Energy Conversion and Management 48 (2007) 1255–1265

www.elsevier.com/locate/enconman

Electrochemical reduction of CO2 to hydrocarbons to store

renewable electrical energy and upgrade biogas
M. Gattrell *, N. Gupta, A. Co
Institute of Chemical Process and Environmental Technology, National Research Council, 1200 Montreal Road, Ottawa, Ont., Canada K1A 0R6

Received 25 March 2006; accepted 27 September 2006

Available online 14 November 2006

Abstract

An approach for synthesis of a hydrocarbon fuel from CO2 has been evaluated. The use of electrochemical reduction of CO2 at a
copper electrode to a hydrocarbon mixture looks like a promising technology, especially when applied to upgrading biogases. The result-
ing gas mixture, containing methane and hydrogen with small amounts of ethylene and carbon monoxide, has a similar energy density
and composition to Hythane. Therefore, it is hoped that the gas mixture could be directly used in existing gasoline engines with minimal
modifications. Estimating from existing literature data, the energy storage efficiency is poor (around 38% based on the fuel product
HHV). However, the process equipment requirements are not complex, and the fuel product is also relatively readily used within stan-
dard engines. Finally, the paper discusses some of the key areas for research to verify and improve this technology.
Ó 2006 Elsevier Ltd. All rights reserved.

Keywords: Renewable energy; CO2 conversion; Electricity storage; Electrochemistry; Hythane; Biogas upgrading

1. Introduction mass based electricity generation facilities that rely on com-

1.1. Background
A key to reducing emissions of CO2 is to utilize energy
sources that do not emit CO2 during their operation. These
can include renewable energy sources such as wind, hydro
and solar, as well as nuclear energy. Issues arise in integrat-
ing such energy sources if they are not matched with energy
demands in time and space. These can be due to the energy
sources not being able to respond to demand requirements,
the energy source being geographically distant from the
demand and the demand being mobile (transportation
needs).
Many non-CO2 emitting power sources are poorly able
to respond to energy demands. Wind, solar and tidal power
produce electricity only when their respective energy source
is naturally available. Nuclear, run-of-river hydro and bio-
*
Corresponding author. Tel.: +1 613 990 3819; fax: +1 613 991 2384.
E-mail address: michael.gattrell@nrc-cnrc.gc.ca (M. Gattrell).
plex processing (e.g., gasification) are best suited to
providing base load, constant power. Many technologies
have been developed to deal with such mismatches between
power availability and demand through power storage. For
electrical power in particular, these can include pumped
hydro, compressed air/gas turbine, batteries and mechani-
cal storage (flywheels) [1,2]. Many large sources of renew-
able energy are geographically located far from areas of
high energy demand. Some authors have looked at trying
to utilize solar energy better in desert regions [3] and hydro-
electric resources in northern Canada [4]. Also, in Canada,
a significant amount of wind energy is located along the
North Atlantic coast (especially Newfoundland and Labra-
dor), while most power demand is in southern parts of the
country [5]. Finally, transportation requires a portable
form of energy.
The most flexible method to address these issues would
be to store the available energy in a portable chemical form
(i.e., as a fuel) for use at a later time or different location. It
should be noted, however, that such fuels would only

0196-8904/$ - see front matter Ó 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.enconman.2006.09.019
1256 M. Gattrell et al. / Energy Conversion and Management 48 (2007) 1255–1265
sensibly be produced if ‘‘true’’ (as opposed to time-of-day)
local excesses of renewable energy existed. Time-of-day
excesses of renewable energy could, through the storage
technologies mentioned previously, be more efficiently used
to off set non-renewable, CO2 emitting power generation.
This is because the round trip efficiencies of most electricity
storage systems exceed those of typically proposed fuel syn-
thesis-storage-combustion cycles. Thus, we would look to
fuel synthesis concepts to export renewable energy and to
use renewable energy in transportation applications. Such
a chemical fuel (or energy transportation vector) should
be easily and efficiently synthesised, easily used (preferably
within existing infrastructures) and have a high energy den-
sity (so as to allow it to be easily and efficiently trans-
ported, again, preferably within existing infrastructures).
Various possibilities have been suggested for such an
energy vector, but none are completely satisfactory. While
much interest and work is associated with hydrogen as a
possible energy carrier, it suffers from a low energy density
and requirements for infrastructure modification or
rebuilding. Hydrocarbon based fuels are compatible with
the existing infrastructure and many have a good energy
density (see Table 1). If such fuels could be made from cap-
tured CO2 using renewable energy, they would then not
result in a net release of CO2 when combusted. This raises
the additional issue, for fuel synthesis concepts based on
CO2, of a source of CO2 in a local region that has a true
excess of renewable energy. However, if CO2 can be found
and converted to fuels with reasonable efficiency, this
would represent a powerful technology to expand the util-
ity of many renewable power sources.
1.2. Possibilities for a CO2 based energy vector
Different concepts for using CO2 to synthesise a fuel
have been considered previously. However, when starting
from CO2, if one desires a simple and efficient process, this
generally implies simple hydrocarbon fuels (i.e., one carbon
to perhaps as high as four carbon fuels). Thus, as can be
seen in Table 1, a balance needs to be found between sim-
plicity of fuel synthesis and final fuel energy density. Also,
liquid fuels are preferable to gaseous fuels because they do
Table 1
Volumetric energy densities of some energy carriers (LHV) [6,7]
Fuel Volumetric energy density (kJ/L
or MJ m3)
Diesel fuel (#2) 35,760
Bio-diesel 32,580
Gasoline 32,020
LPG (liquefied petroleum gas) (mostly 23,500
propane)
Ethanol 21,200
Methanol 15,800
207 bar NG (3000 psi natural gas) 9900
(mostly methane)
207 bar H2 (3000 psi) 1810
not require energy for their compression and are more eas-
ily transported.
The group of Weiner, Specht, Bandi and collaborators
produced a series of papers looking at the concept of pro-
ducing methanol from atmospheric CO2 to obtain a CO2
neutral fuel [4,8–12]. In their work, they concluded that,
in the longer term, for a CO2 neutral fuel, the CO2 must
be recovered from the atmosphere. To this end, they con-
ducted experiments concentrating CO2 from the air using
adsorption in a counter current packed column with a
KOH solution (resulting in K2CO3). This required approx-
imately 100 m3 of air to be processed and about 70 kJ/mol
of captured CO2. The CO2 was then released by adding
acid (H2SO4), and the resulting K2SO4 salt was regenerated
to KOH and H2SO4 using electrodialysis. The electrodialy-
sis was found to require 180 kJ per mole of OH regener-
ated and, thus, 360 kJ/mol of CO2 captured. Thus, a
total energy cost for obtaining CO2 from the air of
430 kJ/mol was found [10]. A high temperature method
using limestone was also considered, which resulted in a
slightly lower energy (320 kJ/mol of CO2) and could make
use of more efficient solar heating as opposed to photovol-
taic energy required for electrodialysis.
The resulting pure CO2 was then reacted with electro-
lytic hydrogen in a low pressure (50–100 bar) methanol
synthesis process, which was estimated to require an addi-
tional 1000 kJ/mol of methanol product. This resulted in
an overall system efficiency of 51% using the higher heating
value (HHV) of methanol and 44% using the lower heating
value (LHV) [10]. This was felt to yield a similar efficiency
with liquid hydrogen fuel systems but with fewer infra-
structure issues. (Direct electrochemical synthesis of meth-
anol from CO2 was tested, but the selectivities and
efficiencies were poor [8,9].) A similar system using off peak
power and starting from more concentrated flue gas as a
CO2 source has been calculated in some detail [13]. This
system used amine scrubbing with thermal regeneration
to capture and concentrate CO2 from a smoke stack. High
pressure electrolysers produced the hydrogen, which was
reacted with CO2 in a low pressure (50 bar) methanol syn-
thesis reactor. This methanol water product was then dis-
tilled to yield methanol fuel. Similar efficiencies were
obtained, but issues were raised about the capital cost of
the equipment (or the related materials and energy required
to fabricate the equipment). There are also the issues raised
previously in relation to the probably better efficiency of
simply storing off peak power and using it to run the pro-
cess that is creating the flue gas.
Another energy cycle concept involving a CO2 neutral
hydrocarbon fuel uses methane. In one example, CO2 is
captured at a stationary point of fuel use (facilitated by
using pure oxygen combustion), the captured CO2 is then
transported to a location with abundant renewable energy.
The renewable energy is used to generate electrolytic
hydrogen, which is reacted over a catalyst with the cap-
tured CO2 to re-synthesise methane [3]. Again the system
is relatively complex, which will increase the energy and
 M. Gattrell et al. / Energy Conversion and Management 48 (2007) 1255–1265
materials required to produce and operate the necessary
equipment.
An ideal system, however, would have few process
stages, be easily scaleable and could operate at ambient
temperature (to allow for rapid changes in production rate
as renewable energy availability changes). A potentially
enabling technology to satisfy these requirements is electro-
chemistry [14,15]. The most interesting result in this area is
the one step electrochemical reduction of CO2 to a mix of
methane and ethylene at a copper electrode with a reason-
able efficiency and reaction rate [16,17]. This paper will,
therefore, investigate how this electrochemical reaction
might be used as the basis for a process to produce a
CO2 neutral fuel. As a short term goal, the technology
might be aimed at creating fuel self sufficiency for remote
communities that have a local excess of renewable energy.
Such small, remote communities are more likely to achieve
first the goal of excess renewable energy and, at present,
often import their fuels from more populated areas with
an economic and environmental cost associated with the
fuel transportation. This raises a further requirement that,
because of the goal of avoiding transportation costs, feed-
stock CO2 must be found locally, although, perhaps, at
some point in the future, such locations, rich in renewable
energy, might become exporters of fuel.
2. Discussion
2.1. Electrochemical synthesis technology
As mentioned above, the most promising results for
direct electrochemical production of fuels from CO2
involved synthesis of a mixture of mostly 1 and 2 carbon
hydrocarbons. The early results found methane, ethylene,
carbon monoxide, and formate were formed at reasonable
rates (5 mA/cm2) at a, non-precious metal, copper elec-
trode [17]. The primary reactions that occur at the copper
electrode during the reduction of CO2 are listed below
(with the standard potentials calculated using formation
energies from [18])
2Hþ þ 2e ¢ H2 E0 ¼ 0:0 V vs: SHE ð1Þ
2CO2 þ 12Hþ þ 12e ¢ C2 H4 þ 4H2 O
E0 ¼ 0:079 V vs: SHE ð2Þ
þ 
CO2 þ 8H þ 8e ¢ CH4 þ 2H2 O E0 ¼ 0:169 V vs: SHE
ð3Þ
CO2 þ 2Hþ þ 2e ¢ CO þ H2 O E0 ¼ 0:103 V vs: SHE
ð4Þ
CO2 þ Hþ þ 2e ¢ HCOO E0 ¼ 0:225 V vs: SHE
ð5Þ
The product distribution has been found to vary with a
number of factors including the electrode potential, the elec-
trode preparation, the solution composition and solution
impurities [19,20]. In particular, the concentration of dis-
solved CO2 and the pH at the surface of the electrode during
the reaction are important, and so, the reactions are also
1257
sensitive to the degree of mixing used [21]. In spite of this sen-
sitivity to reaction conditions, if care is taken, reasonably
promising results can be obtained. Experimental results
from a few different research groups are shown in Fig. 1.
Generally, the reduction of CO2 initially leads to CO and for-
mate with large amounts of hydrogen also evolved (see the
less negative voltage regions in Fig. 1a and b). As the elec-
trode potential is made more negative and the CO2 reduction
increases, adsorbed CO tends to accumulate on the electrode
surface, which acts to suppress hydrogen evolution. At
increasingly more negative potentials, CO begins to be
reduced leading to hydrocarbon products (primarily meth-
ane and ethylene). Eventually, the rate of CO reduction to
hydrocarbons begins to exceed its formation (influenced in
part by the depletion of CO2 near the electrode surface).
When this happens, the coverage of CO on the electrode
decreases and hydrogen evolution begins again on the
uncovered copper surface [20] (see the more negative voltage
regions in Fig. 1b and c). Thus, there is an optimal reaction
rate to maximise the conversion of CO2 to hydrocarbons
(as also suggested by Ref. [24]).
In Fig. 2, the product distributions are shown from var-
ious reported results taken at the point of optimal current
efficiency (i.e., where the largest fraction of current goes to
hydrocarbon production). As well as a range of CO2 pres-
sures from 1 to 40 atm, different levels of mass transport
were also used with active mixing leading to a higher opti-
mal reaction rate (versus passive mixing due to CO2 bub-
bling and gas evolution at the electrode surface) [24].
Considering the relatively wide range of reaction condi-
tions, the optimum reaction rate for best hydrocarbon cur-
rent efficiency tends to produce a roughly similar product
distribution. Thus, if one wishes to produce a gaseous fuel,
the results in Fig. 2 can be used to estimate the typical com-
position that might be expected to be possible for such a
fuel. This average composition, based on the data in
Fig. 2 is presented in Table 2.
The gas produced, even at these optimal operating
points, contains a significant amount of hydrogen. A
higher hydrogen content will result in a lower energy den-
sity (in this case about 70% of that of pure methane). The
combustion characteristics of hydrogen methane blends in
internal combustion engines has been the subject of much
study, which has been reviewed recently [25]. Adding
hydrogen to methane lowers the fuel energy density, but
increases the combustion temperature, the lower flamma-
bility limit and the rate of propagation of a flame front dur-
ing combustion.
When using such hydrogen methane fuels in a spark
ignited piston engine, the lower energy density results in
less power and slightly lower engine efficiency. The addi-
tion of hydrogen and the increased flame temperature pro-
duce lower hydrocarbon emissions but increased NOx.
Changes to the rate of propagation of a flame front are
important in spark ignited engines because it affects the
ignition timing. Because the flame front travels more slowly
in methane than gasoline, converting gasoline engines to
1258 M. Gattrell et al. / Energy Conversion and Management 48 (2007) 1255–1265

70
a H2 Hydrocarbons
60

Current Eff. (%)

50

40

30
HCOO-
20

10
CO
0
-0.9 -1 -1.1 -1.2 -1.3 -1.4 -1.5 -1.6 -1.7
Potential / V vs. SHE
70
b
60
H2

Current Eff. (%)

50

40
-
HCOO 30

CO 20

10
Hydrocarbons
0
-0.9 -1 -1.1 -1.2 -1.3 -1.4 -1.5 -1.6 -1.7
Potential / V vs. SHE
70
c
Hydrocarbons 60

HCOO- 50

Current Eff. (%)

40
CO H2
30

20

10

0
-0.9 -1 -1.1 -1.2 -1.3 -1.4 -1.5 -1.6 -1.7
Potential / V vs. SHE

Fig. 1. Current efficiencies at different potentials for CO2 reduction at copper electrodes. (a) 0.1 M KHCO3, 1 atm CO2 bubbled, 19 °C (current range
0.12–7 mA/cm2), data from [22], (b) 0.1 M KHCO3, 1 atm CO2 bubbled, 25 °C, data from [23], (c) 0.1 M KHCO3, 30 atm CO2, stirred, 25 °C (current
range 75–900 mA/cm2), data from [24].

run on methane requires changes to the ignition timing.
However, if one adds the correct amount of hydrogen to
the methane, the rate of propagation of a flame front can
be adjusted to be comparable to that of gasoline, and so,
the mixed fuel can be used in existing gasoline engines with
fewer modifications. A blend of around 15% hydrogen and
85% natural gas has been found to be suitable for gasoline
engines and has been trademarked by Hydrogen Consul-
tants Inc. as ‘‘Hythane G’’ [26]. (Note that the natural
gas used in the example blend contained 92.3% methane,
3.5% inerts and the remainder of higher hydrocarbons.)
Thus, research on these electrochemical reactions directed
to raising the ratio of hydrocarbon to hydrogen closer to
Hythane G values would result in a more useful fuel. Also,
work to raise the CO2 conversion to hydrocarbons from
the 69% value in Table 2 would be helpful in making this
approach more viable. However, even with existing results,
this technology can produce a fuel with an energy density
of about 2.2 times that of hydrogen.
2.2. The CO2 source
A second issue is the most effective method of obtaining
CO2 for the process. As discussed earlier, for a remote
community, it is desirable to obtain the CO2 locally. Thus,
one may consider methods to capture and concentrate
 M. Gattrell et al. / Energy Conversion and Management 48 (2007) 1255–1265 1259

0.7

0.6

0.5
M ole fraction in product

0.4

0.3

0.2

0.1

0
hydrogen methane ethylene CO formate

1 atm bubbled 7 mA cm-2 1 atm bubbled 30 atm bubbled 75 mA cm-2

40 atm bubbled 163 mA cm-2 10 atm stirred 163 mA cm-2 30 atm stirred 600 mA cm-2

Fig. 2. Product distributions reported for maximum current efficiency for hydrocarbon production and the reaction conditions. Values from [22–24].

Table 2
Average composition of optimal products gas mixes from Fig. 2
Product Mole fraction of Mole fraction of CO2 Mole fraction of gaseous Enthalpy of combustion/ Heat value in 1 mol of
products reacted products kJ mol1 gases/kJ
Hydrogen 0.38 0.45 285.8 129.9
Methane 0.33 0.51 0.40 890.8 355.4
Ethylene 0.07 0.10 0.08 1411.2 111.6
CO 0.06 0.09 0.07 283.0 19.1
Formate 0.20 0.31
Gas 0.69 616.0
mixture

atmospheric CO2. Two possible adsorbents are caustic
solutions (such as KOH) and amine solutions (such as
monoethanolamine (MEA)). These two systems for captur-
ing and concentrating CO2 from the air are diagrammed in
Figs. 3 and 4. The diagrams are shown using counter cur-
rent packed columns, although hollow fibre membrane
contactors could also be used [27]. The caustic/electrodial-
ysis approach (Fig. 3) has been suggested previously [10],
however, most interest in systems, for example to recover
CO2 from flue gases, have focused on amine based systems
(Fig. 4) [28]. The additional complexity (and capital cost)
of electrodialysis equipment and the ability to make use
of available sources of process heat within the amine based
process (especially if scrubbing CO2 from flue gas) are both
factors that favour the amine based process.
As well as additional operating energy requirements,
such systems require large contacting areas because of the
low concentration of CO2 in the atmosphere. One also
wishes to design the absorption tower to load fully the
absorbent as it drops through the tower, so as to maximize
the effectiveness of energy spent on regeneration. This
would favour a high ratio of gas to liquid flow rate and/
or a high column. Thus, as well as the energy required to
recover CO2 from the atmosphere, there will also be a sig-
nificant amount of energy and materials investment in
building the necessary equipment.
Thus, a higher concentration source of CO2 would be
desirable. As was mentioned previously, flue gases are
not being considered because, if excess renewable energy
were available, it could be more effectively used (possibly
through electricity storage technologies) to replace directly
the energy being provided by combustion. However, a very
promising source of CO2 is in biogases from anaerobic
digestion of wastes such as sewage and manure, and from
municipal landfill sites. Anaerobic digestion produces bio-
gases with compositions around 60% methane, 40% CO2
and small amounts of N2, H2S and volatile organic com-
pounds (VOCs) [29]. Such biogases can be used for space
1260 M. Gattrell et al. / Energy Conversion and Management 48 (2007) 1255–1265

Make-up water
Concentrated
CO2 output
KOH solution

CO2
depleted
air

CO2
absorber Acidification

KHSO4
Air solution H2SO4
K2CO3 solution
solution
Compressor
Pump

KOH
- K+ HSO4
-
+
solution

Electrodialysis
Pump Pump

Fig. 3. Process flow concept for CO2 capture and concentration from the atmosphere using caustic absorption.

Make-up water

Make-up Concentrated
MEA MEA CO2 output

CO2
depleted 40°C
air Condenser
90°C
CO2
absorber
CO2
stripper

Air
120°C
Heat
Compressor exchanger

Pump Reheater

Pump
Fig. 4. Process flow concept for CO2 capture and concentration from the atmosphere using amine absorption (MEA, monoethanolamine).

heating, but require upgrading to boost the fuel value mix or simply the addition of higher hydrocarbons (such
before they can be used for more demanding applications. as propane) to increase the fuel value [30,31]. However,
Upgrading methods can involve separation processes to electrochemical reaction of the CO2 fraction of such gases
recover the methane and higher hydrocarbons from the could be used to upgrade the fuel value without adding any
 M. Gattrell et al. / Energy Conversion and Management 48 (2007) 1255–1265 1261

additional carbon to the system and by making use of CO2
that would otherwise have been vented (and so, still, a CO2
neutral fuel).
2.3. The electrochemical synthesis reactors
The electrochemical synthesis would typically be per-
formed using a filter press flow by type reactor [32]. In such
a reactor, the solution travels along the electrode or
through the electrode if it is three-dimensional (e.g.,
stacked copper screens). The expected reactions that will
occur as the solution passes along the electrode are dia-
grammed in Fig. 5. The reaction of CO2 will result in pro-
duction of, primarily, methane, ethylene, CO and formate
with the formate being water soluble. The CO that is
Cell
Inlet
CH4
C2H4
H2
formed from CO2 would itself react as it moves further
along the electrode to produce additional methane and eth-
ylene. Methane, ethylene and formate are essentially unre-
active and, so, will accumulate and hydrogen will also be
produced along the electrode surface and will also accumu-
late [20]. One would like to achieve a high conversion of
CO2,and so, it is likely in a real system that a series of reac-
tors would be used, each optimized for a progressively
lower CO2 partial pressure. As was seen in Fig. 1, this
would involve adjusting the electrode current density
(through changing the current or changing the electrode
area) and the degree of mass transport to obtain the opti-
mal hydrocarbon production point.
Unfortunately, the available data to date are measured
in small lab electrochemical cells using a single electrode
condition (instead of flowing along a longer electrode with
changing conditions). Therefore, for the purposes of the
Cell calculations in this paper, the average product distribution
Outlet
from Table 2 will be used.
CH4
C2H4
2.4. The biogas upgrading process
H2

CO CO As discussed above, the process being considered is

CO2 CO2 upgrading anaerobic biogases using renewable energy
gas phase sourced electricity. A schematic of a system to produce
upgraded biogas is shown in Fig. 6. Depending on the
HCOO
-
HCOO
- end use, the degree of upgrading or gas clean up will be dif-
liquid phase
ferent (with the most stringent requirements being for the
- production of pipeline grade natural gas). Different separa-
e reactions electrode tion processes, such as membrane processes [33] or pressure
Fig. 5. Expected changes to the gas and liquid phase compositions as the swing adsorption, can also be used [30,31]. The removed
gas–liquid mixture moves along the electrode. CO2 is typically vented to the atmosphere.

Enriched gas Waste gases

CO2 <10% CO2 and
CH4 >90% H2S (to oxidative treatment)

Thermophillic Gas Absorbent

digester scrubbing regeneration
55°C, 2 days RT column column
Absorbent
liquid flow
Raw
sludge
Pump

Sludge
Biogas
CO2 40% Air
CH4 60%
Mesophillic H2S 500 ppm
Digester
37°C, 5 days RT
Pump

Bio-solids

Fig. 6. A system for the production of upgraded biogas.

1262 M. Gattrell et al. / Energy Conversion and Management 48 (2007) 1255–1265

Biogas Enriched gas

CO2 40% CO2 <10%
CH4 60% CH4 >90%
H2S 500 ppm

Thermophillic Electrical
digester energy
55° C, 2 days RT
H2 S
removal
Electrical
Raw energy
sludge
Pump

Electrical
Sludge energy

Electrochemical
CO2 to CH4
Mesophillic
Digester conversion
37°C, 5 days RT
Pump

Bio-solids

Fig. 7. A process flow concept for sewage sludge biogas enrichment using a series of electrochemical reactors to convert the CO2 to fuels.

In the envisioned electrochemical upgrading process
(shown in Fig. 7), the normally vented CO2 is converted
to additional fuel. A process step for removal of hydrogen
sulphide is shown, since this is reported to have some neg-
ative effects on the CO2 electroreduction reaction [34]. (One
possible process that is selective for hydrogen sulphide ver-
sus CO2 is described in [35]). To obtain the best gas enrich-
ment, the CO2 content should be reduced as low as
possible. To achieve reasonable reaction rates as one nears
complete conversion, high area electrodes can be used
(using, for example, stacked fine copper screen), and pres-
surized operation can be used to increase the partial pres-
sure of CO2 and, hence, the concentration of dissolved
CO2 available for reaction. If five cells were used in series,
each with 50% conversion, an overall conversion of the
available CO2 of close to 97% could be achieved. Based
on such a set up and using the product distribution from
Table 2, an estimate of the composition of the possible
enriched gas is given in Table 3.
One can see in Table 3 that this approach raises the
methane fraction of the product gas to 73% with the hydro-
gen amounting to about 19%. The improved fuel value can
be seen in Fig. 8, where the energy densities of the various
gas mixes discussed in the paper are plotted. Combining
electrochemical CO2 conversion and biogas production
yields a product fuel gas with a similar energy density to
that of Hythane. Thus, this technology shows promise
for using renewable energy to upgrade biogases to a fuel

Table 3
Estimated reaction product mass balance
Species Number of electrons Moles Moles Moles in gas Mole fraction in Additional energy stored (based
in synthesis initially reacting product gas product on the enthalpy of combustion)/kJ
HHV LHVa
CO2 0.4 0.388 0.013 0.012
Methane 8 0.6 +0.179 0.779 0.734 159.4 144.9
Ethylene 12 +0.035 0.035 0.033 50.0 47.2
CO 2 +0.030 0.030 0.029 8.6 8.6
Formate 2 +0.107
Hydrogen 2 +0.204 0.204 0.192 58.2 50.0
Total 1.0 1.061 276.3 250.5
(Using a per mole of biogas basis, assuming 5 cells, each with 50% conversion so 96.9% total conversion, using a product distribution based on the average
data in Table 2, and enthalpy data from [36]).
a
Corrected using an enthalpy of vaporization of water at 100 °C of 40.65 kJ mol.
 M. Gattrell et al. / Energy Conversion and Management 48 (2007) 1255–1265 1263

900

800

Enthalpy of combustion / kJ mole-1

700

600

500

400

300

200

100

ne
t

as
en

e
s

as
uc

an
ga

og

ha
og

g
od

h
io

al
yt
bi

et
r

pr
yd

ur
H

m
d
H

al

at
de

re
ic

en
ra

Pu
m

lin
pg
he

pe
U
oc

Pi
tr
ec
El

Fig. 8. The enthalpies of combustion (HHV) for the gaseous fuels discussed in this work [36].

mix that can be directly used by existing gasoline engines
with minimal modifications, although more work on the
synthesis reaction, or possibly treatments such as the addi-
tion of propane, would be required to try to reach pipeline
grade natural gas (equivalent to approximately 95%
methane).
From Table 3, the total energy added to the biogas in
this manner is about 276 kJ/mol of biogas. The total
charge required based on the number of electrons required
and the number of moles synthesised works out to 2.54 mol
of electrons per mole of biogas upgraded or 245,000 C. To
determine the energy consumed, one needs to estimate the
electrochemical cell voltage. This has been done in Table 4.
The cathode potential is a rough average of the potentials
shown in Fig. 1. The thermodynamic potential for oxygen
evolution (the counter reaction in the other half of the elec-
trochemical cell) is 0.816 V vs. SHE (standard hydrogen
electrode) at pH 7 and a further 0.4 V is assumed to be
required to drive the reaction at a reasonable rate (50–
100 mA cm2). Another 0.3 V loss is assumed due to the
resistance of the electrolyte and cell membrane or separa-
tor. This results in an estimated total cell voltage of
Table 4
Estimated voltages in an electrochemical cell reducing CO2
Source
Cathodic reaction
Anodic reaction (oxygen evolution at pH 7)
Anode overvoltage (assuming IrO2)
Cell membrane or separator and electrolyte voltage
drops
Total cell voltage
3.0 V, which, when multiplied by the estimated charge
required, results in 738 kJ/mol of biogas upgraded, and
so, the efficiency for the electrochemical conversion of elec-
trical energy to chemical energy is around 38%. Note that
this would be 34% if LHVs are used, which would be more
correct if the intended end use was in an internal combus-
tion engine (ICE). Other losses due to pumping would fur-
ther slightly reduce this efficiency.
The cell voltage used here is higher than that estimated
by Hori (2.52 V) [37]. This is because we are assuming a
higher production rate. In his work, he assumed a reaction
current of 5–10 mA/cm2. While we are also assuming cur-
rents as low as 5–10 mA/cm2 at the electrode surface for
some stages, we are assuming the use of a high area, three
dimensional, stacked copper screen electrode to increase
the total current flowing through the cell membrane to
the anode to around 100 mA/cm2 (a more typical industrial
value). This results in a higher production rate for a given
electrochemical reactor but a somewhat lower efficiency.
A key issue with the reduction of CO2 at copper elec-
trodes is the very negative voltage required to achieve good
reaction rates and product efficiencies (see Fig. 1), espe-
cially when compared to the thermodynamic requirements
(see Eqs. (1)–(5)). Thus, any research that could decrease
this voltage would be useful. Energy is also wasted in the
production of the by product formate. In a small system,
Voltage
the formate could be removed by oxidation at the anode,
1.5 V vs. SHE
however, adjustments to the reaction conditions to
0.8 V vs. SHE
0.4 V decrease formate production would also be useful,
0.3 V although, possibly, on a large scale system, the formate
could be recovered as a useful product. Also, for large scale
3.0 V systems, if one wished to export the fuel, higher density
1264 M. Gattrell et al. / Energy Conversion and Management 48 (2007) 1255–1265
fuels would be desirable. Some possibilities might be to
react the hydrogen, methane, ethylene mix to higher hydro-
carbons, such as propane and butane (research to increase
the ethylene content might help with such upgrading).
Other technologies, such as ‘‘methane to gasoline’’ might
also be of use [38].
3. Summary
One promising application for the electrochemical
reduction of CO2 to hydrocarbons might be upgrading of
biogases. While more research is needed to improve the
energy storage efficiency, the process offers a simple design
(and so, potentially a low investment of energy and mate-
rials to build) and simplicity of direct fuel use in a standard
gasoline engine (by producing a Hythane G type product).
Thus, one might envision the situation where remote com-
munities with a local excess of renewable energy could use
their renewable energy to achieve local fuel self sufficiency.
As well as directly decreasing green house gas emissions by
replacing existing gasoline consumption with a CO2 neutral
fuel, the CO2 emissions related to the transport of fuel to
the remote community are also avoided. Perhaps, at some
point in the future, they might become exporters of fuel (as
envisioned by Prof. Hashimoto [3]), but in the near term,
this type of process represents a good initial goal.
Based on the available data, the reaction seems well
behaved in that reasonably good hydrocarbon yields can
be obtained under a variety of reaction conditions through
control of the electrode potential (and related reaction rate
or current density). More research is needed to verify this
approach and to try to improve the energy storage effi-
ciency and the product distribution. Work is also needed
to assess the effect of impurities, which have been reported
to influence negatively the CO2 reduction reaction [34,39].
Acknowledgements
The authors acknowledge useful discussions with Profs.
Hori and Koga of Chiba University and Prof. Colin Olo-
man and Dr. Li Hui of the University of British Columbia.
We also thank Prof. Koji Hashimoto for discussions on
global warming and his infectious enthusiasm for finding
solutions through green chemistry. Finally, we would like
to thank the Canadian Office of Energy Research and
Development’s Innovative Research Initiative for funding
this work.
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