WO2001072932A1 - Mazout pour pile a combustible et procede de production d'hydrogene a utiliser dans une pile a combustible - Google Patents

Mazout pour pile a combustible et procede de production d'hydrogene a utiliser dans une pile a combustible Download PDF

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Publication number
WO2001072932A1
WO2001072932A1 PCT/JP2001/002649 JP0102649W WO0172932A1 WO 2001072932 A1 WO2001072932 A1 WO 2001072932A1 JP 0102649 W JP0102649 W JP 0102649W WO 0172932 A1 WO0172932 A1 WO 0172932A1
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WO
WIPO (PCT)
Prior art keywords
fuel cell
fuel
fuel oil
oil
volume
Prior art date
Application number
PCT/JP2001/002649
Other languages
English (en)
Japanese (ja)
Inventor
Hiroto Matsumoto
Tadashi Kisen
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.
Priority to AU2001244626A priority Critical patent/AU2001244626A1/en
Publication of WO2001072932A1 publication Critical patent/WO2001072932A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/323—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the present invention relates to a method for producing fuel oil for fuel cells and hydrogen for fuel cells. More specifically, the present invention relates to a fuel cell fuel oil that can efficiently produce hydrogen, does not adversely affect the reforming catalyst and the fuel cell electrode, and the fuel oil. The present invention relates to a method for efficiently producing hydrogen for fuel cells by catalytic partial oxidation treatment. Background art
  • Known types of fuel cells include a phosphoric acid type, a molten carbonate type, a solid oxide type, and a solid polymer type, depending on the type of electrolyte used.
  • hydrogen sources include methanol, liquefied natural gas mainly composed of methane, city gas mainly composed of natural gas, synthetic liquid fuel composed of natural gas as raw material, and petroleum-based fuel.
  • hydrocarbon oils such as gasoline, naphtha, and kerosene has been studied.
  • gasoline has disadvantages such as difficulty in reforming compared to methanol and the like, and short life of the reforming catalyst when producing hydrogen by reforming it. I have. Disclosure of the invention
  • the present invention provides a fuel oil for a fuel cell, which can efficiently produce hydrogen under such a circumstance and does not adversely affect a reforming catalyst or a fuel cell electrode, and this fuel. It is an object of the present invention to provide a method for efficiently producing hydrogen for fuel cells by catalytic partial oxidation using oil.
  • the present inventors have conducted intensive studies to achieve the above object, and as a result, a petroleum-based hydrocarbon oil such as gasoline naphtha containing a specific ratio of an orefin compound has been used as a fuel oil for fuel cells. As a result, they have found that they can meet the purpose, and that hydrogen can be produced efficiently by subjecting the petroleum hydrocarbon oil to catalytic partial oxidation treatment.
  • the present invention has been completed based on such findings.
  • the present invention provides a fuel oil for a fuel cell, characterized by containing 1 to 50% by volume of a modified compound.
  • the present invention also provides a method for producing hydrogen for a fuel cell, which comprises subjecting the fuel oil to a catalytic partial oxidation treatment.
  • Fuel oil of the present invention are those containing Orefi emissions compound at a rate of 1-5 0 volume 0/0.
  • the content of the olefin compound is less than 1% by volume, the effect of promoting the reaction is not exhibited in the catalytic partial oxidation treatment, and the object of the present invention cannot be achieved.
  • the content of the olefin compound exceeds 50% by volume, the reaction promoting effect is not sufficiently exhibited for the amount, and carbon deposition on the catalyst becomes remarkable in the catalytic partial oxidation treatment.
  • the catalyst rapidly deteriorates.
  • the content of the olefin compound is preferably in the range of 5 to 30% by volume in view of the effect of promoting the reaction in the catalytic partial oxidation treatment and the effect of suppressing the deterioration of the catalyst.
  • This olefin compound may be a single substance or a mixture.
  • Preferred examples of the substrate containing this olefin compound include catalytically decomposed gasoline and polymerized gasoline.
  • Catalytic cracking gasoline usually contains 30-40% by volume of off-line components.
  • the polymerization gasoline Li emissions obtained by polymerizing the light Orefi emissions such as propylene Renya butene by-produced by the catalytic cracking unit or a thermal cracking unit containing 9 0 volume 0/0 or more Orefi emissions Compound There is also.
  • the above-mentioned olefin compound or a substrate containing this olefin compound is mixed with another non-genuine refin base material or a non-genuine refin compound, and the content of the olefin compound is adjusted to the above-mentioned range.
  • the range can be controlled and used as fuel oil.
  • non-refined refining base material used at this time for example, desulfurized light naphtha, desulfurized heavy naphtha, isomerized naphtha, or alkylate may be used.
  • unrefined refining base materials may be used alone. Alternatively, two or more kinds may be used in combination.
  • the fuel oil of the present invention one comprising desulfurized light naphtha and / or desulfurized heavy naphtha and polymerized gasoline is preferably used.
  • the ratio between the desulfurized light naphtha and / or the desulfurized heavy naphtha and the polymerized gasoline may be adjusted so that the content of the orefin compound is within the above range. From the viewpoint of reducing the amount, it is preferable that the added amount of the polymerized gasoline is 20 to 30% by volume.
  • the sulfur concentration is preferably 0.5 wt ppm or less.
  • the fuel oil is partially oxidized and reformed in the presence of a reforming catalyst, but the reforming catalyst used at this time is poisoned by the sulfur content in the fuel oil. From the viewpoint of life, it is important to keep the sulfur content in fuel oil below 0.1 ppm by weight. Therefore, if the sulfur concentration exceeds 0.5 weight ppm, it is necessary to install a complicated desulfurization process. If the sulfur concentration is less than 0.5 ppm by weight, for example, a commonly used sulfur adsorbent of Nigel or iron type is installed upstream of the reforming process and is passed through to achieve the desired sulfur concentration. It can be easily desulfurized.
  • the fuel oil is subjected to a contact partial oxidation treatment to produce hydrogen.
  • Methods for producing hydrogen for fuel cells include partial oxidation reforming and steam reforming.
  • the steam reforming method involves the presence of a small amount of an olefin compound.
  • carbon deposition on the catalyst is promoted, and there is not much improvement in reactivity that can reduce the amount of the catalyst. Therefore, in the present invention, the partial oxidation reforming method is employed.
  • a reforming catalyst used in this partial oxidation reforming process there is no limitation, and any known ones can be appropriately selected and used from known catalysts conventionally known as partial oxidation reforming catalysts for hydrocarbon oils.
  • a partial oxidation reforming catalyst for example, a catalyst in which a suitable carrier supports a noble metal such as nickel, zirconium, or ruthenium, rhodium, or platinum can be exemplified.
  • a suitable carrier supports a noble metal such as nickel, zirconium, or ruthenium, rhodium, or platinum
  • ruthenium-based catalyst are preferable.
  • the supported amount of ruthenium 0. 0 5-2 0 weight 0/0 ranges favored arbitrarily by a carrier reference. If the supported amount is less than 0.05% by weight, the partial oxidation reforming activity may not be sufficiently exerted. On the other hand, if it exceeds 20% by weight, the effect of improving the catalytic activity may not be obtained despite the supported amount. It is not so well recognized, but rather economically disadvantaged. Taking into account the catalytic activity and economic efficiency, the more preferable loading amount of ruthenium is from 0.05 to 15% by weight, and particularly preferably from 0.1 to 2% by weight.
  • ruthenium When ruthenium is supported, it can be supported in combination with another metal, if desired.
  • the other metal include zirconium, cono-court, and magnesium.
  • a heat-resistant inorganic oxide is preferable, and specific examples thereof include alumina, silica, zirconia, magnesia, and a mixture thereof. Of these, alumina and zirconia are particularly preferred.
  • alumina and zirconia are particularly preferred.
  • the fuel oil for a fuel cell of the present invention can produce hydrogen efficiently and has no adverse effect on the reforming catalyst and the fuel cell electrode. Also, by using this fuel oil, the reactivity can be increased without adversely affecting the life of the reforming catalyst, so that the amount of the reforming catalyst can be reduced and the apparatus can be downsized.
  • the desulfurized light naphtha containing no Orefi down amount, as a Orefi down compounds, 1 - hexene and (guaranteed reagent) was added at 2 0 volume 0/0 of percentage based on the total amount.
  • the sulfur content at this time was 0.3 ppm by weight. It is then, using a nickel-based adsorptive desulfurization agent (diatomaceous earth carrier 5 0 wt% on the nickel on), normal pressure reactor flow system, 1 2 0 ° C, LHSV 0. Of 5 h 1 Conditions To obtain a desulfurized oil having a sulfur content of less than 0.1 ppm by weight.
  • a partial oxidation reforming treatment was performed by the following method.
  • Flow reactor and ruthenium catalysts (0 ruthenium alumina responsible body. 5 wt%, 1 cobalt. 0 wt%, in terms of oxide of zirconium Niumu 5 weight 0/0, 2 magnesium in terms of oxide
  • ruthenium catalysts (0 ruthenium alumina responsible body. 5 wt%, 1 cobalt. 0 wt%, in terms of oxide of zirconium Niumu 5 weight 0/0, 2 magnesium in terms of oxide
  • the heating temperature of the furnace was set at 450 ° C, The reaction was performed for 5 hours.
  • the conversion of the desulfurized oil was 100%.
  • the hydrogen concentration when this is 6 2 capacity 0/0 on a dry gas composition excluding nitrogen, methane concentration 3 volumes 0/0 der ivy.
  • the conversion was determined by the following equation from the composition of the product gas by gas chromatography and the flow rate of the introduced desulfurized oil.
  • the carbon deposition rate / Q) was calculated from [(length of carbon deposition layer) / (length of total catalyst layer)] X100.
  • Example 1 was carried out in the same manner as in Example 1 except that the amount of 1-hexene was changed from 20% by volume to 5% by volume.
  • the conversion of desulfurized oil is 1 0 0 Q / o
  • the hydrogen concentration is 6 0 Capacity 0 / o
  • main Yun concentration 4 capacity 0/0
  • the highest point temperature is 6 1 0 ° C Atsuta.
  • the carbon deposition rate after 5 hours was 0 Q / 6.
  • Example 3 Example 1 was carried out in the same manner as in Example 1 except that the amount of 1-hexene was changed from 20% by volume to 40% by volume.
  • the conversion of the desulfurized oil was 100% and the hydrogen concentration was 64% by volume.
  • the methane concentration was 1% by volume and the maximum temperature was 65 ° C.
  • the carbon deposition rate was 2%, and the amount of hydrogen generated increased, but slight carbon deposition was observed.
  • Example 1 was carried out in the same manner as in Example 1 except that polymerized gasoline was used instead of 11-hexene.
  • the polymerized gasoline used was produced from propylene as a raw material and using synthetic zeolite as a catalyst. Its composition, Orefu fin min 9 4 wt 0/0, paraffin content of 3 by weight%, has an aromatic content of 3 wt%.
  • the conversion of the desulfurized oil was 100% and the hydrogen concentration was 64% by volume.
  • the methane concentration was 1% by volume and the maximum temperature was 640 ° C.
  • the carbon deposition rate after 5 hours was 0%, and no carbon deposition was observed.
  • Example 1 was carried out in the same manner as in Example 1, except that 11-hexene was not added.
  • the conversion of the desulfurized oil was 100%, the hydrogen concentration was 56% by volume, and the methane concentration was 10% by volume.
  • the amount of methane produced was large and the amount of hydrogen produced was low.
  • the heat generation pattern was gentler than in the example, and the highest point temperature was only 560 ° C. From this fact, when an orefine compound is added, an exothermic reaction occurs rapidly at the inlet of the catalyst layer, and the temperature rise due to heat generation increases, thereby accelerating the hydrogen generation reaction. Therefore, it can be interpreted that the generation of methane is suppressed.
  • the carbon deposition rate after 5 hours was 0%.
  • Example 1 except for changing the addition amount of cyclohexene from 2 0 volume 0/0 6 0% by volume to was carried out in the same manner as in Example 1.
  • the fuel oil of the present invention relates to the production of hydrogen for fuel cells, particularly hydrogen for fuel cells. More specifically, the present invention provides a fuel oil for a fuel cell which can efficiently produce hydrogen, does not adversely affect a reforming catalyst or a fuel cell electrode, and It is suitable for a method for efficiently producing hydrogen for fuel cells by catalytic partial oxidation using this fuel oil.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Health & Medical Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Hydrogen, Water And Hydrids (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Catalysts (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Fuel Cell (AREA)

Abstract

Ce mazout pour pile à combustible se caractérise par le fait qu'il contient de 1 à 50 volumes en pourcentage de composés oléfiniques. L'invention porte également sur un procédé de production d'hydrogène à utiliser dans une pile à combustible, se caractérisant par le fait que le mazout est soumis à une oxydation catalytique partielle. Le mazout et le procédé selon l'invention, qui permettent de produire de l'hydrogène à rendement élevé, n'influent pas de manière préjudiciable sur le catalyseur de reformage ou sur une électrode de la pile à combustible.
PCT/JP2001/002649 2000-03-29 2001-03-29 Mazout pour pile a combustible et procede de production d'hydrogene a utiliser dans une pile a combustible WO2001072932A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2001244626A AU2001244626A1 (en) 2000-03-29 2001-03-29 Fuel oil for fuel cell and method for producing hydrogen for use in fuel cell

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2000-90392 2000-03-29
JP2000090392A JP2001279276A (ja) 2000-03-29 2000-03-29 燃料電池用燃料油及び燃料電池用水素の製造方法

Publications (1)

Publication Number Publication Date
WO2001072932A1 true WO2001072932A1 (fr) 2001-10-04

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PCT/JP2001/002649 WO2001072932A1 (fr) 2000-03-29 2001-03-29 Mazout pour pile a combustible et procede de production d'hydrogene a utiliser dans une pile a combustible

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JP (1) JP2001279276A (fr)
AU (1) AU2001244626A1 (fr)
WO (1) WO2001072932A1 (fr)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH022878A (ja) * 1988-03-12 1990-01-08 Tonen Corp 燃料電池用水蒸気改質触媒
US5510056A (en) * 1993-11-29 1996-04-23 Shell Oil Company Process for the catalytic partial oxidation of hydrocarbons
JPH08196907A (ja) * 1995-01-27 1996-08-06 Idemitsu Kosan Co Ltd ルテニウム触媒の製造方法及び該触媒を用いた炭化水素の水蒸気改質方法
JPH0971789A (ja) * 1995-07-06 1997-03-18 Idemitsu Kosan Co Ltd 無鉛ガソリン
JPH10121064A (ja) * 1996-10-22 1998-05-12 Idemitsu Kosan Co Ltd 無鉛ガソリン
JPH11311136A (ja) * 1998-04-28 1999-11-09 Hitachi Ltd ハイブリッド自動車およびその駆動装置

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10271706A (ja) * 1997-03-24 1998-10-09 Toyota Motor Corp 電源装置および電気自動車
JPH11130405A (ja) * 1997-10-28 1999-05-18 Ngk Insulators Ltd 改質反応装置、触媒装置、それらに用いる発熱・触媒体、及び改質反応装置の運転方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH022878A (ja) * 1988-03-12 1990-01-08 Tonen Corp 燃料電池用水蒸気改質触媒
US5510056A (en) * 1993-11-29 1996-04-23 Shell Oil Company Process for the catalytic partial oxidation of hydrocarbons
JPH08196907A (ja) * 1995-01-27 1996-08-06 Idemitsu Kosan Co Ltd ルテニウム触媒の製造方法及び該触媒を用いた炭化水素の水蒸気改質方法
JPH0971789A (ja) * 1995-07-06 1997-03-18 Idemitsu Kosan Co Ltd 無鉛ガソリン
JPH10121064A (ja) * 1996-10-22 1998-05-12 Idemitsu Kosan Co Ltd 無鉛ガソリン
JPH11311136A (ja) * 1998-04-28 1999-11-09 Hitachi Ltd ハイブリッド自動車およびその駆動装置

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AU2001244626A1 (en) 2001-10-08
JP2001279276A (ja) 2001-10-10

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