US20130228470A1 - Method and apparatus for an electrolytic cell including a three-phase interface to react carbon-based gases in an aqueous electrolyte - Google Patents

Method and apparatus for an electrolytic cell including a three-phase interface to react carbon-based gases in an aqueous electrolyte Download PDF

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US20130228470A1
US20130228470A1 US13/783,102 US201313783102A US2013228470A1 US 20130228470 A1 US20130228470 A1 US 20130228470A1 US 201313783102 A US201313783102 A US 201313783102A US 2013228470 A1 US2013228470 A1 US 2013228470A1
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catalyst
aqueous electrolyte
carbon
reaction
electrolytic cell
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Ed Ite Chen
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VICEROY CHEMICAL Inc
Viceroy Chemical
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Viceroy Chemical
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Priority to RU2014139975A priority Critical patent/RU2014139975A/ru
Priority to CN201380012374.9A priority patent/CN104428449A/zh
Priority to CA2866306A priority patent/CA2866306A1/fr
Priority to US13/783,102 priority patent/US20130228470A1/en
Priority to PCT/US2013/028748 priority patent/WO2013134078A1/fr
Assigned to VICEROY CHEMICAL, INC. reassignment VICEROY CHEMICAL, INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: CHEN, ED I
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    • C25B3/04—
    • 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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
    • C25B11/031—Porous electrodes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • 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
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
    • C25B11/081—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the element being a noble metal
    • 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
    • C25B3/23—Oxidation
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T156/00—Adhesive bonding and miscellaneous chemical manufacture
    • Y10T156/10—Methods of surface bonding and/or assembly therefor

Definitions

  • Some common industrial processes involve the conversion of a gas or components of a gaseous mixture into another gas. These types of processes are performed at high pressures and temperatures. Operational considerations such as temperature and pressure requirements frequently make these types of processes energy inefficient and costly. The industries in which these processes are used therefore spend a great deal of effort in improving the processes with respect to these kinds of considerations.
  • an electrolytic cell comprises: at least one reaction chamber into which, during operation, a aqueous electrolyte and a gaseous feedstock including are introduced, wherein the gaseous feedstock comprises a carbon-based gas; and a pair of reaction electrodes disposed within the reaction chamber, at least one of the reaction electrodes including a solid catalyst and defining, in conjunction with the aqueous electrolyte and the gaseous feedstock, a three-phase interface.
  • a method for chain modification of hydrocarbons and organic compounds comprises: contacting a gaseous feedstock including a carbon-based gas, an aqueous electrolyte, and a catalyst in a reaction area; and activating the carbon-based gas in an aqueous electrochemical reaction at the reaction electrode and yield a product.
  • a method for chain modification of hydrocarbons and organic compounds comprises: contacting an aqueous electrolyte with a a catalyst and a gaseous feedstock including a carbon-based gas within a reaction area; and reacting the aqueous electrolyte, the catalyst, and the gaseous feedstock at temperatures in the range of ⁇ 10 C to 1000 C and at pressures in the range of 0.1 ATM to 100 ATM to yield a long chained hydrocarbon.
  • a gas diffusion electrode comprises: a hydrophobic layer porous to carbon dioxide and impermeable to aqueous electrolytes; a hydrophilic layer bonded to the hydrophobic layer; and a cuprous halide coating disposed about the bonded hydrophobic and hydrophilic layers.
  • a method for fabricating a gas diffusion electrode comprising: bonding a hydrophobic layer porous to carbon dioxide and impermeable to aqueous electrolytes to a hydrophilic layer supporting, a copper catalyst; and treating the copper catalyst to create a cuprous
  • FIG. 1 depicts one particular embodiment of an electrolytic cell in accordance with some aspects of the presently disclosed technique.
  • FIG. 2 graphically illustrates the electrochemical Fischer-Tropsch process in accordance with other aspects of the presently disclosed technique.
  • FIG. 3A-FIG . 3 B depict a copper mesh reaction electrode as may be used in some embodiments.
  • FIG. 4A-FIG . 4 B depict a gas diffusion electrode as may be used in some embodiments.
  • FIG. 5A-FIG . 5 B depict a gas diffusion electrode as may be used in some embodiments.
  • FIG. 6 depicts a portion of an embodiment in which the electrodes are electrically short circuited.
  • FIG. 7 graphically illustrates the process of carbon dioxide to ethylene in accordance with one particular embodiment of the presently disclosed technique.
  • FIG. 8 depicts another embodiment of an electrolytic cell in accordance with another aspect of the presently disclosed technique.
  • FIG. 9 depicts another embodiment of an electrolytic cell in accordance with another aspect of the presently disclosed technique.
  • FIG. 10A-FIG . 10 B depict another embodiment of an electrolytic cell in accordance with another aspect of the presently disclosed technique.
  • FIG. 11 depicts another embodiment of an electrolytic cell in accordance with another aspect of the presently disclosed technique.
  • the presently disclosed technique is a process for converting carbon-based gases such as non-polar organic gases and carbon oxides to longer chained organic gases such as liquid hydrocarbons, longer chained gaseous hydrocarbons, branched-chain liquid hydrocarbons, branched-chain gaseous hydrocarbons, as well as chained and branched-chain organic compounds.
  • the method is for chain modification of hydrocarbons and organic compounds, including chain lengthening, and eventual conversion into liquids including, but not limited to, hydrocarbons, alcohols, and other organic compounds.
  • This process more particularly uses aqueous electrolytes to act as a reducing or oxidizing atmosphere and hydrogen and oxygen source for hydrocarbon gases.
  • the process in the disclosed technique is a chain modification of hydrocarbons and organic compounds using aqueous electrochemical activation of carbon based gases at three-phase interface of a gas-liquid-solid electrode surface.
  • This process turns hydrocarbon gases including, but not limited to, gaseous methane, natural gas, other hydrocarbons, carbon monoxide, carbon dioxide, and/or other organic gases into C 2 + hydrocarbons, alcohols, and other organic compounds.
  • One exemplary product is ethylene (C 2 H 4 ) and alcohols.
  • the process may also turn carbon dioxide (CO 2 ) into one or more of isopropyl alcohol, hydroxyl-3-methyl-2-butanone, tetrahydrofuran, toluene, 2-heptanone, 2-butoxy ethanol, 1-butoxy-2-propanol, benzaldehyde, 2-ethyl-hexanol, methyl-undecanol, methyl-octanol, 2-heptene, nonanol, diethyl-dodecanol, dimethyl-cyclooctane, dimethyl octanol, dodecanol, ethyl-1,4-dimethyl-cyclohexane, dimethyl-octanol, hexadecene, ethyl-1-propenyl ether, dimethyl-silanediol, toluene, hexanal, methyl-2-hexanone, xylene isomer
  • the reaction of carbon based gases may be successfully achieved with an aqueous electrochemical solution serving as a liquid ion source along with the supply for hydrogen or singlet oxygen being provided by the aqueous source through acids and bases.
  • an aqueous electrochemical solution serving as a liquid ion source along with the supply for hydrogen or singlet oxygen being provided by the aqueous source through acids and bases.
  • the reaction may also be adjusted with different pHs or any kind of additive in the electrolytic solution.
  • the reaction utilizes a three phase interface which defines a reaction area.
  • a catalyst, a liquid, and a gas are contacted in the reaction area and an electric potential is applied to make electrons available to the reaction site.
  • hydrocarbons are used as the reactant gas it is possible to create hydrocarbon radicals which then join with other molecules or parts of molecules or themselves to create longer chained hydrocarbons and/or organic molecules.
  • the reaction site can also cause branched chain production by reacting with a newly created molecule and building on that or continuous chain building.
  • propane C 3 H 8
  • chains of molecules can be built by activating the propane molecule.
  • Existing chained molecules can be lengthened, and existing chained molecules can be branched.
  • a simple example is methane (CH 4 ), can be converted to propanol (C 3 H 7 (OH)).
  • Different voltages create different reaction product distributions or facilitate different reaction types.
  • This aqueous electrochemical reaction includes a reaction that proceeds at room temperature and pressure, although higher temperatures and pressures may be used. In general, temperatures may range from ⁇ 10 C to 240 C, or from ⁇ 10 C to 1000 C, and pressures may range from 0.1 ATM to 10 ATM, or from 0.1 ATM to 100 ATM.
  • the process generates reactive activated carbon-based gases through the reaction on the reaction electrodes. On the reaction electrode, the production of activated carbon-based gases occurs.
  • the method introduces a liquid ion source and a gaseous feedstock into a chamber in contact with a catalyst supporting reaction electrode submerged in an electrolyte.
  • the reaction electrode is powered.
  • the technique employs an electrochemical cell such as the one illustrated in FIG. 1 .
  • the electrochemical cell 100 generally comprises a reactor 105 in one chamber 110 of which are positioned two electrodes 115 , 116 , a cathode and an anode, separated by a liquid ion source, i.e., an electrolyte 120 .
  • a liquid ion source i.e., an electrolyte 120 .
  • the identity of the electrodes 115 , 116 as cathode and anode is a matter of polarity that can vary by implementation.
  • the electrode 115 is the anode and the electrode 116 is the cathode. Because of the interchangeability between electrode 115 and 116 and because in some embodiments of the design the electrodes are electrically short circuited, the reaction electrode is considered to be either or both of the electrode 115 and electrode 116 .
  • the gaseous feedstock 130 may be a carbon-based gas, for example, non-polar organic gases, carbon-based oxides, or some mixture of the two.
  • the two chambers are joined by apertures 135 through the wall 140 separating the two chambers 110 , 125 .
  • the reactor 105 may be constructed in conventional fashion except as noted herein. For example, materials selection, fabrication techniques, and assembly processes in light of the operational parameters disclosed herein will be readily ascertainable to those skilled in the art.
  • Catalysts will be implementation specific depending, at least in part, on the implementation of the reaction electrode 116 .
  • suitable catalysts may include, but are not limited to, nickel, copper, iron, tin, zinc, ruthenium, palladium, rhenium, or any of the other transition or lanthanide and actinide metals, or a noble metal such as platinum, palladium, gold, or silver. They may also include products thereof, including for example cuprous chloride or cuprous oxide, other inorganic compounds of catalytic metals, as well as organometallic compounds. Exemplary organometallic compounds include, but are not limited to, tetracarbonyl nickel, lithiumdiphenylcuprate, pentamesitylpentacopper, and etharatedimer.
  • the electrolyte 120 will also be implementation specific depending, at least in part, on the implementation of the reaction electrode 116 .
  • Exemplary liquid ionic substances include, but are not limited to, Polar Organic Compounds, such as Glacial Acetic Acid, Alkali or alkaline Earth salts, such as halides, sulfates, sulfites, carbonates, nitrates, or nitrites.
  • the electrolyte 120 may therefore be, depending upon the embodiment, magnesium sulfate (MgS), sodium chloride (NaCl), sulfuric acid (H 2 SO 4 ), potassium chloride (KCl), hydrogen chloride (HCl), hydrogen bromide (HBr), hydrogen fluoride (HF), potassium chloride (KCl), potassium bromide (KBr), and potassium iodide (KI), or any other suitable electrolyte and acid or base known to the art.
  • the pH of the electrolyte 120 may range from ⁇ 4 to 14 and concentrations of between 0.1M and 3M inclusive may be used. Some embodiments may use water to control pH and concentration, and such water may be industrial grade water, brine, sea water, or even tap water.
  • the liquid ion source, or electrolyte 120 may comprise essentially any liquid ionic substance. In some embodiments, the electrolyte 120 is a halide to benefit catalyst lifetime.
  • the electrochemical cell 100 includes a gas source 145 and a power source 150 , and an electrolyte source 163 .
  • the gas source 145 provides the gaseous feedstock 130 while the power source 150 is powering the electrodes 115 , 116 at a selected voltage sufficient to maintain the reaction at the three phase interface 155 .
  • the three phase interface 155 defines a reaction area.
  • the reaction pressure might be, for example, 10000 pascals or 0.1 ATM to 10 ATM, or from 0.1 ATM to 100 ATM, and the selected pressure may be, for example, between 0.01 V and 10 V.
  • the electrolyte source 163 provides adequate levels of the electrolyte 120 to ensure proper operations.
  • the three phases at the interface 155 are the liquid electrolyte 120 , the solid catalyst of the reaction electrode 116 , and the gaseous feedstock 130 as illustrated in FIG. 6 .
  • the reaction products 160 are generated in both the electrolyte 120 and in the chamber 125 and may be collected in a vessel 165 of some kind in any suitable manner known to the art.
  • the products 160 may be forwarded to yet other processes either after collection or without ever being collected at alt in these embodiments, the products 160 may be streamed directly to downstream processes using techniques well known in the art.
  • FIG. 1 includes only a single reactor 105 . However, in alternative embodiments, multiple units of these may be arranged for greater efficiencies. In a larger single chamber, pressure would more likely have to be adjusted with electrolyte level rather than changes in the pressure of the gaseous feedstock 130 in the chamber 125 .
  • FIG. 1 For example, various instrumentation such as flow regulators, mass regulators, a pH regulator, and sensors for temperatures and pressures are not shown but will typically be found in most embodiments. Such instrumentation is used in conventional fashion to achieve, monitor, and maintain various operational parameters of the process. Exemplary operational parameters include, but are not limited to, pressures, temperatures, pH, and the like that will become apparent to those skilled in the art. However, this type of detail is omitted from the present disclosure because it is routine and conventional so as not to obscure the subject matter claimed below.
  • the reaction is conceptually illustrated in FIG. 2 .
  • the feedstock 130 ′ is natural gas and the electrolyte 120 ′ is Sodium Chloride.
  • Reactive hydrogen ions (H + ) are fed to the natural gas stream 130 ′ through the electrolyte 120 ′ with an applied cathode potential of
  • the molecules may also in turn react with water on the interface to form alcohols, oxygenates, and ketones.
  • the reaction occurs at room temperature and with an applied cathode potential of 0.01V versus SHE to 1.99V versus SHE.
  • the voltage level can be used to control the resulting product.
  • a voltage of 0.01V may result in a methanol product whereas a 0.5V voltage may result in butanol as well as higher alcohols such as dodecanol.
  • These specific examples may or may not be reflective of the actual product yield and are meant only to illustrate how a product produced can be altered with a change in voltage.
  • FIG. 7 graphically illustrates the process of carbon dioxide to ethylene in accordance with one particular embodiment of the presently disclosed technique.
  • the gaseous feedstock 730 is carbon dioxide.
  • a voltage is applied across the cathode 716 and the anode 715 or a electrically short circuited reaction electrode illustrated in FIG. 11 .
  • the electrochemical interface in this reactor prevents the deactivation of carbon dioxide by providing sufficient reactants to the surface of the catalyst to consistently produce the desired products without the buildup of carbon black.
  • the reaction occurs at a temperature of ⁇ 10 C to 210 C and a pressure of 0.1 ATM to 10 ATM to yield ethylene product 765 found in both the gas and electrolyte
  • the reactor 105 can be fabricated from conventional materials using conventional fabrication techniques. Notably, the presently disclosed technique operates at room temperatures and pressures whereas conventional processes are performed at temperatures and pressures much higher. Design considerations pertaining to temperature and pressure therefore can be relaxed relative to conventional practice. However, conventional reactor designs may nevertheless be used in some embodiments.
  • reaction electrode the electrode at which the reaction occurs
  • reaction electrode either the electrode 115 or the electrode 116 , or both, may be considered to be the reaction electrode depending upon the embodiment.
  • an 80 mesh copper mesh is used.
  • This mesh may be plated with high current densities to produce fractal foam structures with high surface areas which may be utilized as catalysts in this reaction.
  • the catalyst 305 is supported on a copper mesh 310 embedded in an ion exchange resin 300 as shown in FIG. 3A .
  • the catalyst 305 can be a plated catalyst or powdered catalyst.
  • the metal catalyst 305 is a catalyst capable of reducing carbon-based gases to products of interest.
  • Exemplary metals include, but are not limited to, metals such as copper, silver, gold, iron, tin, zinc, ruthenium, platinum, palladium, rhenium, or any of the other transition or lanthanide and actinide metals.
  • the metal catalyst is silver, copper, copper chloride or copper oxide.
  • Ion exchange resins are well known in the art and any suitable ion exchange resin known to the art may be used.
  • the ion exchange resin is NAFION 117 by Dupont.
  • the copper wire mesh 310 can be used to structure the catalyst 305 within the resin 300 or it may be used without a resin.
  • the assembly 315 containing the catalyst 305 can be deposited onto or otherwise structurally associated with an electrically conducting paper 320 , as shown in FIG. 3B .
  • Electrical leads (not shown) can then be attached to the copper wire mesh 310 in conventional fashion.
  • the reaction electrode 320 is but one implementation of the reaction electrode 116 in FIG. 1 .
  • the electrical leads may also be connected to short circuit the electrodes. Alternative implementations will be discussed below.
  • the counter electrode 115 and the reaction electrode 116 are disposed within a reactor 105 so that, in use, it is submerged in the electrolyte 120 and the catalyst 305 forms one part of the three-phase interface 155 .
  • electrochemical reduction discussed above takes place to produce hydrocarbons and organic chemicals.
  • the reaction electrode 320 receives the electrical power and catalyzes a reaction between the hydrogen in the electrolyte 120 and the gaseous feedstock 130 .
  • the copper mesh 310 in the illustrated embodiment is a mesh in the range of 1-400 mesh.
  • a gas diffusion electrode 400 comprises a hydrophobic layer 405 that is porous to carbon-based gases but impermeable or nearly impermeable to aqueous electrolytes.
  • a 1 mil thick advcarb carbon paper 410 treated with TEFLON® (i.e., polytetrafluoroethylene) dispersion (not separately shown) is coated with activated carbon 415 with copper 420 deposited in the pores of the activated carbon 415 .
  • the copper 420 may be deposited through a wet impregnation method, electrolytic reduction, or other means of reduction of copper, silver other transition metals into the porous carbon material.
  • This material is then mixed with a hydrophilic binding agent (not shown), such as polyvinyl alcohol (PVA), polyvinyl acetate (PVAc), or Nafion.
  • a hydrophilic binding agent such as polyvinyl alcohol (PVA), polyvinyl acetate (PVAc), or Nafion.
  • An ink is made from the mixture of impregnated graphite, binding agent, and alcohol or other organic solvent. The ink is painted onto the hydrophobic layer 405 and then bonded through any means, such as atmospheric drying, heat press, or other means of application of heat.
  • the copper 420 impregnated into the ion electrode 400 is then made into a cuprous halide through any suitable procedure.
  • One embodiment of the procedure to make the cuprous halide is to submerge the electrode in a solution of hydrochloric acid and cupric chloride, heat to 100° C. for 2 hours.
  • Another embodiment submerges the impregnated electrode 400 in 3 M KBr or 3 M Kl and run a 4 V pulse of electricity to the electrode 400 in order to form a thin film of cuprous halide 425 , shown in cross-section FIG. 4B , in the electrode 400 .
  • the copper particles in the electrode are first plated with silver by electroless plating or another method, creating a thin film of silver over the copper. Copper may then be plated onto the silver and transformed into a halide through procedure previously described.
  • silver particles are deposited into the hydrophilic layer, coated with copper electrolytically, and then the same procedure for the conversion of the copper layer to a copper halide layer is conducted.
  • the gas diffusion electrode uses nanoparticles reduced from a solution of Cupric Chloride with an excess of ascorbic acid and 10 grams of carbon graphite.
  • the amalgam was heated to 100° C. for eight hours. It is then mixed with equal amounts in weight of a hydrophilic binder.
  • a high mesh copper of 200 mesh is allowed to form cuprous chloride in a solution of cupric chloride and hydrochloric acid.
  • This layer of halide on the surface of the catalyst material allows for catalyst regeneration. This accounts for the abnormally high lifetime of the three phase reaction.
  • the result is then treated in a 0.1 to 3M solution of Cupric Chloride heated to 100° C. This treatment is not necessary for the wire mesh catalyst to function.
  • the electrode 400 therefore includes a covering or coating 425 of cuprous chloride to prevent “poisoning” or fouling of the electrode 400 during operation.
  • the electrodes in this embodiment must be copper so that no other metals foul the reaction by creating intermediate products which ruin the efficacy of the surface of the copper.
  • Some embodiments also treat the copper with a high surface area powder by electroplating, which will allow for the generation of greater microturbulence, thereby creating more contact and release between the three phase reaction surface.
  • the cathode and anode are allowed to remain in the same electrolyte in this embodiment. (The electrolyte is filtered through a pump not shown.) The electrolyte is therefore contacted directly to the gas diffusion electrode 400 rather than through the intercession of a polymer exchange membrane.
  • Catalysts in this particular embodiment may include copper, silver, gold, iron, tin, zinc, ruthenium, platinum, palladium, rhenium, or any of the other transition or lanthanide and actinide metals.
  • the catalysts may be formed into a metal foam or alternatively it may be deposited through electroless or electrolytic deposition onto a porous support with a hydrophobic and hydrophilic layer.
  • the electrodes are electrically short circuited (“shorted”) within the electrolyte while maintaining a three phase interface between carbon-based gases and electrolyte in a mixed slurry pumped through the reactor.
  • the catalyst in powder form is mixed with the electrolyte to make a slurry.
  • FIG. 6 depicts a portion 600 of an embodiment in which the electrodes are shorted. In this drawing, only a single electrode 605 is shown but the electric potential is drawn across the electrode 605 . The companion electrode (not shown) is similarly shorted.
  • carbon-based gases or electrolyte gaseous mixture including gaseous feedstock 130 is introduced into the reaction chamber 125 of the reactor 105 under enough pressure to overcome the gravitational pressure of the column of electrolyte, which depends on the height of the electrolyte, to induce the reaction.
  • liquid ion source e.g., a liquid electrolyte
  • the method of operation generally comprises introducing the electrolyte 120 into the reaction chamber 110 into direct contact with the powered electrode surfaces 115 and 116 .
  • the gaseous feedstock 130 is then introduced into the second chamber 125 under enough pressure to overcome the gravitational pressure of the column of electrolyte, which depends on the height of the electrolyte, to induce the reaction to induce the reaction.
  • the electrolyte 120 is filtered, the gaseous feedstock 130 is maintained at a selected pressure to ensure its presence at the three phase interface 155 , and the product 165 is collected.
  • the second chamber 125 is an area for the introduction of a cathode reaction electrode 116 where the three-phase interface 155 will form.
  • Catalysts supported by the reaction electrode 116 include copper, silver, gold, iron, tin, zinc, ruthenium, platinum, palladium, rhenium, or any of the other transition or lanthanide and actinide metals.
  • the catalysts may be formed into a metal foam or alternatively it may be deposited through electroless or electrolytic deposition onto a porous support with a hydrophobic and hydrophilic layer as previously described above.
  • the electrolyte 120 may comprise, for example, potassium chloride (KCI), potassium bromide (KBr), potassium iodide (Kl), or any other suitable electrolyte known to the art.
  • This particular embodiment implements the reaction electrode 116 as the gas diffusion electrode described above with the cuprous halide coating.
  • Alternative embodiments may use another cuprous halide coating the surface of the metal. Cuprous Oxide, Cupric Oxide, and other varying valence states of copper will also work in the reaction.
  • the carbon-based gases will form organic chemicals and form a nearly complete conversion when there is continuous contact to the gaseous feedstock 130 on the three phase interfaces 155 between the liquid electrolyte 120 , the solid catalyst, and the gaseous feedstock 130 .
  • this reaction mechanism also produces organic compounds such as ethers, epoxides, and C5+ alcohols, among other compounds such as ethers, epoxies and long C5+ hydrocarbons which have not been reported in the prior art.
  • the electrolyte 120 should be relatively concentrated at 0.1M-3M and should be a halide electrolyte as discussed above to increase catalyst lifetime.
  • Operating pressures could be ranged from only 10000 pascals or 0.1 atm to 10 atm, though Standard Temperature and Pressures (STP) were sufficient for the reaction.
  • an antioxidant layer of ascorbic acid is mixed with the GDE high porosity carbon.
  • the high porosity carbon includes nanotubes, fullerines, and other specialized formations of carbon as described above.
  • the high porosity carbon is impregnated through reduction of cupric chloride, or other form of carbon. It is then made into a halide by treatment with a chloride solution under the proper pH and temperature of EMF conditions. It also includes a reaction in the solid polymer phase.
  • a paste is made from the impregnated carbon, ascorbic acid, and a hydrophilic binding agent. This paste is painted onto a hydrophobic layer.
  • FIG. 8-FIG . 11 The principles discussed above can readily be scaled up to achieve higher yield. Four such embodiments are shown in FIG. 8-FIG . 11 .
  • reactants 805 e.g., gaseous feedstock and liquid electrolyte, or gaseous feedstock and a slurry of the catalyst and liquid electrolyte
  • a reaction chamber 840 e.g., a reaction chamber 810 in which they are mixed, the resulting mixture 835 then entering a reaction chamber 840 .
  • a plurality of alternating anodes 820 and cathodes 815 are positioned in the reaction chamber 840 .
  • Each of the anodes 820 , cathodes 815 is a reaction electrode at which a three-phase reaction area forms as described above.
  • the resultant product 845 is collected in the chamber 825 , a portion of which is then recirculated back to the chamber 810 via the line 830 .
  • the gaseous feedstock 915 and liquid electrolyte 920 are separately introduced at the bottom of the reaction chamber 925 .
  • a plurality of chambers 930 (only one indicated) are disposed between respective anodes 820 and cathodes 815 .
  • Gaseous feedstock 935 and liquid electrolyte 940 are then reacted in the chambers 930 and the resultant gas product 905 and fouled electrolyte 910 are drawn off the top.
  • a cylindrical embodiment 1000 is shown in FIG. 10A-FIG . 10 B.
  • a mixture 1005 of gaseous feedstock and liquid electrolyte is introduced into the bottom of the embodiment 1000 .
  • the embodiment includes a plurality of alternating, nested anodes 1016 and cathodes 1015 (only one of each indicated). As the mixture 1005 bubbles up it reacts with the catalyst (not shown) on the anodes 1016 and cathodes 1015 that define a plurality of three-phase interface as discussed above. Eventually, the product and fouled electrolyte 1020 are drawn off the top.
  • FIG. 11 Another stacked embodiment 1100 is shown in FIG. 11 .
  • a mixture 1105 of gaseous feedstock and liquid electrolyte is introduced into a chamber 1110 , from which it is then introduced into a reaction chamber 1130 in which a plurality of alternating anodes 1016 and cathodes 1015 are stacked.
  • the anodes 1016 and cathodes 1015 are powered, they are shorted together.
  • they lose their identity as a “cathode” or an “anode” because they all have the same polarity and instead all become reaction electrodes.
  • As the mixture 1105 rises in the reaction chamber 1130 it forms a three-phase reaction at each reaction electrode.
  • the gas product 1405 and the fouled electrolyte 1410 are drawn from the chamber 1125 at the top of the embodiment 1100 .

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US13/783,102 2012-03-03 2013-03-01 Method and apparatus for an electrolytic cell including a three-phase interface to react carbon-based gases in an aqueous electrolyte Abandoned US20130228470A1 (en)

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RU2014139975A RU2014139975A (ru) 2012-03-03 2013-03-01 Электролитическая ячейка, включающая трехфазную границу раздела, для проведения реакций газов на основе углерода в водном электролите
CN201380012374.9A CN104428449A (zh) 2012-03-03 2013-03-01 包括三相界面以使水性电解质中的碳基气体反应的电解装置
CA2866306A CA2866306A1 (fr) 2012-03-03 2013-03-01 Cellule electrolytique comprenant une interface triphasee pour faire reagir des gaz a base de carbone dans un electrolyte aqueux
US13/783,102 US20130228470A1 (en) 2012-03-03 2013-03-01 Method and apparatus for an electrolytic cell including a three-phase interface to react carbon-based gases in an aqueous electrolyte
PCT/US2013/028748 WO2013134078A1 (fr) 2012-03-03 2013-03-01 Cellule électrolytique comprenant une interface triphasée pour faire réagir des gaz à base de carbone dans un électrolyte aqueux

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WO2015051211A3 (fr) * 2013-10-03 2015-11-26 Brown University Réduction électrochimique du co2 à des nanomousses de cuivre
CN106521544A (zh) * 2015-09-15 2017-03-22 中国科学院大连化学物理研究所 二氧化碳电化学还原用多孔电极复合体及其制备和应用
WO2018067632A1 (fr) * 2016-10-04 2018-04-12 Johna Leddy Réduction de dioxyde de carbone et électrochimie de composés carbonés en présence de lanthanides
WO2018232515A1 (fr) * 2017-06-21 2018-12-27 The Governing Council Of The University Of Toronto Catalyseurs à interface de réaction nette pour réduction électrochimique de co2 avec sélectivité améliorée
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
WO2019145112A1 (fr) * 2018-01-29 2019-08-01 Siemens Aktiengesellschaft Électrode poreuse pour la conversion électrochimique de composés organiques en deux phases non miscibles dans un réacteur à flux électrochimique
US10675681B2 (en) 2017-02-02 2020-06-09 Honda Motor Co., Ltd. Core shell
CN113151849A (zh) * 2021-03-24 2021-07-23 厦门大学 一种利用丙烷制备乳酸的方法
WO2021243199A1 (fr) * 2020-05-29 2021-12-02 Newchem21 Inc. Procédé d'oxydation électrochimique d'hydrocarbures
US11299811B2 (en) 2018-01-29 2022-04-12 Board Of Regents, The University Of Texas System Continuous flow reactor and hybrid electro-catalyst for high selectivity production of C2H4 from CO2 and water via electrolysis
CN114373940A (zh) * 2021-12-16 2022-04-19 清华大学 气体扩散电极及其制备方法和应用
WO2022184905A3 (fr) * 2021-03-04 2022-11-03 Totalenergies Onetech Électroréduction de co2 en des produits à carbone multiple dans un acide fort
US11686004B2 (en) * 2019-10-22 2023-06-27 University Of Cincinnati Gas diffusion electrodes with segmented catalyst layers for CO2 reduction

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CN109811364B (zh) * 2019-01-10 2020-10-27 北京化工大学 一种钌/氧化亚铜电催化材料及其制备方法

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US11131028B2 (en) 2012-07-26 2021-09-28 Avantium Knowledge Centre B.V. Method and system for electrochemical reduction of carbon dioxide employing a gas diffusion electrode
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
WO2014160321A3 (fr) * 2013-03-14 2015-02-26 Ed Chen Procédé et appareil pour l'activation électrique d'un catalyseur
WO2015051211A3 (fr) * 2013-10-03 2015-11-26 Brown University Réduction électrochimique du co2 à des nanomousses de cuivre
US10161051B2 (en) 2013-10-03 2018-12-25 Brown University Electrochemical reduction of CO2 at copper nanofoams
CN106521544A (zh) * 2015-09-15 2017-03-22 中国科学院大连化学物理研究所 二氧化碳电化学还原用多孔电极复合体及其制备和应用
WO2018067632A1 (fr) * 2016-10-04 2018-04-12 Johna Leddy Réduction de dioxyde de carbone et électrochimie de composés carbonés en présence de lanthanides
US10774430B2 (en) 2016-10-04 2020-09-15 Johna Leddy Carbon dioxide reduction and carbon compound electrochemistry in the presence of lanthanides
US10675681B2 (en) 2017-02-02 2020-06-09 Honda Motor Co., Ltd. Core shell
WO2018232515A1 (fr) * 2017-06-21 2018-12-27 The Governing Council Of The University Of Toronto Catalyseurs à interface de réaction nette pour réduction électrochimique de co2 avec sélectivité améliorée
US11613819B2 (en) 2017-06-21 2023-03-28 The Governing Council Of The University Of Toronto Catalysts with sharp reaction interface for electrochemical CO2 reduction with enhanced selectivity
WO2019145112A1 (fr) * 2018-01-29 2019-08-01 Siemens Aktiengesellschaft Électrode poreuse pour la conversion électrochimique de composés organiques en deux phases non miscibles dans un réacteur à flux électrochimique
US11299811B2 (en) 2018-01-29 2022-04-12 Board Of Regents, The University Of Texas System Continuous flow reactor and hybrid electro-catalyst for high selectivity production of C2H4 from CO2 and water via electrolysis
US11686004B2 (en) * 2019-10-22 2023-06-27 University Of Cincinnati Gas diffusion electrodes with segmented catalyst layers for CO2 reduction
WO2021243199A1 (fr) * 2020-05-29 2021-12-02 Newchem21 Inc. Procédé d'oxydation électrochimique d'hydrocarbures
WO2022184905A3 (fr) * 2021-03-04 2022-11-03 Totalenergies Onetech Électroréduction de co2 en des produits à carbone multiple dans un acide fort
CN113151849A (zh) * 2021-03-24 2021-07-23 厦门大学 一种利用丙烷制备乳酸的方法
CN114373940A (zh) * 2021-12-16 2022-04-19 清华大学 气体扩散电极及其制备方法和应用

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CN104428449A (zh) 2015-03-18
WO2013134078A1 (fr) 2013-09-12

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