WO2012090326A1 - 触媒構造物及びそれを用いた水素反応用モジュール - Google Patents
触媒構造物及びそれを用いた水素反応用モジュール Download PDFInfo
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- WO2012090326A1 WO2012090326A1 PCT/JP2010/073803 JP2010073803W WO2012090326A1 WO 2012090326 A1 WO2012090326 A1 WO 2012090326A1 JP 2010073803 W JP2010073803 W JP 2010073803W WO 2012090326 A1 WO2012090326 A1 WO 2012090326A1
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- catalyst
- wire
- coil
- hydrogen
- winding
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- 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
- C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
- C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
- C01B3/0015—Organic compounds; Solutions thereof
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
- C01B3/24—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons
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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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00051—Controlling the temperature
- B01J2219/00132—Controlling the temperature using electric heating or cooling elements
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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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00051—Controlling the temperature
- B01J2219/00139—Controlling the temperature using electromagnetic heating
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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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00051—Controlling the temperature
- B01J2219/00159—Controlling the temperature controlling multiple zones along the direction of flow, e.g. pre-heating and after-cooling
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1235—Hydrocarbons
- C01B2203/1252—Cyclic or aromatic hydrocarbons
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/32—Hydrogen storage
Definitions
- the present invention is particularly useful as a catalyst structure for hydrogenation reaction / dehydrogenation reaction that exhibits catalytic activity for hydrogenation reaction to an aromatic compound or dehydrogenation reaction of a hydrogen derivative of an aromatic compound.
- the present invention relates to a catalyst structure with improved catalyst efficiency and a hydrogen reaction module using the same.
- the hydrogen storage means obtained for example, a storage system using a hydrogen storage alloy and a system development using a carbon material such as carbon nanotube or carbon nanofiber have been proposed (for example, Patent Documents 3 and 4). reference.).
- JP 2007-117992 A Japanese Patent Laid-Open No. 2-144154 Japanese Unexamined Patent Publication No. 7-192746 JP-A-5-270801
- the present invention is a hydrogen-supported catalyst that has a high reaction rate of hydrogen uptake and extraction, and excellent hydrogen response performance, and a catalyst structure with improved catalyst function and a hydrogen reaction using the same.
- the purpose is to provide modules.
- the first invention of the present invention is a catalyst structure used for hydrogen reaction or dehydrogenation reaction, and is a first coil catalyst formed by winding a catalyst wire carrying a catalyst substance on the surface of a metal core wire It includes a wire and a second catalyst member disposed on the inner surface and / or outer surface of the coil catalyst wire.
- a second invention of the present invention comprises the catalyst structure according to any one of claims 1 to 13 and a housing container that accommodates the catalyst structure.
- the catalyst structure has an internal flow path through which the fluid to be treated is connected, and the axis of the first coil catalyst wire is incorporated in the flow direction of the fluid to be treated. This is a hydrogen reaction module.
- the surface area can be increased by winding the catalyst wire around the coil catalyst wire.
- the second catalyst member is arranged in the space region on either the inner or outer surface side of the first coil catalyst wire occupying a predetermined volume, the support density of the catalyst substance per predetermined constant volume is further increased, Performance is improved.
- the use range of the catalyst structure of the present invention is expanded, and can contribute to, for example, improvement of hydrogen storage and supply efficiency and hydrogen response performance to a fuel cell system and an internal combustion engine.
- the second invention which is a module for hydrogen reaction using the above catalyst structure, it is possible to configure the catalyst material that is fixedly supported on the increased surface area as an easy-to-handle apparatus component that can be used more effectively.
- the application range of such a hydrogen reaction module is expanded.
- the catalyst structure 1 of the present invention has, for example, a hydrogen reaction on an aromatic compound or a dehydrogenation reaction of a hydrogenated derivative of the aromatic compound on the surface of a metal core wire 2.
- the first coil catalyst wire 4 (hereinafter simply referred to as “first coil”) in which a catalyst wire 3 carrying a catalyst substance X such as platinum or transition metal for use is wound in a coil shape with a predetermined winding diameter.
- the second catalyst member 5 disposed in the space area on the inner surface side and / or outer surface side of the first coil catalyst wire body 4.
- the second catalyst member 5 of FIGS. 1 and 2 is a second coil catalyst formed by winding a catalyst wire similar to the above in the shape of a wire coil having a smaller diameter than the first coil catalyst wire 4. It consists of a linear body 4B (hereinafter, simply referred to as “second coil”). The second catalyst member 5 is coaxially disposed in the internal space 6 of the first coil catalyst wire 4. The outer first coil 4A and the inner second coil 4B are configured to be combined in a contact or non-contact state.
- the two coiled catalyst wires have the same configuration.
- the reference numeral A is added to the end of each reference numeral 2 to 3 thereof.
- the reference numeral B is added to the end of each reference numeral 2 to 3.
- symbol A and B may be abbreviate
- a first coil 4A and a second coil 4B are each made of a catalyst wire 3 carrying a catalyst substance X on the surface of a selected core wire 2, each having a predetermined winding diameter (D) and pitch (P). It consists of a coil molded product wound by.
- the dimensions and cross-sectional shape of each catalyst wire 3 are not particularly limited.
- the catalyst wire 3A of the outer first coil 4A has a wire diameter of 0.8 mm or less, more preferably 0.2 to 0. 0. 0.
- a long material adjusted to a relatively small diameter of 6 mm is preferably used, but a material exceeding this length may be used.
- the catalyst wire 3B of the second coil 4B has the same diameter as that of the catalyst wire 3A of the first coil 4A or a diameter smaller than that.
- the wire diameter of the catalyst wire 3B is arbitrarily set according to the winding diameter of the coil.
- the catalyst wire 3 has a small diameter, it is possible to incorporate more in the case where the coiled product has a smaller winding diameter and is incorporated into a predetermined container. Accordingly, it is possible to densely arrange the coil molded products, which is preferable in that the amount of the catalyst substance X supported per unit volume is increased.
- the cross-sectional shape of the catalyst wire 3 can be easily adopted as a circular cross-section such as a normal wire wire, but other than this, for example, an elliptical shape, a triangular shape, a strip shape, a rectangular shape or a star shape can be used. It may be circular.
- a cross-sectional shape such as a circular shape, an ellipse, or a polygonal shape such as a star shape
- the surface area is remarkably increased, and the accommodation efficiency of the catalyst substance X can be improved as in the case of the wire diameter.
- the catalyst wire 3 of the present invention includes a non-circular cross section, the wire diameter is represented by an equivalent conversion wire diameter calculated from the cross-sectional area.
- both the first coil 4A and the second coil 4B may be the same metal material or different metal materials, but it is desirable that at least one core wire 2 is made of the metal material.
- the chemical composition of the alloy suitable for the core wire 3 is, for example, Cr: 15 to 25 wt%, Ni + Co: 55% or more, C: 0.15% or less, Si: 0.5 to 1.5%, Mn : JIS-NCH1 to NCH2 containing 2.5% or less, and balance Fe and some inevitable impurities, or Cr: 15 to 25 wt%, C: 0.10% or less, Si: 1.5% or less, Mn : 1.0% or less, Al: 2 to 6%, and JIS-FCH1 and FCH2 composed of the remaining Fe and inevitable impurities.
- the nickel material for example, an N200 material of Ni: 99 wt% or more is preferable because the heat generation property is particularly close to aluminum and excellent in workability of a small diameter.
- the above metal material has a characteristic that its electrical resistivity is 5 ⁇ .cm or more, for example, 5 to 200 ⁇ .cm.
- the catalyst wire 3 and its coil wire 4 made of such a metal material can be easily heated to a predetermined set temperature (for example, 200 to 600 ° C.) by direct current heating or electromagnetic induction heating at the time of use. it can. For this reason, there is no restriction
- the catalyst wire 3 for example, a coated wire in which an aluminum metal layer (also simply referred to as “aluminum layer”) 7 is previously coated on the surface of the core wire 2 made of the metal material is used.
- the coated wire is formed with an alumite layer 8 having a fine porous structure on the outermost surface side of the aluminum layer, for example, as shown in FIGS. can do.
- the anodized layer 8 can be formed, for example, by anodizing the aluminum layer 7.
- the aluminum layer 7 is formed by, for example, a coating process using a plating technique or a clad technique, and the core wire 2 is made of a metal material containing aluminum, and an aluminum element is deposited in layers on the surface thereof by a precipitation heat treatment that does not exemplify this. It can also be formed.
- the covering composite ratio of the aluminum layer (including the anodized layer 8) in the catalyst wire 3 is, for example, expressed as [(volume of anodized layer + aluminum layer) / total volume of the catalyst wire] in consideration of the variation. It is preferable that the ratio is 2 to 40%. When the volume ratio is less than 2%, it is difficult to obtain a sufficient thickness of the anodized layer. On the other hand, when it exceeds 40%, the production efficiency is lowered, causing problems due to the heat effect during use and deterioration of strength characteristics. There is a fear. More preferably, the coating composite rate is set within the range of 5 to 30%, and more preferably 8 to 25%.
- the thickness of the aluminum layer 7 is, for example, 0.2 mm or less, preferably about 10 to 100 ⁇ m.
- the anodized layer 8 is formed by anodizing and baking the aluminum layer 7 as described above.
- this treatment includes an electrochemical treatment in a predetermined electrolytic solution, and a heating and baking treatment at about 350 to 600 ° C. Will be implemented. Although the details of the generation phenomenon are omitted, the growth of the fine particles in which the colloid of aluminum oxide is agglomerated causes a part of the surface portion where the fine particles are not present to become pores, resulting in the porous structure described above. It is inferred.
- this porous structure is a mesoporous structure in which fine bottomed pores S distributed in a turtle shell shape are formed in the thickness direction, and the pores S have, for example, an inner diameter of about 10 to 100 nm.
- the pores S Preferably, it has a fine opening of 30 to 50 nm and a bottomed cylindrical shape having a length (L) of 500 ⁇ m or less. If necessary, it is preferable to adjust the aspect ratio (length L / inner diameter d) of the opening to about 3 to 2000 by widening the pores S or post-plowing treatment.
- the catalyst wire 3 covered with the insulating film is used as another member (the other coil wire). It can be used without taking special insulation measures to prevent electrical shorts due to contact with the housing and the housing container. Further, since the porous structure of the alumite layer 8 is very fine and hard, the catalyst substance X is supported on the inner surfaces of the pores S as shown in FIG. Therefore, the catalyst substance X is not separated by contact with other members or friction during use, and deformation and sealing of the pores are prevented.
- 3 and 4 are examples of enlarged photographs showing a cross section of the composite state of the catalyst wire 3
- FIG. 3 is a clad state of the surface aluminum layer
- FIG. 4 is an anodized film (alumite layer) of the aluminum layer. Is shown.
- catalytic substances X are selected depending on the purpose of use, such as platinum, rhodium, rhenium, nickel, zirconium, titanium, zinc, magnesium, molybdenum or tungsten salts, and their hydrochlorides, nitrates, oxalic acids. It can be impregnated and supported in an alumite clad metal thin wire having a porous alumina surface layer from water, ethanol or methanol solution using a salt and an oxyacid salt simultaneously or sequentially.
- the present invention includes a material in which the catalyst material X is directly supported on the core wire 2 without going through the alumite layer.
- the catalyst material X includes the first coil 4A and the second coil 4B (second catalyst member 5). ) May be of the same type or different types.
- platinum solution containing platinum is applied as the catalyst substance X
- a supporting method in which this is applied to the porous alumite layer 8 and press-fitted into the bottomed pores S is recommended.
- platinum solution used in this step include hexachloroplatinum (IV) acid hexahydrate, dinitrodiammineplatinum (II) nitric acid solution, hexaammineplatinum (IV) chloride solution, and tetraammineplatinum (II) hydrochloride solution.
- hexachloroplatinum (IV) acid hexahydrate dinitrodiammineplatinum (II) nitric acid solution
- hexaammineplatinum (IV) chloride solution hexaammineplatinum (IV) chloride solution
- tetraammineplatinum (II) hydrochloride solution are preferably used.
- the platinum and / or transition metal salt solution can be simultaneously or sequentially supported by a method such as dipping, dropping, coating or spraying in a predetermined temperature range while energizing or electromagnetically heating the alumite clad metal fine wire. .
- stepwise firing in a temperature range of 250 to 600 ° C. in an oxygen-containing atmosphere, and further in a hydrogen gas atmosphere
- stepwise heating in the temperature range of 100 to 450 ° C.
- Platinum and / or by hydrogen activation treatment or reduction treatment with a reducing agent such as hydrazine or boron hydride.
- the aluminum clad metal wire catalyst supporting the transition metal can be adjusted.
- the amount of platinum and transition metal supported on the anodized clad metal wire is, for example, The weight ratio is 0.01 to 10%, preferably 0.1 to 5%, and the supported amount of platinum and transition metal is 0.1 to 10 in atomic ratio, preferably 0.1 to 0. It is not limited to the selection of the catalyst precursors described above, the catalyst production process, the activation treatment conditions, and the like.
- the catalyst wire 3 carrying a catalyst substance is used as each of the above-described coil molded products in which a predetermined winding diameter, for example, an average winding diameter of about 3 to 30 mm is wound as shown in FIG. It is desirable to implement the winding shape in consideration of the wire diameter of the catalyst wire 3 and the alumite layer 8 on the surface.
- the anodized layer 8 of the present embodiment is hard and brittle, and strong processing such as coil forming causes large distortion on the wire surface. For this reason, the design which considered that the alumite layer 8 does not crack or peel by the expansion
- the alumite treatment is performed after coil forming, and / or the ratio (D / d) between the winding average diameter (D) of each coil wire 4 and the equivalent diameter (d) of the catalyst wire 3 is tripled.
- the winding pitch (P) of the coil wire bodies 4A and 4B is also preferably 2 times or less, more preferably about 1.01 to 1.50 times the equivalent diameter (d) of the catalyst wire 3.
- the catalyst performance is improved while securing the flow path of the supplied raw material fluid, and the entanglement of the other side catalyst member (for example, the second coil wire) between the pitches can be prevented.
- the configuration in which the first coil 4A is combined with the second coil 4B having the same configuration arranged in the first coil 4A has been described.
- Combining the catalyst members with three or four or more types is possible.
- Such a complex allows more catalytic material to be present in a given volume.
- a third or fourth catalyst member further supporting a catalyst can be combined inside and / or outside of the catalyst structure composed of the first coil 4A and the second coil 4B.
- These catalyst members are preferably temporarily fixed so that the arrangement interval, winding pitch, and the like are not displaced.
- the second catalyst member 5 instead of such a coil-formed product by winding the catalyst wire 3, for example, a rod-like, tubular tube body, a plurality of fine wire-like catalyst wires are twisted together or woven. It is also possible to use a rod-like body or a cylindrical product constituted by winding a molded product, or a non-woven structure made of a fibrous metal material.
- the second catalyst member 5 may be formed as a woven screen.
- the screen of the second catalyst member 5 is woven in a mesh pattern with a predetermined mesh with a catalyst wire carrying the catalyst substance X in the same manner, and the woven fabric sheet 9 has a predetermined pitch in advance. The process of corrugation of the uneven shape is done.
- the woven fabric sheet 9 has, for example, an opening of about 100 to 300 # and a corrugated pitch of about 6 to 20 mm. And in the concave groove
- the catalyst structure 1 ′ thus formed has a flow path formed by the first coil 4 ⁇ / b> A and a fine flow path between the woven fabric sheets 9, which are the second catalyst members, in the cross section. Since the catalyst substance X is supported on the surface, the hydrogenation reaction can be performed efficiently by increasing the chance of contact with the raw material fluid. Further, such a catalyst structure 1 ′ is easy to mold and has a high elasticity. Therefore, the catalyst structure 1 ′ can be easily inserted and incorporated into a limited space such as a pipe. Furthermore, since the first coil 4A is securely held by the woven fabric sheet 9, the catalyst structure 1 'is prevented from moving, and the heat generation temperature is stabilized and the processing performance is improved.
- the catalyst structure 1 ′ can heat the raw material fluid with good response and efficiency by applying a predetermined current to the woven fabric sheet 9 and the first coil 4A, respectively, and can be used for a wide range of applications. is there.
- the woven fabric sheet 9 can be selectively energized only to one of the woven wires constituting it.
- the second catalyst member 5 may be formed as a small-diameter tube body that further encloses the first coil wire body 4A. Similar to the above, the catalyst substance X is supported on the inner surface of the tube body.
- a thin tube of aluminum metal can be adopted as the core metal of the tube body.
- an alumite layer can be directly formed on the surface of this aluminum metal, or the catalyst substance X can be supported without forming this alumite layer.
- the tube body can be manufactured at a low cost while enhancing the heat retaining effect by encapsulating the first coil wire body 4 ⁇ / b> A disposed on the inside thereof substantially over the entire body.
- the tube body of this embodiment can also be used as a supply pipe for the fluid to be processed, the structure thereof is, for example, as shown in FIG. Understood as an encapsulating configuration.
- the hydrogen storage / hydrogen generation system 20 adds hydrogen to an aromatic compound (e.g., toluene) to store hydrogen as an organic hydride (e.g., methylcyclohexane) that is a hydrogenated derivative and dehydrogenates the organic hydride. It is an apparatus that can generate hydrogen by decomposing it into an aromatic compound and hydrogen.
- the system 20 includes a reactor 22, a first tank 23 containing an aromatic compound, a second tank 24 containing an organic hydride, and a third tank for storing a reaction product generated in the reactor 22.
- the tank 25 is mainly provided.
- the reactor 22 includes, for example, a heating means 26 including an energized or electromagnetic heater, and a platinum-supported alumite clad metal wire catalyst (hereinafter simply referred to as “platinum”) for the hydrogenation / dehydrogenation reaction heated by the heating means 26. "Supported anodized clad fine wire catalyst”) 27. Above the reactor 22, the 1st piping 28 for supplying a liquid raw material penetrates, and the end is arrange
- a heating means 26 including an energized or electromagnetic heater, and a platinum-supported alumite clad metal wire catalyst (hereinafter simply referred to as “platinum”) for the hydrogenation / dehydrogenation reaction heated by the heating means 26.
- the three-way valve 32 and the first tank 23 are connected by a pipe 31, and a liquid feed pump 33 is connected to the pipe 31.
- the three-way valve 32 and the second tank 24 are connected by a pipe 34, and a liquid feed pump 35 is connected to the pipe 34.
- the three-way valve 32 is a) Opening only between the first tank 23 and the reactor 22 b) Opening only between the second tank 24 and the reactor 22, or c) Opening between the reactor 22, the first tank 23, and the second tank 24 Can be switched to either closed or closed.
- a second pipe 36 for supplying hydrogen passes through the reactor 22 and one end thereof is disposed.
- a valve 37 is connected to the second pipe 36.
- a hydrogen supply means (not shown) is connected to the other end of the second pipe 36 outside the reactor 22.
- the vicinity of the bottom of the reactor 22 and the upper part of the third tank 25 are connected by a third pipe 38.
- a pump 39 and a cooler 40 are connected to the third pipe 38.
- a pipe 41 for exhausting a gas such as hydrogen is connected above the third tank 25.
- the operation is performed as follows. First, the platinum-supported alumite clad metal fine wire catalyst 27 is heated using the heating means 26. Next, the valve 37 is opened, and hydrogen is supplied into the reactor 22 via the second pipe 36. At this time, it is preferable to drive the pump 39 so that hydrogen flows through the piping 41 to the outside of the reactor 22. Next, the three-way valve 32 is switched to open only the path between the first tank 23 and the reactor 22, and the liquid feed pump 33 is driven. Thereby, the aromatic compound in the first tank 23 is supplied into the reactor 22. For example, the aromatic compound is sprayed from the spray nozzle 29 into the reactor 22 at regular intervals by opening the valve 30 at regular intervals.
- a hydrogenation reaction between the sprayed aromatic compound and hydrogen occurs on the surface of the platinum-supported alumite clad fine wire catalyst 27, and organic hydride is generated.
- the organic hydride is supplied into the third tank 25 through the pump 39.
- the gaseous product passing through the third pipe 38 is cooled by the cooler 40 and stored as a liquid in the third tank 25. Since hydrogen is not liquefied even if it is cooled by the cooler 40, it is discharged to the outside through the pipe 41.
- the operation is performed as follows. First, the platinum-supported alumite clad fine wire catalyst 27 is heated using the heating means 26. Next, the pump 39 is driven, and the three-way valve 32 is switched to open only the path between the second tank 24 and the reactor 22. In addition, the organic hydride in the second tank 24 is supplied into the reactor 22 by driving the liquid feed pump 35. Then, by opening the valve 30 at regular intervals, the organic hydride is sprayed into the reactor 22 from the spray nozzle 29 at regular intervals. The sprayed organic hydride comes into contact with the surface of the platinum-supported alumite clad metal fine wire catalyst 27 to cause a dehydrogenation reaction.
- the aromatic compound is supplied into the third tank 25 through the pump 39.
- the gaseous aromatic compound passing through the third pipe 38 is cooled by the cooler 40 and stored as a liquid in the third tank 25. Hydrogen is discharged outside through the pipe 41.
- a platinum-supported alumite clad fine wire catalyst is used for both the aromatic hydrocarbon hydrogenation reaction / dehydrogenation derivative dehydrogenation reaction, but only the aromatic hydrocarbon hydrogenation reaction. It may be used to perform the dehydrogenation reaction of the hydrogenated derivative (organic hydride).
- each catalyst structure 1 in the system 20 are arranged in a housing or expanded housing container 12 and the raw material fluid flows into the internal flow path. Moreover, each catalyst structure 1 is used as a self-heatable module by being connected to an external power source. Such modularization enables easy handling.
- first coil 4A and the second coil 4B are coaxially inserted are accommodated in a housing container 12 (for example, piping).
- the first coil 4A and the second coil 4B are separately wired in series, and are adjusted so that the heat generation temperature is constant as a whole.
- a predetermined amount of electricity may be added to each coil wire as shown in FIG. 1 without connecting the coil wires.
- first coil 4 ⁇ / b> A and the second coil 4 ⁇ / b> B are interleaved with a resistor having a predetermined resistance value (not shown), and the amount of electricity on the side of the second coil 4 ⁇ / b> B having a smaller diameter is suppressed, thereby generating heat from both coil wires.
- the temperature may be configured to be constant.
- the housing container 12 is provided with openings through which the fluid to be processed flows in and out before and after the internal flow path in which the first coil 4A and the second coil 4B are accommodated, so that the housing container 12 is made of the fluid to be processed. It can be used as part of the supply piping.
- FIG. 9 shows still another embodiment of the present invention.
- the catalyst structure 1 of this embodiment includes a first coil 4A, a second coil 4B inserted through the first coil 4A, and a metallic tube capillary 13 serving as a third catalyst member enclosing the first coil 4A.
- a plurality of the catalyst structures 1 are arranged in parallel, and a first chamber 15 and a second chamber 16 are provided at both ends thereof.
- the first chamber 15 has a substantially cylindrical shape, and is provided with an opening 15a to which a processing fluid is supplied at one end (in this example, the upper part). Further, on the other end (lower part in this example) side of the first chamber 15, there is a perforated plate 15 ⁇ / b> A provided with an opening 15 b at a position corresponding to the upper end (one end) of the metallic tube capillary 13 of each catalyst structure 1. Provided.
- the second chamber 16 also has a substantially cylindrical shape, and an opening 16a through which a fluid that has undergone a catalytic reaction is discharged on one end (lower part in this example) side. Further, on the other end (upper part in this example) side of the second chamber 16, a porous plate 16 ⁇ / b> A provided with an opening 16 b is provided at a position corresponding to the other end of the metallic tube capillary 13 of each catalyst structure 1. .
- the fluid to be treated is sprayed in a pulse form from the opening 15a of the first chamber 15, and supplied to the catalyst structure 1 through the hole 15b of the perforated plate 15A. Then, after a catalytic reaction is performed in the catalyst structure 1, the catalyst is aggregated at the opening 16 a through the hole 16 b of the porous plate 16 A of the second chamber 16 and discharged out of the system.
- the metallic tube capillary 13 as the third catalyst member carries the catalyst substance X on the inner surface of an aluminum metal tube, for example.
- the first and second chambers 15 and 16 are connected by a housing container 12.
- the housing container 12 is disposed so as to surround all the catalyst structures 1 and has an inlet 12a and an outlet 12b into which exhaust gas heated by an engine such as an engine flows.
- each catalyst structure 1 is indirectly heated also by exhaust heat, such as exhaust gas, in addition to energization heating.
- the second catalyst member 5 used in the present invention can be modified into various forms such as a sheet member such as a mesh or a woven material, a pipe member or a bar, in addition to the coil molded product. is there. And any one of them is used alone or in combination and arranged on the inner or outer surface of the first coil wire body 4A. Moreover, when each of the first coil wire 4A and the second coil wire 4B is energized, the heat generation response of each catalyst member can be enhanced. Furthermore, the second catalyst member 5 is a multifilament cotton-like aggregate (nonwoven web) in which a catalyst is supported on a wire rod having a diameter of 0.1 mm or less, and this is used as the first coil.
- Such a cotton-like aggregate is shown in, for example, Japanese Patent No. 110424, and since it has a small mass, it can be heated by the radiant heat of the first coil catalyst wire 4A itself.
- FIG. 3 shows an enlarged covering state of the cross section of the first clad fine wire.
- Each of these thin clad wires was set in a coiling machine, and the ratio (D / d) between the wire diameter d and the average coil winding diameter D was adjusted to be 8 to 15 times. Then, two types of close contact coil wires each having a length of 120 mm were manufactured. 1st coil wire: winding average diameter 6mm Second coil wire: winding average diameter 4mm Each winding pitch was adjusted to 1.05 times the wire diameter d. Each coil wire was confirmed to have a good coil state without any defects such as peeling on the surface aluminum layer.
- each coil wire was anodized under the conditions of a 4% wt oxalic acid aqueous solution at a temperature of 35 ° C. and a current density of 50 to 70 A / m 2 . Then, it was acid-treated in a state of being immersed in the same kind of oxalic acid treatment solution for 6 hours, followed by pore widening treatment and drying in the air. Next, after baking at 300 to 450 ° C. for about 1 hour, hydration was performed at 80 ° C. or higher for about 2 hours and dried. Thereafter, a further baking treatment was carried out at 500 ° C.
- FIG. 4 shows an enlarged view of a cross section of an alumite clad nickel fine wire provided with a porous alumite surface layer having a thickness of 20 mm.
- FIG. 6 further shows an enlarged photograph of the outer surface of the microscope.
- Example 1 0.01, 0.015, 0.02 gr of chloroplatinic acid H 2 PtCl 6 6H 2 O was used as a platinum salt as a catalyst substance and dissolved in 10 cc ethanol to prepare a chloroplatinic acid solution. Further, each of the alumite nickel clad fine wires A and B having a porous alumina surface layer having a thickness of 10 to 30 ⁇ m and having a coil shape as shown in FIG. After platinum was supported on the substrate, it was heated to a predetermined temperature and dried to obtain two types of target supported catalyst wires. This is designated as specimens A and B.
- a coil-shaped alumite having a porous alumina surface layer with a thickness of 30 ⁇ m using 5 cc of an ethanol solution (4% concentration) containing a platinum colloid having a particle diameter of 2 nm as a catalyst material is applied to the same clad fine wire as described above.
- the same is applied to the target supported catalyst wire obtained by immersing the nickel-clad fine wire C in the above solution and supporting platinum in the porous structure on the surface, followed by heating to a predetermined temperature and drying.
- This is designated as Specimen C.
- test specimens A and B are coaxially externally and interpolated, and the coil wire bodies are arranged so that no change in the winding pitch or eccentricity occurs due to expansion or contraction due to expansion or contraction during use or energization heating.
- a set of catalyst structure elements was obtained by combining with a dedicated glass fixture in between. As a result, the arrangement of the coil wire bodies is made constant, partial variations in the heat generation temperature are reduced, and stable catalytic action is expected.
- the loading density of the catalyst substance is drastically improved per unit volume by arranging these two types of coil wires substantially in the space of the first coil wire. By the compounding, the hydrogen production efficiency has been dramatically improved.
- Example 2 In the same manner as in Example 1, a first clad fine wire (aluminum layer thickness 30 ⁇ m) having a wire diameter of 0.45 mm was set in a coiling machine, and the coil winding average diameter was 4.5 mm and the length was 120 mm. The second coil wire was manufactured. Then, in order to the catalyst structures of the composite structure in combination with the first coil wire body using this in Example 1, similarly performs anodized and catalyst supporting each 0.02gr of chloroplatinic acid H 2 PtCl 6 The first coil wire and the second coil wire are immersed in a chloroplatinic acid solution in which 6H 2 O is dissolved in 10 cc of ethanol so that the platinum catalyst penetrates into the porous structure on each surface.
- a first clad fine wire (aluminum layer thickness 30 ⁇ m) having a wire diameter of 0.45 mm was set in a coiling machine, and the coil winding average diameter was 4.5 mm and the length was 120 mm.
- the second coil wire was
- the platinum catalyst was supported by the above-mentioned support method for press-fitting into the plate, heat-dried and the surface was reduced to obtain two types of coil wires having different coil diameters.
- the ratio of the wire diameter (d) to the winding diameter (D) is 13.3 times and 10.0 times, respectively, and they are combined coaxially.
- the catalyst material carrying / accommodating area per unit volume occupied by the large-diameter first coil catalyst that is, the total surface area is increased by about 40% or more, and each coil catalyst when combined is used.
- a heating test was performed to confirm the heat generation efficiency, coil shape, and presence of surface defects associated with heating.
- the second coil catalyst is housed inside the space of the first coil catalyst, and both are connected in series and gradually energized and heated from an external power source outside the system. Then, cooling by stopping the energization was repeated for every 10 minutes for a total of 10 hours.
- the coil shape change of each coil catalyst with heating and cooling and the presence or absence of surface defects in the alumite layer were investigated, but no serious defects were found in any of the coil wires, and such a plurality of members Since these are arranged in an approaching state, the electrical efficiency is improved by mutual radiant heat between the members, which contributes to a reduction in the amount of electricity.
- Example 3 Similar to the catalyst wire of Example 1, an aluminum clad fine wire having a wire diameter of 0.45 mm was used to produce a first coil catalyst wire having a winding average diameter of 8 mm and a length of 120 mm, and the outside was placed inside the inner space. Twisted together using seven fine wires having a diameter of 0.8 mm and carrying a catalyst in the same manner to form a stranded wire body (second catalyst member) having a length of 120 mm, and a copper metal core wire in the gap between the two members Similarly, a composite catalyst element module was prepared by combining a catalyst-supported fiber diameter of 20 ⁇ m and a cotton-like non-woven web (third catalyst member) having a density of 2%.
- the first and third catalyst members were each heated by energization, and the conditions for setting the total heating temperature to 350 ° C. were set.
- the non-woven web which is the third catalyst member, is made of copper metal having excellent electrothermal properties. Therefore, even if it is not directly energized, the non-woven web is affected by the heat of the first and third catalyst members disposed on both sides thereof. Thus, it was possible to easily heat to a relatively close temperature.
- the supporting efficiency of the catalyst substance in the predetermined volume as a whole can be further improved, and the holding of the internal third catalyst wire can be further stabilized by the intervention of the nonwoven web, and the cyclohexane used as the processing fluid It was very preferable without affecting the flow resistance of the liquid.
- the intermediate nonwoven web is very fine and can greatly increase the surface area, and the nonwoven web has endothermic properties and the positions of the first coil wire and the second catalyst member disposed on both sides thereof. This is preferable because it has a merit that a good relationship can be secured and the flow resistance of the fluid to be treated can be reduced.
- Example 4 An aluminum clad wire having an outer diameter of 0.5 mm, which is configured in the same manner as the catalyst wire of Example 1, is set in a coiling machine and molded to a length of 120 mm by close winding with an average coil diameter of 8 mm and a pitch of 1.1 d.
- the first coil wire body A and the second coil wire body similarly loaded with a catalyst having an average coil diameter of 4.5 mm, a pitch of 1.1 d, and a length of 120 mm, similarly wound in the opposite direction.
- the outer part of the catalyst structure provided coaxially with the test body C) is used as a third catalyst member, and a porous alumina surface layer having an outer diameter of 12 mm, an inner diameter of 10 mm, and an inner surface and an outer surface of 30 ⁇ m in thickness.
- a composite catalyst element surrounded by an aluminum cylinder having a length of 120 mm was prepared. Then, 50 of them were assembled into an apparatus as shown in FIG. 9 to prepare a methylcyclohexane dehydrogenation reaction apparatus, and methylcyclohexane dehydrogenation reaction was performed. In this configuration, since the first coil wire and the second coil wire are reversely wound, no entanglement between them occurred.
- methylcyclohexane was flowed from four pulse-type spray nozzles of the reactor in a nitrogen stream, a flow rate of 200 ml / min, a spray cycle of 1 second, a spray amount of 5.8 gr per spray nozzle, a spray interval of 10 seconds, and 350 ° C. It was supplied to each catalyst structure element heated to a predetermined temperature, and the hydrogen generation rate and the toluene conversion rate of methylcyclohexane were analyzed and measured by gas chromatography.
- the platinum-supported anodized clad fine wire catalyst was directly energized and heated by an electric current / voltage stable power source outside the system with an amount of electricity corresponding to each coil wire.
- the outer surface of the cylindrical catalyst was 280 ° C. by circulating hot exhaust gas in the container housing.
- the present invention can be widely used in automobiles, ships, locomotive industries and chemical industries that use hydrogen as a fuel.
Abstract
Description
A)天然ガス、プロパンガス、メタノールなど水素を含む原料物質から水蒸気改質や水素分離技術によって水素のみを得る方法
B)表面にγ-アルミナ層を介して触媒を担持して板状、リボン状、ハニカム状に形成した触媒体を用いる方法、又は
C)光合成細菌や嫌気性水素発生細菌等を用いる方法
などが提案されている(例えば、特許文献1及び2参照。)。
2 芯材
3 触媒ワイヤー
4 第一のコイル触媒
5 第二触媒部材
X 触媒物質
図1及び2に例示されるように、本発明の触媒構造物1は、金属製芯線2の表面に、例えば芳香族化合物への水素反応又は当該芳香族化合物の水素化誘導体の脱水素化反応用の白金や遷移金属等の触媒物質Xを担持させた触媒ワイヤー3が、所定の巻き径でコイル状に巻回されてなる第一のコイル触媒線体4(以下、単に「第一コイル」ということがある。)と、該第一コイル触媒線体4の内面側及び/又は外面側の空間領域に配置された第二の触媒部材5とを含んで構成される。
a)第1タンク23と反応器22との間のみを開通
b)第2タンク24と反応器22との間のみを開通、又は
c)反応器22と第1タンク23、第2タンク24との間を閉鎖
のいずれかに切り替え可能である。
通電加熱機能を有するニッケル線(純度99%)をアルミニウム(純度99.9%)の帯材で被包したアルミクラッド線材(線径12mm)が母材として作られた。そして、この母材に伸線加工と温度600℃での熱処理加工とを繰り返し行い、下記の2種類のクラッド細線が製造された。
第一のクラッド細線:線径0.45mm、アルミニウム層の平均厚さ30μm
第二のクラッド細線:線径0.24mm、アルミニウム層の平均厚さ20μm
なお、上記第一クラッド細線の横断面の拡大被覆状態が図3に示される。
第一コイル線体:巻回平均径6mm
第二コイル線体:巻回平均径4mm
なお、各巻回ピッチは、前記線径dの1.05倍に調整された。各コイル線体は、表面のアルミニウム層に剥離などの欠陥は見られず、良好なコイル状態を具えていることが確認できた。
次に、各コイル線体を、温度35℃の4%wtしゅう酸水溶液、電流密度50~70A/m2の条件で陽極酸化処理が行われた。その後、同種のしゅう酸処理液に6時間浸漬した状態で酸処理をし、ポアサイズの拡幅処理をして大気中で乾燥させた。次に、300~450℃で約1時間の焼成処理をした後、80℃以上で約2時間水和処理を行なって乾燥させた。その後、さらに500℃で3時間相当に焼成処理を行い、所要の耐熱性多孔質アルミナ皮膜の厚さ10~30μmの表面層を備えるアルマイトクラッド金属細線A,Bが得られた。図4には、20mm厚の多孔質アルマイト表面層を備えたアルマイトクッラドニッケル細線の断面を500倍に拡大したものが示される。また、図6には、さらにその外表面の顕微鏡の拡大写真が示される。
触媒物質となる白金塩として0.01、0.015、0.02grの塩化白金酸H2PtCl66H2Oを用いて10ccエタノールにそれぞれ溶解し、塩化白金酸溶液を作成した。また、厚さ10~30μmの多孔質アルミナ表面層を有しかつ図1に示すようなコイル形状の各アルマイトクニッケルクラッド細線A,Bを前記溶液内に浸漬し、その表面の多孔質構造内に白金を担持させた後、所定温度に加熱し乾燥して、目標の担持触媒線体2種類を得た。これを試験体A及びBとする。
各試験体A、B及びCのコイル線体が、図10に示した水素化反応および脱水素化反応装置の触媒として組み込まれ、メチルシクロヘキサンの脱水素反応が行われた。そして、水素発生速度及びメチルシクロヘキサンのトルエン転化率がガスクロマトグラフィーにより分析・測定された。実験は、反応装置に設けられたパルス型噴霧ノズルよりメチルシクロヘキサンが窒素気流中、流速150ml/min、噴霧サイクル0.5秒(1回噴霧量0.39gr)、噴霧間隔10秒又は20秒とし、310℃に加熱された各試験体A乃至C(触媒)を用いて行われた。各試験体A、B及びCは、各々系外の電流・電圧安定電源により各コイル線体に応じた電気量で直接通電加熱が行なわれた。
実験の結果、白金担持のアルマイトクラッド細線触媒A、B及びCについて、それぞれメチルシクロヘキサン転化率は53%、72%及び85%であった。また、トルエン選択率は、それぞれ97%、98%及び96%であった。さらに、平均水素生成速度は、それぞれ0.42L/分、0.57L/分及び0.67L/分であった。これらの結果より、試験体A、B及びCの各コイル線体について水素製造の有効性が確認された。
前記実施例1で用いたのと同様に、線径0.45mmの第一クラッド細線(アルミニウム層の厚さ30μm)をコイリングマシンにセットし、コイル巻回平均径が4.5mm、長さ120mmの第二コイル線体を製造した。そして、これを実施例1で用いた第一コイル線体と組み合わせた複合構造の触媒構造物にするべく、同様にアルマイト処理と触媒担持を行い、各々0.02grの塩化白金酸H2PtCl66H2Oを10ccのエタノール液に溶解した塩化白金酸溶液中に、前記第一コイル線体と第二コイル線体を浸漬して、各表面上の多孔質構造内に白金触媒が浸透するように前記圧入浸透させる担持法によって白金触媒を担持させ、加熱乾燥及び表面の還元処理をして、コイル径の異なる2種類のコイル線体を得た。この第一及び第二の2種類のコイル線体は、その巻回径(D)に対する線径(d)の比が、それぞれ13.3倍と10.0倍であり、各々同軸に組み合わせることで、太径の第一コイル触媒が占める単位容積当たりにおける触媒物質の担持収容面積、すなわち合計表面積は約40%以上の増加をさせることになり、またこれを組み合わせて使用する際の各コイル触媒の加熱に伴う発熱効率、コイル形状及び表面欠陥の有無を確認する加熱試験を行った。試験は、前記第一コイル触媒の空間内部に第二コイル触媒を内装して、両者を直列配線して系外の外部電源から徐々に通電加熱するようにしており、目標の360℃への加熱と通電停止による冷却を1分毎に繰り返しながら合計10時間行った。その結果、加熱・冷却に伴う各コイル触媒のコイル形状の変化及びアルマイト層の表面欠陥の有無を調査したが、いずれのコイル線体も重大な欠陥は見られず、またこのような複数の部材が接近状態で配置されることから、各部材同士の相互の輻射熱によって電気効率を良好にし、電気量の削減に寄与するものであった。
実施例1の触媒ワイヤーと同様に、線径0.45mmのアルミクラッド細線を用い、これを巻回平均径8mm及び長さ120mmの第一コイル触媒線体を作成し、その内部空間内に外径0.8mmでかつ同様に触媒担持した7本の細線を用いて撚り合わせ、長さ120mmの撚線体(第二触媒部材)とし、更にこの両者部材間の隙間内に、銅製金属の芯線に同様に触媒担持した繊維径20μmで密度2%の綿状の不織ウエブ(第三の触媒部材)とを組み合わせ、複合型触媒エレメントのモジュールを作成した。
実施例1の触媒ワイヤーと同様に構成した外径0.5mmのアルミクラッドワイヤーをコイリングマシンにセットして、平均コイル径8mm、ピッチ1.1dの密着巻きによる長さ120mmに成形し、触媒担持した第一コイル線体Aと、同様に逆方向に巻回した平均コイル径4.5mm、ピッチ1.1d、長さ120mmで同様に触媒担持した第二コイル線体(ただし、触媒付与方法を試験体Cで形成)とを同軸に具えた触媒構造物の外部を、更に第三の触媒部材として、外径12mm及び内径10mmで内表面と外表面を厚さ30μmの多孔質アルミナ表面層を有した長さ120mmのアルミニウム円筒で囲んだ複合型触媒エレメントが作成された。そして、その50本を図9に示したような装置に組み立ててメチルシクロヘキサン脱水素反応装置が作成され、メチルシクロヘキサンの脱水素反応が行われた。この構成で、前記第一コイル線体と第二コイル線体とは逆巻きであることから、両者の絡み合いは生じなかった。
Claims (15)
- 水素反応又は脱水素反応に用いる触媒構造物であって、
金属製芯線の表面に触媒物質を担持した触媒ワイヤーの巻回で形成された第一のコイル触媒線体と、
該コイル触媒線体の内面側及び/又は外面側に配置された第二の触媒部材とを含むことを特徴とする触媒構造物。 - 前記触媒ワイヤーの等価直径(d)が0.8mm以下である請求項1に記載の触媒構造物。
- 前記第二の触媒部材は、金属製芯線の表面に触媒物質を担持した触媒ワイヤーを前記第一のコイル触媒線体とは異なる巻径で巻回して形成された第二のコイル触媒線体であり、
しかも前記第二のコイル触媒線体は、前記第一コイル触媒線体と同軸に配置されている請求項1又は2に記載の触媒構造物。 - 前記第一のコイル触媒線体及び第二のコイル触媒線体の少なくとも一方は、その触媒ワイヤーの等価直径(d)の3~20倍の巻回平均径(D)を有する請求項3に記載の触媒構造物。
- 前記第一のコイル触媒線体及び第二のコイル触媒線体の少なくとも一方は、その触媒ワイヤーの等価直径(d)の1.01~1.50倍の巻回ピッチ(P)で成形されている請求項3又は4に記載の触媒構造物。
- 前記第一のコイル触媒線体と前記第二のコイル触媒線体とは、各々コイル巻回方向が逆である請求項3乃至5のいずれかに記載の触媒構造物。
- 前記第一のコイル触媒線体及び/又は前記第二のコイル触媒線体の触媒ワイヤーは、金属製芯線と、その表面に形成された多孔質構造のアルマイト層と、該アルマイト層に担持された触媒物質とを含む請求項3乃至6のいずれかに記載の触媒構造物。
- 前記第二の触媒部材は、内面又は外面のいずれかの表面上に前記第一コイル線体と同種又は異種の触媒物質を担持したチューブ体からなる請求項1乃至7のいずれかに記載の触媒構造物。
- 前記チューブ体は、金属材料からなる芯材と、該芯材の表面層に形成された多孔質構造のアルマイト層と、該アルマイト層に固着された触媒物質とを含む請求項8に記載の触媒構造物。
- 前記アルマイト層は、その下層に設けたアルミニウムをアルマイト処理することによって表面に断面U字状の有底細孔が形成されたメソポーラス構造体を有する請求項7又は9に記載の触媒構造物。
- 前記金属製芯線は、常温での電気抵抗率が5μΩ.cm以上の特性を具え、かつ、ステンレス鋼、ニッケル、ニッケル合金、クロム、クロム合金、チタン、チタン合金、アルミニウム、アルミニウム合金、タングステン及びタングステン合金からなる群から選ばれたいずれかの金属材料である請求項1乃至10のいずれかに記載の触媒構造物。
- 前記金属材料からなる芯材は、常温での電気抵抗率が5μΩ.cm以上の特性を具え、かつ、ステンレス鋼、ニッケル、ニッケル合金、クロム、クロム合金、チタン、チタン合金、アルミニウム、アルミニウム合金、タングステン及びタングステン合金からなる群から選ばれたいずれかの金属材料である請求項9に記載の触媒構造物。
- 前記第一のコイル触媒線体及び/又は第二の触媒部材は、通電又は電磁誘導により使用温度に加熱される請求項1乃至12のいずれかに記載の触媒構造物。
- 前記請求項1乃至13のいずれかに記載の触媒構造物と、該触媒構造物を収容するハウジング容器とからなり、
前記ハウジング容器は、内部に、一方の開口と他方の開口とを繋ぐ被処理流体が流れる内部流路を有し、
前記触媒構造物は、前記第一のコイル触媒線体の軸線が前記被処理流体の流れ方向に組み込まれてなることを特徴とする水素反応用モジュール。 - 前記触媒構造物の外側を覆う触媒物質を担持した第二のチューブ部材をさらに含む請求項14に記載の水素反応用モジュール。
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US13/123,913 US8568665B2 (en) | 2010-12-28 | 2010-12-28 | Catalyst structure and hydrogenation/dehydrogenation reaction module using the same catalyst structure |
PCT/JP2010/073803 WO2012090326A1 (ja) | 2010-12-28 | 2010-12-28 | 触媒構造物及びそれを用いた水素反応用モジュール |
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