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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 resulting 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 standard 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 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 integrating 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*
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mass based electricity generation facilities that rely on complex 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 mechanical storage (ﬂywheels) [1,2]. Many large sources of renewable 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  and hydroelectric resources in northern Canada . Also, in Canada, a signiﬁcant amount of wind energy is located along the North Atlantic coast (especially Newfoundland and Labrador), while most power demand is in southern parts of the country . 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
9].7] Fuel Diesel fuel (#2) Bio-diesel Gasoline LPG (liqueﬁed petroleum gas) (mostly propane) Ethanol Methanol 207 bar NG (3000 psi natural gas) (mostly methane) 207 bar H2 (3000 psi) Volumetric energy density (kJ/L or MJ m3) 35. The resulting pure CO2 was then reacted with electrolytic hydrogen in a low pressure (50–100 bar) methanol synthesis process.2. This raises the additional issue.800 9900 1810 not require energy for their compression and are more easily transported. for fuel synthesis concepts based on CO2. 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) . The renewable energy is used to generate electrolytic hydrogen. we would look to fuel synthesis concepts to export renewable energy and to use renewable energy in transportation applications. thus.200 15. in the longer term. If such fuels could be made from captured CO2 using renewable energy. be more eﬃciently used to oﬀ set non-renewable. liquid fuels are preferable to gaseous fuels because they do Table 1 Volumetric energy densities of some energy carriers (LHV) [6. Another energy cycle concept involving a CO2 neutral hydrocarbon fuel uses methane. CO2 emitting power generation. which resulted in a slightly lower energy (320 kJ/mol of CO2) and could make use of more eﬃcient solar heating as opposed to photovoltaic energy required for electrodialysis. This was felt to yield a similar eﬃciency with liquid hydrogen fuel systems but with fewer infrastructure issues. This system used amine scrubbing with thermal regeneration to capture and concentrate CO2 from a smoke stack. Hydrocarbon based fuels are compatible with the existing infrastructure and many have a good energy density (see Table 1). Such a chemical fuel (or energy transportation vector) should be easily and eﬃciently synthesised. which was reacted with CO2 in a low pressure (50 bar) methanol synthesis reactor. Similar eﬃciencies were obtained. Bandi and collaborators produced a series of papers looking at the concept of producing methanol from atmospheric CO2 to obtain a CO2 neutral fuel [4. if CO2 can be found and converted to fuels with reasonable eﬃciency. To this end.) A similar system using oﬀ peak power and starting from more concentrated ﬂue gas as a CO2 source has been calculated in some detail . one carbon to perhaps as high as four carbon fuels). for a CO2 neutral fuel. 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 process that is creating the ﬂue gas. the CO2 must be recovered from the atmosphere. This methanol water product was then distilled to yield methanol fuel. a balance needs to be found between simplicity of fuel synthesis and ﬁnal fuel energy density. they concluded that. of a source of CO2 in a local region that has a true excess of renewable energy. In one example. this would represent a powerful technology to expand the utility of many renewable power sources. they conducted experiments concentrating CO2 from the air using adsorption in a counter current packed column with a KOH solution (resulting in K2CO3). CO2 is captured at a stationary point of fuel use (facilitated by using pure oxygen combustion). Also. Gattrell et al. which is reacted over a catalyst with the captured CO2 to re-synthesise methane . This is because the round trip eﬃciencies of most electricity storage systems exceed those of typically proposed fuel synthesis-storage-combustion cycles.760 32. The group of Weiner. Again the system is relatively complex. A high temperature method using limestone was also considered. a total energy cost for obtaining CO2 from the air of 430 kJ/mol was found . / 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. which will increase the energy and .. this generally implies simple hydrocarbon fuels (i. High pressure electrolysers produced the hydrogen. While much interest and work is associated with hydrogen as a possible energy carrier. through the storage technologies mentioned previously. it suﬀers from a low energy density and requirements for infrastructure modiﬁcation or rebuilding. but issues were raised about the capital cost of the equipment (or the related materials and energy required to fabricate the equipment). the captured CO2 is then transported to a location with abundant renewable energy. Thus. and the resulting K2SO4 salt was regenerated to KOH and H2SO4 using electrodialysis. (Direct electrochemical synthesis of methanol from CO2 was tested.1256 M. In their work. which was estimated to require an additional 1000 kJ/mol of methanol product. Thus. but none are completely satisfactory. This required approximately 100 m3 of air to be processed and about 70 kJ/mol of captured CO2. but the selectivities and eﬃciencies were poor [8. Specht. The CO2 was then released by adding acid (H2SO4). Possibilities for a CO2 based energy vector Diﬀerent concepts for using CO2 to synthesise a fuel have been considered previously.500 21. easily used (preferably within existing infrastructures) and have a high energy density (so as to allow it to be easily and eﬃciently transported.020 23. Various possibilities have been suggested for such an energy vector. Thus.e. they would then not result in a net release of CO2 when combusted. However. when starting from CO2. However. as can be seen in Table 1.580 32. preferably within existing infrastructures). The electrodialysis was found to require 180 kJ per mole of OHÀ regenerated and. 1. if one desires a simple and eﬃcient process. again. 360 kJ/mol of CO2 captured.8–12].
converting gasoline engines to . feedstock CO2 must be found locally. the reactions are also sensitive to the degree of mixing used . at present. there is an optimal reaction rate to maximise the conversion of CO2 to hydrocarbons (as also suggested by Ref. be easily scaleable and could operate at ambient temperature (to allow for rapid changes in production rate as renewable energy availability changes). Electrochemical synthesis technology As mentioned above. Changes to the rate of propagation of a ﬂame front are important in spark ignited engines because it aﬀects the ignition timing. 2 is presented in Table 2.M.. if one wishes to produce a gaseous fuel. however. because of the goal of avoiding transportation costs. 2. ethylene. would have few process stages. but increases the combustion temperature. When using such hydrogen methane fuels in a spark ignited piston engine. In Fig. When this happens. 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 ) 2Hþ þ 2eÀ ¢ H2 E0 ¼ 0:0 V vs: SHE ð1Þ 2CO2 þ 12Hþ þ 12eÀ ¢ C2 H4 þ 4H2 O ð2Þ E0 ¼ 0:079 V vs: SHE þ À CO2 þ 8H þ 8e ¢ CH4 þ 2H2 O E0 ¼ 0:169 V vs: SHE ð3Þ CO2 þ 2Hþ þ 2eÀ ¢ CO þ H2 O E0 ¼ À0:103 V vs: SHE ð4Þ CO2 þ Hþ þ 2eÀ ¢ HCOOÀ E0 ¼ À0:225 V vs: SHE ð5Þ The product distribution has been found to vary with a number of factors including the electrode potential. which acts to suppress hydrogen evolution. therefore. reasonably promising results can be obtained. This paper will. The gas produced. 1b and c). 1. As well as a range of CO2 pressures from 1 to 40 atm. Adding hydrogen to methane lowers the fuel energy density. Discussion 2. As the electrode potential is made more negative and the CO2 reduction increases. and so. contains a signiﬁcant amount of hydrogen. As a short term goal. the product distributions are shown from various reported results taken at the point of optimal current eﬃciency (i. the rate of CO reduction to hydrocarbons begins to exceed its formation (inﬂuenced in part by the depletion of CO2 near the electrode surface). Thus. Because the ﬂame front travels more slowly in methane than gasoline. Generally. At increasingly more negative potentials. A higher hydrogen content will result in a lower energy density (in this case about 70% of that of pure methane). the solution composition and solution impurities [19. A potentially enabling technology to satisfy these requirements is electrochemistry [14. 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 reasonable eﬃciency and reaction rate [16. if care is taken. the technology might be aimed at creating fuel self suﬃciency for remote communities that have a local excess of renewable energy. copper electrode . Thus. and formate were formed at reasonable rates (5 mA/cm2) at a. perhaps. at some point in the future. based on the data in Fig. often import their fuels from more populated areas with an economic and environmental cost associated with the fuel transportation. the electrode preparation. the coverage of CO on the electrode decreases and hydrogen evolution begins again on the uncovered copper surface  (see the more negative voltage regions in Fig. The early results found methane. diﬀerent levels of mass transport were also used with active mixing leading to a higher optimal reaction rate (versus passive mixing due to CO2 bubbling and gas evolution at the electrode surface) . which has been reviewed recently . Considering the relatively wide range of reaction conditions. such locations. In particular. 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 reduction of CO2 initially leads to CO and formate with large amounts of hydrogen also evolved (see the less negative voltage regions in Fig. ). carbon monoxide. 2. adsorbed CO tends to accumulate on the electrode surface. the lower energy density results in less power and slightly lower engine eﬃciency. even at these optimal operating points. the optimum reaction rate for best hydrocarbon current eﬃciency tends to produce a roughly similar product distribution. / Energy Conversion and Management 48 (2007) 1255–1265 1257 materials required to produce and operate the necessary equipment. although.e. Eventually. The combustion characteristics of hydrogen methane blends in internal combustion engines has been the subject of much study. The addition of hydrogen and the increased ﬂame temperature produce lower hydrocarbon emissions but increased NOx. rich in renewable energy.20]. non-precious metal. CO begins to be reduced leading to hydrocarbon products (primarily methane and ethylene). This average composition. remote communities are more likely to achieve ﬁrst the goal of excess renewable energy and. Gattrell et al. In spite of this sensitivity to reaction conditions. might become exporters of fuel. where the largest fraction of current goes to hydrocarbon production).15].1. 2 can be used to estimate the typical composition that might be expected to be possible for such a fuel. the lower ﬂammability limit and the rate of propagation of a ﬂame front during combustion. Experimental results from a few diﬀerent research groups are shown in Fig. Such small.17]. 1a and b). An ideal system. the results in Fig. investigate how this electrochemical reaction might be used as the basis for a process to produce a CO2 neutral fuel. This raises a further requirement that. the concentration of dissolved CO2 and the pH at the surface of the electrode during the reaction are important.
1. 25 °C (current range 75–900 mA/cm2). 25 °C. 19 °C (current range 0. run on methane requires changes to the ignition timing. stirred. (c) 0. data from . As discussed earlier.4 -1. 2. Current eﬃciencies at diﬀerent potentials for CO2 reduction at copper electrodes. and so. The CO2 source A second issue is the most eﬀective method of obtaining CO2 for the process.2 -1. if one adds the correct amount of hydrogen to the methane.6 Potential / V vs.7 Potential / V vs. 30 atm CO2. / Energy Conversion and Management 48 (2007) 1255–1265 a 70 H2 Hydrocarbons 60 50 40 HCOO- 30 20 10 CO -0. (%) 50 Current Eff. 1 atm CO2 bubbled. Also. 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. SHE b H2 HCOO - 30 20 10 CO Hydrocarbons -0.) Thus.6 0 -1. Thus.7 70 60 50 40 Potential / V vs.9 -1 -1.5 -1.1 M KHCO3. 1 atm CO2 bubbled. this technology can produce a fuel with an energy density of about 2.3 -1. Gattrell et al.6 0 -1. work to raise the CO2 conversion to hydrocarbons from the 69% value in Table 2 would be helpful in making this approach more viable.2 -1. as ‘‘Hythane G’’ .5% inerts and the remainder of higher hydrocarbons.9 -1 -1.4 -1.12–7 mA/cm2). data from . (Note that the natural gas used in the example blend contained 92. 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 Consultants Inc.4 -1. 3. SHE c Hydrocarbons HCOOCO H2 70 60 40 30 20 10 0 -1.1 M KHCO3.3 -1. the rate of propagation of a ﬂame front can be adjusted to be comparable to that of gasoline. one may consider methods to capture and concentrate Current Eff. (a) 0.1258 M.3% methane.3 -1. (%) Current Eff. (%) . data from . even with existing results. SHE Fig. (b) 0.2 times that of hydrogen.7 -0.5 -1.2.1 -1. for a remote community.9 -1 -1.2 -1.1 M KHCO3. the mixed fuel can be used in existing gasoline engines with fewer modiﬁcations.1 -1. it is desirable to obtain the CO2 locally. However.5 -1.1 -1. However.
This would favour a high ratio of gas to liquid ﬂow rate and/ or a high column. although hollow ﬁbre membrane contactors could also be used .08 0. As was mentioned previously.06 0.20 Mole fraction of CO2 reacted 0.2 0.M.69 Mole fraction of gaseous products 0.6 19. 2 Product Hydrogen Methane Ethylene CO Formate Gas mixture Mole fraction of products 0. As well as additional operating energy requirements.10 0. Two possible adsorbents are caustic solutions (such as KOH) and amine solutions (such as monoethanolamine (MEA)).0 Heat value in 1 mol of gases/kJ 129. Values from [22–24].8 890.7 1259 0.1 0 hydrogen methane ethylene 1 atm bubbled 10 atm stirred 163 mA cm-2 CO formate 1 atm bubbled 7 mA cm-2 40 atm bubbled 163 mA cm-2 30 atm bubbled 75 mA cm-2 30 atm stirred 600 mA cm-2 Fig. Table 2 Average composition of optimal products gas mixes from Fig. Such biogases can be used for space .07 Enthalpy of combustion/ kJ molÀ1 285. it could be more eﬀectively used (possibly through electricity storage technologies) to replace directly the energy being provided by combustion. 40% CO2 and small amounts of N2. have focused on amine based systems (Fig. there will also be a signiﬁcant amount of energy and materials investment in building the necessary equipment.45 0. a very promising source of CO2 is in biogases from anaerobic digestion of wastes such as sewage and manure.6 M ol f acton i product e r i n 0. a higher concentration source of CO2 would be desirable. however. ﬂue gases are not being considered because.2 283. 3 and 4. These two systems for capturing and concentrating CO2 from the air are diagrammed in Figs.4 111.33 0.0 atmospheric CO2. for example to recover CO2 from ﬂue gases. so as to maximize the eﬀectiveness of energy spent on regeneration.1 616. and from municipal landﬁll sites.9 355. if excess renewable energy were available. 3) has been suggested previously .8 1411. However.07 0.31 0. 4) . Anaerobic digestion produces biogases with compositions around 60% methane. The diagrams are shown using counter current packed columns.5 0.4 0. as well as the energy required to recover CO2 from the atmosphere. Thus. H2S and volatile organic compounds (VOCs) . One also wishes to design the absorption tower to load fully the absorbent as it drops through the tower. The caustic/electrodialysis approach (Fig. most interest in systems. / Energy Conversion and Management 48 (2007) 1255–1265 0. Thus. such systems require large contacting areas because of the low concentration of CO2 in the atmosphere. Product distributions reported for maximum current eﬃciency for hydrocarbon production and the reaction conditions.40 0.3 0. 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.09 0.51 0. 2.38 0. Gattrell et al.
3. Upgrading methods can involve separation processes to recover the methane and higher hydrocarbons from the mix or simply the addition of higher hydrocarbons (such as propane) to increase the fuel value [30. / Energy Conversion and Management 48 (2007) 1255–1265 Make-up water Concentrated CO2 output KOH solution CO2 depleted air CO2 absorber Acidification Air K2CO3 solution Compressor Pump KOH solution KHSO4 solution H2SO4 solution - K+ HSO4 - + Pump Electrodialysis Pump Fig. but require upgrading to boost the fuel value before they can be used for more demanding applications. Process ﬂow concept for CO2 capture and concentration from the atmosphere using caustic absorption. monoethanolamine). Gattrell et al. electrochemical reaction of the CO2 fraction of such gases could be used to upgrade the fuel value without adding any . However. heating.31]. Make-up water MEA CO2 depleted air CO2 absorber CO2 stripper Air Heat exchanger Pump 120°C 40°C Condenser 90°C Make-up MEA Concentrated CO2 output Compressor Reheater Pump Fig.1260 M. Process ﬂow concept for CO2 capture and concentration from the atmosphere using amine absorption (MEA. 4.
the degree of upgrading or gas clean up will be different (with the most stringent requirements being for the production of pipeline grade natural gas). Enriched gas CO2 <10% CH4 >90% Thermophillic digester 55°C. .g. it is likely in a real system that a series of reactors would be used. The removed CO2 is typically vented to the atmosphere. Gattrell et al. The expected reactions that will occur as the solution passes along the electrode are diagrammed in Fig. such as membrane processes  or pressure swing adsorption. Diﬀerent separation processes. stacked copper screens). CO and formate with the formate being water soluble. HCOO - HCOO liquid phase reactions electrode - e - Fig. 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). so. Methane. 5 days RT Pump Bio-solids Biogas CO2 40% CH4 60% H2S 500 ppm Air Fig. 5. 2 days RT Gas scrubbing column Waste gases CO2 and H2S (to oxidative treatment) Absorbent regeneration column Absorbent liquid flow Raw sludge Pump Sludge Mesophillic Digester 37°C. methane. Therefore.M. 5. Expected changes to the gas and liquid phase compositions as the gas–liquid mixture moves along the electrode. for the purposes of the calculations in this paper.3. 1.. each optimized for a progressively lower CO2 partial pressure.and so. primarily. A schematic of a system to produce upgraded biogas is shown in Fig. / 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. The CO that is Cell Inlet CH4 C2H4 H2 CO CO2 Cell Outlet CH4 C2H4 H2 CO gas phase CO2 formed from CO2 would itself react as it moves further along the electrode to produce additional methane and ethylene. will accumulate and hydrogen will also be produced along the electrode surface and will also accumulate . 2.31]. One would like to achieve a high conversion of CO2. 6. In such a reactor. the average product distribution from Table 2 will be used. Depending on the end use. still. ethylene and formate are essentially unreactive and. the process being considered is upgrading anaerobic biogases using renewable energy sourced electricity. a CO2 neutral fuel). 6. The reaction of CO2 will result in production of. can also be used [30. The electrochemical synthesis reactors The electrochemical synthesis would typically be performed using a ﬁlter press ﬂow by type reactor . the solution travels along the electrode or through the electrode if it is three-dimensional (e. A system for the production of upgraded biogas. As was seen in Fig. Unfortunately.4. ethylene. 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 optimal hydrocarbon production point. 2. The biogas upgrading process As discussed above.
035 0.0 8.9 47.388 +0. One can see in Table 3 that this approach raises the methane fraction of the product gas to 73% with the hydrogen amounting to about 19%. hence. the normally vented CO2 is converted to additional fuel. assuming 5 cells. 8.179 +0. high area electrodes can be used (using.6 À0.033 0. A process ﬂow concept for sewage sludge biogas enrichment using a series of electrochemical reactors to convert the CO2 to fuels.3 1.2 8.779 0. 7. using a product distribution based on the average data in Table 2. A process step for removal of hydrogen sulphide is shown. To obtain the best gas enrichment.9% total conversion.192 159. the CO2 content should be reduced as low as possible.4 0. and enthalpy data from ).204 1.6 58.030 +0.012 0.0 (Using a per mole of biogas basis. a Corrected using an enthalpy of vaporization of water at 100 °C of 40.6 50.0 250. (One possible process that is selective for hydrogen sulphide versus CO2 is described in ).204 0.061 0. The improved fuel value can be seen in Fig.1262 M.030 0. the concentration of dissolved CO2 available for reaction.65 kJ mol.5 CO2 Methane Ethylene CO Formate Hydrogen Total 8 12 2 2 2 0. for example. Combining electrochemical CO2 conversion and biogas production yields a product fuel gas with a similar energy density to that of Hythane. Based on such a set up and using the product distribution from Table 2. stacked ﬁne copper screen). Table 3 Estimated reaction product mass balance Species Number of electrons in synthesis Moles initially Moles reacting each with 50% conversion. an estimate of the composition of the possible enriched gas is given in Table 3. Gattrell et al.2 276.035 +0. If ﬁve cells were used in series. 2 days RT Enriched gas CO2 <10% CH4 >90% Electrical energy H2 S removal Raw sludge Pump Electrical energy Sludge Electrical energy Electrochemical CO2 to CH4 conversion Mesophillic Digester 37°C. this technology shows promise for using renewable energy to upgrade biogases to a fuel Moles in gas product Mole fraction in gas product Additional energy stored (based on the enthalpy of combustion)/kJ HHV LHVa 144. an overall conversion of the available CO2 of close to 97% could be achieved.013 0. / Energy Conversion and Management 48 (2007) 1255–1265 Biogas CO2 40% CH4 60% H2S 500 ppm Thermophillic digester 55° C. In the envisioned electrochemical upgrading process (shown in Fig. 7). .029 0. and pressurized operation can be used to increase the partial pressure of CO2 and.734 0.4 50. To achieve reasonable reaction rates as one nears complete conversion. Thus. where the energy densities of the various gas mixes discussed in the paper are plotted.107 +0. since this is reported to have some negative eﬀects on the CO2 electroreduction reaction . 5 days RT Pump Bio-solids Fig. each with 50% conversion so 96.
From Table 3.3 V 3.0 V El ec tr 3. In his work.5 V vs. Note that this would be 34% if LHVs are used. although more work on the synthesis reaction. The thermodynamic potential for oxygen evolution (the counter reaction in the other half of the electrochemical cell) is 0. mix that can be directly used by existing gasoline engines with minimal modiﬁcations. Also.M. any research that could decrease this voltage would be useful.8 V vs. SHE (standard hydrogen electrode) at pH 7 and a further 0. In a small system. especially when compared to the thermodynamic requirements (see Eqs. A key issue with the reduction of CO2 at copper electrodes is the very negative voltage required to achieve good reaction rates and product eﬃciencies (see Fig.4 V 0. we are assuming the use of a high area. Another 0.816 V vs.52 V) . results in 738 kJ/mol of biogas upgraded. which would be more correct if the intended end use was in an internal combustion engine (ICE). if one wished to export the fuel. To determine the energy consumed. adjustments to the reaction conditions to decrease formate production would also be useful. or possibly treatments such as the addition of propane.000 C. 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 Voltage À1. SHE 0. one needs to estimate the electrochemical cell voltage. Other losses due to pumping would further slightly reduce this eﬃciency. 1. (1)–(5)). possibly. The enthalpies of combustion (HHV) for the gaseous fuels discussed in this work . and so. The cell voltage used here is higher than that estimated by Hori (2. / Energy Conversion and Management 48 (2007) 1255–1265 900 1263 Enthalpy of combustion / kJ mole-1 800 700 600 500 400 300 200 100 0 uc t en ne as ga s og og ha al g od yd r B pr ur H H al de at ic ra en he pg oc Fig. he assumed a reaction current of 5–10 mA/cm2. 8.4 V is assumed to be required to drive the reaction at a reasonable rate (50– 100 mA cmÀ2). however. which.0 V. The cathode potential is a rough average of the potentials shown in Fig. The total charge required based on the number of electrons required and the number of moles synthesised works out to 2. when multiplied by the estimated charge required. for large scale systems.3 V loss is assumed due to the resistance of the electrolyte and cell membrane or separator. Thus. the total energy added to the biogas in this manner is about 276 kJ/mol of biogas. three dimensional. SHE 0. 1). the formate could be recovered as a useful product. This results in a higher production rate for a given electrochemical reactor but a somewhat lower eﬃciency. 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). would be required to try to reach pipeline grade natural gas (equivalent to approximately 95% methane). higher density Pi pe U lin Pu m re m d et h io bi yt an e as . although. Energy is also wasted in the production of the by product formate. This is because we are assuming a higher production rate. This has been done in Table 4. the formate could be removed by oxidation at the anode. Gattrell et al. the eﬃciency for the electrochemical conversion of electrical energy to chemical energy is around 38%.54 mol of electrons per mole of biogas upgraded or 245. on a large scale system. While we are also assuming currents as low as 5–10 mA/cm2 at the electrode surface for some stages.
33(5–8):537–43. such as propane and butane (research to increase the ethylene content might help with such upgrading). Chem Lett 1986:897–8. 1999.energystorage.  Hori Y. Suzuki S.36:161–72. Gattrell M. Alternative Fuels Data Center. 15th ed. Katagiri H. . catalyzed by metal electrodes. Energy eﬃciency and renewable energy. 145. Other technologies. potentially a low investment of energy and materials to build) and simplicity of direct fuel use in a standard gasoline engine (by producing a Hythane G type product). Int J Hydrogen Energy 2003.php/>. Bandi A.  Gupta N. Murata A.  Specht M. Comparison of the renewable transportation fuels. methane.23(5):387–96. 3. CO2 removal and ﬁxation solar high temperature syngas regeneration for fuel synthesis. Specht M. Hori and Koga of Chiba University and Prof. Mennenkamp E. Gupta N. such as ‘‘methane to gasoline’’ might also be of use . Sasaki T. Maier CU.A304–306:88–96.28:455–64. Baselt JP. Maier CU.energy. Summary One promising application for the electrochemical reduction of CO2 to hydrocarbons might be upgrading of biogases. Internal combustion engines fuelled by natural gas–hydrogen mixtures. Advanced materials for global carbon dioxide recycling. Dulger Z. In: Veziroglu TN. Lave LB. editors. p. Koji Hashimoto for discussions on global warming and his infectious enthusiasm for ﬁnding solutions through green chemistry. ethylene mix to higher hydrocarbons.windatlas. Colin Oloman and Dr. Veziroglu TN. Thus. CO2-reduction. Electrochemical and electrocatalytic reactions of carbon dioxide. Bandi A. Weimer T. Ikeda S. Weimer T. they might become exporters of fuel (as envisioned by Prof. Washington. Energy Convers Mgmt 1997. Electrochemical reduction of CO2 at solid electrodes. Int J Hydrogen Energy 1998.29:1–69. J Electroanal Chem 2006. Energy Convers Mgmt 1996. / Energy Conversion and Management 48 (2007) 1255–1265  Specht M. et al. References  Electricity Storage Association web site. Potential dependencies of the products on electrochemical reduction of carbon dioxide at a copper electrode. Schwarz J. J Chem Soc. Kudo A.38(Suppl. Guard HE.  Hori Y. Habazaki H. Murata A. J Appl Electrochem 2006. Oda Y. Methanol from atmospheric carbon dioxide: a liquid zero emission fuel for the future. Finally. the CO2 emissions related to the transport of fuel to the remote community are also avoided. Schaber K. Specht M. the process oﬀers a simple design (and so. Kreysa G.39].eere.  Frese Jr KW. Hashimoto ). Electrochem Soc Interf 2001. Hydrogen energy progress XI. Palo Alto. Sakata T. MacDougall B.  EPRI-DOE Handbook of energy storage for transmission and distribution applications. Energetics of solar methanol synthesis from atmospheric carbon dioxide compared to solar liquid hydrogen generation.gov/afdc/>. Handbook of fuel cells. <http://www. Liquid fuels from hydrogen and atmospheric CO2 a climate-neutral energy concept. West Sussex (UK): Wiley. Gattrell et al. Calculation for the cathode surface concentrations in the electrochemical reduction of CO2 in KHCO3 solutions. Winter C-J.29:1527–39.  Tryk DA. Tsuneto A.):S379–84.  U. 1993. editor.  Akansu SO. Fujishima A.  Gattrell M. which have been reported to inﬂuence negatively the CO2 reduction reaction [34.  MacLean HL. DC.1264 M.  Hashimoto K. at some point in the future. Li Hui of the University of British Columbia.141(8):2097–103. but in the near term. Kikuchi K. Bandi A.  Weimer T. Sahibzada M. Work is also needed to assess the eﬀect of impurities. 1311–5.37(6-8):1351–6. Schaber K. we would like to thank the Canadian Oﬃce of Energy Research and Development’s Innovative Research Initiative for funding this work.10(1):32.  Hori Y. Faraday Trans 1 1989. Amsterdam: Elsevier. Methanol synthesis from ﬂue-gas CO2 and renewable electricity: a feasibility study.S.  Environment Canada’s Wind Energy Atlas. editors. Takahashi R. Krist K. liquid hydrogen and methanol with gasoline – energetic and economic aspects. Co A. p. Yamasaki M. this type of process represents a good initial goal. Based on the available data. Schaber K. Lamm A.ca/en/maps. Chem Lett 1985:1695–8. Schaber K. Formation of hydrocarbons in the electrochemical reduction of carbon dioxide at a copper electrode in aqueous solution. As well as directly decreasing green house gas emissions by replacing existing gasoline consumption with a CO2 neutral fuel. Electrochemical reduction of CO2 on a Cu electrode under high pressure. A review of the aqueous electrochemical reduction of CO2 to hydrocarbons at copper. Acknowledgements The authors acknowledge useful discussions with Profs. Weimer T. <http://www. Mater Sci Eng 2001.594:1–19. Bandi A. 2003. Prog Energy Combust Sci 2003. Energy Convers Mgmt 1992. fuels would be desirable. J Electrochem Soc 1994. 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). 1996. Ito K.  Weimer T. Specht M.  Specht M. Gasteiger HA. editors. CO2 recycling for hydrogen storage and transportation – electrochemical CO2 removal and ﬁxation. In: Sullivan BP. Bandi A. Energy Convers Mgmt 1995. Perhaps.  Dean JA. Staiss F.  Mignard D. Production of CO and CH4 in electrochemical reduction of CO2 at metal electrodes in aqueous hydrogen carbonate solution. 720–33 [chapter 48]. Kikuchi K. 2003. EPRI. p. Electrochemists enlisted in war on global warming: the carbon dioxide reduction battle. Duthie JM. 2. Suzuki S. Frankfurt: Dechema. Kahraman N. Int J Hydrogen Energy 2004. CA and the US Department of Energy.  Bandi A. Lange’s handbook of chemistry. While more research is needed to improve the energy storage eﬃciency. We also thank Prof.  Hara K. <http:www.  Hori Y. Chem Lett 1989:289–92.  Noda H. Production of methane and ethylene in electrochemical reduction of carbon dioxide at copper electrode in aqueous hydrogen carbonate solution. vol. More research is needed to verify this approach and to try to improve the energy storage eﬃciency and the product distribution. Evaluating automobile fuel/propulsion system technologies.org/>. Department of Energy. In: Vielstich W.85(8):2309–26. New York: McGraw-Hill.36(6–9):899–902. Report #1001834. Some possibilities might be to react the hydrogen. one might envision the situation where remote communities with a local excess of renewable energy could use their renewable energy to achieve local fuel self suﬃciency. Whittington HW. Meguro S.
S. Sakata T.M. London: Chapman & Hall. Exergy analysis of alkanolamine-based CO2 removal unit with AspenPlus. Industrial electrochemistry. et al. Futamura T. / Energy Conversion and Management 48 (2007) 1255–1265  Lynch FE. 2nd ed. Fuess DJ. U. July 2001.784.ecn. Jonsson O. Special purpose blends of hydrogen and natural gas. Zwart RWR. Jensen JK. In: Tomkiewicz M. Amatoa WS.41:109–22. Energy 2004.50(27):5354–69. Polman E. Swedish Gas Center. Myken A.  Mozaﬀarian M. Kudo A. Murata A. <http://www.S.29:1241–8. Petten (Holland): Energy Research Centre of the Netherlands (ECN).  Sterna SA. Deactivation of copper electrode in electrochemical reduction of O2. Dahl A. 1–10. U. Chen B-H. New York: Wiley. Koga O. Energy Utilization system and electrochemical reduction of carbon dioxide. Schneiders LHJM. Hori Y. Patent 1998.nl/>. Report SGC 118. Boca Raton (FL): CRC Press. Sakurai H. Marmaro RW.139. p. Chang CD. liquid fuels. Konishi H. Feasibility of biomass/waste-related SNG production technologies. Patent 1992.151:63–74. Electrochim Acta 2005. editorCRC handbook of chemistry and physics.  Pletcher D.  Hagen M. Haynes R. Todd D. Krishnakumar B. Ellenor R.002. Friedmanb AA. Fuels. . Kirk–Othmer encyclopedia of chemical technology. editors. ¨ Adding gas from biomass to the gas grid. New York: Wiley. 1990. J Electroanal Chem 1997. Charati SG. Hori Y. Walsh F. Harbinson JN. ECN–C-03-066.434: 239–43. #5. PV93-18. Change in the product selectivity for the electrochemical CO2 reduction by adsorption of sulﬁde ion on metal electrodes. Tsuneto A. Biomass energy. Hara K. Han S. 2003. #5. J Membr Sci 1998.  Li J-L. Sep Purif Technol 2005. Gattrell et al. Process for the removal of hydrogen sulﬁde from a gas stream. 1993. Pennington (NJ): The Electrochemical Society. Feron PHM. 2003.  Paisley MA.730. Review of CO2 absorption using chemical solvents in hollow ﬁber membrane contactors. Proceedings of the symposium on environmental aspects of electrochemistry and photo-electrochemistry. Smith JW. July 2003.  Geuzebroek FH. Performance of a bench-scale membrane pilot plant 1265       for the upgrading of biogas in a wastewater treatment plant. Kraaijveld GJC. 1999. Hori Y. Kirk–Othmer encyclopedia of chemical technology. Lide DR. Yoneyama Y. synthetic.
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