Viewpoint
http://pubs.acs.org/journal/aelccp
Integrating CO2 Electrolysis into the Gas-to-
Liquids−Power-to-Liquids Process
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hell’s gas-to-liquids (GTL) technology converts natural
gas into high-quality liquid products that would
otherwise be made from crude oil. These products
include transportation fuels (such as aviation fuel and diesel),
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motor oils, process oils, and the ingredients for everyday
necessities like detergents and cosmetics.1 GTL products are
colorless, odorless, and contain almost none of the impurities
like sulfur, aromatics, and nitrogen containing compounds that
are found in crude oil. There is a high flexibility in the product
slate, viz. types and amounts of fuels and nonfuel products that
can be made using GTL technology. The current GTL process
consists of the following steps: (1) converting natural gas into
synthesis gas, i.e., mixture of carbon monoxide (CO) and
hydrogen (H2); (2) Fischer−Tropsch synthesis, i.e., con-
version of synthesis gas into highly paraffinic wax; and (3)
upgrading of Fischer−Tropsch wax into final hydrocarbon
products in a hydroprocessing step or steps, which can include
hydrocracking, hydro-isomerization, and/or hydrogenation.2,3
As the world transitions to a lower-carbon energy system,
GTL technology could be an enabler for making a variety of
low-carbon products (such as low-carbon aviation fuel, low-
carbon diesel for heavy-duty transportation, chemicals, and
specialties with low carbon intensity) by replacing (a part of)
the hydrocarbon feedstock with the (intermittent) renewable
H2 and carbon dioxide (CO2) as feedstock (Figure 1). This
Figure 1. Schematic of a future gas-to-liquids−power-to-liquids
(GTL−PTL) process comprising H2O and CO2 electrolyzers
integrated with conventional Fischer−Tropsch synthesis. Depend-
ing on the availability of intermittent renewable power, H2, and
CO, the natural gas feed can be dialed up or down yielding a
hybrid GTL−PTL process.
© 2020 American Chemical Society
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mixture, converted to synthesis gas, can be subsequently
introduced into Fischer−Tropsch synthesis (going through
steps 2 and 3 of the conventional GTL process).4,5 Sources of
CO2 could include CO2-rich off gas from internal recycles,
concentrated point sources (e.g., from cement, steel, fertilizer,
or fermentation plants), or direct air capture (DAC).5−7
Technology building blocks for the conversion of CO2 to CO
can include CO2 electrolysis (CO2 → CO + 0.5O2), reverse
water gas shift (CO2 + H2 → CO + H2O), all-electric
thermochemical redox conversion of CO2 and water to syngas,
dry reforming (CH4 + CO2 → 2CO + 2H2), and methanation
(CO2 + 4H2 → CH4 + 2H2O) followed by the partial
oxidation of methane (CH4 + 0.5O2 → CO + 2H2).5,8−11
Renewable H2 and CO2 could be used as the only feedstocks
to the process, which will be termed PTL (power-to-liquids)
throughout this Viewpoint, or they can be coprocessed along
with a natural gas feed in a so-called “hybrid” GTL−PTL
process. In such a hybrid, or coprocessing, approach,
(intermittent) renewable H2 is utilized as much as possible
during the times when renewable power is available (such as
during the day for solar power and during periods of high wind
intensity for wind power, while natural gas is utilized as much
as possible during the times when renewable power is not
available, like in conventional GTL). This approach reduces
the need for costly electricity storage in batteries or as H2 and
CO, which is required for PTL. Natural gas becomes a way of
addressing the intermittency of renewables in hybrid GTL.
Compared to PTL, the renewable element of a hybrid GTL
plant is much more flexible, bringing such concepts closer to
commercialization and fitting in well with intermittent
renewable power or H2.
In this Viewpoint we focus on the integration of the CO2
electrolysis block (an emerging technology option) into PTL
and hybrid GTL−PTL lineups. Starting with the early seminal
work of Hori et al. in the 1980s and 1990s,9 the electrolysis of
CO2 (low-temperature membraneless, anion or cation
exchange polymer membrane-based, or high-temperature
solid oxide-based) to molecules such as CO, formic acid,
Received: July 2, 2020
Accepted: July 14, 2020
Published: July 24, 2020
https://dx.doi.org/10.1021/acsenergylett.0c01418
ACS Energy Lett. 2020, 5, 2597−2601
ACS Energy Letters http://pubs.acs.org/journal/aelccp Viewpoint

Figure 2. Power-to-liquids (PTL) process scheme based on low-temperature CO2 electrolysis and Fischer−Tropsch (FT) synthesis
representing (a) an option to recycle the off-gases using an oxy-combustion (oxy-burner) unit or solid oxide fuel cell and (b) an option to
recycle the off gases using a gasifier (here denoted by the Shell gasification process, i.e., SGP). Blocks in dashed red show optional blocks
required to handle intermittency and enable a continuous production facility. “S” block represents the unit operation (e.g., amine scrubbing,
hydroxide scrubbing, membranes, pressure swing adsorption, etc.) required to remove the excess CO2 from the CO2 electrolyzer cathode
exhaust. Note that HC in the off-gas denotes hydrocarbons. For inerts rejection (“bleed”) and CO recovery, a CO-PSA (carbon monoxide
PSA) can be used. Similar integration schemes can be considered for the high-temperature coelectrolysis of CO2 and H2O in solid oxide
electrolyzers with the additional input or recycle (from exothermic Fischer−Tropsch synthesis and/or exothermic SGP) of steam being
required. Variations of the process scheme can also include CO2 being fed to the CO2 electrolyzer as loaded onto a solvent in the form of
carbonate, bicarbonate, or carbamate. In such a scheme, the CO2 is regenerated in situ in the CO2 electrolyzer followed by conversion to CO
and the lean solvent being recycled back to the CO2 capture step.

ethylene, and ethanol has received significant research
interest.12 In particular the electrolysis of CO2 to CO has
recently come of age through the work of several startups and
electrolyzer companies (Opus 12, Dioxide Materials, Air
Company, Sunfire, Lectrolyst, Siemens, Haldor Topsoe,
Avantium, etc.) improving its technological readiness level
(TRL) from 1 to 3 (per the API 17 N scale).10,13,14 However,
further improvement of the TRLs of CO2 to CO electrolysis to
4 and beyond will require the design and testing of scaled
systems integrated with both upstream CO2 capture units and
downstream syngas processing unit such as GTL. While some
early work on the topic of integrating CO2 electrolysis into
process flow schemes (as the basis for preliminary techno-
economic analysis) are available,7,8,15−18 they can be nontrivial
for real-world industrial (brownfield or greenfield) implemen-
tation, thus serving as the focus of this work.
The electrolysis of CO2 to CO can be integrated into a
GTL−PTL process scheme in several ways (Figures 2 and 3).
To minimize process upsets, maximize the carbon efficiency as
well as energy efficiency, and minimize capital costs,
2598
techniques/design rules to handle intermittency, recycle off-
gases, prevent inert (N2, argon) buildup, and utility (heat/
steam) integration with the exothermic Fischer−Tropsch (FT)
synthesis need to be considered. There are three types of off-
gases in a GTL−PTL process, coming from (1) FT synthesis
containing unconverted CO and H2 from syngas, light
hydrocarbons (C4 minus), and CO2; (2) the products
upgrading section containing light (C4 minus) saturated
hydrocarbons (paraffins); and (3) flue gas obtained when
natural gas or off-gas is used as fuel gas for utilities resulting in
a CO2-rich stream.
In PTL process schemes (Figure 2), intermittent renewable
power (solar or wind) can be used to drive CO2 and H2O
electrolysis, producing CO and H2. The CO2 feed can be
sourced from the air using a DAC unit or from point sources.
Delivery of the CO2 feed to the electrolyzer can be in two
forms, i.e., either (i) as a gas wherein CO2 is first captured
using a solid sorbent or a liquid solvent, regenerated thermally
or electrochemically,19,20 and then fed to the electrolyzer for
conversion to CO, or (ii) as loaded onto a liquid solvent in the
https://dx.doi.org/10.1021/acsenergylett.0c01418
ACS Energy Lett. 2020, 5, 2597−2601
ACS Energy Letters http://pubs.acs.org/journal/aelccp Viewpoint

Figure 3. Hybrid GTL−PTL lineups based on low temperature CO2 electrolysis and FT synthesis representing (a) an option to recycle the
off-gases using an oxy-combustion (oxy-burner) unit or solid oxide fuel cell and (b) an option to recycle the off-gases using a gasifier (here
denoted by the Shell gasification process, i.e., SGP). Overall scheme coprocesses renewable feed (renewable power, CO2, and H2O) and
fossil (natural gas) feed to address intermittency and storage issues. Blocks in dashed red show optional blocks required to handle
intermittency and enable a continuous production facility. “S” block represents the unit operation (e.g., amine scrubbing, hydroxide
scrubbing, membranes, pressure swing adsorption, etc.) required to remove the excess CO2. For inerts rejection (“bleed”) and CO recovery,
a CO-PSA (carbon monoxide PSA) can be used. Note that HC in the off-gas denotes hydrocarbons. Similar integration schemes can be
considered for the high-temperature coelectrolysis of CO2 and H2O in solid oxide electrolyzers with the additional input or recycle (from
exothermic Fischer−Tropsch synthesis or exothermic SGP) of steam being required. Oxygen from the CO2 electrolyzer can be sent to the
liquid O2 storage, similar to O2 from water electrolyzer. Battery storage can be used along with, or instead of H2 storage, to power water
electrolyzer as well as CO2 electrolyzer. Variations of the process scheme can also include CO2 being fed to the CO2 electrolyzer as loaded
onto a solvent in the form of carbonate, bicarbonate, or carbamate. In such a scheme, the CO2 is regenerated in situ in the CO2 electrolyzer
followed by conversion to CO and the lean solvent being recycled back to the CO2 capture step.

form of bicarbonate, carbonate, carbamates, etc., which is then
fed to the electrolyzer for in situ regeneration of the CO2
followed by conversion to CO.21−23 However, given CO2 is the
reacting species for electrolysis to CO,24 it is still unclear
whether this single-electrolyzer concept will be advantageous
over a separate CO2 regeneration step followed by a separate
conversion step from a capital cost perspective. Consider CO2
regeneration is rate-limiting for the direct reduction of
bicarbonate/carbonate electrolytes; hence, for a combined
process, one will need a large (and expensive as catalyst
coated) electrolyzer for CO production instead of a large
regeneration (electrodialysis) unit plus a small electrolyzer for
a two-step process. Hence, to simplify the scope of the
2599
discussion in this Viewpoint, we describe integration schemes
assuming the CO2 delivered to the electrolyzer is in the form of
a gas.
To allow for the continuous operation of the PTL process,
i.e., when solar or wind electricity is unavailable, battery
storage, CO2 storage, H2 storage, and/or CO storage might be
needed. To increase the overall efficiency, unconverted CO2
from the outlet of the CO2 electrolysis can be separated from
the CO stream (as indicated by block “s” in Figure 2) by
means of amine scrubbing, hydroxide scrubbing, membranes,
pressure swing adsorption (PSA), or other separation
technology blocks, and recycled back to the inlet of the CO2
electrolyzer. Off-gas from FT synthesis and the products
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ACS Energy Letters http://pubs.acs.org/journal/aelccp
upgrading section can be burnt thermochemically in an oxy-
burner or electrochemically in a solid oxide fuel cell (SOFC)
for higher efficiency, with the resulting CO2 routed to the CO2
electrolyzer inlet and the power generated being used to run
the H2O electrolyzer, CO2 electrolyzer, DAC unit, and/or
charging batteries (Figure 2a). O2 for oxy-combustion can be
supplied from the anode of the H2O electrolyzer and/or CO2
electrolyzer. For anion exchange membrane-based low-temper-
ature CO2 electrolyzers producing mixed streams of CO2 and
O2 at the anode,25 the anode exhaust can be fed to the oxy-
combustion unit, generating clean CO2 streams which can then
be recycled back to the CO2 electrolyzer inlet and thus
avoiding safety issues related to the handling of pure O2.
Another option for recycling off-gases from the FT synthesis or
products upgrading section would be to first separate the CO2
and recycle to the CO2 electrolyzer while routing the
remaining hydrocarbon stream to a gasification unit (here
denoted by SGP or Shell gasification process)26 to make more
synthesis gas (CO + H2) as shown in Figure 2b. Note that it is
highly likely that the off-gas from the FT unit would require a
bleed or a separation unit such as pressure swing adsorption
(PSA) before recycle to prevent the buildup of inerts such as
N2 (potentially coming from DAC or leakages) in the overall
process.
For energy integration, the heat or steam produced in the
exothermic FT synthesis can be used to supply heat/steam or
power to the H2O electrolyzer, CO2 electrolyzer, CO2 capture
unit, and separation units and/or for charging batteries. Similar
integration can be considered with the high-temperature
coelectrolysis of CO2 and H2O in SOECs with the additional
input of steam being required, which can be recycled from the
exothermic FT synthesis and/or exothermic gasification
process (SGP) or renewably generated using electric steam
generators.
In contrast, for hybrid GTL−PTL process schemes (Figure
3), renewable feed (electrons as well as CO2 and H2O),
whenever available (during the day for solar or during periods
of high wind intensity for wind power), is coprocessed with
fossil natural gas feed to handle intermittency as well as run
through periods of low renewable power availability. In such a
scheme, the CO2 and H2O electrolyzers operate in sync
(intermittently) on renewable power without the need for
expensive large-scale batteries, producing CO and H2.
Meanwhile, the fossil natural gas-based GTL process operates
24/7 with the electrolyzers supplying the additional CO and
H2 whenever they are produced. As a result, compared to PTL
schemes, extra syngas (CO/H2) storage could be downsized or
completely avoided, which also translates to lower overcapacity
of renewable power generation and smaller scale of CO2
electrolyzer and water electrolyzer, all of which can reduce
capital investment. Similar to the PTL schemes, unconverted
CO2 from the outlet of the CO2 electrolyzer can be separated
from the CO stream and recycled back to its inlet. Off-gas from
FT synthesis and the products upgrading section can be burnt
thermochemically in an oxy-burner or electrochemically in a
SOFC for power with the resulting CO2 routed to the CO2
electrolyzer (Figure 3a) or recycled to the gasification unit to
make CO and H2 after first separating the excess CO2 (Figure
3b). O2 for oxy-combustion or gasification can be optionally
supplied from the anode of the H2O electrolyzer and/or CO2
electrolyzer. Also, the extra O2 available from the H2O and
CO2 electrolyzers could be sent to available liquid oxygen
storage, thereby downsizing the air separation unit compared
2600
Viewpoint
to a conventional GTL lineup. To avoid buildup of N2 or
argon (coming from the air separation unit (ASU), direct air
capture (DAC), or natural gas feed) in the process, the off-gas
from the FT unit will likely require a bleed stream or a
separation unit (such as a PSA) to remove the excess inerts
before recycling. Also similar to PTL lineups, heat and/or
steam from the exothermic FT synthesis or gasification can be
used for supplying heat/steam or power to the H2O
electrolyzer, CO2 electrolyzer, CO2 capture unit, direct air
capture (DAC) unit, or separation units. Similar integration
schemes can be considered with the high-temperature
coelectrolysis of CO2 and H2O in SOECs with the additional
input of steam being required, which can be recycled from the
exothermic FT synthesis and/or gasification section or
renewably generated using electric steam generators.
In summary, although much progress has been made in the
field of CO2 electrolysis to progress the technology from TRL
1 to 3, process integration strategies such as the PTL and
hybrid GTL−PTL archetype lineups described in this work
will be critical toward maturing it beyond TRL 4, thus making
the technology a credible option to enable the energy
transition. Also, as shown in this work, design rules to
minimize process upsets, maximize the carbon as well as
energy efficiency, minimize capital costs, handle intermittency,
recycle off-gases, and prevent inerts buildup need to be
incorporated. As next steps, further plant-level optimization of
the process schemes proposed in this work will be needed to
select the most credible option(s) and optimally size the
equipment. This should be followed by demonstration
activities at a relevant (kilowatt or megawatt) scale to further
derisk the technology in a real-world setting.
Svetlana van Bavel
Sumit Verma orcid.org/0000-0001-8365-180X
Emanuela Negro
Maarten Bracht
■ AUTHOR INFORMATION
Complete contact information is available at:
https://pubs.acs.org/10.1021/acsenergylett.0c01418
Notes
Views expressed in this Viewpoint are those of the authors and
not necessarily the views of the ACS.
The authors declare the following competing financial
interest(s): The authors are employed by Shell. This work is
related to the field of GTL (gas-to-liquids) technology within
Shell.
■ ACKNOWLEDGMENTS
The authors gratefully acknowledge Dr. HP Calis, Dr. Albert
Harvey, Dr. Clara F. Heuberger, Dr. Fu Xiao, Dr. Abhinav
Verma, Marco Smaling, Dr. Ronald Wolf, Dr. Esther van Soest-
Vercammen, Robert Schouwenaar, and Dr. Paul Corbett for
their critical review of the manuscript.
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