Chemistry–Sustainability–Energy–Materials

Accepted Article

Title: Integrated Capture and Conversion of CO2 to Methane using a

Water-lean, Post-Combustion CO2 Capture Solvent

Authors: David Heldebrant, Jotheeswari Kothandaraman, Johnny

Saavedra Lopez, Yuan Jiang, Eric D. Walter, Sarah D.
Burton, and Robert A. Dagle

This manuscript has been accepted after peer review and appears as an
Accepted Article online prior to editing, proofing, and formal publication
of the final Version of Record (VoR). This work is currently citable by
using the Digital Object Identifier (DOI) given below. The VoR will be
published online in Early View as soon as possible and may be different
to this Accepted Article as a result of editing. Readers should obtain
the VoR from the journal website shown below when it is published
to ensure accuracy of information. The authors are responsible for the
content of this Accepted Article.

To be cited as: ChemSusChem 10.1002/cssc.202101590

Link to VoR: https://doi.org/10.1002/cssc.202101590

01/2020
ChemSusChem 10.1002/cssc.202101590

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Integrated Capture and Conversion of CO2 to Methane using a
Water-lean, Post-Combustion CO2 Capture Solvent
Jotheeswari Kothandaraman, Johnny Saavedra Lopez, Yuan Jiang, Eric D. Walter, Sarah D. Burton,
Robert A. Dagle, and David J. Heldebrant*

Abstract: Integrated Carbon Capture and Conversion of CO2 into The direct conversion of captured CO2 overcomes the
materials (IC3M) is an attractive solution to meet global energy challenges associated with the CCUS as the exothermic
demand, reduce our dependence on fossil fuels, and lower CO2 hydrogenation offsets the energy required for the regeneration of

Accepted Manuscript
emissions. Herein, using a water-lean post-combustion capture carbon capture solvent. There has been a surge in the literature
solvent, (N-(2-ethoxyethyl)-3-morpholinopropan-1-amine) (2- for integrated capture and conversion of CO2. [3] While advances
EEMPA), >90% conversion of captured CO2 to hydrocarbons, mostly have been made in reducing CO2 to chemicals and fuels, the
methane, is achieved in the presence of a heterogenous Ru catalysts majority of amine and alcohol-based capture solvents (used by us
under relatively mild reaction conditions (170 °C and <15 bar H2 and others) for thermocatalytic conversion are not viable solvents
pressure). The catalytic performance was better in 2-EEMPA than for CO2 capture as they are costly, too viscous (eg.
aqueous 5M monoethanol amine (MEA). Operando nuclear magnetic polyethylenimine), or volatile (e.g., triethylamine/ethanol) to be
resonance (NMR) study showed in situ formation of N-formamide used in post-combustion CO2 capture. With the groundwork
intermediate, which underwent further hydrogenation to form methane reactivity demonstrated, there is a need to apply this knowledge
and other higher hydrocarbons. The technoeconomic analyses (TEA) and design reactions and conditions that could proceed in
showed that the proposed integrated process can potentially improve promising carbon capture solvents.
the thermal efficiency by 5% and reduce the total capital investment Aqueous systems have a higher energy demand and cost
and minimum synthetic natural gas (SNG) selling price by 32% and compared to water-lean solvents.[5] The commercially used
12% respectively compared to conventional Sabatier process, aqueous post-combustion solvents (e.g., 5M MEA) are not
highlighting the energetic and economic benefits of integrated capture suitable for combined capture and thermocatalytic hydrogenation
and conversion. Methane derived from CO2 and renewable H2 to products that involve the formation of water as a by-product
sources is an attractive fuel, and it has great potential as a renewable since the water shifts the equilibria backward (e.g., methanol,
hydrogen carrier as an environmentally responsible carbon capture ethanol, methane, and others). Thus, the water-lean solvents are
and utilization approach. viable for thermocatalytic reductions because of the limited
amount of water. Another advantage of water-lean capture
solvents is the higher physical solubility of CO2 that can be
Introduction dissolved as compared to aqueous solvents, lowering the
pressures of CO2 required to promote the reaction. We note that
Carbon capture, utilization, and storage (CCUS) has been widely
there are elegant electrocatalytic approaches for utilizing CO2 in
considered as a solution to reduce the CO2 emitted into the
aqueous carbon capture solvents such as 5M aqueous MEA,
atmosphere, thus mitigating global warming, ocean acidification, though such approaches decompose CO2 into CO and proceed
and climate change.[1] Amine-based solvents are commonly to make products via conventional synthesis gas.[6] Nonetheless,
employed as solvents to capture CO2, which then is released,
demonstratable examples of thermocatalytic reduction of CO2 in
compressed, and transported/stored to reduce CO2 emissions
real solvents are limited.
from large scale industrial processes. [2] Significant investments
Here, we show the combined capture and thermocatalytic
are being made in carbon capture technologies, but the cost
conversion of CO2 to methane using an advanced water-lean
associated with separation, compression, transportation, and
post-combustion capture solvent with the lowest total costs of
storage is still economically prohibitive. On the other hand, CO2 is
capture ($47.1/tonne CO2) of most of the reported CO2 capture
an attractive and inexpensive C1 feedstock to produce value- technologies. [5b] The required H2 for this process can be obtained
added chemicals and fuels such as methane, methanol, ethanol, from renewable energy sources, namely, wind, solar, geothermal,
dimethylcarbonate, formic acid, CO, cyclic carbonates,
or biomass. Synthetic natural gas (SNG) is a type of gas that
methylformate, polycarbamates, and polycarbonates.[3, 4]
serves as a substitute for natural gas and is suitable for
transmission in natural gas pipelines, consisting primarily of
methane, and small amounts of light hydrocarbons, nitrogen,
Dr. Jotheeswari Kothandaraman, Dr. Johnny Saavedra Lopez, Dr.
etc.[7] It is considered as a promising sustainable energy storage
Yuan Jiang, Dr. Eric D. Walter, Dr. Sarah D. Burton, Mr. Robert A.
Dagle and Dr. David J. Heldebrant* material to efficiently integrate intermittent renewable energy
Pacific Northwest National Laboratory, Advances Energy Systems, sources into the electrical grid. Furthermore, SNG is also
902 Battelle Blvd, Richland, Washington 99352, USA attractive because the existing natural gas infrastructure can be
E-mail: [email protected],
readily adapted.
[email protected], [email protected],
[email protected], [email protected], Materials with dual function have been reported in the
[email protected], [email protected] literature for combined CO2 capture and conversion to methane.
[8]
Supporting information for this article is given via a link at the end of the
These materials are composed of a sorbent and catalytic active
document. component. The oxides (e.g., CaO) and carbonates (e.g.,

1
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ChemSusChem 10.1002/cssc.202101590

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Na2CO3) are used as CO2 sorbent. Metals such as Ni, Ru, and Rh conversion is slower in the aqueous solvent because the excess
act as catalysts for the conversion of adsorbed CO2. However, water in the reaction does not favor the dehydration step. This
both the adsorption and hydrogenation reaction are performed at shows water-lean solvents are a superior option for integrated
high temperature (300 °C–750 °C). Other proposed technologies capture and conversion. A prolonged reaction time in EEMPA
include utilizing traditional aqueous amine CO2 capture solvents solvent resulted in >90% conversion of captured CO2 (entry 12,
and employing gas-phase CO2 hydrogenation using methane Table 1).
synthesis catalysts. However, these approaches are
economically less viable due to the energy penalty of CO2 MTable 1. Hydrogenation of captured CO2 to methane
separation and compression prior to the gas-phase CO2 Step 1 Step 2

hydrogenation. CO2 4H2

N N CH4 + N
H Capture H
-2H2O
(recycle)
Amine moiety O O-
Results and Discussion of a capture solvent

Accepted Manuscript
O
N N OH
H H H 2N
2-EEMPA, was chosen for the initial batch reactor studies Capture solvents:
O
N
N

to form methane from CO2 (Table 1). 2-EEMPA 2-EEMPA Aminopydridine MEA

is a single- component, water-lean post- CO2 Selectivity (%)

T
combustion CO2 capture solvent with high Entry Catalyst t (h) conversion
(°C)
durability, low total capture cost and high (%) CH4 C2H6 C3-C4
capture efficiency (>95% with coal derived flue
1 5wt% Ru/Al2O3 170 3 75.8 87.4 4.6 8
gas).[5a] A post-combustion capture solvent is
preferred as it can separate CO2 from dilute 2 5wt% Ru/Al2O3 145 3 20.4 94 2.2 3.7
streams. When CO2 is captured in 2-EEMPA, it
3 5wt% Ru/Al2O3 120 3 3.6 98 2 0
forms a carbamate intermediate, which is an
excellent intermediate to accomplish CO2 4[a] 5wt% Ru/Al2O3 170 3 82.6 99 0.8 0.2
hydrogenation instead of using gaseous CO2 at
5 5wt% Pd/ZnO/Al2O3 170 3 <1 trace - -
high-pressure. Gas-phase CO2 methanation
has been shown to be catalyzed by transition 6 5wt% Pd/ZnO 170 3 0 - - -
metals such as Ru, Rh, Ni, Co, Pt, and Pd.[9]
7 64wt% Cu/ZnO/Al2O3 170 3 <1 trace - -
Among these metals, Ru is often reported as a
most active catalyst for CO2 methanation. 8 35wt% Ni/alumina 170 3 1.3 97.1 2.9 -
Thus, we decided to screen a commercial Ru
9 5wt% Ru/C 170 3 12.3 90.2 5.9 3.8
catalyst, Ru/Al2O3, for hydrogenation of
EEMPA-carbamate. 10[b] 5wt% Ru/Al2O3 170 3 21.6 91.8 8 0.2

11[c] 5wt% Ru/Al O

2 3 170 3 29.8 79.2 5.2 15.6
There was no detectable amount of
methanol observed in the presence of Ru/Al2O3 12 5wt% Ru/Al2O3 170 6 >99 87.1 3.8 9
(Table 1, entry 1). However, >75% conversion
[d]
13 5wt% Ru/Al2O3 170 6 73.6 92.2 6.8 1
of captured CO2 was observed with 87%
selectivity for methane at 170 °C. Small
Initial P(H2) =15 bar, t = 3 h, captured” CO2=~14.5 mmol, 2-EEMPA=5 g (23 mmol), catalysts = 200
amounts of ethane and other higher mg, T = 170 °C, the capture solvent was sparged with CO2 for a given time (~15 min - 1 h depending
hydrocarbons were also detected by gas on the capture solvent) to load ~15 mmol of CO2, the amount of CO2 captured was determined
chromatography (GC). CO2 methanation was gravimetrically with an analytical balance.[a]using CO2 gas and in the absence of EEMPA,
[b]
aminopyridine (5g) – 15.2 mmol CO2 captured, [c]30wt% MEA in water – 15.4 mmol CO2 captured,
also observed at low temperatures (145 °C [d]
4wt% water in 2-EEMPA-carbamate was used. CO2 conversion = (mol CH4*1 + mol C2H4*2 + mol C3-
and 120 °C (temperatures where CO2 is C4 *3.5) (mol CO2*1)-1
thermally released from 2-EEMPA), entry 2
and 3, Table 1), albeit at slower rate. It is The hydrogenation of EEMPA-carbamate was performed
noteworthy that in the presence of a capture solvent (entry 1, with H2O and/or O2 in order to understand the influence of
Table 1), ethane and higher hydrocarbons are formed at higher impurities on catalytic conversion. Water loading was set at
selectivity than gas-phase CO2 methanation (entry 4, Table 1). ~4wt% H2O, its projected steady state water load in operation.
Only small amounts of methane were formed in presence of The presence of water lowered the reaction rate, and the CO2
Pd and Cu catalysts (Table 5-7, Table 1). The gas-phase conversion decreased to 74% (entry 13, Table 1) from 99% (entry
methanation of CO2 over Ni catalysts has been shown in the 10, Table 1). Note that the O2 solubility is in ppm quantities for
literature. [10] However, the Ni/Al2O3 was not very active in the most amine-based carbon capture solvents,[11] thus most of the
presence of 2-EEMPA solvent (entry 8, Table 1). The Ru on O2 from flue gas is expected to leave from absorber, and only
alumina support performed better than the carbon support (entry trace amounts will be carried from CO2-rich solvent and fed into
1 vs entry 9, Table 1). The use of aminopyridine-based CO2 the methanation reactor. A reaction performed in the presence of
capture solvent decreased the methane yield (entry 10, Table 1). O2 (with a O2/Ru ratio of 10) under similar conditions (Table 1,
The commonly used aqueous capture solvent, MEA, was also entry 13) showed no change in the selectivity and conversion.
screened (entry 11, Table 1). In 30wt% aqueous MEA solution,
<20% conversion of CO2 to hydrocarbon was observed. The CO2

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ChemSusChem 10.1002/cssc.202101590

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We extended the favorable conditions identified for a batch
process to a continuous flow process. We calculated a Weight
Hourly Space Velocity (WHSV) equivalent for a continuous
reaction system (fixed bed) using reaction time, solvent, and
catalyst loading in the batch system. In the presence of the
Ru/Al2O3 catalyst, we performed CO2 methanation at 170 °C with
10 wt% CO2 loaded 2-EEMPA. Figure 1 and Table 2 show
increase in CO2 conversion at lower WHSV (higher contact time)
while selectivity toward methane remained unaffected, making it
the primary product (>86% selectivity); other secondary products
formed include ethane, methanol, and ethanol. Methanol (and
ethanol) selectivity drastically decreased at higher contact time
from 7% (WHSV=0.3 h-1) to <1% (WHSV=0.03 h-1), indicating that

Accepted Manuscript
these alcohols are reactive species and that upon formation they
are quickly reduced to methane and ethane. Increase in the
reaction temperature from 170 °C to 190 °C with a WHSV (gCO2
gcat-1 h-1) of 0.3 h-1, increased the CO2 conversion from 17.6 to
52.1%, while methane selectivity remained the same (entry 1 vs Figure 2. Methanation of 2-EEMPA-carbamate in the presence of 5wt%
3, Table 2). Overall, prolonged contact time and higher Ru/Al2O3 catalyst at 170 °C under 70 bar H2 (initial pressure).
temperature, decreased the selectivity to alcohols and increased
the selectivity to methane and ethane (Table 2). CO2
(a) N N
H Capture

100 100 Amine moiety of EEMPA solvent O O-

CH4 Carbamate

80 80 HCO2-
CO2 Conversion (%)

H2 -H2O N
Selectivity (%)

N
H2
60 60 + N-formylation
O H
CO2 Conversion 1 2

40 40
2H2 N N-methylation
20 20 -H2O CH3
C2H6 (b)
CH3OH N
3H2
C2H5OH N + CH4
0 0 O H -H2O H
0 0.1 0.2 0.3 2
2H2
WHSV (gCO2 gcat-1 h-1) N + CH3OH
H
Figure 1. Selectivity (left axis) and CO2 conversion (right axis) vs Weight Hourly
Space Velocity (WHSV) in fixed bed experiments using 2-EEMPA solvent (10 Scheme 1. Hydrogenation of CO2 to different products via formamide
wt% CO2 load) over 5 wt% Ru/Al2O3 catalyst at 170 ºC. Reaction conditions: 1g intermediate.
catalyst load, 60 bar, 38 sccm H2, 5 sccm N2. Change in WHSV is achieved by
changing the liquid feed flow (0.05, 0.025, 0.005 mL min-1), CO2 conversion =
((mol CH4*1 + mol C2H4*2 + mol CH3OH *1 + mol C2H5OH *2)*min-1) (mol CO2
min-1)-1 Operando magic angle spinning (MAS) 13C NMR
spectroscopy was performed to identify the reactive species and
Table 2. Conversion and selectivity in fixed bed experiments using 2-EEMPA understand the reaction mechanism. NMR analysis of
solvent (10 wt% CO2 load) over 5 wt% Ru/Al2O3 catalyst. hydrogenation of CO2 captured EEMPA solution in the presence
of Ru/Al2O3 showed in situ formation of EEMPA N-CHO (2) and
WHSV CO2 Selectivity (%) simultaneous formation of methane and ethane (Figure 2). It is
Entry (gCO2 conversion notable that alcohols were observed in the continuous flow
gcat-1 h-1) (%) CH4 C2H4 CH3OH C2H5OH experiments at short contact time or at low temperatures but not
in the batch or in situ NMR experiments, suggesting alcohols are
1 0.3 17.6 86.7 4.8 7.2 1.2
short-lived reactive species that quickly undergo hydrogenation to
2 0.03 43.2 90.1 8.5 0.4 0.9 form hydrocarbons. Based on this observation, the methanation
[a]
in 2-EEMPA is proposed to proceed as shown in Scheme 1a. The
3 0.3 52.1 87.7 9.1 2.7 0.6
EEMPA N-CHO (2) is formed via formate intermediate (1), which,
Reaction conditions: 1g catalyst load, 170 ºC, 60 bar, 38 sccm H2, 5 sccm N2. depending on the catalyst and reaction conditions (Scheme 1b),
Change in WHSV is achieved by changing the liquid feed flow (0.05, 0.025, then forms many products, namely, methanol, methane, and N-
0.005 mL min-1), [a]190 ºC, CO2 conversion = ((mol CH4*1 + mol C2H4*2 + mol methylated capture solvent. N-methylation of capture solvent will
CH3OH *1 + mol C2H5OH *2)*min-1) (mol CO2 min-1)-1
lead to solvent deactivation as the active amine moiety (- NH) is
not available to form carbamate species and thus preventing the
successive reuse of the capture solvent for continuous CO2

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Accepted Manuscript
Figure 3. Literature FG-to-SNG process.[13, 16, 17]

capture and utilization. It is important to note that no N- rich solvent from the absorber (containing condensed-phase CO2)
methylation of 2-EEMPA was observed in any of the experiments is pumped to 15 bar and the mixed with hydrogen for Ru/Al2O3
The gas-phase CO2 methanation typically occurs via CO as catalyzed methanation. The product stream from the condensed-
an intermediate species. In the solvent promoted methanation phase reactor contains SNG, solvent, and by-product water,
process demonstrated here, there was no detectable amount of which is cooled to 35°C for downstream separation. As mentioned
CO in both GC and NMR analysis as the reaction temperature is before, the methanation reaction is highly exothermic, and
low for the reverse water gas shift (RWGS) reaction. However, therefore, a significant amount of steam is generated for power
hydrogenation of metal bound CO (in situ formed from CO2) to generation. SNG is recovered in a flash drum by vapor–liquid
methane can also take place without forming gaseous CO. [12] To separation. By-product water is removed by the pressure driven
test the involvement of EEMPA N-CHO, 2 in the reaction membrane process to prevent water accumulation in the system.
[14]
mechanism, we hydrogenated a surrogate N-formyl species, N-
formylpiperidine, at 170 °C under 30 bar H2. Without addition of
external CO2, >80% conversion to methane in the gas phase was Table 3. Comparison between the proposed IC3M and literature[13,16,17] FG-to-
observed after the reaction, which shows that both CO and N- NG processes.
formamide routes are possible in the solvent promoted CO2
methanation reaction. To the best of our knowledge, this is the Process Proposed Literature
first demonstration of integrated low-temperature thermocatalytic Scale (Million MMBtu SNG/year) 33.8 33.8
capture and conversion of CO2 to methane in an economically
Carbon Capture Condition
viable post-combustion CO2 capture solvent.
The TEA was conducted for the proposed and the literature Lean / Rich Loading (mol CO2/mol solvent) 0 / 0.136
processes that produce SNG from flue gas (FG) from natural gas Regeneration Heat Duty (GJ/tonne CO2) ≈ 2.5 2.65[13]
combined cycle (NGCC) power plants. It is assumed the CO2 CO2 Capture Cost ($/tonne CO2) 71[13]
capture and conversion plant is co-located with the NGCC power
Methanation Condition
plant. Therefore, the scale of the plant was set to be the same as
the NETL’s NGCC baseline with a net power output of 550MW. Temperature (°C) 170 350[16,17]
In the literature process (as shown in Figure 3) model, FG is first Pressure (bar) 15 30[16,17]
sent to a carbon capture process that uses Cansolv
CO2 Conversion (%) 99.8 99[16,17]
technology.[13] Here, CO2 in the FG is captured in the absorber
and released in the stripper at about 2 bars with thermal Heat of Reaction (GJ/tonne CO2) -3.75 -3.75
regeneration. The pure CO2 from the stripper is compressed and Key Performance Measures
mixed with hydrogen before going to the methanation reactor,
Thermal Efficiency (%, HHV) 79.75 76.14
where the Sabatier reaction (CO2 + 4H2 à CH4 + 2H2O; ∆H=-
165kJ/mol) takes place at 350 °C and 30 bar with the Ru/Al2O3 Hydrogen Consumption (kg/kg SNG) 0.503 0.505

catalyst. The Sabatier reaction is exothermic, and most of the CO2 Compression/Pump (kWh/tonne CO2) 18.33 57.95
reaction heat is used to supply the energy required in the CO2 Key Economic Measures
stripper, while the remaining is used for power generation. The
Total Plant Cost (MM$) 556.2 823.0
hot product from the methanation reactor is used to preheat
reactor feed. By-product water is removed by condensation. The Minimum SNG Selling Price ($/MMBtu) 25.0 28.4
unconverted hydrogen is recovered in a membrane separator Cost Distribution
and recycled back to the reactor.
H2 Cost ($/MMBtu SNG) 20.2 20.2
The proposed solvent promoted methanation process uses
the IC3M technology enabled by the water-lean solvents Carbon Credit ($/MMBtu SNG) -1.8 -1.8
developed by PNNL (2-EEMPA in this case). As shown in Figure O & M and Other Cost ($/MMBtu SNG) 4.1 6.3
4, instead of stripping off CO2 from the rich solvent and Capital Cost ($/MMBtu SNG) 2.5 3.7
compressing vapor-phase CO2, in the IC3M process, the entire
4

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ChemSusChem 10.1002/cssc.202101590

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Accepted Manuscript
Figure 4. Proposed FG-to-SNG process with the IC3M technology.

supplementary information. Aspen Process Economic Analyzer

was used for capital cost estimation. The simple annualized cost
As 2-EEMPA has a molecular weight of 216 g/mol, approach described in PEP Yearbook [18] was used to estimate
significantly higher than that of water, a nano filtration process [15] the minimum SNG selling price with 15% rate of return (ROI)
with a pressure difference of 5–40 bar can be applied to partially respectively in 2014 US dollars. In this TEA, the H2 price and
remove water at 35 °C. The membrane process is not expected carbon credits were set to $2.1/kg H2 and $35/tonne CO2, in the
to take extra energy as the wet solvent from the reactor is already base case. Figures 3 and 4 also present the operating condition
at an elevated pressure. Note that the proposed process aims to and utility consumptions of major equipment as well as key stream
produce SNG instead of pure methane. Due to the relatively small information, including temperature, pressure, and concentration
size of the SNG process, instead of considering a stand-alone of key components. More details can be found in the
separation unit, SNG can be further processed in a typical natural supplementary information. Table 3 gives a detailed comparison
gas processing plant along with conversional natural gas.[7] between the proposed and literature FG-to-SNG processes, while
Therefore, downstream separation is out of the scope of this work. Figure 5 presents a sensitivity study regarding H2 price.
The NGCC power plant described in Case B31B in the
National Energy Technology Laboratory (NETL) Rev3 Report, 60
Proposed
2015[13] was used as the baseline for plant scale (550 MW net
Minimum SNG Selling Price

50 Conventional
power output) and FG condition (3.9 mol% CO2, 8.4 mol% H2O, NG Price (PEP Yearbook, 2014)
74.4 mol% N2, 12.4 mol% O2, and 0.9 mol% Argon). Process 40
($ MMBtu-1)

models were developed in Aspen Plus V10 to calculate mass and

energy balance and to estimate equipment sizes for the entire 30
IC3M process proposed by the researchers and the CO2
20
conversion section of the literature FG-to-SNG process. For the
literature FG-to-SNG process, the mass and energy balance as 10
well as capital cost of the carbon capture section can be found in
the NETL Report. [13] The methanation process is modeled based 0
on open literature.[16,17] ENRTL-RK property package was used 0 1 2 3 4 5
for the operations involving solvents, while Peng-Robinson Hydrogen Feedstock Cost ($ kg-1)
equation-of-state was used for the operations not involving
Figure 5. Impact of H2 cost on the Minimum SNG Selling Price.
solvents. For EEMPA, property characteristics, performance
testing of carbon capture and development of property models
can be found in our previous publications. [5] The condensed-
phase methanation reactor is modeled as an adiabatic reactor in The results indicate that the proposed technology can
Aspen Plus with CO2 conversion at equilibrium (similar to entry 12, potentially increase the thermal efficiency of the entire process by
Table 1). Entry 13 indicates a slight drop in CO2 conversion by 5%, potentially reducing the energy consumption for CO2
adding water and keeping the same reaction time. To understand pressurization, total capital investment, O&M cost, and minimum
whether this decrease is caused by chemical equilibrium or SNG selling price of FG-to-SNG processing by 68%, 32%, 35%,
kinetics, chemical equilibrium calculations with and without H2O and 12%, respectively. The reduction on the minimum SNG
in the feedstock was conducted in Aspen Plus using RGibbs selling price is not as significant as the other performance and
reactor minimizing Gibbs free energy. The result indicates a less economic measures because the H2 cost dominates the minimum
than 1% reduction in equilibrium CO2 conversion by adding 4 wt% SNG selling price (more than 70%), while H2 consumptions of
water to the feedstock at 170 °C. Therefore, a higher conversion both processes are the same. The contribution from H2 cost of this
is expected as reaction time increases. More details of modeling work agrees with open literature.[16] Figure 5 suggests that the
assumptions and equipment design can be found in benefits of the proposed IC3M process over literature process
increase as the H2 price decreases.
5

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ChemSusChem 10.1002/cssc.202101590

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Conclusions Standard procedure for continuous flow experiments: Fixed bed
experiments were performed in a stainless-steel tubular reactor (3/8
In conclusion, we have demonstrated an efficient and cost- nominal OD, 0.305 ID), the reactor wall is heated with a stainless-steel
block (3 in) wrapped with a fiberglass heating tape (briskheat). Liquid is
effective integrated carbon capture and utilization approach to
fed to the reactor using a high-pressure ISCO pump (Teledyne) and gases
produce SNG. Selective formation of hydrocarbons, primarily (H2, N2) are fed using mass flow controllers (Brooks). In a typical
methane, was achieved from captured CO2 at low temperatures experiment, 1 g of catalyst (60-100 mesh) is loaded between quartz wool
and pressures using an advanced water-lean post-combustion in the heated part of the reactor. Reaction conditions: pressure (60 bar) is
capture solvent. Operando NMR showed formation of methane controlled using a Tescom back pressure regulator, temperature (120 –
through a distinctive formamide reaction intermediate. The 190 ºC) is controlled using a digisense R/S controller. After reaction, liquid
proposed IC3M approach offsets energy of capture with the products are condensed and collected in a stainless-steel 50 mL cylinder
energy of conversion, where the exothermicity of the maintained at 0 ºC using recirculatory thermostat (VWR). Gas products are
analyzed using a 4 channel Fusion MicroGC (Inficon), and liquid products
hydrogenation is used to offset the endothermic regeneration of
are analyzed using liquid chromatography.
the capture solvent. The conversion of CO2 captured in solution

Accepted Manuscript
bypasses the energies associated with CO2 compression and
transportation that are inherently sunk in a conventional Sabatier
process. Integration of these two units of operation could improve Acknowledgements
the thermal efficiency by 5% and reduce the total capital
investment and minimize SNG selling price by 32% and 12% The authors would like to acknowledge the U.S. Department of
respectively compared to a conventional Sabatier process. We Energy’s (DOE’s) Technology Commercialization Fund (TCF) and
posit that other integrated approaches would exhibit similar SoCalGas for co-funding this work. This material is based upon
energy and cost reductions, thereby creating attractive CO2 work supported by the DOE’s Office of Science, Office of Basic
utilization approaches, which could be deployed as a part of an Energy Sciences, Chemical Sciences, Geosciences, and
all-of-the-above CCUS strategy. Biosciences Division. The authors thank Dr. Phillip Koech and Dr.
Deepika Malhotra for providing 2-EEMPA. The HT/HP solid-state
NMR experiments were performed under proposal number 51704
Experimental Section at the Environmental Molecular Sciences Laboratory (EMSL), a
Department of Energy (DOE) Office of Science user facility
Materials: 5wt% Ru/Al2O3 and 5wt% Ru/C were obtained from Strem sponsored by the Office of Biological and Environmental
chemicals. 64wt% Cu/Zn/Al2O3 was purchased from Alfa Aeser. 2-EEMPA Research. The Pacific Northwest National Laboratory is operated
was synthesized by following the procedure reported in the literature [5a, 19]. by Battelle for the DOE.
N-(2-Pyridinylmethyl)ethanamine was obtained from Sigma-Aldrich.
35wt% Ni/Al2O3 was synthesized by incipient wetness impregnation with
Keywords: CO2 • CO2 methanation • CO2 Capture • CO2
nickel nitrate solution, followed by calcination in open air at 350 °C for 3 h.
All other materials were purchased from commercial suppliers and used utilization • water-lean solvent • TEA
without further purification unless otherwise mentioned. MEA was
purchased from Sigma-Aldrich. All deuterated solvents were purchased
from Cambridge Isotope Laboratories, Inc. 1,3,5-Trimethoxybenzene References
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In the presence of a heterogenous Ru catalyst, >90% conversion of captured CO2 to hydrocarbons, mostly methane, is achieved
under relatively mild reaction conditions using a water-lean post-combustion capture solvent. Based on the technoeconomic analyses
performed, the proposed integrated process can potentially reduce the total capital investment and minimum synthetic natural gas
(SNG) selling price by 32% and 12%, respectively, compared to the conventional Sabatier process.

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