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WO2006068069A1 - Combustible liquide pour pile a combustible et procede de desulfuration - Google Patents

Combustible liquide pour pile a combustible et procede de desulfuration Download PDF

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Publication number
WO2006068069A1
WO2006068069A1 PCT/JP2005/023229 JP2005023229W WO2006068069A1 WO 2006068069 A1 WO2006068069 A1 WO 2006068069A1 JP 2005023229 W JP2005023229 W JP 2005023229W WO 2006068069 A1 WO2006068069 A1 WO 2006068069A1
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WO
WIPO (PCT)
Prior art keywords
desulfurization
fuel
liquid fuel
temperature
fuel cell
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.)
Ceased
Application number
PCT/JP2005/023229
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English (en)
Japanese (ja)
Inventor
Toshimasa Utaka
Kazuhito Saito
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.)
Idemitsu Kosan Co Ltd
Original Assignee
Idemitsu Kosan Co Ltd
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 Idemitsu Kosan Co Ltd filed Critical Idemitsu Kosan Co Ltd
Publication of WO2006068069A1 publication Critical patent/WO2006068069A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0662—Treatment of gaseous reactants or gaseous residues, e.g. cleaning
    • H01M8/0675—Removal of sulfur
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
    • H01M8/0612—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
    • 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
    • Y02E60/50—Fuel cells

Definitions

  • the present invention relates to a liquid fuel for a fuel cell and a method for desulfurizing the liquid fuel. More specifically, the sulfur compound having a ring structure of two or more rings has a content of 2 ppm by mass or less and can be easily desulfurized at a temperature of 80 ° C. or less.
  • the present invention relates to a liquid fuel for a fuel cell and a desulfurization method for a liquid fuel for a fuel cell, which can achieve reduction in cost and cost, and can contribute to higher efficiency and lower cost of a fuel cell system.
  • Saturated content is 50% or more, aromatic content is 50% or less, 1-ring aromatic is 30% or less, 2-ring aromatic is 15% or less, 3 or more aromatics are 10%, and olefin Is 5% by volume or less and the fuel for fuel cell system has a hydrocarbon compound power with an initial distillation point of 130 ° C or higher (see, for example, Patent Document 3), saturated content is 70% by volume or higher, aromatic content Is a fuel for a fuel cell system that has a hydrocarbon compound power with a distillation initial boiling point of 100 ° C. or more (for example, Patent Document 4). Etc.) are known.
  • a desulfurization agent for organic sulfur compounds silver Z alumina, silver Z silica alumina, etc., in which a silver component is supported on a support such as alumina or silica monoalumina, are known (for example, see Patent Document 5). ).
  • a desulfurization agent in which nickel oxide and zinc oxide are supported on activated carbon is also known as a desulfurization agent for hydrocarbons (see, for example, Patent Document 6).
  • Patent Document 1 Japanese Patent Laid-Open No. 2001-279274
  • Patent Document 2 Japanese Patent Laid-Open No. 2001-294874
  • Patent Document 3 Japanese Patent Laid-Open No. 2002-83626
  • Patent Document 4 Japanese Patent Laid-Open No. 2002-80868
  • Patent Document 5 Japanese Unexamined Patent Application Publication No. 2002-316043
  • Patent Document 6 Japanese Patent Laid-Open No. 2003-144930
  • the present invention has been made under such circumstances, and can be easily desulfurized even at a temperature of 80 ° C or lower, and the desulfurizing agent used has a long life and low cost. It is another object of the present invention to provide a liquid fuel for a fuel cell and a desulfurization method for the liquid fuel for a fuel cell that can contribute to higher efficiency and lower cost of the fuel cell system. Means for solving the problem
  • liquid fuels that can be suitably used for fuel cells have a sulfur compound with a ring structure of two or more rings that has a mass of 2 mass ppm or less.
  • the desulfurization treatment can be easily performed, the life of the desulfurization agent used can be increased, and the low cost can be achieved, and the present invention has been completed based on such knowledge.
  • the present invention is composed of
  • a method for desulfurizing a liquid fuel for a fuel cell wherein the liquid fuel for a fuel cell according to any one of (1) to (4) is desulfurized at a temperature of 80 ° C or lower.
  • desulfurization treatment can be easily performed even at a temperature of 80 ° C or lower, and it is possible to achieve a long life and low cost of the desulfurizing agent used, and to achieve high efficiency of the fuel cell system. Further, it is possible to provide a liquid fuel for a fuel cell that can contribute to cost reduction and a method for desulfurizing the liquid fuel for a fuel cell.
  • the liquid fuel for a fuel cell of the present invention requires that the content of a sulfur compound having two or more ring structures be 2 mass ppm or less. If the content of the sulfur compound is 2 mass ppm or less, desulfurization treatment can be easily performed even at a temperature of 80 ° C or less, and the life of the desulfurizing agent to be used can be extended and low cost can be achieved. be able to.
  • the preferred content is 1.5 ppm or less.
  • the liquid fuel for a fuel cell in which the content of the sulfur compound having a ring structure of two or more rings of the present invention is 2 mass ppm or less can be obtained, for example, by the following method.
  • a liquid fuel is produced using a raw material that has a small amount of a sulfur compound having a ring structure of two or more rings or that does not easily produce the sulfur compound in the liquid fuel production process.
  • Hydrodesulfurization treatment is performed using a catalyst containing at least one element selected from Groups 5 to 12 of the periodic table.
  • hydrodesulfurization treatment is carried out by increasing at least one of these operating conditions among the amount of hydrogen addition, hydrogen partial pressure, reaction temperature and reaction pressure.
  • Acid-desulfurization treatment is performed using an oxidizing agent such as ozone or hydrogen peroxide.
  • a liquid fuel is produced by a method combining (1) to (5).
  • Examples of sulfur compounds having two or more ring structures targeted in the present invention are not particularly limited.
  • dibenzothiophene, methyldibenzothiophene, dimethyldibenzothiophene examples thereof include til dibenzothiophene, propyl dibenzothiophene, and butyl dibenzothiophene.
  • dibenzothiophene, 4-methyldibenzothiophene, and 4,6-dimethyldibenzothiophene are examples of sulfur compounds having two or more ring structures targeted in the present invention.
  • dibenzothiophene examples include til dibenzothiophene, propyl dibenzothiophene, and butyl dibenzothiophene.
  • dibenzothiophene, 4-methyldibenzothiophene, and 4,6-dimethyldibenzothiophene examples of sulfur compounds having two or more ring structures targeted in the present invention.
  • the liquid fuel of the present invention includes naphtha, gasoline, kerosene, light oil, heavy oil, and asphaltene oil.
  • kerosene is preferred among the powers including one or a mixture selected from oil sand oil, coal liquefied oil, shale oil oil, GTL, waste plastic oil and biomass fuel.
  • the sulfur content in these liquid fuels is usually 1 ppm by mass or more, and the upper limit is about 50 ppm by mass. If it is less than 1 ppm by mass, the production cost of the liquid fuel becomes high, and problems such as difficulty in handling due to easy foaming. Preferably about 3 mass ppm, and more preferably about 5 mass ppm. On the other hand, if it exceeds 50 ppm, the amount of desulfurizing agent used will increase and the service life will be shortened.
  • the sulfur compound having a ring structure of two or more rings and dibenzothiophene, 4-methyldibenzothiophene, 4,6-dimethyldibenzothiophene, etc. in the liquid fuel of the present invention can be identified by the following method. . That is, dibenzothiophene (Aldrich, 98%), 4-methyldibenzothiophene (Aldrich, 96%) and 4,6 dimethyldibenzothiophene (Aldrich, 97%) are each adjusted to a sulfur concentration of about 1 ppm by mass.
  • Dissolve in toluene to obtain a standard solution introduce it into a gas chromatograph equipped with a sulfur chemiluminescence detector, and identify the reading time of the detected gas chromatograph.
  • a sulfur compound having a longer retention time than dibenzothiophene is identified as a sulfur compound having two or more ring structures.
  • the sulfur content is measured according to JIS K2541-2.
  • the liquid fuel desulfurization method of the present invention includes a method of circulating a sulfur compound-containing liquid fuel in a desulfurization agent, and a sulfur compound-containing liquid in a container such as a tank in which the desulfurization agent is fixed. A method of allowing the fuel to stand or stir is preferred.
  • the desulfurization temperature is 80 ° C or lower. If the desulfurization temperature is 80 ° C or less, the energy cost is low and it is economically advantageous.
  • the lower limit of the desulfurization temperature is appropriately selected in consideration of the fluidity of the liquid fuel to be desulfurized and the desulfurization activity of the desulfurizing agent.
  • the liquid fuel to be desulfurized is kerosene, it is about 40 ° C from the viewpoint of fluidity, and a preferable desulfurization temperature is ⁇ 30 to 60 ° C, particularly around room temperature. If the temperature is lower than ⁇ 40 ° C, the fluidity of the liquid fuel will decrease, and if it exceeds 80 ° C, the adsorption capacity of the desulfurizing agent may decrease.
  • the desulfurization conditions other than the temperature can be appropriately selected according to the properties of the liquid fuel to be desulfurized without any particular limitation.
  • hydrocarbons as fuel for example
  • the temperature is about room temperature and the pressure is about normal pressure to about IMPa'G.
  • Desulfurization treatment is preferable under the condition of liquid hourly space velocity (LHSV) 20hr- 1 or less. At this time, if necessary, a small amount of hydrogen may coexist.
  • LHSV liquid hourly space velocity
  • the desulfurization agent used in the desulfurization method of the present invention is not limited as long as it can be desulfurized at 80 ° C or less, preferably at room temperature, but it is not limited to nickel component, cobalt component, zinc component,
  • a material in which a silver component or the like is supported on a carrier as an active metal component is preferably used.
  • those having at least a silver component supported on a carrier are preferable.
  • the supported silver component include silver nitrate, silver fluoride, silver chloride, silver acetate and silver carbonate. Of these, silver nitrate is preferable in terms of easy availability and handling.
  • a porous carrier is preferred.
  • alumina, silica, silica-alumina, zeolite, cerium oxide, zirconium oxide, cerium oxide-zirconium oxide, oxide There may be mentioned at least one selected from titanium, zinc oxide, white clay, clay, diatomaceous earth and activated carbon. Among them, at least one selected from among the medium strengths of alumina, silica, silica-alumina, acid cerium and acid zirconium. Is preferred.
  • These carriers preferably those large specific surface area instrument such as alumina, silica, silica - the carrier ⁇ alumina and Sani ⁇ titanium, over a specific surface area of 50 m 2 / g things preferred instrument 100 m 2 Zg more Those are more preferred.
  • those having a specific surface area of 20 m 2 / g or more are preferred, and those having a specific surface area of 80 m 2 / g or more are more preferred.
  • the desulfurizing agent after the silver component is supported on alumina, silica or a silica-alumina carrier has the following physical properties. That is, it has physical properties of a specific surface area of 50 m 2 Zg or more, a pore volume of 0.6 ml Zg or less, preferably 0.2 to 0.5 ml Zg, an average pore radius of 60 A or less, preferably 20 to 60 A. is there.
  • the specific surface area should be 50 m 2 Zg or more, the pore diameter is large and relatively small than the pore diameter, and the pore diameter adsorbs sulfur effectively, so the preferred pore diameter is small. If too much, the diffusion of adsorbed sulfur compounds is inhibited.
  • the adsorbent after the silver component is supported on the cerium oxide carrier preferably has the following physical properties. That is, the specific surface area is 20 m 2 / g or more, the crystallite of cerium oxide is 10 ⁇ m or less, and the hydrogen consumption at a temperature of 600 ° C. or less in the temperature reduction test is 200 ⁇ mol / g or more, more preferably 300 ⁇ m. Those having physical properties of molZg or more are preferred.
  • the average crystallite diameter of cerium oxide in the desulfurizing agent is the particle diameter of primary particles measured by a transmission electron microscope.
  • the specific surface area can be measured, for example, by using a specific surface area measuring device manufactured by UASA Iotas Co., Ltd. as follows. That is, about 100 mg of sample is filled in a sample tube, heated and dehydrated in a nitrogen stream at 200 ° C for 20 minutes as a pretreatment, then mixed with nitrogen (30%) Z helium (70%) at liquid nitrogen temperature The specific surface area is obtained from the amount of nitrogen adsorbed by TCD (thermal conductivity detector) gas chromatography method after nitrogen is adsorbed and adsorbed.
  • TCD thermal conductivity detector
  • the pore diameter and pore volume are measured by the BJH method.
  • the supported amount of silver is preferably 0.5 to 50% by mass, more preferably 3 to 30% by mass, based on the total amount of the desulfurizing agent. If the amount is less than 5% by mass, sufficient desulfurization performance may not be exhibited. If the amount exceeds 50% by mass, the particle size of the supported silver component increases and sufficient desulfurization performance may not be exhibited.
  • a known method such as impregnation method, coprecipitation method, kneading method, physical kneading method, vapor deposition method, ion exchange method, evaporation to dryness method, and the like is not particularly limited. Among them, the impregnation method and the coprecipitation method are preferable. With respect to the shape of the desulfurizing agent, there are no particular restrictions, and examples thereof include powder, pulverized, pellet, tablet, and harcum.
  • a carrier is impregnated with a solution of silver nitrate, silver fluoride, silver chloride, silver acetate, silver carbonate or the like as a silver component, and a hydrate thereof, and the solution is applied at a temperature of about 80 to 150 ° C.
  • the desired desulfurization agent is obtained by drying about night and baking at a temperature of about 80-500 ° C.
  • silica-alumina supporting a silver component As an example of the coprecipitation method, first, an acidic aqueous solution or dispersion of a silver component source and an aluminum source, a key source and an inorganic base are included. A basic aqueous solution is prepared.
  • the former silver component source the salts shown in the above impregnation method and hydrates thereof can be used.
  • the aluminum source alumina hydrates such as aluminum nitrate, pseudoboehmite, boehmite alumina, bayerite and dibsite, and ⁇ -alumina can also be used.
  • the key source for the silica-alumina carrier is not particularly limited as long as it is soluble in an alkaline water solution and becomes silica upon firing.
  • inorganic bases include alkali metal carbonates and hydroxides.
  • the produced solid is thoroughly washed and then separated into solid and liquid, or the produced solid is separated into solid and liquid and washed sufficiently, and then the solid is obtained by a known method at 80 to 150 °. Dry at a temperature of about C.
  • a desulfurization agent in which a silver component is supported on a silica-alumina carrier can be obtained by firing the dried product thus obtained, preferably at a temperature in the range of 80 to 500 ° C.
  • the desulfurization treatment of the sulfur-containing compound-containing liquid fuel can be efficiently performed by using the desulfurization agent supporting the silver component and the other predesulfurization agent in combination. . That is, the breakthrough time can be extended by using the preliminary desulfurization agent in combination.
  • the preliminary desulfurization agent another adsorptive desulfurization agent or hydrodesulfurization catalyst without particular limitation may be used.
  • the adsorptive desulfurization agent is at least selected from the group consisting of manganese component, iron component, cobalt component, nickel component, copper component, zinc component, niobium component, molybdenum component, tungsten component, tantalum component and palladium component.
  • Examples include one in which a porous material is supported, and in particular, one in which at least one selected from among the iron, molybdenum, niobium and tungsten components is selected.
  • the same porous material as that used for supporting the silver component can be used.
  • These adsorptive desulfurization agents can be improved by dehydrogenation beforehand. When a hydrodesulfurization catalyst is used as a preliminary desulfurization agent, a small amount of hydrogen may be added.
  • the numbers in the liquid fuel () used are the total concentrations of dibenzothiophene (DBT), 4-methyldibenzothiophene (4-MDBT), and 4,6-dimethyldibenzothiophene (4,6-DMDBT).
  • Kerosene 1 to 5 as Example 1 and kerosene 6 and 7 as Comparative Example 1 were passed through the obtained desulfurizing agent (5 ml) at room temperature and a liquid hourly space velocity (LHSV) of 20 hr- 1 , respectively.
  • the sulfur concentration in the recovered kerosene obtained after 9 hours was measured according to JIS K2541-2. The results are shown in Table 1.
  • JIS K2541-2 coulometric titration method
  • N.D . is below the lower limit of measurement.
  • the present invention can perform desulfurization easily even at a temperature of 80 ° C or lower, and can achieve a long life and low cost of the desulfurizing agent used, and also achieve high efficiency and low cost of the fuel cell system.
  • the present invention provides a liquid fuel for a fuel cell that can contribute to a strike and a method for desulfurizing the liquid fuel for a fuel cell.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Fuel Cell (AREA)

Abstract

L’invention concerne un procédé de désulfuration permettant de réaliser facilement une désulfuration en préparant un combustible liquide dont la teneur en composés soufrés comportant au moins deux cycles est inférieure ou égale à 2 ppm en masse, et en réalisant la désulfuration à l’aide de ce combustible liquide à une température inférieure ou égale à 80°C. L’invention concerne également un combustible liquide pour pile à combustible permettant non seulement de prolonger la durée de vie utile de l’agent de désulfuration utilisé et d’en réduire le coût, mais aussi d’améliorer le rendement et de réduire le coût du système à pile à combustible. L’invention concerne également un procédé de désulfuration utilisant le combustible liquide pour pile à combustible.
PCT/JP2005/023229 2004-12-20 2005-12-19 Combustible liquide pour pile a combustible et procede de desulfuration Ceased WO2006068069A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2004-367419 2004-12-20
JP2004367419A JP2006173045A (ja) 2004-12-20 2004-12-20 燃料電池用液体燃料および脱硫方法

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WO2006068069A1 true WO2006068069A1 (fr) 2006-06-29

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PCT/JP2005/023229 Ceased WO2006068069A1 (fr) 2004-12-20 2005-12-19 Combustible liquide pour pile a combustible et procede de desulfuration

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JP (1) JP2006173045A (fr)
KR (1) KR20070091296A (fr)
CN (1) CN101084599A (fr)
WO (1) WO2006068069A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5148072B2 (ja) * 2006-05-17 2013-02-20 Ｊｘ日鉱日石エネルギー株式会社 燃料電池コージェネレーションシステム用液体原燃料及び燃料電池コージェネレーションシステム
JP2009209252A (ja) * 2008-03-04 2009-09-17 Cosmo Oil Co Ltd 燃料電池用燃料油
JP2011240273A (ja) * 2010-05-19 2011-12-01 Jx Nippon Oil & Energy Corp 吸着剤及びその製造方法、並びに燃料の脱硫方法
JP5421857B2 (ja) * 2010-05-19 2014-02-19 Ｊｘ日鉱日石エネルギー株式会社 吸着剤及びその製造方法、並びに燃料の脱硫方法

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JPH02307803A (ja) * 1989-05-18 1990-12-21 Osaka Gas Co Ltd リン酸電解液燃料電池の燃料ガスの製造方法
JPH06315628A (ja) * 1992-04-06 1994-11-15 Nippon Oil Co Ltd 燃料電池用燃料ガスの製造方法
JP2001089773A (ja) * 1999-07-21 2001-04-03 Idemitsu Kosan Co Ltd 水素製造用原料油およびその製造方法
JP2001262161A (ja) * 2000-03-15 2001-09-26 Idemitsu Kosan Co Ltd 燃料電池用燃料油
JP2001279274A (ja) * 2000-03-31 2001-10-10 Idemitsu Kosan Co Ltd 燃料電池用燃料油、脱硫方法及び水素の製造方法
JP2002316043A (ja) * 2001-04-18 2002-10-29 Idemitsu Kosan Co Ltd 有機硫黄化合物含有燃料油用脱硫剤及び燃料電池用水素の製造方法
JP2003049172A (ja) * 2001-08-08 2003-02-21 Corona Corp 液体炭化水素燃料の脱硫方法
JP2003064386A (ja) * 2001-08-23 2003-03-05 Mitsubishi Heavy Ind Ltd 燃料ガス中の硫黄化合物を除去するための脱硫剤、この脱硫剤を利用した燃料電池発電システム
JP2004228016A (ja) * 2003-01-27 2004-08-12 Tokyo Gas Co Ltd 固体高分子形燃料電池システム及びその運転方法
JP2004305869A (ja) * 2003-04-04 2004-11-04 Idemitsu Kosan Co Ltd 硫黄化合物除去用吸着剤及び燃料電池用水素の製造方法

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Publication number Priority date Publication date Assignee Title
JPH02307803A (ja) * 1989-05-18 1990-12-21 Osaka Gas Co Ltd リン酸電解液燃料電池の燃料ガスの製造方法
JPH06315628A (ja) * 1992-04-06 1994-11-15 Nippon Oil Co Ltd 燃料電池用燃料ガスの製造方法
JP2001089773A (ja) * 1999-07-21 2001-04-03 Idemitsu Kosan Co Ltd 水素製造用原料油およびその製造方法
JP2001262161A (ja) * 2000-03-15 2001-09-26 Idemitsu Kosan Co Ltd 燃料電池用燃料油
JP2001279274A (ja) * 2000-03-31 2001-10-10 Idemitsu Kosan Co Ltd 燃料電池用燃料油、脱硫方法及び水素の製造方法
JP2002316043A (ja) * 2001-04-18 2002-10-29 Idemitsu Kosan Co Ltd 有機硫黄化合物含有燃料油用脱硫剤及び燃料電池用水素の製造方法
JP2003049172A (ja) * 2001-08-08 2003-02-21 Corona Corp 液体炭化水素燃料の脱硫方法
JP2003064386A (ja) * 2001-08-23 2003-03-05 Mitsubishi Heavy Ind Ltd 燃料ガス中の硫黄化合物を除去するための脱硫剤、この脱硫剤を利用した燃料電池発電システム
JP2004228016A (ja) * 2003-01-27 2004-08-12 Tokyo Gas Co Ltd 固体高分子形燃料電池システム及びその運転方法
JP2004305869A (ja) * 2003-04-04 2004-11-04 Idemitsu Kosan Co Ltd 硫黄化合物除去用吸着剤及び燃料電池用水素の製造方法

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JP2006173045A (ja) 2006-06-29
CN101084599A (zh) 2007-12-05

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