WO2006070908A1 - 燃料電池発電装置 - Google Patents
燃料電池発電装置 Download PDFInfo
- Publication number
- WO2006070908A1 WO2006070908A1 PCT/JP2005/024207 JP2005024207W WO2006070908A1 WO 2006070908 A1 WO2006070908 A1 WO 2006070908A1 JP 2005024207 W JP2005024207 W JP 2005024207W WO 2006070908 A1 WO2006070908 A1 WO 2006070908A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- fuel
- hydrogen
- hydrogen production
- electrode
- fuel cell
- Prior art date
Links
- 239000000446 fuel Substances 0.000 title claims abstract description 595
- 238000010248 power generation Methods 0.000 title claims abstract description 50
- 239000001257 hydrogen Substances 0.000 claims abstract description 836
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 836
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 822
- 239000007789 gas Substances 0.000 claims abstract description 155
- 239000007800 oxidant agent Substances 0.000 claims abstract description 54
- 230000001590 oxidative effect Effects 0.000 claims abstract description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000005416 organic matter Substances 0.000 claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 claims description 510
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 252
- 238000007254 oxidation reaction Methods 0.000 claims description 109
- 230000003647 oxidation Effects 0.000 claims description 107
- 238000006243 chemical reaction Methods 0.000 claims description 65
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 53
- 239000001301 oxygen Substances 0.000 claims description 53
- 229910052760 oxygen Inorganic materials 0.000 claims description 53
- 239000012528 membrane Substances 0.000 claims description 39
- 239000003054 catalyst Substances 0.000 claims description 32
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 26
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- 239000007788 liquid Substances 0.000 claims description 20
- 239000000126 substance Substances 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 239000001569 carbon dioxide Substances 0.000 claims description 12
- 239000007784 solid electrolyte Substances 0.000 claims description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 11
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 239000011810 insulating material Substances 0.000 claims description 4
- CFQCIHVMOFOCGH-UHFFFAOYSA-N platinum ruthenium Chemical compound [Ru].[Pt] CFQCIHVMOFOCGH-UHFFFAOYSA-N 0.000 claims description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 3
- 229910000929 Ru alloy Inorganic materials 0.000 claims description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 3
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims description 3
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 claims description 3
- 239000006096 absorbing agent Substances 0.000 claims 1
- 238000005192 partition Methods 0.000 abstract description 4
- 238000000354 decomposition reaction Methods 0.000 abstract 1
- 210000004027 cell Anatomy 0.000 description 307
- 239000003570 air Substances 0.000 description 267
- 239000007864 aqueous solution Substances 0.000 description 33
- 239000000243 solution Substances 0.000 description 26
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 20
- 230000007423 decrease Effects 0.000 description 19
- 238000009792 diffusion process Methods 0.000 description 18
- 239000003792 electrolyte Substances 0.000 description 17
- 238000012360 testing method Methods 0.000 description 17
- 230000003247 decreasing effect Effects 0.000 description 14
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 14
- 238000010586 diagram Methods 0.000 description 13
- 238000004817 gas chromatography Methods 0.000 description 13
- 150000002431 hydrogen Chemical class 0.000 description 12
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 239000005518 polymer electrolyte Substances 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- -1 hydrogen ions Chemical class 0.000 description 8
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 7
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 7
- 235000019253 formic acid Nutrition 0.000 description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 7
- 238000003860 storage Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 229920000557 Nafion® Polymers 0.000 description 6
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000005868 electrolysis reaction Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 4
- 230000003750 conditioning effect Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- FHKPLLOSJHHKNU-INIZCTEOSA-N [(3S)-3-[8-(1-ethyl-5-methylpyrazol-4-yl)-9-methylpurin-6-yl]oxypyrrolidin-1-yl]-(oxan-4-yl)methanone Chemical compound C(C)N1N=CC(=C1C)C=1N(C2=NC=NC(=C2N=1)O[C@@H]1CN(CC1)C(=O)C1CCOCC1)C FHKPLLOSJHHKNU-INIZCTEOSA-N 0.000 description 3
- 238000005341 cation exchange Methods 0.000 description 3
- 239000002828 fuel tank Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000002407 reforming Methods 0.000 description 3
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 2
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 2
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 2
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 2
- 210000005056 cell body Anatomy 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000020169 heat generation Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- SFMJNHNUOVADRW-UHFFFAOYSA-N n-[5-[9-[4-(methanesulfonamido)phenyl]-2-oxobenzo[h][1,6]naphthyridin-1-yl]-2-methylphenyl]prop-2-enamide Chemical compound C1=C(NC(=O)C=C)C(C)=CC=C1N1C(=O)C=CC2=C1C1=CC(C=3C=CC(NS(C)(=O)=O)=CC=3)=CC=C1N=C2 SFMJNHNUOVADRW-UHFFFAOYSA-N 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000005871 repellent Substances 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910002848 Pt–Ru Inorganic materials 0.000 description 1
- JAWMENYCRQKKJY-UHFFFAOYSA-N [3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-ylmethyl)-1-oxa-2,8-diazaspiro[4.5]dec-2-en-8-yl]-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]methanone Chemical compound N1N=NC=2CN(CCC=21)CC1=NOC2(C1)CCN(CC2)C(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F JAWMENYCRQKKJY-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000004650 carbonic acid diesters Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000013626 chemical specie Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000011549 displacement method Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000008400 supply water Substances 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
- H01M8/04089—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
- H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
- H01M8/0612—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/22—Fuel cells in which the fuel is based on materials comprising carbon or oxygen or hydrogen and other elements; Fuel cells in which the fuel is based on materials comprising only elements other than carbon, oxygen or hydrogen
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Definitions
- the present invention relates to a fuel cell power generation apparatus combined with a fuel reformer (hydrogen production apparatus), and more particularly to an improved technique for a hydrogen production apparatus used in a fuel cell power generation apparatus such as a package type fuel cell power generation apparatus. is there. Background art
- a power generation device (power supply device) incorporating a fuel cell has been proposed in consideration of environmental problems.
- this fuel cell power generation device is used as a mobile power source or an on-site power source, its transportation and installation
- a package type fuel cell power generation apparatus is used in which each device constituting the power generation apparatus is integrated and accommodated in a single metal package.
- the fuel reformer for reforming into a fuel mainly composed of hydrogen is a single package ( Built in the unit case).
- the package (unit case) has a fuel cell body, a power converter that converts DC power generated in the fuel cell into a power output specification, a controller that controls the entire system, and a fuel cell.
- auxiliary equipment such as pumps and fans is built-in (for example, see Patent Documents 1 to 5).
- Patent Document 1 Japanese Patent Laid-Open No. 5-290868.
- Patent Document 2 Japanese Patent Laid-Open No. 10-2841 05
- Patent Document 3 Japanese Patent Application Laid-Open No. 2002-1 7059 1
- Patent Document 4 Japanese Patent Laid-Open No. 2003-2 1 7635
- Patent Document 5 Japanese Unexamined Patent Publication No. 2003-297409
- a fuel reformer is usually composed of a reformer, a CO converter, and a CO remover, and each of these devices is filled with a predetermined catalyst. It must be heated because it works at high temperatures. For this reason, a reformer is equipped with a panner, and at the time of start-up, the raw fuel is burned by this panner, and the temperature of the catalyst in the reformer is raised to about 65.degree. As the reformer temperature rises, the temperature of the CO converter and the CO remover catalyst also gradually rises. However, the reformed gas at startup is unstable, so it is not immediately supplied to the fuel cell. It is sent to the PG burner and burned (Patent Document 5, paragraph [0 0 0 3]).
- Patent Documents 1 and 3 a technology for providing a heat insulating partition between the fuel reformer and the controller, and as in Patent Documents 1 and 2, the inside of the package is forcibly ventilated by a blower or a ventilation fan.
- a technology for cooling the device and the like, and a technology for arranging the control device so as not to be affected by the heat of the fuel reformer as in Patent Documents 4 and 5 have been developed.
- Patent Document 6 Japanese Patent Laid-Open No. 6-600 8 94
- Patent Document ⁇ Japanese Patent Laid-Open No. 10-9 2 4 5 6
- the fuel cell power generators of Patent Documents 6 and 7 do not require means for preventing thermal effects as in the case of using a conventional fuel reformer, but the hydrogen storage alloy releases hydrogen. Since the process is an endothermic reaction, the temperature of the hydrogen storage alloy decreases when supplying hydrogen fuel, and the hydrogen release capacity of the hydrogen storage alloy decreases as the temperature decreases, so a sufficient hydrogen flow rate is secured. In order to achieve this, it is necessary to heat the hydrogen storage alloy by introducing the heat generated in the fuel cell body to the hydrogen storage cylinder. In addition, since the cylinder is used, the power generation time is limited. was there. .
- Patent Documents 8 and 10 Furthermore, the invention of a method for generating hydrogen by an electrochemical reaction (see Patent Documents 8 and 10), and the invention of a fuel cell using hydrogen generated by an electrochemical method (see Patent Documents 9-: L 1) are known.
- Patent Document 8 Japanese Patent No. 3 3 2 8 9 9 3 Patent Document 9: Japanese Patent No. 3360349
- Patent Document 10 US Pat. No. 6,299,744, US Pat. No. 6,368,492, US Pat. No. 6,432,284, US Pat. No. 6,533,91 No. 9, US Patent Publication 2003 0226763 Patent Document 1 1: JP 2001-297779 A
- Patent Document 8 states that “a pair of electrodes is provided on opposite sides of a cation exchange membrane, and a fuel including at least methanol and water is brought into contact with an electrode including a catalyst provided on one side, and the pair of electrodes is contacted. By applying a voltage to the electrode and extracting electrons from the electrode, a reaction for generating hydrogen ions from the methanol and water is allowed to proceed on the electrode, and the generated hydrogen ions are converted into the cation exchange membrane.
- a hydrogen generation method characterized in that an electrode provided on the other side of a pair of opposed surfaces is converted into hydrogen molecules by supplying electrons.
- Patent Document 9 discloses an invention of a fuel cell using hydrogen generated by such a method. (Paragraphs [0052] to [00 56]).
- the invention described in Patent Document 10 also passes through the diaphragm 110, and the proton produced by the anode 11 12 as the fuel electrode passes through the counter electrode.
- One power sword 1 14 generates hydrogen, but the anode is the anode.
- the counter electrode is the cathode and a voltage is applied from the DC power source 120 to electrolyze organic fuel such as methanol.Hydrogen is generated on the counter electrode side of the fuel electrode. Since it does not supply an oxidant, it is clearly different from the hydrogen production apparatus used in the fuel cell power generator of the present invention. ,
- Patent Document 11 describes that in a fuel cell system, a hydrogen generating electrode for generating hydrogen is provided (Claim 1).
- “Porous electrode (fuel electrode) 1 contains alcohol and water.
- air is supplied to the gas diffusion electrode (oxidant electrode) 2 on the opposite side, and a load is connected between the terminal of the porous electrode 1 and the terminal of the gas diffusion electrode 2, the normal fuel An electrical connection is established such that a positive potential is applied to the porous electrode 1 via the load from the gas diffusion electrode 2 which is the positive electrode of the MEA 2 having a battery function, so that alcohol reacts with water.
- Carbon dioxide and hydrogen ions are generated, and the generated hydrogen ions are generated as hydrogen gas at the central gas diffusion electrode 6 via the electrolyte layer 5.
- Patent Document 12 Japanese Patent Laid-Open No.
- Patent Document 13 Japanese Patent Laid-Open No. 6-7 3 5 8 3 (Claim 1, 8, paragraphs [0 0 0 6], [0 0 1 9]) Disclosure of the invention
- the present invention solves the above problems, can easily supply hydrogen to the fuel cell, can continuously produce a gas containing hydrogen at a low temperature, and It is an object of the present invention to provide a fuel cell power generation device such as a package type fuel cell power generation device using a hydrogen production device that does not require large electric energy. Means for solving the problem
- the present invention employs the following means.
- a hydrogen production apparatus decomposes a fuel containing organic matter to produce a gas containing hydrogen, a diaphragm, a fuel electrode provided on one surface of the diaphragm, and a fuel containing organic matter and water in the fuel electrode.
- the hydrogen production device produces a gas containing hydrogen by decomposing fuel containing organic matter.
- a diaphragm, a fuel electrode provided on one surface of the diaphragm, a means for supplying a fuel containing organic matter and water to the fuel electrode, an oxidation electrode provided on the other surface of the diaphragm, the oxidation A fuel cell power generator comprising: means for supplying an oxidant to the electrode; and means for generating and extracting a gas containing hydrogen from the fuel electrode side.
- the hydrogen production apparatus is an open circuit having no means for taking out electric energy from the hydrogen production cell constituting the hydrogen production apparatus and means for applying electric energy from the outside to the hydrogen production cell. Characterized in (1) or (2) above Fuel cell power generator.
- a hydrogen production apparatus that is an open circuit without means for taking out electrical energy from a hydrogen production cell constituting the hydrogen production apparatus and means for applying electric energy from the outside to the hydrogen production cell;
- Hydrogen production apparatus having a fuel electrode as a negative electrode and means for taking out electric energy to the outside with the oxidation electrode as a positive electrode and hydrogen production having means for applying electric energy from the outside with the fuel electrode as a force sword and the oxidation electrode as an anode (1) or (2) fuel cell : pond power generation device, wherein two or more hydrogen production devices selected from the group of devices are used in combination.
- the voltage between the fuel electrode and the oxidation electrode and the generation amount of Z or the gas containing hydrogen are adjusted by adjusting the electric energy to be extracted in the hydrogen production apparatus.
- the voltage between the fuel electrode and the oxidation electrode and the generation amount of Z or gas containing hydrogen are adjusted by adjusting the applied electric energy in the hydrogen production apparatus.
- the amount of gas containing hydrogen is adjusted by adjusting a voltage between the fuel electrode and the oxidation electrode.
- the voltage between the fuel electrode and the oxidation electrode and the amount of Z or gas containing hydrogen are adjusted by adjusting the concentration of the oxidant.
- the fuel cell power generator according to any one of (1) to (14).
- the organic substance supplied to the fuel electrode of the hydrogen production apparatus is one or more organic substances selected from the group consisting of alcohol, aldehyde, carboxylic acid, and ether. 1) The fuel cell power generator according to any one of (19).
- the oxidant supplied to the oxidation electrode of the hydrogen production apparatus is a gas containing oxygen or The fuel cell power generator according to any one of (1) to (21), wherein the fuel cell power generator is oxygen.
- the hydrogen production apparatus includes a fuel electrode separator provided with a flow channel for flowing the fuel and an oxide electrode separator provided with a flow channel for flowing the oxidant.
- the fuel cell power generator according to any one of (1) to (28).
- the fuel electrode separator and the oxidation electrode separator of the hydrogen production apparatus are configured so that a flow channel groove of the fuel electrode separator faces at least a part of a flange portion other than the flow channel groove of the oxidation electrode separator.
- the hydrogen production apparatus used in the fuel cell power generation apparatus of (3) to (5) has means for supplying fuel and oxidant, and as this means, a pump, a probe or the like is used. be able to.
- electric energy is applied to the hydrogen production cell. It has a second electrolysis means.
- the case (3) is an open circuit type having no discharge control means for taking out electric energy from the hydrogen production cell and electrolysis means for applying electric energy to the hydrogen production cell.
- the hydrogen production device used in the fuel cell power generation device of (1) and the package type fuel cell power generation device of (2) is a hydrogen production device used in the fuel cell power generation device of (3) to (5). Is included. These hydrogen production equipment can be used in combination of two or more. In addition, these hydrogen production devices monitor the hydrogen production cell voltage (open circuit voltage or operating voltage) and the amount of Z or hydrogen-containing gas generated, and supply and concentration of fuel and oxidant, and It has a function to control the electric energy to be extracted (in the case of (4) above) or the electric energy to be applied (in the case of (5) above).
- the basic structure of the hydrogen production cell constituting the hydrogen production apparatus is that a fuel electrode is provided on one surface of the diaphragm and fuel is supplied to the fuel electrode, and an oxidation electrode is provided on the other surface of the diaphragm. It has a structure for supplying an oxidizing agent to the oxidation electrode.
- the fuel cell power generation device of the present invention uses a hydrogen production device that can reform fuel at a temperature significantly lower than the conventional reforming temperature of room temperature to 10 ° C. or less, Not only can the start-up time be shortened, but the energy required to raise the temperature of the reformer can be reduced, and it is possible to eliminate the need for a heat insulation material to shut off the heat generated by the reformer. In addition, it does not require special means such as heat insulating material to protect the control device built in the package from heat, and it can be easily applied to the fuel cell without cooling the gas containing hydrogen generated from the hydrogen production device. The effect is that it can be supplied.
- the hydrogen production device used in the fuel cell power generation device of the present invention is a case where hydrogen can be generated without supplying electric energy from the outside to the hydrogen production cell, but it has a means for taking out electric energy. However, even when a means for applying electric energy from the outside is provided, hydrogen can be generated. If there is a means to extract electric energy, the electric energy can be used to move auxiliary equipment such as pumps and blowers, and so on, so the effect is great from the viewpoint of energy utilization. ⁇
- FIG. 1 (a) is a schematic diagram showing an example of the configuration of the packaged fuel cell power generator of the present invention.
- FIG. 1 (b) is a schematic diagram showing the relationship between the hydrogen production apparatus and the fuel cell in the packaged fuel cell power generator of the present invention.
- FIG. 2 is a schematic view of a hydrogen production cell (without supplying electric energy from the outside) in Example 1.
- Fig. 3 is a diagram showing the relationship between the air flow rate, the hydrogen generation rate, and the open voltage at different temperatures (30 to 70 ° C) (hydrogen production example 1-11).
- Figure 4 shows the relationship between the open voltage and the hydrogen production rate at different temperatures (30 to 70 ° C) (hydrogen production example 1-11).
- Figure 5 shows the relationship between the air flow rate, hydrogen production rate, and open voltage (temperature 70 ° C) at different fuel flow rates (hydrogen production example 1 1-2).
- Figure 6 shows the relationship between the open voltage and hydrogen production rate (temperature 70 ° C) at different fuel flow rates (hydrogen production example 1 1-2).
- Figure 7 shows the relationship between the air flow rate at different fuel concentrations, hydrogen production rate, and open voltage (temperature 70 ° C) (hydrogen production example 1-3).
- Figure 8 shows the relationship between open voltage and hydrogen production rate (temperature 70 ° C) at different fuel concentrations (hydrogen production example 1-3).
- Fig. 9 is a diagram showing the relationship between the air flow rate, hydrogen generation rate, and open voltage in electrolyte membranes with different thicknesses (hydrogen production example 1-14).
- FIG. 10 is a diagram showing the relationship between the open voltage and the hydrogen generation rate in electrolyte membranes with different thicknesses (hydrogen production example 1-14).
- Figure 11 shows the relationship between the air flow rate, hydrogen production rate, and open voltage at different temperatures (30 to 90 ° C) (hydrogen production example 1-5).
- Fig. 12 shows the relationship between the open voltage and hydrogen production rate (oxidant: air) at different temperatures (30 to 90 ° C) (hydrogen production example 1-5).
- Figure 13 shows the air flow rate, hydrogen production rate and open voltage at different fuel flow rates. Is a diagram showing the relationship (temperature 50 ° C) (hydrogen production example 1-6).
- Figure 14 shows the relationship between open voltage and hydrogen production rate (temperature 50 ° C) at different fuel flow rates (hydrogen production example 1-6).
- Fig. 15 is a diagram showing the relationship (temperature 50 ° C) between the air flow rate, hydrogen production rate, and open voltage at different fuel concentrations (temperature production example 1-7).
- Figure 16 shows the relationship between the open voltage and hydrogen production rate (temperature 50 ° C) at different fuel concentrations (hydrogen production example 1-7).
- Figure 1 7 is a diagram showing the relationship between the oxidizing gas flow rate and the hydrogen generation rate and the open voltage at different oxygen concentrations (temperature 50 D C) (Hydrogen Production Example 1 one 8).
- Figure 18 shows the relationship between open voltage and hydrogen production rate (temperature: 50 ° C) at different oxygen concentrations (hydrogen production example 1-8).
- Figure 19 is a diagram showing the relationship of H 2 ⁇ 2 flow rate and the hydrogen production rate ⁇ beauty open voltage at different temperatures (30 to 90 ° C) (Hydrogen Production Example 1 10).
- FIG. 20 is a graph showing the relationship (oxidant: H 2 0 2 ) between the open voltage and the hydrogen production rate at different temperatures (30 to 90 ° C) (hydrogen production example 1-10).
- FIG. 21 is a schematic view of a hydrogen production cell (with a means for extracting electric energy) in Example 2.
- Fig. 22 shows the relationship between the extracted current density and operating voltage at different air flow rates (discharge: temperature 50 ° C) (hydrogen production example 2-1).
- Figure 23 shows the relationship between the operating voltage and the hydrogen production rate at different air flow rates (discharge: temperature 50 ° C) (hydrogen production example 2-1).
- Figure 24 shows the relationship between the extracted current density and operating voltage at different air flow rates (discharge: temperature 30 ° C) (hydrogen production example 2-2).
- Figure 25 shows the relationship between the operating voltage and the hydrogen production rate at different air flow rates (discharge: temperature 30 ° C) (hydrogen production example 2-2).
- Fig. 26 shows the relationship between the extracted current density and operating voltage at different air flow rates (discharge: temperature 70 ° C) (hydrogen production example 2-3). '
- Figure 27 shows the relationship between the operating voltage and the hydrogen production rate at different air flow rates (discharge: temperature 70 ° C) (hydrogen production example 2-3).
- Figure 28 shows the relationship between the extracted current density and operating voltage at different air flow rates (discharge: temperature 90 ° C) (hydrogen production example 2-4).
- Figure 29 shows the relationship between the operating voltage and the hydrogen production rate at different air flow rates (discharge: temperature 90 ° C) (hydrogen production example 2.-4).
- FIG. 30 is a diagram showing the relationship between the extracted current density and the operating voltage at different temperatures (discharge: air flow rate of 50 mI).
- Figure 31 shows the relationship between the operating voltage and the hydrogen production rate at different temperatures (discharge: air flow 50 ml l Z).
- FIG. 32 is a diagram showing the relationship between the extracted current density and the operating voltage at different temperatures (discharge: air flow rate of 100 m 1 Z).
- FIG. 33 is a diagram showing the relationship between the operating voltage and the hydrogen production rate at different temperatures (discharge: air flow rate 10 Oml / min).
- Figure 34 shows the relationship between the extracted current density and the operating voltage (discharge: temperature 50 ° C) for different amounts of fuel (hydrogen production example 2-5).
- Figure 35 shows the relationship between the operating voltage and the hydrogen production rate at different fuel flow rates (discharge: temperature 50 ° C) (hydrogen production example 2-5).
- Fig. 36 shows the relationship between the extracted current density and operating voltage at different fuel concentrations (discharge: temperature 50 ° C) (hydrogen production example 2-6).
- Figure 37 shows the relationship between the operating voltage and the hydrogen production rate at different fuel concentrations (discharge: temperature 50 ° C) (hydrogen production example 2-6).
- Figure 38 shows the relationship between the extracted current density and operating voltage at different oxygen concentrations (discharge: temperature 50 ° C) (hydrogen production example 2-7).
- Figure 39 shows the relationship between the operating voltage and hydrogen production rate at different oxygen concentrations (discharge: temperature 5 ° C) (hydrogen production example 2-7).
- FIG. 40 is a graph showing the relationship between the extracted current density and the operating voltage at different temperatures (discharge: oxidizing agent H 2 0 2 ) (hydrogen production example 2-8).
- FIG. 41 is a graph showing the relationship between the operating voltage and the hydrogen production rate at different temperatures (discharge: oxidant H 2 0 2 ) (hydrogen production example 2-8).
- Fig. 42 shows a hydrogen production cell in Example 3 (applying electric energy from the outside).
- Figure 43 shows the relationship between applied current density and hydrogen production rate at different air flow rates.
- Figure 44 shows the relationship between operating voltage and hydrogen production rate (charging: temperature 50 ° C) at different air flow rates (hydrogen production example 3-1).
- Figure 45 shows the relationship between applied current density and operating voltage at different air flow rates (charging: temperature 50 ° C) (hydrogen production example 3-1).
- Fig. 46 shows the relationship between operating voltage and energy efficiency at different air flow rates (charging: temperature 50 ° C) (hydrogen production example 3-1).
- Figure 47 shows the relationship between applied current density and hydrogen production rate at different air flow rates.
- Fig. 48 shows the relationship between the operating voltage and the hydrogen production rate at different air flow rates (charging: temperature 30 ° C) (hydrogen production example 3-2).
- Fig. 49 shows the relationship between operating voltage and energy efficiency at different air flow rates (charging: temperature 30 ° C) (hydrogen production example 3-2).
- Figure 50 shows the relationship between the applied current density and the hydrogen production rate at different air flow rates (charging: temperature 70 ° C) (hydrogen production example 3-3).
- Figure 51 shows the relationship between the operating voltage and the hydrogen production rate at different air flow rates (charging: temperature 70 ° C) (hydrogen production example 3-3).
- Fig. 52 shows the relationship between operating voltage and energy efficiency at different air flow rates (charging: temperature 70 ° C) (hydrogen production example 3-3).
- Figure 53 shows the relationship between the applied current density and the hydrogen production rate at different air flow rates (charging: temperature 90 ° C) (hydrogen production example 3-4).
- Figure 54 shows the relationship between the operating voltage and the hydrogen production rate at different air flow rates (charging: temperature 90 ° C) (hydrogen production example 3-4).
- Fig. 55 shows the relationship between operating voltage and energy efficiency at different air flow rates (charging: temperature 90 ° C) (hydrogen production example 3-4).
- Fig. 56 is a diagram showing the relationship between the applied current density and the hydrogen production rate at different temperatures (charging: air flow rate of 5 Om l).
- Fig. 57 shows the relationship between operating voltage and hydrogen generation rate at different temperatures (charging: air flow rate 5 Oml).
- Figure 58 shows the relationship between operating voltage and energy efficiency at different temperatures (charging: air flow 50 ml).
- Figure 59 shows the relationship between the applied current density and the hydrogen production rate at different fuel flow rates (charging: temperature 50 ° C) (hydrogen production example 3-5).
- Figure 60 shows the relationship between the operating voltage and the hydrogen production rate at different fuel flow rates (charging: temperature 50 ° C) (hydrogen production example 3-5).
- Figure 61 shows the relationship between operating voltage and energy efficiency at different fuel flow rates (charging: temperature 50 ° C) (hydrogen production example 3-5).
- Figure 62 shows the relationship between the applied current density and the hydrogen production rate at different fuel concentrations (charging: temperature 50 ° C) (hydrogen production example 3-6).
- Figure 63 shows the relationship between operating voltage and hydrogen production rate (charging: temperature 50 ° C) at different fuel concentrations (hydrogen production example 3_6) '.
- Figure 64 shows the relationship between operating voltage and energy efficiency at different fuel concentrations (charging: temperature 50 ° C) (hydrogen production example 3-6).
- Figure 65 shows the relationship between the applied current density and the hydrogen production rate (charge: temperature 50 ° C) at different oxygen concentrations (hydrogen production example 3_7).
- Figure 66 shows the relationship between the operating voltage and the hydrogen production rate at different oxygen concentrations (charging: temperature 50 ° C) (hydrogen production example 3-7).
- Figure 67 shows the relationship between operating voltage and energy efficiency at different oxygen concentrations (charging: temperature 50 ° C) (hydrogen production example 3-7).
- Figure 68 shows the relationship between the applied current density at different temperatures and the hydrogen production rate (charging: oxidizing agent H 2 0 2 ) (hydrogen production example 3-8).
- Figure 69 shows the relationship between operating voltage and hydrogen production rate at different temperatures (charging: oxidant H 2 0 2 ) (hydrogen production example 3-8).
- Figure 70 shows the relationship between operating voltage and energy efficiency at different temperatures (charging: oxidizer ⁇ 2 0 2 ) (hydrogen production example 3-8).
- Figure 71 shows the relationship between air flow rate and hydrogen production rate (open circuit: temperature 50 ° C). (Example 8).
- Figure 72 shows the relationship between the open voltage and the hydrogen production rate (open circuit: temperature 50 ° C) (Example 8).
- FIG. 73 shows the relationship between the air flow rate and the hydrogen production rate (open circuit: no fuel electrode separator) (Example 9).
- Fig. 74 shows the relationship between the open voltage and the hydrogen production rate (open circuit: no fuel electrode separator) (Example 9).
- Fuel cell 3 Power conversion device that converts DC power generated by 0 into specified power 3 7
- Control device that controls the entire power generation device 3 8
- the hydrogen production apparatus used in the fuel cell power generation apparatus of the present invention is basically a novel one, and what is described below is only one embodiment, and the present invention is not limited thereby. .
- FIGS. 1 (3) and (13) show an example of a package type fuel cell power generation device which is an embodiment of the fuel cell power generation device of the present invention.
- the basic configuration of the packaged fuel cell power generator of the present invention is supplied to a fuel cell (30) and a fuel cell (30) that generate power by supplying hydrogen and an oxidant.
- a hydrogen production cell (10) that produces hydrogen-containing gas
- a power converter (36) that converts DC power generated by the fuel cell (30) into predetermined power, and controls the entire power generator
- the control device (37), auxiliary equipment such as the fuel pump (16), air blower (17), etc. are built in at least the package (38).
- the hydrogen production cell (10) constituting the 7k 'element production apparatus is operated at a low temperature, which is different from the conventional fuel reformer. It is possible to arrange the control device (37) close to the hydrogen production zel (10). Also, a heat insulating material for protecting the control device (37) from the heat generated by the hydrogen production cell (10) can be eliminated.
- the fuel tank (20) and fuel adjustment tank (2 1) are built in the package, but fuel (methanol aqueous solution) is supplied from the outside of the package without incorporating them.
- fuel methanol aqueous solution
- only the fuel adjustment tank (2 1) may be included in the package.
- the hydrogen-containing gas generated from the hydrogen production cell (10) can be supplied directly to the fuel cell (30).
- a hydrogen tank (24) for storing the hydrogen-containing gas is provided. 24) is preferably supplied to the fuel cell (30).
- a gas-liquid separator (23) for separating the gas containing hydrogen and the unreacted methanol aqueous solution, and to circulate the unreacted methanol aqueous solution to the hydrogen production cell (10).
- the generated water and the unreacted aqueous methanol solution are separated from the exhaust air.
- a gas-liquid separator (27) may be provided.
- a backup battery can be provided in addition to these.
- Hydrogen generating device used in the package type fuel cell power generating apparatus of the present invention as shown in Zu ⁇ (b), the hydrogen generating cell (1 0), and those having an auxiliary machine for driving the hydrogen generating device is there.
- the structure of the hydrogen production cell (10) is to provide a fuel electrode (12) on one side of the diaphragm (1 1) and to supply fuel (methanol aqueous solution) containing organic matter and water to the fuel electrode (1 2).
- a fuel pump (16) that supplies methanol aqueous solution to the fuel electrode (12) is provided as an auxiliary machine for operating the hydrogen production system.
- the flow path (1 3) in the fuel electrode is connected by a conduit via a fuel pump (1 6) and a flow control valve (1 8).
- Fuel (100% methanol) is stored in the fuel tank (20), transferred from there to the fuel conditioning tank (2 1) and mixed with water in the fuel conditioning tank (2 1), for example 3% It is adjusted to a methanol aqueous solution to the extent that it is supplied to the fuel electrode (12).
- an air blower (17) can be installed as an auxiliary machine, and air can be supplied directly to the oxidation electrode (14). In this figure, air is blown to the fuel cell (30) by the air blower (17). The unreacted air (exhaust air) discharged from the fuel cell (30) is used.
- this exhaust air has a temperature (about 80 ° C) that is almost the same as the operating temperature of the fuel cell (30), this protects the control device (37) from the heat of the fuel cell (30).
- the heat of the exhaust air can be used as a heat source for heating the hydrogen production cell (10).
- the air supplied to the oxidation electrode (14) of one hydrogen production cell (10) is discharged from the other hydrogen production cell (1 0) force.
- the exhausted air can be utilized.
- the amount of gas containing hydrogen is determined by providing a voltage regulator (22) that monitors the voltage (open circuit voltage or operating voltage) of the hydrogen production cell (10). In addition, it can be adjusted by controlling the electric energy to be taken out or applied.
- the generated hydrogen-containing gas is passed through a gas-liquid separator (23) and separated into hydrogen-containing gas and unreacted aqueous methanol solution, and the hydrogen-containing gas is stored in a hydrogen tank (24).
- Part or all of the separated unreacted aqueous methanol solution is circulated back to the fuel conditioning tank (21) through the conduit (25).
- water may be supplied from outside the system.
- the exhausted air discharged from the hydrogen production system contains unreacted methanol water that has permeated from the fuel electrode due to the generated water and crossover phenomenon. This exhausted air is separated from the gas-liquid separator ( 2) Separate the product water from the unreacted methanol aqueous solution through 7), remove the carbon dioxide with the carbon dioxide removal device (28), and discharge it into the atmosphere.
- Part or all of the separated product water and unreacted aqueous methanol solution are returned to the fuel conditioning tank (21) through the conduit (29) and circulated.
- the hydrogen electrode (32) of the fuel cell (30) is stored in the hydrogen tank (24). Hydrogen is supplied through the flow control valve (26), and air is supplied to the air electrode (34) from the air probe (17) through the flow control valve (19).
- the reaction of Formula [1] occurs on the air electrode side, and the reaction of Formula [2] occurs on the air electrode side, and the reaction of Formula [3] occurs in the fuel cell as a whole, producing water (steam), and electricity (DC power) ) Occurs.
- any fuel cell can be used as long as the fuel is hydrogen, but a polymer electrolyte fuel cell (PEFC) that can be operated at a low temperature of 100 ° C or lower is preferred.
- PEFC polymer electrolyte fuel cell
- a fuel cell stack in which a plurality of well-known single cells are stacked can be employed.
- One unit cell consists of a solid polymer electrolyte membrane (3 1) such as naphthion (trademark of DuPont), a hydrogen electrode (32) and an air electrode (34), which are diffusion electrodes sandwiching it from both sides, and both from both sides. Equipped with two separators etc. to sandwich.
- Concavities and convexities are formed on both sides of the separator, and gas flow paths (33), (35) in the single cell are formed between the sandwiched hydrogen electrode and air electrode.
- gas flow paths (33), (35) in the single cell are formed between the sandwiched hydrogen electrode and air electrode.
- the supplied hydrogen gas is on the other hand, the gas flow path in the single cell (35) formed with the air electrode (35). ) Each has air.
- the power generation of the fuel cell (30) involves heat generation.
- the polymer electrolyte fuel cell PEF C
- the polymer electrolyte membrane exhibits proton conductivity in a water-containing state. Therefore, the polymer electrolyte membrane dries as the fuel cell generates heat, and the moisture content If the value decreases, the internal resistance of the fuel cell increases and the power generation capacity decreases. Therefore, in order to prevent the polymer electrolyte membrane from drying, it is necessary to cool the fuel cell and maintain it at an appropriate operating temperature (about 80 ° C).
- the hydrogen production apparatus has higher hydrogen generation efficiency at higher temperatures. Therefore, the heat generation of this fuel cell is used for heating the hydrogen production apparatus by providing heat exchange means. Is preferred.
- the hydrogen production apparatus used in the present invention is an organic substance and From the fuel electrode side that supplies water-containing fuel (such as aqueous methanol solution) A gas containing hydrogen is taken out. Since the hydrogen is humidified, a humidifier can be dispensed with. Furthermore, since the gas containing hydrogen generated from the hydrogen production cell (10) is not as hot as the reformed gas produced by the conventional reformer, it can be supplied to the fuel cell (30) without cooling. it can.
- the DC power generated by the fuel cell (30) is introduced into the power converter (36), boosted by the DC / DC converter, or converted to AC power by the DCZAC inverter and output.
- the DC power stabilized by the auxiliary converter is used as a drive power source for auxiliary equipment such as fuel pumps (16) and air blowers (17), and AC power is the drive power source for household electrical equipment. Used as
- control device (37) is, the voltage regulator (22) of the hydrogen production cell (10), the fuel cell (30), the power converter (36), the fuel pump (16), the air Controls the operation of auxiliary equipment such as blowers (17).
- the hydrogen production cell (1 0) in the hydrogen production apparatus used in the fuel cell power generator of the present invention has the diaphragm (1 1) and the fuel electrode (1 2) on one surface of the diaphragm (1 1). ) And an oxidation electrode (14) on the other surface is the basic structure.
- an ME A electroactive metal oxide film
- an ME A electroactive metal oxide film
- the production method of ME A is not limited, but it can be produced by a method similar to the conventional method in which the fuel electrode and the oxidation electrode (air electrode) are joined to both surfaces of the diaphragm by hot pressing.
- MEA produced as described above is a fuel electrode separator provided with a flow channel groove (13) for flowing fuel containing organic matter and water to the fuel electrode, and a flow channel groove for flowing an oxidant to the oxidation electrode.
- a hydrogen production cell is constructed by sandwiching it with an oxidation electrode separator provided with (15).
- the flow groove of the fuel electrode separator has an oxidation electrode separator. It is preferable that both the flow channel grooves are provided so as to be opposed to at least a part of the flange portion other than the flow channel groove.
- a flow path for flowing fuel containing organic matter and water can be provided at the fuel electrode, and only the oxidation electrode separator can be combined with the MEA to form a hydrogen production cell.
- a proton conductive solid electrolyte membrane used as a polymer electrolyte membrane in a fuel cell can be used.
- the proton conductive solid electrolyte membrane is preferably a perfluorocarbon sulfonic acid membrane having a sulfonic acid group, such as a naphthion membrane manufactured by DuPont.
- the fuel electrode and the oxidation electrode are preferably electrodes having conductivity and catalytic activity.
- a catalyst and PTFE resin supported on a carrier made of carbon powder or the like in a gas diffusion layer It can be prepared by applying and drying a catalyst paste containing a binder such as naphtho ion solution and a substance for imparting ionic conductivity such as naphthion solution.
- the gas diffusion layer is preferably made of a carbon paper treated with water repellent.
- Any fuel electrode catalyst can be used, but a catalyst in which a platinum-ruthenium alloy is supported on carbon powder is preferable.
- Any air electrode catalyst can be used, but a catalyst in which platinum is supported on carbon powder is preferred.
- the hydrogen production apparatus configured as described above, when a fuel containing organic matter such as a methanol aqueous solution is supplied to the fuel electrode, and an oxidizing agent such as air, oxygen or hydrogen peroxide is supplied to the oxidation electrode (air electrode), Under certain conditions, gas containing hydrogen is generated at the anode.
- the hydrogen generation method of the hydrogen production apparatus used in the fuel cell power generator of the present invention is completely different from the conventional hydrogen generation method, and it is difficult to explain the mechanism at the present time. The estimation at the present time is shown below, but the possibility of a completely new reaction cannot be denied.
- the hydrogen production apparatus used in the fuel cell power generator of the present invention has a low temperature of 30 to 90 ° C and water from the fuel electrode side where methanol and water are supplied. Gas containing element is generated. When electric energy is not supplied to the hydrogen production cell from the outside, a gas with a hydrogen concentration of about 70 to 80% is generated. When electric energy is externally applied to the hydrogen production cell, 80% or more Hydrogen concentration gas is generated. Moreover, the gas generation is known to depend on the open circuit voltage or operating voltage of both poles. From these results, the mechanism of hydrogen generation is estimated as follows. Hereafter, in order to simplify the explanation of the mechanism, explanation will be given under open circuit conditions.
- protons are produced at the fuel electrode by the catalyst. Conceivable.
- H + (proton) generated by the reaction of equation (3) moves through the proton conductive solid electrolyte membrane, and the following reaction occurs at the fuel electrode, generating hydrogen.
- the formula (1) is the positive electrode and the formula (4) is the negative. Since the reaction in equation (1) tends to proceed to the left side and the reaction in equation (4) also attempts to proceed to the left side, hydrogen is not generated.
- equation (1) in order to allow the reaction of equation (1) to proceed to the right side and the reaction of equation (4) to proceed to the right side, it is indispensable to make equation (1) function as a negative electrode and equation (4) as a positive electrode. Assuming that the entire area of the fuel electrode is equipotential, it is necessary to shift the hydrogen oxidation potential to the high potential side. However, if the fuel electrode is not equipotential, H + is extracted from methanol and water in the fuel electrode, and the reaction in Eq. (1) combines with H + and e- to produce hydrogen (4 It is possible that the reaction in equation (4) may be in progress at the same time.
- a hydrogen production cell having the same structure as a typical direct methanol fuel cell is used, and an oxidizing agent (air electrode) separator is provided with an oxidizing agent ( Air) is provided, so that a large amount of air flows in the channel groove, and the reactions (2) and (6) are dominant. If it is low, air (oxygen) will be insufficient in parts other than the channel groove. (3) It is thought that the H + production reaction of the formula is dominant.
- discharge conditions it is considered that hydrogen is generated by a mechanism similar to the hydrogen generation mechanism under open circuit conditions. However, unlike the open circuit condition, it is necessary to maintain the electrical neutral condition of the entire cell by moving H + corresponding to the discharge current from the fuel electrode to the oxidation electrode. From equation (1), it is considered that equation (1) progresses, and at the oxidation electrode, equation (2) proceeds from equation (3).
- the energy efficiency is high in a range where the supply amount of oxygen (air) is small and the applied voltage (operating voltage) is as low as 400 to 60 mV. This is because in this range, as described above, even when the open circuit condition or discharge condition in which electric energy is not supplied from the outside is used, methanol that has permeated to the air electrode side is oxidized by the equation (6). Air (oxygen) is deficient in the part other than the flow channel groove of the air electrode separator plate, and the H + production 'reaction in Eq. (3) becomes dominant, and in the fuel electrode on the opposite side, Eq.
- the meaning of the cell potential is explained.
- the voltage of a cell in which a gas electrode is formed on both electrodes across an electrolyte membrane is generated by the difference in chemical potential between the two electrodes of the ion conducting in the electrolyte.
- a proton (hydrogen ion) conducting solid electrolyte membrane is used for the electrolyte, so the voltage being observed is the chemical potential of hydrogen at the poles of the cell, in other words, the hydrogen content.
- the pressure difference is shown.
- hydrogen is generated from the fuel electrode side when the voltage between the fuel electrode and the oxidation electrode is within a certain range as in the examples described later. It is estimated that the reaction of the above formulas (1) to (6) proceeds and hydrogen is generated when the difference between the values becomes a certain range.
- a hydrogen production cell Even if the electric energy is not taken out from the outside and the electric energy is not supplied from the outside to the hydrogen production cell, the electric energy is taken out from the hydrogen production cell, or the electric energy is supplied from the outside to the hydrogen production cell. Even when it is applied, the amount of gas containing hydrogen can be adjusted by adjusting the voltage (open circuit voltage or operating voltage) between the fuel electrode and the oxidation electrode (air electrode). .
- the open circuit voltage or operating voltage and / or the amount of hydrogen-containing gas is as follows: Supply of oxidant (gas containing oxygen or liquid containing hydrogen peroxide) By adjusting the amount, adjusting the concentration of oxidizer (oxygen concentration in the gas containing oxygen), adjusting the amount of fuel containing organic matter, and adjusting the concentration of fuel containing organic matter. Can be adjusted.
- the electrical energy extracted to the outside in the case of discharge conditions, adjust the electrical energy extracted to the outside (by adjusting the current extracted to the outside, and by using a power source capable of constant voltage control, a so-called potentiostat.
- adjust the electric energy to be applied by adjusting the voltage to be taken out to the outside) (adjusting the applied current, and furthermore, a power supply capable of constant voltage control, so-called By adjusting the voltage to be applied by using a potentiostat, the operating voltage and / or the amount of gas containing hydrogen can be adjusted.
- the fuel containing the organic matter can be decomposed at 100 ° C.
- the operating temperature of the hydrogen production apparatus is set to 100 ° C. or lower. be able to.
- the operating temperature is preferably 30 to 90 ° C.
- the open circuit voltage or operating voltage and / or the amount of gas containing hydrogen can be adjusted as shown in the following examples.
- the present invention is advantageous in this respect because it is necessary to separately use a means for separating hydrogen.
- the present invention operates the hydrogen production apparatus of the present invention at a temperature slightly exceeding 10 ° C. It is not a denial of making it happen.
- the fuel containing organic matter may be a liquid or gaseous fuel that permeates the Proton conductive membrane and is oxidized electrochemically to produce Proton.
- a liquid fuel containing an alcohol such as ethanol, ethylene glycol or 2-propanol, an aldehyde such as formaldehyde, a carboxylic acid such as formic acid, or an ether such as Jethyl ether is preferred. Since the fuel containing organic substances is supplied together with water, a solution containing these liquid fuels and water, among them, an aqueous solution containing alcohol, particularly methanol, is preferable.
- the aqueous solution containing methanol as an example of the fuel described above is a solution containing at least methanol and water, and the concentration thereof can be arbitrarily selected in a region where a gas containing hydrogen is generated.
- a gas or liquid oxidant can be used.
- a gas containing oxygen or oxygen is preferable.
- the oxygen concentration of the gas containing oxygen is
- a liquid containing hydrogen peroxide is preferred as the liquid oxidant.
- the fuel input to the hydrogen production apparatus is consumed once in the apparatus and decomposed into hydrogen is low, it is possible to increase the conversion rate to hydrogen by providing a fuel circulation means. preferable.
- the hydrogen production apparatus used in the fuel cell power generator of the present invention is provided with means for extracting a gas containing hydrogen from the fuel electrode side and recovers hydrogen, but it is also preferable to recover carbon dioxide. Since it operates at a temperature as low as 10 ° C. or less, a carbon dioxide absorption part that absorbs carbon dioxide contained in a gas containing hydrogen can be provided by simple means.
- examples (hydrogen production examples) of the present invention will be shown.
- the ratios of the catalyst, PTFE, naphthion, etc., the thickness of the catalyst layer, gas diffusion layer, electrolyte membrane, etc. can be appropriately changed. It is not limited by.
- Example 1 Example 1
- Example 1 The hydrogen production cell in Example 1 (Production Example 1-11-1-10) has the same structure as a typical direct methanol fuel cell.
- Figure 2 shows an outline of the hydrogen production cell.
- DuPont's Proton conductive electrolyte membrane (Nafion 1 1 5) was used as the electrolyte, and carbon paper (Toray) was immersed in a 5% agricultural grade polytetrafluoroethylene dispersion at the air electrode. After that, it was fired at 360 ° C to be water-repellent, and the air electrode catalyst (platinum-supported carbon: made by Tanaka Kikinzoku), PTFE fine powder, and 5% Nafion solution (made by Aldrich) were mixed on one side. An electrode catalyst paste was applied to form a gas diffusion layer with an air electrode catalyst.
- the weight ratio of the air electrode catalyst, PTFE, and Nafion was 65%: 15%: 20%.
- the amount of catalyst in the air electrode thus prepared was 1 mgZcm 2 in terms of platinum.
- the carbon paper was treated with water repellency, and on one side, a fuel electrode catalyst (platinum ruthenium-supported carbon: made by Tanaka Kikinzoku), PTFE fine powder, and a 5% Nafion solution were mixed.
- a gas diffusion layer with a fuel electrode catalyst was constructed by applying paced soot.
- the weight ratio of the fuel electrode catalyst, PTFE, and naphthion was 55%: 15%: 30%.
- the catalyst amount of the fuel electrode produced in this way was 1 mgZ cm 2 in terms of platinum-ruthenium.
- the electrolyte membrane, the gas diffusion layer with an air electrode catalyst, and the gas diffusion layer with a fuel electrode catalyst were joined by hot press at 140 ° C. and 100 kgZcm 2 to prepare MEA.
- the effective electrode area of ME A produced in this way is 60.8 cm 2 (80 mm long, The width was 76 mm).
- the thicknesses of the catalyst layer of the air electrode and the fuel electrode after fabrication, and the thickness of the gas diffusion layer of the air electrode and the fuel electrode were approximately the same at about 30 m and 1 70 / xm, respectively.
- Each of the above ME A is provided with a flow path for flowing air and fuel, and a graphite air electrode separator plate impregnated with phenol resin to prevent gas leakage, fuel A single cell was constructed by sandwiching it with a pole separator plate.
- a conventional typical direct methanol fuel cell for example, Japanese Patent Laid-Open No. 2 002-2084 19, paragraph [0020], FIG. 1, Japanese Patent Laid-Open No. 2003-123799, paragraph [00 15
- the air electrode separator plate and the fuel electrode separator plate were grooved to provide air flow and fuel flow channels.
- Both the air electrode separator plate and the fuel electrode separator plate have a thickness of 2 mm, and the air electrode separator plate has three parallel flow paths (groove width: 2 mm, ridge width: lmm).
- the groove depth: 0.6 mm) is formed by meandering from the upper part of the separator plate diagonally to the lower part of the separator plate (number of folds: 8 times), and the fuel electrode separator plate has a flow path for flowing fuel.
- Three parallel grooves (groove width: 1.46mm, ridge width: 0.97mm, groove depth: 0.6mm) meander from the bottom of the separator plate to the upper diagonal (number of turns: 10) Formed.
- silicone rubber packing was installed around the MEA.
- the amount of hydrogen generation varies depending on the positional relationship between the groove and the flange of the air electrode separator plate and the fuel electrode separator plate. That is, as described above, it is presumed that methanol diffuses into the portion (the ridge portion) other than the flow channel groove of the air electrode separator, and the H + production reaction of equation (3) occurs. If the ridge part of the separator is at the same position facing the ridge part of the fuel electrode separator, diffusion of methanol from the fuel electrode is hindered, and hydrogen is hardly generated. Therefore, the groove ( ⁇ ) between the air electrode separator and the fuel electrode separator was provided at a slightly shifted position.
- the hydrogen production cell produced in this way is installed in a hot air circulation type electric furnace, the cell temperature (operating temperature) is 30 to 70 ° C, the air is supplied to the air electrode at a flow rate of 0 to 400m 1 / min, fuel A 0.5 M to 2 M aqueous methanol solution (fuel) is flowed to the pole side at a flow rate of 2 to 15 ml, and the voltage difference (open voltage) between the fuel electrode and the air electrode at that time is generated on the fuel electrode side.
- the amount of gas to be used and gas composition were examined.
- the flow rate of the aqueous methanol solution (fuel) to the cell is constant at 8 m1 min, and the air flow rate is changed at each temperature of 30 ° C, 50 ° C, and 70 ° C.
- the amount of generated gas was measured.
- An underwater displacement method was used to measure the amount of gas generated.
- the hydrogen concentration in the generated gas was analyzed by gas chromatography to determine the hydrogen production rate. The results are shown in Fig. 3.
- Figure 4 summarizes the results of Figure 3 as the relationship between open circuit voltage and hydrogen production rate.
- the maximum hydrogen production rate of 14.48 ml l Z was obtained.
- the hydrogen concentration in the evolved gas at an air flow rate of 100 ml was determined by gas chromatography in the same manner as in Hydrogen Production Example 1-1, and was about 70%.
- Hydrogen production example 1-11 Using the same hydrogen production cell as in 1, then, at a cell temperature of 70 ° C, a methanol aqueous solution (fuel) at a constant flow rate of 8 m 1 Z and a fuel concentration of 0.5
- Figure 7 shows the relationship between the fuel flow rate, the air flow rate and the hydrogen generation rate, and the cell open circuit voltage when the air flow rate is changed under the conditions of 1 and 2 M.
- Figure 8 summarizes the results of Figure 7 as the relationship between open circuit voltage and hydrogen production rate.
- a similar hydrogen production cell was constructed using a temperature of 70 ° C, a fuel concentration of 1M, a fuel flow rate of 8 ml / min, and the fuel flow rate and air flow when the air flow rate was changed. The relationship between the amount of hydrogen, the hydrogen production rate, and the open circuit voltage of the cell was examined. .
- Naphions 1 1 5 and 1 1 2 are made of the same material, and here the effect of the thickness of the electrolyte membrane was examined purely. The examination results are shown in Fig. 9.
- Figure 10 summarizes the results of Figure 9 as the relationship between open circuit voltage and hydrogen production rate.
- Hydrogen production example 1 1 Using the same hydrogen production cell as in 1, install the hydrogen production cell in a hot air circulation type electric furnace, and the cell temperature is 30 ° C, 50 ° C, 70 ° C, 90 ° C, air Air is flown to the pole side at a flow rate of 0 to 25 Om 1 / min, and 1M methanol aqueous solution (fuel) is flowed to the fuel electrode side at a flow rate of 5m 1 min. The rate of hydrogen production was investigated.
- Figure 11 shows the relationship between the air flow rate and the hydrogen production rate.
- Figure 12 summarizes the results of Figure 11 as the relationship between open circuit voltage and hydrogen production rate. This shows that the hydrogen generation rate tends to depend on the open circuit voltage, and hydrogen is generated at an open circuit voltage of 300 to 70 OmV. The peak of hydrogen production rate was observed around 470-48 OmV at 30-70 ° C, and around 440 mV at 90 ° C.
- Example of hydrogen production 1 1 Using the same hydrogen production cell as 1 1, at a cell temperature of 50 ° C, the fuel is 1.5, 2.5, 5.0, 7.5, 10.0 m 1 / min.
- Figure 13 shows the relationship between the fuel flow rate, air flow rate, and hydrogen generation rate when the air flow rate is changed.
- Figure 14 summarizes the results of Figure 13 as the relationship between open circuit voltage and hydrogen production rate. From this, it was found that the hydrogen generation rate under each condition depends on the open circuit voltage, and hydrogen is generated at 300 to 70 OmV. In addition, a peak of hydrogen generation rate was observed around 450-50 OmV.
- Figure 16 summarizes the results of Figure 15 as the relationship between open circuit voltage and hydrogen production rate. From this, it was found that the hydrogen generation rate under each condition depends on the open circuit voltage, and hydrogen is generated at 300 to 70 OmV. At any fuel concentration, a peak of hydrogen production rate was observed around 47 OmV.
- Hydrogen production example 1-11 Using the same hydrogen production cell as in 1 (however, the air electrode is an oxidation electrode that flows oxidizing gas), at a cell temperature of 50 ° C, fuel concentration 1M, fuel flow rate 5 ml Z min Figure 17 shows the relationship between the oxidant gas flow rate and the hydrogen generation rate when the oxidant gas flow rate is changed under the conditions where the oxygen concentration is changed to 10, 2, 1, 40, and 100%.
- air is used for a gas with an oxygen concentration of 21%, and for a gas with an oxygen concentration of 10%.
- the peak of the hydrogen production rate was observed where the oxidant gas flow rate decreased as the oxygen concentration increased.
- Figure 18 summarizes the results of Figure 17 as the relationship between open circuit voltage and hydrogen production rate. From this, the hydrogen production rate under each condition depends on the open circuit voltage, 400 ⁇
- Hydrogen production example 1-11 Using the same hydrogen production cell as in 1, with a cell temperature of 50 ° C, air flow rate of 60 ml at the air electrode side, 2.6 M of 1 M aqueous methanol solution (fuel) at the fuel electrode side The gas was generated at a flow rate of 1 min, gas was generated, 200 cc was sampled, and the CO concentration in the gas was measured using gas chromatography. As a result, no CO was detected in the sampling gas (I p pm or less). Under these conditions, the open circuit voltage of the cell was 477 mV, and the hydrogen production rate was approximately 10 ml / extra.
- Hydrogen production example 1-11 Using the same hydrogen production cell as in 1 (however, the air electrode is an oxidation electrode that allows liquid hydrogen peroxide to flow), the hydrogen production cell is installed in a hot air circulation type electric furnace. , at a cell temperature 30 ° C, 50 ° C, 70 ° C, 90 ° C, the H 2 ⁇ 2 1M in oxidizing electrode side (hydrogen peroxide) 1 ⁇ 8 m 1 / min flow rate, the fuel electrode side A 1 M aqueous methanol solution (fuel) was flowed at a flow rate of 5 m 1 Z, and the open circuit voltage of the cell and the hydrogen generation rate generated on the fuel electrode side were investigated.
- Figure 19 shows the relationship between the H 2 0 2 flow rate and the hydrogen production rate.
- Figure 20 summarizes the results of Figure 19 as the relationship between open circuit voltage and hydrogen production rate. This shows that the hydrogen generation rate tends to depend on the open circuit voltage, and hydrogen is generated at an open circuit voltage of 30 to 60 OmV. In addition, the peak of hydrogen production rate was observed near 50 OmV at 30 to 50 ° C, and around 45 OmV at 70 to 90 ° C.
- Example 1 no current or voltage is applied to the hydrogen production cell from the outside, and it is simply opened with an internal impedance of 1 GQ or higher. Only the fuel and oxidant are supplied while measuring the circuit voltage.
- Shika is also a reformation at a critical low temperature of 30 ° C to 90 ° C, and is considered to be a completely new hydrogen production device that has never existed before. Can be used in a packaged fuel cell power generator with a built-in control device that needs to be protected from high heat.
- Example 2
- FIG. 1 An outline of a hydrogen production cell equipped with means for extracting electric energy in Example 2 (Production Example 2- :! to 2-8) is shown in FIG.
- the structure is the same as that of the hydrogen production cell of Example 1 of hydrogen production except that a means for taking out electrical energy is provided using the fuel electrode as the negative electrode and the air electrode as the positive electrode.
- This hydrogen production cell is installed in a hot air circulation type electric furnace, and the cell temperature (operating temperature) is 5 At 0 ° C, air is supplied to the air electrode side at a flow rate of 10 to 100 m 1 Z, and 1 M methanol aqueous solution (fuel) is supplied to the fuel electrode side at a flow rate of 5 m 1 Z.
- the air electrode and fuel While changing the current flowing between the electrodes, we examined the operating voltage of the fuel electrode and air electrode, the amount of gas generated on the fuel electrode side, and the gas composition. In addition, the hydrogen concentration in the generated gas was analyzed by gas chromatography, and the hydrogen production rate was determined.
- Figure 22 shows the relationship between the extracted current density and the operating voltage in this test. As the air flow rate decreased, the operating voltage decreased, and a decrease in the limit current density that could be discharged was observed.
- Figure 23 summarizes the results of Figure 22 as the relationship between operating voltage and hydrogen production rate. 'From this, it was found that the hydrogen generation rate (hydrogen generation amount) tends to depend on the operating voltage, and gas is generated at an operating voltage of 300-60 OmV. It was also found that hydrogen is most likely to be generated when the air flow rate is 50 to 6 Om 1 Z min. In addition, when the air flow rate was higher than this, hydrogen was hardly generated, and almost no hydrogen was generated at 10 Oml.
- gas was generated under the conditions of high hydrogen generation rate, temperature 50 ° C, fuel flow rate 5m l min, air flow rate 60m l // min, current density 8.4mAZc m 2 , and in the gas
- the hydrogen concentration was measured using a gas chromatography.
- the generated gas contained about 74% hydrogen and the hydrogen production rate was 5.1 ml. CO was not detected.
- Hydrogen production example 2-1 Using the same hydrogen production cell as in 1, at a cell temperature of 30 ° C, air was supplied to the air electrode side at a flow rate of 30 to 100 m 1 min, and 1 M aqueous methanol solution (fuel) on the fuel electrode side. ) At a flow rate of 5 m 1 min, and the current flowing between the air electrode and the fuel electrode is changed, and the operating voltage of the fuel electrode and the air electrode and the rate of hydrogen generation generated on the fuel electrode side are examined. went.
- Figure 24 shows the relationship between the extracted current density and the operating voltage in this test. As the air flow rate decreased, the operating voltage decreased, and a decrease in the limit current density that could be discharged was observed.
- Figure 25 summarizes the results of Figure 24 as the relationship between operating voltage and hydrogen production rate. This shows that the hydrogen generation rate tends to depend on the operating voltage, and that hydrogen is generated at the operating voltage of 20 to 5 4 O mV. It was also found that hydrogen is generated when the air flow rate is 30 to 7 O m 1 / min. At an air flow rate of 100 m / min, almost no hydrogen was generated.
- Hydrogen production example 2-1 Using the same hydrogen production cell as in 1, with a cell temperature of 70 ° C, air is supplied to the air electrode side at a flow rate of 50 to 200 m 1 Z, and 1 M methanol on the fuel electrode side Flowing an aqueous solution (fuel) at a flow rate of 5 m 1 min. While changing the current flowing between the air electrode and the fuel electrode, the operating voltage of the fuel electrode and the air electrode, and the rate of hydrogen generated on the fuel electrode side A study was conducted.
- Figure 26 shows the relationship between the output current density and the operating voltage in this test. As the air flow rate decreased, the operating voltage decreased, and a decrease in the limit current density that could be discharged was observed.
- Figure 27 summarizes the results of Figure 26 as the relationship between operating voltage and hydrogen production rate.
- Hydrogen production example 2-1 Using the same hydrogen production cell as in Example 1, at a cell temperature of 90 ° C, air is supplied to the air electrode side at a flow rate of 50 to 25 O m 1 Z, and 1 M methanol is supplied to the fuel electrode side. Flowing an aqueous solution (fuel) at a flow rate of 5 m1 and changing the current flowing between the air electrode and the fuel electrode at that time, the operating voltage of the fuel electrode and the air electrode, and generation of hydrogen generated on the fuel electrode side The speed was examined.
- Figure 28 shows the relationship between the extracted current density and the operating voltage in this test. As the air flow rate decreases, the operating voltage decreases, and the limit current density that can be discharged. A decrease in was observed.
- Figure 29 summarizes the results of Figure 28 as the relationship between operating voltage and hydrogen production rate.
- Figure 30 shows the relationship between the extracted current density and the operating voltage when the air flow rate is 5 Oml at each temperature of hydrogen production examples 2-1 to 2-4.
- Figure 31 shows the degree relationship.
- the air flow rate is 5 Om 1 min on the air electrode side
- the fuel flow rate on the fuel electrode side is 1.5, 2. 5, 5.0, 7.5, 10. Om 1 / min.
- the production rate of hydrogen generated on the side was investigated.
- Figure 34 shows the relationship between the extracted current density and the operating voltage in this test. It was observed that the limit current density that can be discharged does not change greatly even if the fuel flow rate changes.
- Figure 35 summarizes the results of Figure 34 as the relationship between operating voltage and hydrogen production rate. From this, it was found that the hydrogen generation rate under each condition depends on the operating voltage, and hydrogen is generated at 300 to 50 OmV. In addition, it was observed that the hydrogen production rate was large around 450-50 OmV.
- cell temperature 50 Using the same hydrogen production cell as in hydrogen production example 2-1, cell temperature 50.
- the air flow rate is 50 ml and the fuel flow rate is 5 m 1 and the fuel concentration is changed to 0.5, 1, 2, and 3M.
- the current flowing between the air electrode and the fuel electrode we examined the operating voltage of the fuel electrode and the air electrode, and the generation rate of hydrogen generated on the fuel electrode side.
- Figure 36 shows the relationship between the extracted current density and the operating voltage in this test. As the fuel concentration increased, the operating voltage decreased, and a decrease in the limit current density that could be discharged was observed. '
- Figure 37 summarizes the results of Figure 36 as the relationship between operating voltage and hydrogen production rate. From this, it was found that the hydrogen generation rate under each condition depends on the operating voltage, and hydrogen is generated at 300 to 60 OmV.
- the cell temperature is 50 ° C
- fuel with a fuel concentration of 1M is placed on the fuel electrode side.
- the oxidizing gas was flowed to the oxidation electrode side at a flow rate of 14.
- Om l the oxygen concentration was changed to 10, 2, 1, 40, 100%.
- Figure 38 shows the relationship between the extracted current density and the operating voltage in this test. When the oxygen concentration was low, the operating voltage decreased, and a decrease in the limit current density that could be discharged was observed.
- FIG 39 summarizes the results of Figure 38 as the relationship between operating voltage and hydrogen production rate. From these results, it was found that the hydrogen generation rate under each condition depends on the operating voltage, and hydrogen is generated at 30 to 60 OmV.
- the hydrogen production cell is installed in a hot air circulation type electric furnace.
- Cell temperature 30 ° C, 50 °. C, 70 ° C, 90 ° C, 1 M methanol aqueous solution (fuel) on the fuel electrode side, 5 ml Z flow, 1 M H 2 0 2 (hydrogen peroxide) on the oxidation electrode side 2.6 to 5.5 m 1 flow rate, and the current flowing between the oxidation electrode and the fuel electrode is changed while the operating voltage of the fuel electrode and the oxidation electrode, and the generation of hydrogen generated on the fuel electrode side.
- the speed was examined.
- the flow rate of hydrogen peroxide was adjusted so that the open circuit voltage was approximately 50 O mV at each temperature.
- Figure 40 shows the relationship between the extracted current density and the operating voltage in this test.
- the relationship between the decrease in operating voltage and the increase in current density was almost the same.However, when the temperature was lowered to 30 ° C, the operating voltage suddenly decreased and discharge was possible. A decrease in critical current density was observed.
- Figure 41 summarizes the results of Figure 40 as the relationship between operating voltage and hydrogen production rate. This shows that the hydrogen generation rate tends to depend on the operating voltage, and hydrogen is generated at the operating voltage of 300 to 50 O mV. It was also observed that hydrogen is most likely to be generated when the temperature is 90 ° C, and that hydrogen is not generated unless the operating voltage is increased at low temperatures.
- Example 2 current is taken out from the hydrogen production cell. In other words, in the hydrogen production cell of Example 2, an electric While taking out the energy, part of the fuel is converted to hydrogen. However, it is a reformation at a threatening low temperature of 30 to 90 ° C and is considered to be a completely new hydrogen production device that has never existed before. The effect of using it in a packaged fuel cell power generator with a built-in control device that needs to be protected from the above is significant.
- Example 3
- FIG. 1 An outline of a hydrogen production cell comprising means for applying electric energy from the outside in Example 3 (Production Example 3- :! to 3-8) is shown in FIG.
- the structure is the same as that of Example 1 of hydrogen production except that a fuel electrode is used as a cathode and means for applying electric energy from the outside using the oxidation electrode as an anode is provided.
- This hydrogen production cell is installed in a hot-air circulation type electric furnace, and the cell temperature (operating temperature) is 50, and air is supplied to the air electrode side from 10 to 80 m 1.
- a 1 M aqueous methanol solution (fuel) is flowed at a flow rate of 5 m 1 Z.
- the current flowing between the air electrode and the fuel electrode is changed by using a DC power supply from the outside.
- the hydrogen concentration in the generated gas was analyzed by gas chromatography to determine the hydrogen production rate.
- energy efficiency The energy efficiency under charging conditions (hereinafter referred to as “energy efficiency”) was calculated using the following formula.
- Figure 43 shows the relationship between the applied current density and the hydrogen generation rate in this test. There is a region where hydrogen generation efficiency (electricity efficiency of hydrogen generation) is 100% or more under the condition of current density of 4 OmAZ cm 2 or less (in Fig. 43, a line with 100% hydrogen generation efficiency is indicated by a broken line). It was found that when operating in the Ning region, hydrogen more than the input electric energy could be obtained. '
- Figure 44 summarizes the results of Figure 43 as the relationship between operating voltage and hydrogen production rate.
- the hydrogen generation rate (hydrogen generation amount) tends to depend on the operating voltage. Hydrogen is generated at an operating voltage of 40 OmV or higher, the hydrogen generation rate is almost constant at an operating voltage of 60 OmV or higher, and the air flow rate is It was found that the smaller the amount, the faster the hydrogen generation rate (hydrogen is likely to be generated).
- Figure 45 shows the relationship between the applied current density and the operating voltage.
- Figure 46 shows the relationship between operating voltage and energy efficiency.
- the energy efficiency is 100% or more, especially when the operating voltage is 600 mV or less and the air flow rate is 30 to 50 m 1 / min. .
- Hydrogen production example 3-1 Using the same hydrogen production cell as in Example 1, at a cell temperature of 30 ° C, the air flow rate is 10 to 70 m1 on the air electrode side, and 1 M aqueous methanol solution ( Is generated at the fuel electrode side while operating the fuel electrode and the air electrode while changing the current flowing between the air electrode and the fuel electrode using a DC power supply from outside. The hydrogen generation rate and energy efficiency were examined.
- Figure 47 shows the relationship between the applied current density and the hydrogen production rate in this test
- Figure 48 shows the relationship between the operating voltage and the hydrogen production rate.
- the hydrogen generation rate tends to depend on the operating voltage.Hydrogen is generated at an operating voltage of 400 mV or more, and hydrogen is more likely to be generated when the air flow rate is low.
- the hydrogen generation rate is almost constant at 60 OmV or more, but when the air flow rate is 3 Om for 1 minute, it shows an increasing trend at 80 OmV or more, and when the air flow rate is higher than this, It was found that hydrogen is not generated unless the operating voltage is high. '
- Figure 49 shows the relationship between operating voltage and energy efficiency.
- the energy efficiency is 100% or more.
- the operating voltage is 60 OmV or less and the air flow rate is 3 Om for 1 minute, the energy efficiency is high.
- the test was conducted under the same conditions as in Hydrogen Production Example 3-2 except that the cell temperature was set to 70 ° C.
- the operating voltage of the fuel electrode and the air electrode, the production rate of hydrogen generated on the fuel electrode side, and the energy efficiency Study was carried out.
- Figure 50 shows the relationship between the applied current density and the hydrogen production rate in this test, and Figure 51 shows the relationship between the operating voltage and the hydrogen production rate.
- the hydrogen generation rate tends to depend on the operating voltage, and the operating voltage is 400m. Hydrogen is generated at V or higher and hydrogen is more likely to be generated when the air flow rate is lower. If the air flow rate is 1 Om for 1 minute, the hydrogen production rate is almost constant at 60 OmV or higher, but the air flow rate is 3 In the case of Om l / min, it showed an increasing tendency at 80 OmV or more, and when the air flow was higher than this, hydrogen was not generated unless the operating voltage was high.
- Figure 52 shows the relationship between operating voltage and energy efficiency.
- the energy efficiency is 100% or more, especially when the operating voltage is 60 OmV or less and the air flow rate is 10 to 3 Om 1 Z min. .
- Hydrogen production example 3-1 Using the same hydrogen production cell as in 1, with a cell temperature of 90 ° C, air is supplied to the air electrode side at a flow rate of 10 to 200 m 1 Z, and 1 M aqueous methanol solution (fuel) on the fuel electrode side. ) At a flow rate of 5m 1 Z, and the operating voltage of the fuel electrode and the air electrode is generated at the fuel electrode side while changing the current flowing between the air electrode and the fuel electrode using a direct power supply from the outside. The hydrogen generation rate and energy efficiency were investigated.
- Figure 53 shows the relationship between the applied current density and the hydrogen production rate in this test
- Figure 54 shows the relationship between the operating voltage and the hydrogen production rate.
- the hydrogen generation rate tends to depend on the operating voltage. Hydrogen is generated at an operating voltage of 300 mV or higher, and hydrogen is more likely to be generated when the air flow rate is low.Air flow rate is 1 Om 1 Z min. However, when the air flow rate is 50 to 100 ml, the increase rate is .800 mV or more, and when the air flow rate is 200 ml / min. It was found that hydrogen would not be generated unless the pressure was 80 OmV or more.
- Figure 55 shows the relationship between operating voltage and energy efficiency.
- the energy efficiency is 100% or more.
- the energy efficiency is high.
- Figure 58 shows the relationship between operating voltage and energy efficiency.
- the energy efficiency is 100% or more, and in particular, it is found that the energy efficiency is high at 600mV or less.
- Hydrogen production example 3-1 Using the same hydrogen production cell as in Example 1, with a cell temperature of 50 ° C, air flow to the air electrode side at a flow rate of 50m 1 min, and fuel flow on the fuel electrode side to 1.5, 2.5 , 5.0, 7.5, 10. Om 1 min., And at that time, the current flowing between the air electrode and the fuel electrode was changed by using a DC power supply from the outside. We examined the operating voltage, the hydrogen generation rate generated on the fuel electrode side, and the energy efficiency.
- Figure 59 shows the relationship between the applied current density and the hydrogen production rate in this test
- Figure 60 shows the relationship between the operating voltage and the hydrogen production rate.
- the hydrogen generation rate tends to depend on the operating voltage. Hydrogen is generated at an operating voltage of 40 OmV or higher, and hydrogen is more likely to be generated when the fuel flow rate is higher. The hydrogen generation rate is 80 at any fuel flow rate. A trend of increasing above OmV was observed.
- Figure 61 shows the relationship between operating voltage and energy efficiency.
- the energy efficiency was 100% or higher even when the operating voltage was around 100 OmV, and it was found that the energy efficiency was particularly high at an operating voltage of 60 OmV or lower.
- Hydrogen production example 3-1 Using the same hydrogen production cell as in Example 1, at a cell temperature of 50 ° C, the air flow rate is 50 ml / min on the air electrode side, and the fuel flow is 5 m 1 / min on the fuel electrode side. The fuel concentration was changed to 0.5, 1, 2, 3M, and the DC power supply was externally applied at that time. Using this, the current flowing between the air electrode and the fuel electrode was varied, and the operating voltage of the fuel electrode and the air electrode, the production rate of hydrogen generated on the fuel electrode side, and energy efficiency were investigated.
- Figure 62 shows the relationship between the applied current density and the hydrogen production rate in this test
- Figure 63 shows the relationship between the operating voltage and the hydrogen production rate.
- the hydrogen generation rate tends to depend on the operating voltage. Hydrogen is generated at an operating voltage of 400 mV or higher, and hydrogen is more likely to be generated at a lower operating voltage when the fuel concentration is higher. The hydrogen generation rate suddenly increases at 400 to 50 OmV, and when the fuel concentration is 1M, the hydrogen generation rate is almost constant at 400 to 80 OmV, but tends to increase at 80 OmV or more. When the fuel concentration is lower than this, it was found that hydrogen is not generated unless the operating voltage is high.
- Figure 64 shows the relationship between operating voltage and energy efficiency.
- the energy efficiency is 100% or more even when the operation voltage is around 100OmV, especially when the operation voltage is 60OmV or less and the fuel concentration is 1, 2, 3M. It was found that energy efficiency was high. When the fuel concentration was 0.5M, there was no hydrogen generation in the low-voltage region, so the energy efficiency behavior was completely different from the other conditions.
- the cell temperature is 50 ° C, and a fuel with a concentration of 1 M is supplied to the fuel electrode side by 5 ml.
- the oxidizing gas was supplied to the oxidation electrode side at a flow rate of 14. Om l, and the oxygen concentration was changed to 10, 21, 40, and 100%.
- air was used for the gas with an oxygen concentration of 21%, the gas with an oxygen concentration of 10% was prepared by mixing nitrogen with the air, and the gas with an oxygen concentration of 40% was acidified with air. What was prepared by mixing elementary (oxygen concentration 100%) was used.
- Figure 65 shows the relationship between the applied current density and the hydrogen production rate in this test
- Figure 66 shows the relationship between the operating voltage and the hydrogen production rate.
- the hydrogen generation rate tends to depend on the operating voltage. Hydrogen is generated at an operating voltage of 400 mV or higher, and hydrogen is more likely to be generated at a lower operating voltage when the oxygen concentration is higher. Was almost constant, but showed an increasing trend above 80 OmV. .
- Figure 67 shows the relationship between operating voltage and energy efficiency.
- the energy efficiency is 100% or more.
- the energy efficiency is high.
- the hydrogen production cell is installed in a hot air circulation type electric furnace.
- fuel electrode side 1 M methanol aqueous solution (fuel) flow rate of 5 ml l Z, 1M H 2 O on oxidation electrode side 2 (hydrogen peroxide) is supplied at a flow rate of 2.6 to 5.5 m 1 Z.
- the current flowing between the oxidation electrode and the fuel electrode is changed by using a DC power supply from the outside.
- the flow rate of hydrogen peroxide was adjusted so that the open circuit voltage was approximately 50 OmV at each temperature.
- Figure 68 shows the relationship between the applied current density and the hydrogen production rate in this test
- Figure 69 shows the relationship between the operating voltage and the hydrogen production rate.
- the hydrogen generation rate tends to depend on the operating voltage, hydrogen is generated at an operating voltage of 500 mV or higher, and increases at 80 OmV or higher, and hydrogen is more likely to be generated at a higher operating temperature.
- Figure 70 shows the relationship between operating voltage and energy efficiency.
- Example 3 Even when the operating voltage is around 100 O mV, the energy efficiency is 100% or more, especially when the operating voltage is 80 mV or less and the temperature is 90 ° C. I understood.
- the important point is that in Example 3 above, hydrogen exceeding the current applied to the hydrogen production cell from the outside is taken out.
- the hydrogen production cell of Example 3 produces hydrogen with an energy higher than the input electric energy.
- it is a reformation at a low temperature of 30 to 90 ° C and is considered to be a completely new hydrogen production device that has never existed before. In particular, this hydrogen production device is protected from high heat.
- the effect of using it in a packaged fuel cell power generator with a built-in control device that needs to be greatly improved.
- hydrogen is produced by a hydrogen production apparatus used in the fuel cell power generation apparatus of the present invention using a fuel other than methanol.
- Example 1 of hydrogen production 1 Using the same hydrogen production cell as in 1, at a cell temperature of 80 ° C, flow an ethylene glycol aqueous solution with a concentration of 1 M to the fuel electrode side at a flow rate of 5 m 1 Z. On the side, air was flowed at a flow rate of 10 5 m 1, and the open circuit voltage of the cell and the generation rate of gas generated from the fuel electrode side were measured. The hydrogen concentration in the evolved gas was analyzed by gas chromatography to determine the hydrogen production rate.
- Example 1 of hydrogen production 1 Using the same hydrogen production cell as in 1, at a cell temperature of 80 ° C, a 1 M concentration of jetyl ether aqueous solution was flowed to the fuel electrode side at a flow rate of 5 m 1 Z. On the side, air was flowed at a flow rate of 2 O m 1, and the open circuit voltage of the cell and the generation rate of gas generated from the fuel electrode side were measured. The hydrogen concentration in the evolved gas was analyzed by gas chromatography to determine the hydrogen production rate.
- Hydrogen was produced by a hydrogen production device (open circuit conditions) used in the fuel cell power generator of the invention.
- Example 1 of hydrogen production 1 Using the same hydrogen production cell as 1 1, at a cell temperature of 50 ° C, 5 M formaldehyde aqueous solution and 1 M oxalic acid aqueous solution were respectively added to the fuel electrode side. Flowed at a flow rate of ml Z, air was flowed to the air electrode side at a flow rate of 0 to 100 m, and the open circuit voltage of the cell and the generation rate of gas generated from the fuel electrode side were measured. The hydrogen concentration in the generated gas was analyzed by gas chromatography to determine the hydrogen production rate.
- Figs. 71 and 72 The results are shown in Figs. 71 and 72 along with the use of methanol.
- Fig. 71 in the case of formaldehyde and formic acid, generation of hydrogen was confirmed from the fuel electrode side of the cell by reducing the air flow rate, as in methanol.
- the hydrogen generation rate was the largest for methanol, followed by formaldehyde and formic acid, and it was found that hydrogen was not generated unless the air flow rate was reduced in this order.
- Figure 7 2 shows that in the case of formaldehyde and formic acid, as with methanol, the rate of hydrogen generation (hydrogen generation amount) tends to depend on the open circuit voltage, and the open circuit voltage 2 0 to 80 O m V It was found that hydrogen was generated. In the case of formic acid, hydrogen is generated at a lower open-circuit voltage than methanol and formaldehyde, and the peak hydrogen generation rate is about 500 mV for methanol and formaldehyde. On the other hand, in the case of formic acid, it was observed at a low open circuit voltage (about 35 O mV).
- Example 9 shows that in the case of formaldehyde and formic acid, as with methanol, the rate of hydrogen generation (hydrogen generation amount) tends to depend on the open circuit voltage, and the open circuit voltage 2 0 to 80 O m V It was found that hydrogen was generated. In the case of formic acid, hydrogen is generated at a lower open-circuit voltage than methanol and formaldehyde, and
- a hydrogen production cell was fabricated in the same manner as in Hydrogen Production Example 1-11, except that only the air electrode separator plate was combined with MEA except for the fuel electrode separator plate of the separator plate.
- Hydrogen was generated at an air flow rate of 30 to 13 O m for 1 minute, but the hydrogen generation was less than when separator plates were used for both the fuel electrode and the air electrode.
- Figure 74 shows the relationship between the open circuit voltage and the hydrogen production rate. From this, as in the case of hydrogen production example 1-11, the hydrogen generation rate (hydrogen generation amount) tends to depend on the open circuit voltage, and hydrogen is generated at an open circuit voltage of 400 to 60 OmV. I found out that The peak of hydrogen production rate was observed around 47 O mV. As described above, the hydrogen production apparatus used in the fuel cell power generator of the present invention can produce a gas containing hydrogen by decomposing a fuel containing organic matter at 10 ° C. or lower. Hydrogen can be easily supplied to the fuel cell. Industrial applicability
- the package type fuel cell power generator does not require any special means for protecting the control device built in the package from the heat generated by the hydrogen production device. Since the device as a whole, including batteries, generates little heat, it is extremely advantageous when used as a mobile power source or on-site power source.
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Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
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EP05851007A EP1843424A1 (en) | 2004-12-28 | 2005-12-26 | Fuel cell power generating device |
US11/794,320 US20080063910A1 (en) | 2004-12-28 | 2005-12-26 | Fuel Cell Power Generating Device |
Applications Claiming Priority (4)
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JP2004-381870 | 2004-12-28 | ||
JP2004381870 | 2004-12-28 | ||
JP2005151124 | 2005-05-24 | ||
JP2005-151124 | 2005-05-24 |
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WO2006070908A1 true WO2006070908A1 (ja) | 2006-07-06 |
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PCT/JP2005/024207 WO2006070908A1 (ja) | 2004-12-28 | 2005-12-26 | 燃料電池発電装置 |
Country Status (4)
Country | Link |
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US (1) | US20080063910A1 (ja) |
EP (1) | EP1843424A1 (ja) |
KR (1) | KR20070097473A (ja) |
WO (1) | WO2006070908A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1892215A1 (en) * | 2005-06-03 | 2008-02-27 | GS Yuasa Corporation | Hydrogen production apparatus, and making use of the same, fuel cell power generator, electric vehicle, submersible ship and hydrogen supply system |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4958059B2 (ja) * | 2005-06-30 | 2012-06-20 | 株式会社Gsユアサ | 水素製造装置 |
JP5567375B2 (ja) * | 2010-04-14 | 2014-08-06 | 東洋炭素株式会社 | 気体発生装置および気体発生方法 |
US11211625B2 (en) | 2016-04-21 | 2021-12-28 | Fuelcell Energy, Inc. | Molten carbonate fuel cell anode exhaust post-processing for carbon dioxide |
CA3022534C (en) | 2016-04-29 | 2021-01-26 | Fuelcell Energy, Inc. | Methanation of anode exhaust gas to enhance carbon dioxide capture. |
KR20230011914A (ko) | 2020-03-11 | 2023-01-25 | 퓨얼셀 에너지, 인크 | 탄소 포집을 위한 증기 메탄 개질 유닛 |
KR102495268B1 (ko) * | 2021-07-06 | 2023-02-06 | 수경화학 주식회사 | 수전해 평가 장치 및 방법 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS62256976A (ja) * | 1986-04-30 | 1987-11-09 | Mitsubishi Heavy Ind Ltd | 水素の製造方法 |
JPH06321501A (ja) * | 1993-05-10 | 1994-11-22 | Sumitomo Electric Ind Ltd | 電気化学装置および水素発生方法 |
JPH11229167A (ja) * | 1998-02-16 | 1999-08-24 | Permelec Electrode Ltd | 電解水素発生装置 |
JP2001297779A (ja) * | 2000-04-13 | 2001-10-26 | Matsushita Electric Ind Co Ltd | 燃料電池システム |
JP2003308869A (ja) * | 2002-04-12 | 2003-10-31 | Takayuki Shimamune | 燃料電池 |
JP2005240064A (ja) * | 2004-02-24 | 2005-09-08 | Seiko Epson Corp | 改質器、燃料電池システムおよび機器 |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6299744B1 (en) * | 1997-09-10 | 2001-10-09 | California Institute Of Technology | Hydrogen generation by electrolysis of aqueous organic solutions |
DE60139114D1 (de) * | 2000-03-07 | 2009-08-13 | Panasonic Corp | Polymer-elektroly-brennstoffzelle und herstellungsverfahren dafür |
AU2001254921A1 (en) * | 2000-05-03 | 2001-11-12 | Zero-M Limited | Fuel system |
JP3719178B2 (ja) * | 2001-09-13 | 2005-11-24 | ソニー株式会社 | 水素ガス製造充填装置及び電気化学装置 |
DE10149779A1 (de) * | 2001-10-09 | 2003-04-10 | Bayer Ag | Verfahren zur Rückführung von Prozessgas in elektrochemischen Prozessen |
CA2448715C (en) * | 2002-11-11 | 2011-07-05 | Nippon Telegraph And Telephone Corporation | Fuel cell power generating system with two fuel cells of different types and method of controlling the same |
WO2004049479A2 (en) * | 2002-11-27 | 2004-06-10 | Hydrogenics Corporation | An electrolyzer module for producing hydrogen for use in a fuel cell power unit |
DE102004024972A1 (de) * | 2004-05-21 | 2005-12-15 | Howaldtswerke-Deutsche Werft Gmbh | Verfahren zur Fahrtplanung eines Unterseebootes |
US8148027B2 (en) * | 2006-09-07 | 2012-04-03 | Nanyang Technological University | Electrode composite material |
-
2005
- 2005-12-26 WO PCT/JP2005/024207 patent/WO2006070908A1/ja not_active Application Discontinuation
- 2005-12-26 US US11/794,320 patent/US20080063910A1/en not_active Abandoned
- 2005-12-26 EP EP05851007A patent/EP1843424A1/en not_active Withdrawn
- 2005-12-26 KR KR1020077014733A patent/KR20070097473A/ko not_active Application Discontinuation
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS62256976A (ja) * | 1986-04-30 | 1987-11-09 | Mitsubishi Heavy Ind Ltd | 水素の製造方法 |
JPH06321501A (ja) * | 1993-05-10 | 1994-11-22 | Sumitomo Electric Ind Ltd | 電気化学装置および水素発生方法 |
JPH11229167A (ja) * | 1998-02-16 | 1999-08-24 | Permelec Electrode Ltd | 電解水素発生装置 |
JP2001297779A (ja) * | 2000-04-13 | 2001-10-26 | Matsushita Electric Ind Co Ltd | 燃料電池システム |
JP2003308869A (ja) * | 2002-04-12 | 2003-10-31 | Takayuki Shimamune | 燃料電池 |
JP2005240064A (ja) * | 2004-02-24 | 2005-09-08 | Seiko Epson Corp | 改質器、燃料電池システムおよび機器 |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1892215A1 (en) * | 2005-06-03 | 2008-02-27 | GS Yuasa Corporation | Hydrogen production apparatus, and making use of the same, fuel cell power generator, electric vehicle, submersible ship and hydrogen supply system |
EP1892215A4 (en) * | 2005-06-03 | 2013-10-16 | Gs Yuasa Int Ltd | METHOD FOR PRODUCING HYDROGEN AND USE THEREOF, FUEL CELL CELL GENERATOR, ELECTRIC VEHICLE, DIVE BOAT AND HYDROGEN SUPPLY SYSTEM |
Also Published As
Publication number | Publication date |
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US20080063910A1 (en) | 2008-03-13 |
EP1843424A1 (en) | 2007-10-10 |
KR20070097473A (ko) | 2007-10-04 |
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