EP0390157A2 - Elektrolysezelle und Verwendungsmethode - Google Patents

Elektrolysezelle und Verwendungsmethode Download PDF

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Publication number
EP0390157A2
EP0390157A2 EP90106050A EP90106050A EP0390157A2 EP 0390157 A2 EP0390157 A2 EP 0390157A2 EP 90106050 A EP90106050 A EP 90106050A EP 90106050 A EP90106050 A EP 90106050A EP 0390157 A2 EP0390157 A2 EP 0390157A2
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EP
European Patent Office
Prior art keywords
cathode
carbon dioxide
article
phthalocyanine
hydrogen
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
EP90106050A
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English (en)
French (fr)
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EP0390157A3 (de
EP0390157B1 (de
Inventor
Trent M. Molter
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Raytheon Technologies Corp
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United Technologies Corp
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Publication of EP0390157A3 publication Critical patent/EP0390157A3/de
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Publication of EP0390157B1 publication Critical patent/EP0390157B1/de
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    • 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
    • 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
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
    • C25B9/23—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms comprising ion-exchange membranes in or on which electrode material is embedded

Definitions

  • electrolysis cells in particular, electrolysis cells having solid polymer electrolyte membranes.
  • the electrochemical reduction of carbon dioxide to produce organic compounds utilizing an electrolysis cell has been known for some time. Such reduction has been carried out in conventional electrolysis cells having an anode, a cathode and an electrolyte. Typically the cells are operated by passing an electric current through the anode and cathode at the same time that a fuel is brought into contact with the catalyst on the anode and a carbon dioxide containing fluid is in contact with the catalyst at the cathode.
  • the typical fuel contains hydrogen and is either hydrogen gas or water.
  • Patent 4,609,441 for the production of methanol, while a second is taught for the production of hydrocarbons in the article entitled: Ambient Temperature Gas Phase CO2 Reduction to Hydrocarbons at Solid Polymer Electrolyte Cells, J.Electrochem. Soc.: Electrochemical Society and Technology, June 1988 p 1470-1471).
  • the present invention is directed toward improving the conversion efficiency of these electrolysis cells.
  • the present invention is directed toward an improved electrolysis cell for the reduction of carbon dioxide wherein said cell comprises an anode, a solid polymer electrolyte membrane and a cathode wherein said cathode comprises a primary carbon dioxide reducing cathode having a hydrogen overvoltage greater than platinum and further contains a secondary carbon dioxide reducing cathode having a hydrogen overvoltage greater than platinum.
  • Fig. 1 depicts a typical electrolysis cell 2 of the present invention containing an anode 4, an anode chamber 5, a cathode 6, a cathode chamber 8 and a solid polymer electrolyte 10 as well as current collectors 12 and 14.
  • a typical electrolysis cell is described in commonly assigned U.S. Patent 3,992,271 the teaching of which is incorporated herein.
  • the anodes useful in these cells are formed of conventional materials such as platinum, ruthenium or iridium. In addition, mixtures or alloys of these and other materials dispersed on a high surface area support may also be used. Conventional anodes which are particularly useful are described in commonly assigned U.S. Patent 4,294,608, the teaching of which is incorporated herein as well as the aforementioned U.S. Patent 3,992,271.
  • the catalyst on the anode should be capable of high reactivity for the half cell reaction. 2H2O ⁇ 4H + 4e ⁇ + O2 (1) or H2 ⁇ 2H+ + 2e ⁇
  • anodes are attached to the solid polymer electrolyte using conventional techniques. This is generally achieved through the process of contacting the anode to one surface of the electrolyte membrane and causing the anode to bond to it through the application of pressure at an elevated temperature.
  • the electrolyte may be any of the conventional solid polymer electrolytes useful in fuel cells or electrolysis cells and capable of transporting positive ions (preferably H+) from the anode to the cathode.
  • One type is a cation exchange membrane in proton form such as Nafion (available from DuPont Corporation).
  • Other possible electrolytes may be perfluorocarboxylic acid polymers, available from Asahi Glass and perfluorosulfonic acid polymers available from Dow Chemical. These and other solid polymer electrolyte materials are well known to those skilled in the art and need not be set forth in detail here.
  • the improvement to the prior art electrolysis cells comprises the selection of a primary cathode material and the introduction of a secondary carbon dioxide reducing cathode into the cell.
  • One or more of these compounds will be generated at the cathode depending on the current density at which the cell is operated and other operating parameters of the electrolysis cell including the type and concentration of the reactants.
  • the primary cathode 6 should be formed of a material having a propensity for reducing carbon dioxide as well as a having a hydrogen overvoltage greater than platinum.
  • a material having a propensity for reducing carbon dioxide as well as a having a hydrogen overvoltage greater than platinum.
  • Such materials are well known and have been used in similar applications. (note the article cited above from the Journal of Electrochem. in which a copper cathode is used.)
  • Other materials which may be used are bismuth, antimony, tin, mercury, lead, copper, zinc and cadmium, gallium, silver, gold, iron, tungsten, molybdenum and carbon.
  • organic materials such as the metal porphyrins and metal phthalocyanines. Typical metal porphyrins are aluminum and zinc. The most preferred materials are the metal phthalocyanines. Any metal phthalocyanine may be used with the preferred material being nickel phthalocyanine. Other representative metal phthalocyanines are listed in Table I below:
  • M may be any metal ion.
  • cobalt, iron, nickel or copper Preferably cobalt, iron, nickel or copper. It is also possible to form the cathode using a mixture of these materials or mixing them with other catalytic materials. However, it should be noted that other catalytic materials may prove detrimental to the conversion efficiency particularly if they have a low hydrogen overvoltage as it may enhance the formation of hydrogen gas.
  • the cathode containing these materials is formed using conventional techniques and is applied directly to the electrolyte membrane in conventional manner typically through the application of heat and pressure.
  • a binder such as polytetrafluoroethylene or other inert material which will not adversely affect the reactivity of the cathode.
  • the mixture will be in a ratio of about 5 percent to about 50 percent by weight with a preferred range of from about 15 percent to about 20 percent by weight of the catalytic material, however the actual amount required will vary depending on the catalytic material chosen.
  • a secondary cathode is introduced into the cell as well.
  • This secondary cathode may be in the form of an overlay on top of the primary cathode as depicted in Fig. 2 as 16 or it may be a separate structure as shown in Fig. 1 as 18. In any configuration the secondary cathode must be in electrical contact with the primary cathode and in physical contact with the carbon dioxide and hydrogen ions.
  • the secondary cathode is situated in the flow path of the carbon dioxide as shown in the figures and preferably supported on a plurality of fine wire mesh screens depicted in Fig. 2 as 18 or supported on a porous substrate.
  • the secondary cathode comprises a catalytic material again having a hydrogen overvoltage greater than platinum and the propensity to reduce carbon dioxide in the presence of hydrogen ions.
  • Catalytic materials which may be useful in the formation of such a secondary cathode may be inorganic metals such as ruthenium, indium, iridium, copper, or mixtures of metals such as steel or stainless steel all of which meet the two requirements for a secondary catalyst.
  • Organic materials may also be used just as those in the primary cathode.
  • the organic materials of particular importance are the macromolecules such as the metal porphyrins or metal phthalocyanines discussed above for use in the primary cathode.
  • the secondary catalyst offers a significant increase in the number of active sites for the reduction of carbon dioxide to take place, thereby resulting in a dramatic increase in efficiency for for the cell.
  • the efficiency of the test cell described below increased from about 60 percent to over 90 percent through the addition of this secondary cathode.
  • this secondary cathode when it is in the form of a metal or metal composition, is as a fine mesh screen. This permits the cathode to have a very high surface area and is easily inserted into the cathode portion of the cell. In this form the secondary cathode may be formed of one or more of these screens.
  • the material is formed of an organic material it may be pressed together to form a cathode or it may be mixed with a binder such as polytetrafluoroethylene and then pressed to form the cathode as is done for the primary cathode. Or it may be deposited on a substrate.
  • the substrate may be formed of an inert material or it may be formed of catalytic material.
  • the support will also have a hydrogen overvoltage greater than platinum so that it will not contribute to hydrogen gas formation.
  • the preferred manner is to plate or deposit the material onto a support structure such as a fine mesh metallic screen. Such is the case with the preferred secondary cathode structure wherein indium is deposited onto a fine mesh stainless steel screen.
  • the electrolysis cells operate when a potential is generated between the anode and the cathode.
  • the magnitude of the potential must be such that hydrogen ions are generated at the anode and carbon dioxide is reduced at the cathode.
  • the actual voltage requirements will vary depending on a number of variables.
  • the nature of the catalysts used in the anode and cathode are important to the voltage requirements as well as the type of anolyte or catholyte is used. For instance an anolyte of hydrogen gas would have lower voltage requirements than a anolyte composed of water.
  • the configuration and structures of the actual cell members, i.e., flow fields may alter the voltage requirements. Typically, these electrical requirements will range from about 2 volts to about 5 volts.
  • the potential may be generated by any conventional means such as general electrical sources i.e., batteries or fuel cells.
  • general electrical sources i.e., batteries or fuel cells.
  • the anode will be positively charged while the cathode will be negatively charged.
  • the potential across the solid polymer electrolyte drives the hydrogen ions across the electrolyte from the anode to the cathode so that it might be available for reaction with the carbon dioxide.
  • the operation of the electrolysis cell during reduction of carbon dioxide is conventional. Typically, the operation entails the introduction of hydrogen or water into the anode side of the cell and carbon dioxide into the cathode side of the cell.
  • the hydrogen gas may be introduced at ambient pressure, however, it is preferred that it be introduced at pressures greater than 50 psig, with a preferred range of 800 psig to 900 psig. While water may be introduced at ambient pressure or above with the preferred range being 800 psig to 900 psig.
  • the carbon dioxide may be introduced as a gas mixture, as a liquid, or dissolved in an aqueous solution such as lithium carbonate or other form which does not impair the function of the solid polymer electrolyte membrane (i.e., too cold or a nonaqueous solution).
  • an electric current is passed between the anode and the cathode sufficient enough to cause the hydrogen or water dissociate and to cause the hydrogen ions to be transported through the electrolyte to the cathode where in the presence of the primary and secondary cathode the carbon dioxide is reduced to an organic compound.
  • An example of an electrolysis cell of the present invention was used to reduce carbon dioxide and is described below.
  • An electrolysis cell for the reduction of carbon dioxide was prepared having a .05 Ft2 cathode of nickel phthalocyanine and teflon in a mixture of 85 % to 15 % by weight pressed onto the electrolyte.
  • a secondary cathode was utilized in the form of 6-40 mesh 316 stainless steel screens electroplated with indium.
  • an Indium plate was tack welded to the fluid distribution plate formed from the collector plate to promote fluid turbulence in the carbon dioxide flow and improve the contact with the two cathodes.
  • a solution of Argon in equilibrium with 0.1 Molar lithium carbonate was passed over the anode at a pressure of 300 psig at a flow rate of about 200 to 500 cm3/min. While a solution of carbon dioxide in equilibrium with 0.1 Molar lithium carbonate at a pressure of 325 psig and a flow rate of about 200 to 500 cm3/minute.
  • the cell was operated at a current density of 50 amperes per square foot for 42 minutes at a temperature between 75°F and 100°F.
EP90106050A 1989-03-31 1990-03-29 Elektrolysezelle und Verwendungsmethode Expired - Lifetime EP0390157B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US33146489A 1989-03-31 1989-03-31
US331464 1989-03-31

Publications (3)

Publication Number Publication Date
EP0390157A2 true EP0390157A2 (de) 1990-10-03
EP0390157A3 EP0390157A3 (de) 1991-04-17
EP0390157B1 EP0390157B1 (de) 2000-01-05

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Family Applications (1)

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EP90106050A Expired - Lifetime EP0390157B1 (de) 1989-03-31 1990-03-29 Elektrolysezelle und Verwendungsmethode

Country Status (4)

Country Link
EP (1) EP0390157B1 (de)
JP (1) JPH03111586A (de)
AT (1) ATE188514T1 (de)
DE (1) DE69033409T2 (de)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2312218A (en) * 1996-04-18 1997-10-22 France Etat Carbon dioxide-reducing cathode
US8617375B2 (en) 2010-04-26 2013-12-31 Panasonic Corporation Method for reducing carbon dioxide

Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2700052B2 (ja) * 1995-03-08 1998-01-19 工業技術院長 水素化物の製造方法
JP5580837B2 (ja) 2009-01-29 2014-08-27 プリンストン ユニバーシティー 二酸化炭素の有機生成物への変換
US20110114502A1 (en) * 2009-12-21 2011-05-19 Emily Barton Cole Reducing carbon dioxide to products
US8721866B2 (en) 2010-03-19 2014-05-13 Liquid Light, Inc. Electrochemical production of synthesis gas from carbon dioxide
US8500987B2 (en) 2010-03-19 2013-08-06 Liquid Light, Inc. Purification of carbon dioxide from a mixture of gases
US8845877B2 (en) 2010-03-19 2014-09-30 Liquid Light, Inc. Heterocycle catalyzed electrochemical process
US8845878B2 (en) 2010-07-29 2014-09-30 Liquid Light, Inc. Reducing carbon dioxide to products
US8524066B2 (en) 2010-07-29 2013-09-03 Liquid Light, Inc. Electrochemical production of urea from NOx and carbon dioxide
JP5624860B2 (ja) * 2010-11-25 2014-11-12 古河電気工業株式会社 電解セル、電解装置、炭化水素の生成方法
US8568581B2 (en) 2010-11-30 2013-10-29 Liquid Light, Inc. Heterocycle catalyzed carbonylation and hydroformylation with carbon dioxide
US8961774B2 (en) 2010-11-30 2015-02-24 Liquid Light, Inc. Electrochemical production of butanol from carbon dioxide and water
US9090976B2 (en) 2010-12-30 2015-07-28 The Trustees Of Princeton University Advanced aromatic amine heterocyclic catalysts for carbon dioxide reduction
US8562811B2 (en) 2011-03-09 2013-10-22 Liquid Light, Inc. Process for making formic acid
WO2012128148A1 (ja) * 2011-03-18 2012-09-27 国立大学法人長岡技術科学大学 二酸化炭素の還元固定化システム、二酸化炭素の還元固定化方法、及び有用炭素資源の製造方法
CA2841062A1 (en) 2011-07-06 2013-01-10 Liquid Light, Inc. Reduction of carbon dioxide to carboxylic acids, glycols, and carboxylates
US8658016B2 (en) 2011-07-06 2014-02-25 Liquid Light, Inc. Carbon dioxide capture and conversion to organic products
JP6492676B2 (ja) * 2015-01-15 2019-04-03 株式会社豊田中央研究所 還元反応用電極及びそれを用いた反応デバイス

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0050373A1 (de) * 1980-10-21 1982-04-28 Oronzio De Nora S.A. Elektrolysezelle und Verfahren zur Herstellung von Halogen
EP0081982A1 (de) * 1981-12-11 1983-06-22 The British Petroleum Company p.l.c. Elektrochemische organische Synthese
US4595465A (en) * 1984-12-24 1986-06-17 Texaco Inc. Means and method for reducing carbn dioxide to provide an oxalate product
US4673473A (en) * 1985-06-06 1987-06-16 Peter G. Pa Ang Means and method for reducing carbon dioxide to a product

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0050373A1 (de) * 1980-10-21 1982-04-28 Oronzio De Nora S.A. Elektrolysezelle und Verfahren zur Herstellung von Halogen
EP0081982A1 (de) * 1981-12-11 1983-06-22 The British Petroleum Company p.l.c. Elektrochemische organische Synthese
US4595465A (en) * 1984-12-24 1986-06-17 Texaco Inc. Means and method for reducing carbn dioxide to provide an oxalate product
US4673473A (en) * 1985-06-06 1987-06-16 Peter G. Pa Ang Means and method for reducing carbon dioxide to a product

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 108, no. 26, 27th June 1988, page 440, abstract no. 228382k, Columbus, Ohio, US; D.W. DEWULF et al.: "The electrochemical reduction of carbon dioxide to methane and ethene at copper/Nafion electrodes", & CATAL. LETT. 1988, 1(1-3), 73-9 *
CHEMICAL ABSTRACTS, vol. 108, no. 8, 22nd February 1988, page 559, abstract no. 64529k, Columbus, Ohio, US; M. MAEDA et al.: "Reduction of carbon dioxide on partially-immersed gold plate electrode and gold-solid polymer electrolyte electrode", & J. ELECTROANAL. CHEM. INTERFACIAL ELECTROCHEM. 1987, 238(1-2), 247-58 *
JOURNAL OF THE ELECTROCHEMICAL SOCIETY, ELECTROCHEMICAL SCIENCE AND TECHNOLOGY, June 1988, pages 1470-1471; "Ambient temperature gas phase Co2 reduction to hydrocarbons at solid polymer electrolyte cells" *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2312218A (en) * 1996-04-18 1997-10-22 France Etat Carbon dioxide-reducing cathode
GB2312218B (en) * 1996-04-18 1999-12-29 France Etat Carbon dioxide reducing cathode
US8617375B2 (en) 2010-04-26 2013-12-31 Panasonic Corporation Method for reducing carbon dioxide

Also Published As

Publication number Publication date
JPH03111586A (ja) 1991-05-13
EP0390157A3 (de) 1991-04-17
DE69033409T2 (de) 2000-08-03
EP0390157B1 (de) 2000-01-05
ATE188514T1 (de) 2000-01-15
DE69033409D1 (de) 2000-02-10

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