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WO2001077267A1 - Combustible destine a etre utilise dans un systeme de pile a combustible - Google Patents

Combustible destine a etre utilise dans un systeme de pile a combustible Download PDF

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Publication number
WO2001077267A1
WO2001077267A1 PCT/JP2001/003096 JP0103096W WO0177267A1 WO 2001077267 A1 WO2001077267 A1 WO 2001077267A1 JP 0103096 W JP0103096 W JP 0103096W WO 0177267 A1 WO0177267 A1 WO 0177267A1
Authority
WO
WIPO (PCT)
Prior art keywords
fuel
fuel cell
volume
cell system
amount
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/JP2001/003096
Other languages
English (en)
Japanese (ja)
Inventor
Kenichirou Saitou
Iwao Anzai
Osamu Sadakane
Michiro Matsubara
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.)
Eneos Corp
Original Assignee
Nippon Mitsubishi Oil Corp
Nippon Oil Corp
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 Nippon Mitsubishi Oil Corp, Nippon Oil Corp filed Critical Nippon Mitsubishi Oil Corp
Priority to AU46890/01A priority Critical patent/AU4689001A/en
Priority to JP2001575121A priority patent/JP4598897B2/ja
Publication of WO2001077267A1 publication Critical patent/WO2001077267A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons

Definitions

  • the present invention relates to a fuel used for a fuel cell system.
  • the fuel for fully utilizing the performance of the fuel cell system has not yet been developed. Not issued.
  • the fuel for a fuel cell system it is often the power generation amount per weight, C 0 2 generation amount per power generation force s larger, good fuel economy force S of the entire fuel cell system, evaporative emission (evaporative Emissions, reformed hornworm medium, water gas shift reaction catalyst, carbon monoxide removal catalyst, fuel cell stack, etc., with low deterioration of the fuel cell system, long initial performance, and short system startup time Good handling properties such as storage stability and bow I fire point are required.
  • the amount of heat required (the amount of heat that balances the amount of preheat and the amount of heat absorbed and absorbed by the reaction) is subtracted from the amount of power generated.
  • Power generation capacity ⁇ The power generation capacity of the entire fuel cell system. Therefore, the temperature required for reforming the fuel is low, the power s and the preheating power s are small, which is advantageous.In addition, the starting time of the system is 5 ', which is advantageous.The weight required for preheating the fuel is also reduced. It is also necessary that the calorific power is small.
  • THC unreacted hydrocarbons
  • an object of the present invention is to provide a fuel suitable for a fuel cell system satisfying the above-mentioned required properties in a well-balanced manner. Disclosure of the invention
  • the present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a fuel containing a specific amount of a hydrocarbon compound having a specific carbon number is suitable for a fuel cell system.
  • the fuel for a fuel cell system according to the present invention is:
  • the content of hydrocarbon compounds having 4 carbon atoms is 15% by volume or less, the content of hydrocarbon compounds having 5 carbon atoms is 5% by volume or more, and the content of hydrocarbon compounds having 6 carbon atoms is contained.
  • the amount is 10% by volume or more.
  • the fuel containing the specified amount of the hydrocarbon compound having the specified number of carbon atoms further includes: Those satisfying such additional requirements are more preferable.
  • a fuel for a fuel cell system having a saturated content of 30% by volume or more having a saturated content of 30% by volume or more.
  • a fuel for a fuel cell system having an aromatic content of 50% by volume or less is a fuel for a fuel cell system having an aromatic content of 50% by volume or less.
  • FIG. 1 is a flowchart of a steam reforming fuel cell system used for evaluating fuel for a fuel cell system according to the present invention.
  • FIG. 2 is a flowchart of a partial oxidation fuel cell system used for evaluating fuel for a fuel cell system of the present invention.
  • the amount of the hydrocarbon compound having a specific carbon number is as follows.
  • the content of hydrocarbon compounds with 4 carbon atoms indicates the content of hydrocarbon compounds with 4 carbon atoms based on the total amount of fuel, and keeps the amount of evaporative gas (evaporation) low. From the point of handling, such as the flash point, it is necessary to have a capacity of 15% by volume or less. It is necessary to have a force of 10% by volume or less. Is most preferred.
  • the content of the hydrocarbon compounds having 5 carbon atoms indicates the content of hydrocarbon compounds having a carbon number of 5 relative to the fuel total amount, it is often the power generation amount per weight, CO 2 occurs It is necessary to be at least 5% by volume because power generation per unit is large and fuel efficiency of the fuel cell system as a whole is low. It is more preferably at least 20% by volume, still more preferably at least 20% by volume, and even more preferably at least 25% by volume. Most preferably, it is 30% by volume or more.
  • the content of hydrocarbon compounds with 6 carbon atoms indicates the content of hydrocarbon compounds with 6 carbon atoms based on the total fuel amount, indicating that the amount of power generation per weight is large and that CO 2 Because of the large amount of power generation per unit and the good fuel efficiency of the fuel cell system as a whole, it is necessary to have a capacity of at least 10% by volume, preferably at least 15% by volume, preferably at least 20% by volume. And more preferably at least 25% by volume, and most preferably at least 30% by volume.In the present invention, the content of the hydrocarbon compound having 7 and 8 carbon atoms is preferred. is not particularly limited about the, since power generation force heard per C0 2 generation amount, usually the total amount of fuel based on the total amount (V (C 7 + C 8 )) as the force element Mashiku of less than 20 volume% used Can be
  • the deterioration of 3ji reforming catalyst can last reduced initial resistance capability s long, the total amount of the number of 10 or more hydrocarbon compounds carbon based fuel total amount (V (C 10 +)) is 20% by volume or less S is preferred, more preferably 10% by volume or less, and most preferably 5% by volume or less.
  • V (C 4 ), V (C 5 ), V (C 6 ⁇ , V (C 7 + C 8 ) ⁇ V (C 10 +) are determined by the gas chromatography method shown below.
  • the column is a methyl silicon capillary column, helium or nitrogen is used as the carrier gas, and a hydrogen ionization detector (FID) is used as the detector.
  • FID hydrogen ionization detector
  • the sulfur content when the sulfur content is 1 mass ppm or more, it means the sulfur content measured by JISK 2541 "Crude oil and petroleum products-sulfur content test method", and when it is less than 1 mass ppm, ASTM D4045-96 It means the sulfur content measured by "Standard Test Method for Sul fur in Petroleum Products by Hydrogenolysis and Rateometric Colorimetry".
  • the content of each of the saturated component, the olefin component and the aromatic component is not limited, but the saturated component (V (S)) is 30% by volume or more, and the olefin component (V (0)) is 35% by volume. % Or less, and the aromatic content (V (Ar)) is preferably 50% by volume or less.
  • the saturated component (V (S)) is 30% by volume or more
  • the olefin component (V (0)) is 35% by volume. % Or less
  • the aromatic content (V (Ar)) is preferably 50% by volume or less.
  • V (S) is often power generation amount per weight, C0 2 generation per generation amount that large heard, good fuel economy force of the entire fuel cell system, THC force s' less that in the exhaust gas, Since the system startup time power S is short, it is preferable that the capacity be 30% by volume or more, more preferably 40% by volume or more, even more preferably 50% by volume or more, and 60% by volume or more. Is still more preferred, 70% by volume or more is even more preferred, 80% by volume or more is even more preferred, and 90% by volume or more is even more preferred. More than 95% by volume is most preferable.
  • V (0) is often power generation amount per weight, C0 2 generation per generation amount that large heard, the deterioration of the reforming catalyst can last reduced initial resistance capability for a long time, that good storage stability
  • the force is preferably 35% by volume or less, more preferably 25% by volume or less, still more preferably 20% by volume or less, and even more preferably 15% by volume or less. Preferably, it is 10% by volume or less.
  • V (S), V (0) and V (A r) are all values measured by the fluorescent indicator adsorption method of JIS K 2 536 “Petroleum products-hydrocarbon type test method”.
  • the ratio of the paraffin content in the saturated component is preferably at least 60% by volume, more preferably at least 65% by volume, even more preferably at least 70% by volume, and at least 75% by volume. % Or more, still more preferably 80% by volume or more, still more preferably 85% by volume or more, and even more preferably 90% by volume or more. Is even more preferred, and is more preferably 95% by volume or more.
  • the above-mentioned saturated content and paraffin content are values determined by the above-described gas chromatography method.
  • the ratio of branched paraffin in paraffin is 30% by volume or more, 50% %, More preferably at least 70% by volume, and most preferably at least 70% by volume.
  • the above paraffin content and the amount of branched paraffin are determined by the gas chromatography This is a value determined by the luffy method.
  • a base material for producing the fuel of the present invention are desulfurized hydrocarbons such as light naphtha, desulfurized light naphtha, isomerized gasoline, desulfurized alkylate obtained by desulfurizing an alkylate, and desulfurized isobutane.
  • desulfurized hydrocarbons such as light naphtha, desulfurized light naphtha, isomerized gasoline, desulfurized alkylate obtained by desulfurizing an alkylate, and desulfurized isobutane.
  • Low sulfur alkylates by low-grade olefins desulfurized light cracked gasoline obtained by desulfurizing the light fraction of cracked gasoline, light fraction of GTL, and desulfurized LPG obtained by desulfurizing LPG.
  • the fuel for the fuel cell system of the present invention includes a colorant for identification, an antioxidant for improving oxidative stability, a metal deactivator, a corrosion inhibitor for corrosion prevention, and cleanliness of the fuel line.
  • Additives such as a detergent for maintaining the lubrication and a lubricity improver for improving the lubricity can be added.
  • the colorant is preferably 1 Oppm or less, more preferably 5 ppm or less.
  • the antioxidant is preferably at most 300 ppm, more preferably at most 200 ppm, even more preferably at most 100 ppm, most preferably at most 1 Opp-m.
  • the metal deactivator is preferably 50 ppm or less, more preferably 30 ppm or less, still more preferably 1 Oppm or less, and most preferably 5 ppm or less.
  • the corrosion inhibitor is preferably 5 Oppm or less, more preferably 3 Oppm or less, still more preferably 1 Oppm or less, and most preferably 5 ppm or less.
  • the detergent is preferably at most 300 ppm, more preferably at most 200 pm, most preferably at most 1,00 ppm.
  • the lubricity improver is preferably 300 ppm or less, more preferably 200 ppm or less, and even more preferably 100 ppm or less.
  • the fuel of the present invention is used as a fuel for a fuel cell system.
  • the fuel cell system according to the present invention includes a fuel reformer, a carbon monoxide purifying device, a fuel cell, and the like, and the fuel of the present invention is suitably used for any fuel cell system.
  • the fuel reformer is for reforming the fuel to obtain hydrogen, which is the fuel of the fuel cell.
  • a reformer specifically, for example,
  • a steam reforming reformer that mixes heated and vaporized fuel with steam and reacts by heating in a catalyst such as copper, nickel, platinum, ruthenium, etc., to obtain a product containing hydrogen as a main component.
  • a partially oxidized reformer that mixes heated and vaporized fuel with air and reacts with or without a catalyst such as copper, nickel, platinum, ruthenium, etc. to obtain a product containing hydrogen as a main component.
  • the heated and vaporized fuel is mixed with steam and air, and the partial oxidation reforming of (2) is performed in the former stage of the catalyst layer of copper, nickel, platinum, ruthenium, etc., and in the latter stage, the partial oxidation reaction (1)
  • the steam reforming of (1) is carried out by using the heat generation to obtain a product comprising hydrogen as a main component.
  • the carbon monoxide purifier removes carbon monoxide contained in the gas generated by the above reformer and becomes a catalyst poison of the fuel cell.
  • a selective oxidation reactor that converts carbon monoxide into carbon dioxide by mixing the reformed gas with compressed air and reacting it in a catalyst such as platinum or ruthenium is mentioned. used.
  • fuel cells include solid polymer fuel cells (PEFC), phosphoric acid fuel cells (PAFC), molten carbonate fuel cells (MCFC), and solid oxide fuel cells (SOFC). ) And the like. .
  • PEFC solid polymer fuel cells
  • PAFC phosphoric acid fuel cells
  • MCFC molten carbonate fuel cells
  • SOFC solid oxide fuel cells
  • Example 1 the fuel cell system as described above is used for electric vehicles, conventional hybrid vehicles of an engine and electricity, portable power sources, distributed power sources, home power sources, and cogeneration systems.
  • Table 1 shows the properties and the like of each base material used for each fuel in the examples and comparative examples.
  • the heat capacity and latent heat of vaporization were determined by the content of each component determined by the gas chromatography method described above, and by the 'I Vo l ⁇ of the Technical Data Data Book 1 e um Ref in ⁇ 1, Chap. 1 Gene ra 1 Data, Table 1 C 1 ”was calculated based on the numerical value per unit weight for each component.
  • Table 2 shows the properties of each fuel used in Examples and Comparative Examples. Table 1
  • the fuel and water were vaporized by electric heating, and led to a reformer filled with a noble metal catalyst and maintained at a specified temperature with an electric heater to generate a reformed gas rich in hydrogen.
  • the temperature of the reformer is the lowest temperature at which reforming is performed completely in the initial stage of the test.
  • the reformed gas is led to a carbon monoxide treatment unit (water gas shift reaction) together with water vapor, and 3i (converts carbon monoxide in the raw gas to carbon dioxide), and the generated gas is led to a polymer electrolyte fuel cell to generate electricity. Done.
  • a carbon monoxide treatment unit water gas shift reaction
  • 3i converts carbon monoxide in the raw gas to carbon dioxide
  • the fuel was gasified by electric heating, and the preheated air was charged with a precious metal catalyst and led to a reformer maintained at 110 ° C with an electric heater to generate hydrogen-rich reformed gas. .
  • the reformed gas is led to a carbon monoxide treatment device (water gas shift reaction) together with water vapor to convert carbon monoxide in the reformed gas into carbon dioxide, and the generated gas is guided to a polymer electrolyte fuel cell to generate electricity.
  • a carbon monoxide treatment device water gas shift reaction
  • Figure 2 shows a flowchart of the partial oxidation fuel cell system used for the evaluation.
  • a sample filling hose was attached to the filler port of a 20-litre gasoline carrying can, and the attachment part was completely sealed. Each liter was filled with 5 liters of fuel while the vent valve of the can was open. After filling, the air vent valve was closed and left for 30 minutes. After standing, an activated carbon adsorption device was attached to the tip of the air release valve, and the valve was opened. Immediately, 10 liters of each fuel were supplied from the filler port. Five minutes after refueling, leaving the air release valve open, the activated carbon was allowed to absorb steam, and then the weight increase of the activated carbon was measured. The test was performed at a constant temperature of 25 ° C.
  • Each fuel was filled with oxygen in a pressure-resistant sealed container, heated to 100 ° C, left for 24 hours while maintaining the temperature, and evaluated by the real gum test method specified in JISK2261 .
  • Table 3 shows the measured values and calculated values.
  • the fuel for a fuel cell system is a fuel that can obtain high-output electric energy with a small performance deterioration ratio and that satisfies various performances for a fuel cell.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Fuel Cell (AREA)

Abstract

L'invention concerne un combustible destiné à être utilisé dans un système de pile à combustible contenant des composés d'hydrocarbures présentant quatre atomes de carbone dans une quantité de 15 % en volume ou moins, des composés d'hydrocarbures présentant cinq atomes de carbone dans une quantité de 5 % en volume ou davantage, des composés présentant six atomes de carbone dans une quantité de 10 % en volume ou davantage. Le combustible présente un rendement énergétique accru généré par son poids et par la quantité CO2 formée, une meilleure consommation du combustible, des émissions par évaporation réduites, de bonnes propriétés de manipulation telle qu'une bonne stabilité de stockage et un point éclair convenable, ainsi que des calories réduites requises pour le préchauffage. De plus, le combustible permet au système de pile à combustible utilisant ce dernier de conserver ses performances initiales pendant une durée prolongée, du fait qu'il réduit la détérioration du système de pile à combustible comprenant un catalyseur de reformage, un catalyseur de réaction de conversion du gaz à l'eau, un catalyseur d'élimination du monoxyde de carbone ainsi qu'un empilement de pile à combustible.
PCT/JP2001/003096 2000-04-10 2001-04-10 Combustible destine a etre utilise dans un systeme de pile a combustible Ceased WO2001077267A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU46890/01A AU4689001A (en) 2000-04-10 2001-04-10 Fuel for use in fuel cell system
JP2001575121A JP4598897B2 (ja) 2000-04-10 2001-04-10 燃料電池システム用燃料

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2000107834 2000-04-10
JP2000-107834 2000-04-10

Publications (1)

Publication Number Publication Date
WO2001077267A1 true WO2001077267A1 (fr) 2001-10-18

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AU (1) AU4689001A (fr)
WO (1) WO2001077267A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010100829A (ja) * 2008-09-25 2010-05-06 Showa Shell Sekiyu Kk パラフィン主体の燃料電池システム用炭化水素燃料油

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63150380A (ja) * 1986-12-13 1988-06-23 Idemitsu Kosan Co Ltd 改良灯油
JPH03199294A (ja) * 1989-12-27 1991-08-30 Sekiyu Sangyo Katsuseika Center 石油系燃料を分解脱硫し改質原料とする方法
JPH0570780A (ja) * 1991-09-12 1993-03-23 Sekiyu Sangyo Kasseika Center 中軽質油の深度脱硫方法
JPH11236580A (ja) * 1997-12-18 1999-08-31 Idemitsu Kosan Co Ltd 無鉛ガソリン組成物
JP2000012061A (ja) * 1998-06-23 2000-01-14 Masayoshi Ishida 燃料電池発電装置

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63150380A (ja) * 1986-12-13 1988-06-23 Idemitsu Kosan Co Ltd 改良灯油
JPH03199294A (ja) * 1989-12-27 1991-08-30 Sekiyu Sangyo Katsuseika Center 石油系燃料を分解脱硫し改質原料とする方法
JPH0570780A (ja) * 1991-09-12 1993-03-23 Sekiyu Sangyo Kasseika Center 中軽質油の深度脱硫方法
JPH11236580A (ja) * 1997-12-18 1999-08-31 Idemitsu Kosan Co Ltd 無鉛ガソリン組成物
JP2000012061A (ja) * 1998-06-23 2000-01-14 Masayoshi Ishida 燃料電池発電装置

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010100829A (ja) * 2008-09-25 2010-05-06 Showa Shell Sekiyu Kk パラフィン主体の燃料電池システム用炭化水素燃料油

Also Published As

Publication number Publication date
JP4598897B2 (ja) 2010-12-15
AU4689001A (en) 2001-10-23

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