WO2004002881A1 - 水素製造方法および水素供給装置 - Google Patents
水素製造方法および水素供給装置 Download PDFInfo
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- WO2004002881A1 WO2004002881A1 PCT/JP2003/006050 JP0306050W WO2004002881A1 WO 2004002881 A1 WO2004002881 A1 WO 2004002881A1 JP 0306050 W JP0306050 W JP 0306050W WO 2004002881 A1 WO2004002881 A1 WO 2004002881A1
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- hydrogen
- iron
- water
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- iron oxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/005—Separating solid material from the gas/liquid stream
- B01J8/006—Separating solid material from the gas/liquid stream by filtration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J7/00—Apparatus for generating gases
- B01J7/02—Apparatus for generating gases by wet methods
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/0242—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid flow within the bed being predominantly vertical
- B01J8/025—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid flow within the bed being predominantly vertical in a cylindrical shaped bed
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/0285—Heating or cooling the reactor
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/061—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of metal oxides with water
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/10—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00008—Controlling the process
- B01J2208/00017—Controlling the temperature
- B01J2208/00106—Controlling the temperature by indirect heat exchange
- B01J2208/00168—Controlling the temperature by indirect heat exchange with heat exchange elements outside the bed of solid particles
- B01J2208/00212—Plates; Jackets; Cylinders
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00008—Controlling the process
- B01J2208/00017—Controlling the temperature
- B01J2208/00477—Controlling the temperature by thermal insulation means
- B01J2208/00495—Controlling the temperature by thermal insulation means using insulating materials or refractories
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- 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
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Definitions
- the present invention relates to a technology for efficiently producing hydrogen by decomposing water.
- Partial oxidation and steam reforming using petroleum and natural gas as raw materials generate a large amount of carbon dioxide gas during hydrogen synthesis. Therefore, solar heat was used as a method of not generating carbon dioxide gas.
- the steam iron method is known as a method for producing hydrogen from water.
- This method uses the oxidation-reduction of iron only (F e ⁇ F e 0 (F e 30 ⁇ ) —F e), but the reaction requires a high temperature of, for example, 600 ° C or more.
- metallic iron aggregates that is, a so-called thin ring occurs, and the activity of metallic iron is rapidly reduced. Therefore, there has been a demand for a hydrogen generating medium (oxidation-reduction material) that does not cause a thin ring phenomenon, has excellent durability, and exhibits high activity.
- the inventors of the present application have disclosed in the previously filed Japanese Patent Application No.
- An object of the present invention is to provide a method capable of decomposing water to produce hydrogen more efficiently than a conventional method for producing hydrogen from water, or a method capable of generating hydrogen at a lower temperature than the conventional method.
- the present invention provides a method for producing hydrogen based on the invention of Japanese Patent Application No. 2001-102845. Disclosure of the invention
- the above problem is solved by a method for producing hydrogen by contacting iron or iron oxide with water, steam or a gas containing steam as described in claim 1, wherein the iron or iron oxide is This is achieved by a hydrogen production method characterized by adding at least one metal of Rh, Ir, Ru, Pd, Pt and 0 s.
- a method for producing hydrogen by contacting iron or iron oxide with water, water vapor, or a gas containing water vapor, wherein Rh, iron, iron oxide, At least one metal of Ir, Ru, Pd, Pt, and 0 s; and Ti, Zr, V, Nb, Cr, Mo, Al, Ga, Mg, Sc, Ni, and Cu
- a hydrogen production method characterized by adding at least one metal of the following.
- the water used as a raw material does not necessarily have to be pure water, and tap water, industrial water and the like are used.
- the iron used in the present invention an iron compound such as pure iron, iron oxide, iron nitrate, iron chloride or iron sulfate is used as a raw material.
- the first metal added to the iron or iron oxide in the present invention is at least one of at least one member of the platinum group, preferably, R h, Ir, Ru, P d, P t And at least one of 0 s is selected.
- the metal added to iron or iron oxide includes at least one of the platinum group and at least one of Ti, Zr, V, Nb, Cr, M At least one of o, Al, Ga, Mg, Sc, Ni and Cu may be added.
- the addition amount of the platinum group to be added to iron or iron oxide is calculated as the number of moles of metal atoms, preferably 0.1 to 3 O mo 1% of all metal atoms, more preferably 0.5 to 15 mo. Adjust to 1%.
- Both the first additive metal (platinum group) and the second additive metal have no effect of improving the hydrogen generation efficiency when the addition amount is less than 0.1 lmo 1%, and the oxidation and reduction when the addition amount is more than 3 Omo 1%. The efficiency of the reaction decreases.
- the metal is added by a physical mixing or impregnation method, preferably a coprecipitation method.
- a shape with a large surface area suitable for the reaction such as powdery or pellet-like, cylindrical, honeycomb, non-woven, etc. is selected for efficient use, and used for the water decomposition reaction .
- This iron compound is placed in a reactor and reduced with hydrogen or the like.
- the reduced iron compound is brought into contact with water, steam or a gas containing steam to produce hydrogen.
- iron reacting with water becomes iron oxide.
- the oxidation / reduction reaction can be performed at a low temperature of less than 600 ° C.
- hydrogen can be supplied inexpensively to a fuel cell for local facilities, factories, homes or vehicles, without generating carbon monoxide that poisons the electrodes of the fuel cell.
- the produced hydrogen can be used not only for fuel cells but also for a wide range of hydrogen supply means such as hydrogen burners.
- the reduced iron compound can be filled in a container and used as a portable hydrogen supply power set for a hydrogen supply means such as a fuel cell as described above.
- the hydrogen generating medium is housed therein and includes a portable cassette having at least two pipe mounting means. Contains iron or iron oxide as a main component, to which a platinum group metal or a platinum group metal and the second additive metal are added.
- the cassette is provided with water through one of the pipe mounting means.
- a hydrogen supply device characterized by being able to supply hydrogen generated by decomposition of water by steam power injection to the hydrogen consuming device from the other connecting hole pipe mounting means.
- a cassette may be provided inside the cassette. Further, the cassette may be provided with a pipe for supplying an inert gas or air. Air is used when the reaction heat of the reaction between air and reduced iron oxide is used for the water splitting reaction during the water splitting reaction.
- Iron oxidized by reacting with water is reduced again by hydrogen or the like, and can be repeatedly used as an oxidizing reduction medium without lowering the activity.
- the above-mentioned effects can be obtained by preventing sintering, accelerating the oxygen diffusion rate in the solid, and improving the water decomposition activity on the surface.
- FIG. 1 is a schematic diagram of a reaction system of an iron compound used in an example of the present invention.
- FIG. 2 is a graph showing the hydrogen generation rate and reaction temperature during the water splitting reaction.
- FIG. 3 is a graph showing the total amount of generated hydrogen.
- FIG. 4 is a diagram showing a configuration of the present invention in which a reaction vessel containing a hydrogen generating medium and a device for supplying water are connected by a tube.
- FIG. 5 is a diagram showing a state in which the cassette containing the reduced hydrogen generating medium is connected to the fuel cell.
- FIG. 1 shows a schematic diagram of the reaction system of the iron-based compound used in this example.
- the apparatus shown in Fig. 1 is a normal-pressure fixed-bed flow-type reaction apparatus. A part of the reaction gas was sampled and measured by gas chromatography.
- the iron compound contained in the reaction vessel was prepared by the following coprecipitation method (urea method). That is, in 5 L of water degassed by ultrasonic for 5 minutes, iron (III) nitrate nonahydrate (F e (NOg) 3 ⁇ 9H n 0: manufactured by Wako Pure Chemical Industries, Ltd.) 0.194m 01, added to that the platinum group metal rhodium chloride is chloride (RhC 1. ⁇ 3H 2 0: Wako Junkusurye industry Co., Ltd.) 0. 006mo 1, 1 Omo 1 of urea as precipitation agent (NH n (CO) H 2 : manufactured by Wako Pure Chemical Industries, Ltd.) and dissolved. The mixed solution was heated to 90 ° C.
- Fig. 2 shows the results of the water splitting reaction when the sample prepared by the above-mentioned coprecipitation method (urea method) was weighed so that the Fe content became 0.2 g and used for the reaction. It is a graph which shows temperature-hydrogen generation rate.
- Ir, Ru, Pd, and Pt of platinum group other than Rh were similarly prepared by the coprecipitation method to prepare samples, and the water splitting reaction was measured in the same manner as for Rh described above.
- the unsubstituted calo iron oxide is 300 ° C Below, there is almost no generation of hydrogen, and the hydrogen generation rate becomes maximum at about 500 ° C.
- the hydrogen generation rate becomes maximum at about 500 ° C.
- Rh-added iron oxide ⁇ symbol
- Rh-added iron oxide ⁇ symbol
- Ir-added iron oxide Ir-added iron oxide
- sufficient hydrogen generation can be confirmed even at a low temperature of 300 ° C or less, as with Rh-added iron oxide, and the peak of hydrogen generation rate is about 350 to 400 ° C. .
- the peak of hydrogen generation rate of Ru-added iron oxide is about 400 ° C, but even below 400 ° C, it exceeds the maximum value of hydrogen generation rate of non-added iron oxide.
- the peak of the hydrogen generation rate of Pd-added iron oxide ( ⁇ symbol) is about 500 ° C, but already exceeds the maximum value of the hydrogen generation rate of non-added oxidized iron at around 400 ° C.
- the Pt-added iron oxide (symbol) has a peak hydrogen generation rate of less than 500 ° C, and already exceeds the maximum value of the hydrogen generation rate of the non-added iron oxide at around 450 ° C. ⁇
- the peak of the hydrogen generation rate of the platinum group-added iron oxide is lower than the peak of the non-added iron oxide, and shows a higher value.
- Example 2 similarly to Example 1, a part of the reaction gas was collected using a normal-pressure fixed-bed flow reactor shown in FIG. 1 and measured by gas chromatography.
- the iron compound contained in the reaction vessel was prepared by the following coprecipitation method (urea method). That is, in 5 L of water degassed by ultrasonic for 5 minutes, ⁇ iron ferrate (III) nonahydrate (F e (NO 0 ) 3 ⁇ 9 Ho 0: manufactured by Wako Pure Chemical Industries, Ltd.) 0 . 188mo l, chlorides is rhodium chloride first metal you added (platinum group) (RhC l '3H 2 0 :. by Wako Pure Chemical Industries, Ltd.) 0. 006mo 1, second metal to be added chloride der Ru aluminum nitrate (a 1 (NO 3) 3 ⁇ 9 H 2 0: manufactured by Wako Pure Chemical Industries, Ltd.) 0.
- urea method that is, in 5 L of water degassed by ultrasonic for 5 minutes, ⁇ iron ferrate (III) nonahydrate (F e (NO 0 ) 3 ⁇ 9 Ho 0: manufactured by Wako Pure Chemical Industries,
- urea 10Mo 1 as the precipitating agent (NHg (CO) NH 2: (Wako Pure Chemical Industries, Ltd.) was added and dissolved.
- the mixed solution was heated to 90 ° C while stirring, and kept at the same temperature for 3 hours. Leave for 16 hours after the reaction is completed.Precipitate and filter by suction. Passed.
- the precipitate was dried at 80 ° C for 24 hours, and then calcined in air at 100 ° C for 5 hours, 300 ° C for 5 hours, and 500 ° C for 10 hours.
- the first platinum group atom and the second metal atom to be added in the sample in the sample were each set to 3 mo 1% of the total metal atom.
- After firing pulverize the sample in a mortar, shape it into a pellet, put the sample in a reaction vessel, purge the air in the system with nitrogen (inert gas), introduce hydrogen, and inject hydrogen at 470 for 1 hour.
- a reduction reaction was performed.
- Fig. 3 is a graph comparing the total amount of hydrogen generated by the above method with the sample prepared by the above-mentioned coprecipitation method (urea method) weighed so that the Fe content becomes 4.0 g. It is.
- the platinum group Pt the combination of Ru ⁇ Pd ⁇ Ir and A1
- the combination of Rh and Mo the combinations of A1 and Mo were also prepared by the coprecipitation method.
- a sample was prepared in the same manner as above, and the total amount of generated hydrogen was measured in the same manner as for Rh described above.
- iron oxide to which Rh alone was added generated much more hydrogen than iron oxide to which no Rh was added, and compared to iron oxide to which A1 and Mo were added alone. Even so, the first and second rounds generate a large amount of hydrogen, and the third round of hydrogen generation is similar.
- Rh oxidized iron (Rh—A 1 -added iron oxide) to which A 1 is added as a second additional metal generates much more hydrogen than iron oxide without addition. Compared to iron oxide to which A1 or Mo is added alone, the amount of generated hydrogen is larger, and the strength is not deteriorated by repetition.
- Rh-Mo added iron oxide are also Rh-A1 added iron oxide. There is a similar tendency.
- a 1 and Mo which are the second added metals, not only have the effect of improving the hydrogen generation efficiency, but also have the effect of preventing inferiority due to repetition.
- Al and Mo are preferable, but Ti, Zr, V, Nb, Cr, Ga, Mg, Sc, Ni and Cu may also be used.
- FIG. 4 shows an embodiment for industrially implementing the present invention.
- FIG. 4 shows a system in which a reaction vessel 1 containing a hydrogen generation medium 9 and a device 2 for supplying water are connected by a tube according to the present invention, and a system 10 is provided as a cassette 10 for supplying hydrogen.
- 1 is a schematic drawing showing one embodiment.
- the hydrogen generation medium 9 is iron oxide to which the metal of the present invention is added, and is mainly composed of iron or iron oxide, and at least one of Rh, Ir, Ru, Pd, Pt, and 0 s.
- the reaction vessel 1 for the water splitting / reduction reaction is connected to a device 2 for supplying water with a pipe 3, and the device 2 for supplying water is connected to a pipe 4 for introducing an inert gas or air.
- the inert gas include nitrogen, argon, and helium.
- Nitrogen (inert gas) is not necessarily needed as a carrier gas to lubricate the reaction or to purge air (oxygen) in the system.
- Air is used when the reaction heat of the reaction between air and reduced iron oxide is used for the water splitting reaction in the water splitting reaction, but is not necessarily required. Instead of air, only oxygen or the above-mentioned inert gas containing oxygen may be used.
- the pipe 5 may be connected so that the water in the cassette 10 can be replenished to the water supply device from outside the cassette 10 as necessary.
- the reaction vessel 1 is connected to a pipe 6 for discharging hydrogen and water vapor, performs a water splitting reaction, and sends the generated hydrogen to a system requiring hydrogen, such as a polymer electrolyte fuel cell.
- a heat source 7 is installed inside the power set 10 as a heat source for supplying heat for the water splitting / reduction reaction and dewatering the water.
- the heat source may be any of commonly used electric furnaces, heaters, induction heating, catalytic combustion heating, and heat generated by chemical reactions.
- the reaction vessel 1 is made of metal such as stainless steel and aluminum, ceramics such as alumina and zirconia, and heat-resistant plastic such as phenol and polyphenylene sulfide, and has a structure capable of withstanding heat and internal and external pressures. I have.
- a heat insulating material 7a such as silica fiber is inserted into the cassette 10 and is covered with a cover 11.
- Each of the gas inlets and outlets of the cassette 10 is provided with a filter 18.
- the water supply device 2 is provided inside the cassette 10, but water is supplied directly from the water supply port pipe 5 into the reaction vessel 1 without providing the water supply device 2. You may do it.
- the water supply pipe 5 may not be provided, and water may be supplied from the pipe 4.
- the heater 7 is installed inside the cassette 10, but the heater may not be installed in the cassette 10, but may be installed separately from the cassette.
- FIG. 5 shows a state in which the cassette 10 containing the reduced hydrogen generating medium is connected to the fuel cell 20.
- the reduced hydrogen generating medium reacts with water to generate hydrogen from cassette 10.
- the generated hydrogen is supplied to the fuel electrode 21 of the polymer electrolyte fuel cell through a tube 15 connected to the polymer electrolyte fuel cell 20.
- Air is introduced into the cathode 22 of the solid polymer fuel cell, and the reaction between hydrogen and oxygen in the air is carried out. Electricity is extracted.
- hydrogen in a method of producing hydrogen by bringing iron, iron oxide into contact with water, water vapor, or a gas containing water vapor, hydrogen is generated at a low temperature by adding a platinum group metal to iron or iron oxide. Hydrogen generation rate is high. And the total amount of hydrogen generated at a constant temperature can be increased.
- the addition of the platinum group metal and the above-mentioned second metal to iron or iron oxide can increase the total amount of generated hydrogen, and maintain the activity even when the water splitting / reducing reaction is repeated. Does not decrease, and the total amount of generated hydrogen remains large. Therefore, it can be recycled by reducing the oxidized / reduced iron medium which has generated and finished hydrogen again.
- ADVANTAGE OF THE INVENTION According to the present invention, the hydrogen generation reaction rate per unit weight and the total amount of generated hydrogen are improved, so that hydrogen can be supplied very efficiently to a system requiring hydrogen, such as a polymer electrolyte fuel cell. be able to.
- the fuel electrode of a low-temperature operation type fuel cell (solid polymer type, phosphoric acid type, KOH type, etc.) is covered. It is not poisonous, does not require a CO removal device, and has a large economic effect because it consists of a simple system.
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Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2004517242A JP4858890B2 (ja) | 2002-06-26 | 2003-05-15 | 水素製造方法および水素供給装置 |
EP03725779A EP1516853A1 (en) | 2002-06-26 | 2003-05-15 | Method for producing hydrogen and apparatus for supplying hydrogen |
AU2003231473A AU2003231473A1 (en) | 2002-06-26 | 2003-05-15 | Method for producing hydrogen and apparatus for supplying hydrogen |
US10/519,080 US20050255037A1 (en) | 2002-06-26 | 2003-05-15 | Method for producing hydrogen and apparatus for supplying hydrogen |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2002-185563 | 2002-06-26 | ||
JP2002185563 | 2002-06-26 |
Publications (1)
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WO2004002881A1 true WO2004002881A1 (ja) | 2004-01-08 |
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PCT/JP2003/006050 WO2004002881A1 (ja) | 2002-06-26 | 2003-05-15 | 水素製造方法および水素供給装置 |
Country Status (6)
Country | Link |
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US (1) | US20050255037A1 (ja) |
EP (1) | EP1516853A1 (ja) |
JP (1) | JP4858890B2 (ja) |
CN (1) | CN1662440A (ja) |
AU (1) | AU2003231473A1 (ja) |
WO (1) | WO2004002881A1 (ja) |
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JP2006106968A (ja) * | 2004-10-01 | 2006-04-20 | Nitto Denko Corp | 携帯型コンピュータ |
JP2006143560A (ja) * | 2004-11-24 | 2006-06-08 | Kiyoshi Otsuka | 水素発生媒体製造方法及び水素製造方法 |
US7374717B2 (en) | 2004-03-22 | 2008-05-20 | Osamu Yamada | Method for producing intermetallic compound porous material |
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- 2003-05-15 US US10/519,080 patent/US20050255037A1/en not_active Abandoned
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JP2005243649A (ja) * | 2004-02-26 | 2005-09-08 | Samsung Sdi Co Ltd | 燃料電池システムの改質器及び燃料電池システム |
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JP2006143560A (ja) * | 2004-11-24 | 2006-06-08 | Kiyoshi Otsuka | 水素発生媒体製造方法及び水素製造方法 |
JP4688477B2 (ja) * | 2004-11-24 | 2011-05-25 | 大塚 潔 | 水素発生媒体製造方法及び水素製造方法 |
US8287098B2 (en) | 2005-11-25 | 2012-10-16 | Canon Finetech Inc. | Liquid ejection head, liquid supply apparatus, liquid ejection apparatus, and liquid supply method |
JP4659923B1 (ja) * | 2010-04-30 | 2011-03-30 | エナジー・イノベーション・ワールド・リミテッド | 水素生成用触媒 |
WO2011135709A1 (ja) * | 2010-04-30 | 2011-11-03 | エナジー・イノベーション・ワールド・リミテッド | 水素生成用触媒 |
Also Published As
Publication number | Publication date |
---|---|
CN1662440A (zh) | 2005-08-31 |
JPWO2004002881A1 (ja) | 2005-10-27 |
JP4858890B2 (ja) | 2012-01-18 |
EP1516853A1 (en) | 2005-03-23 |
US20050255037A1 (en) | 2005-11-17 |
AU2003231473A1 (en) | 2004-01-19 |
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