WO2009058170A9 - Cellule d'électrolyse renfermant une anode dépolarisée au dioxyde de soufre et procédé d'utilisation de celle-ci dans la génération d'hydrogène - Google Patents

Cellule d'électrolyse renfermant une anode dépolarisée au dioxyde de soufre et procédé d'utilisation de celle-ci dans la génération d'hydrogène Download PDF

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Publication number
WO2009058170A9
WO2009058170A9 PCT/US2008/009331 US2008009331W WO2009058170A9 WO 2009058170 A9 WO2009058170 A9 WO 2009058170A9 US 2008009331 W US2008009331 W US 2008009331W WO 2009058170 A9 WO2009058170 A9 WO 2009058170A9
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Prior art keywords
anode
electrolysis cell
sulfur dioxide
cathode
separator
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PCT/US2008/009331
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English (en)
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WO2009058170A1 (fr
Inventor
Simon G Stone
Lawrence J Gestaut
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Giner Electrochemical Systems
Univ Northwest
Simon G Stone
Lawrence J Gestaut
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Application filed by Giner Electrochemical Systems, Univ Northwest, Simon G Stone, Lawrence J Gestaut filed Critical Giner Electrochemical Systems
Priority to EP08844637A priority Critical patent/EP2171129A4/fr
Priority to CN200880105455A priority patent/CN101796220A/zh
Priority to JP2010519946A priority patent/JP2010535942A/ja
Publication of WO2009058170A1 publication Critical patent/WO2009058170A1/fr
Publication of WO2009058170A9 publication Critical patent/WO2009058170A9/fr

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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
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • 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
    • C25B1/01—Products
    • C25B1/22—Inorganic acids
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Definitions

  • the present invention relates generally to electrolysis cells and relates more particularly to a novel electrolysis cell comprising a sulfur dioxide-depolarized anode and to a method of using said electrolysis cell to generate molecular hydrogen from water.
  • the sulfur trioxide of above Reaction (1) is then decomposed as follows: (2)
  • the sulfur dioxide of above Reaction (2) is then used to reduce molecular iodine as follows:
  • the hybrid sulfur process begins like the sulfur-iodine process with the decomposition of sulfuric acid into water and sulfur trioxide and with the subsequent decomposition of sulfur trioxide into molecular oxygen and sulfur dioxide.
  • the hybrid sulfur process then differs from the sulfur-iodine process in that the hybrid sulfur process then uses an electrolyzer to conduct the following reactions at its anode and at its cathode, respectively: SO 2 + 2 H 2 O ⁇ H 2 SO 4 + 2H + + 2e " (8)
  • Fig. 1 there is schematically shown a first conventional hybrid sulfur electrolysis cell for performing above Reactions (8) and (9), the first conventional hybrid sulfur electrolysis cell being represented generally by reference numeral 1 1. (For simplicity and clarity, certain standard elements of electrolysis cell 1 1 are not shown or described herein.)
  • Electrolysis cell 1 1 comprises a frame 13.
  • a proton exchange membrane (PEM) 15 is appropriately positioned within frame 13, and an anode 17 and a cathode 19 are positioned against opposing surfaces of PEM 15.
  • Each of anode 17 and cathode 19 typically consists of a metallic material or another electrically-conductive structure.
  • PEM 15, anode 17 and cathode 19 collectively define an electrode membrane assembly 21, assembly 21 dividing the interior of frame 13 into an anode chamber 13-1 and a cathode chamber 13-2.
  • Anode chamber 13-1 includes an inlet 23 and an outlet 25, and cathode chamber 13-2 includes an outlet 27.
  • inlet 23 is used to admit into anode chamber 13-1 a solution of gaseous sulfur dioxide dissolved in aqueous sulfuric acid
  • outlet 25 is used to remove from anode chamber 13-1 the excess aqueous sulfuric acid, as well as any excess suifur dioxide.
  • outlet 27 is used to remove from cathode chamber 13-2 the molecular hydrogen generated at cathode 19, as well as any excess water.
  • electrolysis cell 11 utilizes dissolved sulfur dioxide as the electroactive species for the anode.
  • sulfur dioxide is sparingly soluble in aqueous sulfuric acid. Consequently, there is a limited ability for the solvent to carry the electroactive species to the electrode, which, in turn, results in a low limiting current.
  • One technique that has been used to mitigate this problem has been to increase the pressure of the gaseous species over the supporting electrolyte.
  • the sulfur dioxide is typically introduced at a high pressure, such as 20 bar.
  • the introduction of sulfur dioxide at such a high pressure requires that electrolyzer system 11 and, in particular, frame 13 be engineered to contain gas safely at such a high pressure.
  • Fig. 2 there is schematically shown a second conventional hybrid sulfur electrolysis cell for performing above Reactions (8) and (9), the second conventional hybrid sulfur electrolysis cell being represented generally by reference numeral 51. (For simplicity and clarity, certain standard elements of electrolysis cell 51 are not shown or described herein.)
  • Electrolysis cell 51 is similar in structure to electrolysis cell 11, the principal structural difference between the two electrolysis cells being that electrolysis cell 51 includes a frame 53 divided by assembly 21 into an anode chamber 53-1 and a cathode chamber 53-2, anode chamber 53-1 comprising an inlet 55 and an outlet 57, cathode chamber 53-2 comprising an inlet 59 and an outlet 61.
  • inlet 55 is used to admit into anode chamber 53-1 gaseous sulfur dioxide
  • outlet 57 is used to remove from anode chamber 53-1 the aqueous sulfuric acid generated at anode 17, as well as any excess sulfur dioxide.
  • inlet 59 is used to admit water into cathode chamber 53-2
  • outlet 61 is used to exit from cathode chamber 53-2 the molecular hydrogen generated at cathode 19, as well as any excess water present in cathode chamber 53-2.
  • the water required for the reaction at anode 17 must be supplied by water diffusing through PEM 15 to anode 17 from cathode chamber 53-2.
  • the protons formed at anode 17 must simultaneously be transported through PEM 15 in the opposite direction to enable the formation of molecular hydrogen at cathode 19.
  • These protons are transported through PEM 15 to cathode 19 in their hydrated form, thereby reducing the effectiveness of water transport through PEM to anode 17.
  • the result is a current density limitation arising from the limited water available to anode 17.
  • electrolysis cell 51 also shares the shortcoming that unreacted sulfur dioxide from anode chamber 53-1 may cross PEM 15 to cathode 19, where it may be reduced to elemental sulfur and/or hydrogen sulfide.
  • Patents and publications of interest may include the following, all of which are incorporated herein by reference: U.S. Patent No. 7,261,874 B2, inventors Lahoda et al., which issued August 28, 2007; U.S. Patent Application Publication No. US 2007/0007147 Al, inventor Lahoda, which was published January 1 1, 2007; U.S. Patent No. 5,512,144, inventor Stauffer, which issued April 30, 1996; U.S. Patent No. 4,357,224, inventors Hardman et al., which issued November 2, 1982; U.S. Patent No. 4,330,378, inventors Boltersdorf et al., which issued May 18, 1982; U.S. Patent No.
  • an electrolysis cell suitable for oxidizing sulfur dioxide at an anode and for generating molecular hydrogen at a cathode
  • the electrolysis cell comprising (a) a frame, said frame having an interior; (b) a separator disposed within the interior of said frame to divide said interior into a plurality of chambers, said separator being ionically-conductive, said separator having an anodic- facing surface and a cathodic-facing surface; (c) an anode disposed within the interior of said frame and spaced apart from said anodic-facing surface of said separator to form a first electrolyte chamber therebetween, said anode comprising a fluid diffusion electrode; (d) a first electrolytic solution present in said first electrolyte chamber; and (e) a cathode disposed within the interior of said frame and ionically coupled to the cathodic-facing surface of the separator.
  • an electrolysis cell suitable for oxidizing sulfur dioxide at an anode and for generating molecular hydrogen at a cathode
  • the electrolysis cell comprising (a) a frame, said frame having an interior; (b) an anode disposed within the interior of said frame, said anode being a fluid diffusion electrode; (c) a cathode disposed within the interior of said frame and spaced apart from said anode, said cathode being a gas diffusion electrode, wherein said cathode and said anode define an electrolyte chamber therebetween, a. sulfur dioxide chamber being formed on the opposite side of said anode, and a hydrogen chamber being formed on the opposite side of said cathode; and (d) an electrolytic solution present in said electrolyte chamber.
  • a method for generating molecular hydrogen comprising the steps of: (a) providing an electrolysis cell, said electrolysis cell comprising (i) a separator, said separator being ionically-conductive, said separator having an anodic-facing surface and a cathodic-facing surface; (ii) an anode spaced apart from said anodic-facing surface of said separator to form a first space, said anode comprising a fluid diffusion electrode; and (iii) a cathode ionically coupled to the cathodic-facing surface of the separator; (b) filling the first space between said anode and said separator with an aqueous electrolytic solution; (c) supplying sulfur dioxide to the anode from the side opposite the aqueous electrolytic solution; and (d) supplying current to the electrolysis cell, whereby sulfur dioxide is oxidized at the anode and molecular hydrogen is generated at the cathode.
  • a method for generating molecular hydrogen comprising the steps of: (a) providing an electrolysis cell, said electrolysis cell comprising an anode and a cathode, the anode and the cathode being spaced apart from one another by a space, the space being filled with an aqueous electrolytic solution, the anode comprising a fluid diffusion electrode, the cathode comprising a gas diffusion electrode; (b) supplying sulfur dioxide to the anode from the side opposite the aqueous electrolytic solution; and (c) supplying current to the electrolysis cell, whereby sulfur dioxide is oxidized at the anode and molecular hydrogen is generated at the cathode.
  • Fig. 1 is a schematic diagram of a first example of a conventional hybrid sulfur electrolysis cell, said conventional hybrid sulfur electrolysis cell using an aqueous sulfur dioxide/sulfuric acid liquid electrolyte feed;
  • Fig. 2 is a schematic diagram of a second example of a conventional hybrid sulfur electrolysis cell, said conventional hybrid sulfur electrolysis cell using a direct sulfur dioxide gas feed;
  • Fig. 3 is a schematic diagram of a first embodiment of a hybrid sulfur electrolysis cell constructed according to the teachings of the present invention
  • Fig. 4 is a schematic diagram of a second embodiment of a hybrid sulfur electrolysis cell constructed according to the teachings of the present invention.
  • Fig. 5 is a schematic diagram of a third embodiment of a hybrid sulfur electrolysis cell constructed according to the teachings of the present invention.
  • Fig. 6 is a schematic diagram of a fourth embodiment of a hybrid sulfur electrolysis cell constructed according to the teachings of the present invention
  • Fig. 7 is a schematic diagram of a fifth embodiment of a hybrid sulfur electrolysis cell constructed according to the teachings of the present invention
  • Fig. 8 is a current-voltage plot, illustrating the performance of the electrolysis cell described in Example 1 ;
  • Figs. 9(a) and 9(b) are exploded perspective and perspective views, respectively, of the electrolysis cell used in Example 2.
  • Fig. 10 is a current- voltage plot, illustrating the performance of the electrolysis cell described in Example 2.
  • the present invention is based, at least in part, on the discovery that an improvement in the performance of an electrolysis cell of the type in which sulfur dioxide is oxidized and molecular hydrogen is produced substantially simultaneously therewith may be achieved by utilizing as the anode a porous fluid diffusion electrode (i.e., a gas- diffusion electrode or a liquid-liquid electrode) and by supplying pure sulfur dioxide to the anode from one side thereof while simultaneously providing water and an electrolyte substantially free of sulfur dioxide to the opposite side thereof, said opposite side lying between the anode and the cathode. In this manner, the sulfur dioxide that ultimately reaches the cathode may be limited.
  • a porous fluid diffusion electrode i.e., a gas- diffusion electrode or a liquid-liquid electrode
  • the electrolysis cells of the present invention may utilize separated and unseparated electrolyte compartments.
  • the separators if used, may include but are not limited to, cation exchange membranes, anion exchange membranes, and electrolyte-containing porous barriers, either installed during assembly or formed in situ.
  • FIG. 3 there is schematically shown a first embodiment of a hybrid sulfur electrolysis cell constructed according to the teachings of the present invention, said hybrid sulfur electrolysis cell being represented generally by reference numeral 111. (For simplicity and clarity, certain standard elements of electrolysis cell 111 are not shown or described herein.)
  • Electrolysis cell 111 comprises a frame 113.
  • a separator 115 is appropriately positioned within frame 113 to divide the interior of frame 113 into a pair of chambers, one of the two chambers being a cathodic chamber 113-1.
  • Separator 115 may be an ion exchange membrane and preferably is a proton exchange membrane (PEM), such as a perfluorinated ion exchange membrane of the type commercially available from E.I. du Pont de Nemours and Company (Wilmington, DE) as NAFION ® membrane.
  • separator 115 may be a porous, chemically inert, non-electrically-conductive material whose pores are filled with electrolyte to permit ionic species to be conducted through the pores from one chamber to the other.
  • a porous gas diffusion electrode 117 which serves as an anode, is positioned in the chamber that is located opposite to cathodic chamber 113-1, porous gas diffusion electrode 1 17 being spaced away from separator 115 to subdivide the non-cathodic chamber into an electrolyte chamber 113-2 and a sulfur dioxide chamber 113-3.
  • Gas diffusion electrode 1 17 may be a conventional gas diffusion electrode but is not limited thereto.
  • electrode 117 possesses some or all of the following properties: (1) It is mechanically stable and is capable of sustaining whatever operating differential pressures it encounters; (2) It is sufficiently electrically conductive to serve as a current collector without substantially increasing the cell voltage; (3) It is sufficiently wettable by the electrolyte to be partially wetted internally; (4) It is sufficiently resistant to electrolyte wetting such that the electrolyte is incapable of wetting through to the gas side of the electrode; (5) It is sufficiently catalytically active to promote the oxidation of sulfur dioxide at meaningful rates; and (6) It is dimensionally stable under the operating conditions and voltages that it encounters.
  • gas diffusion electrodes of the type that may be suitable for use in electrolysis cell 111 are disclosed in the following patents, all of which are incorporated herein by reference: U.S. Patent No. 5,047,133, inventor Allen, which issued September 10, 1991; U.S. Patent No. 4,877,694, inventor Solomon et al., which issued October 31, 1989; U.S. Patent No. 4,459,197, inventor Solomon, which issued July 10, 1984; U.S. Patent No. 4,440,617, inventor Solomon, which issued April 3, 1984; U.S. Patent No. 4,431,567, inventors Gestaut et al., which issued February 14, 1984; U.S. Patent No. 4,377,496, inventor Solomon, which issued March 22, 1983; U.S. Patent No.
  • gas diffusion electrode 117 may contain materials, such as carbon, that would not normally be utilized in anode structures for industrial electrolysis applications.
  • anode potential raises to a point that carbon can be directly oxidized to carbon dioxide.
  • specialized valve metal based electrodes are utilized to provide dimensionally stable catalytic structures.
  • the oxidation of sulfur dioxide occurs at potentials less positive than the oxidation of carbon and, under that circumstance, carbon is an acceptable structural material.
  • a cathode 1 19 is positioned within cathodic chamber 1 13-1 and is ionically coupled to with the cathodically-facing surface of separator 115.
  • Cathode 1 19 may consist of a conventional, freestanding, metallic electrode, or cathode 1 19 may take the form of a catalytic decal or structure affixed either by pressure or by bonding to the surface of separator 115.
  • cathode 119 may be a gas diffusion electrode, for example, a porous bonded structure containing platinum and/or carbon.
  • cathode 119 is a gas diffusion electrode
  • such an electrode is preferably fabricated to possess some or all of the following properties: (a) mechanically stable, capable of sustaining whatever operating differential pressures it encounters; (b) sufficiently electrically conductive to serve as a current collector without substantially increasing the cell voltage; (c) sufficiently wettable by the electrolyte to be partially wetted internally; (d) sufficiently resistant to electrolyte wetting such that the electrolyte is incapable of wetting through to the gas side of the electrode; (e) capable of providing gas paths to the side of the GDE opposite the membrane/separator such that the hydrogen gas generated by the GDE is released to that side; (f) sufficiently catalytically active to promote the electrochemical generation of hydrogen at meaningful rates; and (g) dimensionally stable under the operating conditions and voltages that it encounters.
  • the components of electrolysis cell 111 should also be stable in the environments to be encountered and should be capable of operating for sustained periods without corrosion or extraordinary maintenance.
  • Cathode chamber 113-1 includes an outlet 123
  • electrolyte chamber 113-2 includes an inlet 125 and an outlet 127
  • sulfur dioxide chamber 113-3 includes an inlet 129.
  • inlet 129 is used to admit sulfur dioxide gas into sulfur dioxide chamber 113-3
  • inlet 125 is used to admit aqueous sulfuric acid into electrolyte chamber 113-2.
  • the water from electrolyte chamber 113-2 and the sulfur dioxide from sulfur dioxide chamber 113-3 react with one another within the pores of gas diffusion electrode 117, thereby resulting in the production of sulfuric acid, protons and electrons (as described in Reaction (8) above).
  • electrolysis cell 11 1 possesses several advantages over electrolysis cells 1 1 and 51. These advantages include the following: First, in electrolysis cell 111, pure gaseous sulfur dioxide is supplied to and diffuses into the reaction zone within the high-surface-area, porous gas diffusion electrode 117. Thus, the limitations associated with the dissolution of sulfur dioxide into an aqueous sulfuric acid electrolyte are obviated. Second, as there are no unreactive species (such as a solvent) in the sulfur dioxide supply, the consumption of sulfur dioxide results in a pressure loss which actively resupplies additional sulfur dioxide without diffusion limitations. Third, the gap between the gas diffusion electrode 117 and separator 115 presents an additional barrier to the crossover of unreacted sulfur dioxide to cathode 119.
  • unreactive species such as a solvent
  • FIG. 4 there is schematically shown a second embodiment of a hybrid sulfur electrolysis cell constructed according to the teachings of the present invention, said hybrid sulfur electrolysis cell being represented generally by reference numeral 211. (For simplicity and clarity, certain standard elements of electrolysis cell 21 1 are not shown or described herein.)
  • Electrolysis cell 211 is similar in most respects to electrolysis cell 111, the principal difference between the two electrolysis cells being that porous gas diffusion electrode 117 of electrolysis cell 111 is replaced with porous liquid-liquid electrode 217 in electrolysis cell 211.
  • Porous liquid-liquid electrode 217 may be similar or even identical in construction to gas diffusion electrode 117, provided that electrode 117 is capable of being partially permeated by liquid sulfur dioxide.
  • Electrolysis cell 211 may be used in a manner similar to that described above for electrolysis cell 111, except that sulfur dioxide in liquid form, as opposed to sulfur dioxide in gaseous form, is provided to sulfur dioxide chamber 113-3 through inlet 129.
  • the fluids within electrolysis cell 211 may be pressurized, preferably in a balanced fashion. While additional complexities may arise from the containment of the pressure, there are additional advantages associated with electrolysis cell 21 1 : First, the pressure differential across separator 115 can be near zero. Second, the supply of liquid sulfur dioxide further reduces mass transfer limitations associated with its supply to the anode reaction.
  • Electrolysis cell 311 comprises a frame 313.
  • a separator 315 which may be identical to separator 1 15 of electrolysis cell 1 11, is appropriately positioned within frame 313 to divide the interior of frame 313 into a pair of chambers.
  • a porous fluid diffusion electrode 317 serving as an anode, is positioned in one of the two chambers defined by separator 315, fluid diffusion electrode 317 being spaced from separator 315 and subdividing the chamber into a sulfur dioxide chamber 313-1 and an electrolyte chamber 313-2.
  • fluid diffusion electrode 317 may be a gas diffusion electrode like gas diffusion electrode 117 or may be a liquid-liquid electrode like liquid-liquid electrode 217, respectively.
  • a gas diffusion electrode 319 serving as a cathode, is positioned within the other of the two chambers defined by separator 315, gas diffusion electrode 319 being spaced from separator 315 and subdividing the chamber into an electrolyte chamber 313-3 and a hydrogen chamber 313-4.
  • Gas diffusion electrode 319 may be similar or identical to electrode 117.
  • Sulfur dioxide chamber 313-1 includes an inlet 323, electrolyte chamber 313-2 includes an inlet 325 and an outlet 327, electrolyte chamber 313-3 includes an inlet 329 and an outlet 331, and hydrogen chamber 313-4 includes an outlet 333.
  • inlet 329 is used to admit sulfur dioxide into sulfur dioxide chamber 313-1
  • inlet 325 is used to admit aqueous sulfuric acid into electrolyte chamber 313-2.
  • the water from electrolyte chamber 313-2 and the sulfur dioxide from sulfur dioxide chamber 313-1 react with one another within the pores of fluid diffusion electrode 317, thereby resulting in the production of sulfuric acid, protons and electrons (as described in Reaction (8) above).
  • Electrolyte chamber 313-3 is filled with aqueous sulfuric acid entering through inlet 329 and exiting through outlet 331.
  • the protons passing through electrolyte chamber 313-3 to gas diffusion electrode 319 are reduced at gas diffusion electrode 319 to form molecular hydrogen, which is then released into hydrogen chamber 313-4 from the un-wetted side of gas diffusion electrode 319.
  • FIG. 6 there is schematically shown a fourth embodiment of a hybrid sulfur electrolysis cell constructed according to the teachings of the present invention, said hybrid sulfur electrolysis cell being represented generally by reference numeral 411. (For simplicity and clarity, certain standard elements of electrolysis cell 411 are not shown or described herein.)
  • Electrolysis cell 411 comprises a frame 413.
  • a porous fluid diffusion electrode 417 serving as an anode, is disposed within frame 413, and a gas diffusion electrode 419, serving as a cathode, is disposed within frame 413, electrodes 417 and 419 being appropriately positioned within frame 413 to divide the interior of frame 413 into a sulfur dioxide chamber 413-1, an electrolyte chamber 413-2, and a hydrogen chamber 413-3.
  • fluid diffusion electrode 417 may be a gas diffusion electrode like gas diffusion electrode 117 or may be a liquid-liquid electrode like liquid- liquid electrode 217, respectively.
  • Sulfur dioxide chamber 413-1 includes an inlet 423
  • electrolyte chamber 413-2 includes an inlet 425 and an outlet 427
  • hydrogen chamber 413-3 includes an outlet 433.
  • inlet 423 is used to admit sulfur dioxide into sulfur dioxide chamber 413-1.
  • Inlet 425 is used to admit aqueous sulfuric acid into electrolyte chamber 413-2.
  • the water from electrolyte chamber 413-2 and the sulfur dioxide from sulfur dioxide chamber 413-1 react with one another within the pores of fluid diffusion electrode 417, thereby resulting in the production of sulfuric acid, protons and electrons (as described in Reaction (8) above).
  • Electrolysis cell 51 1 is similar in most respects to electrolysis cell 111 and operates in substantially the same manner.
  • electrolysis cell 511 includes a gas diffusion anode 541 that is used in conjunction with a cathode 544 immediately adjacent to a membrane/separator 543.
  • Gaseous sulfur dioxide is provided to a chamber formed by the side of the anode 541 opposite the membrane/separator 543 and an anode flow plate 545. The sulfur dioxide is oxidized within the anode according to Reaction (8) above.
  • the sulfuric acid thus produced accumulates in the aqueous sulfuric acid electrolyte within a gap support 542 and is removed via channels in a gasket about the gap support 542 or in the anode flow plate 545 while the hydrogen ions are transported through the membrane/separator 543 to be reduced at the cathode 544 according to Reaction 9 above. This yields the following net reaction.
  • the cathode flow plate 547 serves the following functions: (i) directs flow of optional water (for membrane hydration) from the cell cathode inlet across the cathode active area; (ii) directs product hydrogen and excess water across the cathode active area and towards the cell cathode outlet; and (iii) provides electrical conductivity to a cathode collector 548, which serves as the negative terminal of the entire assembly.
  • An anode collector 546 serves as the positive terminal and is in mechanical and electrical contact with the anode flow plate 545, which provides electrical conductivity between the anode 541 and the anode collector 546.
  • the following examples are illustrative only and do not limit the present invention.
  • a porous gas diffusion electrode for use as a gas diffusion anode was fabricated by depositing 4 mg/cm 2 of platinum black (Engelhard) suspended in a NAFION ® (1 100EW) ionomer-containing media onto a hydrophobic woven carbonaceous backing (ETEK ELAT). The backing was laminated under elevated temperature and pressure to form a gas diffusion anode. This anode was placed in an unseparated cell equipped with a platinized titanium cathode. As a control, this configuration was operated with hydrogen as the depolarizing gas: hydrogen was supplied to the side of the gas diffusion anode opposite the membrane and a current-voltage curve was obtained.
  • the current-voltage curve so obtained is an approximation of the resistive losses within the cell.
  • reactive gases were excluded from the anode so as to effect the oxidation of water in the aqueous sulfuric acid to oxygen when current was applied to the cell.
  • a current-voltage curve for the water oxidation reaction was obtained.
  • a porous gas diffusion electrode for use as a gas diffusion anode was fabricated by depositing 4 mg/cm 2 of platinum black (Engelhard) suspended in a NAFION ® (1100EW) ionomer-containing media onto a hydrophobic woven carbonaceous backing (ETEK ELAT). The backing was laminated under elevated temperature and pressure to form a gas diffusion anode.
  • This anode was placed in a test cell, equipped with a) a plastic electrolyte gap frame (PEEK), b) a coarse plastic mesh gap support (HDPE), c) a NAFION ® 1 17 membrane, and d) a platinized cathode (see Figs. 9(a) and 9(b)).
  • this configuration was operated with hydrogen as the depolarizing gas, as performed in Example I above: hydrogen was supplied to the side of the gas diffusion anode opposite the membrane and a current-voltage curve was obtained, said curve being shown in Fig. 10. Subsequently, sulfur dioxide was supplied to the side of the gas diffusion anode opposite the membrane and a voltage-current curve was obtained, said curve being shown in Fig. 10.
  • a liquid-liquid depolarized anode could be incorporated into a membrane cell.
  • the membrane cell could be pressurized to approximately 5 atmospheres and liquid sulfur dioxide could be introduced into the non- electrolyte side of the anode, wherein it would permeate into the porous liquid-liquid anode.
  • the electrolysis would be initiated and the pressure on the catholyte would rise due to the generation of hydrogen gas.
  • the catholyte Upon reaching a pressure equal to the anolyte pressure, the catholyte would exit the cell, thereby establishing a balanced pressure across the membrane.
  • a cell could be constructed in an identical fashion to that described in Example 2 except that an asymmetric gas diffusion cathode could be substituted for the platinized titanium cathode.
  • the asymmetric cathode could be fabricated by laminating a porous hydrophilic carbon-polymer layer to a porous, conductive hydrophobic layer with a layer of high surface area platinum deposited onto the side to be joined to the hydrophilic layer.
  • the laminated gas diffusion cathode so fabricated could be operated such that the hydrogen generated would escape the structure to the non-electrolyte side of the cathode, thereby effecting the phase separation of the hydrogen gas from the electrolyte.
  • EXAMPLE 5 A cell could be fabricated as described in Example 4 except that no membrane would be included. In this manner, a common sulfuric acid electrolyte would be established between the anode and the cathode. As the sulfur dioxide utilized to depolarize the anode would be supplied to the gas diffusion anode to the non-electrolyte side and as the hydrogen generated at the cathode would be released to the non-electrolyte side, electrolysis in the absence of a separator would proceed.

Abstract

L'invention porte sur une cellule d'électrolyse et sur un procédé d'utilisation de celle-ci dans la génération d'hydrogène. Conformément à un mode de réalisation, la cellule d'électrolyse inclut un cadre possédant un intérieur. Une membrane échangeuse de protons (PEM) est disposée à l'intérieur du cadre pour diviser l'intérieur en deux chambres. Une anode, sous la forme d'une électrode à diffusion de gaz, est disposée à l'intérieur du cadre et est espacée de la PEM, l'espace entre l'anode et la PEM étant rempli par un acide sulfurique aqueux. Une cathode est disposée à l'intérieur du cadre et est couplée ioniquement à la PEM. Lors de l'utilisation, du dioxyde de soufre gazeux est amené vers le côté de l'anode tourné à l'opposé de la solution d'acide sulfurique, et un courant est appliqué à la cellule d'électrolyse. En conséquence, le dioxyde de soufre est oxydé à l'anode et de l'hydrogène moléculaire est généré à la cathode.
PCT/US2008/009331 2007-08-03 2008-08-01 Cellule d'électrolyse renfermant une anode dépolarisée au dioxyde de soufre et procédé d'utilisation de celle-ci dans la génération d'hydrogène WO2009058170A1 (fr)

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EP08844637A EP2171129A4 (fr) 2007-08-03 2008-08-01 Cellule d'électrolyse renfermant une anode dépolarisée au dioxyde de soufre et procédé d'utilisation de celle-ci dans la génération d'hydrogène
CN200880105455A CN101796220A (zh) 2007-08-03 2008-08-01 包含二氧化硫去极化阳极的电解槽和使用其产生氢的方法
JP2010519946A JP2010535942A (ja) 2007-08-03 2008-08-01 二酸化硫黄によって減極される陽極を備えた電解槽および水素生成における同電解槽の使用方法

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US96347807P 2007-08-03 2007-08-03
US60/963,478 2007-08-03

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WO2009058170A9 true WO2009058170A9 (fr) 2009-06-18

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US20090045073A1 (en) 2009-02-19
WO2009058170A1 (fr) 2009-05-07
JP2010535942A (ja) 2010-11-25
ZA201000807B (en) 2010-10-27

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