WO2014202855A1 - Method of producing formic acid - Google Patents

Method of producing formic acid Download PDF

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Publication number
WO2014202855A1
WO2014202855A1 PCT/FR2014/051238 FR2014051238W WO2014202855A1 WO 2014202855 A1 WO2014202855 A1 WO 2014202855A1 FR 2014051238 W FR2014051238 W FR 2014051238W WO 2014202855 A1 WO2014202855 A1 WO 2014202855A1
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Prior art keywords
formic acid
electrochemical
cathode
c0
heat exchanger
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PCT/FR2014/051238
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French (fr)
Inventor
Beatrice Fischer
David Pasquier
Antoine Fecant
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IFP Energies Nouvelles
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Priority to FR13/55.845 priority Critical
Priority to FR1355845A priority patent/FR3007425B1/en
Application filed by IFP Energies Nouvelles filed Critical IFP Energies Nouvelles
Publication of WO2014202855A1 publication Critical patent/WO2014202855A1/en

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    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00Electrolytic production of organic compounds
    • C25B3/04Electrolytic production of organic compounds by reduction
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/02Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • C25B11/03Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
    • C25B11/035Porous electrodes
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00Operating or servicing of cells
    • C25B15/08Supplying or removing reactants or electrolytes; Regeneration of electrolytes

Abstract

The invention concerns a method of producing formic acid from carbon dioxide and water by electroreduction of the CO2 in the gaseous phase. The method uses electrochemical cells of which the cathode consists of a conductive porous solid and an active layer containing dispersed metal nanoparticles and catalysing the reaction selectively to formic acid. The resulting formic acid is then separated from the residual CO2 by crystallization, the CO2 being recycled to the electrochemical cell.

Description

PROCESS FOR PRODUCING FORMIC

FIELD OF INVENTION Increasing the amount of carbon dioxide in the atmosphere, mainly due to the burning of fossil fuels, is now recognized as a major factor of global warming. Many solutions have been proposed to capture carbon dioxide from combustion fumes, particularly for sequestration. However, the final sequestration of carbon dioxide has many technical difficulties and generates a lot of concern because of the risks, including those related to the sudden release into the atmosphere large amounts of carbon dioxide stored eg in the sea in aquifers, as has happened in the past with carbon dioxide of natural origin. A complementary solution to sequester captured carbon dioxide is to develop the latter, by converting it into a chemical active recoverable, that is to say a chemical used by the industry.

The present invention relates to a novel process for producing formic acid from C0 2. This method is electrochemical, that is to say, it uses electricity to produce formic acid and oxygen from C0 2 and water. This process is much simpler than current methods of producing formic acid, so could be competitive if the electricity price is not too high. This method may advantageously be used for storing electrical energy produced intermittently (solar, wind) or in addition (peak production).

REVIEW OF THE PRIOR ART

The electrochemical conversion of C0 2 was discovered in the nineteenth century (Royer, MECRHebd.Seances Acad.Sci.Paris 1870 T70, 731-732). It was proposed in the 1980s, for example in US patent 4,673,473, or in the article by Cook, MacDuff and Sammels (J. Electrochem. Soc., 1988, 135 (6), 1470-1471), including the hydrocarbon production.

In the 2000s, with concerns related to C0 2, new proposals were made.

At the level of an industrial electrochemical process, a difficulty is to obtain a sufficient current density and a good selectivity towards the desired product. largely determines the current density in fact the economic viability of the process. US patent 2012/0228147 reports that purpose of using a solid metal cathode (indium, lead, tin, cadmium or bismuth), and an aqueous electrolyte containing heterocyclic aromatic amines such as 4- hydroxypyridine which act as homogeneous catalyst. The process described in the cited patent has some drawbacks: first of all it is necessary to maintain the pH of the aqueous solution between 4.3 and 5.5, pH range within which a majority of the acid formic is in its basic form.

The material balance then shows that consumes a large amount of a base, which is unfavorable. Moreover the cited patent mentions the need to maintain the concentration of formic acid of less than 500 ppm, which makes the separation of this product virtually impossible, vapor-liquid equilibrium C0 2 / H 2 0 / formic acid being highly unfavorable in this case. US Patent 2008/223727 describes an electrochemical process for converting the continuous supply by carbon dioxide from a gas-liquid biphasic mixture containing C0 2 and an aqueous electrolyte. In this case the selectivity to formic acid is obtained only for greater than or equal to pH 7.

As the patent cited above (US 2012/0228147), the pH constraint is a hindrance to the development of this type of process. Indeed formic acid has a pKa of 3.75, which means that the formic acid is obtained in its basic form and therefore a quantity of stoichiometric base is consumed. The material balance is unfavorable.

On the other hand, formic acid present with water an azeotrope which greatly complicates its extraction. It is the problem of the traditional method for producing formic acid which requires a series of three distillation columns in order to separate 95% formic acid.

Patent US2012 / 0171583 uses a fuel cell by injecting hydrogen and C0 2 as fuel and claims the synthesis of methanol and propanol from the C0 2 by means of an aromatic polyamine-type catalyst deposited on an electrode gas diffusion.

In this case, the hydrogen provides the energy, is dissociated at the anode (oxidation) and allows the reduction of C0 2. It is the combination of platinum particles and an aromatic polyamine which is claimed as a selectivity for the reduction of C0 2 to the alcohols (methanol, propanol).

It is known in the field of catalytic hydrogenation processes C0 2j that conversion to alcohols can be achieved at relatively high temperatures, typically above 220 ° C to promote the reaction (Razali et al. Ren. Sust. Ener. Rev. 16 (2012) 4951). Employees catalysts and temperature conditions do not in any case the synthesis of formic acid. In fact this compound is degraded thermally at temperatures above 170 ° C.

The novelty of this invention resides in the generation of formic acid by an electrolytically in the compartment C0 2 directly in vapor form (that is to say that the formic acid is generated at a partial pressure lower than the saturation vapor pressure of formic acid at the operating temperature).

This generation of formic directly in the vapor state acid permits separation facilitated by condensation (in solid or liquid form) of formic acid from the gas stream. In doing so, the C0 2 in direct contact with electrons via the porous electrode on the metal particles which are the centers of the reaction and with protons via a solid polymer electrolyte. The protons involved in the reduction of C0 2 produced directly from water molecules introduced at the anode.

In contrast, catalytic processes of hydrogenation of the C0 2 which necessarily use hydrogen having a small carbon footprint and thus generally resulting from the electrolysis of water or as a byproduct of chlor-alkali electrochemical processing, using necessarily two stages.

The first step is the electrolysis for hydrogen generation, its storage pressure, and then in a second step, a catalytic conversion, in a second method, with specific conditions which generally are not adapted to the conditions of a intermittent method (such as wind power or solar power).

The method according to the present invention offers the advantage of using only water, C0 2 and electricity for the generation of formic acid by reduction of C0 2. The use of porous electrodes with high surface area associated with the use of metal particles which catalyze the selective formation of formic acid, provides the ability to produce formic acid in high current density conditions and facilitated separation . BRIEF DESCRIPTION OF FIGURES

1 shows a formic acid production module showing the anode portion and the cathode portion, the two portions being separated by a porous membrane allowing passage of H + ions.

Figure 2 is a diagram of the process according to the invention in a first embodiment showing the formic acid recovery circuit by means of a liquid formic acid loop. Figure 3 is a diagram of the process according to the invention in a second embodiment showing the recycling of the residual C02 to the electrolytic cell. BRIEF DESCRIPTION OF THE INVENTION

The present invention can be defined as an electrochemical method for producing formic acid from C02 and steam introduced to the cathode and steam introduced at the anode, using one or more electrochemical cells in parallel or stacked, said method using electrochemical cells, the cathode is composed of a porous solid conductor and an active layer containing dispersed metallic nanoparticles and catalyzing the reaction selectively to formic acid according to the reaction: C0 2 + H 2 0 → HCOOH + ½ 0 2

- at the anode: the steam being decomposed at the anode to oxygen and protons H + H 2 0 → ½ 0 2 + 2H + + 2e and

- At the cathode: carbon dioxide is reduced directly in the vapor phase under the effect of an electrochemical potential in contact with a porous cathode and a solid polymer electrolyte, C0 2 + 2H + + 2e → HCOOH

- formic acid produced is then preferably separated from the CO 2 residual by crystallization,

method wherein the surface current density is greater than 0.1 A / cm2 and preferably between 0.2 A / cm 2 and 2 A / cm2, and the potential difference between the anode and the cathode is less than 4 volts . According to a preferred characteristic of the electrochemical process for producing formic acid according to the invention, the catalyst used in the cathode of the electrolytic cell consists of metal particles selected from among those which exhibit a selectivity to formic acid is indium, tin, lead, bismuth, cadmium, thallium, taken alone or in admixture. Preferably, the catalyst used in the cathode of the electrolytic cell is selected from the following metals: indium, tin, lead, bismuth.

According to another preferred characteristic of the electrochemical process for producing formic acid according to the invention, the temperature measured at the electrochemical cell level is between 20 ° C and 160 ° C.

According to another preferred characteristic of the electrochemical process for producing formic acid according to the invention, the pressure in the electrolytic chamber is between 1 and 60 bar, and preferably between 1 and 10 bar.

According to another preferred characteristic of the electrochemical process for producing formic acid according to the invention, the steam introduced to the anode is driven by an inert carrier gas with respect to the electro-oxidation.

According to another preferred characteristic of the electrochemical process for producing formic acid according to the invention, the C02 introduced to the cathode of the electrolytic cell is driven by an inert carrier gas with respect to the electro-reduction. According to another characteristic of the electrochemical process for producing formic acid method according to the invention, a loop of liquid formic acid flowing at a moderate temperature of 25 ° C to 50 ° C allows the removal of crystals of formic acid formed in the '19a or 19b exchanger, formic acid from the liquid storage 22 is sucked by the pump 24 through the conduit 23 and then warmed in heat exchanger 25 using tempered water, or any other heating means, before being sent via line 26 in the exchanger 19 a or b, wherein the flow of coolant (20 a or b) has been stopped.

Finally, in a preferred variant of the process according to the present invention, the residual C02 obtained after 19a or 19b exchanger is recompressed in a compressor and reintroduced C02 at the cathode compartment constituting the feed for the process. DETAILED DESCRIPTION OF THE INVENTION

The process will be better understood in view of Figures 1, 2, and 3 described below. Description of figure 1

1 shows an electrochemical cell used in the process according to the invention. A current is applied between an anode composed of elements 2, 3 and 4 and a cathode composed of the elements 6, 7 and 8. The elements 2 and 6 are conductive plates, optionally in the case of bipolar stack of several electrochemical cells , responsible for distributing the gas and collect the electric current. conventionally encountered in the electrolyzers (e.g. for the electrolysis of water) or fuel cells. These conductive plates are stamped or machined so as to distribute the gas in conduit (9,10) hollowed out in these plates.

3 and 7 are elements of the diffusion layers of porous conductive material (typically carbon fiber), and 4 and 8 elements are deposited catalytically active layers is on the diffusion layers or on the membrane 5. The membrane 5 is a solid polymer electrolyte allowing the transfer of H + ions between the anode and the cathode.

The active layer 8 of the cathode is composed of a porous conductive material (such as porous carbon) containing metal nanoparticles. The metal particles for the cathode used for the invention are chosen from those which exhibit a selectivity to formic acid, such as indium, tin, lead, bismuth, cadmium, thallium, alone or in admixture .

Is sent from the anode side into the cavity 9 of the water, liquid or preferably in the form of steam supplied through conduit 11. When it is desired to work with water vapor, the water can be optionally driven by a gas which is inert in relation to electrolysis such as nitrogen so as to have water vapor to temperatures lower than the water vaporization temperature at the operating pressure. The cathode side, it sends the gaseous C0 2 in the cavity 10 through conduit 13 at a pressure between 1 and 60 bar absolute and at a temperature between 20 ° C and 160 ° C.

The anode side, the water under the effect of the current, breaks down into oxygen and protons H +. The oxygen is released through line 12, optionally in admixture with steam and optionally with an inert carrier gas such as nitrogen, from conduit 11.

H + protons under the effect of the current, migrate through the membrane in solid polymer electrolyte from the anode compartment to the cathode compartment, and preferably react with the metal sites of the cathode with the C0 2 to give formic acid which leaves the cell in admixture with C0 2 and any other gases contained in the C02 arriving through the pipe 14.

In a manner known to those skilled in the art of electrolysis, more electrochemical cells may be used in parallel or in stack, to achieve the desired capacity of formic acid. The current applied is optimized to ensure high current densities while reducing the cell voltage to a value less than or equal to 4V, and preferably less than or equal to 3V. In this way it is avoided to the maximum side reactions, such as the generation of hydrogen.

The surface current density is usually between 0.1 and 2 A / cm2, and preferably greater than 0.2 A / cm2, and more preferably greater than 0.4 A / cm2. Description of figure 2

2 shows a first flow diagram for producing formic acid according to the invention. The water or steam, optionally in admixture with an inert carrier gas, is fed through line 11 in the electrochemical cell (or the electrochemical cells in parallel or stacked) as 1. The outlet 12 contains oxygen (or oxygen-water mixture and optionally an inert gas, which can be separated by water condensation).

The C0 2 is passed through conduit 15 into heat exchanger 16 where it is preheated by steam, or any other means, before being sent through line 13 to the cell or cells 1.

Output of the electrochemical cell 1, a C0 2 mixture and formic acid, and any other gases contained in the C02 arriving via conduit 13, and possibly some traces of hydrogen, CO, and water are fed through line 14 to heat exchanger 17 wherein the mixture is cooled and partially condensed with cooling water or air.

The partially condensed mixture is then passed through line 18 to the heat exchanger 19a or 19b, in which it is cooled to around 5 ° C by propane or another compound or mixture refrigerant circulating in the duct 20 a or b . At this temperature, formic acid crystallizes and is deposited on the walls of the exchanger.

The residual gas, which contains essentially C0 2, can be discharged through line 21, preferably to a flare to eliminate possible traces of hydrogen, CO, methane or formic acid contained in said residual gas .

When the pressure drop is too high in the heat exchanger 19a (19b respectively) due to the deposition of crystals of formic acid, the flow duct 18 is directed towards the other 19b exchanger (respectively 19 a), which was freed meantime formic acid crystallized therein. The two exchangers 19a and 19b thus operate alternately one being deposition position crystals formic acid when the other is in crystal phase-position).

The elimination of formic acid crystals is obtained by circulation of liquid formic acid from the storage 22 is sucked by the pump 24 through the conduit 23 and then warmed in heat exchanger 25 using water tempered, or by any other heating means, before being sent via line 26 in the exchanger 19 a or b, wherein the flow of coolant (20 a or b) has been stopped.

Formic acid circulated at a moderate temperature (25-50 ° C) for melting the crystalline formic deposited in the exchanger 19a or 19b acid and return it to storage 22 via line 27.

Description of Figure 3

Figure 3 shows a second process diagram for producing formic acid according to the invention wherein the residual C02 emitted through line 21 is recompressed in a compressor 29 to be reintroduced into the input stream 15 to the cell level electrochemical 1. This embodiment is an improvement of the basic version corresponding to Figure 2 which does not re-release of C02 into the atmosphere. Water or steam is fed through line 11 in the electrochemical cell (or the electrochemical cells in parallel) 1.

The outlet 12 contains oxygen (or oxygen-water mixture and optionally an inert gas, which can be separated by water condensation). The C0 2 is passed through conduit 15 into the heat exchanger 16 wherein it is preheated by steam, or any other means, before being sent through line 13 to the cell or cells 1.

Output of the electrochemical cell 1, a C0 2 mixture and formic acid is passed through conduit 14 to the heat exchanger 17, wherein the mixture is cooled and partially condensed by means of cooling water, or air.

The partially condensed mixture is then passed through line 18 to the heat exchanger 19 a or 19b wherein it is cooled to around 5 ° C by propane or another compound or refrigerant mixture flowing through the conduit 20 has or b.

At this temperature, formic acid crystallizes and is deposited on the walls of 19a or 19b exchanger. When the pressure drop is too high in the exchanger due to crystal deposition of formic acid, the flow duct 18 is directed towards the other exchanger 19b or 19a, which has been stripped meantime acid formic crystallized it contains, by circulation of liquid formic acid. This liquid formic acid from the storage 22 is sucked by the pump 24 through the conduit 23, and then is heated in the heat exchanger 25 with the aid of heated water or other heating means, before be sent via line 26 in the exchanger 19 a or b, wherein the coolant flow (20 a or b) has been stopped. Formic acid circulated at a moderate temperature (25-50 ° C) for melting the crystalline formic acid on the walls of the heat exchanger 19b or 19a, and return it to storage through line 27.

The residual gas, which contains essentially C0 2, and some traces of formic acid (and optionally a carrier gas) is passed through line 21 to the compressor 29, mixed with the extra C0 2 fed through line 28.

At the outlet of the compressor 29, the gas is returned by line 15 to the heat exchanger 16.

EXAMPLE INVENTION

In this example, the coulombic efficiency was 80%, the current density is 0.4 A / cm and the potential difference between the electrodes is 3V.

The formic acid produced is 10,000 tons / year (1.25 ton / h)

The oxygen product is 3470 tons / year, or 300 Nm / h

The amount of C0 2 consumption is 9560 tons / year (1.2 t / h)

The amount of water consumed is 3910 tons / year (0.49 ton / h)

The necessary electrode surface is 455 m 2

utilities consumption is as follows:

Electricity: kWh / h

Compressor cell 1 5460 29 82

Pump 24 1

Chiller 58 Total 5601 kWh / h

Water consumption is as follows:

Vapor low-pressure water (ton / h)

Exchanger 16 0.4

Total: 0.4 tonnes / h

Cooling water: m / h

water is assumed at 25 ° C to 35 ° C returned. Part of water (15.3 m) was cooled from 25 to 20 ° C in exchanger 25 for heating the formic acid storage which will allow to melt the crystalline formic acid in the exchanger 19 a or b

chiller 25 m / h

3

Exchanger 17 27 m / h

Total 52 m 3 / h

This example demonstrates the economic feasibility of the method of the invention, provided that the cost of electricity remains in the current values.

Claims

1) electrochemical method for producing formic acid from C02 fed to the cathode and steam introduced at the anode, using one or more electrochemical cells in parallel or stacked, said method using electrochemical cells which the cathode is composed of a conductive porous solid and an active layer containing dispersed metallic nanoparticles and catalyzing the reaction selectively to formic acid according to the reaction:
C0 2 + H 2 0 → HCOOH + ½ 0 2
- at the anode: the steam is decomposed into oxygen and proton H + according
→ H 2 0 0 2 ½ + 2H + + 2e
- At the cathode: carbon dioxide is reduced directly in the vapor phase under the effect of an electrochemical potential in contact with a porous cathode and a solid polymer electrolyte according to: C0 2 + 2H + + 2e → HCOOH
- formic product is then separated from the CO 2 residual acid, preferably by crystallization,
method wherein the surface current density is greater than 0.1 A / cm2 and preferably between 0.2 A / cm 2 and 2 A / cm2, and the potential difference between the anode and the cathode is less than 4 volts.
2) An electrochemical process for producing formic acid according to claim 1, wherein the catalyst used in the cathode of the electrolytic cell consists of metal particles selected from those which exhibit a selectivity to formic acid is indium, the tin, lead, bismuth, cadmium, thallium, taken alone or in admixture.
3) An electrochemical method for producing formic acid method according to claim 1, wherein the catalyst used in the cathode of the electrolytic cell is selected from the following metals: indium, tin, lead, bismuth. 4) electrochemical production of formic acid method according to claim 1, wherein the temperature measured at the electrolytic cell is between 20 ° C and 160 ° C. 5) electrochemical production of formic acid method according to claim 1, wherein the pressure in the electrolytic chamber is between 1 and 60 bar, and preferably between 1 and 10 bar.
6) An electrochemical process for producing formic acid according to claim 1, wherein the steam introduced to the anode is driven by an inert carrier gas with respect to the electro-oxidation.
7) electrochemical production of formic acid method according to claim 1, wherein the C02 introduced to the cathode of the electrolytic cell is driven by an inert carrier gas with respect to the electro-reduction.
8) electrochemical production of formic acid method according to claim 1, wherein one carries out the following sequence of steps:
- water or steam, optionally in admixture with an inert carrier gas, is fed through line 11 in the electrochemical cell (or the electrochemical cells in parallel or stacked) denoted 1,
- the outlet 12 contains oxygen (or oxygen-water mixture and optionally an inert gas, which can be separated by water condensation),
- C0 2 is passed through conduit 15 into the heat exchanger 16 wherein it is preheated by steam, or any other means, before being sent through line 13 to the cell or cells 1 ,
- the output of the electrochemical cell 1, a C0 2 mixture and formic acid, and any other gases contained in the C02 are fed through line 14 to the heat exchanger 17, wherein the mixture is cooled and condensed partially using cooling water or air,
- the partially condensed mixture leaving the heat exchanger (17) is then sent through line 18 to the heat exchanger 19a or 19b, in which it is cooled to around 5 ° C by propane (or other compound or mixed refrigerant) flowing in the duct 20 a or b,
- formic acid crystallizes and is deposited on the walls of the exchanger 19a or 19b (which operate alternately crystallization or circulating to melt the crystals formed),
- the residual gas, containing mainly C0 2 is discharged through line 21, preferably to a flare to eliminate possible traces of hydrogen, CO, methane or formic contained in said residual gas acid ,
- when the pressure drop is too high in the heat exchanger 19a (19b respectively) due to the deposition of crystals of formic acid, the flow duct 18 is directed towards the other 19b exchanger (respectively 19 a), which was freed meanwhile crystallized formic acid which it contains,
- elimination of formic acid crystals is obtained by circulation of liquid formic acid from the storage 22 is sucked by the pump 24 through the conduit 23 and then warmed in heat exchanger 25 with the aid of warm water (or by any other heating means), before being sent via line 26 in the exchanger 19 a or b, wherein the flow of coolant (20 a or b) has been stopped.
- moderate temperature circulates formic acid (25 to 50 ° C) and melts the deposited crystalline formic acid in the heat exchanger 19a or 19b, and the back in the storage 22 via line 27.
9) An electrochemical method for producing formic acid method according to claim 8, wherein the residual C02 obtained after the exchanger 19a or 19b is recompressed in a compressor 29 and re-introduced with C02 at the cathode compartment constituting the feed for the process.
PCT/FR2014/051238 2013-06-20 2014-05-27 Method of producing formic acid WO2014202855A1 (en)

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CN108193225A (en) * 2018-01-09 2018-06-22 大连理工大学 CO2-electroreduction electrolytic cell with membrane electrode configuration
EP3358042A1 (en) * 2017-02-02 2018-08-08 Kabushiki Kaisha Toshiba Electrolysis cell and electrolytic device for carbon dioxide

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3358042A1 (en) * 2017-02-02 2018-08-08 Kabushiki Kaisha Toshiba Electrolysis cell and electrolytic device for carbon dioxide
CN108193225A (en) * 2018-01-09 2018-06-22 大连理工大学 CO2-electroreduction electrolytic cell with membrane electrode configuration

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