WO2013006711A1 - Reduction of carbon dioxide to carboxylic acids, glycols, and carboxylates - Google Patents

Reduction of carbon dioxide to carboxylic acids, glycols, and carboxylates Download PDF

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Publication number
WO2013006711A1
WO2013006711A1 PCT/US2012/045578 US2012045578W WO2013006711A1 WO 2013006711 A1 WO2013006711 A1 WO 2013006711A1 US 2012045578 W US2012045578 W US 2012045578W WO 2013006711 A1 WO2013006711 A1 WO 2013006711A1
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WIPO (PCT)
Prior art keywords
alloy
acid
carboxylic acid
compartment
carbon dioxide
Prior art date
Application number
PCT/US2012/045578
Other languages
French (fr)
Inventor
Emily Barton Cole
Kyle Teamey
Andrew B. Bocarsly
Narayanappa Sivasankar
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Liquid Light, Inc.
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Publication date
Application filed by Liquid Light, Inc. filed Critical Liquid Light, Inc.
Priority to AU2012278949A priority Critical patent/AU2012278949A1/en
Priority to CA2841062A priority patent/CA2841062A1/en
Priority to CN201280033322.5A priority patent/CN103649374A/en
Priority to KR1020147003051A priority patent/KR20140050038A/en
Priority to JP2014519297A priority patent/JP2014518335A/en
Priority to BR112014000052A priority patent/BR112014000052A2/en
Priority to EP12808004.1A priority patent/EP2729601B1/en
Publication of WO2013006711A1 publication Critical patent/WO2013006711A1/en

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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
    • 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
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • 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
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/50—Processes
    • C25B1/55—Photoelectrolysis
    • 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
    • C25B15/00—Operating or servicing cells
    • C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
    • C25B15/085—Removing impurities
    • 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
    • C25B3/01—Products
    • C25B3/07—Oxygen containing compounds
    • 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
    • C25B3/26—Reduction of carbon dioxide
    • 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
    • C25B9/21—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms two or more diaphragms

Definitions

  • the present disclosure generally relates to the field of electrochemical reactions, and more particularly to methods and /or systems for electrochemical production of carboxylic acids, glycols, and carboxylates from carbon dioxide.
  • a mechanism for mitigating emissions is to convert carbon dioxide into economically valuable materials such as fuels and industrial chemicals. If the carbon dioxide is converted using energy from renewable sources, both mitigation of carbon dioxide emissions and conversion of renewable energy into a chemical form that can be stored for later use may be possible.
  • the present invention is directed to using particular cathode materials, homogenous heterocyclic amine catalysts, and an electrolytic solution to reduce carbon dioxide to a carboxylic acid intermediate preferably including at least one of formic acid, glycolic acid, glyoxylic acid, oxalic acid, or lactic acid.
  • the carboxylic acid intermediate may be processed further to yield a glycol-based reaction product.
  • the present invention includes the process, system, and various components thereof.
  • FIGS. 1A and 1 B depict a block diagram of a preferred system in accordance with an embodiment of the present disclosure
  • FIG. 2 is a flow diagram of a preferred method of electrochemical production of a reaction product from carbon dioxide.
  • FIG. 3 is a flow diagram of another preferred method of electrochemical production of a reaction product from carbon dioxide.
  • an electrochemical system that converts carbon dioxide to carboxylic acid intermediates, carboxylic acids, and glycols.
  • Use of a homogenous heterocyclic catalyst facilitates the process.
  • the reduction of the carbon dioxide to produce carboxylic acid intermediates, carboxylic acids, and glycols may be preferably achieved in a divided electrochemical or photoelectrochemical cell having at least two compartments.
  • One compartment contains an anode suitable to oxidize water, and another compartment contains a working cathode electrode and a homogenous heterocyclic amine catalyst.
  • the compartments may be separated by a porous glass frit, microporous separator, ion exchange membrane, or other ion conducting bridge. Both compartments generally contain an aqueous solution of an electrolyte.
  • Carbon dioxide gas may be continuously bubbled through the cathodic electrolyte solution to preferably saturate the solution or the solution may be pre-saturated with carbon dioxide.
  • System 100 may be utilized for electrochemical production of carboxylic acid intermediates, carboxylic acids, and glycols from carbon dioxide and water (and hydrogen for glycol production).
  • the system (or apparatus) 100 generally comprises a cell (or container) 102, a liquid source 104 (preferably a water source, but may include an organic solvent source), an energy source 106, a gas source 108 (preferably a carbon dioxide source), a product extractor 1 10 and an oxygen extractor 1 12.
  • a product or product mixture may be output from the product extractor 1 10 after extraction.
  • An output gas containing oxygen may be output from the oxygen extractor 1 12 after extraction.
  • the cell 102 may be implemented as a divided cell.
  • the divided cell may be a divided electrochemical cell and /or a divided photochemical cell.
  • the cell 102 is generally operational to reduce carbon dioxide (C0 2 ) into products or product intermediates.
  • the cell 102 is operational to reduce carbon dioxide to carboxylic acid intermediates (including salts such as formate, glycolate, glyoxylate, oxalate, and lactate), carboxylic acids, and glycols.
  • the reduction generally takes place by introducing (e.g., bubbling) carbon dioxide into an electrolyte solution in the cell 102.
  • a cathode 120 in the cell 102 may reduce the carbon dioxide into a carboxylic acid or a carboxylic acid intermediate.
  • the production of a carboxylic acid or carboxylic acid intermediate may be dependent on the pH of the electrolyte solution, with lower pH ranges favoring carboxylic acid production.
  • the pH of the cathode compartment may be adjusted to favor production of one of a carboxylic acid or carboxylic acid intermediate over production of the other, such as by introducing an acid (e.g., HCl or H 2 S0 4 ) to the cathode compartment.
  • Hydrogen may be introduced to the carboxylic acid or carboxylic acid intermediate to produce a glycol or a carboxylic acid, respectively.
  • the hydrogen may be derived from natural gas or water.
  • the cell 102 generally comprises two or more compartments (or chambers) 1 14a- 1 14b, a separator (or membrane) 116, an anode 1 18, and a cathode 120.
  • the anode 118 may be disposed in a given compartment (e.g., 1 14a).
  • the cathode 120 may be disposed in another compartment (e.g., 1 14b) on an opposite side of the separator 116 as the anode 1 18.
  • the cathode 120 includes materials suitable for the reduction of carbon dioxide including cadmium, a cadmium alloy, cobalt, a cobalt alloy, nickel, a nickel alloy, chromium, a chromium alloy, indium, an indium alloy, iron, an iron alloy, copper, a copper alloy, lead, a lead alloy, palladium, a palladium alloy, platinum, a platinum alloy, molybdenum, a molybdenum alloy, tungsten, a tungsten alloy, niobium, a niobium alloy, silver, a silver alloy, tin, a tin alloy, rhodium, a rhodium alloy, ruthenium, a ruthenium alloy, carbon, and mixtures thereof.
  • materials suitable for the reduction of carbon dioxide including cadmium, a cadmium alloy, cobalt, a cobalt alloy, nickel, a nickel alloy, chromium, a chromium alloy
  • An electrolyte solution 122 may fill both compartments 1 14a-1 14b.
  • the aqueous solution 122 preferably includes water as a solvent and water soluble salts for providing various cations and anions in solution, however an organic solvent may also be utilized.
  • the organic solvent is present in an aqueous solution, whereas in other implementations the organic solvent is present in a non-aqueous solution.
  • the catholyte 122 may include sodium and/or potassium cations or a quaternary amine (preferably tetramethyl ammonium or tetraethyl ammonium).
  • the catholyte 122 may also include divalent cations (e.g., Ca 2+ , Mg 2+ , Zn 2+ ) or a divalent cation may be added to the catholyte solution.
  • a homogenous heterocyclic catalyst 124 is preferably added to the compartment 1 14b containing the cathode 120.
  • the homogenous heterocyclic catalyst 124 may include, for example, one or more of 4- hydroxy pyridine, adenine, a heterocyclic amine containing sulfur, a heterocyclic amine containing oxygen, an azole, a benzimidazole, a bipyridine, furan, an imidazole, an imidazole related species with at least one five-member ring, an indole, a lutidine, methylimidazole, an oxazole, phenanthroline, pterin, pteridine, a pyridine, a pyridine related species with at least one six-member ring, pyrrole, quinoline, or a thiazole, and mixtures thereof.
  • the homogenous heterocyclic catalyst 124 is preferably present in the compartment 114b at a concentration of between about 0.001 M and about 1M, and more preferably between about 0.01M and 0.5M.
  • the pH of the compartment 1 14b is preferably between about 1 and 8.
  • a pH range of between about 1 to about 4 is preferable for production of carboxylic acids from carbon dioxide.
  • a pH range of between about 4 to about 8 is preferable for production of carboxylic acid intermediates from carbon dioxide.
  • the liquid source 104 preferably includes a water source, such that the liquid source 104 may provide pure water to the cell 102.
  • the liquid source 104 may provide other fluids to the cell 102, including an organic solvent, such as methanol, acetonitrile, and dimethylfuran.
  • the liquid source 104 may also provide a mixture of an organic solvent and water to the cell 102.
  • the energy source 106 may include a variable voltage source.
  • the energy source 106 may be operational to generate an electrical potential between the anode 1 18 and the cathode 120.
  • the electrical potential may be a DC voltage.
  • the applied electrical potential is generally between about -1 .5V vs. SCE and about -4V vs. SCE, preferably from about -1 .5V vs. SCE to about -3V vs. SCE, and more preferably from about -1 .5 V vs. SCE to about -2.5V vs. SCE.
  • the gas source 108 preferably includes a carbon dioxide source, such that the gas source 108 may provide carbon dioxide to the cell 102.
  • the carbon dioxide is bubbled directly into the compartment 1 14b containing the cathode 120.
  • the compartment 1 14b may include a carbon dioxide input, such as a port 126a configured to be coupled between the carbon dioxide source and the cathode 120.
  • the carbon dioxide may be obtained from any source (e.g., an exhaust stream from fossil-fuel burning power or industrial plants, from geothermal or natural gas wells or the atmosphere itself).
  • the carbon dioxide may be obtained from concentrated point sources of generation prior to being released into the atmosphere.
  • high concentration carbon dioxide sources may frequently accompany natural gas in amounts of 5% to 50%, exist in flue gases of fossil fuel (e.g., coal, natural gas, oil, etc.) burning power plants, and high purity carbon dioxide may be exhausted from cement factories, from fermenters used for industrial fermentation of ethanol, and from the manufacture of fertilizers and refined oil products.
  • Certain geothermal steams may also contain significant amounts of carbon dioxide.
  • the carbon dioxide emissions from varied industries, including geothermal wells, may be captured on-site.
  • the capture and use of existing atmospheric carbon dioxide in accordance with some embodiments of the present invention generally allow the carbon dioxide to be a renewable and essentially unlimited source of carbon.
  • the product extractor 1 10 may include an organic product and/or inorganic product extractor.
  • the product extractor 1 10 generally facilitates extraction of one or more products (e.g., carboxylic acid, and /or carboxylic acid intermediate) from the electrolyte 122.
  • the extraction may occur via one or more of a solid sorbent, carbon dioxide- assisted solid sorbent, liquid-liquid extraction, nanofiltration, and electrodialysis.
  • the extracted products may be presented through a port 126b of the system 100 for subsequent storage, consumption, and/or processing by other devices and /or processes.
  • the carboxylic acid or carboxylic acid intermediate is continuously removed from the cell 102, where cell 102 operates on a continuous basis, such as through a continuous flow-single pass reactor where fresh catholyte and carbon dioxide is fed continuously as the input, and where the output from the reactor is continuously removed.
  • the carboxylic acid or carboxylic acid intermediate is continuously removed from the catholyte 122 via one or more of adsorbing with a solid sorbent, liquid-liquid extraction, and electrodialysis.
  • the separated carboxylic acid or carboxylic acid intermediate may be placed in contact with a hydrogen stream to produce a glycol or carboxylic acid, respectively. For instance, as shown in FIG.
  • the system 100 may include a secondary reactor 132 into which the separated carboxylic acid or carboxylic acid intermediate from the product extractor 1 10 and hydrogen stream from a hydrogen source 134 are introduced.
  • the secondary reactor 132 generally permits interaction between the separated carboxylic acid or carboxylic acid intermediate from the product extractor 110 and the hydrogen to produce a glycol or carboxylic acid, respectively.
  • the secondary reactor 132 may include reactor conditions that differ from ambient conditions.
  • the secondary reactor 132 preferably includes a temperature range and a pressure range that is higher than that of ambient conditions. For instance, a preferred temperature range of the secondary reactor 132 is between about 50°C and about 500°C, and a preferred pressure range of the secondary reactor 132 is between about 5 atm and 1000 atm.
  • the secondary reactor may include a solvent and a catalyst to facilitate the reaction between the separated carboxylic acid or carboxylic acid intermediate from the product extractor 1 10 and the hydrogen stream from the hydrogen source 134.
  • Preferred catalysts include Rh, Ru0 2 , Ru, Pt, Pd, Re, Cu, Ni, Co, Cu-Ni, and binary metals and /or metal oxides thereof.
  • the catalyst may be a supported catalyst, where the support may include Ti, Ti0 2 , or C.
  • Preferred solvents include aqueous and non-aqueous solvents, such as water, ether, and tetrahydrofuran.
  • the oxygen extractor 1 12 of FIG. 1A is generally operational to extract oxygen (e.g., 0 2 ) byproducts created by the reduction of the carbon dioxide and /or the oxidation of water.
  • the oxygen extractor 1 12 is a disengager/flash tank.
  • the extracted oxygen may be presented through a port 128 of the system 100 for subsequent storage and /or consumption by other devices and /or processes.
  • Chlorine and/or oxidatively evolved chemicals may also be byproducts in some configurations, such as in an embodiment of processes other than oxygen evolution occurring at the anode 118. Such processes may include chlorine evolution, oxidation of organics to other saleable products, waste water cleanup, and corrosion of a sacrificial anode. Any other excess gases (e.g., hydrogen) created by the reduction of the carbon dioxide and water may be vented from the cell 102 via a port 130.
  • the method (or process) 200 generally comprises a step (or block) 202, a step (or block) 204, a step (or block) 206, and a step (or block) 208.
  • the method 200 may be implemented using the system 100.
  • a liquid may be introduced to a first compartment of an electrochemical cell.
  • the first compartment may include an anode.
  • Introducing carbon dioxide to a second compartment of the electrochemical cell may be performed in the step 204.
  • the second compartment may include a solution of an electrolyte, a cathode, and a homogenous heterocyclic amine catalyst.
  • the cathode may be selected from the group consisting of cadmium, a cadmium alloy, cobalt, a cobalt alloy, nickel, a nickel alloy, chromium, a chromium alloy, indium, an indium alloy, iron, an iron alloy, copper, a copper alloy, lead, a lead alloy, palladium, a palladium alloy, platinum, a platinum alloy, molybdenum, a molybdenum alloy, tungsten, a tungsten alloy, niobium, a niobium alloy, silver, a silver alloy, tin, a tin alloy, rhodium, a rhodium alloy, ruthenium, a ruthenium alloy, carbon, and mixtures thereof.
  • an electric potential may be applied between the anode and the cathode in the electrochemical cell sufficient for the cathode to reduce the carbon dioxide to a carboxylic acid intermediate.
  • the production of the carboxylic acid intermediate is preferably controlled by selection of particular cathode materials, catalysts, pH ranges, and electrolytes, such as disclosed in U.S. Application No. 12/846,221 , the disclosure of which is incorporated by reference.
  • Contacting the carboxylic acid intermediate with hydrogen to produce a reaction product may be performed in the step 208.
  • the secondary reactor 132 may permit interaction /contact between the carboxylic acid intermediate and the hydrogen, where the conditions of the secondary reactor 132 may provide for production of particular reaction products. [0025] Referring to FIG.
  • the method (or process) 300 generally comprises a step (or block) 302, a step (or block) 304, a step (or block) 306, a step (or block) 308, a step (or block) 310, and a step (or block) 312.
  • the method 300 may be implemented using the system 100.
  • a liquid may be introduced to a first compartment of an electrochemical cell.
  • the first compartment may include an anode.
  • Introducing carbon dioxide to a second compartment of the electrochemical cell may be performed in the step 304.
  • the second compartment may include a solution of an electrolyte, a cathode, and a homogenous heterocyclic amine catalyst.
  • an electric potential may be applied between the anode and the cathode in the electrochemical cell sufficient for the cathode to reduce the carbon dioxide to at least a carboxylate.
  • Acidifying the carboxylate to convert the carboxylate into a carboxylic acid may be performed in the step 308.
  • the acidifying step may include introduction of an acid from a make-up acid source.
  • the carboxylic acid may be extracted.
  • Contacting the carboxylic acid with hydrogen to form a reaction product may be performed in the step 312.
  • the reaction product includes one or more of formaldehyde, methanol, glycolic acid, glyoxal, glyoxylic aid, glycolaldehyde, ethylene glycol, acetic acid, acetaldehyde, ethanol, propylene glycol, or isopropanol.

Abstract

Methods and systems for electrochemical conversion of carbon dioxide to carboxylic acids, glycols, and carboxylates are disclosed. A method may include, but is not limited to, steps (A) to (D). Step (A) may introduce water to a first compartment of an electrochemical cell. The first compartment may include an anode. Step (B) may introduce carbon dioxide to a second compartment of the electrochemical cell. The second compartment may include a solution of an electrolyte and a cathode. Step (C) may apply an electrical potential between the anode and the cathode in the electrochemical cell sufficient to reduce the carbon dioxide to a carboxylic acid intermediate. Step (D) may contact the carboxylic acid intermediate with hydrogen to produce a reaction product.

Description

REDUCTION OF CARBON DIOXIDE TO CARBOXYLIC ACIDS, GLYCOLS,
AND CARBOXYLATES
FIELD
[0001 ] The present disclosure generally relates to the field of electrochemical reactions, and more particularly to methods and /or systems for electrochemical production of carboxylic acids, glycols, and carboxylates from carbon dioxide. BACKGROUND
[0002] The combustion of fossil fuels in activities such as electricity generation, transportation, and manufacturing produces billions of tons of carbon dioxide annually. Research since the 1970s indicates increasing concentrations of carbon dioxide in the atmosphere may be responsible for altering the Earth's climate, changing the pH of the ocean and other potentially damaging effects. Countries around the world, including the United States, are seeking ways to mitigate emissions of carbon dioxide.
[0003] A mechanism for mitigating emissions is to convert carbon dioxide into economically valuable materials such as fuels and industrial chemicals. If the carbon dioxide is converted using energy from renewable sources, both mitigation of carbon dioxide emissions and conversion of renewable energy into a chemical form that can be stored for later use may be possible.
SUMMARY OF THE PREFERRED EMBODIMENTS
[0004] The present invention is directed to using particular cathode materials, homogenous heterocyclic amine catalysts, and an electrolytic solution to reduce carbon dioxide to a carboxylic acid intermediate preferably including at least one of formic acid, glycolic acid, glyoxylic acid, oxalic acid, or lactic acid. The carboxylic acid intermediate may be processed further to yield a glycol-based reaction product. The present invention includes the process, system, and various components thereof. [0005] It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not necessarily restrictive of the disclosure as claimed. The accompanying drawings, which are incorporated in and constitute a part of the specification, illustrate an embodiment of the disclosure and together with the general description, serve to explain the principles of the disclosure.
BRIEF DESCRIPTION OF THE DRAWINGS
[0006] The numerous advantages of the present disclosure may be better understood by those skilled in the art by reference to the accompanying figures in which:
FIGS. 1A and 1 B depict a block diagram of a preferred system in accordance with an embodiment of the present disclosure;
FIG. 2 is a flow diagram of a preferred method of electrochemical production of a reaction product from carbon dioxide; and
FIG. 3 is a flow diagram of another preferred method of electrochemical production of a reaction product from carbon dioxide.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0007] Reference will now be made in detail to the presently preferred embodiments of the present disclosure, examples of which are illustrated in the accompanying drawings.
[0008] In accordance with some embodiments of the present disclosure, an electrochemical system is provided that converts carbon dioxide to carboxylic acid intermediates, carboxylic acids, and glycols. Use of a homogenous heterocyclic catalyst facilitates the process.
[0009] Before any embodiments of the invention are explained in detail, it is to be understood that the embodiments described below do not limit the scope of the claims that follow. Also, it is to be understood that the phraseology and terminology used herein is for the purpose of description and should not be regarded as limiting. The use of terms such as "including," "comprising," or "having" and variations thereof herein are generally meant to encompass the item listed thereafter and equivalents thereof as well as additional items. Further, unless otherwise noted, technical terms may be used according to conventional usage.
[0010] In certain preferred embodiments, the reduction of the carbon dioxide to produce carboxylic acid intermediates, carboxylic acids, and glycols may be preferably achieved in a divided electrochemical or photoelectrochemical cell having at least two compartments. One compartment contains an anode suitable to oxidize water, and another compartment contains a working cathode electrode and a homogenous heterocyclic amine catalyst. The compartments may be separated by a porous glass frit, microporous separator, ion exchange membrane, or other ion conducting bridge. Both compartments generally contain an aqueous solution of an electrolyte. Carbon dioxide gas may be continuously bubbled through the cathodic electrolyte solution to preferably saturate the solution or the solution may be pre-saturated with carbon dioxide.
[001 1 ] Referring to FIG. 1 , a block diagram of a system 100 is shown in accordance with an embodiment of the present invention. System 100 may be utilized for electrochemical production of carboxylic acid intermediates, carboxylic acids, and glycols from carbon dioxide and water (and hydrogen for glycol production). The system (or apparatus) 100 generally comprises a cell (or container) 102, a liquid source 104 (preferably a water source, but may include an organic solvent source), an energy source 106, a gas source 108 (preferably a carbon dioxide source), a product extractor 1 10 and an oxygen extractor 1 12. A product or product mixture may be output from the product extractor 1 10 after extraction. An output gas containing oxygen may be output from the oxygen extractor 1 12 after extraction.
[0012] The cell 102 may be implemented as a divided cell. The divided cell may be a divided electrochemical cell and /or a divided photochemical cell. The cell 102 is generally operational to reduce carbon dioxide (C02) into products or product intermediates. In particular implementations, the cell 102 is operational to reduce carbon dioxide to carboxylic acid intermediates (including salts such as formate, glycolate, glyoxylate, oxalate, and lactate), carboxylic acids, and glycols. The reduction generally takes place by introducing (e.g., bubbling) carbon dioxide into an electrolyte solution in the cell 102. A cathode 120 in the cell 102 may reduce the carbon dioxide into a carboxylic acid or a carboxylic acid intermediate. The production of a carboxylic acid or carboxylic acid intermediate may be dependent on the pH of the electrolyte solution, with lower pH ranges favoring carboxylic acid production. The pH of the cathode compartment may be adjusted to favor production of one of a carboxylic acid or carboxylic acid intermediate over production of the other, such as by introducing an acid (e.g., HCl or H2S04) to the cathode compartment. Hydrogen may be introduced to the carboxylic acid or carboxylic acid intermediate to produce a glycol or a carboxylic acid, respectively. The hydrogen may be derived from natural gas or water. [0013] The cell 102 generally comprises two or more compartments (or chambers) 1 14a- 1 14b, a separator (or membrane) 116, an anode 1 18, and a cathode 120. The anode 118 may be disposed in a given compartment (e.g., 1 14a). The cathode 120 may be disposed in another compartment (e.g., 1 14b) on an opposite side of the separator 116 as the anode 1 18. In particular implementations, the cathode 120 includes materials suitable for the reduction of carbon dioxide including cadmium, a cadmium alloy, cobalt, a cobalt alloy, nickel, a nickel alloy, chromium, a chromium alloy, indium, an indium alloy, iron, an iron alloy, copper, a copper alloy, lead, a lead alloy, palladium, a palladium alloy, platinum, a platinum alloy, molybdenum, a molybdenum alloy, tungsten, a tungsten alloy, niobium, a niobium alloy, silver, a silver alloy, tin, a tin alloy, rhodium, a rhodium alloy, ruthenium, a ruthenium alloy, carbon, and mixtures thereof. An electrolyte solution 122 (e.g., anolyte or catholyte 122) may fill both compartments 1 14a-1 14b. The aqueous solution 122 preferably includes water as a solvent and water soluble salts for providing various cations and anions in solution, however an organic solvent may also be utilized. In certain implementations, the organic solvent is present in an aqueous solution, whereas in other implementations the organic solvent is present in a non-aqueous solution. The catholyte 122 may include sodium and/or potassium cations or a quaternary amine (preferably tetramethyl ammonium or tetraethyl ammonium). The catholyte 122 may also include divalent cations (e.g., Ca2+, Mg2+, Zn2+) or a divalent cation may be added to the catholyte solution. [0014] A homogenous heterocyclic catalyst 124 is preferably added to the compartment 1 14b containing the cathode 120. The homogenous heterocyclic catalyst 124 may include, for example, one or more of 4- hydroxy pyridine, adenine, a heterocyclic amine containing sulfur, a heterocyclic amine containing oxygen, an azole, a benzimidazole, a bipyridine, furan, an imidazole, an imidazole related species with at least one five-member ring, an indole, a lutidine, methylimidazole, an oxazole, phenanthroline, pterin, pteridine, a pyridine, a pyridine related species with at least one six-member ring, pyrrole, quinoline, or a thiazole, and mixtures thereof. The homogenous heterocyclic catalyst 124 is preferably present in the compartment 114b at a concentration of between about 0.001 M and about 1M, and more preferably between about 0.01M and 0.5M.
[0015] The pH of the compartment 1 14b is preferably between about 1 and 8. A pH range of between about 1 to about 4 is preferable for production of carboxylic acids from carbon dioxide. A pH range of between about 4 to about 8 is preferable for production of carboxylic acid intermediates from carbon dioxide.
[0016] The liquid source 104 preferably includes a water source, such that the liquid source 104 may provide pure water to the cell 102. The liquid source 104 may provide other fluids to the cell 102, including an organic solvent, such as methanol, acetonitrile, and dimethylfuran. The liquid source 104 may also provide a mixture of an organic solvent and water to the cell 102. [0017] The energy source 106 may include a variable voltage source. The energy source 106 may be operational to generate an electrical potential between the anode 1 18 and the cathode 120. The electrical potential may be a DC voltage. In preferred embodiments, the applied electrical potential is generally between about -1 .5V vs. SCE and about -4V vs. SCE, preferably from about -1 .5V vs. SCE to about -3V vs. SCE, and more preferably from about -1 .5 V vs. SCE to about -2.5V vs. SCE.
[0018] The gas source 108 preferably includes a carbon dioxide source, such that the gas source 108 may provide carbon dioxide to the cell 102. In some embodiments, the carbon dioxide is bubbled directly into the compartment 1 14b containing the cathode 120. For instance, the compartment 1 14b may include a carbon dioxide input, such as a port 126a configured to be coupled between the carbon dioxide source and the cathode 120.
[0019] Advantageously, the carbon dioxide may be obtained from any source (e.g., an exhaust stream from fossil-fuel burning power or industrial plants, from geothermal or natural gas wells or the atmosphere itself). Most suitably, the carbon dioxide may be obtained from concentrated point sources of generation prior to being released into the atmosphere. For example, high concentration carbon dioxide sources may frequently accompany natural gas in amounts of 5% to 50%, exist in flue gases of fossil fuel (e.g., coal, natural gas, oil, etc.) burning power plants, and high purity carbon dioxide may be exhausted from cement factories, from fermenters used for industrial fermentation of ethanol, and from the manufacture of fertilizers and refined oil products. Certain geothermal steams may also contain significant amounts of carbon dioxide. The carbon dioxide emissions from varied industries, including geothermal wells, may be captured on-site. Thus, the capture and use of existing atmospheric carbon dioxide in accordance with some embodiments of the present invention generally allow the carbon dioxide to be a renewable and essentially unlimited source of carbon.
[0020] The product extractor 1 10 may include an organic product and/or inorganic product extractor. The product extractor 1 10 generally facilitates extraction of one or more products (e.g., carboxylic acid, and /or carboxylic acid intermediate) from the electrolyte 122. The extraction may occur via one or more of a solid sorbent, carbon dioxide- assisted solid sorbent, liquid-liquid extraction, nanofiltration, and electrodialysis. The extracted products may be presented through a port 126b of the system 100 for subsequent storage, consumption, and/or processing by other devices and /or processes. For instance, in particular implementations, the carboxylic acid or carboxylic acid intermediate is continuously removed from the cell 102, where cell 102 operates on a continuous basis, such as through a continuous flow-single pass reactor where fresh catholyte and carbon dioxide is fed continuously as the input, and where the output from the reactor is continuously removed. In other preferred implementations, the carboxylic acid or carboxylic acid intermediate is continuously removed from the catholyte 122 via one or more of adsorbing with a solid sorbent, liquid-liquid extraction, and electrodialysis. [0021 ] The separated carboxylic acid or carboxylic acid intermediate may be placed in contact with a hydrogen stream to produce a glycol or carboxylic acid, respectively. For instance, as shown in FIG. 1 B, the system 100 may include a secondary reactor 132 into which the separated carboxylic acid or carboxylic acid intermediate from the product extractor 1 10 and hydrogen stream from a hydrogen source 134 are introduced. The secondary reactor 132 generally permits interaction between the separated carboxylic acid or carboxylic acid intermediate from the product extractor 110 and the hydrogen to produce a glycol or carboxylic acid, respectively. The secondary reactor 132 may include reactor conditions that differ from ambient conditions. In particular implementations, the secondary reactor 132 preferably includes a temperature range and a pressure range that is higher than that of ambient conditions. For instance, a preferred temperature range of the secondary reactor 132 is between about 50°C and about 500°C, and a preferred pressure range of the secondary reactor 132 is between about 5 atm and 1000 atm. The secondary reactor may include a solvent and a catalyst to facilitate the reaction between the separated carboxylic acid or carboxylic acid intermediate from the product extractor 1 10 and the hydrogen stream from the hydrogen source 134. Preferred catalysts include Rh, Ru02, Ru, Pt, Pd, Re, Cu, Ni, Co, Cu-Ni, and binary metals and /or metal oxides thereof. The catalyst may be a supported catalyst, where the support may include Ti, Ti02, or C. Preferred solvents include aqueous and non-aqueous solvents, such as water, ether, and tetrahydrofuran.
[0022] The oxygen extractor 1 12 of FIG. 1A is generally operational to extract oxygen (e.g., 02) byproducts created by the reduction of the carbon dioxide and /or the oxidation of water. In preferred embodiments, the oxygen extractor 1 12 is a disengager/flash tank. The extracted oxygen may be presented through a port 128 of the system 100 for subsequent storage and /or consumption by other devices and /or processes. Chlorine and/or oxidatively evolved chemicals may also be byproducts in some configurations, such as in an embodiment of processes other than oxygen evolution occurring at the anode 118. Such processes may include chlorine evolution, oxidation of organics to other saleable products, waste water cleanup, and corrosion of a sacrificial anode. Any other excess gases (e.g., hydrogen) created by the reduction of the carbon dioxide and water may be vented from the cell 102 via a port 130.
[0023] Referring to FIG. 2, a flow diagram of a preferred method 200 for electrochemical conversion of carbon dioxide is shown. The method (or process) 200 generally comprises a step (or block) 202, a step (or block) 204, a step (or block) 206, and a step (or block) 208. The method 200 may be implemented using the system 100. [0024] In the step 202, a liquid may be introduced to a first compartment of an electrochemical cell. The first compartment may include an anode. Introducing carbon dioxide to a second compartment of the electrochemical cell may be performed in the step 204. The second compartment may include a solution of an electrolyte, a cathode, and a homogenous heterocyclic amine catalyst. The cathode may be selected from the group consisting of cadmium, a cadmium alloy, cobalt, a cobalt alloy, nickel, a nickel alloy, chromium, a chromium alloy, indium, an indium alloy, iron, an iron alloy, copper, a copper alloy, lead, a lead alloy, palladium, a palladium alloy, platinum, a platinum alloy, molybdenum, a molybdenum alloy, tungsten, a tungsten alloy, niobium, a niobium alloy, silver, a silver alloy, tin, a tin alloy, rhodium, a rhodium alloy, ruthenium, a ruthenium alloy, carbon, and mixtures thereof. In the step 206, an electric potential may be applied between the anode and the cathode in the electrochemical cell sufficient for the cathode to reduce the carbon dioxide to a carboxylic acid intermediate. The production of the carboxylic acid intermediate is preferably controlled by selection of particular cathode materials, catalysts, pH ranges, and electrolytes, such as disclosed in U.S. Application No. 12/846,221 , the disclosure of which is incorporated by reference. Contacting the carboxylic acid intermediate with hydrogen to produce a reaction product may be performed in the step 208. The secondary reactor 132 may permit interaction /contact between the carboxylic acid intermediate and the hydrogen, where the conditions of the secondary reactor 132 may provide for production of particular reaction products. [0025] Referring to FIG. 3, a flow diagram of another preferred method 300 for electrochemical conversion of carbon dioxide is shown. The method (or process) 300 generally comprises a step (or block) 302, a step (or block) 304, a step (or block) 306, a step (or block) 308, a step (or block) 310, and a step (or block) 312. The method 300 may be implemented using the system 100.
[0026] In the step 302, a liquid may be introduced to a first compartment of an electrochemical cell. The first compartment may include an anode. Introducing carbon dioxide to a second compartment of the electrochemical cell may be performed in the step 304. The second compartment may include a solution of an electrolyte, a cathode, and a homogenous heterocyclic amine catalyst. In the step 306, an electric potential may be applied between the anode and the cathode in the electrochemical cell sufficient for the cathode to reduce the carbon dioxide to at least a carboxylate. Acidifying the carboxylate to convert the carboxylate into a carboxylic acid may be performed in the step 308. The acidifying step may include introduction of an acid from a make-up acid source. In the step 310, the carboxylic acid may be extracted. Contacting the carboxylic acid with hydrogen to form a reaction product may be performed in the step 312. In preferred implementations, the reaction product includes one or more of formaldehyde, methanol, glycolic acid, glyoxal, glyoxylic aid, glycolaldehyde, ethylene glycol, acetic acid, acetaldehyde, ethanol, propylene glycol, or isopropanol.
[0027] It is believed that the present disclosure and many of its attendant advantages will be understood by the foregoing description, and it will be apparent that various changes may be made in the form, construction and arrangement of the components thereof without departing from the scope and spirit of the disclosure or without sacrificing all of its material advantages. The form herein before described being merely an explanatory embodiment thereof, it is the intention of the following claims to encompass and include such changes.

Claims

What is claimed is: 1. A method for electrochemical conversion of carbon dioxide, comprising:
(A) introducing a liquid to a first compartment of an electrochemical cell, the first compartment including an anode;
(B) introducing carbon dioxide to a second compartment of the electrochemical cell, the second compartment including a solution of an electrolyte, a cathode, and a homogenous heterocyclic amine catalyst, the cathode selected from the group consisting of cadmium, a cadmium alloy, cobalt, a cobalt alloy, nickel, a nickel alloy, chromium, a chromium alloy, indium, an indium alloy, iron, an iron alloy, copper, a copper alloy, lead, a lead alloy, palladium, a palladium alloy, platinum, a platinum alloy, molybdenum, a molybdenum alloy, tungsten, a tungsten alloy, niobium, a niobium alloy, silver, a silver alloy, tin, a tin alloy, rhodium, a rhodium alloy, ruthenium, a ruthenium alloy, carbon, and mixtures thereof;
(C) applying an electrical potential between the anode and the cathode sufficient for the cathode to reduce the carbon dioxide to a carboxylic acid intermediate; and
(D) contacting the carboxylic acid intermediate with hydrogen to produce a reaction product.
2. The method of claim 1 , wherein the carboxylic acid intermediate includes at least one of formate, formic acid, glycolate, glycolic acid, glyoxylate, glyoxylic acid, lactate, lactic acid, oxalate, or oxalic acid.
3. The method of claim 1 , wherein the reaction product includes at least one of formaldehyde, formic acid, methanol, glyoxylic acid, glycolic acid, glyoxal, glycolaldehyde, ethylene glycol, acetic acid, acetaldehyde, ethanol, lactic acid, oxalic acid, propylene glycol, or isopropanol.
4. The method of claim 1 , wherein the carboxylic acid intermediate includes formic acid, and wherein the reaction product includes at least one of formaldehyde or methanol.
5. The method of claim 1 , wherein the carboxylic acid intermediate includes oxalic acid, and wherein the reaction product includes at least one of glyoxylic acid, glycolic acid, glyoxal, glycolaldehyde, ethylene glycol, acetic acid, acetaldehyde, or ethanol.
6. The method of claim 1 , wherein the carboxylic acid intermediate includes lactic acid, and wherein the reaction product includes at least one of propylene glycol or isopropanol.
7. The method of claim 1 , wherein the carboxylic acid intermediate includes glyoxylic acid, and wherein the reaction product includes at least one of glycolic acid, glyoxal, glycolaldehyde, ethylene glycol, acetic acid, acetaldehyde, or ethanol.
8. The method of claim 1 , wherein the carboxylic acid intermediate includes glycolic acid, and wherein the reaction product includes at least one of glycolaldehyde, ethylene glycol, acetic acid, acetaldehyde, or ethanol.
9. The method of claim 1 , wherein a pH of the second compartment is between about 1 and about 8.
10. The method of claim 1 , further comprising:
adjusting a pH of the second compartment to favor production of one of a carboxylic acid and a carboxylic acid intermediate over production of the other of the one of a carboxylic acid and a carboxylic acid intermediate.
1 1 . A system for electrochemical reduction of carbon dioxide, sing:
an electrochemical cell including:
a first cell compartment;
an anode positioned within said first cell compartment;
a second cell compartment;
a separator interposed between said first cell compartment and said second cell compartment, said second cell compartment containing an electrolyte; and a cathode and a homogenous heterocyclic amine catalyst positioned within said second cell compartment, said cathode selected from the group consisting of cadmium, a cadmium alloy, cobalt, a cobalt alloy, nickel, a nickel alloy, chromium, a chromium alloy, indium, an indium alloy, iron, an iron alloy, copper, a copper alloy, lead, a lead alloy, palladium, a palladium alloy, platinum, a platinum alloy, molybdenum, a molybdenum alloy, tungsten, a tungsten alloy, niobium, a niobium alloy, silver, a silver alloy, tin, a tin alloy, rhodium, a rhodium alloy, ruthenium, a ruthenium alloy, carbon, and mixtures thereof;
an energy source operably coupled with said anode and said cathode, said energy source configured to apply a voltage between said anode and said cathode to reduce carbon dioxide at said cathode to an intermediate product stream including a carboxylic acid;
an extractor configured to extract the carboxylic acid from the intermediate product stream; and a secondary reactor configured to introduce the carboxylic acid to hydrogen from a hydrogen source, the secondary reactor configured to produce at least one of formaldehyde, methanol, glycolic acid, glyoxal, glyoxylic acid, glycolaldehyde, ethylene glycol, acetic acid, acetaldehyde, ethanol, propylene glycol, or isopropanol.
12. A method for electrochemical conversion of carbon dioxide, comprising:
(A) introducing a liquid to a first compartment of an electrochemical cell, the first compartment including an anode;
(B) introducing carbon dioxide to a second compartment of the electrochemical cell, the second compartment including a solution of an electrolyte, a cathode, and a homogenous heterocyclic amine catalyst;
(C) applying an electrical potential between the anode and the cathode sufficient for the cathode to reduce the carbon dioxide to at least a carboxylate;
(D) acidifying the carboxylate to convert the carboxylate into a carboxylic acid;
(E) extracting the carboxylic acid; and
(F) contacting the carboxylic acid with hydrogen to form a reaction product.
13. The method of claim 12, wherein the carboxylate includes at least one of formate, glycolate, glyoxylate, lactate, or oxalate.
14. The method of claim 12, wherein the carboxylic acid includes at least one of formic acid, glycolic acid, glyoxylic acid, lactic acid, or oxalic acid.
15. The method of claim 12, wherein the reaction product includes at least one of formaldehyde, methanol, glycolic acid, glyoxal, glyoxylic aid, glycolaldehyde, ethylene glycol, acetic acid, acetaldehyde, ethanol, propylene glycol, or isopropanol.
16. The method of claim 12, wherein the carboxylate includes formate, the carboxylic acid intermediate includes formic acid, and the reaction product includes at least one of formaldehyde or methanol.
17. The method of claim 12, wherein the carboxylate includes oxalate, the carboxylic acid intermediate includes oxalic acid, and the reaction product includes at least one of glyoxylic acid, glycolic acid, glyoxal, glycolaldehyde, ethylene glycol, acetic acid, acetaldehyde, or ethanol.
18. The method of claim 12, wherein the carboxylate includes lactate, the carboxylic acid intermediate includes lactic acid, and the reaction product includes at least one of propylene glycol or isopropanol.
19. The method of claim 12, wherein the carboxylate includes glycolate, the carboxylic acid intermediate includes glycolic acid, and the reaction product includes at least one of glycolaldehyde, ethylene glycol, acetic acid, acetaldehyde, or ethanol.
20. The method of claim 12, wherein the carboxylate includes glyoxylate, the carboxylic acid intermediate includes glyoxylic acid, and the reaction product includes at least one of glycolic acid, glyoxal, glycolaldehyde, ethylene glycol, acetic acid, acetaldehyde, or ethanol.
PCT/US2012/045578 2011-07-06 2012-07-05 Reduction of carbon dioxide to carboxylic acids, glycols, and carboxylates WO2013006711A1 (en)

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BR112014000052A BR112014000052A2 (en) 2011-07-06 2012-07-05 reduction of carbon dioxide in carboxylic acids, glycols and carboxylates
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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8956990B2 (en) 2010-03-26 2015-02-17 Dioxide Materials, Inc. Catalyst mixtures
US9012345B2 (en) 2010-03-26 2015-04-21 Dioxide Materials, Inc. Electrocatalysts for carbon dioxide conversion
US9181625B2 (en) 2010-03-26 2015-11-10 Dioxide Materials, Inc. Devices and processes for carbon dioxide conversion into useful fuels and chemicals
US9193593B2 (en) 2010-03-26 2015-11-24 Dioxide Materials, Inc. Hydrogenation of formic acid to formaldehyde
US9566574B2 (en) 2010-07-04 2017-02-14 Dioxide Materials, Inc. Catalyst mixtures
US9790161B2 (en) 2010-03-26 2017-10-17 Dioxide Materials, Inc Process for the sustainable production of acrylic acid
US9815021B2 (en) 2010-03-26 2017-11-14 Dioxide Materials, Inc. Electrocatalytic process for carbon dioxide conversion
US9957624B2 (en) 2010-03-26 2018-05-01 Dioxide Materials, Inc. Electrochemical devices comprising novel catalyst mixtures
US10023967B2 (en) 2010-03-26 2018-07-17 Dioxide Materials, Inc. Electrochemical devices employing novel catalyst mixtures
US10173169B2 (en) 2010-03-26 2019-01-08 Dioxide Materials, Inc Devices for electrocatalytic conversion of carbon dioxide
WO2019141827A1 (en) 2018-01-18 2019-07-25 Avantium Knowledge Centre B.V. Catalyst system for catalyzed electrochemical reactions and preparation thereof, applications and uses thereof
US10647652B2 (en) 2013-02-24 2020-05-12 Dioxide Materials, Inc. Process for the sustainable production of acrylic acid
US10774431B2 (en) 2014-10-21 2020-09-15 Dioxide Materials, Inc. Ion-conducting membranes
US10975480B2 (en) 2015-02-03 2021-04-13 Dioxide Materials, Inc. Electrocatalytic process for carbon dioxide conversion

Families Citing this family (60)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2382174A4 (en) 2009-01-29 2013-10-30 Trustees Of The University Of Princeton Conversion of carbon dioxide to organic products
US8721866B2 (en) 2010-03-19 2014-05-13 Liquid Light, Inc. Electrochemical production of synthesis gas from carbon dioxide
US8845877B2 (en) 2010-03-19 2014-09-30 Liquid Light, Inc. Heterocycle catalyzed electrochemical process
US8500987B2 (en) 2010-03-19 2013-08-06 Liquid Light, Inc. Purification of carbon dioxide from a mixture of gases
US9370773B2 (en) 2010-07-04 2016-06-21 Dioxide Materials, Inc. Ion-conducting membranes
US9945040B2 (en) 2010-07-04 2018-04-17 Dioxide Materials, Inc. Catalyst layers and electrolyzers
WO2016064440A1 (en) 2014-10-21 2016-04-28 Dioxide Materials Electrolyzer and membranes
US10047446B2 (en) 2010-07-04 2018-08-14 Dioxide Materials, Inc. Method and system for electrochemical production of formic acid from carbon dioxide
US9849450B2 (en) 2010-07-04 2017-12-26 Dioxide Materials, Inc. Ion-conducting membranes
US8845878B2 (en) 2010-07-29 2014-09-30 Liquid Light, Inc. Reducing carbon dioxide to products
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
US9943841B2 (en) 2012-04-12 2018-04-17 Dioxide Materials, Inc. Method of making an anion exchange membrane
US9982353B2 (en) 2012-04-12 2018-05-29 Dioxide Materials, Inc. Water electrolyzers
US8641885B2 (en) 2012-07-26 2014-02-04 Liquid Light, Inc. Multiphase electrochemical reduction of CO2
US20140206896A1 (en) 2012-07-26 2014-07-24 Liquid Light, Inc. Method and System for Production of Oxalic Acid and Oxalic Acid Reduction Products
US8692019B2 (en) 2012-07-26 2014-04-08 Liquid Light, Inc. Electrochemical co-production of chemicals utilizing a halide salt
US10329676B2 (en) 2012-07-26 2019-06-25 Avantium Knowledge Centre B.V. Method and system for electrochemical reduction of carbon dioxide employing a gas diffusion electrode
US9175407B2 (en) 2012-07-26 2015-11-03 Liquid Light, Inc. Integrated process for producing carboxylic acids from carbon dioxide
US8858777B2 (en) 2012-07-26 2014-10-14 Liquid Light, Inc. Process and high surface area electrodes for the electrochemical reduction of carbon dioxide
WO2014043651A2 (en) 2012-09-14 2014-03-20 Liquid Light, Inc. High pressure electrochemical cell and process for the electrochemical reduction of carbon dioxide
KR20150056634A (en) * 2012-09-19 2015-05-26 리퀴드 라이트 인코포레이티드 Electrochemical reduction of co2 with co-oxidation of an alcohol
CA2895253C (en) 2012-12-21 2022-03-01 Liquid Light, Inc. Method and system for production of oxalic acid and oxalic acid reduction products
JP6258467B2 (en) * 2014-03-24 2018-01-10 株式会社東芝 Photoelectrochemical reaction system
US9255057B2 (en) 2014-04-14 2016-02-09 Alstom Technology Ltd Apparatus and method for production of formate from carbon dioxide
EP3140312B1 (en) * 2014-05-05 2018-07-25 Centre National de la Recherche Scientifique (CNRS) Porphyrin molecular catalysts for selective electrochemical reduction of co2 into co
WO2016030749A1 (en) * 2014-08-29 2016-03-03 King Abdullah University Of Science And Technology Electrodes, methods of making electrodes, and methods of using electrodes
US10724142B2 (en) 2014-10-21 2020-07-28 Dioxide Materials, Inc. Water electrolyzers employing anion exchange membranes
US9435042B2 (en) 2014-10-24 2016-09-06 Toyota Motor Engineering & Manufacturing North America, Inc. System and method for selective electrochemical reduction of carbon dioxide employing an anodized silver electrode
US10576413B2 (en) 2014-12-10 2020-03-03 Ethan J. Novek Systems and methods for separating gases
US10280378B2 (en) 2015-05-05 2019-05-07 Dioxide Materials, Inc System and process for the production of renewable fuels and chemicals
JP6548954B2 (en) 2015-05-21 2019-07-24 株式会社東芝 Reduction catalyst and chemical reactor
CN104846393B (en) * 2015-06-17 2017-04-26 哈尔滨工业大学 CO2 electrochemical reduction method with Ag-containing electrode as working electrode
US10465303B2 (en) * 2015-09-15 2019-11-05 Kabushiki Kaisha Toshiba Producing system of reduction product
WO2017062788A1 (en) * 2015-10-09 2017-04-13 Rutgers, The State University Of New Jersey Nickel phosphide catalysts for direct electrochemical co2 reduction to hydrocarbons
CN105297067B (en) * 2015-11-16 2018-02-09 昆明理工大学 A kind of multicell diaphragm electrolysis method and apparatus by carbon dioxide electroreduction for carbon monoxide
WO2017100867A1 (en) * 2015-12-17 2017-06-22 Commonwealth Scientific And Industrial Research Organisation Acid gas regenerable battery
WO2017112557A1 (en) * 2015-12-22 2017-06-29 Shell Oil Company Methods and systems for generating a renewable drop-in fuels product
WO2017176599A1 (en) 2016-04-04 2017-10-12 Dioxide Materials, Inc. Ion-conducting membranes
WO2017192787A1 (en) 2016-05-03 2017-11-09 Opus 12 Incorporated Reactor with advanced architecture for the electrochemical reaction of co2, co, and other chemical compounds
CN106391013A (en) * 2016-08-31 2017-02-15 北京福美加能源科技有限公司 Catalyst for electrochemically reducing carbon dioxide into carbon monoxide and preparation method of catalyst
JP6636885B2 (en) * 2016-09-12 2020-01-29 株式会社東芝 Reduction catalyst and reduction reactor
DE102016218235A1 (en) * 2016-09-22 2018-03-22 Siemens Aktiengesellschaft Process for the preparation of propanol, propionaldehyde and / or propionic acid from carbon dioxide, water and electrical energy
DE102016220297A1 (en) * 2016-09-27 2018-03-29 Siemens Aktiengesellschaft Process and apparatus for the electrochemical utilization of carbon dioxide
CA3038340A1 (en) * 2016-10-14 2018-04-19 Stafford Wheeler Sheehan Systems and methods for variable pressure electrochemical carbon dioxide reduction
JP6649293B2 (en) 2017-01-25 2020-02-19 株式会社東芝 Reduction catalyst, and chemical reaction device, reduction method and reduced product production system using the same
CN106994367B (en) * 2017-03-09 2019-08-06 盐城复华环保产业开发有限公司 The graphene-supported cadmium catalyst with base of molybdenum and its preparation method and application of sulfur doping
US10147974B2 (en) 2017-05-01 2018-12-04 Dioxide Materials, Inc Battery separator membrane and battery employing same
US10396329B2 (en) 2017-05-01 2019-08-27 Dioxide Materials, Inc. Battery separator membrane and battery employing same
CN107183508A (en) * 2017-06-12 2017-09-22 江南大学 A kind of method that free state heterocycle amine content is reduced based on acid amides active component
US11649472B2 (en) 2017-06-30 2023-05-16 Massachusetts Institute Of Technology Controlling metabolism by substrate cofeeding
US10696614B2 (en) 2017-12-29 2020-06-30 Uchicago Argonne, Llc Photocatalytic reduction of carbon dioxide to methanol or carbon monoxide using cuprous oxide
CA3089119A1 (en) 2018-01-22 2019-07-25 Opus 12 Incorporated System and method for carbon dioxide reactor control
DE102018202184A1 (en) * 2018-02-13 2019-08-14 Siemens Aktiengesellschaft Separatorless double GDE cell for electrochemical conversion
JP7468975B2 (en) 2018-11-28 2024-04-16 トゥエルブ ベネフィット コーポレーション Electrolyzer and method of use
BR112021011768A2 (en) 2018-12-18 2021-08-31 Opus 12 Incorporated ELECTROLYZER AND METHOD OF USE
BR112022010144A2 (en) 2019-11-25 2022-09-06 Twelve Benefit Corp MEMBRANE ELECTRODE SET FOR COX REDUCTION
EP3831982A1 (en) 2019-12-02 2021-06-09 Vito NV Electrochemical co2 conversion
WO2024035474A1 (en) 2022-08-12 2024-02-15 Twelve Benefit Corporation Acetic acid production

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060102468A1 (en) * 2002-08-21 2006-05-18 Battelle Memorial Institute Photolytic oxygenator with carbon dioxide and/or hydrogen separation and fixation
US20110114504A1 (en) * 2010-03-19 2011-05-19 Narayanappa Sivasankar Electrochemical production of synthesis gas from carbon dioxide

Family Cites Families (181)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR853643A (en) 1938-05-04 1940-03-23 Ig Farbenindustrie Ag Process for producing halogenated hydrocarbons
US2967806A (en) * 1953-04-02 1961-01-10 Hooker Chemical Corp Electrolytic decomposition with permselective diaphragms
US3019256A (en) 1959-03-23 1962-01-30 Union Carbide Corp Process for producing acrylic acid esters
US3399966A (en) 1964-05-18 1968-09-03 Trurumi Soda Company Ltd Novel cobalt oxide and an electrode having the cobalt oxide coating
US3401100A (en) 1964-05-26 1968-09-10 Trw Inc Electrolytic process for concentrating carbon dioxide
US3560354A (en) 1967-10-16 1971-02-02 Union Oil Co Electrolytic chemical process
GB1203434A (en) 1967-10-23 1970-08-26 Ici Ltd Oxidation of organic materials
DE1668102A1 (en) 1968-02-28 1971-06-03 Hoechst Ag Process for the production of acetylene
US3636159A (en) 1968-12-19 1972-01-18 Phillips Petroleum Co Hydroformylation process and catalyst
BE787771A (en) * 1971-08-20 1973-02-19 Rhone Poulenc Sa PREPARATION OF GLYOXYLIC ACID
BE791653A (en) * 1971-12-28 1973-05-21 Texaco Development Corp ELECTROLYTIC PROCESS FOR THE PREPARATION OF ACID
DE2301032A1 (en) * 1973-01-10 1974-07-25 Dechema Oxalic acid prodn. - by electro-chemical reductive dimerisation of carbon dioxide
DE2343054C2 (en) 1973-08-25 1975-10-09 Basf Ag, 6700 Ludwigshafen Process for the electrochemical production of pinacols
US3959094A (en) 1975-03-13 1976-05-25 The United States Of America As Represented By The United States Energy Research And Development Administration Electrolytic synthesis of methanol from CO2
US4088682A (en) * 1975-07-03 1978-05-09 Jordan Robert Kenneth Oxalate hydrogenation process
US4072583A (en) 1976-10-07 1978-02-07 Monsanto Company Electrolytic carboxylation of carbon acids via electrogenerated bases
US4160816A (en) 1977-12-05 1979-07-10 Rca Corporation Process for storing solar energy in the form of an electrochemically generated compound
IL54408A (en) 1978-03-31 1981-09-13 Yeda Res & Dev Photosynthetic process for converting carbon dioxide to organic compounds
IT1122699B (en) 1979-08-03 1986-04-23 Oronzio De Nora Impianti RESILIENT ELECTRIC COLLECTOR AND SOLID ELECTROLYTE ELECTROCHEMISTRY INCLUDING THE SAME
GB2058839B (en) 1979-09-08 1983-02-16 Engelhard Min & Chem Photo electrochemical processes
US4478699A (en) 1980-05-09 1984-10-23 Yeda Research & Development Company, Ltd. Photosynthetic solar energy collector and process for its use
US4334095A (en) * 1980-10-06 1982-06-08 Miles Laboratories, Inc. Extraction of organic acids from aqueous solutions
US4439302A (en) 1981-11-24 1984-03-27 Massachusetts Institute Of Technology Redox mediation and hydrogen-generation with bipyridinium reagents
NO824150L (en) 1981-12-11 1983-06-13 British Petroleum Co ELECTROCHEMICAL ORGANIC SYNTHESIS.
US4451342A (en) 1982-05-03 1984-05-29 Atlantic Richfield Company Light driven photocatalytic process
US4414080A (en) 1982-05-10 1983-11-08 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Photoelectrochemical electrodes
US4460443A (en) 1982-09-09 1984-07-17 The Regents Of The University Of California Electrolytic photodissociation of chemical compounds by iron oxide electrodes
DE3246070A1 (en) 1982-12-13 1984-06-14 Helmut Prof. Dr. 7400 Tübingen Metzner METHOD AND DEVICE FOR REDUCING, IN PARTICULAR METHANIZING, CARBON DIOXIDE
US4450055A (en) 1983-03-30 1984-05-22 Celanese Corporation Electrogenerative partial oxidation of organic compounds
US4476003A (en) 1983-04-07 1984-10-09 The United States Of America As Represented By The United States Department Of Energy Chemical anchoring of organic conducting polymers to semiconducting surfaces
DE3334863A1 (en) 1983-09-27 1985-04-11 Basf Ag, 6700 Ludwigshafen Process for obtaining aqueous glyoxylic acid solutions
US4478694A (en) 1983-10-11 1984-10-23 Ska Associates Methods for the electrosynthesis of polyols
JPS60184041A (en) * 1984-02-29 1985-09-19 チヤイナ，パテント，エ−ジエント（ホンコン），リミテツド Extraction of organic acid from aqueous solution
US4609451A (en) 1984-03-27 1986-09-02 Texaco Inc. Means for reducing carbon dioxide to provide a product
DE3428321A1 (en) * 1984-08-01 1986-02-13 Hüls AG, 4370 Marl Process for the production of formic acid
GB8424672D0 (en) 1984-09-29 1984-11-07 Bp Chem Int Ltd Production of formic acid
US4595465A (en) 1984-12-24 1986-06-17 Texaco Inc. Means and method for reducing carbn dioxide to provide an oxalate product
US4620906A (en) 1985-01-31 1986-11-04 Texaco Inc. Means and method for reducing carbon dioxide to provide formic acid
US4608132A (en) 1985-06-06 1986-08-26 Texaco Inc. Means and method for the electrochemical reduction of carbon dioxide to provide a product
US4673473A (en) 1985-06-06 1987-06-16 Peter G. Pa Ang Means and method for reducing carbon dioxide to a product
US4608133A (en) 1985-06-10 1986-08-26 Texaco Inc. Means and method for the electrochemical reduction of carbon dioxide to provide a product
US4921586A (en) 1989-03-31 1990-05-01 United Technologies Corporation Electrolysis cell and method of use
US4619743A (en) 1985-07-16 1986-10-28 Texaco Inc. Electrolytic method for reducing oxalic acid to a product
US5443804A (en) 1985-12-04 1995-08-22 Solar Reactor Technologies, Inc. System for the manufacture of methanol and simultaneous abatement of emission of greenhouse gases
US4609441A (en) 1985-12-18 1986-09-02 Gas Research Institute Electrochemical reduction of aqueous carbon dioxide to methanol
US4609440A (en) 1985-12-18 1986-09-02 Gas Research Institute Electrochemical synthesis of methane
US4732655A (en) 1986-06-11 1988-03-22 Texaco Inc. Means and method for providing two chemical products from electrolytes
US4702973A (en) 1986-08-25 1987-10-27 Institute Of Gas Technology Dual compartment anode structure
US4756807A (en) 1986-10-09 1988-07-12 Gas Research Institute Chemically modified electrodes for the catalytic reduction of CO2
US4668349A (en) 1986-10-24 1987-05-26 The Standard Oil Company Acid promoted electrocatalytic reduction of carbon dioxide by square planar transition metal complexes
US4776171A (en) 1986-11-14 1988-10-11 Perry Oceanographics, Inc. Self-contained renewable energy system
US4945397A (en) 1986-12-08 1990-07-31 Honeywell Inc. Resistive overlayer for magnetic films
FR2609474B1 (en) 1987-01-09 1991-04-26 Poudres & Explosifs Ste Nale PROCESS FOR THE ELECTROCHEMICAL SYNTHESIS OF CARBOXYLIC ACIDS
US4793904A (en) 1987-10-05 1988-12-27 The Standard Oil Company Process for the electrocatalytic conversion of light hydrocarbons to synthesis gas
FR2624884B1 (en) 1987-12-18 1990-04-20 Poudres & Explosifs Ste Nale METHOD FOR THE ELECTROCHEMICAL SYNTHESIS OF SATURATED ALPHA KETONES
US4897167A (en) 1988-08-19 1990-01-30 Gas Research Institute Electrochemical reduction of CO2 to CH4 and C2 H4
US4959131A (en) 1988-10-14 1990-09-25 Gas Research Institute Gas phase CO2 reduction to hydrocarbons at solid polymer electrolyte cells
DE69033409T2 (en) 1989-03-31 2000-08-03 United Technologies Corp Electrolytic cell and method of use
US5064733A (en) 1989-09-27 1991-11-12 Gas Research Institute Electrochemical conversion of CO2 and CH4 to C2 hydrocarbons in a single cell
JP3009703B2 (en) 1990-05-02 2000-02-14 正道 藤平 Electrode catalyst for carbon dioxide gas reduction
US5198086A (en) 1990-12-21 1993-03-30 Allied-Signal Electrodialysis of salts of weak acids and/or weak bases
US5246551A (en) 1992-02-11 1993-09-21 Chemetics International Company Ltd. Electrochemical methods for production of alkali metal hydroxides without the co-production of chlorine
CA2135138C (en) 1993-11-04 2006-03-14 Takao Ikariya Method for producing formic acid or its derivatives
US5587083A (en) 1995-04-17 1996-12-24 Chemetics International Company Ltd. Nanofiltration of concentrated aqueous salt solutions
US5514492A (en) 1995-06-02 1996-05-07 Pacesetter, Inc. Cathode material for use in an electrochemical cell and method for preparation thereof
IN190134B (en) 1995-12-28 2003-06-21 Du Pont
US6024935A (en) 1996-01-26 2000-02-15 Blacklight Power, Inc. Lower-energy hydrogen methods and structures
FR2747694B1 (en) 1996-04-18 1998-06-05 France Etat CATHODE FOR THE REDUCTION OF CARBON DIOXIDE AND METHOD OF MANUFACTURING SUCH A CATHODE
US5928806A (en) 1997-05-07 1999-07-27 Olah; George A. Recycling of carbon dioxide into methyl alcohol and related oxygenates for hydrocarbons
US6187465B1 (en) 1997-11-07 2001-02-13 Terry R. Galloway Process and system for converting carbonaceous feedstocks into energy without greenhouse gas emissions
FR2780055A1 (en) 1998-06-22 1999-12-24 Jan Augustynski Tungsten oxide-coated electrode, especially for water photo-electrolysis or organic waste photo-electrochemical decomposition or for an electrochromic display cell
US6270649B1 (en) 1998-07-09 2001-08-07 Michigan State University Electrochemical methods for generation of a biological proton motive force and pyridine nucleotide cofactor regeneration
US6267864B1 (en) 1998-09-14 2001-07-31 Nanomaterials Research Corporation Field assisted transformation of chemical and material compositions
WO2000025380A2 (en) 1998-10-27 2000-05-04 Quadrise Limited Electrical energy storage compound
SE518454C2 (en) 1999-01-15 2002-10-08 Forskarpatent I Uppsala Ab Method for making an electrochemical cell and electrochemical cell
US6251256B1 (en) 1999-02-04 2001-06-26 Celanese International Corporation Process for electrochemical oxidation of an aldehyde to an ester
DE19929509A1 (en) 1999-06-29 2001-01-11 Inst Angewandte Photovoltaik G Photoelectrochemical cell and method for producing a counterelectrode for a photoelectrochemical cell
US6936143B1 (en) 1999-07-05 2005-08-30 Ecole Polytechnique Federale De Lausanne Tandem cell for water cleavage by visible light
US6828054B2 (en) 2000-02-11 2004-12-07 The Texas A&M University System Electronically conducting fuel cell component with directly bonded layers and method for making the same
HUP0302080A2 (en) 2000-08-07 2003-09-29 Energieonderzoek Centrum Nederland Mixed oxide material, electrode and method of manufacturing the electrode and electrochemical cell comprising it
WO2002059987A2 (en) 2000-10-30 2002-08-01 Ztek Corporation Multi-function energy system operable as a fuel cell, reformer, or thermal plant
US6656978B2 (en) 2001-04-05 2003-12-02 Chiyoda Corporation Process of producing liquid hydrocarbon oil or dimethyl ether from lower hydrocarbon gas containing carbon dioxide
DE20107921U1 (en) 2001-05-10 2001-07-26 Schulze Dirk Device for generating ozone, oxygen, hydrogen and / or other water electrolysis products
US6656873B2 (en) 2001-06-14 2003-12-02 Sanjay Chaturvedi Mixed metal oxide catalyst
US6569309B2 (en) 2001-07-05 2003-05-27 Asahi Kasei Kabushiki Kaisha Fuel cell type reactor and method for producing a chemical compound by using the same
GB0116505D0 (en) 2001-07-06 2001-08-29 Univ Belfast Electrosynthesis of organic compounds
WO2003016592A2 (en) 2001-08-14 2003-02-27 3-One-2, Llc Electrolytic cell and electrodes for use in electrochemical processes
US6942767B1 (en) 2001-10-12 2005-09-13 T-Graphic, Llc Chemical reactor system
CN1585735A (en) 2001-11-09 2005-02-23 巴斯福股份公司 Method for production of formic acid formates
WO2003048424A1 (en) 2001-12-03 2003-06-12 Japan Techno Co., Ltd. Hydrogen-oxygen gas generator and hydrogen-oxygen gas generating method using the generator
FR2842536B1 (en) 2002-07-19 2005-06-03 Commissariat Energie Atomique ELECTROLYTIC REACTOR
KR100468049B1 (en) 2002-07-26 2005-01-24 학교법인 서강대학교 Formic Acid Synthesis by Electrochemical Reduction of Carbon Dioxide
US6887728B2 (en) 2002-08-26 2005-05-03 University Of Hawaii Hybrid solid state/electrochemical photoelectrode for hydrogen production
US7718293B2 (en) 2002-10-14 2010-05-18 Reinz-Dichtungs-Gmbh Electrochemical system with fluid passage integrated within a sealing bead
EP1443091A1 (en) 2003-01-31 2004-08-04 Ntera Limited Electrochromic compounds
ES2337147T3 (en) 2003-05-19 2010-04-21 Michael Trachtenberg GAS SEPARATION PROCEDURE AND APPARATUS
JP2004344720A (en) 2003-05-20 2004-12-09 Hasshin Tech Kk Co2 reduction method, artificial photosynthesis induction substance and co2 reduction apparatus
US20070184309A1 (en) 2003-05-30 2007-08-09 Gust Jr John D Methods for use of a photobiofuel cell in production of hydrogen and other materials
US7052587B2 (en) 2003-06-27 2006-05-30 General Motors Corporation Photoelectrochemical device and electrode
US7037414B2 (en) 2003-07-11 2006-05-02 Gas Technology Institute Photoelectrolysis of water using proton exchange membranes
US7378011B2 (en) 2003-07-28 2008-05-27 Phelps Dodge Corporation Method and apparatus for electrowinning copper using the ferrous/ferric anode reaction
US20050051439A1 (en) 2003-09-08 2005-03-10 Jang Bor Z. Photo-electrolytic catalyst systems and method for hydrogen production from water
JP2005126427A (en) * 2003-09-30 2005-05-19 Nippon Steel Corp Method for producing formic acid ester and methanol
JP4811844B2 (en) 2003-11-11 2011-11-09 ペルメレック電極株式会社 Method for producing percarbonate
FR2863911B1 (en) 2003-12-23 2006-04-07 Inst Francais Du Petrole CARBON SEQUESTRATION PROCESS IN THE FORM OF A MINERAL IN WHICH THE CARBON IS AT THE DEGREE OF OXIDATION +3
PL1716609T3 (en) 2003-12-31 2019-02-28 Lg Chem, Ltd. Electrode active material powder with size dependent composition and method to prepare the same
US9786925B2 (en) 2004-04-22 2017-10-10 Nippon Steel & Sumitomo Metal Corporation Fuel cell and fuel cell use gas diffusion electrode
US20060243587A1 (en) 2004-05-05 2006-11-02 Sustainable Technologies International Pty Ltd Photoelectrochemical device
DE102004028761A1 (en) 2004-06-16 2006-01-12 Uhdenora Technologies S.R.L. Electrolysis cell with optimized shell construction and minimized membrane area
FR2872174B1 (en) 2004-06-23 2007-06-15 Electricite De France METHOD AND DEVICE FOR ELECTROLYSIS OF WATER COMPRISING A PARTICULAR ELECTRODE OXIDE MATERIAL
EP1778583A2 (en) 2004-07-12 2007-05-02 Aytec Avnim Ltd. Method for producing fuel from captured carbon dioxide
US7419623B2 (en) 2004-08-03 2008-09-02 Air Products And Chemicals, Inc. Proton conducting mediums for electrochemical devices and electrochemical devices comprising the same
US7314544B2 (en) 2004-09-07 2008-01-01 Lynntech, Inc. Electrochemical synthesis of ammonia
JP2006188370A (en) 2004-12-28 2006-07-20 Nissan Motor Co Ltd Photoelectrochemical cell
EP1871731B1 (en) 2005-04-15 2012-12-26 University Of Southern California Efficient and selective conversion of carbon dioxide to methanol, dimethyl ether and derived products
US7608743B2 (en) 2005-04-15 2009-10-27 University Of Southern California Efficient and selective chemical recycling of carbon dioxide to methanol, dimethyl ether and derived products
EP1900850B1 (en) 2005-06-09 2014-08-20 Arturo Solis Herrera Photoelectrochemical method of separating water into hydrogen and oxygen, using melanins as the central electrolysing element
BRPI0612832A2 (en) 2005-06-23 2010-11-30 Grdc Llc efficient hydrogen production
DE102005032663A1 (en) 2005-07-13 2007-01-18 Bayer Materialscience Ag Process for the preparation of isocyanates
US8075746B2 (en) 2005-08-25 2011-12-13 Ceramatec, Inc. Electrochemical cell for production of synthesis gas using atmospheric air and water
WO2007027876A2 (en) 2005-08-31 2007-03-08 Battelle Memorial Institute Power device and oxygen generator
US20070054170A1 (en) 2005-09-02 2007-03-08 Isenberg Arnold O Oxygen ion conductors for electrochemical cells
JP2009511740A (en) 2005-10-13 2009-03-19 マントラ エナジー オールターナティヴス リミテッド Continuous cocurrent electrochemical reduction of carbon dioxide
AU2012202601B2 (en) 2005-10-13 2014-01-16 Mantra Energy Alternatives Ltd Continuous co-current electrochemical reduction of carbon dioxide
SE531126C2 (en) 2005-10-14 2008-12-23 Morphic Technologies Ab Publ Method and system for production, conversion and storage of energy
US7338590B1 (en) 2005-10-25 2008-03-04 Sandia Corporation Water-splitting using photocatalytic porphyrin-nanotube composite devices
JP4845530B2 (en) * 2006-02-17 2011-12-28 新日本製鐵株式会社 Methanol synthesis catalyst, method for producing the catalyst, and method for producing methanol
ITPD20060141A1 (en) 2006-04-18 2007-10-19 Univ Padova ELECTROCATALIZERS BASED ON CARBO-NITRURI MONO / PLURI-METALLICI FOR POLYMERIC FUEL CELLS, PEFC AND DMFC TYPE AND FOR H2 ELECTRIC GENERATORS
US20070282021A1 (en) 2006-06-06 2007-12-06 Campbell Gregory A Producing ethanol and saleable organic compounds using an environmental carbon dioxide reduction process
US7951283B2 (en) 2006-07-31 2011-05-31 Battelle Energy Alliance, Llc High temperature electrolysis for syngas production
GB0615731D0 (en) 2006-08-08 2006-09-20 Itm Fuel Cells Ltd Fuel synthesis
US7378561B2 (en) 2006-08-10 2008-05-27 University Of Southern California Method for producing methanol, dimethyl ether, derived synthetic hydrocarbons and their products from carbon dioxide and water (moisture) of the air as sole source material
JP2008095173A (en) 2006-09-13 2008-04-24 Sanyo Electric Co Ltd Electrode for electrolysis, electrolytic process using the electrode and electrolytic apparatus using them
US8147659B2 (en) 2006-11-20 2012-04-03 The Regents Of The University Of California Gated electrodes for electrolysis and electrosynthesis
US20080145721A1 (en) 2006-12-14 2008-06-19 General Electric Company Fuel cell apparatus and associated method
JP2007185096A (en) 2007-02-13 2007-07-19 Isao Kajisa Device for reducing carbon dioxide utilizing artificial diamond and artificial sun
EP2132820A4 (en) 2007-04-03 2014-12-24 New Sky Energy Inc Electrochemical system, apparatus, and method to generate renewable hydrogen and sequester carbon dioxide
WO2008147623A2 (en) 2007-04-30 2008-12-04 University Of Florida Research Foundation, Inc. Concurrent o2 generation and co2 control for advanced life support
CA2685866A1 (en) 2007-05-03 2009-01-29 Battelle Memorial Institute Oxygen generation for battlefield applications
AU2008247280A1 (en) 2007-05-04 2008-11-13 Principle Energy Solutions, Inc. Production of hydrocarbons from carbon and hydrogen sources
US20080287555A1 (en) 2007-05-20 2008-11-20 Quaid-E-Azam University Novel process and catalyst for carbon dioxide conversion to energy generating products
US7906559B2 (en) 2007-06-21 2011-03-15 University Of Southern California Conversion of carbon dioxide to methanol and/or dimethyl ether using bi-reforming of methane or natural gas
US8563183B2 (en) 2007-06-26 2013-10-22 The Board Of Trustees Of The Leland Stanford Junior University Integrated dry gasification fuel cell system for conversion of solid carbonaceous fuels
EP2011782A1 (en) 2007-07-02 2009-01-07 Huntsman International Llc Process for the synthesis of carbamates using co2
US8138380B2 (en) 2007-07-13 2012-03-20 University Of Southern California Electrolysis of carbon dioxide in aqueous media to carbon monoxide and hydrogen for production of methanol
WO2009012154A2 (en) 2007-07-13 2009-01-22 University Of Southern California Electrolysis of carbon dioxide in aqueous media to carbon monoxide and hydrogen for production of methanol
US8177946B2 (en) 2007-08-09 2012-05-15 Lawrence Livermore National Security, Llc Electrochemical formation of hydroxide for enhancing carbon dioxide and acid gas uptake by a solution
US20090069452A1 (en) 2007-09-07 2009-03-12 Range Fuels, Inc Methods and apparatus for producing ethanol from syngas with high carbon efficiency
JP5439757B2 (en) 2007-12-07 2014-03-12 ソニー株式会社 Fuel cells and electronics
US20110014100A1 (en) 2008-05-21 2011-01-20 Bara Jason E Carbon Sequestration Using Ionic Liquids
WO2009145624A1 (en) 2008-05-30 2009-12-03 Inoviakem B.V. Use of activated carbon dioxide in the oxidation of compounds having a hydroxy group
CN101328590B (en) * 2008-06-17 2011-03-23 昆明理工大学 Method for converting carbon dioxide into organic compound
FR2934281B1 (en) 2008-07-22 2010-08-27 Inst Francais Du Petrole PROCESS FOR OBTAINING FORMIC ACID BY ELECTRO-REDUCTION OF CO2 IN THE APROTICAL ENVIRONMENT
JP5493572B2 (en) 2008-08-11 2014-05-14 株式会社豊田中央研究所 Photocatalyst and reduction catalyst using the same
US20100133110A1 (en) 2008-10-08 2010-06-03 Massachusetts Institute Of Technology Catalytic materials, photoanodes, and photoelectrochemical cells for water electrolysis and other, electrochemical techniques
CA2694971C (en) 2008-12-11 2012-03-20 Calera Corporation Processing co2 utilizing a recirculating solution
US20100213046A1 (en) 2009-01-06 2010-08-26 The Penn State Research Foundation Titania nanotube arrays, methods of manufacture, and photocatalytic conversion of carbon dioxide using same
EP2382174A4 (en) 2009-01-29 2013-10-30 Trustees Of The University Of Princeton Conversion of carbon dioxide to organic products
US8163429B2 (en) 2009-02-05 2012-04-24 Ini Power Systems, Inc. High efficiency fuel cell system
US8834688B2 (en) 2009-02-10 2014-09-16 Calera Corporation Low-voltage alkaline production using hydrogen and electrocatalytic electrodes
US8506784B2 (en) 2009-05-29 2013-08-13 Uchicago Argonne, Llc Carbon dioxide capture using resin-wafer electrodeionization
US8986621B2 (en) 2009-06-03 2015-03-24 Ixys Corporation Methods and apparatuses for converting carbon dioxide and treating waste material
US7993511B2 (en) 2009-07-15 2011-08-09 Calera Corporation Electrochemical production of an alkaline solution using CO2
GB0912972D0 (en) 2009-07-24 2009-09-02 Univ Exeter Electromechanical methods
WO2011048727A1 (en) * 2009-10-23 2011-04-28 高砂香料工業株式会社 Novel ruthenium carbonyl complex having a tridentate ligand and manufacturing method and usage therefor
US8956525B2 (en) 2009-12-01 2015-02-17 Wisconsin Alumni Research Foundation Buffered cobalt oxide catalysts
US20110114502A1 (en) * 2009-12-21 2011-05-19 Emily Barton Cole Reducing carbon dioxide to products
AU2011208460B2 (en) 2010-01-25 2014-03-06 Ramot At Tel-Aviv University Ltd. Energy storage and generation systems
WO2011094153A1 (en) 2010-01-29 2011-08-04 Conocophillips Company Electrolytic recovery of retained 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
US20110237830A1 (en) 2010-03-26 2011-09-29 Dioxide Materials Inc Novel catalyst mixtures
WO2011123907A1 (en) 2010-04-08 2011-10-13 Katholieke Universiteit Leuven Photo-electrochemical cell
US8591718B2 (en) 2010-04-19 2013-11-26 Praxair Technology, Inc. Electrochemical carbon monoxide production
US8524066B2 (en) * 2010-07-29 2013-09-03 Liquid Light, Inc. Electrochemical production of urea from NOx and carbon dioxide
US9062388B2 (en) 2010-08-19 2015-06-23 International Business Machines Corporation Method and apparatus for controlling and monitoring the potential
CN101931081B (en) * 2010-08-27 2012-03-28 西安交通大学 Preparation method of air diffusion electrode for preparing methanol by electrochemically reducing carbon dioxide
WO2012046362A1 (en) 2010-10-06 2012-04-12 パナソニック株式会社 Method for reducing carbon dioxide
US20120298522A1 (en) 2011-01-11 2012-11-29 Riyaz Shipchandler Systems and methods for soda ash production
SA112330516B1 (en) 2011-05-19 2016-02-22 كاليرا كوربوريشن Electrochemical hydroxide systems and methods using metal oxidation
US8692019B2 (en) 2012-07-26 2014-04-08 Liquid Light, Inc. Electrochemical co-production of chemicals utilizing a halide salt

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060102468A1 (en) * 2002-08-21 2006-05-18 Battelle Memorial Institute Photolytic oxygenator with carbon dioxide and/or hydrogen separation and fixation
US20110114504A1 (en) * 2010-03-19 2011-05-19 Narayanappa Sivasankar Electrochemical production of synthesis gas from carbon dioxide

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP2729601A4 *

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9815021B2 (en) 2010-03-26 2017-11-14 Dioxide Materials, Inc. Electrocatalytic process for carbon dioxide conversion
US10023967B2 (en) 2010-03-26 2018-07-17 Dioxide Materials, Inc. Electrochemical devices employing novel catalyst mixtures
US9181625B2 (en) 2010-03-26 2015-11-10 Dioxide Materials, Inc. Devices and processes for carbon dioxide conversion into useful fuels and chemicals
US9193593B2 (en) 2010-03-26 2015-11-24 Dioxide Materials, Inc. Hydrogenation of formic acid to formaldehyde
US8956990B2 (en) 2010-03-26 2015-02-17 Dioxide Materials, Inc. Catalyst mixtures
US9555367B2 (en) 2010-03-26 2017-01-31 Dioxide Materials, Inc. Electrocatalytic process for carbon dioxide conversion
US9012345B2 (en) 2010-03-26 2015-04-21 Dioxide Materials, Inc. Electrocatalysts for carbon dioxide conversion
US10173169B2 (en) 2010-03-26 2019-01-08 Dioxide Materials, Inc Devices for electrocatalytic conversion of carbon dioxide
US9464359B2 (en) 2010-03-26 2016-10-11 Dioxide Materials, Inc. Electrochemical devices comprising novel catalyst mixtures
US9957624B2 (en) 2010-03-26 2018-05-01 Dioxide Materials, Inc. Electrochemical devices comprising novel catalyst mixtures
US9790161B2 (en) 2010-03-26 2017-10-17 Dioxide Materials, Inc Process for the sustainable production of acrylic acid
US9566574B2 (en) 2010-07-04 2017-02-14 Dioxide Materials, Inc. Catalyst mixtures
US10647652B2 (en) 2013-02-24 2020-05-12 Dioxide Materials, Inc. Process for the sustainable production of acrylic acid
US10774431B2 (en) 2014-10-21 2020-09-15 Dioxide Materials, Inc. Ion-conducting membranes
US10975480B2 (en) 2015-02-03 2021-04-13 Dioxide Materials, Inc. Electrocatalytic process for carbon dioxide conversion
WO2019141827A1 (en) 2018-01-18 2019-07-25 Avantium Knowledge Centre B.V. Catalyst system for catalyzed electrochemical reactions and preparation thereof, applications and uses thereof

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