13C NMR could be considered
suitable for the analysis of CO2/amine solutions where the
amount of carbamate formed is reasonably high so as to
minimize issues relating to the sensitivity of the NMR signal to
carbamate concentration. A significant limitation of the NMR
method here is the formation of CO2 gas bubbles resulting
from the reduced solubility at low pH. Thus, the investigation
of equilibrium behavior at significantly higher, and industrially
relevant, amine concentrations is not possible without
significant modification of the procedure. While the conditions
here result in adequate and quantifiable amounts of carbamate,
the formation of considerable amounts of CO2 gas (bubbles) in
the solutions at lower pH conditions somewhat restrict the
method and analysis. Moreover, for this reason the inclusion of
a reaction defining the protonation of the carbamate into the
chemical model, K8, was found to have little impact on the
quality of the data fitting. Thus, this reaction is essentially not
defined in the measurements here.
3.2.1.1. Comparison of log K9 Values with MEA and Other
Cyclic Amines. A comparison of the carbamate stability
constants and thermodynamic values here with the correspond-
ing values for MEA and a series of cyclic amines in our previous
work reveals several similarities.16 The average value (from the
low and high concentration NMR series) for log K9 = 0.84 at
25.0 °C here is considerably lower than the corresponding
value for the unhindered parent cyclic amine piperidine (log K9
= 1.38) and is aligned with the lower end of the range of values
(log K9 = 0.79−2.69) for sterically unhindered cyclic secondary
amines at similar temperatures. Considering the stability of 3-
PM carbamate is potentially influenced by the formation of an
intramolecularly hydrogen bonded structure, any further
16722
Article
convolution of this behavior on the magnitude of stability
constants is highly complex and beyond the scope of this work.
The temperature dependence of log K9 here, expressed in the
ΔH° values, is within the range of values for similar cyclic
secondary amines we have assessed previously. The use of
lower amine concentrations in our previous study, and the
observation (or not) of carbamates in similar hindered amines
to 3-PM with alcohol groups in close proximity to the reactive
amine group, further complicates any in-depth analysis of any
trends.
3.2.2. Vapor−Liquid Equilibrium. Direct measurement of
CO2 solubility in 3.0 M solutions of 3-PM and MEA at 40.0 to
80.0 °C were performed using a vapor−liquid equilibrium
apparatus. CO2 solubility data for a 3.0 M 3-PM solution is
presented graphically in Figure 4.
Figure 4. Equilibrium CO2 partial pressure as a function of CO2
loading in a 3.0 M 3-PM solution from 40 to 80 °C. The solid black
line corresponds to 15 kPa CO2 partial pressure (15% CO2).
From the data in Figure 4 the gas phase CO2 partial pressure
increases marginally with increasing CO2 loading at low
loadings and rapidly at high loadings above 0.3 at each of the
temperatures. The highest CO2 solubility is observed at low
temperatures, which decreases significantly with increasing
temperature. Further changes in the CO2 partial pressure with
increasing CO2 loading above ∼15 kPa are similar at each of the
temperatures. While the quality and definition of the data at
low CO2 loadings are somewhat discerning, related to the
limited sensitivity of the pressure measurements at very low
loadings below 20 kPa, the data presented here are useful for
the purpose of defining the approximate absorption capacity of
the solvents. Such effects are commonly encountered in VLE
measurements.
Absorption capacities, expressed on a moles per mole basis,
at 40 °C and 15 kPa CO2 partial pressure (from the data),
together with estimated cyclic capacities calculated from the
absolute difference in CO2 loading from 40 to 80 °C at 15 kPa
CO2 partial pressure, are presented in Table 3. Absorption
capacity at low temperature is some 20% larger for 3-PM than
MEA. The larger capacity is a function of the low carbamate
stability in the case of 3-PM which chemically favors the
formation of larger amounts of bicarbonate and lower amounts
of carbamate at CO2 partial pressures similar to those of MEA.
The result of this behavior is perpetually higher CO2 loadings
beyond 0.5:1.0 mol of CO2 per mol of amine can be achieved.
Moreover, the cyclic capacity of 3-PM over the temperature
range here is almost double that of MEA for similar reasons. It
is important to emphasize that any realistic comparison of the
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Industrial & Engineering Chemistry Research
Table 3. Estimated Absorption and Cyclic Capacities from
Experimental CO2 Solubility Measurements in 3-PM and
MEA Solutions
amine (3.0 M) absorption capacitya cyclic capacityb
3-PM 0.63/83c 0.21/28c
MEA 0.51/110c 0.11/24c
a
Moles of CO2 per mole of amine: 40 °C; 15 kPa CO2 partial
pressure. bMoles of CO2 per mole of amine; difference in loading
between 40 and 80 °C at 15 kPa CO2 partial pressure. cGrams of CO2
per liter of solvent.
maximum CO2 loading and cyclic capacities of amine solvents
should be performed on a mass basis (grams of CO2 per liter of
solvent), particularly in the case of solvents which will be
operated at significantly different concentrations as is presented
here. The higher chemical efficiency of the 3.0 M 3-PM solvent
is captured more effectively on a mass basis, and the overall
capacity approaches that in a 5.0 M MEA solution.
Furthermore, on a mass basis, the larger cyclic capacity of 3-
PM results in a larger overall CO2 cycle in 3.0 M 3-PM than in
5.0 M MEA. Thus, a process in which the two solvents would
be operated would require similar solvent inventories to achieve
comparable cyclic capacities despite the significantly lower
concentration in the former solution. This, in turn, results in
advantages in terms of the capitol and operating costs related to
solvent makeup. Detailed process simulations will reveal the
optimum operating temperature and CO2 loading ranges of the
solvent.
4. CONCLUSION
The fundamental chemical and CO2 absorption behavior of 3-
piperidinemethanol has been investigated via a series of fast
kinetic stopped-flow, 1H/13C NMR equilibrium, wetted wall
column, and vapor−liquid equilibrium measurements. The
fundamental kinetic constants describing the formation of 3-
PM carbamic acid are significantly larger when compared to
corresponding values for MEA at similar temperatures while
carbamate stability constants are lower and thus highly favored.
3-PM offers reasonable overall absorption rates compared to
MEA at similar concentrations and loadings. The results here
have additionally demonstrated that, in the absence of
measured absorption flux data, the values can be reasonably
predicted using the fundamental chemical data including rate
and equilibrium constants and corresponding physical property
data of the amine solutions. Significantly larger equilibrium
absorption and cyclic capacities were found for 3-PM over
MEA at similar conditions.
From a strictly chemical point of view the rapid kinetics and
low carbamate stability highlight 3-PM as an interesting
candidate for CO2 capture processes. The marginally slower
absorption rates position 3-PM as a promising candidate for use
in a blended solvent which could potentially increase the
solubility of 3-PM and overall CO2 absorption rates. A more
comprehensive investigation of cyclic amines should be
undertaken to exhaustively determine if any further relation-
ships (of these molecules) to the cyclic amine piperazine exist
and what is their overall suitability for PCC processes.
■
ASSOCIATED CONTENT
*
S Supporting Information
Figures showing density and viscosity data in 3-PM and MEA
solutions and a range of CO2 loadings, stacked 1H and 13C
16723
Article
NMR equilibrium plots, DEPT-135 and HSQC spectra, and
calculated and measured equilibrium concentration profiles
from 1H NMR analysis. This material is available free of charge
via the Internet at http://pubs.acs.org.
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: will.conway@csiro.au. Tel.: + 61249 606098.
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
This work was carried out within CSIRO’s Energy Flagship,
and it was supported by the Australian Government through
the Australia-China Joint Coordination Group on Clean Coal
Technology (JCG). The views expressed herein are not
necessarily the views of the Commonwealth, and the
Commonwealth does not accept responsibility for any
information or advice contained herein.
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