International Journal of Greenhouse Gas Control 39 (2015) 79–90

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International Journal of Greenhouse Gas Control

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

Investigation of carbon dioxide capture with aqueous piperazine on a

post combustion pilot plant–Part I: Energetic review of the process
Markus Rabensteiner a,∗ , Gerald Kinger b , Martin Koller c , Günter Gronald c ,
Christoph Hochenauer a
a
Institute of Thermal Engineering, Graz University of Technology, Inffeldgasse 25b, 8010 Graz, Austria
b
EVN AG, EVN Platz 1, 2344 Maria Enzersdorf, Austria
c
ANDRITZ Energy & Environment GmbH, Waagner-Biro-Platz 1, 8074 Raaba, Austria

a r t i c l e i n f o a b s t r a c t

Article history: 37.6 wt% piperazine (7 molal) was investigated in a PCC-test facility on the power plant in Dürnrohr,
Received 15 December 2014 Austria. Through the use of real power plant flue gas and the well-conceived dimensions of the test facility,
Received in revised form 30 March 2015 industry-related conditions for full scale applications can be provided. Deviations from measurement
Accepted 2 May 2015
results, generated on other test facilities in which piperazine was tested, are discussed scientifically. The
Available online 19 May 2015
specific energy consumption for solvent regeneration can be reduced to 3.17 GJ/tCO2 (without absorber
intercooler and multi-stage flash), resulting in an energy saving of 14% in comparison to 30 wt% MEA.
Keywords:
The low CO2 absorption heat of piperazine and the low sensible heat are crucial for the low energy
Post combustion CO2 capture
Reactive absorption
consumption. The optimal solvent flow rate is 20% lower in comparison to that of 30 wt% MEA, resulting
Piperazine in less pumping and cooling demand.
Pilot plant study Especially for the regenerated solvent there is a risk of solidification. Even a small temperature reduction
Specific energy for solvent regeneration of the regenerated solvent in operation can lead to failure. A sudden system failure leads to a rapid
solidification. Endangered areas have to be trace heated.
A detailed parameter study and an emission measurement on the pilot plant will be presented in Part
II of this paper.
© 2015 Elsevier Ltd. All rights reserved.

1. Introduction A 30 wt% aqueous solution of monoethanolamine (MEA) is the

Carbon dioxide capture and storage (CCS) is an important contri-
bution to reducing greenhouse gas emissions and stopping global
warming. At low partial pressures of CO2 , aqueous amines are the
most suitable solvents for the absorption and desorption process
for post combustion CO2 capture (PCC) (Kohl and Nielsen, 1997).
Compared to other CCS techniques like pre combustion capture or
oxy-fuel technology, PCC is a mature process and can be imple-
mented on a large scale in a relatively short time (Mangalapally and
Hasse, 2011). However, the capital requirements and especially the
operation cost of PCC remain high. This complicates the implemen-
tation of the absorption/desorption process with aqueous amine
solutions for large scale PCC-plants (Davis, 2006).
∗ Corresponding author. Tel.: +43 650 8108232, fax: +43 316 873 7305.
E-mail addresses: markus.rabensteiner@tugraz.at,
bgerald.kinger@evn.at (M. Rabensteiner),
martin.koller@andritz.com (M. Koller), guenter.gronald@andritz.com (G. Gronald),
christoph.hochenauer@tugraz.at (C. Hochenauer).
benchmark solvent of the PCC-process. Several system exten-
sions, such as vapor re-compression and absorber intercooling
(Fisher et al., 2005; Knudsen et al., 2011) enable a reduction of
the energy consumption. By taking into account the properties of
the solvent and setting the optimal operation parameters, large
energy savings are possible (Oexmann and Kather, 2010). Nev-
ertheless, the energy required for the process with MEA is still
high. Moreover, MEA is highly corrosive, foams by pollution and
degrades under the influence of O2 , NOx , SO2 (Notz, 2009) and high
temperature.
In order to improve the process, it is important to find new more
efficient solvents. Using concentrated piperazine (PZ) is an alterna-
tive to the standard MEA-based process. Extensive laboratory based
research has indicated that aqueous PZ solutions possess the fol-
lowing benefits under laboratory conditions (Freeman et al., 2010,
2009; Rochelle et al., 2011):
• Double CO2 absorption rate in comparison to MEA.
• Nearly double CO2 absorption capacity compared to MEA.
• Thermal stability up to a temperature of 150 ◦ C.

http://dx.doi.org/10.1016/j.ijggc.2015.05.003
1750-5836/© 2015 Elsevier Ltd. All rights reserved.
80 M. Rabensteiner et al. / International Journal of Greenhouse Gas Control 39 (2015) 79–90
Table 1
Properties of monoethanolamine and piperazine (Cottrell et al., 2013).
Monoethanolamine(MEA) Piperazine(PZ)
Formula C2 H7 NO C4 H10 N2
Structure
Molecular mass [g/mol] 61.08 86.14
Melting point [◦ C] 10.3 106
Boiling point [◦ C] 170 146
Cost [$/kg] 2 6
• Much lower oxidative degradation than MEA.
• Low solvent vapor pressure.
The measurement campaign was carried out on a PCC-pilot plant
at the EVN power plant in Dürnrohr. The test facility CO2 SEPPL
(acronym for CO2 SEParation PLant) was built as Austriaı́s first car-
bon dioxide removal plant for flue gases originating from a thermal
conversion of fossil fuels. The test facility has an absorber height
of 12 m and operates with flue gas from an industrial coal-fired
or natural gas-fired boiler. Due to the realistic conditions, valuable
measurement results for larger demonstration plants and full-scale
plants can be obtained.37.6 wt% PZ (7 m PZ) was investigated in the
present work. This concentration was adjusted in preliminary stud-
ies on the test facility carried out by Posch (2012). In the tests on
the J.J. Pickle pilot plant (USA), piperazine concentrations of 5, 8
and 9 m were investigated (Plaza, 2011; Van Wagener 2011). For
comparison, the measurement results of 8 m PZ were used. The
experiments at the Tarong pilot plant (Australia) were only carried
out with 8 m PZ (Cottrell et al., 2013).
2. Aqueous piperazine as a solvent for CO2 absorption
Piperazine is a polycyclic amine and can be used in a concen-
trated form or as a reaction rate promoter for other solvents. A
detailed description of the chemical structure of piperazine and its
speciation can be found in Freeman (2011). Initial work focused on
the use of piperazine promoted potassium carbonate (Behr et al.,
2011; Chen et al., 2006 Cullinane, 2005; Cullinane and Rochelle,
2006, 2005, 2004; Hilliard, 2008; Oexmann and Kather, 2009;
Oexmann et al., 2008). Such a blend was also investigated in the
pilot plant in Dürnrohr (Posch, 2012). Since the 2010s, the focus is
on concentrated aqueous piperazine. Especially the University of
Texas in Austin researches intensively on the use of this absorption
liquid.
Compared to MEA, piperazine has nearly double loading capac-
ity of CO2 at double reaction rate (Freeman et al., 2010). The
majority of the increased CO2 capacity is due to the fact that each
mol of piperazine has two functional nitrogen groups (Table 1). This
allows piperazine to react twice in the CO2 reaction, whereas MEA
can only react once (Dugas, 2009). The liquid-film mass transfer
coefficient, k g , for 8 m PZ (40.8 wt% PZ) is 1.5 to 3 times higher than
that of 30 wt% MEA (Freeman et al., 2010). The heat of CO2 absorp-
tion at mid-loading (Fig. 9) is lower than those of aqueous MEA
solutions (Xu and Rochelle, 2011). The investigation of Svensson
et al. (2013) shows similar absorption heats and weak temperature
dependence.
In earlier literature (Aroua and Mohd Salleh, 2004; Bishnoi and
Rochelle, 2000; Derks et al., 2005; Ermatchkov et al., 2006; Kamps
et al., 2003), the CO2 solubility of only low concentrated piper-
azine solutions (up to 26 wt% PZ) was investigated. Hilliard (2008)
showed that the CO2 solubility in the range from 19.7 wt% and
30.1 wt% PZ (0.9 to 5 m PZ) changes only slightly with piperazine
concentration. The investigations of Dugas and Rochelle (2009) and
Freeman et al. (2010, 2009),) could extend this assertion up to
piperazine concentrations of 50.4 wt% (12 m PZ). CO2 solubility data
between 40 and 160 ◦ C were regressed by Xu and Rochelle (2011)
as shown in Fig. 7. The CO2 solubility of MEA is also shown as a
comparison.
Understanding solvent stability and robustness is an impor-
tant feature to understand when scaling up a PCC-process. Solvent
degradation can increase plant operating costs through solvent
make-up costs and reduced capture capacity (Freeman et al., 2010).
Piperazine does not have an alcohol group that could promote ther-
mal degradation. Hence it can be regenerated at higher temperature
and pressure than MEA, resulting in a decreasing CO2 compression
work (Cottrell et al., 2013). The oxidative degradation is also lower
than those of MEA (Freeman et al., 2010). The volatility of piper-
azine in aqueous solution is less than that of MEA, despite the lower
boiling point of piperazine (Table 1) (Rochelle et al., 2011).
Pre-investigations in laboratory scale were carried out before
the pilot plant in Dürnrohr was filled with the solvent. Screen-
ing apparatuses as described in Wappel (2010), Wappel et al.
(2010) and Rabensteiner et al. (2014b) were used for the pre-
investigations. 30 wt% PZ was compared with 30 wt% MEA. The
fast kinetics of piperazine under absorber conditions could be
demonstrated with the screening experiments according Wappel
(2010) and Wappel et al. (2010). The Investigation according to
Rabensteiner et al. (2014b) results in a similar CO2 absorption
capacity of the fresh solvent as the standard solvent, 30 wt% MEA.
The measured CO2 absorption capacity of the regenerated solvent
is higher.
The piperazine concentration in Dürnrohr was determined by
acid-base titration with hydrochloric acid. A back titration with
sodium hydroxide showed only a small influence on the calculated
piperazine concentration.
3. Handling of aqueous piperazine solutions
When using aqueous piperazine as a solvent, certain proper-
ties of this solvent have to be considered, in particular, the risk
of solidification during operation and downtime. Building of foam
can also result in operation failure. In this section, measured val-
ues from literature are confirmed by operating experience gained
at the Dürnrohr pilot plant.
3.1. Production and filling of the aqueous piperazine solution
Piperazine is commercially available as a solid flake or as 68 wt%
aqueous solution (the latter was used in Dürnrohr). In either case
the solvent has a solid component at ambient conditions and there-
fore requires additional preparation before it can be added to the
pilot plant. Low piperazine concentrations are advantageous for
handling of piperazine solutions at low temperatures. Preparing
solid piperazine flake into a 10 wt% solution enables easy handling
and avoidance of precipitation down to temperatures of 10 ◦ C (as
shown in Fig. 1). The excess water in the pilot plant is a drawback
(Cottrell et al., 2013).
3.2. Solidification and precipitation
The attractive properties of aqueous piperazine as a solvent for
CO2 capture have been known for some time. It is used as an absorp-
tion rate promoter in solvent blends. However, in these applications
only piperazine concentrations less than 2 molal (∼10 wt% PZ)
were examined (Cottrell et al., 2013). One challenge with aqueous
piperazine solutions is the high melting point of pure piperazine
(Table 1). When diluting piperazine with water, the melting point
 M. Rabensteiner et al. / International Journal of Greenhouse Gas Control 39 (2015) 79–90 81

120

100

80
temperature [°C]

60

40

20

-20
0 20 40 60 80 100
PZ concentration [wt%]

Fig. 1. Freezing point (atmospheric pressure) of aqueous piperazine solutions as a Fig. 2. Solid–liquid transition temperature (atmospheric pressure) for 8 m PZ
function of the piperazine concentration (Data from Bishnoi (2000) ( ), Hilliard (40.8 wt% PZ) (Freeman et al., 2010). The marked areas indicate the operating ranges
(2008) ( ), Merck Corporation (2009) ( ), Muhammad et al. (2009) ( ) and The of the measurement series in Section 5.3.
DOW Chemical Company (2001) ( ).

can be significantly reduced. Unloaded 37.6 wt% PZ is only in solu- solution (Chen et al., 2011). After one week of operation, foam-
tion at temperatures above 40 ◦ C (Fig. 1). The data from Bishnoi ing was observed at the pilot plant (Fig. 3). The entire absorber
(2000), Hilliard (2008), Merck Corporation (2009), Muhammad column was filled with foam, which lowers the absorption capac-
et al. (2009) and the DOW Chemical Company (2001) show a ity, reduces mass transfer coefficients and tremendously increases
eutectic point at around 60 wt% PZ. Studies show evidence of a column pressure drop. The foam was able to be broken within a
metastable freezing point in the region of 20 wt% PZ. short time by adding small amounts of a silicon anti-foaming agent
The solid solubility of 8 and 10 m PZ (about 40.8 and 46.3 wt% (MERCK, catalogue number 107,743) (Posch, 2012).
PZ) over a range of CO2 loadings and temperatures was studied
by Freeman et al. (2010) (Fig. 2). The transition temperature is the 4. Pilot plant and process description
temperature at which a liquid solution will first precipitate when
cooled slowly. The transition temperature of 8 and 10 m PZ is sim- This section explains the design and operation of the pilot plant
ilar. Therefore, the measurement results of 8 m PZ from Freeman in Dürnrohr. Subsequently, the test facility is compared with two
et al. (2010) were used for approximation for 37.6 wt% PZ (7 m PZ). other pilot plants, the J.J. Pickle pilot plant in Austin (USA) and the
At low CO2 loadings, piperazine hydrate (PZ·6H2 O(s))is noted to Tarong pilot plant in Nanango (Australia). In these test facilities,
precipitate from solution. In this case, the regenerated solvent is in
danger of solidification. With increasing CO2 loading, the tempera-
ture at which piperazine hydrate is formed can be greatly reduced.
In addition, at high CO2 loadings, protonated piperazine carbamate
(H+ PZCOO- ·H2 O(s)) is thought to precipitate out of solution. The
CO2 loading, at which the carbamate is formed, is almost indepen-
dent of the temperature. Thus at typical operating temperatures
(e.g. 40–150 ◦ C) CO2 loadings should be maintained between 0.1
and 0.4 molCO2 /molequivalentamine . When temperatures drop below
40 ◦ C, CO2 loadings need to be restricted to a narrower range to
avoid precipitation issues (0.32 to 0.37 molCO2 /molequivalentamine ).
In addition, Fig. 2 shows the operating ranges of the measurement
series performed on the considered test facilities. An explanation
of these operating ranges is given in Section 5.3.

3.3. Foaming

Concentrated aqueous piperazine for CO2 capture has a high

foaming tendency. In general, foaming is promoted when fine par-
ticles, condensed liquid hydrocarbons, amine degradation products
or chemical additives like corrosion inhibitors are present in the Fig. 3. Escape of foam from the absorber (Posch, 2012)
82 M. Rabensteiner et al. / International Journal of Greenhouse Gas Control 39 (2015) 79–90
Fig. 4. Flow scheme of the pilot plant.
aqueous piperazine solutions in a similar concentration range as in
Dürnrohr were also investigated.
4.1. CO2 SEPPL pilot plant (Dürnrohr/Austria)
The Dürnrohr power plant is operated with hard coal. The CO2
content of the flue gas varies between 11 and 13 vol% (dry). A few
hours before and after the annual revision of the power plant, inves-
tigations with flue gases of a natural gas-fired boiler are possible.
The following description refers to Fig. 4. A slipstream of the
flue gas is branched off to the test unit downstream to the flue gas
cleaning line and the draught fan of the power plant. With flue gases
being taken from an industrial boiler, real operating conditions are
reached.
Flue gas from the desulfurization plant passes a dust filter, where
fine dust is separated. A downstream blower increases the pres-
sure and enables flue gas flow rates up to 100 standard cubic

meters per hour. This corresponds to an F-factorof about 2 Pa0.5

F = ug ∗ p8 ; ug = gasvelocity; pg = gasdensity in the absorber
column. Through a heat exchanger, which is connected down-
stream of the blower, the temperature of the flue gas at the absorber
entry can be set. The pre-washer column operates with an aqueous
solution of sodium hydroxide.
The absorber consists of four sections (3 m height per section)
which are equipped with structured packing, resulting in a total
packing height of 12 m. Both, the absorber and the desorber are
equipped with a demister unit. In order to maintain the water bal-
ance for the entire system, there is a water washing section located
at the top of the absorber above the solvent inlet, which addition-
ally reduces various degradation products in the treated gas. The
desorber consists of two sections, both equipped with 4 m of the
structured packing. The solvent is heated by an electrical heating
rod in the desorber sump which produces the stripping steam.
The vapor exiting the desorption unit contains water, CO2 and
some traces of other volatile components. In order to reduce the
emissions, a washing section is installed at the top of the desorber
as well. In contrast to the absorber washing section, the washing
water is not pumped in a circuit, but provided by a downstream
condenser. The total water balance is closed by recirculating con-
densate.
The whole test facility is equipped with a sophisticated measur-
ing system. For example, there are thirteen temperature sensors
installed along the absorber column. This enables a high resolu-
tion temperature curve. Furthermore, the pressure loss of the flue
gas flow is monitored along the entire flow path. System control
through a PCS (process control system) allows comprehensive con-
trol concepts.
An overview of the test facility is shown in Fig. 4. The separation
plant is located in the large tower in the middle of the picture.
The 20 m tower consists of seven levels (the first two levels are
enclosed). A CO2 compression unit is situated on the left side of the
separation plant.
The pilot plant has been described in detail by Fraubaum (2013)
and Posch (2012). A detailed description of each test rig component
was done by Stöger (2011). A summary of the last three years of
operating experience generated on the pilot plant can be found in
Rabensteiner et al. (2014c). In Table 2, a list of the technical data of
the pilot plant is shown.
4.2. J.J. Pickle pilot plant (Austin/USA)
In order to demonstrate the practicality of new solvents and
configurations, the University of Texas at Austin operates a PCC-
pilot plant. The pilot plant is located at the J.J. Pickle Research
Center in North Austin (USA). The flue gas is artificially produced
by mixing ambient air and CO2 . The separated CO2 stream is
recycled. In Dugas (2006), the dimensions of the pilot plant are
described in detail. The maximum flue gas flow rate is approx-
imately 1275 m3 /h. Therefore, this pilot plant can process about
ten times higher flue gas flow rates than the pilot plant in Dürn-
rohr. Table 2 lists technical data of the J.J. Pickle pilot plant.
Three measurement series were carried out with 8 m PZ (40.8 wt%
PZ) (Plaza, 2011; Van Wagener, 2011). After the first measure-
ment series the absorber of the pilot plant was equipped with
an intercooler. In the second stage of expansion the desorber was
replaced by a two-stage flash. The measurement results of the first
 M. Rabensteiner et al. / International Journal of Greenhouse Gas Control 39 (2015) 79–90 83

Table 2
Comparison of the test facilities, in which aqueous piperazine solutions were tested.

CO2 SEPPL pilot plant J.J. Pickle pilot plant Austin/USA Tarong pilot plant
Dürnrohr/Austria (Dugas, 2006; Plaza, 2011; Van Nanango/Australia
Wagener, 2011) (Cottrell et al., 2013; Cousins et al., 2012, 2011,
2010; Saimpert et al., 2013)

Image source: Plaza (2011)

Image source: Cottrell (2012)
General information
Flue gas source Hard coal (natural gas) Air/CO2 + recycled CO2 Hard coal
CO2 content of the flue gas [vol% (dry)] 11–13 (7 at a naural gas fired 12a 9.8–13b
boiler)
Maximal flue gas flow ratec [m3 /h] 120 1275d ∼700e
  
Maximal F-factor [Pa0.5 ] 2 2.59 2.12
Heat loss of the pilot plant [kW] 0.9 (absorber) 12.1–32.3 (desorber) –
1.2 (desorber)
Heat loss with respect to the flue gas flow 36 58–155f –
[kJ/m3 ]
Pinch temperature of the main heat exchanger 4–7 – –
[K]
Absorber
Inner diameter [mm] 150 427 350
Total height of packing [m] 12 6.1 7
Type of packing Rasching Super-Pak 250-Y Sulzer Mellapak 2Xg -h
Desorber
Maximal pressure [barabs ] 3 – –
Inner diameter [mm] 100 427 250
Total height of packing [m] 8 6.1 7
Type of packing Rasching Super-Pak 250-Y -g -h
Pre-washer
Total height of packing [m] 2 – 2.7
Type of packing Raschig Super-Pak 200-X – 25 mm pall rings
Washing section absorber
Total height of packing [m] 2 – 1.561
Type of packing Raschig Super-Pak 200-X – Sulzer Mellapak 250.X
Washing section desorber
Total height of packing [m] 2 – 1.12
Type of packing Raschig Super-Pak 200-X – Sulzer Mellapak 350.X
a
No information regarding the water content was taken into account.
b
Measured in previous MEA-experiments (Cousins et al., 2012).
c
This value refers to a flue gas temperature of 40 ◦ C and atmospheric pressure.
d
Highest measured flue gas flow rate of Plaza (2011).
e
No information available → calculation by the captured CO2 stream.
f
Only the heat losses of the desorber unit were taken into account.
g
According to Van Wagener (2011), absorber and desorber column are equipped with 6.1 meter of Sulzer Mellapak 250.Y. The present work used the data from the
PhD.-Thesis from Plaza because of the explicit specification of the used packings for the piperazine tests.
h
Sulzer Mellapak 250.X and Sulzer Mellapak 350.X were used for the absorber and desorber column during the experiments with 30 wt% MEA (Cousins et al., 2012).
According to Cottrell et al. (2013), packages were replaced to provide better mass transfer performance with the more viscous piperazine based solvent.

measurement series can be compared with the results of the test
campaign in Dürnrohr. 14 measurement points were recorded in
this measurement series. At this early stage of investigation, a clos-
ing of the mass and energy balance was impossible (Van Wagener,
2011). In addition, the heat loss to the environment of the desor-
ber is enormous. The heat loss of the desorber with respect to the
flue gas flow is up to seven times larger than in Dürnrohr (Table 2).
The specific energy for solvent regeneration in Fig. 6 is calculated
by taking into account the desorber energy loss. If the desorber
energy loss is not considered, the energy demand for solvent regen-
eration increases by an average of 0.9 GJ/tCO2 . Based on these facts,
a comparison of the measurement results is only partially possi-
ble.
4.3. Tarong pilot plant (Nanango/Australia)
CSIRO (Commonwealth Scientific and Industrial Research
Organisation) investigated 8 m PZ (40.8 wt% PZ) in a test facility
with real flue gases at the Tarong pilot plant in Nanango (Australia).
Hard coal is used as fuel in the Tarong power plant. Therefore, the
CO2 content of the flue gas is in the same order of magnitude as
that of the Dürnrohr power plant. The pilot plant separated approx-
84 M. Rabensteiner et al. / International Journal of Greenhouse Gas Control 39 (2015) 79–90

5.0

specific energy for solvent regeneration [GJ/tCO2]

4.5

30 wt% MEA
4.0

3.5

3.0
concentrated PZ

2.5
1.5 2.5 3.5 4.5 5.5 6.5
L/G-ratio [l/m³]
Fig. 5. Comparison of the HETP-value (solid line) and pressure loss (dashed line) for
different absorber packings (Schultes, 2008; Sulzer, 2013). Fig. 6. Specific energy for solvent regeneration as a function of the L/G-ratio. Experi-
mental data for concentrated piperazine and 30 wt% MEA generated at the CO2 SEPPL
pilot plant in Dürnrohr (♦ and 䊐), J.J. Pickle pilot plant () from Plaza (2011) and
Tarong pilot plant () from Cottrell et al. (2013). The lines for the J.J. Pickle pilot
plant (— —) and for the Tarong pilot plant (- -) are estimated curves.

imately 100 kg CO2 per hour, corresponding a flue gas flow rate of
about 700 m3 /h (Cottrell et al., 2013).
The tests with concentrated piperazine were carried out after
the investigation of the standard solvent, 30 wt% MEA. The pilot
plant has been converted for these experiments. Because of the
higher viscosity of piperazine based solutions, the packing mate-
rials in the columns have been replaced. Due to the higher
temperatures of the process with concentrated piperazine, the gas-
ket materials had to be replaced. The absorber has been equipped
with an intercooler, in order to achieve higher CO2 loadings of the
enriched solvent. A larger main heat exchanger has been installed,
due to the lower heat transfer coefficients of the more viscous
piperazine based solvents (Cottrell et al., 2013).
4.4. Comparison of the absorber columns
The influence of packing used is not negligible. The design of the
absorber column is very important for the performance of the entire
test facility. Fig. 5 shows the HETP-value (height equivalent to a
theoretical plate) and the pressure loss of the structured packings
used for different F-factors. Although the HETP-value is depen-
dent on various operation parameters such as column pressure and
reflux ratio, it can be used as reference value. In the diagram, the
approximate investigation range of the test facilities is marked (up
to 2 Pa0.5 ). The absorber column of the Dürnrohr test facility is 12 m
high. If the F-factor is set to 2 Pa0.5 , which corresponds to a flue gas

Fig. 7. CO2 solubility (single line) and heat of CO2 absorption (double line) regressed by Xu and Rochelle (2011) cover 7.2 to 50.4 wt% PZ (solid line) and 17.6 to 44.3 wt% MEA
(dashed line).
 M. Rabensteiner et al. / International Journal of Greenhouse Gas Control 39 (2015) 79–90
Table 3
Operating parameters of the series of measurements with concentrated piperazine.
CO2 SEPPL pilot plant
Piperazine concentration [wt%] 37.6
  a
7 8
CO2 content of the flue gas [vol% (dry)] 11–13
Flue gas flow rate [m3 /h] 100
 
F-factor [Pa0.5 ] 1.65
Desorber pressure [barabs ] 2 2f
Separation efficiency [%] 90 (±1)
Temperature of the regenerated solvent [◦ C] 40
Temperature of the flue gas [◦ C] 40
a
Average value.
b
No information regarding the water content was taken into account.
c
Measured in previous MEA-experiments (Cousins et al., 2012).
d
Not specified. Calculated by L/G-ratio and solvent flow rate.
e
No information available → calculation by the captured CO2 stream.
f
Calculated by the desorber sump temperature.
g
Indication of the temperature range in Cottrell et al. (2013) (Fig. 2).
h
The flue gas is artificially produced by the mixture of air and CO2 . Since no flue gas heat exchanger exists and the pilot plant is outdoors, the temperature of the inflowing
flue gas is mainly dependent on the outside temperature, resulting in very highly fluctuations.
flow rate of 120 m3 /h, the HETP-value of the structured packing
is about 0.33 m. Therefore the absorber column at the test facility
in Dürnrohr has 35 separation plates. The absorber column of the
J.J. Pickle and Tarong pilot plant have 9 and 14 theoretical sepa-
ration plates at the same F-factor. The influence of the number of
theoretical separation plates is discussed in Part II (Rabensteiner
et al., 2015) of this paper. Because piperazine has fast kinetics, the
number of theoretical separation plates has only a small influence
on the measurement results. This does not apply to 30 wt% MEA.
Due to the small number of theoretical separation plates of the
absorber column of the Tarong pilot plant, an increased energy
demand was measured for 30 wt% MEA (see Fig. 6). The investi-
gation of concentrated piperazine on the Tarong pilot plant were
carried out with unknown packings in the absorber and desorber
column. Because of the small absorber height, a smaller number of
theoretical separation plates can be assumed.
5. Results and discussion
In this section, the measurement results of the 37.6 wt% PZ test
campaign are compared with experimental data from the J.J. Pickle
pilot plant and Tarong pilot plant. Technical data of these test
facilities can be found in Table 2. In addition, the measurement
results were compared with experimental data from a 30 wt% MEA
measurement campaign, which were carried out at the same test
facility.
5.1. Operating parameters
The optimal operating point is searched by variation of the sol-
vent flow rate (liquid to gas ratio). At the Tarong pilot plant, a series
of experiments in which the L/G-ratio was changed was also carried
out. Measuring points of the J.J. Pickle pilot plant based on secure
and sufficient data are used for an energy comparison. From the 14
measurement points of the test facility in Austin, three measure-
ment points could be taken where similar operating parameters
were set as in Dürnrohr. These three measurement points were
also recorded with variable L/G-ratio. Due to insufficient closing
mass and energy balances (Van Wagener, 2011), only a limited
comparison of measurement results generated at the J.J. Pickle pilot
plant is possible. In Table 3, the operating parameters of the consid-
ered pilot plants are shown. The operating parameters in Dürnrohr
are default values from literature. Only the flue gas flow rate was
obtained by pre-investigation on the pilot plant, as described in
Rabensteiner et al. (2014b).
85
J.J. Pickle pilot plant Tarong pilot plant
(Plaza, 2011; Van (Cottrell et al., 2013; Cousins
Wagener, 2011) et al., 2012, 2011)
40.8a 40.8

8
12b 9.8–13c
∼750d ∼700e
 
∼1.50 ∼2.10
4.8 (±0.25)f
– 82 (±5)
∼40 33g
–h 45
5.2. Specific energy for solvent regeneration
Fig. 6 shows the specific energy for solvent regeneration as a
function of the L/G-ratio for 37.6 wt% PZ and the standard solvent
30 wt% MEA. The energy demand can be reduced to 3.17 GJ/tCO2 at
the pilot plant in Dürnrohr when using 37.6 wt% PZ. The minimum
measured specific regeneration energy when using 30 wt% MEA in
the standard case is 3.68 GJ/tCO2 , resulting in an energy saving of
14% when using 37.6 wt% PZ.
The CO2 absorption heat at the optimal operating point for
37.6 wt% PZ at mid-loading (CO2 loading see Fig. 9) according to
Fig. 7 is 77 kJ/molCO2 . When using 30 wt% MEA, the CO2 absorption
heat increased to 88.5 kJ/kmolCO2 . That means that 13% less heat
is necessary to desorb the CO2 from solution. For both solvents,
the solvent must be regenerated to 0.12 molCO2 /molequivalentamine
(Fig. 9). The temperature in the lower region of the desorber is
approximately 120 ◦ C. The CO2 partial pressure in the lower part of
the desorber for the regeneration to 0.12 molCO2 /molequivalentamine
(Fig. 7) is similar for both solvents. Therefore, the heat of evapora-
tion for producing stripping steam is similar.
Because of the more viscous piperazine solvent, the heat trans-
fer coefficient in the main heat exchanger decreases, resulting in a
increasing pinch temperature. The temperature when using 30 wt%
MEA is in the range of 4.9–5.5 K. When using 37.6 wt% PZ, this tem-
perature difference increases to 6.2 to 6.8 K.
In order to compensate the lower heat transfer coefficient, a
larger main heat exchanger has been installed in the Tarong pilot
plant (Cottrell et al., 2013).
In addition, the optimum operating point by using 37.6 wt% PZ
occurs at very low solvent flow rates. The optimum operating point
is between 2.5 and 2.75 l/m3 (Fig. 6). When using 30 wt% MEA, an
L/G-ratio of 3.2 l/m3 is necessary for reaching the optimum operat-
ing point. This means that up to 22% less solvent has to be pumped in
a circle. The dissipated heat from power plants is a crucial factor in
the design. A reduction of the solvent flow rate leads to a lowering of
the heat to be dissipated in the heat exchanger of the regenerated
solvent. Smaller dimensions of the entire piping and aggregates
leads to a further reduction in operating and capital costs.
In addition, the lower solvent flow rate results in less solvent
that must be heated in the desorber. The specific regeneration
energy increases with increasing sensible heat (Oexmann, 2011).
The specific heat capacity of the solvents is dependent on the CO2
loading and temperature (Fig. 8). The specific heat capacities of 30
wt% MEA and 37.6 wt% PZ (in Fig. 8 approximate with 40.8 wt%
86 M. Rabensteiner et al. / International Journal of Greenhouse Gas Control 39 (2015) 79–90
3.9
CO2 loading [molCO2/molequivalent amine]
3.7
specific heat capacity [kJ/kg*K]
3.5
3.3
3.1
2.9
20 40 60 80
temperature [°C]
Fig. 8. Comparison of the heat capacity from 8 m PZ (40.8 wt% PZ) and 30 wt% MEA.
Fig. 9. Dependence of CO2 loading on the L/G-ratio. Measured CO2 loading of the
rich (filled symbols) and lean solvent (unfilled symbols). Experimental data for con-
centrated piperazine generated in Dürnrohr (♦) and generated at the J.J. Pickle pilot
plant from Van Wagener (2011) (). Measurement results marked with are the three
measurement points in Fig. 6, where similar operating parameters as in Dürnrohr
were set. The dashed lines indicate the equilibrium CO2 loading at the prevailing
temperature in the Dürnrohr pilot plant (according Fig. 7).
PZ), at mid-loading and average desorber column temperature, are
equal. The heat transfer coefficient in the main heat exchanger is
lower because of the reduced solvent flow rate when using 37.6 wt%
PZ. Moreover the high viscosity of piperazine degraded the heat
transfer further. Therefore, the temperature difference of the liq-
uid phase in the desorber column (difference of the desorber sump
temperature and incoming solvent temperature) is higher when
using 37.6 wt% PZ. Nevertheless, approximately 13% of the sensible
heat can be saved compared to 30 wt% MEA.
There are high fluctuations in the measurement results of the
other two test facilities (Fig. 6). Therefore, Fig. 6 shows also smooth
lines of these measurement campaigns. Experiments at the J.J.
Pickle pilot plant, were preferably carried out with high solvent
flow rates. An increase in energy consumption at low solvent flow
rates is not visible. The lower increase in energy demand with
increasing solvent flow rate compared to the measured results gen-
erated in Dürnrohr is obvious. After completing of measurements
with basic configuration, the J.J. Pickle pilot plant was expanded. An
absorber intercooler and a two-stage flash were installed. After this
conversion, a 10 to 20% lower energy consumption than by using
30 wt% MEA (same configuration) was measured (Dombrowski,
2010).
At the Tarong pilot plant, a minimum energy demand of
2.9 GJ/tCO2 was measured. Concentrated piperazine was noted to
have consistently lower regeneration energy requirements than
the standard solvent 30 wt% MEA, nearly 15%, similar to Dürnrohr
(Cottrell et al., 2013). Reasons for the lower energy demand com-
pared to the pilot plant in Dürnrohr are the significantly higher
desorber pressure, the somewhat higher F-factor in the absorber
100 120 column and maybe the slightly higher piperazine concentration.
Effects of these operating parameters on the process are discussed
in Part II (Rabensteiner et al., 2015) of this paper. In addition, the
absorber is equipped with an intercooler. The location of the pre-
cise optimum solvent flow rate cannot be elicited exactly, but is
apparently in the range of the optimal operating point of the pilot
plant in Dürnrohr. According to Rabensteiner et al. (2014a), the
separation efficiency influences the location of the optimal oper-
ating point. The test campaign at the Tarong pilot plant was not
carried out with the standard separation efficiency of 90% but of
82%. Therefore, less vapor needs to be generated in the desorber.
The gradient of the heat of evaporation below the optimal operat-
ing point is steeper than the gradient of sensible heat for L/G-ratios
above the optimal operating point. Accordingly the minimum of
sensible heat and heat of evaporation shifts to smaller solvent flow
rates. The measured energy demand for 30 wt% MEA at the Tarong
pilot plant is significantly higher than in Dürnrohr. This may be due
to the low absorber column height. Since MEA has slower kinet-
ics, only small CO2 loadings are possible, resulting in lower lean
loadings.
5.3. CO2 loading
Fig. 9 shows the CO2 loading of the rich and lean solvent as
a function of the L/G-ratio. The CO2 loading was measured by
acid-base titration. If the L/G-ratio is increased, the CO2 loading
difference between the rich and lean solvent is reduced. Both
37.6 wt% PZ and 30 wt% MEA don’t reach an equilibrium loading
in the absorber sump. By increasing L/G-ratio, the rich loading
decreases slightly. The reason for this is the higher temperature
in the absorber column (Fig. 11). A high temperature reduces the
equilibrium CO2 loading of the aqueous piperazine solution (Fig. 7).
The comparison of the measured CO2 loadings of the regener-
ated solvent with Fig. 2 shows that there is a risk of solidification
over the entire studied range. When small L/G-ratios are set, the
CO2 loading of the regenerated solvent is at the edge of the solid-
ification range under operating conditions. In the case of a system
failure, there is especially a risk of fast solidification in the line of
the regenerated solvent between desorber and absorber. During a
brief system failure, the entire line has to be trace heated. A tem-
perature above 35 to 40 ◦ C (depending on the L/G-ratio) must be
maintained at any point. In order to ensure a safe plant shutdown
 M. Rabensteiner et al. / International Journal of Greenhouse Gas Control 39 (2015) 79–90 87

12 12

absorber height [m] 9 9

absorber height [m]

6 6

L/G-ratio = 5.0 [l/m³]

3 3

L/G-ratio = 5.0 [l/m³]

0 0
0.05 0.15 0.25 0.35 0 2 4 6 8 10 12 14
CO2 loading [molCO2/molequivalent amine] flue gas CO2 content [vol% (dry)]

Fig. 10. CO2 loading of 37.6 wt% PZ and flue gas CO2 content across the absorber height.

at lower outdoor temperatures, the entire solvent inventory must to the measurement results of Chen et al. (2010), higher CO2 load-
circulate twice without regeneration to increase the CO2 loading. ings by absorber intercooling cannot be reached on this pilot plant.
In addition to the three measurement points generated on the J.J. This could be due to already low absorption temperatures.
Pickle pilot plant, which were carried out under similar operating The measured CO2 loading at the Tarong pilot plant during oper-
parameters as in Dürnrohr, CO2 loadings of the remaining measure- ation is between 0.26 and 0.44 molCO2/ molequivalentamine (Fig. 2)
ment points are plotted in Fig. 9. Higher CO2 loadings and smaller (Cottrell et al., 2013). Thus, also significantly higher CO2 loadings
CO2 loading differences are recognized. Due to the same CO2 flue were measured during operation in this system. The reason for
gas concentration as in Dürnrohr, the reason must be a lower CO2 this is the integrated absorber intercooler which increases the CO2
separation efficiency. Because of the low inlet temperature of the equilibrium pressure, especially in the lower part of the column.
artificially generated flue gas, the absorption temperatures are sig- A significant increase in CO2 loading in the absorber column has
nificantly lower than in the pilot plant in Dürnrohr (Fig. 5). This already been proven by Sanpasertparnich et al. (2011).
again leads to higher CO2 loadings of the enriched solvent. Due to Fig. 10 shows the CO2 loading of the solvent and the flue gas
the higher CO2 loading of the regenerated solvent and the warmer CO2 content across the absorber height at different L/G-ratios. At
climate in Austin, solidification can be easily prevented. According low solvent flow rates, the majority of CO2 is absorbed in the upper

12 6

10
absorber height (J.J. Pickle pilot plant) [m]
absorber height (Dürnrohr pilot plant) [m]

8 4

6 3

4 2

2 1

L/G-ratio= 5.0 [l/m³]

0 0
0 10 20 30 40 50 60 70 80
temperature [°C]

Fig. 11. Dependence of the absorber temperature profile on the L/G-ratio. Experimental data for 37.6 wt% PZ (♦) and 30 wt% MEA (䊐) from the pilot plant in Dürnrohr.
Measured absorber temperature in the J.J. Pickle pilot plant for concentrated piperazine and L/G-ratios of 4.0 (×), 5.0 () and 6.0 l/m3 (). The solvent temperature (—) and
flue gas temperature (- -) was reconciled by Plaza (2011).
88 M. Rabensteiner et al. / International Journal of Greenhouse Gas Control 39 (2015) 79–90
part of the absorber column. With increasing solvent flow rates, the
region of the maximum CO2 absorption moves downwards.
5.4. Absorption temperature
Fig. 11 shows the temperature profile of the absorber column.
At a height of 12 meters, the temperature of the treated flue gas is
measured. The lowest temperature sensor is located in the sump of
the absorber column and measures the temperature of the enriched
solvent. The eleven intermediate temperature sensors measure a
combination of the solvent and flue gas temperature, which is
denoted as absorption temperature in the following. The highest
absorption temperature is in the vicinity of the inlet of the regener-
ated solvent. The large temperature change at the top of the column
suggests an intense reaction of carbon dioxide with the absorbent
liquid. In the lower part of the absorber column the temperature
decrease is due to heat transfer from the liquid to the gaseous
phase. Excessive solvent flow from the top to the bottom of the
absorber column causes high downward transport of the absorp-
tion heat. Therefore, at high L/G-ratios, the temperature across the
entire lower absorber column increases.
The temperature of the enriched solvent increases at high sol-
vent flow rates. According to the law of energy conservation, the
temperature of the treated flue gas (top temperature measurement
point) drops. This can be confirmed by the temperature profile.
The same theoretical consideration is confirmed by the measured
temperatures in the absorber column of the J.J. Pickle pilot plant.
Because of the low inlet temperature of the flue gas (8 to 21 ◦ C),
the prevailing absorption temperatures are generally lower than in
the absorber of the Dürnrohr pilot plant. With increasing solvent
flow rates, more and more absorption heat is transported down-
wards. The maximum temperature at high solvent flow rates is in
the lower part of the absorber column. The low position of the tem-
perature maximum and the associated problems has been already
discussed in Rabensteiner et al. (2014b).
5.5. Absorber column pressure loss
Fig. 12 shows the absorber column pressure loss as a function
of the L/G-ratio. When using 37.6 wt% PZ, the average pressure loss
is 3.5 mbar higher than when using 30 wt% MEA. There are sev-
eral possible reasons for this. The average absorption temperature
(shown in Fig. 12) when using 37.6 wt% PZ is higher than when
using 30 wt% MEA. Therefore, the operating flue gas flow in the col-
umn increases, resulting in a growing pressure drop. The dynamic
viscosity of the solvent at average CO2 loading and absorption
temperature is shown in Fig. 12. Despite higher absorption tem-
peratures of 37.6 wt% PZ, this solvent has a higher viscosity during
operation.
According to traditional flooding and pressure drop charts
(Strigle, 1993), the pressure drop dependency on liquid viscos-
ity can be seen from the capacity factor, which is proportional
to the square of the gas flow and to the liquid viscosity to the
power 0.1 (assuming constant liquid density). In the correlations
of Rocha et al. (1993), the liquid hold-up is an important parameter
in the pressure drop estimation. The liquid hold-up and then also
the pressure drop are expected to increase with increasing liquid
viscosity.
Also, according to traditional hydraulic diagrams, the flood-
ing velocity should decrease slightly with increased viscosity (to a
power of about 0.05). Experiments from Zakeri et al. (2011) show a
small flooding velocity increase with increased viscosity. This slight
effect can be explained by an increased liquid density. In a diagram
given by Strigle (1993), the liquid density dependence is given by a
power law exponent of −0.5. A liquid density increase of 30% will
have a slightly greater influence on flooding velocity than a 600%
30
pressure loss in the absorber column [mbar]
25
20
viscosity [mPa*s]
average absorption
15 70
temperature [°C]
65
37.6 wt% PZ
10 60
30 wt% MEA
37.6 wt% PZ
(Freeman and Rochelle, 2011) 55
5
30 wt% MEA
(Amundsen et al., 2009)
0
1.5 2.5 3.5 4.5 5.5
L/G-ratio [l/m³]
Fig. 12. Absorber column pressure loss (—), viscosity of the solvent at the average
absorption temperature (— —) and average absorption temperature (- -) as a function
of the L/G-ratio (Amundsen et al., 2009; Freeman and Rochelle, 2011).
increase in liquid viscosity, and is the reason for the observations
by Zakeri et al. (2011).
6. Conclusions
This paper provides the first scientific investigation of aqueous
piperazine as a solvent in a realistic PCC-pilot plant. Due to the
ability to close the energy and material balances meaningful results
have been achieved. The near-industrial height of the absorber and
desorber column and the operation with real flue gas from a hard
coal-fired power plant enables a reliable characterization of this
absorption liquid. Different operating conditions of the pilot plant
can be easily adapted.
37.6 wt% PZ (7 m PZ) was investigated in this research work.
The default operating parameters (flue gas flow rate: 100 m3 /h,
desorber pressure: 2 barabs , separation efficiency: 90%, flue gas
temperature: 40 ◦ C, regenerated solvent temperature: 40 ◦ C were
set. A measurement series with varying solvent flow rate was car-
ried out. The excellent characteristics of piperazine, which have
already been shown in laboratory scale and in other pilot plant
investigations (J.J. Pickle pilot plant, Tarong pilot plant), were able
to be confirmed in this test campaign. The minimal specific energy
for solvent regeneration is 3.17 GJ/tCO2 , resulting in an energy sav-
ing of 14% in comparison to the standard solvent 30 wt% MEA. In
addition, about 20 % less solvent (2.5 l/m3 ) has to be pumped in
a circuit for achieving the optimal operating point. The low sol-
vent flow rate means that less waste heat has to be dissipated. The
required energy for pumping is also reduced. The low energy con-
sumption of aqueous piperazine is largely owing to the lower CO2
absorption heat and the lower sensible heat.
The measured CO2 loadings are significantly lower compared to
the CO2 loadings measured in the J.J. Pickle pilot plant and Tarong
pilot plant. Reason for the lower CO2 loadings could be the high CO2
separation efficiency. As a result, the solvent must be more regen-
erated. The absorption temperature in the other two test facilities
 M. Rabensteiner et al. / International Journal of Greenhouse Gas Control 39 (2015) 79–90
is also lower. The inflowing flue gas at the J.J. Pickle pilot plant is
cold. This leads to a low absorption temperature over the whole
absorber column. Due to the low temperature, the CO2 equilibrium
loading and thus the driving force for CO2 absorption increases. The
Tarong pilot plant is equipped with an absorber intercooler which
lowers mainly the temperature in the lower part of the column.
Thus, in this area a higher CO2 loading is also enabled.
Even a small decrease in temperature of the regenerated solvent
can lead to solidification. For the loaded solvent, however, there
is no risk of solidification. After normal operation of the system
it must be ensured, that the entire solvent inventory is circulated
twice without regeneration in the desorber. The achievable CO2
loading allows a standstill without solidification at ambient condi-
tions near freezing point. In a sudden system failure, the line of the
regenerated solvent and the desorber sump must be heated.
Part II (Rabensteiner et al., 2015) of this paper presents the
attempt to reduce the energy consumption further by a detailed
parameter study. The pilot plant operation with flue gases of a nat-
ural gas-fired boiler is investigated. Emission measurements show
that the solvent degradation depends on the operating point.
Acknowledgements
This work was enabled and supported by ANDRITZ Energy &
Environment GmbH and EVN AG. Thanks go to the participating
PhD. students and staff members.
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