+

US20030187310A1 - Fuel for fuel cell system - Google Patents

Fuel for fuel cell system Download PDF

Info

Publication number
US20030187310A1
US20030187310A1 US10/297,934 US29793403A US2003187310A1 US 20030187310 A1 US20030187310 A1 US 20030187310A1 US 29793403 A US29793403 A US 29793403A US 2003187310 A1 US2003187310 A1 US 2003187310A1
Authority
US
United States
Prior art keywords
fuel
mol
less
fuel cell
hydrocarbons
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.)
Abandoned
Application number
US10/297,934
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
Individual
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 Individual filed Critical Individual
Assigned to NIPPON OIL CORPORATION reassignment NIPPON OIL CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: ANZAI, IWAO, MATSUBARA, MICHIRO, SADAKANE, OSAMU, SAITOU, KENICHIROU
Publication of US20030187310A1 publication Critical patent/US20030187310A1/en
Abandoned legal-status Critical Current

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/56Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
    • C01B3/58Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids including a catalytic reaction
    • C01B3/583Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids including a catalytic reaction the reaction being the selective oxidation of carbon monoxide
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32Production 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
    • C01B3/34Production 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 by reaction of hydrocarbons with gasifying agents
    • C01B3/38Production 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 by reaction of hydrocarbons with gasifying agents using catalysts
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32Production 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
    • C01B3/34Production 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 by reaction of hydrocarbons with gasifying agents
    • C01B3/48Production 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 by reaction of hydrocarbons with gasifying agents followed by reaction of water vapour with carbon monoxide
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L3/00Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/06Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0606Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
    • H01M8/0612Combination 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
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02Processes for making hydrogen or synthesis gas
    • C01B2203/0205Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0233Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02Processes for making hydrogen or synthesis gas
    • C01B2203/025Processes for making hydrogen or synthesis gas containing a partial oxidation step
    • C01B2203/0261Processes for making hydrogen or synthesis gas containing a partial oxidation step containing a catalytic partial oxidation step [CPO]
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02Processes for making hydrogen or synthesis gas
    • C01B2203/0283Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0435Catalytic purification
    • C01B2203/044Selective oxidation of carbon monoxide
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465Composition of the impurity
    • C01B2203/047Composition of the impurity the impurity being carbon monoxide
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/06Integration with other chemical processes
    • C01B2203/066Integration with other chemical processes with fuel cells
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08Methods of heating or cooling
    • C01B2203/0805Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/085Methods of heating the process for making hydrogen or synthesis gas by electric heating
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041Composition of the catalyst
    • C01B2203/1047Group VIII metal catalysts
    • C01B2203/1064Platinum group metal catalysts
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205Composition of the feed
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205Composition of the feed
    • C01B2203/1211Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1217Alcohols
    • C01B2203/1223Methanol
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205Composition of the feed
    • C01B2203/1211Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1235Hydrocarbons
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1288Evaporation of one or more of the different feed components
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/16Controlling the process
    • C01B2203/1642Controlling the product
    • C01B2203/1647Controlling the amount of the product
    • C01B2203/1652Measuring the amount of product
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/50Fuel cells

Definitions

  • the present invention relates to a fuel to be used for a fuel cell system.
  • Methanol is advantageous in a point that it is relatively easy to reform, however power generation quantity per weight is low and owing to its toxicity, handling has to be careful. Further, it has a corrosive property, special facilities are required for its storage and supply.
  • a fuel to sufficiently utilize the performances of a fuel cell system has not yet been developed.
  • a fuel for a fuel cell system the following are required: power generation quantity per weight is high; power generation quantity per CO 2 emission is high; a fuel consumption is low in a fuel cell system as a whole; an evaporative gas (evapo-emission) is a little; deterioration of a fuel cell system comprising such as a reforming catalyst, a water gas shift reaction catalyst, a carbon monoxide conversion catalyst, fuel cell stacks and the like is scarce to keep the initial performances for a long duration; a starting time for the system is short; and storage of the system, storage stability and handling easiness are excellent.
  • the net power generation quantity of the entire fuel cell system is equivalent to the value calculated by subtracting the energy necessary for keeping the temperature (the energy for keeping balance endothermic and exothermic reaction following the preheating energy) from the actual power generation quantity. Consequently, if the temperature for the reforming is lower, the energy for preheating is low and that is therefore advantageous and further the system starting time is advantageously shortened. In addition, it is also necessary that the energy for preheating per fuel weight is low.
  • THC unreacted hydrocarbon
  • the present invention aims to provide a fuel suitable for a fuel cell system satisfying the above-described requirements in good balance.
  • Inventors of the present invention have extensively investigated to solve the above-described problems and found that a fuel comprising a specific amount of oxygenates (oxygen-containing compounds) and hydrocarbons with specific compositions of respective carbon atoms is suitable for a fuel cell system.
  • the fuel for a fuel cell system comprises:
  • the fuel comprising the specific amount of oxygenates described above and hydrocarbons with specific compositions is preferable to satisfy the following additional requirements;
  • a sulfur content is 50 ppm by mass or less
  • said hydrocarbons comprises 60 mol. % or more of saturates, 40 mol. % or less of olefins, 0.5 mol. % or less of butadiene, 0.1 mol. % or more of isoparaffin in saturates having carbon atoms of 4 or more.
  • heat capacity of the fuel is 1.7 kJ/kg ° C. or less at 15° C. in gaseous phase.
  • FIG. 1 shows a flow chart of a steam reforming type fuel cell system employed for evaluation of a fuel for a fuel cell system of the invention.
  • FIG. 2 is a flow chart of a partial oxidation type fuel cell system employed for evaluation of a fuel for a fuel cell system of the invention.
  • the oxygenates contained the specific amount in the fuel mean alcohols having carbon numbers of 2 to 4, ethers having carbon numbers of 2 to 8 and the like. More particularly, the oxygenates include methanol, ethanol, dimethyl ether, methyl tertiary butyl ether (MTBE), ethyl tertiary butyl ether, tertiary amyl methyl ether (TAME), tertiary amyl ethyl ether and the like.
  • MTBE methyl tertiary butyl ether
  • TAME tertiary amyl methyl ether
  • the content of these oxygenates is required to be 0.5 mass % or more in terms of an oxygen content based on the whole fuel in view of a low fuel consumption of a fuel cell system as a whole, a small THC in an exhaust gas, short starting time of a system and the like, and further is required to be 20 mass % or below taking into consideration of a balance of a power generation quantity per weight.
  • the fuel for a fuel cell system of the invention in addition to the oxygenates mentioned-above, is a mixture of the oxygenates and the hydrocarbons in view of a high power generation quantity per weight, a high power generation quantity per CO 2 emission and the like and an amount of formulation for hydrocarbons is 5 mol. % or more based on the whole fuel.
  • the composition of respective carbon atoms means that a content of hydrocarbons having carbon numbers of 2 or less is 5 mol. % or less, a content of hydrocarbons having carbon numbers of 3 and 4 in total is 90 mol. % or more, and a content of hydrocarbons having carbon numbers of 5 or more is 5 mol. % or less.
  • the content of hydrocarbons having carbon numbers of 2 or less is preferably 5 mol. % or less and more preferably 3 mol. % or less in relation to the storage, inflammability and evapo-emissiontand the like.
  • the content of hydrocarbons having carbon numbers of 3 and 4 in total is 90 mol. % or more and more preferably 95 mol. % or more in view of a high power generation quantity per weight, a high power generation quantity per CO 2 emission, a low fuel consumption of a fuel cell system as a whole, a low THC in an exhaust gas, short starting time of a system, small deterioration of a reforming catalyst to maintain the initial performances for a long duration, and the like.
  • the content of hydrocarbons having carbon numbers of 5 or more is 5 mol. % or less and more preferably 2 mol. % or less in view of a high power generation quantity per weight, a high power generation quantity per CO 2 emission, a low fuel consumption of a fuel cell system as a whole, a low THC in an exhaust gas, short starting time of a system, small deterioration of a reforming catalyst to maintain the initial performances for a long duration, and the like.
  • compositions of respective carbon atoms mentioned above are values measured by JIS K 2240, “Liquefied Petroleum Gases 5.9 Methods for Chemical Composition Analysis”.
  • the content of sulfur in a fuel of the invention is not particularly restricted, however; because deterioration of a fuel cell system comprising such as a reforming catalyst, a water gas shift reaction catalyst, a carbon monoxide removal catalyst, fuel cell stacks, and the like can be suppressed to low and the initial performances can be maintained for a long duration, the content is preferably 50 ppm by mass or less, more preferably 10 ppm by mass or less, further more preferably 1 ppm by mass or less.
  • sulfur content means sulfur measured by JIS K. 2240, “Liquefied Petroleum Gases 5.5 or 5.6 Determination of sulfur content”.
  • the compositions for hydrocarbons are not particularly restricted, however, saturates (M(S)) is preferably 60 mol. % or more, olefins (M(O)) is preferably 40 mol. % or less, butadiene (M(B)) is 0.5 mol. % or less, isoparaffin (M(IP)) in saturates having carbon atoms of 4 or more is preferably 0.1 mol. % or more.
  • S saturates
  • M(O) preferably 40 mol. % or less
  • M(B)) is 0.5 mol. % or less
  • isoparaffin (M(IP)) in saturates having carbon atoms of 4 or more is preferably 0.1 mol. % or more.
  • the saturates (M(S)) is preferably 60 mol. % or more, more preferably 80 mol. % or more, further more preferably 95 mol. % or more and most preferably 99 mol. % or more in view of a high power generation quantity per weight, a high power generation quantity per CO 2 emission, a low fuel consumption of a fuel cell system as a whole, a low THC in an exhaust gas, short starting time of a system, and the like.
  • the olefins (M(O)) is preferably 40 mol. % or less, more preferably 10 mol. % or less and most preferably 1 mol. % or less in view of a high power generation quantity per weight, a high power generation quantity per CO 2 emission, a low fuel consumption of a fuel cell system as a whole, a low THC in an exhaust gas, short starting time of a system, small deterioration of a reforming catalyst to maintain the initial performances for a long duration, a good storage stability, and the like.
  • the butadiene (M(B)) is preferably 0.5 mol. % or less and most preferably 0.1 mol. % or less in view of a high power generation quantity per weight, a high power generation quantity per CO 2 emission, a low fuel consumption of a fuel cell system as a whole, a low THC in an exhaust gas, short starting time of a system, small deterioration of a reforming catalyst to maintain the initial performances for a long duration, a good storage stability, and the like.
  • the isoparaffin (M(IP)) in saturates having carbon atoms of 4 or more is preferably 0.1 mol. % or more, more preferably 1 mol. % or more, furthermore preferably 10 mol. % or more, much more preferably 20 mol. % or more and most preferably 30 mol. % or more in view of a low fuel consumption of a fuel cell system as a whole, a low THC in an exhaust gas, short starting time of a system, small deterioration of a reforming catalyst to maintain the initial performances for a long duration, and the like.
  • vapor pressure of a fuel of the invention is not particularly restricted, however, it is preferably 1.55 MPa or less and more preferably 1.53 MPa or less at 40° C. in relation to the storage, inflammability and evapo-emission and the like.
  • the vapor pressure at 40° C. is measured by JIS K 2240, “Liquefied Petroleum Gases 5.4 Calculation method for density and vapor pressure”.
  • density of hydrocarbons contained in a fuel of the invention is not particularly restricted, however, it is preferably 0.620 g/cm 3 or less at 15° C. in view of a high power generation quantity per weight, a high power generation quantity per CO 2 emission, a low fuel consumption of a fuel cell system as a whole, a low THC in an exhaust gas, short starting time of a system, small deterioration of a reforming catalyst to maintain the initial performances for a long duration, and the like, and more preferably 0.500 g/cm 3 or less to exhibit the effects of the invention.
  • the density at 15° C. is measured by JIS K 2240, “Liquefied Petroleum Gases 5.7 or 5.8 Calculation method for density and vapor pressure”.
  • the corrosiveness to copper of a fuel according to the invention is not particularly restricted, however, the corrosiveness thereof is preferable to 1 or less at 40° C. for 1 hour because deterioration of a fuel cell system comprising such as a reforming catalyst, a water gas shift reaction catalyst, a carbon monoxide removal catalyst, fuel cell stacks, and the like can be suppressed to low and the initial performances can be maintained for a long duration.
  • the corrosiveness to copper at 40° C. for 1 hour is measured by JIS K 2240, “Liquefied Petroleum Gas 5.10 Testing Method for Corrosiveness to copper”.
  • heat capacity of a fuel is not particularly restricted, however, the heat capacity is preferably 1.7 kJ/kg ⁇ ° C. or less at 15° C. and in gaseous phase in view of a low fuel consumption of a fuel cell system as a whole.
  • the heat capacity is measured by means of calorimeters such as water calorimeter, ice calorimeter, vacuum calorimeter, adiabatic calorimeter and the like.
  • a production method for the fuel of the invention is not particularly restricted.
  • the fuel can be prepared by including the specific amount of oxygenates defined in the invention in one or more of the following hydrocarbon base materials.
  • the hydrocarbons can be produced, for example, by the following hydrocarbon base materials; a straight-run propane fraction containing propane as a main component obtained by treating heavy oils with a distillation apparatus, naphtha reforming apparatus and the like, a straight-run desulfurized propane fraction obtained by desulfurizing the straight-run propane fraction, a straight-run butane fraction containing butane as a main component obtained by treating heavy oils with a distillation apparatus, naphtha reforming apparatus, alkylation apparatus and the like, a straight-run desulfurized butane fraction obtained by desulfurizing the straight-run butane fraction, a cracked propane fraction containing propane and propylene as main components obtained by cracking heavy oils with a fluid catalytic cracking apparatus (FCC) and the like, a cracked but
  • FCC fluid catalytic
  • preferable materials as the base materials for the production of the fuel of the invention are the straight-run desulfurized propane fraction, the straight-run desulfurized butane fraction and the like, and dimethylether and methanol.
  • a fuel of the invention is to be employed as a fuel for a fuel cell system.
  • a fuel cell system mentioned herein comprises a reformer for a fuel, a carbon monoxide conversion apparatus, fuel cells and the like, however, a fuel of the invention may be suitable for any fuel cell system.
  • the reformer is an apparatus for obtaining hydrogen, by reforming a fuel. Practical examples of the reformer are:
  • a steam reforming type reformer for obtaining products of mainly hydrogen by treating a heated and vaporized fuel and steam with a catalyst such as copper, nickel, platinum, ruthenium and the like;
  • a partial oxidation type reformer for obtaining products of mainly hydrogen by treating a heated and vaporized fuel and air with or without a catalyst such as copper, nickel, platinum, ruthenium and the like;
  • an auto thermal reforming type reformer for obtaining products of mainly hydrogen by treating a heated and vaporized fuel, steam and air, which carries out the partial oxidation of (2) in the prior stage and carries out the steam type reforming of (1) in the posterior stage while using the generated heat of the partial oxidation reaction with a catalyst such as copper, nickel, platinum, ruthenium and the like.
  • the carbon monoxide conversion apparatus is an apparatus for removing carbon monoxide which is contained in a gas produced by the above-described reformer and becomes a catalyst poison in a fuel cell and practical examples thereof are:
  • a water gas shift reactor for obtaining carbon dioxide and hydrogen as products from carbon monoxide and steam by reacting a reformed gas and steam in the presence of a catalyst of such as copper, nickel, platinum, ruthenium and the like;
  • a preferential oxidation reactor for converting carbon monoxide into carbon dioxide by reacting a reformed gas and compressed air in the presence of a catalyst of such as platinum, ruthenium and the like, and these are used singly or jointly.
  • PEFC proton exchange membrane type fuel cell
  • PAFC phosphoric acid type fuel cell
  • MCFC molten carbonate type fuel cell
  • SOFC solid oxide type fell cell
  • the above-described fuel cell system can be employed for an electric automobile, a hybrid automobile comprising a conventional engine and electric power, a portable power source, a dispersion type power source, a power source for domestic use, a cogeneration system and the like.
  • a fuel and water were evaporated by electric heating and led to a reformer filled with a noble metal type catalyst and kept at a prescribed temperature by an electric heater to generate a reformed gas enriched with hydrogen.
  • the temperature of the reformer was adjusted to be the minimum temperature (the minimum temperature at which no THC was contained in a reformed gas) at which reforming was completely carried out in an initial stage of the test.
  • a reformed gas was led to a carbon monoxide conversion apparatus (a water gas shift reaction) to convert carbon monoxide in the reformed gas to carbon dioxide and then the produced gas was led to a solid polymer type fuel cell to carry out power generation.
  • a carbon monoxide conversion apparatus a water gas shift reaction
  • FIG. 1 A flow chart of a steam reforming type fuel cell system employed for the evaluation was illustrated in FIG. 1.
  • a fuel is evaporated by electric heating and together with air, the evaporated fuel was led to a reformer filled with a noble metal type catalyst and kept at a 1100° C. by an electric heater to generate a reformed gas enriched with hydrogen.
  • FIG. 2 A flow chart of a partial oxidation type fuel cell system employed for the evaluation was illustrated in FIG. 2.
  • a fuel of the invention comprising a specific amount of oxygenates and hydrocarbons with specific compositions of respective carbon atoms has performances with small deterioration by using in a fuel cell system and can provide high output of electric energy and other than that, the fuel can satisfy a variety of performances for a fuel cell system.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Electrochemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Energy (AREA)
  • Sustainable Development (AREA)
  • Manufacturing & Machinery (AREA)
  • Fuel Cell (AREA)
  • Hydrogen, Water And Hydrids (AREA)

Abstract

A fuel for a fuel cell system comprises wherein said fuel comprises 5 mol. % or more of hydrocarbons, 0.5-20 mass % of oxygenates therein in terms of an oxygen content batsed on the whole fuel and 5 mol. % or less of hydrocarbons having carbon numbers of 2 or less, 90 mol. % or more of hydrocarbons having carbon numbers of 3 and 4 in total, 5 mol. % or less of hydrocarbons having carbon numbers of 5 or more and is a gaseous phase under normal temperature and pressure. The fuel for a fuel cell system has a high power generation quantity per weight, a high power generation quantity per CO2 emission, a low fuel consumption, a small evaporative gas (evapo-emission), small deterioration of a fuel cell system comprising such as a reforming catalyst, a water gas shift reaction catalyst, a carbon monoxide removal catalyst, fuel cell stacks and the like to maintain the initial performances for a long duration, good handling properties in view of storage stability and inflammability, and a low preheating heat quantity.

Description

    TECHNICAL FIELD
  • The present invention relates to a fuel to be used for a fuel cell system. [0001]
  • BACKGROUND ART
  • Recently, with increasing awareness of the critical situation of future global environments, it has been highly expected to develop an energy supply system harmless to the global environments. Especially urgently required are to reduce CO[0002] 2 to prevent global warming and reduce harmful emissions such as THC (unreacted hydrocarbons in an exhaust gas), NOx, PM (particulate matter in an exhaust gas: soot, unburned high boiling point and high molecular weight fuel and lubricating oil). Practical examples of such a system are an automotive power system to replace a conventional Otto/Diesel engine and a power generation system to replace thermal power generation.
  • Hence, a fuel cell, which has high energy efficiency and emits only H[0003] 2O and CO2, has been regarded as a most expectative system to response to respond to social requests. In order to achieve such a system, it is necessary to develop not only the hardware but also the optimum fuel.
  • Conventionally, as a fuel for a fuel cell system, hydrogen, methanol, and hydrocarbons have been candidates. [0004]
  • As a fuel for a fuel cell system, there is methanol except for hydrogen. Methanol is advantageous in a point that it is relatively easy to reform, however power generation quantity per weight is low and owing to its toxicity, handling has to be careful. Further, it has a corrosive property, special facilities are required for its storage and supply. [0005]
  • Like this, a fuel to sufficiently utilize the performances of a fuel cell system has not yet been developed. Especially, as a fuel for a fuel cell system, the following are required: power generation quantity per weight is high; power generation quantity per CO[0006] 2 emission is high; a fuel consumption is low in a fuel cell system as a whole; an evaporative gas (evapo-emission) is a little; deterioration of a fuel cell system comprising such as a reforming catalyst, a water gas shift reaction catalyst, a carbon monoxide conversion catalyst, fuel cell stacks and the like is scarce to keep the initial performances for a long duration; a starting time for the system is short; and storage of the system, storage stability and handling easiness are excellent.
  • Incidentally, in a fuel cell system, it is required to keep a fuel and a reforming catalyst at a proper temperature, the net power generation quantity of the entire fuel cell system is equivalent to the value calculated by subtracting the energy necessary for keeping the temperature (the energy for keeping balance endothermic and exothermic reaction following the preheating energy) from the actual power generation quantity. Consequently, if the temperature for the reforming is lower, the energy for preheating is low and that is therefore advantageous and further the system starting time is advantageously shortened. In addition, it is also necessary that the energy for preheating per fuel weight is low. If the preheating is insufficient, unreacted hydrocarbon (THC) in an exhaust gas increases and it results in not only decrease of the power generation quantity per weight but also possibility of becoming causes of air pollution. To say conversely, when some kind of fuels are reformed by the same reformer and the same temperature, it is more advantageous that THC in an exhaust gas is lower and the conversion efficiency to hydrogen is higher. [0007]
  • The present invention, taking such situation into consideration, aims to provide a fuel suitable for a fuel cell system satisfying the above-described requirements in good balance. [0008]
  • DISCLOSURE OF THE INVENTION
  • Inventors of the present invention have extensively investigated to solve the above-described problems and found that a fuel comprising a specific amount of oxygenates (oxygen-containing compounds) and hydrocarbons with specific compositions of respective carbon atoms is suitable for a fuel cell system. [0009]
  • That is, the fuel for a fuel cell system according to the present invention comprises: [0010]
  • (1) 5 mol. % or more of hydrocarbons, 0.5-20 mass % of oxygenates therein in terms of an oxygen content based on the whole fuel and 5 mol. % or less of hydrocarbons having carbon numbers of 2 or less, 90 mol. % or more of hydrocarbons having carbon numbers of 3 and 4 in total, 5 mol. % or less of hydrocarbons having carbon numbers of 5 or more and being a gaseous phase under normal temperature and pressure. [0011]
  • The fuel comprising the specific amount of oxygenates described above and hydrocarbons with specific compositions is preferable to satisfy the following additional requirements; [0012]
  • (2) a sulfur content is 50 ppm by mass or less; [0013]
  • (3) said hydrocarbons comprises 60 mol. % or more of saturates, 40 mol. % or less of olefins, 0.5 mol. % or less of butadiene, 0.1 mol. % or more of isoparaffin in saturates having carbon atoms of 4 or more. [0014]
  • (4) vapor pressure at 40° C. is 1.55 MPa or less; [0015]
  • (5) density of hydrocarbons at 15° C. is 0.500 to 0.620 g/cm[0016] 3;
  • (6) corrosiveness to copper at 40° C. for 1 hour is 1 or less; [0017]
  • (7) heat capacity of the fuel is 1.7 kJ/kg ° C. or less at 15° C. in gaseous phase.[0018]
  • BRIEF DESCRIPTION OF THE DRAWINGS
  • FIG. 1 shows a flow chart of a steam reforming type fuel cell system employed for evaluation of a fuel for a fuel cell system of the invention. FIG. 2 is a flow chart of a partial oxidation type fuel cell system employed for evaluation of a fuel for a fuel cell system of the invention.[0019]
  • BEST MODE FOR CARRYING OUT THE INVENTION
  • Hereinafter, the contents of the invention will be described further in detail. [0020]
  • In the present invention, the oxygenates contained the specific amount in the fuel mean alcohols having carbon numbers of 2 to 4, ethers having carbon numbers of 2 to 8 and the like. More particularly, the oxygenates include methanol, ethanol, dimethyl ether, methyl tertiary butyl ether (MTBE), ethyl tertiary butyl ether, tertiary amyl methyl ether (TAME), tertiary amyl ethyl ether and the like. [0021]
  • The content of these oxygenates is required to be 0.5 mass % or more in terms of an oxygen content based on the whole fuel in view of a low fuel consumption of a fuel cell system as a whole, a small THC in an exhaust gas, short starting time of a system and the like, and further is required to be 20 mass % or below taking into consideration of a balance of a power generation quantity per weight. [0022]
  • The fuel for a fuel cell system of the invention, in addition to the oxygenates mentioned-above, is a mixture of the oxygenates and the hydrocarbons in view of a high power generation quantity per weight, a high power generation quantity per CO[0023] 2 emission and the like and an amount of formulation for hydrocarbons is 5 mol. % or more based on the whole fuel.
  • In the fuel according to the invention, the composition of respective carbon atoms means that a content of hydrocarbons having carbon numbers of 2 or less is 5 mol. % or less, a content of hydrocarbons having carbon numbers of 3 and 4 in total is 90 mol. % or more, and a content of hydrocarbons having carbon numbers of 5 or more is 5 mol. % or less. [0024]
  • The content of hydrocarbons having carbon numbers of 2 or less is preferably 5 mol. % or less and more preferably 3 mol. % or less in relation to the storage, inflammability and evapo-emissiontand the like. The content of hydrocarbons having carbon numbers of 3 and 4 in total is 90 mol. % or more and more preferably 95 mol. % or more in view of a high power generation quantity per weight, a high power generation quantity per CO[0025] 2 emission, a low fuel consumption of a fuel cell system as a whole, a low THC in an exhaust gas, short starting time of a system, small deterioration of a reforming catalyst to maintain the initial performances for a long duration, and the like. The content of hydrocarbons having carbon numbers of 5 or more is 5 mol. % or less and more preferably 2 mol. % or less in view of a high power generation quantity per weight, a high power generation quantity per CO2 emission, a low fuel consumption of a fuel cell system as a whole, a low THC in an exhaust gas, short starting time of a system, small deterioration of a reforming catalyst to maintain the initial performances for a long duration, and the like.
  • Incidentally, the compositions of respective carbon atoms mentioned above are values measured by JIS K 2240, “Liquefied Petroleum Gases 5.9 Methods for Chemical Composition Analysis”. [0026]
  • Further, the content of sulfur in a fuel of the invention is not particularly restricted, however; because deterioration of a fuel cell system comprising such as a reforming catalyst, a water gas shift reaction catalyst, a carbon monoxide removal catalyst, fuel cell stacks, and the like can be suppressed to low and the initial performances can be maintained for a long duration, the content is preferably 50 ppm by mass or less, more preferably 10 ppm by mass or less, further more preferably 1 ppm by mass or less. [0027]
  • Here, sulfur content means sulfur measured by JIS K. 2240, “Liquefied Petroleum Gases 5.5 or 5.6 Determination of sulfur content”. [0028]
  • In the present invention, the compositions for hydrocarbons are not particularly restricted, however, saturates (M(S)) is preferably 60 mol. % or more, olefins (M(O)) is preferably 40 mol. % or less, butadiene (M(B)) is 0.5 mol. % or less, isoparaffin (M(IP)) in saturates having carbon atoms of 4 or more is preferably 0.1 mol. % or more. Hereinafter, these compositions are explained separately. [0029]
  • The saturates (M(S)) is preferably 60 mol. % or more, more preferably 80 mol. % or more, further more preferably 95 mol. % or more and most preferably 99 mol. % or more in view of a high power generation quantity per weight, a high power generation quantity per CO[0030] 2 emission, a low fuel consumption of a fuel cell system as a whole, a low THC in an exhaust gas, short starting time of a system, and the like.
  • The olefins (M(O)) is preferably 40 mol. % or less, more preferably 10 mol. % or less and most preferably 1 mol. % or less in view of a high power generation quantity per weight, a high power generation quantity per CO[0031] 2 emission, a low fuel consumption of a fuel cell system as a whole, a low THC in an exhaust gas, short starting time of a system, small deterioration of a reforming catalyst to maintain the initial performances for a long duration, a good storage stability, and the like.
  • The butadiene (M(B)) is preferably 0.5 mol. % or less and most preferably 0.1 mol. % or less in view of a high power generation quantity per weight, a high power generation quantity per CO[0032] 2 emission, a low fuel consumption of a fuel cell system as a whole, a low THC in an exhaust gas, short starting time of a system, small deterioration of a reforming catalyst to maintain the initial performances for a long duration, a good storage stability, and the like.
  • The isoparaffin (M(IP)) in saturates having carbon atoms of 4 or more is preferably 0.1 mol. % or more, more preferably 1 mol. % or more, furthermore preferably 10 mol. % or more, much more preferably 20 mol. % or more and most preferably 30 mol. % or more in view of a low fuel consumption of a fuel cell system as a whole, a low THC in an exhaust gas, short starting time of a system, small deterioration of a reforming catalyst to maintain the initial performances for a long duration, and the like. [0033]
  • Incidentally, the above-described (M(S)), (M(O)), (M(B)) and (M(IP)) are values measured by JIS K 2240, “Liquefied Petroleum Gases 5.9 Methods for Chemical Composition Analysis”. [0034]
  • Then, it is most preferably to satisfy the above-described preferable ranges of sulfur and the above-described preferable ranges of compositions since deterioration of a fuel cell system comprising such as a reforming catalyst, a water gas shift reaction catalyst, a carbon monoxide removal catalyst, fuel cell stacks, and the like can be suppressed to low and the initial performances can be maintained for a long duration. [0035]
  • Further, vapor pressure of a fuel of the invention is not particularly restricted, however, it is preferably 1.55 MPa or less and more preferably 1.53 MPa or less at 40° C. in relation to the storage, inflammability and evapo-emission and the like. [0036]
  • Incidentally, the vapor pressure at 40° C. is measured by JIS K 2240, “Liquefied Petroleum Gases 5.4 Calculation method for density and vapor pressure”. [0037]
  • Further, density of hydrocarbons contained in a fuel of the invention is not particularly restricted, however, it is preferably 0.620 g/cm[0038] 3 or less at 15° C. in view of a high power generation quantity per weight, a high power generation quantity per CO2 emission, a low fuel consumption of a fuel cell system as a whole, a low THC in an exhaust gas, short starting time of a system, small deterioration of a reforming catalyst to maintain the initial performances for a long duration, and the like, and more preferably 0.500 g/cm3 or less to exhibit the effects of the invention.
  • Incidentally, the density at 15° C. is measured by JIS K 2240, “Liquefied Petroleum Gases 5.7 or 5.8 Calculation method for density and vapor pressure”. [0039]
  • Further, the corrosiveness to copper of a fuel according to the invention is not particularly restricted, however, the corrosiveness thereof is preferable to 1 or less at 40° C. for 1 hour because deterioration of a fuel cell system comprising such as a reforming catalyst, a water gas shift reaction catalyst, a carbon monoxide removal catalyst, fuel cell stacks, and the like can be suppressed to low and the initial performances can be maintained for a long duration. [0040]
  • Incidentally, the corrosiveness to copper at 40° C. for 1 hour is measured by JIS K 2240, “Liquefied Petroleum Gas 5.10 Testing Method for Corrosiveness to copper”. [0041]
  • Further, in the invention, heat capacity of a fuel is not particularly restricted, however, the heat capacity is preferably 1.7 kJ/kg·° C. or less at 15° C. and in gaseous phase in view of a low fuel consumption of a fuel cell system as a whole. [0042]
  • The heat capacity is measured by means of calorimeters such as water calorimeter, ice calorimeter, vacuum calorimeter, adiabatic calorimeter and the like. [0043]
  • A production method for the fuel of the invention is not particularly restricted. As a practical method, for example, the fuel can be prepared by including the specific amount of oxygenates defined in the invention in one or more of the following hydrocarbon base materials. The hydrocarbons can be produced, for example, by the following hydrocarbon base materials; a straight-run propane fraction containing propane as a main component obtained by treating heavy oils with a distillation apparatus, naphtha reforming apparatus and the like, a straight-run desulfurized propane fraction obtained by desulfurizing the straight-run propane fraction, a straight-run butane fraction containing butane as a main component obtained by treating heavy oils with a distillation apparatus, naphtha reforming apparatus, alkylation apparatus and the like, a straight-run desulfurized butane fraction obtained by desulfurizing the straight-run butane fraction, a cracked propane fraction containing propane and propylene as main components obtained by cracking heavy oils with a fluid catalytic cracking apparatus (FCC) and the like, a cracked butane fraction containing butane and butene as main components obtained by treating heavy oils with a fluid catalytic cracking apparatus (FCC) and the like. [0044]
  • Among them, preferable materials as the base materials for the production of the fuel of the invention are the straight-run desulfurized propane fraction, the straight-run desulfurized butane fraction and the like, and dimethylether and methanol. [0045]
  • A fuel of the invention is to be employed as a fuel for a fuel cell system. A fuel cell system mentioned herein comprises a reformer for a fuel, a carbon monoxide conversion apparatus, fuel cells and the like, however, a fuel of the invention may be suitable for any fuel cell system. [0046]
  • The reformer is an apparatus for obtaining hydrogen, by reforming a fuel. Practical examples of the reformer are: [0047]
  • (1) a steam reforming type reformer for obtaining products of mainly hydrogen by treating a heated and vaporized fuel and steam with a catalyst such as copper, nickel, platinum, ruthenium and the like; [0048]
  • (2) a partial oxidation type reformer for obtaining products of mainly hydrogen by treating a heated and vaporized fuel and air with or without a catalyst such as copper, nickel, platinum, ruthenium and the like; and [0049]
  • (3) an auto thermal reforming type reformer for obtaining products of mainly hydrogen by treating a heated and vaporized fuel, steam and air, which carries out the partial oxidation of (2) in the prior stage and carries out the steam type reforming of (1) in the posterior stage while using the generated heat of the partial oxidation reaction with a catalyst such as copper, nickel, platinum, ruthenium and the like. [0050]
  • The carbon monoxide conversion apparatus is an apparatus for removing carbon monoxide which is contained in a gas produced by the above-described reformer and becomes a catalyst poison in a fuel cell and practical examples thereof are: [0051]
  • (1) a water gas shift reactor for obtaining carbon dioxide and hydrogen as products from carbon monoxide and steam by reacting a reformed gas and steam in the presence of a catalyst of such as copper, nickel, platinum, ruthenium and the like; and [0052]
  • (2) a preferential oxidation reactor for converting carbon monoxide into carbon dioxide by reacting a reformed gas and compressed air in the presence of a catalyst of such as platinum, ruthenium and the like, and these are used singly or jointly. [0053]
  • As a fuel cell, practical examples are a proton exchange membrane type fuel cell (PEFC), a phosphoric acid type fuel cell (PAFC), a molten carbonate type fuel cell (MCFC), a solid oxide type fell cell (SOFC) and the like. [0054]
  • Further, the above-described fuel cell system can be employed for an electric automobile, a hybrid automobile comprising a conventional engine and electric power, a portable power source, a dispersion type power source, a power source for domestic use, a cogeneration system and the like. [0055]
  • EXAMPLES
  • The properties of base materials (LPG) employed for the respective fuels for examples and comparative examples are shown in Table 1. [0056]
  • Also, the compositions and properties of the respective fuels employed for examples and comparative examples are shown in Table 2. [0057]
    TABLE 1
    straight-run
    straight-run desulfurized FCC-C3 FCC-C4
    C3 fraction C4 fraction fraction fraction
    *1 *2 *3 *4 DME *5
    sulfur mass ppm 7 <1 5 34 <1
    density @ 15° C. g/m3 0.509 0.577 0.518 0.591 0.600
    vapor pressure @ 40° C. Mpa 1.33 0.34 1.50 0.39 0.88
    corrosiveness to copper 1a 1a 1a 1
    carbon number C2− mol. % 2.5 0.0 0.0 0.0
    carbon number C3 mol. % 96.6 0.0 99.8 2.4
    carbon number C4 mol. % 0.9 99.9 0.29 92.4
    carbon number C5+ mol. % 0.0 0.1 0.0 5.2
    saturates mol. % 99.9 99.9 19.7 53.9
    olefins mol. % 0.1 0.1 80.3 46.1
    butadiene mol. % 0.0 0.0 0.0 0.2
    isoparaffines in mol. % 78.2 35.8 100.0 81.4
    saturates having carbon
    numbers of 4 or more
  • [0058]
    TABLE 2
    Ex. 1 Ex. 2
    Mixing ratio (vol. %)
    straight-run C3 fraction 20
    straight-run desulfurized C4 90 75
    fraction
    FCC-C3 fraction
    FCC-C4 fraction
    DME 10 5
    methanol
    Analytical results of properties
    sulfur mass ppm <1 1
    density g/cm3 0.509 0.563
    vapor pressure Mpa 0.40 0.57
    distribution of carbon
    numbers (hydrocarbon moieties)
    carbon number: C2− mol. % 2.5 0.6
    carbon number: C3 mol. % 96.6 23.0
    carbon number: C4 mol. % 0.9 76.4
    carbon number: C5+ mol. % 0.0 0.1
    composition
    saturates mol. % 99.9 99.9
    olefins mol. % 0.1 0.1
    butadiene mol. % 0.0 0.0
    isoparafines in saturates having mol. % 78.2 35.9
    carbon numbers of 4 or more
    oxygen ratio mass % 4.0 2.1
    corrosiveness to copper 1a 1a
    net heat of combustion kJ/kg 43750 44800
    heat capacity kJ/kg · ° C. 1.60 1.61
    gas
    Comp. 1 Comp. 2
    Mixing ratio (mol. %)
    straight-run C3 fraction
    straight-run desulfurized C4
    fraction
    FCC-C3 fraction
    FCC-C4 fraction 100
    DME
    methanol 100
    Analytical results of properties
    sulfur mass ppm <1 34
    density g/cm3 0.796 0.591
    vapor pressure Mpa 0.03 0.36
    distribution of carbon
    numbers (hydrocarbon moieties)
    carbon number: C2 mol. % 0.0
    carbon number: C3 mol. % 2.4
    carbon number: C4 mol. % 92.4
    carbon number: C5+ mol. % 5.2
    composition
    saturates mol. % 53.9
    olefins mol. % 46.1
    butadiene mol. % 0.2
    isoparafines in saturates having mol. % 80.6
    carbon numbers of 4 or more
    oxygen ratio mass % 49.9 0.0
    corrosiveness to copper 1
    net heat of combustion kJ/kg 19920 45440
    heat capacity kJ/kg · ° C. 1.34 1.55
    gas
  • These respective fuels were subjected to evaluation tests for a fuel cell system. [0059]
  • Fuel Cell System Evaluation Test [0060]
  • (1) Steam Reforming [0061]
  • A fuel and water were evaporated by electric heating and led to a reformer filled with a noble metal type catalyst and kept at a prescribed temperature by an electric heater to generate a reformed gas enriched with hydrogen. [0062]
  • The temperature of the reformer was adjusted to be the minimum temperature (the minimum temperature at which no THC was contained in a reformed gas) at which reforming was completely carried out in an initial stage of the test. [0063]
  • Together with steam, a reformed gas was led to a carbon monoxide conversion apparatus (a water gas shift reaction) to convert carbon monoxide in the reformed gas to carbon dioxide and then the produced gas was led to a solid polymer type fuel cell to carry out power generation. [0064]
  • A flow chart of a steam reforming type fuel cell system employed for the evaluation was illustrated in FIG. 1. [0065]
  • (2) Partial Oxidation [0066]
  • A fuel is evaporated by electric heating and together with air, the evaporated fuel was led to a reformer filled with a noble metal type catalyst and kept at a 1100° C. by an electric heater to generate a reformed gas enriched with hydrogen. [0067]
  • Together with steam, a reformed gas was led to a carbon monoxide conversion apparatus (a water gas shift reaction) to convert carbon monoxide in the reformed gas to carbon dioxide and then the produced gas was led to a solid polymer type fuel cell to carry out power generation. [0068]
  • A flow chart of a partial oxidation type fuel cell system employed for the evaluation was illustrated in FIG. 2. [0069]
  • (3) Evaluation Method [0070]
  • The amounts of H[0071] 2, CO, CO2 and THC in the reformed gas generated from a reformer were measured immediately after starting of the evaluation test. Similarly, the amounts of H2, CO, CO2 and THC in the reformed gas generated from a carbon monoxide conversion apparatus were measured immediately after starting of the evaluation test.
  • The power generation quantity, the fuel consumption, and the CO[0072] 2 amount emitted out of a fuel cell were measured immediately after starting of the evaluation test and 100 hours later from the starting.
  • The energy (preheating quantities) necessary to heat the respective fuels to a prescribed reforming temperature were calculated from the heat capacities and the heat of vaporization. [0073]
  • Further, these measured values, calculated values and the heating values of respective fuels were employed for calculation of the performance deterioration ratio of a reforming catalyst (the power generation amount after 100 hours later from the starting divided by the power generation amount immediately after the starting), the thermal efficiency (the power generation amount immediately after the starting divided by the net heat of combustion of a fuel), and the preheating energy ratio (preheating energy divided by the power generation amount). [0074]
  • The respective measured values and the calculated values are shown in Table 3. [0075]
    TABLE 3
    Ex. 1 Ex. 2
    Evaluation results
    Electric power generation by steam reforming method
    (reforming temperature = optimum reforming
    temperature 1))
    Optimum reforming temperature ° C. 540 590
    Electric energy kJ/fuel kg
    initial performance 29580 30200
    100 hours later 29580 30190
    performance deterioration ratio 0.00% 0.03%
    100 hours later
    Thermal efficiency 2)   68%   67%
    initial performance
    CO2 generation kg/fuel kg 2.901 2.956
    initial performance
    Energy per CO2 KJ/CO2-kg 10196 10217
    initial performance
    Preheating energy 3) kJ/fuel kg 830 910
    Preheating energy ratio 4)  2.8%  3.0%
    Electric power generation by partial oxidation
    reforming method (reforming temperature 1100° C.)
    Electric energy kJ/fuel kg
    initial performance 15100 15440
    100 hours later 15100 15430
    performance deterioration ratio 0.00% 0.06%
    100 hours later
    Thermal efficiency 2)   35%   34%
    initial performance
    CO2 generation kg/fuel kg 2.900 2.955
    initial performance
    Energy per CO2 KJ/CO2-kg 5207 5225
    initial performance
    Preheating energy 3) kJ/fuel kg 1720 1729
    Preheating energy ratio 4) 11.4% 11.2%
    Comp. Comp.
    1 2
    Evaluation results
    Electric power generation by steam reforming method
    (reforming temperature = optimum reforming
    temperature 1))
    Optimum reforming temperature ° C. 360 670
    Electric energy kJ/fuel kg
    initial performance 17140 29460
    100 hours later 17140 28520
    performance deterioration ratio 0.00% 3.19%
    100 hours later
    Thermal efficiency 2)   86%   65%
    initial performance
    CO2 generation kg/fuel kg 1.374 3.079
    initial performance
    Energy per CO2 KJ/CO2-kg 12475 9568
    initial performance
    Preheating energy 3) kJ/fuel kg 1590 1000
    Preheating energy ratio 4)  9.3%  3.4%
    Electric power generation by partial oxidation
    reforming method (reforming temperature 1100° C.)
    Electric energy kJ/fuel kg
    initial performance 10280 14420
    100 hours later 10280 14220
    performance deterioration ratio 0.00% 1.39%
    100 hours later
    Thermal efficiency 2)   52%   32%
    initial performance
    CO2 generation kg/fuel kg 1.373 3.077
    initial performance
    Energy per CO2 KJ/CO2-kg 7487 4686
    initial performance
    Preheating energy 3) kJ/fuel kg 2590 1670
    Preheating energy ratio 4) 25.2% 11.6%
  • Industrial Applicability [0076]
  • As described above, a fuel of the invention comprising a specific amount of oxygenates and hydrocarbons with specific compositions of respective carbon atoms has performances with small deterioration by using in a fuel cell system and can provide high output of electric energy and other than that, the fuel can satisfy a variety of performances for a fuel cell system. [0077]

Claims (7)

1. A fuel for use in a fuel cell system, wherein said fuel comprises 5 mol. % or more of hydrocarbons, 0.5-20 mass % of oxygenates therein in terms of an oxygen content based on the whole fuel and 5 mol. % or less of hydrocarbons having carbon numbers of 2 or less, 90 mol. % or more of hydrocarbons having carbon numfbers of 3 and 4 in total, 5 mol. % or less of hydrocarbons having carbon numbers of 5 or more and is a gaseous phase under normal temperature and pressure.
2. A fuel according to claim 1, wherein a sulfur content is 50 ppm by mass or less.
3. A fuel according to claims 1 or 2, wherein said hydrocarbons comprises 60 mol. % or more of saturates, 40 mol. % or less of olefins, 0.5 mol. % or less of butadione, 0.1 mol. % or more of isoparaffin in saturates having carbon atoms of 4 or more, and is a gaseous phase under normal temperature and pressure.
4. A fuel according to any one of claims 1 to 3, wherein vapor pressure at 40° C. is 1.55 MPa or less.
5. A fuel according to any one of claims 1 to 4, wherein density at 15° C. is 0.500 to 0.620 g/cm3.
6. A fuel according to any one of claims 1 to 5, wherein corrosiveness to copper at 40° C. for 1 hour is 1 or less,
7. A fuel according to any one of claims 1 to 6, wherein heat capacity of the fuel is 1.7 kJ/kg ° C. or less at 15° C. in gaseous phase.
US10/297,934 2000-06-29 2001-06-29 Fuel for fuel cell system Abandoned US20030187310A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2000-196650 2000-06-29
JP2000196650 2000-06-29

Publications (1)

Publication Number Publication Date
US20030187310A1 true US20030187310A1 (en) 2003-10-02

Family

ID=18695103

Family Applications (1)

Application Number Title Priority Date Filing Date
US10/297,934 Abandoned US20030187310A1 (en) 2000-06-29 2001-06-29 Fuel for fuel cell system

Country Status (3)

Country Link
US (1) US20030187310A1 (en)
AU (1) AU2001266357A1 (en)
WO (1) WO2002000814A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004050257A1 (en) * 2002-12-03 2004-06-17 Robert Bosch Gmbh Heated metering device for the reformer of a fuel cell arrangement

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5358696A (en) * 1993-12-01 1994-10-25 Texaco Inc. Production of H2 -rich gas
US5904740A (en) * 1997-06-03 1999-05-18 Motorola, Inc. Fuel for liquid feed fuel cells
US6660050B1 (en) * 2002-05-23 2003-12-09 Chevron U.S.A. Inc. Method for controlling deposits in the fuel reformer of a fuel cell system
US6824573B2 (en) * 2000-04-10 2004-11-30 Nippon Oil Corporation Fuel for use in fuel cell
US6837909B2 (en) * 2000-04-10 2005-01-04 Nippon Oil Corporation Fuel for use in a fuel cell system
US6869706B2 (en) * 2002-01-25 2005-03-22 Exxonmobil Research And Engineering Company Alkoxylated alkyl ester and alcohol emulsion compositions for fuel cell reformer start-up
US6884531B2 (en) * 2001-05-21 2005-04-26 Saudi Arabian Oil Company Liquid hydrocarbon based fuels for fuel cell on-board reformers
US6884272B2 (en) * 2000-04-10 2005-04-26 Nippon Oil Corporation Fuel for fuel cell system
US6939459B2 (en) * 2000-04-10 2005-09-06 Nippon Oil Corporation Fuel for use in fuel cell system
US6958117B2 (en) * 2000-04-10 2005-10-25 Nippon Oil Corporation Fuel for use in a fuel cell system
US6962650B2 (en) * 2000-04-10 2005-11-08 Nippon Oil Corporation Fuel for use in a fuel cell system

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05260612A (en) * 1992-03-13 1993-10-08 Hitachi Ltd Electric car
JPH0975721A (en) * 1995-09-12 1997-03-25 Tokyo Gas Co Ltd Adsorbent for removing trace components in hydrocarbon gas and removal method
JPH10121069A (en) * 1996-10-22 1998-05-12 Cosmo Sogo Kenkyusho:Kk Auto gas composition
JPH10189022A (en) * 1996-12-27 1998-07-21 Nkk Corp Fuel cell
JPH10330101A (en) * 1997-05-27 1998-12-15 Sanyo Electric Co Ltd Hydrogen-manufacturing apparatus and method therefor
JPH1150070A (en) * 1997-08-05 1999-02-23 Cosmo Sogo Kenkyusho:Kk Fuel composition for two-stroke engine
JPH11263712A (en) * 1998-03-16 1999-09-28 Shiseido Co Ltd Aerosol composition
JP3050850B2 (en) * 1998-08-28 2000-06-12 大阪瓦斯株式会社 Fuel cell power generation system

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5358696A (en) * 1993-12-01 1994-10-25 Texaco Inc. Production of H2 -rich gas
US5904740A (en) * 1997-06-03 1999-05-18 Motorola, Inc. Fuel for liquid feed fuel cells
US6824573B2 (en) * 2000-04-10 2004-11-30 Nippon Oil Corporation Fuel for use in fuel cell
US6837909B2 (en) * 2000-04-10 2005-01-04 Nippon Oil Corporation Fuel for use in a fuel cell system
US6884272B2 (en) * 2000-04-10 2005-04-26 Nippon Oil Corporation Fuel for fuel cell system
US6939459B2 (en) * 2000-04-10 2005-09-06 Nippon Oil Corporation Fuel for use in fuel cell system
US6958117B2 (en) * 2000-04-10 2005-10-25 Nippon Oil Corporation Fuel for use in a fuel cell system
US6962650B2 (en) * 2000-04-10 2005-11-08 Nippon Oil Corporation Fuel for use in a fuel cell system
US6884531B2 (en) * 2001-05-21 2005-04-26 Saudi Arabian Oil Company Liquid hydrocarbon based fuels for fuel cell on-board reformers
US6869706B2 (en) * 2002-01-25 2005-03-22 Exxonmobil Research And Engineering Company Alkoxylated alkyl ester and alcohol emulsion compositions for fuel cell reformer start-up
US6660050B1 (en) * 2002-05-23 2003-12-09 Chevron U.S.A. Inc. Method for controlling deposits in the fuel reformer of a fuel cell system

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004050257A1 (en) * 2002-12-03 2004-06-17 Robert Bosch Gmbh Heated metering device for the reformer of a fuel cell arrangement

Also Published As

Publication number Publication date
WO2002000814A1 (en) 2002-01-03
AU2001266357A1 (en) 2002-01-08

Similar Documents

Publication Publication Date Title
JPWO2002031090A1 (en) Gasoline vehicle and fuel for fuel cell system, and storage and / or supply system thereof
US6824573B2 (en) Fuel for use in fuel cell
US6958117B2 (en) Fuel for use in a fuel cell system
JP4583666B2 (en) Fuel for fuel cell system
US6939459B2 (en) Fuel for use in fuel cell system
JP4598889B2 (en) Fuel for fuel cell system
EP1273651A1 (en) Fuel for use in fuel cell system
US20030187310A1 (en) Fuel for fuel cell system
US20030105369A1 (en) Fuel for use in a fuel cell system
US6837909B2 (en) Fuel for use in a fuel cell system
US6884272B2 (en) Fuel for fuel cell system
JP4598890B2 (en) Fuel for fuel cell system
JP4632281B2 (en) Fuel for fuel cell system
US6962650B2 (en) Fuel for use in a fuel cell system
US7141084B2 (en) Fuel for fuel cell system
JP4601869B2 (en) Fuel for fuel cell system
JP4598897B2 (en) Fuel for fuel cell system
JP4598896B2 (en) Fuel for fuel cell system

Legal Events

Date Code Title Description
AS Assignment

Owner name: NIPPON OIL CORPORATION, JAPAN

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:SAITOU, KENICHIROU;ANZAI, IWAO;SADAKANE, OSAMU;AND OTHERS;REEL/FRAME:013662/0756

Effective date: 20021129

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION

点击 这是indexloc提供的php浏览器服务,不要输入任何密码和下载