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Improving the regeneration of CO2-binding organic

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liquids with a polarity change†

Cite this: Energy Environ. Sci., 2013, 6,
2233
Paul. M. Mathias,a Kash Afshar,a Feng Zheng,b Mark D. Bearden,b Charles J. Freeman,b
Tamer Andrea,c Phillip K. Koech,b Igor Kutnyakov,b Andy Zwoster,b Arnold R. Smith,a
Philip G. Jessop,c Omid Ghaffari Nikc and David J. Heldebrant*b

This paper describes a solvent regeneration method unique to CO2-binding organic liquids (CO2BOLs) and
other switchable ionic liquids: utilizing changes in polarity to shift the free energy of the system. The
degree of CO2 loading in CO2BOLs is known to control the polarity of the solvent; conversely, polarity
can be exploited as a means to control CO2 loading. In this process, a chemically inert nonpolar
“antisolvent” (AS) such as hexadecane (C16) is added to aid in de-complexing CO2 from a CO2-rich
CO2BOL. The addition of this polarity assist reduces the temperature required for regeneration of our
most recent CO2BOL, 1-((1,3-dimethylimidazolidin-2-ylidene)amino)propan-2-ol by as much as 73
C. The
lower regeneration temperatures realized with this polarity change allow reduced solvent attrition and
thermal degradation. Furthermore, the polarity assist shows considerable promise for reducing the
regeneration energy of CO2BOL solvents, and separation of the CO2BOL from the AS is as simple as a
cooling the mixture to promote phase separation. Based on vapor–liquid and liquid–liquid equilibrium
measurements of a candidate CO2BOL with CO2, with and without an AS, we present the evidence and
impacts of a polarity change on a CO2BOL. Equilibrium thermodynamic models and analysis of the
Received 25th March 2013
Accepted 30th May 2013
system were constructed using Aspen Plus
, and forecasts of preliminary process configurations and
feasibility are also presented. Lastly, projections of solvent performance for removing CO2 from a
DOI: 10.1039/c3ee41016a
subcritical coal-fired power plant (total net power and parasitic load) are presented with and without
www.rsc.org/ees this polarity assist and compared to the U.S. Department of Energy's Case 10 monoethanolamine baseline.

Broader context
To combat climate change, new technologies must be developed to efficiently and economically remove CO2 from ue gas. Traditional water-based amine
systems are the only proven technology to date and will likely represent the rst generation of CO2 capture technologies, but the energy cost of CO2 removal is
very high. We present in this experimental and modeling study the application of our anhydrous CO2BOLs solvent technology in a way that exploits a polarity
change. There are two benets from CO2BOLs technology: (1) the low water level in the circulating solvent vastly reduces the energy cost due to vaporizing water;
and (2) the use of an antisolvent signicantly reduces the stripper reboiler temperature, which opens up the possibility of novel stripper technology
enhancements, namely reduced thermal degradation of CO2BOL, lower fugitive emissions, and potential for higher net power produced. Our analysis suggests
that CO2BOLs solvent technology has potential to be an efficient CO2 separating solvent system with estimated parasitic loads one third less than conventional
aqueous amine processes. While further solvent development is necessary to make the technology viable, the initial projected energy savings indicate
considerable promise for this second-generation of carbon capture solvents.

Introduction
Considerable effort has been applied to removal of CO2 from
coal-red power plant ue gas, which is a primary source of
anthropogenic CO2. Currently, absorption of CO2 from the
a
Fluor Corporation, 3 Polaris Way, Aliso Viejo, CA, 92628, USA. E-mail: Paul.M.
Mathias@Fluor.com; Tel: +1-949-349-3595
b
Battelle Pacic Northwest Division, Richland, WA, 99352, USA. E-mail: David.
Heldebrant@PNNL.gov; Fax: +1-509-375-2186; Tel: +1-509-372-6359
c
Queens University, 90 Bader Lane, Kingston, Ontario, K7L 4N3 Canada
† Electronic supplementary information (ESI) available: NMR spectra of LLE
measurements and let-down turbine conguration. See DOI: 10.1039/c3ee41016a
power plant ue gas with a solution of aqueous amines, and
subsequent regeneration of the amine solution is commercially
available and effective.1–3 However, this method consumes a
substantial amount of steam from the power plant steam cycle
and can reduce the net power from the plant by as much
as 29%.4
The primary advantage of using all-organic solvents to sepa-
rate CO2 from power plant ue gas is to exploit the potentially
lower heat required for regeneration compared to water-based
solvents. Numerous classes of “next generation” water-free
solvents are gaining attention for CO2 separations, assuming
water tolerance can be proven. Current advances in water-free

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systems include conventional ionic liquids (ILs),5 amines in ILs,6
task-specic ILs (TSILs),5,7–9 nanoparticle organic hybrid mate-
rials (NOHMs),10 phase changing solvents,11 and alkanolamines
and hindered amines in organic co-solvents.12–14 Keeping with
this trend, a class of switchable ILs, originally developed by Jes-
sop et al.,15 was specically modied for CO2 capture.16 This
particular class, referred to as CO2-binding organic liquids
(CO2BOLs) acts like aqueous amines, but uses alcohols in place
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of water and a non-nucleophilic base in place of nucleophilic
primary and secondary amines. The CO2BOL base does not
directly react with CO2, as do amines that form carbamates.
Rather, the alcohol group in the CO2BOL reacts with CO2 to rst
form an alkylcarbonic acid, which then protonates the base to
form a liquid alkylcarbonate.16 Some alkylcarbonate salts have
CO2 capacities as high as 20 wt% at 1 atm CO2.15 The resulting
polar ILs can revert to the less-polar nonionic solvent by thermal
removal of CO2.15–17
Recent advances in switchable ILs for CO2 capture include
different chemistries and improvements in material perfor-
mance. Other derivatives of switchable ILs were developed by
Eckert and Liotta et al. using liquid carbamate salts from the
reaction of CO2 with siloxated amines.18,19 Other advances in
switchable alkylcarbonate ILs, notably reducing the vapor
pressure of superbases and alcohols (to reduce evaporative
losses), have been achieved by conjoining the alcohol and base
constituents into one molecule, a strategy employed by us20 and
by Park and Kim.21 Dai et al. has shown two strategies to reduce
volatility of alkylcarbonate-based systems by making them
completely ionic (thus removing the switch between ionic and
nonionic) by pairing superbases with alcohol-functionalized ILs
or by pairing highly acidic alcohols with superbases to form
protic ILs (PILs).22,23
The rst-generation CO2BOLs combined an individual base
and an alcohol. A drawback of this dual-component system is
the relatively high volatility of the individual constituents,
which severely hinders the industrial applicability because of
solvent losses in the absorber distillate. Similar to alkanol-
amines, the second-generation CO2BOL candidates utilized
alkanolamidine and alkanolguanidine bases, which reacted
with CO2 to form zwitterionic liquids upon carboxylation.20
Unfortunately, such molecules based on amidine cores such as
(diazabicyclo[5.4.0]-undec-7-ene) or guanidine cores such as
1,1,3,3-tetramethylguanidine, while nonvolatile, exhibited
limited CO2 uptake compared to their theoretical maximums
due to their high viscosity.24 Aer a number of development
variations, a low-viscosity alkanolguanidine (A), based on a
cyclic guanidine derived from 1,3-dimethylimidazolidine, was
discovered.25 This second-generation CO2BOL (A) reacts like the
rst-generation version and can be thermally reversed, but as a
zwitterionic guanidinium alkylcarbonate IL (Fig. 1).
One unique property of CO2BOLs and other switchable ILs is
the fundamental polarity change when CO2 is chemically
bound.15,17,26 Based on this, we hypothesized that CO2 loading
could be inuenced by an external polarity change. Note that
aqueous amines do not exhibit polarity shis with CO2 loading,
nor do amines dissolved in organic solvents. No reported
polarity changes are reported for conventional TSILs, and PILs22
2234 | Energy Environ. Sci., 2013, 6, 2233–2242
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Paper
Fig. 1 Proposed reaction between CO2 and 1-((1,3-dimethylimidazolidin-2-yli-
dene)amino)propan-2-ol, (A).
undergo minor polarity changes, which are not estimated to be
signicant enough to reverse CO2 loading.
The rst example of a polarity swing used to decomplex
chemically bound gases from a capture solvent was demon-
strated with a solvent developed for hydrogen sulde capture
(H2SBOL). Here, adding a nonpolar chemically inert hexane
“antisolvent” (AS) to the H2S-loaded solvent drove the removal of
97% of the bound H2S from the H2SBOL at 25
C.27 The degree of
H2S release was dependent on the AS molar loading as well as its
miscibility with the BOL. CO2BOLs exhibit behavior similar to
H2SBOLs but require slightly higher temperature for full CO2
release due to the higher binding strength of CO2 than H2S.
Polarity-swing assisted regeneration (PSAR) primarily shis
the free energy of the reaction but also may impact the kinetics
of CO2 release. Conceptually the PSAR can be considered “self-
actuating;” mild heating induces CO2 release from the CO2BOL,
making it less polar, but the temperature increase also
increases the miscibility of the AS in the CO2BOL, which in turn
forces more CO2 release. One would expect the nonpolar AS to
destabilize the ionic form of a CO2BOL (the alkylcarbonate) and
shi the equilibrium to the le (Fig. 2), in turn releasing CO2.
While AS is present, the CO2 release is still equilibrium
controlled at a given temperature, but the equilibrium favors
lower CO2 loading than it would without AS. Thus, the AS aids in
CO2 release from the CO2BOL, allowing regeneration at
temperatures as much as 73
C lower than when using a
conventional thermal swing.
Fig. 3 shows a high-level schematic of a process envisioned
for CO2BOLs with the added PSAR. The incoming ue gas is
cooled to promote condensation of water to reduce the water
Fig. 2 Conceptual “switching” of (A) polarity as a function of CO2 loading using
a solvatochromatic scale (lmax, nm) of nile-red dye. Increasing polarity is nonpolar
(green, left) to polar (pink, right).26,28,29
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Fig. 3 Conceptual absorption and polarity-swing-assisted regeneration process.
accumulation into the CO2BOL solvent. The CO2 is chemically
reacted with the CO2BOL in the absorber, aer which the CO2-
rich CO2BOL solvent is pumped to a regeneration column. A
non-polar AS is added to the regeneration column to decrease
the bulk polarity of the CO2BOL aiding in decomplexation of the
CO2 (with mild heating). Aer the CO2 is released, it is delivered
for compression, while the AS and CO2BOL are separated by a
phase separation promoted by cooling in a coalescing tank.
Aer separation, both the AS and CO2BOL are recirculated and
the process continues with the CO2BOL pumped back to the
absorber and the AS delivered back to the regeneration column.
We describe here in detail the science and engineering required
to achieve this envisioned conguration.
Results and discussion
VLE/VLLE behavior (PTx method)
To evaluate the PSAR impacts on CO2BOL performance, the
vapor–liquid/vapor–liquid–liquid equilibrium (VLE/VLLE)
behavior of a representative CO2BOL had to rst be quantied.
All VLE measurements for a representative CO2BOL (A) were
collected using the total-pressure method (PTx) and CO2 load-
ings are reported in moles CO2 per mole BOL. Fig. 4 shows the
VLE results for the tested 1-((1,3-dimethylimidazolidin-2-yli-
dene)amino)propan-2-ol (A) only (no water or AS additions).
Here the total headspace pressure corresponds to the equilib-
rium partial pressure of CO2 (P) because of the low vapor
pressure contribution from the solvent. The VLE curves were
run in duplicate at 40, 60, 80 and 100
C. (A) shows markedly
greater CO2 uptake compared to previous CO2BOLs, indicating
a stronger reaction with CO2. The heat of solution calculated
from the data is on the order of 80 kJ mol1 of CO2.
Fig. 4 Gas–liquid isotherms for (A) and CO2 without water or AS additions (A–D
corresponds to run number).
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Fig. 5 Gas–liquid isotherms for (A) and CO2 with one molar equivalent of water.
(A–D corresponds to run number).
Previous studies conrmed that (A) had high water tolerance
with respect to viscosity (<10% increase) and the resulting
solution was a single phase and there is no evidence of bicar-
bonate precipitation.25 However, VLE data was needed to
conrm water's impact on CO2 uptake. Therefore, VLE data was
also collected with one molar equivalent of water (10 wt%)
added to the solvent, as a worst-case scenario (Fig. 5) (at load-
ings of >10 wt% water the CO2BOL becomes the solute and not
the solvent, and thus the CO2BOL would act like any aqueous
amine system and no PSAR could occur). Here, the higher total
pressure is due to the high volatility of water (i.e. relatively high
vapor pressure). The loading values in Fig. 5 were based on the
total amount of CO2 injected. Actual solvent loading was slightly
lower, as some injected CO2 remained in the gas phase. The
drop in total pressure as CO2 is loaded into the CO2BOL
corresponds to the consumption of water to form either a
bicarbonate salt (similar to aqueous amine systems) or a water-
solvated alkylcarbonate; however, no solid precipitation or
phase separation was observed in the liquid phase.25
Isotherm measurements were also performed with hexadecane
(C16) AS to determine the effect of the PSAR on equilibrium
loading of CO2 (Fig. 6). C16 was chosen due to its low cost and low
vapor pressure. The data in Fig. 6 shows little to no PSAR effect at
40 or 60
C, which is consistent with the immiscibility of the
CO2BOL with the C16 phase as observed in the VLLE measure-
ments. This is advantageous because as the solvent is continu-
ously circulated between absorption and desorption, any AS that
would carry over back into the absorber (CO2 absorption column)
would have minimal impact on absorber performance. There was,
however, a noticeable increase in CO2 partial pressure over the
Fig. 6 Gas–liquid isotherms for (A) and CO2 plus 1 molar equivalent of C16 AS.
(A–D corresponds to run number).
Energy Environ. Sci., 2013, 6, 2233–2242 | 2235

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CO2BOL at 80
C, where the phases became miscible. It should be
noted that the CO2 loadings in the PTx measurements were lower
than those in the miscibility tests indicating that the AS was more
miscible at lower CO2 loadings. In all measurements, cooling to 40


C promoted phase separation between the C16 and the CO2-rich
BOL, supporting a straightforward approach of AS separation
from the CO2BOL in a full-scale process.
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Separation of CO2BOL and antisolvent
In order to prevent biphasic conditions inside the absorber
column, AS carryover to the absorber needs to be minimized.
Currently two strategies are envisioned for removing the AS
from the lean CO2BOL (A) aer it leaves the reboiler (regener-
ation column): liquid–liquid partitioning and liquid–solid par-
titioning. Simply carrying over the AS into the absorber is
another option.
Miscibility tests were performed on multiple hydrocarbon-
based ASs (Table 1). Here, the miscibility temperature for
mixtures of 1 : 1 mole ratio of lean (A) and solvent (heptane,
decane (C10), dodecane or C16), was found to be linked to the
chain length of AS—the upper critical solution temperature
decreased with shorter chains. This nding allows candidate
ASs to be selected that will promote phase separation upon
cooling to projected operating temperatures. For the initial
vapor–liquid–liquid equilibrium (VLLE) and liquid–liquid
equilibrium (LLE) measurements, C16 was chosen as the most
viable AS due to its low vapor pressure. However, C16 carryover
does not help lower the viscosity of (A) at high CO2 loadings.
Therefore, further testing is required to include viscosity attri-
butes in AS evaluations and selection. It should be noted that
hydrocarbon-based ASs were tested as a proof of concept of the
PSAR, however environmentally benign or “greener” AS are a
focus of current study.
Fig. 7 shows the phase diagram for C16 or C10 and “lean” or
“rich” (A). In this experiment, “lean” (A) contains 4 mol% of the
carbonated species and 96 mol% of the CO2-free species as
determined by proton nuclear magnetic resonance (1H-NMR)
(Fig. S1†). Complete exclusion of CO2 by high vacuum and
heating for more than 4 h did not show signicant change in
the phase behavior (Fig. 7, red 7). Fig. 7 red B indicates
miscibility of the C16 and lean-(A) above 62
C, and sponta-
neous separation of the mixture into two liquid phases below
that temperature. For example, if the lean-(A)–C16 mixture is
cooled to 40
C, the lower liquid phase (le side of diagram) will
contain 92 wt% (A) and 8 wt% C16. The upper liquid phase
(right in the diagram) will contain 22 wt% (A) and 78 wt% C16
AS. Cooling to 20
C ensures that more (A) is recovered from the
Table 1 Temperatures of miscibility for 50 mol% mixtures of various hydro-
carbon-based ASs in CO2-lean (A)
Antisolvent Chain length Tmiscibility (
C)
Heptane 7 > 30
Decane 10 38
Dodecane 12 39.3
Hexadecane 16 62
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Fig. 7 Phase diagram for CO2-lean (A)/decane (O), CO2-lean (A)/hexadecane
(B), CO2-rich (A)/decane (:), partially carbonated (A) (20% mol CO2)/hex-
adecane (C) and CO2-free (A)/hexadecane () as a function of temperature.
upper C16 phase, but only slightly decreases the carryover of AS
in the recovered (A) stream (6 wt% C16 instead of 8 wt%).
Process simulations take into consideration an estimated
carryover of 0.3 wt% of AS into the absorber.
Similar tests were performed with C10 as the AS and lean (A)
(Fig. 7, blue O). CO2-lean (A) and C10 are miscible in all
proportions above 40
C, but at 25
C or below they split into a
lower liquid phase ((A)-rich phase: 81% (A) and 19% C10) and
an upper liquid phase (AS-rich phase: 16% (A) and 84% C10).
Therefore, choosing C10 as the AS causes more AS carryover in
the recovered (A).
When CO2 is added to the (A)–AS mixture, the phase
behavior changes dramatically. Partial carbonation of the
compound (20 mol% which we dene as “partially carbonated”,
Fig. 7, red C) dropped the amount of C16 in the lower liquid
phase at 40
C from 8 wt% to less than 1.5 wt% as determined
by gas chromatography with thermal conductivity detection
(GC-TCD), and increased the amount of C16 in the upper liquid
phase from 78 wt% to 91 wt%. CO2-saturated “rich” (A) showed
very low miscibility with C10 (Fig. 7, blue :); two phases are
observed even at 90
C and the CO2-rich (A) did not completely
dissolve in C10 in the temperature range that our controlled
temperature bath allows (<95
C). At lower temperatures, the
addition of CO2 to the (A)–C10 mixture expands the two-phase
region of the phase diagram, so that the C10 carryover in the (A)-
rich phase is as low as 4%. The high viscosity and the two-phase
behavior at high temperatures are only observed at CO2 satu-
ration (estimated stripper conditions). Note that some AS
carryover in the recovered (A) could help lower the solvent
viscosity.
C16 was the preferred AS for this study due to its low vapor
pressure compared to C10, however C16 will be unlikely to be
used industrially due to environmental concerns. Preferred ASs
would be biodegradable, non-toxic, and cheap and have low
ammability. The search for more environmentally benign ASs
is currently a focus of study in our laboratory.
Thermodynamic model
A thermodynamic model was developed based on consideration
of the solution chemistry and used the four types of PTx data
(herein BOL is dened as CO2-free, and CO2BOL is CO2-rich):
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 absorption of CO2 on the neat BOL.

 effect of water on the absorption of CO2 on BOL.
 effect of the AS on the absorption of CO2 on BOL. It should
be noted that the BOL-AS system has a region of liquid–
liquid immiscibility that is affected by the addition of CO2.
 quaternary data with all four principal components (BOL,
CO2, water and AS) present.
Special attention was devoted to ensuring that the thermo-
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dynamic model captures the key effects of the solvent system

(BOL, water and AS). The rst effect is the complexation of CO2
and BOL, which is enhanced by addition of water and dimin-
ished when AS is added. Due to the thermodynamic nonideality
Fig. 8 Estimated CO2 partial pressures in BOL–H2O–C16 at 100
C. The relative
of the system, the ElecNRTL-RK model in Aspen Plus was
solvent concentrations are equimolar.
chosen, together with the chemistry capability. The chemistry
capability enables the effect of chemical reactions (chemical
complexation) to be captured in the thermodynamic model. The
ElecNRTL-RK model uses Chen's electrolyte activity-coefficient
model and the Redlich–Kwong equation of state to describe the
vapor phase. Further details are available in documentation
from Aspen Technology Inc.
The chemistry model for the CO2BOL-PSAR system is based
on the understanding of the fundamental chemistry, as well as
practical experience with electrolyte process simulation. When
tting the data, it was found that a zwitterionic guanidinium
alkylcarbonate (B) (Fig. 1) with a 1 : 1 stoichiometry of BOL : CO2
t the data more closely than a conventional 2 : 1 ionic complex
with a separated guanidinium cation and alkylcarbonate anion.
Thus, for the model, two complexes are postulated that result in
the following two chemical-equilibrium equations: Fig. 9 Fraction of CO2 in BOL–H2O–C16 at 100
C that is complexed. The relative
solvent concentrations are equimolar.

2CO2 + 2BOL 4 BOLCO2+ + BOLCO2 (1)

The enthalpy of solution of CO2 in the solvent is extremely
+
H2O + BOL + CO2 4 BOLH + HCO3 (2) important because the paramount goal of CO2 capture processes
is to reduce the energy cost of CO2 capture and this energy cost is
Breaking out separate charges for the zwitterionic CO2BOL- directly related to the enthalpy of solution. For reasons discussed
CO2 ionic species (BOLCO2 alkylcarbonate anion and in a later section, the enthalpy of solution of most interest is that
BOLCO2+ guanidinium cation) was needed for Aspen Plus to with BOL–H2O mixtures as the solvent, and these are presented
enable the Born term, which accounts for the effect of the ionic next. Fig. 10 shows the enthalpy of solution of CO2 in BOL as a
strength and the solvent dielectric constant.30 This term is vital function of temperature and CO2 loading. At 40
C (typical
in predicting the effect of the low-dielectric-constant AS to absorber temperature), the enthalpy of solution is about 82 kJ
reduce the tendency of the mixed solvent to complex CO2. mol1 at low CO2 loadings and then decreases in magnitude with
The resulting model quantitatively describes the data and CO2 loading. The model accounts for expected behavior; as the
captures the relative solubility of CO2 in the system as the
composition of the BOL–H2O–C16 solvent changes. Fig. 8
presents the CO2 calculated partial pressure at 100
C for four
representative solvent compositions. The composition on the x-
axis is the CO2 loading with respect to the BOL. Fig. 8 shows that
adding 1 mole of H2O to 1 mole of BOL signicantly reduces the
CO2 partial pressure, while adding 1 mole of C16 to 1 mole of
BOL sharply increases the CO2 partial pressure. The 1 : 1 : 1
BOL–H2O–C16 solvent has an absorption strength between
those of neat BOL and 1 : 1H2O : BOL. Fig. 9, which presents the
fraction of CO2 that is complexed, provides an explanation of
the results in Fig. 8. The reduction of the CO2 partial pressure is
caused by increased complexation of the CO2, and conversely,
the increase of the partial pressure is due to decomplexation of
CO2 from the BOL. Fig. 10 Calculated enthalpy of solution of CO2 in BOL.

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Fig. 11 Calculated enthalpy of solution of CO2 in 1 : 1H2O : BOL.
temperature increases, the magnitude of the enthalpy of solution
decreases, as does the CO2 loading at which the enthalpy of
solution drops. Fig. 11 presents the calculated CO2 enthalpy of
solution in the 1 : 1H2O : BOL solvent. The difference here is that
the enthalpy of solution rst increases with CO2 loading, and
may decrease if the temperature is sufficiently high (say, $80
C).
Process concept
Fig. 12 shows a high-level process ow diagram of the CO2BOL
process using PSAR. The envisioned process would operate
similarly to a conventional aqueous amine system, with the
main difference being the introduction of an AS to aid desorp-
tion of CO2 from the rich solvent. As with other solvents that
work on chemical absorption, the incoming ue gas is cooled
and conditioned in a direct contact cooler using process cooling
water. The CO2 is absorbed at about 40
C in the lean CO2BOL
solvent, where “lean” refers to the low CO2 content of the stream
leaving the stripper. Aer exiting the absorber, the rich CO2BOL
solvent (“rich” refers to the low CO2 content of the stream
exiting the absorber) is mixed with the AS, heated in the cross
exchanger to improve energy efficiency, and then pumped to a
regenerator (e.g., a stripper) column. The AS changes the
polarity of the rich CO2BOL solution, which destabilizes the
chemically bound CO2 so that release can occur at lower
temperatures. The hot rich solution exchanges heat with the
lean solution to recover heat, and then is separated into two
liquid phases in a coalescer. Similar analysis using the Kirk-
wood–Onsager approach will be the focus of future studies.
Fig. 12 Block flow diagram for the CO2BOL/PSAR process.
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Fig. 13 Flow diagram of the CO2BOL/PSAR process showing heat and material
flows to a subsection containing the stripper, cross exchanger and coalescer. The
rich stream (SR) flows into the section, and the lean solvent (SL) and CO2 product flow
out of the section. The heat flows QR and QC are the reboiler and condenser duties.
Fig. 13 is a simplied representation of the material and heat
ows to/from a owsheet subsection (within the dashed square)
containing the stripper, cross exchanger and coalescer. The
representation is simplied because it neglects any make-up
solvents, and assumes that the coalescer removes all AS from
the rich solvent leaving the stripper. Note that this gure also
does not include equipment such as a lean cooler to control
coalescer temperature. The purpose of the simplied analysis is
simply to understand the dominant energy effects of the
process. A more detailed process analysis will be performed
later to determine a suitable process conguration.
Fig. 13 indicates that adding antisolvent does not directly
affect the reboiler duty, QR, since the AS is entirely within the
envelope chosen. eqn (3) presents the energy balance for the
subsystem.
HSR  HSL  HCO2 + QR  QC ¼ 0 (3)
QR ¼ (HSL + HCO2  HSR) + QC (4)
Note that both QC and QR are positive in the present analysis
since their ow direction has been taken into account. The rst
term on the right side of eqn (4) is the integral heat of solution
from adding CO2 to the lean solvent as well as sensible heat
effects since the lean solvent is warmer than the rich solvent,
and the temperature difference is the temperature approach in
the cross exchanger.
Any condenser duty increases the reboiler duty, and, as
noted above, QC is strongly related to the condensation of water;
reduced water ows in the reboiler will reduce QC and conse-
quently reduce QR.
With this analysis as background, we can now propose ways
in which the AS can reduce the heat rate of the process (QR)
relative to the process without the AS.
The AS releases CO2 from the rich solvent, and hence the
lean loading of CO2 may be reduced. For the same rich loading,
the BOL ow rate could be reduced.
The present analysis does not directly consider the effect of
water. It is known from the measured absorption data that
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Paper
water makes BOL a stronger solvent for CO2. Since the use of an
AS reduces the lean CO2 loading, it is possible that for a spec-
ied BOL rate, the water level in the process may be reduced.
Water is the main contributor to QC, so a lower water ow rate
will reduce QR at a given BOL ow rate.
Another way of viewing the AS effect is that it drops the
required reboiler temperature. Given the present analysis, a
lower reboiler temperature does not directly reduce QR, but a
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lower temperature will increase the applicability of advances in
the use of steam to supply QR, and thus to increase process
efficiency. The steam used to supply the reboiler duty QR now
may be expanded to lower pressure, thus generating more
power before proceeding (still at a sufficient temperature) to
drive the stripper reboiler.
As noted above, this simplied analysis is intended to be
complementary to detailed Aspen Plus simulations.
Full-scale projections of reboiler duty
Once the thermodynamic model was completed, process
simulations were run to estimate the energy impacts of the
CO2BOL-PSAR system. The Aspen Plus simulations were aimed
at understanding the effect of AS concentration on the stripping
conditions and duties. A key assumption in the simulations was
that the rich solvent viscosity was 20 cP – a development target
for the solvent. Further, mass transfer and kinetics were not
considered, i.e. equilibrium columns were used to model the
Absorber and Stripper. In these simulations, the molar ratio of
AS to BOL in the stripper rich-solvent feed was varied from no
AS to 2 moles of AS per mole of BOL. The results indicated a
wide variation of reboiler temperatures and heat rates
depending on the specied molar ratio of AS to BOL. Fig. 14
shows a plot of the predicted heat rates and reboiler tempera-
tures as a function of AS loading. Here, the predicted reboiler
temperatures are signicantly reduced with increasing AS
loading, as expected. At two molar equivalents the calculated
reboiler temperature is projected to decrease to 86
C from a
starting point of around 159
C. However, the corresponding
heat rates, or reboiler duties, are not predicted to change
signicantly. The initial increase in heat rate is due to the
additional mass and sensible heat of the AS prior to it having
Fig. 14 Heat rate and regeneration temperature as a function of AS (C16)
loading.
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any signicant impact on solution polarity. As more AS is
added, its mole fraction is high enough to decrease the solution
polarity and reduce the reboiler temperature, but the effect of
the specic heat still appears to overcome any net reduction in
heat rate. In summary, the ow of AS has a relatively small effect
on the calculated heat rate (10–15%), but a signicant effect on
reducing the reboiler temperature (up to 73
C).
One reason for the small heat rate reduction with PSAR has
to do with the large molecular weight of C16 as an AS (224 g
mol1) compared to the mass of the CO2BOL (171 g mol1). If
lighter ASs, such as C10, or solid ASs are utilized, the reboiler
heat rate could be signicantly reduced. The initial AS studied
(C16) also has a high upper critical solution temperature (62
C
CO2 free, and 120
C CO2 loaded), requiring higher tempera-
tures to make the C16 miscible with the CO2-rich CO2BOL. If
more miscible ASs such as C10 (critical solution temperature
38
C CO2 free and 92
C CO2 rich) are used, the regeneration
temperature is projected to decrease compared to the C16 case.
If full optimization of ASs was performed, a minimum regen-
eration temperature $65
C is expected, as indicated by critical
solution temperatures of ASs.
Simulations with water added to the BOL showed signicant
increases in reboiler heat rates (Fig. 14). However, this increase
must be balanced with the energy required to remove the water
upstream, and requires further process optimization.
Benet of lower regeneration temperatures available through
PSAR
There are three primary benets to reducing the regeneration
temperature of the CO2BOL solvent: reduced thermal degrada-
tion of CO2BOL, lower fugitive emissions and potential for
higher net power produced. The rst two benets are self
explanatory, while the third requires a more thorough discus-
sion (vide infra).
The previous section outlines a number of potential
improvements to the PSAR system that could lower the corre-
sponding reboiler duty relative to aqueous amines. However,
even if the reboiler duty is unchanged with AS additions, the
lower regeneration temperature offers signicant efficiency
gains from the steam cycle of the power plant. A simple let-down
turbine could expand the reboiler steam prior to its condensing,
to produce more power from reboiler steam while it was cooled
to the lower operating temperatures.
Net electric power predictions of PSAR
Projections of the net power production from a full-scale power
plant were also estimated for the CO2BOLs-PSAR process using
the previously described ASPEN Plus models. The DOE refer-
ence Case 10 using monoethanolamine (550 MWe net electric
power, subcritical PC plant) was used as the basis for the
analyses.4 Case 10 is a conventional coal red 550 MWe net
electric power plant. The ue gas ow rate (3 213 000 kg h1)
and composition (13.5 vol% CO2 and 15.4 vol% H2O, balance
mostly N2) from Case 10 was xed for all of the CO2BOL-PSAR
cases evaluated.4 The ue gas ow rate and composition from
Case 10 were xed for all of the CO2BOL-PSAR cases evaluated.
Energy Environ. Sci., 2013, 6, 2233–2242 | 2239

Energy & Environmental Science
Table 2 Projected net electric power output for CO2BOL-PSAR as a function of
AS (C16) loading
Antisolvent loading Regeneration Net electric power
(molar equivalent) temperature (
C) produced (MWe)
0 159 594
0.5 132 603
1 109 621
2 86 637
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TBDa 65 652
a
Based on projections of upper critical solution temperature.
This means that processes more efficient than Case 10 will be
projected to produce more net electricity than 550 MWe.
Table 2 shows the estimates for net electric power as a
function of AS loading for CO2BOLs-PSAR cases using C16 AS.
As presented in Table 2, the predicted net power of the CO2BOL
case with no AS addition is 44 MWe higher than that of Case 10.
This corresponds to a parasitic power of 25%, versus 30% for
Case 10. When the PSAR is applied, the net power for the
CO2BOL process rises with increases in AS loading. The addi-
tion of AS produces more predicted power because of the
described let-down turbine benet, with as much as 90 MWe net
electric power increase using 2 molar equivalents of C16. The
lowest theoretical reboiler temperature is estimated to be 65
C
with a best-case AS. Assuming this temperature, and no further
reductions in reboiler duty, the net electric power for the PSAR
at full strength is estimated to increase by over 100 MWe
compared to the baseline Case 10, which corresponds to a
parasitic load of 17% (nearly half that of Case 10).
Conclusions
CO2BOLs (when paired with polarity-swing regeneration) are
estimated to be efficient solvents for CO2 separations from ue
gas. Equilibrium measurements show CO2 loadings of CO2BOLs
are comparable to those of aqueous amines, and that our
current candidate molecule (A) has high water tolerance.
CO2BOLs show a stronger temperature dependence on CO2
loading than aqueous amines but still require high regenera-
tion temperatures (159
C) for conventional thermal regenera-
tion. Addition of the polarity swing using C16 as a
representative AS was found to impact equilibrium loading
through a reduction in the CO2BOL's polarity, allowing for
similar CO2 stripping quantities at far lower stripping temper-
atures (86
C) and a projected theoretical minimum regenera-
tion temperature of 65
C. The stripping temperature was found
to be dependent on the amount of AS added, indicating the
PSAR is tunable.
The lower regeneration temperatures available in the PSAR
allow two key process benets: reduced solvent attrition and
higher net power output. The low regeneration temperatures
reduce fugitive emissions and reduce thermal degradation of
CO2BOL compared to conventional thermal regeneration. The
lower regeneration temperature also allows for a simple let-
down turbine to be used to extract power before delivery to the
reboiler. This extra power coupled with the low reboiler heat
2240 | Energy Environ. Sci., 2013, 6, 2233–2242
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Paper
duty is estimated to reduce the parasitic load of the CO2BOL/
PSAR process at 65
C to 17%, about half that of the DOE Case
10 baseline of 30%. This equates to as much as 100 MWe more
Parasitic
load net power production than the DOE Case 10 baseline, at an
equivalent coal feed rate.
25% This assessment of the CO2BOL/PSAR system is still new and
23% the results are preliminary as these results were derived from
21%
19%
equilibrium simulations of (A) with a representative AS. As we
17% test other candidate ASs we will extend our simulations to
quantify their behavior in the PSAR process and compare it to
incumbent systems.
Experimental
Solvent preparation and handling
(A) was synthesized according to literature methods25 and was
stored under N2. (A) was evacuated overnight before each use to
remove any N2 or water in the sample. (A) was then delivered via
syringe for each use.
(A) was either used fresh or “regenerated” in situ by heating
to 60–80
C under vacuum until all water and CO2 were removed
from the sample. Neat 13C NMR conrmed the integrity of the
sample before each subsequent use.
VLE measurements
Equilibrium PTx data were obtained using a custom-made
stainless steel cell of approximately 430 cm3 internal volume
with a chamber diameter of 5.08 cm. Two opposing borosilicate
sight glass windows provided for visual observation of the liquid
level and phase behavior. The cell vessel was submerged in a
silicone oil bath to control temperature. The test sample in the
cell chamber was mixed by a magnetic stir bar. Liquid solvent
sample was injected through a valve on the cell top ange. A gas
injection device and a vacuum pump were connected to the cell
via another valve manifold. The injection device consisted of a
gas-tight syringe with pressure transducers at the syringe and
the manifold. A third pressure transducer was installed on the
cell main chamber.
VLE measurements were done under isothermal conditions.
The cell was initially loaded with a known quantity of solvent
sample between 20 and 50 mL. The cell was then evacuated to
remove any residual absorbed gas and volatile vapor. A series
of gas injections between 0.1  103 and 10  103 mol was
made using a supercritical grade CO2 from Praxair. The cell
pressure and temperature were allowed to reach a new steady
state prior to each injection. The equilibrium pressure and
temperature were then recorded. The solvent CO2 loading was
not directly measurable. Assuming ideal VLE behavior, gas
phase compositions were calculated from pure component
vapor pressures using Raoult's law. The CO2 concentration in
the liquid phase was then calculated from the mass balance
within the cell.
LLE experiments
n-C16 (99%) and 2-dimethylamino ethanol (>95.5%) were
purchased from Sigma-Aldrich. n-C10 (99%) was purchased
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Paper
from Alfa Aesar. high performance liquid chromatography
(HPLC) grade methanol was purchased from Fisher. CO2 (CD
3.0 grade, 99.9%) was purchased from Praxair. All chemicals
were used as received without further purication.
A constant temperature bath (Cannon CT500 series II) was
used to get accurate temperature for phase behavior studies. A
Shimadzu GC-17A gas chromatograph and silica column (CP-
Volamine by Agilent J&W) were used to determine the compo-
Published on 31 May 2013. Downloaded by University of Illinois at Chicago on 28/10/2014 10:00:09.
sition of the different phases.
Liquid phase behavior of (A)/antisolvent
(A) (650 mg, 3.8  103 mol) and n-C16 (860 mg, 3.8  103 mol)
or n-C10 (508.1 mg, 3.8  103 mol) were added to a 10 mL glass
vial equipped with a Teon
magnetic stir bar. The vial was
closed with a rubber septum, which was then pierced with a
venting needle to prevent pressure buildup. The vial was
inserted into a constant temperature water bath and stirred for
1 h at a specic temperature. The stirring was then stopped and
the phases were allowed to separate for at least 2 h. A sample
was then carefully taken from one of the two phases. The
remaining liquids were then stirred again for 1 h, aer which
they were allowed to resettle for 1 h before a sample was taken
from the other phase. Each phase was dissolved in 100 mL
methanol solution containing 30 mL of 2-dimethylamino
ethanol as internal standard. The diluted solutions were injec-
ted into the GC, and the AS weight fraction was determined
from the AS/internal standard ratio using a calibration curve
obtained for each AS system.
Liquid phase behavior of (A)/antisolvent/CO2
The phase behavior of ((A) + CO2) was performed in a similar
way: (A) (650 mg, 3.8  103 mol) and n-C16 (860 mg, 3.8  103
mol) or n-C10 were added to a 10 mL glass vial equipped with a
Teon magnetic stir bar. The vial was closed with a rubber
septum and pierced with a needle to prevent pressure buildup.
The vial was placed in a constant temperature water bath and
stirred for 1 h. Then CO2 was bubbled into the solution at a
specic temperature via a second needle for 1 h. The stirring
was stopped and the phases allowed to separate at the specic
temperature for 2 h under CO2-saturated atmosphere. The AS
weight fraction was determined for each phase by GC using the
same method as before.
Liquid phase behavior of (A)/C16/20 mol% CO2
Partially carbonated (A) was prepared by weighing the required
amount of lean (A) (600.0 mg, 3.50  103 mol) into a 10 mL
glass vial equipped with Teon magnetic bar. CO2 bone-dry
grade (30.8 mg) was then bubbled directly into it while the
weight increase was monitored with an analytical balance. The
vial was then sealed with a rubber septum and C16 added via a
syringe. The mixture was heated in the sealed vial at the
required temperature and stirred for 1 h. Stirring was stopped
and the phases allowed to separate at the specic temperature
for 2 h. GC determined the C16 weight fraction in each phase as
specied before.
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Acknowledgements
The authors would like to acknowledge the Department of
Energy's Office of Fossil Energy for funding, (award # DE-
FE0007466), Mike Elliot for discussions on process congura-
tions and Don Camaioni for thermodynamic discussions. PNNL
is proudly operated by Battelle for the United States Department
of Energy.
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