EP2823091A1 - Cellule électrolytique comprenant une interface triphasée pour faire réagir des gaz à base de carbone dans un électrolyte aqueux - Google Patents

Cellule électrolytique comprenant une interface triphasée pour faire réagir des gaz à base de carbone dans un électrolyte aqueux

Info

Publication number
EP2823091A1
EP2823091A1 EP13757822.5A EP13757822A EP2823091A1 EP 2823091 A1 EP2823091 A1 EP 2823091A1 EP 13757822 A EP13757822 A EP 13757822A EP 2823091 A1 EP2823091 A1 EP 2823091A1
Authority
EP
European Patent Office
Prior art keywords
catalyst
aqueous electrolyte
carbon
reaction
gaseous feedstock
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP13757822.5A
Other languages
German (de)
English (en)
Other versions
EP2823091A4 (fr
Inventor
Ed Chen
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Viceroy Chemical Inc
Original Assignee
Viceroy Chemical Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Viceroy Chemical Inc filed Critical Viceroy Chemical Inc
Publication of EP2823091A1 publication Critical patent/EP2823091A1/fr
Publication of EP2823091A4 publication Critical patent/EP2823091A4/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/20—Processes
    • C25B3/25—Reduction
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
    • C25B11/031—Porous electrodes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • 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
    • C25B11/032—Gas diffusion 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
    • C25B3/01—Products
    • C25B3/03—Acyclic or carbocyclic hydrocarbons
    • 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
    • C25B3/05—Heterocyclic 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
    • C25B3/01—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
    • C25B3/23—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
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • 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

  • an electrolytic cell comprises: at least one reaction chamber into 5 which, during operation, a aqueous electro! vie 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 elecirodes 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; andactivatmg 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 is 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 J ATM to 100 ATM to yield a long chained hydrocarbon, so
  • a method for fabricating a gas diffusion electrode comprising :;s 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 halide.
  • ⁇ 16 ⁇ The above presents a simplified summary of the presently disclosed subject matter in order to provide a basic undmtanding of some aspects thereof. The summary is not an exhaustive overview, nor is it intended to identify key or critical elements to delineate the scope of the subject matter claimed below. Its sole pitrpose is to present some concepts in a simplified form as a prelude to the more detailed description set forth below.
  • Figure 1 depicts one particular embodiment of an electrolytic cell in accordance with some aspects of the presently disclosed technique.
  • Figure 2 graphically illustrates the electrochemical Fiseher-Tropsch process in accordance with other aspects of the presently disclosed technique.
  • Figure 3A.- Figure 3B depict a copper mesh reaction electrode as may be used in some embodiments.
  • Figure 4A ⁇ figure 4B depict a gas diffusion electrode as may be used in some embodiments.
  • Figure 5A- Figure 5B depict a gas diffusion electrode as may be used in some embodiments.
  • Figure 6 depicts a portion of an embodiment in which the electrodes are electrically short circuited.
  • Figure 7 graphically illustrates the process of carbon dioxide to ethylene in accordance with one particular embodiment of the presently disclosed technique.
  • Figure 8 depicts another embodiment of aa electrolytic cell in. accordance with another aspect of the presently disclosed technique.
  • Figure 9 depicts another embodiment of an electrolytic cell, in accordance with another aspect of the presently disclosed technique.
  • Figure 1 OA- Figure I OB depict another embodiment of an electrolytic cell in accordance with, another aspec t of the. presently disclosed technique..
  • FIG. 5 depicts another embodiment, of an electrolytic ceil 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 inio 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 s oxidizing atmosphere and hydroge 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 interlace of a g.as ⁇ Siqu.id ⁇ soIid electrode surface.
  • This process turns hydrocarbon gases including, but not limited to, gaseous methane, natural gas, other hydrocarbons, carbon monoxide, carbon
  • 10 dioxide, , and/or other organic gases into (3 ⁇ 4 ⁇ hydrocarbons, alcohols, and other organic coropounds.
  • One exemplary product is ethylene (C2H4) and alcohols.
  • the process may also turn carbon dioxide (CO;;) into one or more of isopropyl alcohol, hydroxyl-3-methyl-2- bi!tanone, tetrahydrofiiran, toluene, 2-heptanone, 2-bu oxy ethano!, l-butoxy-2-propanoL ben .aklebyde, 2-elhyl-hexanol, methyl-undecanoi, etbyl-ocianol, 2-heptene, nonanoi,
  • the reaction of carbon based gases may be successfully achieved with an aqueous electrochemical solution serving as a liquid ion source along with die supply for hydrogen or singlet oxygen being provided by the aqueou source through acids and bases.
  • an aqueous electrochemical solution serving as a liquid ion source along with die supply for hydrogen or singlet oxygen being provided by the aqueou source through acids and bases.
  • the reaction may also be adjusted with differenl 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 30 applied io make electrons avaiiable 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 reaciion 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 ⁇ 4
  • 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 propanoi (Cd:i ? (OB)). Different voltages create different reaciion product distributions or facilitate different reaction types.
  • CH 4 methane
  • OB propanoi
  • 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 -10C to 240C, or from -.I C to !OOOC, and pressures may range from .1 ATM to 10 ATM, or from .1 ATM to 1 0 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 gase occurs.
  • 0036 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 Figure 1 .
  • the electrochemical cell 100 generally comprises a reactor 105 in one chamber 1 10 of which are positioned two electrodes 1 15, 1 16, 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 electrode 1 15 is the anode and the electrode 1 16 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 1 1 5 and electrode 116.
  • the gaseous feedstock .13 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 i 10, 125.
  • the reactor 1 5 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 disciosed 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 1 .16.
  • suitable catalysts may include, but are not limited to, nickel, copper, iron, tin, -zinc, ruthenium, palladium, rhenium, or any of the other transition or ianthanide 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 organometailic compounds.
  • Exemplary organomeialiic compounds include, but are not limited to, tetracarbonyl nickel, litliiirmdiphesiylcuprate, pentamesitylpentacopper, and etharatediroer.
  • the electrolyte 120 will also be implementation specific depending, at least in pari., on the implementation of the reaction electrode ! 16.
  • 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 haf ides, sulfates, sulfites, carbonates, nitrates, or nitrites.
  • the electrolyte 120 may therefore be, depending upon the embodiment, magnesium sulfate ( gS), sodium chloride (NaCl), sulfuric acid (H 2 SO 4 ), potassium chloride (KC1), hydrogen chloride (HCl), hydrogen bromide (HBr), hydrogen fluoride (H ), potassium chloride C!), potassium bromide (KBr), and potassium iodide ( l), 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 0.1 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 i n 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 1 15, 1 16 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, 1 000 pascals or 0.1 .ATM to 10 ATM, or from .1 ATM to 100 ATM, and the selected pressure may be, for example, between .01 V and 10 V.
  • the electrolyte source 163 provides adequate levels of the electrolyte 120 to ensure proper operations.
  • 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, hi some embodiments, the products .160 may be lonvarded to yet other processes either after collection or without ever being collected at all, la these embodiments, the products 160 may be streamed directly to downstream processes using techniques well known in the art.
  • Figure 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 press ure of the gaseous feedstock 130 in the chamber 125.
  • Exemplary operational parameters include, but. are not limited to, pressures, temperatures, pH, and the like thai 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 conceptuall illustrated in Figure 2, In this embodiment 200, the feedstock 1.30' is natural gas and the electrolyte 120' is Sodium. Chloride. Reactive hydrogen ions (FT) 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. In one example of this reaction, the reaction occurs at room temperature and with an applied cathode potential of 0.0.1V versus SHE to 1.99V versus SHE.
  • FT reactive hydrogen ions
  • 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 7H and the anode 715 or a electrically short, circuited reaction electrode illustrated, in Figure 1 1.
  • the electrochemical interlace in this reactor prevents the deactivation of carbon dioxide by
  • reaction occurs at a temperature of - I OC to 210C and a pressure of .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. 3 practice. However, conventional reactor designs may nevertheless he used in some embodiments.
  • the presently disclosed technique admits variation in the implementation of the electrode at which the reaction occurs, hereafter referred to as the '"reaction electrode".
  • the electrode I ⁇ 5 or the electrode 11 6, or both may be considered to be the reaction eleciode 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 catalysis in this reaction.
  • the catalyst 305 is supported on a copper mesh 310 embedded i» an ion exchange resin 300 as shown in Figure 3 A.
  • 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 lanfhanide and actirside 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 he used.
  • the ion exchange resin is AFION 117 by Dtrpont
  • 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 Figure 3.8, 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 i 16 hi Figure 1.
  • the electrical leads may also be connected to short circuit the electrodes. Alternative implementations will be discussed ' below.
  • the counter electrode 1 15 and the reaction electrode 1 6 are.
  • 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 3 it) in the illustrated embodiment is a mesh in the range of I - 400 mesh.
  • a gas diffusion electrode 400 comprises a hydrophobic layer 405 that is parens to carbon-based gases but impermeable or nearly impermeable to aqueous electrolytes, lit one embodiment of tire electrode 400, a Irail (hick advcarb carbon paper 410 treated with TEFLON® (i.e. , polytetrafluaroe&y!ene) 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, 5 silver other transition metals into the porous carbon .
  • This material is then mixed with a hydrophilic binding agent (not shown), such as .polyvinyl alcohol (FVA), polyvinyl acetate (PVAc), or National.
  • a hydrophilic binding agent such as .polyvinyl alcohol (FVA), polyvinyl acetate (PVAc), or National.
  • An ink is made front 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 jo atmospheric drying, heat press, or other means of application of beat,
  • the copper 42 impregnated into the ion electrode 400 is then made into a •cuprous haiide through any suitable procedure.
  • One embodiment of the procedure to make the cuprous haiide is to submerge the electrode in a solution of hydrochloric acid, and cupnc chloride, heat to 100X for 2 hours.
  • Another embodiment submerges the impregnated !i 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 cuproits haiide 425, shown in cross-section Figure 48, 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.
  • :3 ⁇ 4t Copper may then be plated onto the silver and transformed into a haiide through procedure previously described, hi another embodiment, silver particles are deposited into the hydrophilic layer, coated with copper eiectro.hlica.Hy, and then the same procedure for the conversion of the copper layer to a copper haiide layer is conducted.
  • the gas diffusion electrode uses nanoparticles reduced 25 from a solution of Cupric Chloride with an excess of ascorbic acid and 10 grams of carbon graphite. The amalgam was heated to KX 'C for eight hours. It is then, mixed with equal amoun ts 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 haiide 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 J to 3 solution of Cupric Chloride heated to 100°C. This treaiment 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 "potsomng" or fouling of the electrode 400 during operation.
  • the electrodes in this embodiment must he 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 ether transition or lanthamde and actintde metals, in addition, 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 hydrophilk 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.
  • Figure 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.
  • liquid ion source e.g., a liquid electrolyte
  • the method of operation generally comprises introducing the electrolyte ! 20 into the reaction chamber 1 10 into direct contact with the powered electrode surfaces 1 15 and 1 16.
  • 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 reactiorito 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 i collected.
  • the second chamber 125 is an area for the introduction of a cathode reaction electrode 1 16 where the three-phase interface 155 will form.
  • Catalysts supported by the reaction electrode .1 16 include copper, silver, gold, iron, tin, zinc, ruthenium, platinum, palladium, rhenium, or an of the other transition or ianthamde and acimide metals, hi addition, the catalysis 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 hydrophilrc layer as previously described above.
  • the electrolyte 120 may comprise, for example, potassium chloride ( Cl), potassium bromide ( Br), potassium iodide ( l), or any other suitable electrolyte known, to the art.
  • This particular embodiment implements the reaction electrode i. 16 as the gas diffusion electrode described above with the cuprous haJide coaling.
  • Alternative embodiments may use another cuprous haiide coating the surface of the metal. Cuprous Oxide, Cupric Oxide, and other varying valence states of copper will also work in the reaction.
  • 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.
  • fOOTO ' l The electrolyte 120 should be relatively concentrated at JM-3M and should be a halide electrolyte as discussed above to increase catalyst lifetime. The higher the surface area between the reaction electrode 116 and the gaseous chamber 125 on one side and the liquid electrolyte 120 on the other side, the higher the conversion rates. Operating pressures could be ranged from only 10000 pascals or . I aim to 10 atm, though Standard Temperature and Pressures (STP) were sufficient for the reaction.
  • STP Standard Temperature and Pressures
  • an antioxidant layer of ascorbic acid is mixed with the GDE high porosity carbon.
  • the high porosity carbon includes nano tubes, fullermes, 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. Thi paste is painted onto a hydrophobic layer.
  • reactants 805 e.g., gaseous feedstock and liquid electrolyte, or gaseous feedstock and a slurry of the catalyst and liquid electrolyte
  • a plurality of alternating anodes 820 and cathodes 81 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 ihe chamber 825, a portion of which is then recirculated back to the chamber 810 via the line 830, [ ⁇ 74]
  • the gaseous feedstock 15 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 Figure 1 OA- Figure 1 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).
  • the catalyst not shown
  • the product and fouled electrolyte 1020 are drawn off the top.
  • FIG. 1 100 Another stacked embodiment. 1 100 is shown in Figure 1 1.
  • a mixture 1 105 of gaseous feedstock and liquid electrolyte is introduced into a chamber 1 1 10, from which it is then introduced into a reaction chamber 1130 in which, a plurality of alternating anodes 101.6 and cathodes 1015 are stacked.
  • the anodes 1 16 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.
  • the gas product 1405 and the fouled electrolyte 1410 are drawn from the chamber 1125 at the top of the embodiment 1 100.
  • phase '"capable of as used herein is & recognition of the feci that some functions described for the various parts of the disclosed apparatus are performed only when the apparatus is powered and/or in operation.
  • the embodiments illustrated herein include a number of electronic or electro-mechanical parts that, to operate, require- electrical power. Even when provided with power, some functions described herein only occur when in operation.
  • some embodiments of the apparatus of the invention are "capable of performing the recited functions even when the are not actually performing them— i.e., when there is no power or when they are powered but not in operation,

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

Abstract

Procédé permettant de convertir des gaz à base de carbone tels que des gaz organiques non polaires et des oxydes de carbone en des gaz organiques à chaîne plus longue tels que des hydrocarbures liquides, des hydrocarbures gazeux à chaîne plus longue, des hydrocarbures liquides à chaîne ramifiée, des hydrocarbures gazeux à chaîne ramifiée, ainsi que des composés organiques à chaîne et à chaîne ramifiée. En général, le procédé est destiné à une modification de chaîne d'hydrocarbures et de composés organiques, y compris un allongement de chaîne, et une conversion éventuelle en liquides comprenant, mais non exclusivement, des hydrocarbures, des alcools, et d'autres composés organiques.
EP13757822.5A 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 Withdrawn EP2823091A4 (fr)

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US201261606398P 2012-03-03 2012-03-03
US201261608583P 2012-03-08 2012-03-08
US201261639544P 2012-04-27 2012-04-27
US201261713487P 2012-10-13 2012-10-13
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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EP2823091A1 true EP2823091A1 (fr) 2015-01-14
EP2823091A4 EP2823091A4 (fr) 2016-04-20

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RU2014139975A (ru) 2016-04-20
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CN104428449A (zh) 2015-03-18
US20130228470A1 (en) 2013-09-05
CA2866306A1 (fr) 2013-09-12

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