International Journal of Greenhouse Gas Control 4 (2010) 119–124

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International Journal of Greenhouse Gas Control

journal homepage: www.elsevier.com/locate/ijggc

Carbon dioxide capture with concentrated, aqueous piperazine

Stephanie A. Freeman, Ross Dugas, David H. Van Wagener, Thu Nguyen, Gary T. Rochelle *
Department of Chemical Engineering, The University of Texas at Austin, 1 University Station C0400, Austin, TX 78712-0231, United States

A R T I C L E I N F O A B S T R A C T

Article history: Concentrated, aqueous piperazine (PZ) has been investigated as a novel amine solvent for carbon dioxide
Received 15 April 2009 (CO2) absorption. The CO2 absorption rate of aqueous PZ is more than double that of 7 m MEA and the
Received in revised form 2 September 2009 amine volatility at 40 8C ranges from 11 to 21 ppm. Thermal degradation is negligible in concentrated,
Accepted 12 October 2009
aqueous PZ up to a temperature of 150 8C, a significant advantage over MEA systems. Oxidation of
Available online 13 November 2009
concentrated, aqueous PZ is appreciable in the presence of copper (4 mM), but negligible in the presence
of chromium (0.6 mM), nickel (0.25 mM), iron (0.25 mM), and vanadium (0.1 mM). Initial system
Keywords:
modeling suggests that 8 m PZ will use 10–20% less energy than 7 m MEA. The fast mass transfer and low
Piperazine
CO2 capture
degradation rates suggest that concentrated, aqueous PZ has the potential to be a preferred solvent for
Amine degradation CO2 capture.
Oxidation ß 2009 Elsevier Ltd. All rights reserved.

1. Introduction
The increase in the anthropogenic carbon dioxide (CO2)
concentration in the atmosphere over the past century is known
to be part of the cause of global warming (IPCC, 2001). A large
impact on CO2 emissions can be made by targeting large point
sources such as coal-fired power plants. Amine-based absorption
and stripping systems have been studied for CO2 capture from
coal-fired power plants and have shown the most promise for
effective CO2 control (Rochelle, 2009). Traditional amines such as
monoethanolamine (MEA) and amine blends such as potassium
carbonate/piperazine (K+CO3/PZ) and methyldiethanolamine/
piperazine (MDEA/PZ) have been investigated extensively for this
application (Bishnoi, 2000; Cullinane and Rochelle, 2005; Hilliard,
2008).
Piperazine (PZ) is a cyclic, diamine that has previously been
studied as a promoter for amine systems such as MDEA/PZ or MEA/
PZ blends to improve CO2 mass transfer rates. The concentration of
PZ when used as a promoter was low, between 0.5 and 2.5 m PZ,
because PZ is not highly soluble. Given the nature and magnitude
of absorption/stripping systems, any possibility of precipitation
ruled out PZ for use at concentrations above its room temperature
solubility. Additionally, the boiling point of PZ (146.5 8C) is lower
than that of MEA (170 8C), indicating the possibility for higher
volatility. Recent work has indicated that the volatility of PZ is
comparable to that of MEA due to the non-ideality of PZ in solution
(Hilliard, 2008). Increasing the concentration of PZ in solution
* Corresponding author. Tel.: +1 512 471 7230; fax: +1 512 471 7060.
E-mail address: gtr@che.utexas.edu (G.T. Rochelle).
allows for increased solvent capacity and faster CO2 absorption
rates.
PZ has been studied as a solvent for absorption/stripping
systems for the removal of CO2 from the flue gas of coal-fired
power plants. The current work examines solid solubility,
oxidation, thermal degradation, and CO2 solubility of concentrated
aqueous PZ solutions. Additionally, extensive work on the mass
transfer of CO2 into PZ is reported. Finally, preliminary modeling
work indicates that stripper performance with a concentrated PZ
solvent is slightly enhanced compared to MEA systems.
2. Materials and methods
2.1. Solution preparation
Aqueous PZ solutions were created by heating anhydrous PZ
(99% pure, Fluka-Sigma–Aldrich, St. Louis, MO) with water until
the solid crystals melted into a solution. The warm solution was
transferred to a glass cylinder with a CO2 gas sparger and the
cylinder was placed on a scale. The scale was used to
gravimetrically add CO2 to achieve the desired CO2 concentration.
2.2. CO2 loading through total inorganic carbon analysis (TIC)
The concentration of CO2, or CO2 loading, in solution was
determined by total inorganic carbon analysis (TIC) (Hilliard,
2008). The sample was diluted and then acidified in 30 wt.%
phosphoric acid to release aqueous CO2, carbamate, and bicarbo-
nate species as gaseous CO2. The CO2 was carried in a nitrogen
stream to an infrared CO2 analyzer which detects and records
changes in voltage (Horiba Instruments Inc., Spring, TX). The
resulting voltage peaks were integrated and correlated to CO2

1750-5836/$ – see front matter ß 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijggc.2009.10.008
120 S.A. Freeman et al. / International Journal of Greenhouse Gas Control 4 (2010) 119–124
concentrations using a 1000 ppm inorganic carbon standard made
from a mixture of potassium carbonate and potassium bicarbo-
nate. CO2 loading is reported as moles CO2 per mole alkalinity or
moles CO2 per equivalence of PZ, where 2 mole of alkalinity per
mole PZ is the conversion factor.
2.3. Amine titration
The concentration of PZ in solution was determined using acid
titration (Hilliard, 2008). An automatic Titrando series titrator with
automatic equivalence point detection was used (Metrohm,
Riverview, FL). A sample was diluted 300 and titrated with
0.1N H2SO4 to a pH of 2.4. The amount of acid needed to reach the
equivalence point at pH 3.9 was used to calculate the total amine
concentration in solution. This equivalence point represents the
addition of two protons to the PZ molecule creating a diprotonated
PZ molecule. Additional equivalence points seen prior to 3.9 were
not used in the analysis. Amine concentrations are reported
throughout in units of molal, m, or moles per kilogram of water.
2.4. Viscosity measurements
Viscosity was measured using a Physica MCR 300 cone and
plate rheometer (Anton Paar GmbH, Graz, Austria). The apparatus
allows for precise temperature control for measuring viscosity at
temperatures ranging from 20 to 70 8C. To determine viscosity, the
angular speed of the top cone is increased from 100 to 1000 s1
over a period of 100 s and the shear stress exerted by the solution is
measured every 10 s. Reported viscosities are averages of these 10
individual measurements.
2.5. Oxidative degradation
Oxidative degradation experiments were performed in a low
gas flow agitated reactor with 100 mL/min of a saturated 98%/2%
O2/CO2 gas mixture fed into the reactor headspace (Sexton, 2008).
The 600-mL jacketed reactor was filled with 350 mL of solvent.
Water at 55 8C was circulated through the jacket. The reactor was
agitated at 1400 rpm to increase the mass transfer of oxygen into
the solution. The reactor was operated continuously for 3–5 weeks,
depending on the experiment. Liquid samples were taken every
two to three days and water was added to maintain the water
balance of the reactor contents. The liquid samples were analyzed
for PZ concentration and CO2 loading as described above with the
concentration of degradation products analyzed using ion chro-
matography.
2.6. Vapor–liquid equilibrium
CO2 solubility and amine volatility were measured in a batch
equilibrium cell with gas recycled through a hot gas FT-IR (Hilliard,
2008). The cell was a jacketed, glass reactor where temperature can
be controlled within 1 8C. The inlet gas was sparged from the
bottom of the reactor and there was additional mechanical
agitation to enhance mass transfer. The gas in the headspace of
the reactor was continuously sampled by the FT-IR. The gas exited
the top of the reactor and passed through a mist eliminator and
into a sample line heated to 180 8C. The heated gas stream was
then analyzed by the multi-component FT-IR analyzer and
recycled to the reactor as the inlet gas stream.
2.7. Thermal degradation
Thermal cylinders were constructed from 5 inches of 1/4- or 1/2-
inch OD stainless steel tubing with two Swagelok1 end caps (Davis
and Rochelle, 2008). Cylinders were filled with either 2 or 10 mL of PZ
solution, sealed, and placed in forced convention ovens at multiple
temperatures. Individual cylinders were removed from the ovens
each week and the contents were analyzed for degradation products,
remaining amine concentration, and CO2 loading. Amine losses are
reported as the percent of amine lost compared to the initial amine
concentration as analyzed using cation chromatography.
2.8. Wetted wall column operation
The wetted wall column countercurrently contacted an aqueous
piperazine solution with a saturated N2/CO2 stream on the surface of
a stainless steel rod with a known surface area (Cullinane and
Rochelle, 2006; Dugas and Rochelle, 2009). This apparatus can
perform both absorption and desorption of CO2 depending on the
inlet CO2 partial pressure of the gas phase. By bracketing CO2 partial
pressures that result in absorption and desorption, the equilibrium
partial pressure of the solution can be determined.
The gas flow rate entering the wetted wall column was
controlled via mass flow controllers. Inlet and outlet CO2
concentrations were measured by Horiba CO2 analyzers. As shown
in Eq. (1), the calculated CO2 flux divided by the CO2 partial
pressure driving force provided an overall mass transfer coefficient
for the experiment (KG). The overall mass transfer coefficient was
related to the liquid and gas phase mass transfer coefficients via a
series resistance relationship shown in Eq. (2):

Flux ¼ K G ðPCO2 ; bulk  PCO2
Þ (1)
1 1 1
¼ þ (2)
K G kg k0g
The gas phase mass transfer coefficient, kg, is correlated to
experimental conditions and is a strong function of the geometry of
0
the apparatus. The liquid-film mass transfer coefficient, kg ,
quantifies how fast the solution will absorb or desorb CO2.
3. Results
3.1. Solid solubility
The solid solubility of PZ was studied over a range of PZ
concentrations, CO2 loadings, and temperatures. Solutions were
prepared to cover the desired solution properties and were allowed
to equilibrate at each condition with stirring before solubility
observations were made. The transition temperature of 8 and 10 m
PZ solutions over a range of CO2 loading is shown in Fig. 1. The
transition temperature is the temperature at which a liquid
solution will first precipitate when cooled slowly. The approximate
temperature ramp for all transitions was 1 8C every 5 min. The two
dashed lines at rich loadings in Fig. 1 represent soluble PZ solutions
indicating that the solubility envelope extends at least this high in
CO2 loading. The transition temperature of unloaded PZ solutions
ranging from 1.0 to 40 m PZ is shown in Fig. 2 (The Dow Chemical
Company, 2001; Bishnoi, 2000; Hilliard, 2008).
The data from this study show a eutectic point around 19 m PZ
(60 wt.%) that was observed in the other data sources shown as
well. For 8 m PZ, a CO2 loading of approximately 0.25 mole CO2 per
mole of alkalinity is required to maintain a liquid solution without
precipitation at room temperature (20 8C). In addition, the
solubility of anhydrous PZ at 20 8C is 14 wt.% PZ, which
corresponds to 1.9 m PZ.
3.2. Viscosity
The viscosity of aqueous PZ solutions has been measured over a
range of loadings, concentrations, and temperatures. The viscosity
 S.A. Freeman et al. / International Journal of Greenhouse Gas Control 4 (2010) 119–124 121

Fig. 1. Solid–liquid transition temperature for aqueous PZ. Fig. 3. Viscosity of amine solutions at typical rich loading and 40 8C.

the oxidation of concentrated, aqueous PZ in the presence of

Fig. 2. Comparison of solid solubility for aqueous PZ solutions.
of 7, 8, 9, and 10 m PZ is compared with other amines in Fig. 3
(Huntsman Corporation, 2005; Closmann et al., 2008). The amine
concentration is plotted in units of moles alkalinity per kilogram of
water in order to compare mono- and diamines on a similar basis.
All of the viscosities shown in Fig. 3 are at 40 8C and at the rich
loading of the system (0.3 mole CO2 per mole alkalinity for MDEA
and MDEA/PZ blend; 0.4 mole CO2 per mole alkalinity for PZ and
DGA; 0.5 mole CO2 per mole alkalinity for MEA).
Comparison of the viscosity on this basis demonstrates how the
amine basic group affects overall viscosity. As the number of basic
groups increases in a molecule, the viscosity increases in a linear
direction. The viscosity of 8 m PZ is higher than that of 7 m MEA,
but compared to 60 wt.% DGA1, the viscosity of PZ is lower for a
higher alkalinity. PZ has the advantage over DGA1 of having two
amine functional groups without suffering an increase in viscosity.
DGA1 solutions at 60 wt.% are successfully used in natural gas
treating (Al-Juaied, 2004).
3.3. Oxidative degradation
Heavy metals are known to catalyze the oxidative degradation,
or oxidation, of amines (Goff and Rochelle, 2004). The results of
several dissolved metals are shown in Table 1. The experiments
simulated four scenarios: (1) leaching of stainless steel metals
(iron (II), chromium (III), and nickel (II)), (2) addition of a copper
(II)-based corrosion inhibitor, (3) addition of a vanadium (V)-
based corrosion inhibitor (low concentration), and (4) addition of
a copper (II)-based corrosion inhibitor and proprietary oxidation
inhibitor A.
Oxidative degradation of concentrated PZ was found to be 4
times slower than that of MEA in the presence of stainless steel
metals (Fe2+, Cr3+, and Ni2+) and a low concentration of vanadium
(V5+). As with MEA solutions, PZ was determined to be highly
susceptible to oxidation in the presence of copper (Cu2+) (Goff and
Rochelle, 2006). The primary degradation products were found to
be ethylenediamine (EDA), formate, oxalate, and formyl amides,
such as N-formylpiperazine or N-formylethylenediamine. The
concentration of individual formyl amides were not measured but
the total was inferred from formate production through the basic
reversal of the formyl amide formation reaction (denoted as
formamide in Table 1). As with MEA, inhibitor A vastly reduced this
degradation to levels comparable with the stainless steel and
vanadium cases (Goff and Rochelle, 2006).
3.4. Thermal degradation
Thermal degradation was investigated in PZ solutions at slightly
above stripper temperature (135 8C) and much higher than
stripper temperatures (150 and 175 8C). The thermal degradation
results are shown in Table 2 and are reported as the percent of
amine lost per week compared with the initial amine concentra-
tion. Experiments ranged from 4 to 18 weeks in length.
PZ thermal degradation was determined to be negligible at 135
and 150 8C compared to 7 m MEA. At 175 8C, PZ thermal
degradation was observed as a loss of 32% of the initial PZ in 4
weeks. EDA was observed as a thermal degradation product at
175 8C but not at lower temperatures. Addition of 5.0 mM Cu2+/
0.1 mM Fe2+, 5.0 mM Cu2+/0.1 mM Fe2+/100 mM inhibitor A, and
0.6 mM Cr3+/0.25 mM Fe2+/0.25 mM Ni2+ did not affect degrada-
tion rates at 175 8C.

Table 1
Oxidative degradation of PZ and MEA at 55 8C (100 mL per min of 98% O2/2% CO2, 350 mL solution).

Case Solution (m) Additives (mM) Rate of formation (mM/hr)

Formate Formamide EDA Amine

– 7 MEA 1.0 Fe 0.29 0.35 – 3.8

1 10 PZ 0.6 Fe2+, 0.25 Cr3+, 0.25 Ni2+ 0.005 0.007 0 1.1
2 10 PZ 4.0 Cu2+ 0.14 0.24 0.43 3.0
3 8 PZ 0.1 Fe2+, 0.1 V4+ 0.006 0.013 0 0.8
4 8 PZ 4.0 Cu2+, 0.1 Fe2+, 100 ‘‘A’’ 0.011 0.016 0.009 1.1
122 S.A. Freeman et al. / International Journal of Greenhouse Gas Control 4 (2010) 119–124

Table 2 
equilibrium partial pressure of CO2, PCO , for 8 m PZ and 7 m MEA at
2
Comparison of thermal degradation for PZ and MEA.
40, 60, 80, and 100 8C in Fig. 5 (Dugas and Rochelle, 2009). Rate data
Temperature (8C) Solvent CO2 loading Amine loss at 60, 80, and 100 8C are plotted as a function of the equilibrium
(mole/mole (% per week) partial pressure of CO2 at 40 8C. This x-axis provides a surrogate
alkalinity)
measurement of CO2 loading and allows comparison of different
135 7 m MEA 0.4 5.3 solvents over their practical operating range.
10 m PZ 0.3 0.25 0
As demonstrated in Fig. 5, this normalized flux, kg , for 8 m PZ is

150 7 m MEA 0.4 11 1.5–3 times greater than 7 m MEA. For example, at 40 8C and a PCO
0 2
10 m PZ 0.3 0.80 of 500 Pa, the kg for 8 m PZ and 7 m MEA are 1.98  106 and
8 m PZ 0.3 0.44 7.66  107 mole/s-Pa-m2, respectively. This shows that the mass
175 8 m PZ 0.3 8.0 transfer rate of CO2 into concentrated PZ is twice as fast as 7 m MEA
at this condition. At the higher CO2 loadings, the improvement over
MEA is less distinct with the mass transfer rate only 1.5–2 times
3.5. CO2 solubility faster than MEA. The same trend is observed at 60 8C. Although PZ
is faster than MEA at 80 and 100 8C as well, mass transfer rates are
The measured solubility of CO2 in 2–8 m PZ solutions ranging the most important from 40 to 60 8C, the expected temperature
from 40 to 100 8C is given in Fig. 4 and compared to previous range of the absorber.
studies (Dugas and Rochelle, 2009; Ermatchkov et al., 2006;
Hilliard, 2008). The CO2 solubility data for PZ were regressed to 3.7. Volatility of PZ solutions
yield the solid lines shown in the figure at the various
temperatures indicated. The regression is the equilibrium partial The volatility of PZ was measured in an equilibrium cell with hot

pressure of CO2, PCO , in Pa, in terms of temperature, T, in Kelvin, gas FT-IR. The volatility of 8 m PZ solutions is compared to that of 5 m
2
CO2 loading, a, in mole CO2 per mole alkalinity, and the universal PZ and 7 m MEA at 40 and 60 8C in Fig. 6. The volatility of each
gas constant, R, in kJ per mole-K, as shown in Eq. (3): solution is normalized by the amine concentration for comparison
purposes. At 40 8C and atmospheric pressure, the partial pressure of
   7 m MEA ranges from 3.5 to 5.6 Pa over a loading range of 0.23–
kJ 1 a
0.40 mole CO2 per mole alkalinity. At 40 8C and atmospheric
LnðP CO2 Þ ¼ 36:1  93:2  13:9a þ 8839 þ 14:3a2
mol RT T pressure, the partial pressure of 8 m PZ ranges from 1.1 to 2.1 Pa
(3) over a loading range of 0.27–0.38 mole CO2 per mole alkalinity.
At 40 8C, the normalized volatility of PZ solutions is in the same
The CO2 solubility of concentrated, aqueous PZ solutions follows range as the normalized volatility of MEA solutions. It was
the trends found previously for lower concentration PZ solutions at anticipated that PZ would have a higher volatility than MEA
40 and 60 8C. CO2 solubility is not a strong function of amine because the boiling point of PZ, 146.5 8C, is lower than that of MEA,
concentration and when plotted on a CO2 loading basis, this is 170 8C. However, the volatility of both 5 and 8 m PZ is slightly
confirmed for high concentration PZ solutions. At 40 8C, 8 m PZ lower at 40 8C. Modeling of PZ systems demonstrates this effect as
provides a working capacity of 0.90 mole per kg (PZ + H2O), which is a greatly reduced activity coefficient for PZ due to the solution’s
calculated based on a change in the equilibrium CO2 partial pressure non-ideality (Hilliard, 2008). At 40 8C and atmospheric pressure, PZ
from 5 (loading of 0.39 mole CO2 per mole alkalinity) to 0.5 kPa volatility varies from 10.6 ppm at 0.38 mole CO2 per mole
(0.30 mole CO2 per mole alkalinity). For 7 m MEA at 40 8C, the alkalinity to 21.1 ppm at 0.27 mole CO2 per mole alkalinity.
working capacity is 0.43 mole CO2 per kg (MEA + H2O) based on a
change in the equilibrium partial pressure of CO2 from 5 (0.53 mole 3.8. Estimated energy requirement
CO2 per mole alkalinity) to 0.5 kPa (0.45 mole CO2 per mole
alkalinity). The selected range of CO2 loading for the 8 m PZ solution The thermodynamic model for PZ developed by Hilliard (2008)
falls within the solubility envelope established in Figs. 1 and 2. was modified to represent the new data for concentrated, aqueous
PZ. The stripper of a CO2 removal system was simulated for 8 m PZ
3.6. CO2 mass transfer rates in PZ and compared with 7 m MEA. One set of these simulations
included a simple stripper with CO2 compression to 15 MPa
Mass transfer rates of CO2 absorption into concentrated aqueous (150 atm), a 5 8C cold side temperature approach for the cross heat
PZ were studied in a wetted wall column. The liquid-film mass exchanger, and a 10 8C approach for the reboiler. The columns were
0
transfer coefficient defined in gas-phase units, kg , is plotted against simulated using the Aspen Plus1 RateSepTM tool that calculated

Fig. 4. CO2 solubility in aqueous PZ solutions ranging from 0.9 to 8 m PZ and from 40 Fig. 5. Comparison of mass transfer coefficients in 8 m PZ (filled shapes) and 7 m
to 100 8C. MEA (open shapes) from 40 to 100 8C.
 S.A. Freeman et al. / International Journal of Greenhouse Gas Control 4 (2010) 119–124
Fig. 6. Comparison of PZ and MEA volatility normalized to amine concentration.
Fig. 7. Flowsheet of a three-stage flash.
heat and mass transfer rates but assumed reactions reached
equilibrium. In each simulation, 15 m of CMR NO-2P packing and
an 80% approach to flood were used.
A second set of simulations was performed in Aspen Plus1
using two- and three-stage flash configurations. The flowsheet for
the three-stage flash is shown in Fig. 7. The two-stage flash is
analogous with one less flash tank. In a multi-stage flash, hot, rich
amine leaving the cross-exchanger enters a series of flash tanks
that are either heated or adiabatic. The figure shows the design
used for these simulations, where each stage is shown heated with
steam. In each tank, CO2 flashes off and is sent to a multi-stage
compressor. A multi-stage compressor collects CO2 at multiple
pressure levels, thereby reducing compression work. There is a
potential opportunity for heat recovery from the water vapor
leaving each of the flash tanks. One option is to use this heat to pre-
heat the boiler feed water used in the coal-fired power plant
(Gibbins and Crane, 2004).
 equivalent work required for stripping of an 8 m PZ solution will be
The rich stream for each case assumed a PCO of 5 kPa at the
2
absorber temperature of 40 8C. Equivalent work, Weq, was

Fig. 8. Equivalent work for stripping with 5 8C approach and rich PCO of 5 kPa for
2
8 m PZ.
123
calculated as shown in Eq. (4) using the CO2 removal rate, nCO2 ,
stripper reboiler duty, Q, reboiler temperature, Treboiler, cooling
water temperature of 40 8C, Tsink, total pumping work, Wpump, and
total CO2 compression work to achieve 15 MPa, Wcomp:
    
1 ðT reboiler þ 10Þ  T sink
W eq ¼ 0:75 Q þ W pumps þ W comp
nCO2 ðT reboiler þ 10Þ
(4)
Each system was optimized for lean loading and the equivalent
work as a function of lean loading as shown in Fig. 8. The baseline
system, 7 m MEA, had an equivalent work of 40.3 kJ per mole CO2.
The 8 m PZ simple stripper system had a minimum equivalent
work of 36.5 kJ per mole CO2. The two- and three-stage flashes
using 8 m PZ had minimum equivalent works of 34.1 and 33.8 kJ
per mole CO2, respectively.
The increased capacity of PZ improved its performance in all
cases over the baseline 7 m MEA case, despite a lower DHabs. For
the PZ cases, the lowest equivalent work was achieved in the three-
stage flash simulation, demonstrating the advantages of multi-
stage compression and heat recovery that can be achieved using a
solvent that is resistant to thermal degradation.
4. Conclusions
Concentrated, aqueous solutions of PZ have shown promise for
improved solvent performance in absorption/stripping systems
used for CO2 capture. For 8 m PZ, a CO2 loading of approximately
0.25 mole CO2 per mole alkalinity is required to maintain a liquid
solution without precipitation at room temperature (20 8C).
Additionally, the solubility of PZ at 20 8C is approximately
14 wt.% PZ, or 1.9 m PZ. The volatility of 8 m PZ systems was
found to be between 10.6 and 21.1 ppm at 40 8C over the useful
range of CO2 loadings, which is slightly lower than 7 m MEA.
Oxidative degradation of concentrated PZ has been shown to be
4 times slower than 7 m MEA in the presence of the combination of
Fe2+/Cr3+/Ni2+ and Fe2+/V5+. In the presence of copper-based
corrosion inhibitors, oxidative degradation is an issue but can be
drastically reduced with the use of inhibitor A. Concentrated PZ is
resistant to thermal degradation up to 150 8C but does degrade at
175 8C, losing 32% of the PZ over 4 weeks. The resistance of PZ to
thermal degradation allows for the possibility of higher pressure
strippers to improve energy performance.
Mass transfer measurements have shown that the rate of CO2
absorption into 8 m PZ is 1.5–3 times that of 7 m MEA. The working
capacity of 8 m PZ is double that of 7 m MEA at 0.90 mole CO2 per
kg (PZ + H2O) compared to 0.43 mole CO2 per kg (MEA + H2O).
Initial modeling of a simple stripper section indicates that the
approximately 10–20% lower than for 7 m MEA. The use of a multi-
stage flash also has demonstrated advantages for a high
temperature operation that is feasible with the thermally stable
8 m PZ.
The rapid rate of CO2 absorption, low degradation rate, and low
predicted equivalent work indicates that 8 m PZ solutions are an
attractive option for CO2 capture in absorption/stripping systems.
Acknowledgement
The Luminant Carbon Management Program provided support
for this research.
References
Al-Juaied, M.A., 2004. Carbon Dioxide Removal from Natural Gas by Membranes in
the Presence of Heavy Hydrocarbons and by Aqueous Diglycolamine1/Morpho-
line. Doctoral Dissertation. The University of Texas at Austin, Austin, TX.
124 S.A. Freeman et al. / International Journal of Greenhouse Gas Control 4 (2010) 119–124
Bishnoi, S., 2000. Carbon Dioxide Absorption and Solution Equilibrium in Piperazine
Activated Methyldiethanolamine. Doctoral Dissertation. The University of
Texas at Austin, Austin, TX.
Closmann, F., Nguyen, T., Rochelle, G.T., 2008. MDEA/piperazine as a solvent for CO2
capture. Energy Procedia 1 (1), 1351–1357.
Cullinane, J.T., Rochelle, G.T., 2005. Thermodynamics of aqueous potassium
carbonate, piperazine, and carbon dioxide. Fluid Phase Equilibr. 227 (2),
197–213.
Cullinane, J.T., Rochelle, G.T., 2006. Kinetics of carbon dioxide absorption into
aqueous potassium carbonate and piperazine. Ind. Eng. Chem. Res. 45 (8),
2531–2545.
Davis, J., Rochelle, G.T., 2008. Thermal degradation of monoethanolamine at strip-
per conditions. Energy Procedia 1 (1), 327–333.
Dugas, R., Rochelle, G.T., 2009. Absorption and desorption rates of carbon dioxide
with monoethanolamine and piperazine. Energy Procedia 1 (1), 1163–1169.
Ermatchkov, V., Kamps, A.P.S., Speyer, D., Maurer, G., 2006. Solubility of carbon
dioxide in aqueous solutions of piperazine in the low gas loading region. J.
Chem. Eng. Data 51 (5), 1788–1796.
Gibbins, J.R., Crane, R.I., 2004. Scope for reductions in the cost of CO2 capture using
flue gas scrubbing with amine solvents. Proceedings of the Institution of
Mechanical Engineers. Part A, J. Power Energy 218 (A4), 231–239.
Goff, G.S., Rochelle, G.T., 2004. Monoethanolamine degradation: O2 mass transfer
effects under CO2 capture conditions. Ind. Eng. Chem. Res. 43 (20), 6400–6408.
Goff, G.S., Rochelle, G.T., 2006. Oxidation inhibitors for copper and iron catalyzed
degradation of monoethanolamine in CO2 capture processes. Ind. Eng. Chem.
Res. 45 (8), 2513–2521.
Hilliard, M.D., 2008. A Predictive Thermodynamic Model for an Aqueous Blend of
Potassium Carbonate, Piperazine, and Monoethanolamine for Carbon Dioxide
Capture from Flue Gas. Doctoral dissertation. The University of Texas at Austin,
Austin, TX.
Huntsman Corporation, 2005. Diglycolamine1 Agent—Product Information.
Author, The Woodlands, TX.
IPCC, 2001. In: Houghton, J.T., Ding, Y., Griggs, D.J., Noguer, M., van der Linden,
P.J., Dai, X., Maskell, K., Johnson, C.A. (Eds.), Climate Change 2001: The
Scientific Basis. Contribution of Working Group I to the Third Assessment
Report of the Intergovernmental Panel on Climate Change. Cambridge Uni-
versity Press, Cambridge, United Kingdom, p. 881 pp.
Rochelle, G.T., 2009. Amine Scrubbing for CO2 Capture. Science 325 (5948), 1652–
1654.
Sexton, A.J., 2008. Amine Oxidation in CO2 Capture Processes. Doctoral dissertation.
The University of Texas at Austin, Austin, TX.
The Dow Chemical Company, 2001. Ethyleneamines. Author, Midland, MI.