EP2686464A2 - Procédé pour la conversion électrochimique sélective de co2 en hydrocarbures en c2 - Google Patents

Procédé pour la conversion électrochimique sélective de co2 en hydrocarbures en c2

Info

Publication number
EP2686464A2
EP2686464A2 EP12715237.9A EP12715237A EP2686464A2 EP 2686464 A2 EP2686464 A2 EP 2686464A2 EP 12715237 A EP12715237 A EP 12715237A EP 2686464 A2 EP2686464 A2 EP 2686464A2
Authority
EP
European Patent Office
Prior art keywords
copper
cathode
hydrocarbons
process according
carbon dioxide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP12715237.9A
Other languages
German (de)
English (en)
Other versions
EP2686464B1 (fr
Inventor
Marta Catarina MARTINS RAMOS GONÇALVES
Tiago COSTA DUARTE PARDAL
José Augusto DÂMASO CONDEÇO
Joaquim Miguel BADALO BRANCO
Tomás Rei CLÁUDIO FERNANDES
Anabela Beatriz MADEIRA GOMES BOAVIDA
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
OMNIDEA Ltda
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OMNIDEA Ltda
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Publication date
Application filed by OMNIDEA Ltda filed Critical OMNIDEA Ltda
Publication of EP2686464A2 publication Critical patent/EP2686464A2/fr
Application granted granted Critical
Publication of EP2686464B1 publication Critical patent/EP2686464B1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/20—Processes
    • C25B3/25—Reduction
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
    • C25B11/031—Porous electrodes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/06—Wires; Strips; Foils
    • C25D7/0614—Strips or foils

Definitions

  • the present invention relates to the field of electrochemistry and, in general, to a method of conversion of C0 2 into hydrocarbons, namely C2 hydrocarbons (ethylene and ethane) .
  • Copper is the only metallic electrode materials that yields hydrocarbons as major products (Gattrell et al., 2006, Jitaru, 2007) .
  • the mixture of hydrocarbons produced by the electroreduction of C0 2 is composed mostly of methane and ethylene.
  • the faradaic efficiency of CH 4 is commonly higher than that for C 2 H 4 .
  • Kyriacou and Anagnostopoulos (1993) reported the following formation efficiencies for the electrochemical reduction of C0 2 on copper in a 0.5 M KHC0 3 solution at 298 K: 16% for methane and 14% for ethylene.
  • Azuma et al. (1990) investigated the C0 2 reduction in a 0.05 M KHC0 3 aqueous solution at 293 K and obtained methane, ethylene and ethane with faradaic efficiencies of 17.8, 12.7 and 0.039%, respectively.
  • honeycomb-like structures were studied by Nikolic et al. (2007), namely the honeycomb-like structures. According to these authors, the main characteristics of honeycomb-like structures are the existence of two groups of craters or holes of distinct nature. They pointed out that a group of holes or craters is formed by the connection of hydrogen bubbles that resulted from an intense hydrogen evolution reaction during the deposition. The other group is originated from the agglomerates of copper grains formed in the initial stage of electrodeposition . They also referred that for longer times of deposition a third class of holes could be formed through the combination of the holes of the first two groups. Nevertheless, these authors did not refer any application of this type of electrodeposits on the electroreduction of C0 2 or any data that allowed the prediction of the behavior of this type of deposits on the referred reaction.
  • the process of this invention concerns the electrochemical conversion of carbon dioxide in aqueous solutions into hydrocarbons and, more specifically to C2 hydrocarbons (ethylene and ethane) without the formation of methane.
  • C2 hydrocarbons ethylene and ethane
  • the achievement of mixtures with a higher C2 hydrocarbons content represents an advantage in relation to the mixtures described in the prior art, since higher energetic densities are attained considering the same content of hydrogen or carbon monoxide. This advantage makes them more appropriated, for instance, to be utilized as fuels.
  • the process is carried out in an electrochemical cell wherein the cathode is a modified electrode with copper electrodeposits that increases the activity and selectivity of the method under stable CO 2 conversion.
  • the conversion of C0 2 is performed in a one step, easily scalable and can operate at ambient temperature and atmospheric pressure.
  • the number of carbon atoms in the generated hydrocarbon molecules can be controlled by the increase of copper active surface area available for CO 2 electroreduction .
  • the hydrocarbons produced can be subsequently used as industrial feedstock.
  • FIG. 1 depicts the SEM image of the electrode surface with electrodeposits having a dendritic crystal structure.
  • the deposits were obtained by an ex-situ electrodeposition of copper on a copper mesh as referred in example I.
  • FIG. 2 depicts the SEM image of the electrode surface with electrodeposits having a honeycomb-like structure.
  • the deposits were obtained by an ex-situ electrodeposition of copper on a copper mesh as referred in example II.
  • Number (1) indicates two distinct craters.
  • FIG. 3 depicts the SEM image of the electrode surface with electrodeposits having a porous 3D sponge structure. It was obtained by electrodeposition ex-situ of copper on a copper foil as mentioned in example IV. Number (2) indicates two pores in distinct layers.
  • FIG. 4 depicts a schematic drawing of an example of a laboratory-size electrochemical cell in which the process of the invention can be carried out.
  • the numbers indicate: (3) cathodic compartment, (4) anodic compartment, (5) membrane compartment (optional), (6) gas inlet, (7) reference electrode inlet, (8) gas outlet, (9) pH sensor inlet .
  • the process of this invention for the conversion of carbon dioxide into hydrocarbons, and more specifically into hydrocarbons with two carbon atoms (C2 hydrocarbons) is performed in an electrochemical cell.
  • the cell is preferentially a two compartment cell in which the cathode and the anode are separated preferentially by an ion exchange membrane .
  • the anode may be any suitable electrically conducting material appropriate for effective operation in an electrolytic cell, for example, platinum, graphite and glassy carbon.
  • the cathode material may be any suitable electrically conducting material such as copper or glassy carbon.
  • the cathode substrate may have any suitable configuration appropriate for electro-deposition, including mesh and foil configurations.
  • the cathode surface is modified by in-situ or ex-situ copper electrodeposition .
  • the ex-situ deposition is preferable to provide a stable and exclusive conversion of carbon dioxide into C2 hydrocarbons and can be performed using preferably copper sulphate as the source of copper cations and sulphuric acid to increase the acidity of the deposition bath.
  • Modified copper electrodes with good mechanical resistance and an extremely large useable surface area were used as obtained.
  • Three types of structures for the copper electrodeposits prepared by ex-situ electrodeposition are presented in Figures 1, 2 and 3.
  • the presence of the electrodeposits at the electrode surface strongly modifies the catalytic behavior of the electrodes for the conversion of carbon dioxide, consequently changing the composition of the gaseous hydrocarbon products created.
  • the catholyte may be any inorganic salt aqueous solution in which the carbon dioxide is soluble, such as KHCO3, NaHC0 3 and KC1, preferably KHC0 3 , in concentrations of around 0.0 ' 3 to 0.5 M, at a pH preferably of around 4 to 9.
  • the anolyte may be preferably the same as the catholyte.
  • a suitable ion exchange membrane that can be used may be any ion exchange membrane that allows the passage of protons, such as Nafion 117, or Nafion 417.
  • the electrochemical reduction of C0 2 to C2 hydrocarbons is achievable by using an electrochemical cell that possesses one cathode with copper electrodeposits submerged in an electrolyte in which the C0 2 is soluble.
  • any suitable shape and disposition of an electrochemical cell can be used.
  • the electrochemical reduction process can be carried out in a continuous mode (galvanostatic or potentiostatic) or in a pulsed electrolytic mode.
  • the modified cathodes presented in Figures 1 to 3 are used in the electrochemical cell for the conversion of carbon dioxide.
  • the electrodeposit at the electrode surface strongly modifies the catalytic behavior of the electrodes used for the carbon dioxide conversion, modifying subsequently the composition of the gaseous hydrocarbons (reaction products) .
  • Fig. 1 The structure shown in Fig. 1 consists of dendritic copper deposits. It was discovered that this type of electrodeposits promotes ethylene production in detriment of methane. Additionally, it was verified that the bigger the coverage of the surface electrode with dendritic copper electrodeposits, the bigger was the selectivity for ethylene .
  • the cathode modified with copper honeycomb-like structures shown in Fig. 2 promotes only the production of C2 hydrocarbons (ethylene and ethane) , not being detected methane. This result is innovative and is due to a high surface area of the electrodeposits, its morphology and structure.
  • the honeycomb-like structure of electrodeposits has a higher quantity of copper grains per volume. This configuration enhances the proximity of the active electro- catalytic sites, which results in an increased likelihood for the formations of hydrocarbons with longer chains.
  • the modified cathode illustrated in Fig. 3 is a three- dimensional copper open structure which is extremely porous. This configuration allows rapid transport of gas and liquid, and its high surface area and mechanically well-supported structure is desirable for electrochemical reactions.
  • the products are C2 hydrocarbons without formation of methane.
  • This result confirms that the availability of the copper active surface and the spatial distribution of the electro-catalytic zones are the key parameters for the conversion of carbon dioxide in hydrocarbons with two carbon atoms. Additionally it was verified that the copper electrodeposits obtained by ex-situ electrodeposition lead to the stability of the carbon dioxide reduction process, this is, to the stability of the hydrocarbon production due to the weak deactivation of the cathode.
  • the present invention and the knowledgment of the state-of- the-art indicate that the selective reduction of the carbon dioxide into C2 hydrocarbons may follow the following reaction mechanism:
  • the modified electrodes have a distinct catalytic behavior from the substrate behavior modifying the distribution of the hydrocarbons resulting from the reaction. This catalytic activity is mainly dependent on the characteristics of the electrodeposits , more specifically on the active surface area, on the morphology, and on the crystalinity (this is the structure of the copper crystals) .
  • a copper mesh cathode was modified with copper electrodeposits by ex-situ electrodeposition, having the configuration of Fig.l.
  • Potentiostatic reduction of carbon dioxide was performed in a flat cell (similar to the one depicted in Figure 4) at room temperature and atmospheric pressure, under conditions of continuous carbon dioxide flow.
  • the electrolytic solution used was of potassium bicarbonate (Merck, p. a.) with a concentration of 0.1 M.
  • a cationic exchange membrane separated the catholyte and anolyte compartments.
  • the anode was a platinum mesh.
  • the applied electrode potential was - 1.9 V, measured against a silver/silver chloride reference electrode .
  • the faradaic efficiencies of the products were calculated on the basis of the number of electrons required for the formation of one molecule of the products from carbon dioxide and water; eight for methane, twelve for ethylene, fourteen for ethane, two for carbon monoxide and two for molecular hydrogen. Only gaseous products were analyzed.
  • the utilization of electrodes with a dendritic morphology resulted in a selective production of ethylene instead of methane.
  • the electrode promotes an almost selective production of ethylene (33.3 %), being the methane production of 3.6 %.
  • Example II To confirm that the products obtained in Example II were an inherent characteristic of the electrode, different potentials and different concentrations of electrolyte were tested.
  • the CO 2 electroreduction was carried out at various cathode potentials and electrolyte concentrations.
  • the results for the potentiostatic reduction in the range -1.5 to -1.9 V in relation to Ag / AgCl are shown in Fig. 5.
  • a high selectivity to C2 hydrocarbons without production of methane was observed for all conditions tested. Only the C2 hydrocarbons composition was modified.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention porte sur un procédé pour la conversion électrochimique sélective de dioxyde de carbone en hydrocarbures, à savoir d'hydrocarbures en C2. Le procédé est effectué dans une cellule électrochimique où la cathode est une électrode modifiée comprenant des électrodépôts de cuivre afin d'améliorer l'activité catalytique et la sélectivité du système. La formation d'un mélange d'hydrocarbures en C2 (C2H4 et C2H6) sans méthane est obtenue avec succès sur des électrodépôts de surface spécifique plus élevée. De plus, de l'éthylène est sélectivement produit au détriment de l'éthane. L'électrodépôt de cuivre ex-situ amène la régularité du procédé de réduction du dioxyde de carbone, c'est-à-dire la stabilité de la production d'hydrocarbures en raison de la faible désactivation de la cathode.
EP12715237.9A 2011-03-15 2012-03-15 Procédé pour la conversion électrochimique sélective de co2 en hydrocarbures en c2 Active EP2686464B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
PT105566A PT105566A (pt) 2011-03-15 2011-03-15 Processo para a conversão electroquímica selectiva de dióxido de carbono
PCT/PT2012/000008 WO2012125053A2 (fr) 2011-03-15 2012-03-15 Procédé pour la conversion électrochimique sélective de co2 en hydrocarbures en c2

Publications (2)

Publication Number Publication Date
EP2686464A2 true EP2686464A2 (fr) 2014-01-22
EP2686464B1 EP2686464B1 (fr) 2018-11-14

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EP (1) EP2686464B1 (fr)
PT (1) PT105566A (fr)
WO (1) WO2012125053A2 (fr)

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Publication number Priority date Publication date Assignee Title
WO2015051211A2 (fr) * 2013-10-03 2015-04-09 Brown University Réduction électrochimique du co2 à des nanomousses de cuivre
US20160253461A1 (en) * 2014-10-01 2016-09-01 Xsolis, Llc System for management and documentation of health care decisions
DE102017208518A1 (de) * 2017-05-19 2018-11-22 Siemens Aktiengesellschaft Herstellung von dendritischen Elektrokatalysatoren zur Reduktion von CO2 und/oder CO
WO2020225315A1 (fr) * 2019-05-07 2020-11-12 Total Se Électrocatalyseurs synthétisés par électroréduction de co2 et procédés et utilisations associés
IT201900014580A1 (it) * 2019-08-09 2021-02-09 Laboratorio Audio Snc Di Niorettini Claudio & Doro Stefano “Procedimento per la formazione e la rigenerazione di un catodo in rame di una cella elettrochimica e cella elettrochimica per la produzione di prodotti industriali”
CN112501649B (zh) * 2020-11-22 2023-11-21 赵玉平 一种复合材料
CN112481663B (zh) * 2020-12-15 2022-03-11 中南大学深圳研究院 一种应用于高效二氧化碳还原反应生成乙烯的铜纳米花的制备方法
CN112501662B (zh) * 2020-12-15 2022-03-15 中南大学深圳研究院 一种应用于高效二氧化碳还原反应生成甲烷的铜纳米片的制备方法
WO2023131604A1 (fr) * 2022-01-10 2023-07-13 Totalenergies Onetech Réduction électrochimique d'oxydes de carbone en éthylène

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US4897167A (en) 1988-08-19 1990-01-30 Gas Research Institute Electrochemical reduction of CO2 to CH4 and C2 H4
AUPS172702A0 (en) * 2002-04-12 2002-05-23 Commonwealth Scientific And Industrial Research Organisation An electrochemical cell, a porous working electrode and a process for he conversion of a species from one oxidation state to another by the electrochemical oxidation or reduction thereof
WO2011150422A1 (fr) * 2010-05-28 2011-12-01 The Trustees Of Columbia University In The City Of New York Dendrites métalliques poreuses utilisées en tant qu'électrodes à diffusion pour une réduction aqueuse à haut rendement de co2 en hydrocarbures
IL207947A0 (en) * 2010-09-02 2010-12-30 Univ Ben Gurion Manufacturing carbon - based combustibles by electrochemical decomposition of co2

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Also Published As

Publication number Publication date
PT105566A (pt) 2012-09-17
WO2012125053A3 (fr) 2013-03-28
WO2012125053A2 (fr) 2012-09-20
WO2012125053A4 (fr) 2013-05-16
EP2686464B1 (fr) 2018-11-14

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