WO2003080504A1 - Dispositif pour produire de l'hydrogene au moyen d'hydrocarbure ou d'un compose contenant de l'oxygene comme substance et electrode de decharge utilisee dans ce dispositif - Google Patents

Dispositif pour produire de l'hydrogene au moyen d'hydrocarbure ou d'un compose contenant de l'oxygene comme substance et electrode de decharge utilisee dans ce dispositif Download PDF

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Publication number
WO2003080504A1
WO2003080504A1 PCT/JP2003/003671 JP0303671W WO03080504A1 WO 2003080504 A1 WO2003080504 A1 WO 2003080504A1 JP 0303671 W JP0303671 W JP 0303671W WO 03080504 A1 WO03080504 A1 WO 03080504A1
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discharge electrode
hydrogen
discharge
raw material
catalyst
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PCT/JP2003/003671
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English (en)
Japanese (ja)
Inventor
Mitsuo Honma
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Jisouken Co., Ltd.
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Priority to AU2003221156A priority Critical patent/AU2003221156A1/en
Publication of WO2003080504A1 publication Critical patent/WO2003080504A1/fr

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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
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J19/087—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy
    • B01J19/088—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges
    • 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
    • B01J15/00—Chemical processes in general for reacting gaseous media with non-particulate solids, e.g. sheet material; Apparatus specially adapted therefor
    • B01J15/005—Chemical processes in general for reacting gaseous media with non-particulate solids, e.g. sheet material; Apparatus specially adapted therefor in the presence of catalytically active bodies, e.g. porous plates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/342—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents with the aid of electrical means, electromagnetic or mechanical vibrations, or particle radiations
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J2219/0803—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy
    • B01J2219/0805—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges
    • B01J2219/0807—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges involving electrodes
    • B01J2219/0824—Details relating to the shape of the electrodes
    • B01J2219/0826—Details relating to the shape of the electrodes essentially linear
    • B01J2219/0828—Wires
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J2219/0803—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy
    • B01J2219/0805—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges
    • B01J2219/0807—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges involving electrodes
    • B01J2219/0824—Details relating to the shape of the electrodes
    • B01J2219/0826—Details relating to the shape of the electrodes essentially linear
    • B01J2219/083—Details relating to the shape of the electrodes essentially linear cylindrical
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J2219/0803—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy
    • B01J2219/0805—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges
    • B01J2219/0807—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges involving electrodes
    • B01J2219/0837—Details relating to the material of the electrodes
    • B01J2219/0841—Metal
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J2219/0873—Materials to be treated
    • B01J2219/0875—Gas
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0861—Methods of heating the process for making hydrogen or synthesis gas by plasma

Definitions

  • the present invention relates to an apparatus for producing hydrogen.
  • Hydrogen is an important industrial gas, and has been widely used in the synthesis of ammonia and methanol, hydrodesulfurization, hydrocracking, hydrogenation of oils and fats, welding, and semiconductor manufacturing. Recently, new applications such as fuel cell reactants, automobiles, aircraft, power generation, and kitchen fuels have attracted attention.
  • steam reforming As a method of producing hydrogen, a method (steam reforming) in which alcohol or hydrocarbon is reacted with water vapor is conventionally known. Steam reforming is also called steam reforming, and is specifically expressed by chemical reaction formulas such as the following equations (1) to (3).
  • This steam reforming has conventionally been performed under a high temperature and high pressure condition of about 250 to 400C and a pressure of about 1 to 50 atm using alumina as a carrier and a noble metal catalyst such as platinum.
  • this method requires an expensive catalyst, and since the reaction is carried out at high temperature and pressure, a robust anti-high temperature and pressure resistance can be achieved. It was necessary to use a reaction device. In addition, various side reactions occurred, and the by-products formed resulted in clogging of the reaction tube and deterioration of the catalyst. Under such circumstances, it can be carried out at a lower temperature and pressure than conventional methods, can be carried out without using an expensive catalyst, has a high conversion rate, and hardly any miscellaneous side reactions occur.
  • a steam reforming method and apparatus have been developed and disclosed in Japanese Patent Application Laid-Open No. 2001-333520.
  • This apparatus comprises a reactor, a pair of electrodes contained in the reactor, and a DC power supply for applying a voltage to the electrodes, and the gaseous chain hydrocarbon and water vapor introduced into the reactor crucible.
  • direct current pulse discharge is performed to make chain hydrocarbon and water vapor react with each other to generate hydrogen.
  • the above-mentioned device is very low cost, and by a small, portable reactor. As it can be implemented, for example, it is expected that it can be installed in automobiles and used for hydrogen supply to fuel cells. To that end, it is desirable to further improve the hydrogen generation efficiency. Further, since the above-described apparatus produces some byproducts such as C 2 compounds, it is also desirable to further reduce these byproducts.
  • the present invention aims to provide a novel generating device capable of generating hydrogen with higher efficiency, and a discharge electrode used for the device.
  • Another object of the present invention is to provide an apparatus for producing hydrogen in which by-products such as acetylene are further reduced, and a discharge electrode used in the apparatus. Disclosure of the invention
  • the present invention comprises a discharge electrode having a capillary for supplying a raw material containing water and one or more substances selected from hydrocarbons and oxygen-containing compounds, and the pulse discharge is performed by the discharge electrode.
  • the present invention provides a hydrogen generator for inducing a reaction of a material supplied by the capillary to generate hydrogen.
  • FIG. 1 is a diagram showing a generation apparatus according to an embodiment of the present invention.
  • FIG. 2 is a partially enlarged view of a discharge electrode in the embodiment of the present invention.
  • FIG. 3 is a partially enlarged view of the discharge electrode in the embodiment of the present invention.
  • FIG. 4 is a partially enlarged view of the discharge electrode in the embodiment of the present invention o
  • FIG. 5 is a partially enlarged view of the discharge electrode in the embodiment of the present invention o
  • FIG. 6 is a partially enlarged view of the discharge electrode in the embodiment of the present invention.
  • FIG. 7 is a view showing a generation apparatus in the embodiment of the present invention
  • FIG. 8 is a view showing a generation apparatus in the embodiment of the present invention
  • FIG. 9 is a view showing the generation apparatus in the embodiment of the present invention BRIEF DESCRIPTION OF THE DRAWINGS
  • FIG. 1 is a diagram showing an embodiment of the invention.
  • the present invention includes, as Claim 1, a discharge electrode having a capillary for supplying a raw material containing water and one or more substances selected from a hydrocarbon and an oxygen-containing compound, and the pulse discharge is performed by the discharge electrode. And providing an apparatus for producing hydrogen which induces a reaction of a raw material supplied by the capillary to produce hydrogen.
  • the raw material containing water and one or more substances selected from hydrocarbon and oxygen-containing compound moves through the capillary of the discharge electrode, receives a pulse discharge and reacts, and produces the target hydrogen.
  • the generated hydrogen is usually discharged out of the system via an outlet or the like.
  • the capillary means a passage or a cavity formed in the discharge electrode, and the raw material is subjected to a pulse discharge by means of a suction force by capillary action, a pump or the like in the passage and the cavity.
  • the hydrocarbons referred to here include aliphatic hydrocarbons and aromatic hydrocarbons Contains the element.
  • an oxygen-containing compound is an organic compound containing an oxygen atom in the molecule, and includes alcohol, ether, phenolide, ketone, ester and the like.
  • a second aspect of the present invention is a discharge electrode including a capillary for supplying a raw material containing one or more substances selected from oxygen-containing compounds, and pulse discharge is performed by the discharge electrode to be supplied by the capillary.
  • an apparatus for producing hydrogen which induces reactions of raw materials to produce hydrogen.
  • the oxygen-containing compound moved through the capillary mainly causes a decomposition reaction to generate hydrogen by receiving pulse discharge.
  • the discharge electrode is configured by bundling a plurality of conductive fibers, and the capillary is interposed between the conductive fibers. It is characterized by having
  • the bundle of conductive fibers functions as a discharge electrode of the pulse discharge, and the raw material moves through the space (hair tube) between the conductive fibers and the other conductive fibers.
  • the conductive fibers metal fibers such as stainless steel are used, and those having corrosion resistance are preferable.
  • the discharge electrode is formed by bundling a plurality of carbon fibers, and a capillary is provided between the carbon fibers.
  • the bundle of carbon fibers functions as a discharge electrode of the pulse discharge, and the raw material moves through the gap (capillary) between the carbon fibers and the other carbon fibers.
  • Carbon fiber is a good conductor and has corrosion resistance, so it is suitable for the reaction system of the present invention.
  • the carbon fibers referred to here include any of PAN-based, rayon-based and pitch-based, and further, so-called graphite fibers obtained by treating carbon fibers at a high temperature (1500 to 300 ° C.) It is a concept that includes activated carbon fiber that has been activated.
  • a seventh aspect of the present invention is the hydrogen generation apparatus according to the fifth or sixth aspect, wherein the end face of the carbon fiber is shaped like an edge.
  • the current is concentrated at the tip of the edge-like end face and the discharge is It is more likely to occur and the energy required for discharge is reduced.
  • the shape of the edge means, for example, that the tip end has a pointed shape, and the tip end has a diameter smaller than that of the other portion, or the tip end has the same diameter as the other portion.
  • the eighth aspect of the present invention is the hydrogen generation apparatus according to any one of the first to sixth aspects, further comprising a heating unit that heats and vaporizes the raw material moving in the capillary.
  • the heating unit heats or vaporizes the raw material moving through the capillary directly or indirectly. Then, the raw material that has become a gas goes out from the inside of the discharge electrode and reacts in the area where the pulse discharge is performed.
  • a ninth aspect of the present invention is the hydrogen generation apparatus according to any one of the first to sixth aspects, wherein a portion of the surface of the discharge electrode excluding the end face facing the area where the pulse discharge is performed is covered. A skin layer is provided. Further, claim 10 is the hydrogen generator according to any one of claims 1 to 6, wherein a portion of the surface of the discharge electrode excluding the end face facing the region where pulse discharge is to be performed and the vicinity thereof It is characterized in that it has a skin layer covering it.
  • the skin layer prevents the raw material from leaking out from the side surface of the discharge electrode, and the raw material is supplied to the area where pulse discharge is performed reliably and efficiently. Also, at that time, the skin layer is coated on the part excluding the end face of the discharge electrode or the part excluding the end face of the discharge electrode and the vicinity thereof. The reaction proceeds reliably without inhibition.
  • claim 11 is characterized in that, in the hydrogen generator according to any one of claims 1 to 6, a conductive core material is provided inside the discharge electrode.
  • the form of the discharge electrode is maintained, and a stable discharge can be obtained in the core portion.
  • the scope of claim 12 is the same as that of hydrogen described in any of claims 1 to 6.
  • the generator further includes: a reactor that accommodates a discharge electrode; and a power source that applies a voltage to the discharge electrode.
  • applying a voltage using a power supply causes pulse discharge to generate hydrogen in the reactor.
  • the claim 13 is the hydrogen generation apparatus according to any one of the claims 1 to 6, characterized in that a reservoir is provided for storing the raw material that has reached the outside of the discharge electrode through the capillary. Do.
  • the raw material is reacted by the pulse discharge while being accumulated in the reservoir, the amount of the raw material supplied is increased, and the hydrogen generation efficiency is improved. Also, the response of hydrogen generation to discharge is improved.
  • the claim 14 is characterized in that, in the apparatus for producing hydrogen according to the claim 13, the reservoir is made of a powder attached to the surface of the discharge electrode.
  • the raw material is accumulated by infiltrating the gaps between the powders.
  • a reservoir for storing the raw material that has reached the outside of the discharge electrode through a capillary is provided, and the reservoir is It is characterized in that it is constituted by the expanded internal space of the reactor in the vicinity of the area where the pulse discharge is performed.
  • claim 16 is characterized in that, in the hydrogen generator according to any one of claims 1 to 6, a catalyst is attached to the discharge electrode.
  • a catalyst is attached to the discharge electrode.
  • the reaction of the hydrocarbon or the oxygen-containing compound with water efficiently proceeds by the catalyst, and the by-products such as the C 2 compound are further reduced.
  • the catalyst is activated by pulse discharge and its catalytic ability is enhanced.
  • the method of depositing the catalyst on the discharge electrode is not particularly limited, and the method may be appropriately carried out by plating, sputtering, vapor deposition, or the like.
  • claim 17 is the hydrogen generator according to claim 16, wherein the catalyst is ruthenium, or a multiple catalyst of ruthenium and another catalyst. It is characterized by
  • claim 18 is characterized in that, in the apparatus for producing hydrogen according to claim 16, the catalyst is a fullerene.
  • the claim 19 is characterized in that, in the apparatus for producing hydrogen according to the claim 16, the catalyst is a ruthenium supporting ruthenium.
  • the type of catalyst suitable in the present invention is specified from the viewpoint of reducing reaction efficiency and by-products.
  • fullerenes and refers to a spherical shell-like carbon molecules, c 60 C 70 C 76 C 78 C 80 82 C 8 4 C 8 6. 88. 90 9 2 C 94 96. 1 20 2
  • claim 20 is the hydrogen generation apparatus according to claim 18 or 19, wherein the fullerene is C 24 . It is characterized by being.
  • C 24 is a particularly superior substance among fullerenes. Is selected. c 24 . Has been found to have high hydrogen storage capacity, which is thought to contribute to the improvement of hydrogen generation efficiency and the reduction of by-products.
  • the invention according to claim 21 is characterized in that a pulse discharge is performed in a raw material containing water and one or more substances selected from hydrocarbons and oxygen-containing compounds to induce a reaction of the raw material to generate hydrogen. It is a discharge electrode which is used for an apparatus for producing and which has a capillary capable of supplying the raw material.
  • a novel discharge electrode in which a raw material containing water and one or more substances selected from hydrocarbons and oxygen-containing compounds can be moved through a capillary.
  • hydrocarbon as used herein includes aliphatic hydrocarbons and aromatic hydrocarbons.
  • oxygen-containing compounds A substance is an organic compound containing an oxygen atom in its molecule, and includes alcohol, ether, aldehyde, ketone, ester and the like.
  • Claim 22 is used for the apparatus which makes the reaction of the said raw material induce, and produces hydrogen by performing a pulse discharge in the raw material containing one or more substances chosen from an oxygen-containing compound, It is a discharge electrode having a capillary capable of supplying
  • the raw material containing one or more substances selected from oxygenated compounds can move through the capillary.
  • the oxygen-containing compound mainly causes a decomposition reaction to generate the target hydrogen.
  • the discharge electrode according to claim 2 1 or 2 2 is configured by bundling a plurality of conductive fibers, and having a capillary between the conductive fibers. It is characterized by
  • the raw material can move through the space (capillary) between the conductive fiber and the other conductive fiber.
  • the conductive fibers metal fibers such as stainless steel are used, and those having corrosion resistance are preferable.
  • the discharge electrode according to claim 21 or 22 is formed by bundling a plurality of carbon fibers and having a capillary between the carbon fibers. It features.
  • the raw material can move through the air gap (capillary) between the carbon fiber and the other carbon fiber. Since carbon fiber is a good conductor and has corrosion resistance, it is suitable as a discharge electrode used in the reaction system of the present invention.
  • the carbon fibers referred to here include any of PAN type, rayon type and pitch type, and further, so-called graphite fibers obtained by treating carbon fibers at a high temperature (1500 to 300 ° C.) It is a concept that includes activated carbon fiber that has been activated.
  • claim 27 is characterized in that, in the discharge electrode according to claim 25 or 26, the end face of the carbon fiber is edge-like.
  • the carbon is concentrated so that the discharge is likely to occur.
  • the end face shape of the elementary fiber is identified.
  • claim 28 is characterized in that, in the discharge electrode according to any one of claims 21 to 26, a skin layer is covered on a part of the surface of the discharge electrode excluding the end face. Do.
  • claim 29 is the discharge electrode according to any one of claims 2 1 to 26.
  • the skin layer is coated on the surface of the discharge electrode except for the end face and the vicinity thereof. It features.
  • the skin layer prevents the raw material from leaking out from the side surface of the discharge electrode, and it becomes possible to supply the raw material reliably and efficiently. Also, at this time, the skin layer is coated on the part excluding the end face of the discharge electrode or the part excluding the end face of the discharge electrode and the vicinity thereof, so the generator was configured using this discharge electrode. Sometimes, the discharge does not occur at an inappropriate site, and the reaction proceeds reliably without being inhibited.
  • claim 30 is characterized in that a conductive core material is provided inside the discharge electrode according to any one of claims 2: to 26.
  • the form of the discharge electrode is maintained, and it is possible to stably discharge in the portion of the core material.
  • the claim 31 is that the discharge electrode according to any one of claims 21 to 26 is provided with a reservoir for storing the raw material that has reached the outside of the discharge electrode through the capillary. It features.
  • the generator when the generator is configured using this discharge electrode, since the raw material reacts while being accumulated in the storage section, the supply amount of the raw material is increased, and the hydrogen generation efficiency is improved. In addition, the response of hydrogen generation to discharge is improved.
  • claim 32 is characterized in that, in the discharge electrode according to claim 31, the storage section is composed of powder adhered to the surface of the discharge electrode.
  • claim 33 is characterized in that the catalyst is attached to the discharge electrode according to any one of claims 212.
  • the reaction of the hydrocarbon or the oxygen-containing compound with water proceeds efficiently by the catalyst.
  • the use of a catalyst can further reduce by-products such as C 2 compounds.
  • the catalyst is activated by pulse discharge and its catalytic ability is enhanced.
  • the method for depositing the catalyst on the discharge electrode is not particularly limited, and may be appropriately carried out by plating, sputtering, vapor deposition or the like.
  • claim 34 is characterized in that, in the discharge electrode according to claim 33, the catalyst is ruthenium, or a multiple catalyst of ruthenium and another catalyst.
  • the claim 35 is characterized in that, in the discharge electrode according to the claim 33, the catalyst is a fullerene.
  • the catalyst is a fullerene supporting ruthenium.
  • the type of catalyst suitably used is specified in terms of reaction efficiency and reduction of by-products.
  • fullerene means a spherical shell-like carbon molecule, C 6 C 7 C 76 C 78 C 8 C 8
  • C 560 etc. are included. Also, for example, C 56 . To C 24 . It also includes those of the bicyclic structure that encloses.
  • the fullerene is C 24 . It is characterized by being.
  • C 240 is selected as a substance having particularly excellent performance among fullerenes.
  • C 240 has been found to have high hydrogen storage capacity, and this is thought to contribute to the improvement of hydrogen generation efficiency and the reduction of by-products.
  • the invention according to claim 38 has a discharge electrode on which a catalyst is attached, and in a raw material containing one or more substances selected from hydrocarbon and oxygen-containing compounds and water, the discharge electrode generates a pulse. It is a generator of hydrogen which is discharged to induce reaction of the raw material to generate hydrogen.
  • the reaction of the hydrocarbon or the oxygen-containing compound with water proceeds efficiently by the catalyst, and the target hydrogen is produced.
  • the use of the catalyst further reduces by-products such as C 2 compounds.
  • the catalyst is activated by pulse discharge and its catalytic ability is enhanced.
  • the method of attaching the catalyst to the discharge electrode is not particularly limited, and the method is appropriately carried out by plating, sputtering, vapor deposition, or the like.
  • the hydrocarbons mentioned here include aliphatic hydrocarbons and aromatic hydrocarbons
  • oxygen-containing compounds mean organic compounds containing an oxygen atom in the molecule, such as alcohol, ether, aldehyde, It is a concept that includes ketones and esters.
  • claim 39 includes a discharge electrode on which a catalyst is attached, and in the raw material containing one or more substances selected from oxygen-containing compounds, a pulse discharge is performed by the discharge electrode to react the raw material. It is a generator of hydrogen that induces hydrogen to generate hydrogen.
  • the catalyst is activated by the pulse discharge to increase the catalytic ability, and the decomposition reaction of the oxygen-containing compound efficiently proceeds to generate the target hydrogen.
  • byproducts such as C 2 compounds are further reduced.
  • claim 40 further comprises: a reactor that accommodates a discharge electrode; and a power supply that applies a voltage to the discharge electrode. It is characterized by
  • applying a voltage using a power source causes pulse discharge to generate hydrogen in the reactor.
  • claim 41 is characterized in that in the hydrogen generator according to claim 38 or 39, the catalyst is ruthenium or a multi-component catalyst of ruthenium and another catalyst.
  • claim 4 is the production of hydrogen according to claim 3 8 or 3 9
  • the catalyst is characterized in that it is a fullerene.
  • claim 43 is characterized in that the catalyst is a ruthenium supporting ruthenium.
  • the type of catalyst suitable in the present invention is specified from the viewpoint of reducing reaction efficiency and by-products.
  • fullerene refers to a spherical shell-like carbon molecule, c 6 C 7 C 76 C 78 C 8 .
  • C 56 . Etc. are included. Also, for example, C 56 . To C 24 . It also includes those of a bicyclic structure that contains.
  • claim 44 is the hydrogen generation apparatus according to claim 42 or 43, wherein the fullerene is C 24 . It is characterized by being.
  • C is a substance with particularly good performance among fullerenes.
  • C 24 Is selected.
  • C 24 Has been found to have high hydrogen storage capacity, which is thought to contribute to the improvement of hydrogen generation efficiency and the reduction of by-products.
  • FIG. 1 an embodiment (1) of the present invention is shown in FIG. 1 and FIG.
  • the production apparatus 1 shown in FIG. 1 includes a reactor 10, in which a pair of discharge electrodes 1 1 1 2 are disposed opposite to each other.
  • a discharge region 13 where pulse discharge is performed is formed between the discharge electrode 11 and the discharge electrode 12.
  • the distance between the discharge electrode 1 1 and the discharge electrode 1 2 can be arbitrarily adjusted.
  • the discharge electrode 11 has a capillary for supplying the raw material A.
  • the capillary means a passage or an air gap in the discharge electrode 11, and the raw material A can move in the capillary.
  • the shape of the capillary can be any shape, such as a tubular shape or a mesh shape.
  • the discharge electrode 11 is configured by bundling a plurality of carbon fibers 110 by using a good conductor such as carbon fibers 110. And, each carbon fiber 110 functions as a capillary 111 through which the raw material A passes.
  • the carbon fiber 110 is schematically shown as having a certain thickness and a bundle of several tens of fibers, but in general, the thickness of the carbon fiber 110 is The order is on the order of meters (specifically, about 1 ⁇ 1 to 1 ⁇ ⁇ ), and the number is also large (for example, several tens of thousands or more) according to the thickness of the discharge electrode 11.
  • the type of raw material and the like it is also possible to use a thicker and smaller number of carbon fibers, and it is not limited to the above numerical range.
  • the carbon fiber 110 various conventionally known carbon fibers can be used. Specific examples thereof include carbon fibers made of polyacrylonitrile (PAN), pitch-based carbon fibers made of petroleum, petroleum tar, liquefied coal and the like, rayon-based carbon fibers and the like.
  • PAN polyacrylonitrile
  • pitch-based carbon fibers made of petroleum, petroleum tar, liquefied coal and the like
  • rayon-based carbon fibers and the like For example, for PAN-based carbon fiber, a special acrylic fiber (precursor 1) is heat-treated in air, and the resulting flame resistant fiber is fired at 100.degree. C. to 100.degree. C. in an inert gas. You can get more.
  • the carbon fiber was activated in a graphite fiber fired at a high temperature of 300 ° C. to 300 ° C., or in an activated gas (mixed gas such as water vapor, carbon dioxide gas, and nitrogen gas).
  • activated carbon fibers are also applicable. Since carbon fibers are chemically stable, they have
  • the end face 112 of the discharge electrode made of carbon fiber is formed in an edge shape.
  • the end face 112 of the discharge electrode made of carbon fiber is formed in an edge shape.
  • the end surface 112 itself becomes edge-like even without processing.
  • the end face 112 may be processed appropriately by cutting, cutting, or the like so that it has a wedge shape.
  • the reactor 10 is made of quartz and other glass, ceramic, synthetic resin and the like.
  • a DC power supply 14 for applying a negative high voltage is connected to a discharge electrode 11 extending to the outside of the reactor 10, and a digital oscilloscope 15 is connected between the DC power supply 14 and the discharge electrode 11. It is connected.
  • a three-way port 16 is connected to the reactor 10, and a discharge electrode 12 extending outward from the reactor 10 penetrates to one end of the three-way port 16 to be grounded. Further, the other of the three-way ports 16 is an outlet 17 for discharging hydrogen H 2 generated by the pulse discharge.
  • an introduction passage 18 for introducing the raw material A into the capillary tube 11 1 of the discharge electrode 1 1 is connected to the discharge electrode 1 1.
  • a raw material A containing at least one substance selected from hydrocarbons and oxygen-containing compounds and water is supplied into the discharge electrode 11 through the introduction passage 18.
  • the supplied raw material A moves through the capillary tube 11 1 of the discharge electrode 1 1, and finally, for example, it exudes from the end face 1 1 2 of the discharge electrode 1 1 to the discharge region 1 Reach 3 (or near).
  • the raw material A which moves the capillary tube 11 and reacts by pulse discharge may be in a liquid state or in a gas state.
  • the raw material A may be vaporized by a slight Joule heat generated by the pulse discharge, and the vaporized raw material A may be reacted.
  • the raw material A can be naturally drawn in the direction of the discharge area 13 by using capillary action.
  • a new material A is aspirated to compensate for it. this
  • the raw material A can be naturally supplied to the discharge region 13 without using a delivery means such as a pump, which is preferable from the viewpoint of generation efficiency.
  • the appropriate value of the inner diameter of the capillary tube 11 is determined by comprehensively considering the length of the capillary tube 111, the density of the raw material A, the surface tension of the raw material A, the contact angle of the raw material A to the discharge electrode surface, etc. be able to.
  • the volume equivalent ratio of ethanol to water is approximately 30 m 1 per minute. It has been found that suction is possible.
  • a pump or the like may be combined with the above-mentioned method using capillary action as appropriate.
  • the raw material A can be moved along with the pulse discharge. That is, although the raw material A can be ionized by the high voltage at the time of the pulse discharge, utilizing this, the ionized raw material A is directed toward the other discharge electrode 12 every time the pulse discharge occurs. It is possible to move using phenomena such as electrophoresis. Also in this case, as in the case of the above-mentioned capillary phenomenon, hydrogen can be efficiently generated at low cost since a delivery means such as a pump is unnecessary. In addition, since the supply of the raw material A is performed in response to the voltage at the time of pulse discharge, the response of hydrogen generation is improved.
  • the hydrocarbon to be reacted is not particularly limited, and can be appropriately selected from various hydrocarbons.
  • examples thereof include aliphatic hydrocarbons such as linear, branched or cyclic alkanes, alkenes and alkynes, various aromatic hydrocarbons, or a mixture of two or more thereof.
  • natural gas, petroleum naphtha, gasoline, kerosene, etc., and their mixtures may be used as they are.
  • the oxygen-containing compound is an organic compound containing an oxygen atom in the molecule, and can be appropriately selected from various substances as in the case of the above-mentioned hydrocarbon.
  • Examples and Alcohol such as methanol, ethanol, propanol, butanol, etc., dimethinolee one-tenole, getinolee tenore, methinoleethinolee tenolee, an ether such as methyl tertiary-butyl ether, etc.
  • ketones such as acetone and methyl ethyl ketone
  • esters such as ethyl acetate, ethyl formate, dimethyl carbonate and the like, and mixtures of two or more of them.
  • the above-mentioned hydrocarbon and an oxygen-containing compound can be used in combination as appropriate.
  • Water is a liquid containing H 2 O in excess or steam, which is a common water. If there is, it is applicable.
  • distilled water ion-exchanged water, etc.
  • hot water is also included in the concept of water of the present invention.
  • the apparatus of the present invention is characterized in that the material A containing one or more kinds of substances selected from the above-mentioned hydrocarbons and oxygen-containing compounds and water is supplied to the discharge region 13 or in the vicinity thereof and then pulse discharge is performed.
  • the pulse discharge is to flow a pulse current between the discharge electrodes, and since electron irradiation is repeated within a minute time of, for example, 1 ⁇ s or less, the temperature of the gas phase does not rise, and the temperature is extremely low. It can be reacted.
  • the pulse discharge is usually performed at regular intervals, but may be intermittent.
  • an oxygen-containing compound alone as the raw material A.
  • oxygen-containing compounds such as alcohols represented by methanol, ethanol and the like do not necessarily have to be used in combination with water, and can be used alone.
  • the decomposition reaction of the oxygen-containing compound itself takes place to produce hydrogen.
  • the various reactions described above are considered to be a discharge current, that is, irradiation of the electron beam from the discharge electrode to generate radicals, which cause the reaction. Therefore, as the discharge current is increased and the distance between the discharge electrodes is increased, the number of molecules colliding with the electron beam is increased, so that the reaction speed is increased, and the conversion rate in a unit time is high. There is a tendency to
  • pulse generation frequency the number of pulse discharges per second
  • the pulse generation frequency increases as the current increases at a constant voltage and decreases as the distance between the discharge electrodes increases. Therefore, the preferred voltage, current and discharge electrode distance are naturally set by adjusting the voltage, current and discharge electrode distance so that the above pulse generation frequency is achieved.
  • the applied voltage is about 1 k V to about: I 0 k V, and the current is:!
  • the distance between the discharge electrodes is about 2 mm to about 10 mm.
  • the applied voltage, the current, and the distance between the discharge electrodes are not limited to the above range, and when using a large reactor with a higher production capacity, the distance between the discharge electrodes is increased, and the above pulse is It can be implemented by increasing the applied voltage and current accordingly to achieve the frequency of occurrence.
  • the raw material A to be reacted may be either liquid or gas.
  • the reaction temperature is not particularly limited, but it is preferable to carry out the reaction at a temperature as low as possible because the energy cost is low.
  • the reaction temperature is preferably about 80 ° C. to 150 ° C. (under normal pressure conditions).
  • the reason that the low temperature side of the above range is lower than 100 ° C. is that the alcohol and water may be vaporized by the azeotropic phenomenon.
  • the total pressure in the reactor 10 in the case of supplying the raw material A in the gaseous state is not particularly limited, and can be performed, for example, at about 0.1 atm to 10 atm. However, since the reaction proceeds sufficiently at normal pressure and there is no need for a robust reactor at that time, it can be said that it is particularly industrially preferable to carry out at normal pressure.
  • the mixing ratio of hydrocarbon or oxygen-containing compound to water may be a stoichiometric amount, but if desired, increase or decrease one substance by about 1/2 to 2 times the stoichiometric amount or more. Is also possible.
  • the feed rate of the raw material A is such that the conversion of the raw material A becomes a certain value or more, for example, 60% or more, by analyzing hydrogen H 2 discharged from the outlet 17. It is preferable to set as appropriate. For example, using a reactor with an inner diameter of 5 mm, the distance between the discharge electrodes is set to about 1 mm to 10 mm, the applied voltage is set to about 1 to 5 kV, and a mixed gas containing alcohol and water vapor is used as the raw material A.
  • the supply flow rate is suitably about 10 to 100 O m 1 / min, particularly about 50 to 10 O m 1 / min.
  • the DC power supply 14 is used as the power supply connected to the discharge electrode 1 1 in the generator 1 of FIG. 1, other power supplies capable of pulse discharge are applicable, for example, a power supply that combines an AC power supply with a diode bridge circuit, load, etc., as appropriate, or a voltage for DC component superimposed on that power supply A power supply etc. can be suitably adopted.
  • the voltage applied to the discharge electrode is preferably unipolar as described above, it is also possible to apply an alternating voltage without being limited thereto.
  • the discharge electrode accommodated in the reactor 10 is not limited to a pair, and a plurality of discharge electrodes may be used as needed.
  • the production apparatus 1 of the present invention by-produces carbon monoxide together with the target hydrogen. Therefore, hydrogen gas and carbon dioxide can be finally produced by separately reacting the produced hydrogen and carbon monoxide with water vapor.
  • This reaction is known as the water gas shift reaction.
  • the water gas shift reaction itself is well known in the art and has the advantage of proceeding at low temperature and pressure.
  • a catalyst for water gas shift reaction such as a zinc oxide copper oxide solid catalyst, etc.
  • the discharge electrode 11 is covered with the skin layer 19 except for the area where the pulse discharge is performed, that is, the end face 112 facing the discharge area 13 and the vicinity thereof. can do.
  • the skin layer 19 holds the carbon fiber 110 in a bundle state, and prevents the raw material A moving in the capillary 11 1 from leaking out from the side of the discharge electrode 1 1 to ensure the raw material A.
  • Send in the direction of end face 1 1 2 The skin layer 19 is composed of a chemically stable substance, and examples thereof include silicone rubber, polytetrafluoroethylene and the like. Further, the thickness of the skin layer 19 is not particularly limited and can be set as appropriate. In the example of FIG.
  • the end face 112 of the discharge electrode 11 and its vicinity are exposed, but as shown in the embodiment (2) of FIG. 3, only the end face 112 is exposed.
  • the other surface may be covered with a skin layer 19.
  • the skin layer 19 may be coated on the discharge electrode 11 via various adhesives as required.
  • the catalyst 20 can be attached to the discharge electrode 11.
  • the catalyst 20 is applicable as long as it can improve the efficiency of the hydrogen generation reaction by pulse discharge or reduce by-products such as C 2 compounds. Examples include palladium or platinum catalysts supported by alumina, nickel catalysts, Lindlar catalysts, and the like. These catalysts can suppress the formation of C 2 compounds such as acetylene, among others.
  • the catalyst 20 is activated by being subjected to pulse discharge, and its catalytic ability is higher than usual.
  • fullerene ruthenium as a method of charge of lifting it is not particularly limited, for example, plated ruthenium relative to fullerene, evaporation A method of supporting by sputtering etc., and a method of evaporating ruthenium at the same time when supporting fullerene by laser evaporation method, etc. can be suitably adopted.
  • Ruthenium particles is no reason to become finer is uncertain in the activated state, the contact between the ruthenium particles by hula one lens, considered or not to grain growth is inhibited.
  • the catalyst 20 As a method of adhering the catalyst 20 to the discharge electrode 11, a method such as vapor deposition, sputtering, plating, etc. of the catalyst 20 on the surface of the discharge electrode 11 is appropriately adopted.
  • the catalyst 20 may be attached to the surface of the carbon fiber 1 10 before bundling by vapor deposition or the like, and then they may be bundled to form a discharge electrode 1 1.
  • the apparatus according to the present invention can generate hydrogen without using a catalyst, it can be said that it can be carried out without using any catalyst.
  • the production apparatus of the present invention is characterized in that it can be carried out at a much lower temperature and pressure and at lower cost as compared with the conventional method of reforming at high temperature and pressure using a catalyst.
  • FIG. 1 an embodiment (3) of the present invention is shown in FIG.
  • a plurality of carbon fibers 110 are bundled to form a discharge electrode 11, and a conductive core material 27 is provided at the center of the discharge electrode 11.
  • the form of the discharge electrode 11 is preferable because it is supported by the core 27 and discharge is stably performed at the portion of the core 27.
  • the material of the core 27 is not particularly limited, and various metals such as SUS, aluminum and copper, carbon and the like can be used as appropriate.
  • a plurality of (four in FIG. 5) conductive core materials 27 may be provided inside the discharge electrode 11.
  • a reservoir 2 for storing the raw material A which has reached the outside of the discharge electrode 11 through the capillary tube 11 5 can be provided.
  • the reservoir 25 is configured by adhering powder 26 such as metal, ceramic, resin, etc. to the surface of the carbon fiber 110 constituting the discharge electrode.
  • the raw material A that has leaked from between the bundled carbon fibers 110 to the outside is stored in the gaps of the powder 26 by being held by surface tension, so that the raw material that can react by the pulse discharge
  • the amount of hydrogen is increased to improve the hydrogen generation efficiency. Further, since the raw material A can always be present in the vicinity of the discharge region, the response of hydrogen generation to the discharge can also be improved.
  • the powder 26 is attached to the surface of the discharge electrode 11
  • the storage unit 25 is configured as described above, but any other means capable of storing the raw material A can be adopted as appropriate.
  • a method of roughening the surface of the discharge electrode 11 with sandplast or the like, a method of attaching an absorber such as a sponge around the discharge electrode 11, and the like can be mentioned.
  • the embodiment (6) is shown in FIG.
  • the inside of the reactor 10 is expanded in the vicinity of the discharge area 13 (the outer diameter of the reactor 1 is large in the vicinity of the discharge area 13), and the expanded part The internal space functions as reservoir 25. That is, since the raw material supplied to the outside from the capillary in discharge electrode 11 (in this case, generally in the form of a gas) is retained in storage unit 25, the amount of the raw material facing discharge area 13 is large accordingly The hydrogen generation efficiency is improved.
  • an embodiment (7) of the present invention is shown in FIG. In FIG.
  • the discharge electrode 11 is a bundle of carbon fibers as in the above embodiments (1) to (6), and the raw material A is in the discharge region 13 through the capillary between carbon fibers. It is supposed to move in the direction.
  • the discharge electrode 1 1 is characterized in that the heating portion 21 is provided.
  • the heating unit 21 is configured to supply a current to the discharge electrode 11 itself and to heat using the generated Joule heat.
  • the vaporized raw material A evaporates from the end face or side face of the discharge electrode 11, reaches the discharge area 13, and reacts by pulse discharge to generate hydrogen.
  • the heating temperature is appropriately set according to the type of the raw material A. For example, when a mixture of alcohol and water is used as the raw material, it may be possible to vaporize at 10 ° C.
  • the heating part 21 is connected to the discharge electrode 11.
  • a heater formed by general means such as a nichrome wire may be used around the discharge electrode 11.
  • the raw material A can be heated directly from the inside of the discharge electrode 11 by disposing a heating portion such as a nichrome wire between carbon fibers.
  • the other configuration of the generation device 1 conforms to the above-mentioned embodiment (1).
  • the discharge electrode 11 is described as being composed of a plurality of carbon fibers 110 bundled into a bundle. Any structure having a capillary which can move can be used without particular limitation.
  • a plurality of conductive fibers can be used as a bundle to form the discharge electrode 11.
  • the space between the conductive fiber and the other conductive fiber functions as a capillary to which the raw material is supplied.
  • the conductive fiber one having corrosion resistance is preferably used.
  • metal fibers such as stainless steel are preferably used.
  • the discharge electrode having a capillary a carbon discharge electrode, a metal discharge electrode formed by cutting using a drilling machine or a laser, etc. to form a capillary, or a woven fabric of carbon fiber, etc.
  • a precursor is prepared by impregnating a thermosetting synthetic resin such as phenol resin or a binder such as petroleum pitch, a plurality of the precursors are laminated, and the binder is cured by pressure and heating.
  • a porous material produced by carbonizing the binder by high-temperature firing in an inert atmosphere, or fine particles of a sintered graphite precursor such as raw coke or mesocarbon microbeads are fired at high temperature while being pressure-formed.
  • the porous material etc. can be illustrated.
  • FIG. 9 an embodiment (8) of the present invention is shown in FIG.
  • a pair of discharge electrodes 2 2 and 2 3 are provided to face each other in the reactor 10.
  • a discharge region 13 is formed between the discharge electrode 22 and the discharge electrode 23.
  • the distance between the discharge electrode 22 and the discharge electrode 23 can be arbitrarily adjusted.
  • a direct current power supply 14 for applying a negative high voltage is connected to the discharge electrode 22, and a digital oscilloscope 15 is connected between the direct current power supply 14 and the discharge electrode 22.
  • an outlet 17 for discharging hydrogen H 2 generated by pulse discharge is formed in the three-way port 16.
  • the material of the discharge electrodes 2 2 and 3 general materials such as SUS, nickel, copper, aluminum, iron, carbon and the like can be used, and among them, corrosion of SUS, carbon etc. is also possible. More difficult ones are more preferable.
  • the shape of the discharge electrode is not particularly limited, and various shapes such as needle shape and flat shape can be used.
  • the catalyst 20 is attached to the end faces 220 and 230 of the discharge electrodes 22 and 23 and the vicinity thereof.
  • the reaction is activated by the catalyst 20, and the hydrogen is reduced. It can be generated efficiently.
  • byproducts such as C 2 compounds can be further reduced.
  • the type of catalyst 20, the method of adhering to the discharge electrode, that an oxygen-containing compound can be used alone as the raw material A, the reaction mechanism of hydrogen generation by pulse discharge, etc. are described in the above embodiment (1). Comply.
  • the hydrogen produced by the above-described production apparatus of the present invention can be effectively used, for example, in synthesis of ammonia, methanol, hydrodesulfurization, hydrocracking, hydrogenation of fats and oils, etc., welding, semiconductor production, etc. it can.
  • the utilization as a turbin fuel there is an advantage that the calorific value is larger if the one converted to hydrogen is burned as compared to the case where the alcohol etc. is burned as it is.
  • it since it can be a compact and portable device, it is suitable as a device for supplying hydrogen to a fuel cell mounted on a car or the like.
  • the device shown in Fig. 1 was produced as a generator.
  • a quartz tube having an outer diameter of 10 mm, an inner diameter of 9 mm, and a length of 200 mm was used, and a pair of opposing discharge electrodes was a bundle of carbon fibers.
  • the surface of the discharge electrode was coated with silicone rubber, leaving 5 mm at the end of the discharge area of the discharge electrode.
  • ruthenium was deposited by vapor deposition on the surface of the exposed end of the discharge electrode.
  • a liquid mixture of water and ethanol (volume ratio 1: 1) is supplied from the introduction path into the discharge electrode using capillary phenomenon, and a constant voltage is applied between the discharge electrodes to perform DC pulse discharge.
  • the discharge conditions are: pulse generation frequency is 50 times per second, voltage is 5 k V, current is up to 1 O mA.
  • the temperature in the reactor was maintained at 100 ° C. at which the raw material can evaporate.
  • Example 2 The amount of gas produced per minute discharged from the outlet was measured by gas chromatography. As a result, it was found that the target hydrogen was obtained in high yield. Also, no by-products such as acetylene were detected. (Example 2)
  • the device shown in Fig. 1 was produced as a generator.
  • the discharge electrode connected to the DC power supply is a bundle of 8 4 0 0 0 carbon fibers with a diameter of 7 ⁇ m (Besufite HTA manufactured by Toho Rayon Co., Ltd.) A bundle of seven 1 2 K (brand names) was used.
  • the diameter of the entire discharge electrode consisting of carbon fiber bundles is about 3 mm.
  • a rod-shaped discharge electrode made of SUS 300 was used.
  • the end of the carbon fiber discharge electrode is replaced with the introduction path 18 in FIG. 1, and it is immersed in a mixed liquid of ethanol and water in an equimolar ratio of ethanol contained in the sample bottle, The raw material was supplied using suction.
  • Example 3 A direct current pulse discharge was performed in the same manner as in Example 2 except that in the above Example 2, a SUS of 0.5 mm in diameter was embedded in the center of the carbon fiber bundle and the discharge electrode was used, Analysis was carried out. As a result, as shown in (Table 3), it became clear that the target hydrogen was efficiently generated. In addition, a blue-purple discharge (emission color associated with the reaction) was observed, and the portion where the discharge occurred was also constant and stable. Table 3
  • the generator of the present invention has the capillary for supplying the raw material at the discharge electrode, so that the raw material can be rapidly supplied to the area where the pulse discharge is performed according to the necessary amount, and as a result, hydrogen
  • a catalyst such as ruthenium or fullerene
  • the reaction efficiency of the raw material in the discharge region is improved, and a by-product such as a C 2 compound is produced. It can be further reduced.
  • C 2 4 Provides excellent performance.
  • the production apparatus of the present invention can be implemented at low pressure, low temperature, at low cost, and does not generate by-products, and is preferably used as, for example, a production apparatus of hydrogen to be supplied to a fuel cell. It can be used.

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Abstract

L'invention porte sur un dispositif (1) destiné à produire de l'hydrogène et qui possède une électrode de décharge (11) dont la capillarité permet d'acheminer une matière brute (A) contenant de l'eau et une ou plusieurs substances sélectionnées à partir d'hydrocarbures et de composés contenant de l'oxygène. Ce dispositif effectue une décharge d'impulsions au moyen de l'électrode de décharge (11) et induit une réaction du matériau brut (A) amené par capillarité de façon à produire l'hydrogène. Le dispositif (1) de production d'hydrogène possède également un catalyseur tel que le ruthénium ou le fullerène lié à l'électrode de décharge. Comparé à un dispositif traditionnel, le dispositif permet de produire l'hydrogène à un rendement plus élevé et avec une réduction de sous-produits tels que l'acétylène.
PCT/JP2003/003671 2002-03-27 2003-03-26 Dispositif pour produire de l'hydrogene au moyen d'hydrocarbure ou d'un compose contenant de l'oxygene comme substance et electrode de decharge utilisee dans ce dispositif WO2003080504A1 (fr)

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WO2004099070A1 (fr) * 2003-05-08 2004-11-18 Jisouken Co. Ltd. Systeme de production d'hydrogene au moyen d'hydrocarbures, compose organique contenant de l'oxygene en tant qu'ingredient de base et electrode de decharge utilisee dans ce systeme
JP2006248847A (ja) * 2005-03-10 2006-09-21 Nissan Motor Co Ltd 燃料改質器および燃料改質装置
JP4872120B2 (ja) * 2005-09-15 2012-02-08 日産自動車株式会社 燃料改質装置
EP2007673B1 (fr) 2006-04-07 2011-06-22 QinetiQ Limited Production d'hydrogène
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