WO2004099070A1 - System for producing hydrogen using hydrocarbon, organic compound containing oxygen as material, and discharge electrode for use therein - Google Patents

Abstract

A novel system capable of generating pulse discharge stably and uniformly and, as a result, capable of producing hydrogen with high efficiency, and a discharge electrode for use therein. A capillary tube for feeding a material A containing one or more substances selected from hydrocarbon and organic compound containing oxygen is provided with a discharge electrode (11) formed in a tubular conductor. The hydrogen production system (1) produces hydrogen H2 by generating pulse discharge from the discharge electrode (11) and inducing reaction of the material A being fed from the capillary tube.

Description

 Specification

Apparatus for producing hydrogen from hydrocarbons and organic oxygenates, and discharge electrodes used for the apparatus

 The present invention relates to a hydrogen generator. Background art

 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 fields of use, such as reactants in fuel cells and fuels for automobiles, aircraft, power generation, and kitchens, are attracting attention.

 As a method for producing hydrogen, a method (steam reforming) of reacting alcohol or hydrocarbon with steam or the like is conventionally known. Steam reforming is also called steam reforming, and is specifically represented by a chemical reaction formula (1) to (3).

CH ₃ OH + H ₂ 0 → 3H ₂ + C 0 ₂ (1) C ₂ H ₅ OH + 3H ₂ 0 → 6H ₂ + 2CO _£ (2) CH ₄ + H ₂ 0 → 3H ₂ + CO (3) This steam Conventionally, reforming has been performed under a high temperature and high pressure condition of about 250 to 400 ° C. and about 1 to 50 atm using alumina as a carrier and a noble metal catalyst such as platinum. However, this method requires an expensive catalyst and performs the reaction at a high temperature and a high pressure. Therefore, it is necessary to use a robust reaction apparatus capable of withstanding a high temperature and a high pressure. In addition, various side reactions occurred, and there was a problem that the generated by-products clogged the reaction tube or deteriorated the catalyst. Under such circumstances, it can be carried out at a lower temperature and normal pressure than the conventional method, it can be carried out without using an expensive catalyst, the conversion is high, and miscellaneous side reactions hardly occur. A new steam reforming method and apparatus has been developed and disclosed in Japanese Patent Application Laid-Open No. 2001-335302. The apparatus includes a reactor, a pair of electrodes housed in the reactor, and a DC power supply for applying a voltage to the electrodes, wherein a gaseous chain hydrocarbon and water vapor introduced into the reactor are provided. In a mixed gas containing, a direct current pulse discharge is performed to react chain hydrocarbons with water vapor to generate hydrogen. The above-mentioned equipment is very low cost and can be implemented with a small and portable reactor, so it can be used, for example, to install it in a car or the like and supply hydrogen to a fuel cell. Be expected. For that purpose, it was desired to further improve the hydrogen generation efficiency.

 On the other hand, the applicant of the present application has proposed a new type of hydrogen generator in Japanese Patent Application No. 2002-227678. The invention according to this application includes a discharge electrode having a capillary for supplying a raw material containing one or more substances selected from hydrocarbons and organic oxygenates and water, and performs pulse discharge by the discharge electrode. It is characterized by inducing the reaction of the raw material supplied by the capillary to generate hydrogen. In other words, since the discharge electrode has a capillary for supplying the raw material, the raw material can be quickly supplied to a region where pulse discharge is performed according to a required amount, and as a result, hydrogen can be efficiently produced. Can be done. With respect to the present invention, it has been desired to generate discharge more stably and uniformly, in addition to the various advantages described above.

 In view of the above circumstances, the present invention provides a novel generator capable of stably and uniformly generating a pulse discharge and, as a result, generating hydrogen with higher efficiency, and a discharge electrode used for the device. It is aimed at. Disclosure of the invention

In order to solve the above problems, the present invention relates to a method for producing a hydrocarbon or an organic oxygen compound. A pipe for supplying a raw material containing at least one substance selected from the group consisting of water and water is provided with a discharge electrode formed inside a pipe-shaped conductor, and a pulse discharge is performed by the discharge electrode; Provided is a hydrogen generator for inducing a reaction of a raw material supplied by a capillary to generate hydrogen. BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is a diagram showing the generation device according to the embodiment (1).

FIG. 2 is a partially enlarged view of the discharge electrode according to the embodiment (1).

FIG. 3 is a partially enlarged view of the discharge electrode according to the embodiment (2).

FIG. 4 is a partially enlarged view of the discharge electrode according to the embodiment (3). BEST MODE FOR CARRYING OUT THE INVENTION

 In the hydrogen generator according to the present invention, a capillary tube for supplying a raw material containing one or more substances selected from hydrocarbons and organic oxygenates and water is formed inside a pipe-shaped conductor. An electrode is provided, wherein a pulse discharge is performed by the discharge electrode, and a reaction of the raw material supplied by the capillary is induced to generate hydrogen.

According to the above configuration, a raw material containing at least one substance selected from hydrocarbons and organic oxygenated compounds and water moves through a capillary formed inside the pipe-shaped conductor, and receives pulse discharge. Reacts to produce the desired hydrogen. The generated hydrogen is discharged to the outside of the system usually through an outlet. Here, the pipe-shaped conductor refers to a cover made of various metals, carbon, and the like, and includes a tubular member having relatively rigidity, a film obtained by winding a film into a cylindrical shape, and the like. The side of the pipe is generally closed, but may be partially open if necessary. Capillaries refer to passages or voids formed along the inside of the pipe, and the raw material passes through the passages and voids in a region where pulse discharge is performed by means of suction by capillary action, pumps, or the like. Move to Since the outer periphery of the discharge electrode is held by a pipe-shaped conductor, the shape is maintained and a stable discharge is obtained. Also, the raw material leaks from the side of the discharge electrode. The raw material is supplied to the region where the pulse discharge is performed reliably and efficiently without leaking. Here, the hydrocarbons include aliphatic hydrocarbons and aromatic hydrocarbons. Further, the organic oxygen-containing compound means an organic compound containing an oxygen atom in a molecule, and includes alcohol, ether, aldehyde, ketone, ester and the like.

 The present invention also provides a capillary tube for supplying a raw material containing at least one substance selected from organic oxygenated compounds, comprising: a discharge electrode formed inside a pipe-shaped conductor; and a pulse discharge by the discharge electrode. And generating hydrogen by inducing a reaction of the raw material supplied by the capillary. According to the above configuration, the organic oxygen-containing compound that has moved through the capillary tube undergoes a pulse discharge, and mainly causes a decomposition reaction to generate hydrogen. Further, the present invention provides the hydrogen generator described above, wherein a plurality of conductive fibers are provided in a bundle inside the pipe-shaped conductor, and a capillary is formed between the conductive fibers. And

 According to the above configuration, the bundle of conductive fibers functions as a discharge electrode at the time of pulse discharge together with the pipe-shaped conductor outside the bundle. In addition, the raw material moves through a gap (capillary) between the conductive fiber and another conductive fiber. As the conductive fibers, metal fibers such as stainless steel are used, and those having corrosion resistance are preferable.

 Further, the present invention is characterized in that, in the above-mentioned hydrogen generating apparatus, the conductive fiber is a carbon fiber.

 According to the above configuration, carbon fibers are particularly selected as the conductive fibers. Since carbon fibers are good conductors and have corrosion resistance, they are suitable for the reaction system of the present invention. The carbon fibers referred to here include PAN-based, rayon-based, and pitch-based, and furthermore, so-called graphite fibers obtained by treating carbon fibers at a high temperature (150-300 ° C). The concept also includes activated carbon fibers that have been activated.

Further, the present invention is characterized in that in the above-described hydrogen generator, a dielectric is provided between discharge electrodes where pulse discharge is performed. According to the above configuration, since pulse discharge is performed via the dielectric, a so-called silent discharge action generates a uniform and stable pulse discharge in the plane on which the dielectric is provided.

 Further, the present invention is characterized in that in the above-described hydrogen generator, the dielectric is a ring-shaped dielectric provided along an end surface of the pipe-shaped conductor.

 According to the above configuration, a uniform and stable pulse discharge is generated over the entire end surface of the pipe-shaped conductor, and the raw material is efficiently supplied to the discharge region.

Further, the present invention provides the apparatus for generating the hydrogen-, _{dielectric, S io 2, C e 0} 2, L a O 3, S m 2 O 3> S i N, BN, one selected from diamond It is characterized by being composed of a substance.

 According to the above configuration, a specific substance constituting the dielectric is specified. Furthermore, the present invention is characterized in that, in the above-described hydrogen generator, the reactor further includes a reactor accommodating a discharge electrode, and a power supply for applying a voltage to the discharge electrode.

 According to the above configuration, pulse discharge is caused by applying a voltage using a power supply, and hydrogen is generated in the reactor.

 Further, the present invention provides various discharge electrodes used for various generation devices having the above-described features.

 Hereinafter, the present invention will be described in detail based on embodiments.

 First, FIG. 1 and FIG. 2 show an embodiment (1) of the present invention. The generating apparatus 1 of FIG. 1 includes a reactor 10, and a pair of discharge electrodes 11 and 12 are provided in the reactor 10 so as to face each other. Between the discharge electrode 11 and the discharge electrode 12 is a discharge region 13 where pulse discharge is performed. The distance between the discharge electrode 11 and the discharge electrode 12 can be arbitrarily adjusted.

The discharge electrode 11 has a schematic configuration in which a capillary for supplying the raw material A is formed inside a pipe-shaped conductor. Here, the capillary refers to a passage or gap formed along the inside of the pipe, Raw material A can move through the capillary. The shape of the capillary can be appropriately determined, such as a tubular shape or a mesh shape.

 FIG. 2 shows a specific example of the above capillary. In FIG. 2, the discharge electrode 11 is configured by providing a bundle of a plurality of good conductors such as carbon fiber 112 inside the inside of the pipe-shaped conductor 110. The space between the carbon fibers 112 functions as a capillary 113 through which the raw material A passes. As the pipe-shaped conductor 110, a material having high conductivity can be appropriately selected and used. Further, it preferably has corrosion resistance to water and the like. Specific examples of the material include metal materials such as SUS, nickel, copper, aluminum, and iron, and materials such as carbon. Among them, sus and carbon are more preferable because they hardly corrode. Note that the shape of the pipe-shaped conductor 110 is not limited to a columnar shape as shown in FIG. 2, but may be various shapes such as a square columnar shape, a polygonal columnar shape, and the like. Further, the thickness (the difference between the outer diameter and the inner diameter) of the pipe-shaped conductor 110 can be appropriately set.

 As shown in FIG. 2, the bundle of carbon fibers 112 is provided at a position slightly recessed inside the pipe-shaped conductor 110 or the end face 114 of the pipe-shaped conductor 110 It is preferable to be provided at the same position.

 Further, in FIG. 2, for convenience, the carbon fibers 112 are schematically shown to have a certain thickness and to be a bundle of about several tens of carbon fibers. It is on the order of micrometers (specifically, about Ιμη! ~ Lmm), and the number is also large (for example, tens of thousands or more) according to the thickness of the discharge electrode 11. However, depending on the scale of the generator 1 and the type of the raw material A, it is possible to use a thicker and smaller number of carbon fibers, and the present invention is not limited to the above numerical range.

As the carbon fibers 112, various carbon fibers known in the art can be used. Specific examples include carbon fibers made from polyacrylonitrile (PAN), pitch-based carbon fibers made from petroleum, petroleum tar, and liquefied coal, and rayon-based carbon fibers. For example, PAN-based carbon fiber is obtained by heat treating special acrylic fiber (precursor) in air. It can be obtained by baking the fire-resistant fiber at 100 to 180 ° C. in an inert gas. In addition, the carbon fiber is activated by a graphite fiber fired at a higher temperature of 2000 to 3000 ° C. or an activation gas (a mixed gas of steam, carbon dioxide, nitrogen gas, etc.). Carbon fiber is also applicable. Since carbon fibers are chemically stable, they have an advantage that they are not corroded by water used in the present invention.

 The end face 115 of the carbon fiber 112 is preferably formed in an edge shape. By doing so, when pulse discharge is performed, current is concentrated at the tip of the edge, so that discharge is likely to occur, and as a result, hydrogen generation efficiency is improved. When the carbon fiber 112 is sufficiently thin (micrometer order), the carbon fiber 112 itself has an edge shape without processing the end face 115. Further, when the carbon fiber 112 has a thickness of about millimeter, the end face 115 may be appropriately processed by means such as cutting and cutting so as to have an edge shape.

 As the other discharge electrode 12, a general electrode such as a columnar electrode rod can be used. As a material of the discharge electrode 12, a general material such as SUS, nickel, copper, aluminum, iron, or carbon can be used. Among them, a material that is hardly corroded, such as SUS or carbon, is preferable. In addition, the shape of the discharge electrode 12 is not limited to the above-described columnar shape, and may be various shapes such as a needle shape, a flat plate shape, and the like. Alternatively, it may be composed of a pipe-shaped conductor 110 and carbon fiber 112. It is preferable that the end face of the discharge electrode 12 facing the discharge region 13 is parallel to the end faces 114 and 115 of the discharge electrode 11.

In FIG. 1, a reactor 10 is made of quartz or other glass, ceramic, synthetic resin, or the like. A DC power supply 14 for applying a negative high voltage is connected to the discharge electrode 11 extending outside the reactor 10, and a digital oscilloscope 15 is provided between the DC power supply 14 and the discharge electrode 11. It is connected. On the other hand, a three-way port 16 is connected to the reactor 10, and a discharge electrode 12 extending from the reactor 10 to the outside penetrates one of the three-way ports 16 and grounded. The other port of the three-way port 16 is an outlet port 17 for discharging hydrogen H 2 generated by the pulse discharge. Further, an introduction path 18 for introducing the raw material A into the capillary tube 113 of the discharge electrode 11 is connected to the discharge electrode 11.

 When using the above-described generating device 1, the process is generally performed as follows. First, a raw material A containing one or more substances selected from hydrocarbons and organic oxygenated compounds and water is supplied into the discharge electrode 11 through the introduction path 18. The supplied raw material A moves through a capillary tube 113 formed inside the discharge electrode 111, and finally, for example, oozes out from the end face 115 of the discharge electrode 111. The discharge reaches the discharge region 13 (or its vicinity).

Subsequently, when a negative voltage is applied to the discharge electrode 11 by the DC power supply 14, the discharge electrode 11 between the discharge electrodes 11 and 12, that is, between the pipe-shaped conductor 110 and the discharge electrode 12, or carbon fiber induced reaction happening pulse discharge between 1 1 2 and the discharge electrode 1 2, hydrogen H ₂ is produced. The generated hydrogen H ₂ is discharged from the outlet 17 and used for various purposes. The raw material A that moves through the capillary tube 11 and reacts by pulse discharge may be in a liquid state or a gas state. When the raw material A is liquid, the raw material A is vaporized by the slight Joule heat generated by the pulse discharge, and the vaporized raw material A may react.

Also, at this time, since the outer periphery of the discharge electrode 11 is held by the pipe-shaped conductor 110, the form of the discharge electrode 11 as a whole is maintained, and a stable discharge can be obtained. . In addition, if the tips of the carbon fibers 112 are microscopically irregular, and if there is no pipe-shaped conductor 110, discharge may occur locally and the hydrogen generation efficiency may decrease. However, by providing the pipe-shaped conductor 110, a uniform pulse discharge is generated mainly in the end face 114 of the pipe-shaped conductor 110, and as a result, the reaction proceeds efficiently. Can be run. Further, the raw material A can be reliably and efficiently supplied to the discharge region 13 without the raw material A leaking from the side surface of the discharge electrode 11. As means for moving the raw material A through the capillary tube 113, various physical phenomena can be used, and forced feeding means can be used, and there is no particular limitation. Specifically, as a preferred example, by appropriately setting the inner diameter of the capillary tube 113, the raw material A can be naturally sucked in the direction of the discharge region 13 by utilizing the capillary phenomenon. When the sucked raw material A is lost by the reaction, a new raw material A is sucked to catch it. This is preferable from the viewpoint of production efficiency because the raw material A can be naturally supplied to the discharge region 13 without using a sending means such as a pump. The appropriate value of the inner diameter of the capillary tube 113 is determined by comprehensively considering the length of the capillary tube 113, the density of the raw material A, the surface tension of the raw material A, the contact angle of the raw material A with the discharge electrode surface, etc. be able to. For example, in the case of a bundle of 100,000 carbon fibers with a diameter of 7 μm (the inner diameter of the formed capillary is several μπι), a raw material with a volume equivalent ratio of ethanol to water is reduced to about 1 minute. We know that 3 O ml can be aspirated.

 In addition, the raw material A can be forcibly supplied into the capillary 11 13 by, for example, connecting a normal pump or the like to the introduction path 18 without depending on the method utilizing the above-mentioned capillary phenomenon. Further, a pump or the like and a method utilizing the above-mentioned capillary phenomenon may be appropriately combined.

 Further, the raw material A can be moved with the pulse discharge. That is, the raw material A is ionized by the high voltage at the time of the pulse discharge. By utilizing this, the ionized raw material A is electrophoresed in the direction of the other discharge electrode 12 every time the pulse discharge occurs. It is possible to move using the phenomenon described above. Also in this case, as in the case of the above-mentioned capillary phenomenon, a delivery means such as a pump is not required, so that hydrogen can be generated efficiently and at low cost. In addition, since the supply of the raw material A is performed according to the voltage at the time of the pulse discharge, the responsiveness of hydrogen generation is improved.

Next, raw material A will be described. First, the hydrocarbon to be reacted is not particularly limited, and can be appropriately selected from various hydrocarbons. Examples include linear, branched or cyclic alkanes, alkenes, alkenes Examples include aliphatic hydrocarbons such as quine, various kinds of aromatic hydrocarbons, and mixtures of two or more kinds thereof. More specifically, natural gas, petroleum naphtha, gasoline, kerosene gas oil, etc. The mixture can be used as it is. Hydrocarbons obtained from biomass are also applicable. Examples of this include methane obtained by fermenting or pyrolyzing waste, food waste, manure, grass and pruned branches, and woody biomass discharged from food factories.

 The organic oxygen-containing compound is an organic compound containing an oxygen atom in the molecule, and can be appropriately selected from various substances similarly to the above-mentioned hydrocarbon. Examples include alcohols such as methanol, ethanol, propanol, butanol, etc. And ketones such as acetone and methylethyl ketone; esters such as ethyl acetate, ethyl formate and dimethyl carbonate; and mixtures of two or more thereof. The organic oxygen-containing compound may be derived from biomass. Examples include alcohols produced by hydrolyzing cellulose such as weeds into glucose using microorganisms' enzymes. Further, in the present invention, the above-mentioned hydrocarbons and organic oxygen-containing compounds can be used in combination as appropriate. .

The water is a means of liquid or vapor containing H ₂ 0 excess, it is applicable as long as one general water. In addition, distilled water, ion-exchanged water, and so-called “hot water” are naturally included in the concept of water of the present invention.

The apparatus of the present invention performs a pulse discharge after supplying a raw material A containing at least one substance selected from the above-mentioned hydrocarbons and organic oxygenates and water to the discharge region 13 or in the vicinity thereof. Features. Here, pulse discharge means passing a pulse current between discharge electrodes.For example, electron irradiation is repeated within a very short time of 1 μS or less. Can be reacted. The pulse discharge is usually performed at regular intervals, but may be intermittent. When, for example, a mixed gas of methane and water vapor is used as the raw material A by pulse discharge, the reaction proceeds as shown in the following formula (4) to produce the target hydrogen. When a mixed solution of ethanol and water is used as the raw material A, the reaction proceeds as in the following equation (5) to generate hydrogen. At that time, no by-products such as acetylene are generated.

CH ₄ + H ₂ 0-3H ₂ + CO (4)

_{C 2 H 5 OH + H 2} 0 -> 4H 2 + 2CO (5) Further, the present invention is, as a raw material A, can also Mochiiruko the organic oxygen-containing compound alone. That is, organic oxygenated compounds such as alcohols typified by methanol, ethanol and the like do not necessarily need to be used in combination with water, and can be used alone. In this case, for example, as shown in (Fig. 6), the decomposition reaction of the organic oxygen-containing compound itself occurs to generate hydrogen.

CH ₃ OH → 2H ₂ + CO (6) In the various reactions described above, it is considered that radicals are generated by the discharge current, that is, the irradiation of the electron beam from the discharge electrode, and the radicals cause the reactions. Therefore, as the discharge current is increased and the distance between the discharge electrodes is increased, the number of molecules that collide with the electron beam increases, so that the reaction speed increases and the conversion rate per unit time increases. Tend to be.

A pulse power supply can be used to perform the discharge, but a DC self-excited pulse discharge in which a constant voltage is applied between the discharge electrodes and a pulse discharge is performed in a self-excited manner is preferably employed. In this case, the appropriate number of pulse discharges per second (hereinafter, sometimes referred to as “pulse generation frequency”) is about 5 to 100 times, especially about 50 to 100 times. Is preferred. The pulse generation frequency increases as the current increases under a constant voltage, and decreases as the distance between the discharge electrodes increases. Therefore, the preferred voltage, current and The distance between the discharge electrode and the discharge electrode is naturally set by adjusting the voltage, the current, and the distance between the discharge electrode so that the above-described pulse generation frequency is achieved. For example, when using a small reactor with an inner diameter of about 5 mm, the applied voltage is about 1 kV to 10 kV, the current is about 1 to 20 mA, and the distance between the discharge electrodes is 2 mm to It is preferable to set it to about 10 mm. Of course, the applied voltage, current, and distance between the discharge electrodes are not limited to the above ranges. When using a large-scale reactor having a higher production capacity, the distance between the discharge electrodes is increased, and the above-described pulse is applied. 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 in a liquid or gas state. In particular, when reacting the raw material A in a gaseous state, the reaction temperature is not particularly limited, but it is preferable to perform the reaction at a temperature as low as possible because the energy cost is low. For example, when using methanol, ethanol, propanol, or the like and steam as raw materials, the reaction temperature is preferably about 80 ° C. to 150 ° C. (under normal pressure). Here, the reason why the low temperature side of the above range is lower than 100 ° C. is that alcohol and water may be vaporized by an azeotropic phenomenon. Since steam tends to be concentrated, when the boiling point of the hydrocarbon or the organic oxygen-containing compound is lower than that of water, the raw material A is pre-heated at a temperature higher than the reaction temperature before the reaction zone 1 Preferably it is supplied to 3. The total pressure in the reactor 10 when the gaseous raw material A is supplied is not particularly limited, and may be, for example, about 0.1 to 10 atm. However, since the reaction proceeds sufficiently at normal pressure and a robust reactor is not required at that time, it can be said that it is particularly industrially preferable to perform the reaction at normal pressure. The mixing ratio of the hydrocarbon or organic oxygenated compound and water may be a stoichiometric amount.1 If desired, increase or decrease one of the substances to about 1 to 2 to 2 times the stoichiometric amount or more. Is also possible.

If the raw material A is configured so as to be continuously supplied into the reactor 10, the efficiency is high and industrially excellent. In the case of the continuous method, the feed rate of the raw material A is determined by analyzing the hydrogen H ₂ discharged from the outlet 17 and the conversion rate of the raw material A is constant. It is preferable to set the value appropriately so as to be not less than the value, for example, not less than 60%. For example, using a reactor with an inner diameter of 5 mm, the distance between the discharge electrodes is set to about l 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. When used, the supply flow rate is suitably about 100 to 1000 m 1 / min, especially about 50 to 100 m 1 min. It is also possible to use a batch system instead of the continuous system shown in FIG.

 Furthermore, in the generator 1 shown in FIG. 1, a DC power supply 14 is used as a power supply connected to the discharge electrode 11, but other than this, any power supply capable of pulse discharge can be applied. For example, a power supply in which an AC power supply is appropriately combined with a diode bridge circuit, a load, or the like, a power supply in which a DC voltage is superimposed on the power supply, or the like can be appropriately used. The voltage applied to the discharge electrode is preferably unipolar as described above, but is not limited to this, and an AC voltage can be applied.

 Further, the number of discharge electrodes accommodated in the reactor 10 is not limited to one pair, and a plurality of discharge electrodes can be used as necessary.

 Furthermore, the generator 1 of the present invention produces carbon monoxide by-product together with the target hydrogen. Therefore, it is possible to produce hydrogen gas and carbon dioxide finally by separately reacting the generated hydrogen and carbon monoxide with water vapor. This reaction is known as a 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 normal pressure. When this water gas shift reaction is incorporated into the generator 1 of the present invention, for example, a catalyst for a water gas shift reaction such as a zinc oxide-copper monoxide solid catalyst is supplied to the outlet 17 of the reactor 10 in FIG. By filling on the side, the carbon monoxide generated by the pulse discharge is further reacted with water vapor to form hydrogen and carbon dioxide, thereby greatly increasing the hydrogen production efficiency.

Then, as shown in FIG. 2, a catalyst 20 can be attached to the discharge electrode 11. The catalyst 20 is one that can improve the efficiency of a hydrogen generation reaction by pulse discharge or reduce by-products such as C 2 compounds. If applicable, it is applicable. Examples include palladium using alumina as a carrier, a platinum catalyst, a nickel catalyst, a Lindlar catalyst and the like. These catalysts can particularly suppress the formation of C2 compounds such as acetylene. In addition, it has been found that the catalyst 20 is activated by receiving a pulse discharge and has a higher catalytic ability than usual.

In particular, it has been found that the use of ruthenium, a multi-component catalyst of ruthenium and another catalyst, fullerene, or fullerene supporting ruthenium as the catalyst 20 in the reaction system of the present invention maximizes the hydrogen generation efficiency. . As the fullerene, various conventionally known fullerenes can be applied, for example, ゝ ^ 60 70 76 80 82 ゝ. 84 ゝ 86 ゝ 88 ゝ 90 92, C ₉₄ 966,. 1 20 240 560 or a combination of them. Among them, c _24. Has the highest effect. This is, c _24. This is probably due to the high hydrogen storage capacity of the steel. In addition, c _6. C ₂₄ containing therein the. (Hereinafter referred to as C _6. @ C _24. Written as), C _24. @C _56. , C _8. @C ₂₄ . @C _56. Fullerenes having a multi-layered shell as described above are also preferably used. The method for supporting ruthenium on fullerene is not particularly limited. Alternatively, a method of evaporating ruthenium at the same time and supporting it can be appropriately employed. The ruthenium supported on fullerene is very fine particles and is in an activated state. The reason why the ruthenium particles become finer is not clear, but it is thought that fullerene inhibits the contact between ruthenium particles and grain growth.

As a method of attaching the catalyst 20 to the discharge electrode 11, a method such as vapor deposition, sputtering, or plating of the catalyst 20 on the surface of the discharge electrode 11 such as the carbon fiber 112 can be appropriately adopted. In addition, after the catalyst 20 is attached to the surface of the carbon fibers 112 before being bundled in advance by vapor deposition or the like, the catalysts 20 are bundled and provided inside the pipe-shaped conductor 110 so that the discharge electrodes 111 are formed. May be produced.

 However, since the apparatus according to the present invention can generate hydrogen without using a catalyst, it is of course possible to implement the apparatus without using any catalyst. The production apparatus of the present invention is characterized in that it can be performed at a much lower temperature and a lower pressure and is lower in cost than a conventional method of performing a reforming at a high temperature and a high pressure using a catalyst.

 Next, an embodiment (2) of the present invention will be described.

 FIG. 3 is a partially enlarged view of the discharge electrode 11. This embodiment (2) is characterized in that a dielectric is provided between discharge electrodes where pulse discharge is performed. Specifically, a ring-shaped dielectric 23 is provided along the end face 114 of the pipe-shaped conductor 110. By doing so, a uniform pulse discharge can be generated on the entire end surface 230 of the ring-shaped dielectric 23 by the action of so-called silent discharge. Therefore, the reaction efficiency of hydrogen generation can be improved. The thickness of the ring-shaped dielectric 23 can be appropriately set in consideration of the distance between the discharge electrodes, the voltage, and the like. In addition, the shape of the dielectric 23 is not limited to a ring shape, and may be various shapes provided that it is located between the discharge electrodes. However, the movement of the raw material A to the discharge region 13 is hindered. Not to be. Further, the dielectric 23 may be provided in contact with the other discharge electrode 12 instead of the discharge electrode 11.

As the above-mentioned dielectric substance 23, any substance having high crystallinity and being non-conductive can be used. Specifically, a quartz (S i 0 _2), as _{C e O 2, L a O} 3, S m 2 O 3, S i N, BN, can be cited or diamond, which is limited to is not.

 Next, an embodiment (3) of the present invention will be described.

FIG. 4 is a partially enlarged view of the discharge electrode 11. This embodiment (3) is characterized in that a bundle of folded carbon fibers 112 is provided inside a pipe-shaped conductor 110 as shown in FIG. Specifically, the carbon fiber 112 is bent into two, and the folded portion 116 is provided so as to be located on the end surface 114 side of the conductor 110. By doing so, it is possible to hold the end face 115 as the folded part 116 only by bending the carbon fiber 112. This makes it possible to easily provide the carbon fibers 112 with the end faces 115 aligned in the interior 111 of the conductor 110. In particular, even when the carbon fibers 112 are thin (micrometer-order metric order), the end faces 115 of the carbon fibers 112 can be easily aligned. Since the end faces 1 15 of the carbon fibers 112 are aligned, a stable pulse discharge can be generated.

 In addition, in the hydrogen generator described in the above embodiments (1) to (3), the storage section for storing the raw material A that has reached the outside of the discharge electrode 11 through the capillary tube 113 is provided. Can be provided. The storage unit can be configured by, for example, a method of attaching powder of metal, ceramic, resin, or the like to the surface of the carbon fiber 112. In this way, the raw material A that has oozed out from the bundled capillary tubes 113 is stored in the gaps between the powders by being held by surface tension. Therefore, the amount of the raw material A that can react by the pulse discharge increases, and the efficiency of hydrogen generation can be improved. In addition, since the raw material A can always be present in the vicinity of the discharge region, the responsiveness of hydrogen generation to pulse discharge can be improved. Regarding the storage section, various configurations can be adopted in addition to the method of attaching the powder. For example, a method of roughening the surface of the carbon fiber 112 by sandblasting or expanding the volume of the reactor 10 in the vicinity of the discharge region 13 (the outer diameter of the reactor 10 is In this case, the amount of the raw material A supplied to the reaction can be increased by keeping the raw material A supplied from the capillary tube 11 in the expanded portion.

Further, in the hydrogen generator described in the above embodiments (1) to (3), a heating unit for heating and vaporizing the raw material A moving in the capillary tube 113 may be provided. . The raw material A vaporized by the heating unit evaporates out of the discharge electrode 11 and reaches the discharge region 13 where it reacts by pulse discharge. It will produce hydrogen. The specific configuration of the heating section is, for example, to apply a current to the discharge electrode 11 itself to heat it using the generated Joule heat, or to install a general heater such as a dichromic wire around the discharge electrode 11. Means for directly heating the raw material A moving through the capillary tube 113 by arranging or embedding a two-chrome wire or the like between the carbon fibers 112 can be used as appropriate.

 Further, in the above embodiments (1) to (3), the case where the discharge electrode 11 is constituted by the pipe-shaped conductor 110 and a bundle of a plurality of carbon fibers 112 has been described. In addition to this, any structure having a capillary in which the raw material A can move can be used without any particular limitation.

 For example, a plurality of conductive fibers are used instead of the carbon fibers described above, and a bundle of the conductive fibers is provided inside a pipe-shaped conductor to discharge the electrodes.

One can make up one. In this case, the space between the conductive fiber and another conductive fiber functions as a capillary to which the raw material is supplied. As the conductive fibers, those having corrosion resistance are preferably used. Specifically, metal fibers such as stainless steel are preferably used.

Also, a plurality of non-conductive fibers can be used instead of the carbon fibers. Also in this case, the space between the non-conductive fibers and the other non-conductive fibers functions as a capillary to which the raw material is supplied. The non-conductive fiber does not act as an electrode, and a pulse discharge is generated between the pipe-shaped conductor 110 and the discharge electrode 11. As the non-conductive fibers, those having corrosion resistance are preferably used. Specifically, fibers such as silicon, glass, and SiO ₂ are preferably used.

Further, in the above embodiments (1) to (3), it is also possible to provide a core material at the center of the fiber bundle. In this case, the shape of the fiber bundle is supported by the core material. In addition, the discharge is stably performed not only in the pipe-shaped conductor 110 but also in the core. The material of the core material is not particularly limited, and various metals such as sus, aluminum, and copper, and carbon can be used as appropriate. It is also possible to provide a plurality of core materials for a bundle of fibers. Another example of the discharge electrode 11 is to form a capillary by cutting a normal carbon or metal material using a drilling machine, a laser, or the like, and forming an outer periphery of the material forming the capillary. Covered with a pipe-shaped conductor, or a carbon fiber woven fabric impregnated with a binder such as a thermosetting synthetic resin such as phenolic resin or petroleum pitch. Heating to cure the binder, and further sintering at a high temperature in an inert atmosphere to carbonize the binder to produce a porous material or sinterable graphite precursor fine particles such as raw coat For example, a porous material which is sintered at a high temperature while being pressed and formed, and the outer periphery of the porous material is covered with a pipe-shaped conductor can be exemplified.

 The hydrogen produced by the above-described production apparatus of the present invention can be effectively used for, for example, synthesis of ammonia and methanol, hydrodesulfurization, hydrocracking, hydrogenation of fats and oils, welding, and semiconductor production. it can. Considering the use as a turbine fuel, there is an advantage that the calorific value is larger when the fuel converted to hydrogen is burned than when the fuel such as alcohol is burned as it is. Furthermore, since it can be a compact and portable device, it is suitable as a device for supplying hydrogen to a fuel cell mounted on an automobile or the like.

 Hereinafter, the present invention will be described more specifically with reference to Examples, but it should not be construed that the invention is limited thereto.

 (Example 1)

 The device shown in Fig. 1 was produced as a generator. The reactor used was a quartz tube with an outer diameter of 10 mm, an inner diameter of 9 mm, and a length of 200 mm, and one of the pair of discharge electrodes facing each other had a diameter of 7 mm inside a pipe made of SUS306. A bundle of 84,000 μm carbon fibers bundled together (7 bundles of Beshuite HTA-12K (trade name) manufactured by Toho Rayon Co., Ltd.) was inserted. The diameter of the bundle of carbon fibers is about 3 mm. Further, a rod-shaped discharge electrode made of SS306 was used as the other discharge electrode.

Subsequently, a mixture of water and ethanol (volume ratio 1: 1) was discharged from the introduction channel. A DC pulse discharge was performed by applying a constant voltage between the discharge electrodes while supplying power to the poles using capillary action. The discharge conditions are as follows: pulse frequency is 50 times per second, voltage is 5 kV, and current is 10 mA at the maximum. In addition, the temperature in the reactor was maintained at 100 ° C. at which the raw materials could be evaporated.

 The amount of gas generated 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. The state of the pulse discharge was very stable. Industrial applicability

 As described above, since the generating device of the present invention includes the discharge electrode formed inside the pipe-shaped conductor, the capillary for supplying the raw material, the shape of the discharge electrode is maintained, and the pulse discharge is stably performed. It can induce the reaction of the raw material supplied through the capillary to efficiently produce the target hydrogen. Further, by providing a dielectric such as quartz between the discharge electrodes, the pulse discharge can be uniformly and stably performed through the dielectric.

 The generator of the present invention can be implemented at a low pressure and a low temperature and at a low cost, and has a feature that by-products are not generated. Therefore, the generator is suitable as, for example, a generator for hydrogen supplied to a fuel cell. Can be used for

Claims

The scope of the claims 1. A capillary tube for supplying a raw material containing water and at least one substance selected from hydrocarbons and organic oxygenated compounds includes a discharge electrode formed inside a pipe-shaped conductor, and the discharge electrode A hydrogen generator that performs pulse discharge and induces a reaction of the raw material supplied by the capillary to generate hydrogen. 2. A capillary for supplying a raw material containing one or more substances selected from organic oxygenates, comprising a discharge electrode formed inside a pipe-shaped conductor, performing a pulse discharge by the discharge electrode, A hydrogen generator for inducing a reaction of a raw material supplied by the capillary to generate hydrogen.  3. The hydrogen generator according to claim 1 or 2, wherein a plurality of conductive fibers are provided in a bundle inside the pipe-shaped conductor, and a capillary is formed between the conductive fibers. An apparatus for producing hydrogen.  4. The hydrogen generator according to claim 3, wherein the conductive fibers are carbon fibers.  5. The hydrogen generator according to claim 1 or 2, wherein a dielectric is provided between discharge electrodes where pulse discharge is performed. 6. The hydrogen generator according to claim 3, wherein a dielectric is provided between discharge electrodes where pulse discharge is performed. 7. The hydrogen generator according to claim 4, wherein a dielectric is provided between discharge electrodes where pulse discharge is performed. 8. The hydrogen generator according to claim 5, wherein the dielectric is a ring-shaped dielectric provided along an end surface of the pipe-shaped conductor.  9. The hydrogen generator according to claim 6, wherein the dielectric is a ring-shaped dielectric provided along an end surface of the pipe-shaped conductor. 10. The hydrogen generator according to claim 7, wherein the dielectric material is An apparatus for producing hydrogen, wherein the apparatus is a ring-shaped dielectric provided along an end surface of a loop-shaped conductor. In 1 1. generator of hydrogen in the range 5 according claims, _{dielectric, S i 0 2, C e} O 2, L A_〇 _{3, Sm 2 O 3, S} i N, BN, selected diamond or al An apparatus for producing hydrogen, comprising: one substance. 1 2. In apparatus for generating hydrogen according to claim 6, wherein, the _{dielectric, S i 0 2, C e} O 2, L a 0 3, Sra 2 O 3, S i N, BN, selected diamond or al An apparatus for producing hydrogen, comprising: one substance. In 1 3. generator of hydrogen in the range 7 wherein claims, _{dielectric, S i O 2, C e} 0 2, L A_〇 _{3, Sm 2 0 3, S} i N, BN, selected diamond or al An apparatus for producing hydrogen, comprising: one substance. In 14. generator of hydrogen according to claim 8, wherein, the _{dielectric, S i O 2, C e} 0 2, L a O s, Sm 2 0 3, S i N one which, BN, selected diamond or al An apparatus for producing hydrogen, comprising: In 1 5. generator of hydrogen in the range 9 wherein claims, _{dielectric, S i O 2, C e} 0 2, L a 0 3, Sm 2 0 3, S i N, BN, selected diamond or al An apparatus for producing hydrogen, comprising: one substance. 1 6. In apparatus for generating hydrogen in the range 1 0 according claims dielectric is selected _{S i 0 2, C e 0} 2, L a 0 3, Sm 2 0 3, S i N, BN, diamond An apparatus for producing hydrogen, comprising: one substance. 1 7. The hydrogen generator according to claim 1 or 2, further comprising: a reactor accommodating a discharge electrode; and a power supply for applying a voltage to the discharge electrode. .  18. The hydrogen generator according to claim 3, further comprising: a reactor accommodating a discharge electrode; and a power supply for applying a voltage to the discharge electrode. 1 9. The hydrogen generator according to claim 4, further comprising a reactor accommodating a discharge electrode, and a power supply for applying a voltage to the discharge electrode. 20. The hydrogen generator according to claim 5, further comprising: a reactor accommodating a discharge electrode; and a power supply for applying a voltage to the discharge electrode.  21. The hydrogen generator according to claim 6, further comprising a reactor accommodating a discharge electrode, and a power supply for applying a voltage to the discharge electrode.  22. The hydrogen generator according to claim 7, further comprising a reactor accommodating a discharge electrode, and a power supply for applying a voltage to the discharge electrode. 23. The hydrogen generator according to claim 8, further comprising: a reactor accommodating a discharge electrode; and a power supply for applying a voltage to the discharge electrode.  24. The hydrogen generator according to claim 9, further comprising: a reactor accommodating a discharge electrode; and a power supply for applying a voltage to the discharge electrode.  25. The hydrogen generator according to claim 10, further comprising: a reactor accommodating a discharge electrode; and a power supply for applying a voltage to the discharge electrode.  26. The hydrogen generator according to claim 11, further comprising: a reactor accommodating a discharge electrode; and a power supply for applying a voltage to the discharge electrode.  27. The hydrogen generator according to claim 12, further comprising: a reactor accommodating a discharge electrode; and a power supply for applying a voltage to the discharge electrode. 28. The hydrogen generator according to claim 13, further comprising: a reactor accommodating a discharge electrode; and a power supply for applying a voltage to the discharge electrode. 29. The hydrogen generator according to claim 14, further comprising a reactor accommodating a discharge electrode, and a power supply for applying a voltage to the discharge electrode. And a hydrogen generator.  30. The hydrogen generator according to claim 15, further comprising: a reactor accommodating a discharge electrode; and a power supply for applying a voltage to the discharge electrode.  31. The hydrogen generator according to claim 16, further comprising: a reactor accommodating a discharge electrode; and a power supply for applying a voltage to the discharge electrode.  32. Used in a device that performs pulse discharge in a raw material containing water and one or more substances selected from hydrocarbons and organic oxygenated compounds to induce the reaction of the raw material to generate hydrogen, A discharge electrode formed by forming a capillary capable of supplying a pressure inside a pipe-shaped conductor.  33. Used in a device that performs pulse discharge in a raw material containing one or more substances selected from organic oxygenated compounds and induces a reaction of the raw material to generate hydrogen, and a capillary capable of supplying the raw material is used. A discharge electrode formed inside a pipe-shaped conductor.  34. The discharge electrode according to claim 32 or 33, wherein a plurality of conductive fibers are provided in a bundle inside the pipe-shaped conductor, and a capillary is formed between the conductive fibers. A discharge electrode. 35. The discharge electrode according to claim 34, wherein the conductive fiber is a carbon fiber.