JP2012236182A - Catalyst carrier, catalyst product using the same, and catalyst module - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a catalyst carrier for carrying a catalyst on it, the carrier being excellent, for example, in hydrogen-storing/supplying capability, increasing the amount, per unit volume, of a catalyst substance to be carried on, and more surely conducting flowing contact with a fluid to be treated; and to provide a catalyst product and a catalyst module.SOLUTION: The catalyst carrier, which carries a catalyst substance on it, comprises a coil wire which is formed by consecutively winding a metallic wire material from one end to the other end. In this case, the gap width (H) between a virtual external diameter (D1) and a virtual internal diameter (D2), which are drawn by the metallic wire material when the winding is projected in the axial direction of the coil wire, is amplified to be at least twice as long as the equivalent wire diameter (d) of the metallic wire material to make a deformed coil form. The catalyst product is produced by carrying on the catalyst a prescribed catalyst substance. The catalyst module comprises the catalyst product.

Description

  The present invention relates to a catalyst carrier suitable for, for example, a hydrogenation reaction / dehydrogenation catalyst product that exhibits catalytic activity in a hydrogenation reaction to an aromatic compound or a dehydrogenation reaction of a hydrogen derivative of an aromatic compound. The present invention relates to the catalyst product used and the catalyst module.

  In recent years, global warming has been seen as a problem, and fuel cell systems have attracted attention as new clean energy alternatives to fossil fuels that have been widely used. Since this fuel cell system uses hydrogen as fuel, and only water is discharged when power is generated, there is an increasing expectation for widespread use as a clean energy technology with the least environmental impact.

  Gasoline automobiles and ship / locomotive diesel generators also improve fuel efficiency through the “hydrogen co-firing technology” that adds hydrogen to fuel oil such as gasoline, while reducing environmental impacts such as CO2, NOx, and CO. Reduction of generation is also under consideration, and the demand trend of hydrogen is increasing more than ever in such technological innovation. However, on the other hand, hydrogen is flammable and has a high risk of explosion, and it is a causative substance of hydrogen embrittlement for metal materials. A wide range of measures such as transportation is necessary.

  Therefore, as a measure to suppress such problems, a hydrogen storage and supply system that can supply responsively as needed is studied. For example, A) Steam reforming and hydrogen separation from raw materials containing hydrogen such as natural gas, propane gas, and methanol. B) Method of obtaining only hydrogen by technology, B) Method of using catalyst body formed on plate, ribbon, or honeycomb by supporting catalyst on the surface via γ-alumina layer, C) Generation of photosynthetic bacteria and anaerobic hydrogen Various approaches such as a method using bacteria are being promoted. (For example, see Patent Document 1 and Patent Document 2.)

  In addition, with respect to the obtained hydrogen storage means, 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 are also being seen. (For example, see Patent Document 3 and Patent Document 4.)

JP 2007-117992 A JP-A-2-144154 JP 7-192746 A Japanese Patent Laid-Open No. 5-270801

  However, in the former hydrogen production system, in order to obtain a predetermined amount of hydrogen more effectively, for example, the module itself needs to be enlarged or complicated, such as using a larger module or simultaneously using multiple modules. For this reason, problems due to installation space and cost increase have been pointed out, which has hindered widespread use, and the storage system using the latter hydrogen storage alloy is limited by the amount of hydrogen stored per unit volume of the alloy used, There is a problem of response performance of response speed, and these alloys are not expensive enough because they are expensive.

  Under such circumstances, the present inventors, as a hydrogen storage / supply system that is low in cost and excellent in production efficiency and excellent in hydrogen response, have a catalyst carrying a predetermined catalytic substance having a hydrogen reaction or dehydrogenation function. By making a coil-shaped product in which the wire is wound with a predetermined winding diameter, a catalyst product using a coiled wire body with increased reaction efficiency per fixed volume due to the increased surface area of the wire rod is manufactured, and the evaluation test of the reaction is performed. proceeding.

  However, according to the implementation results so far, the coil wire body is wound in the usual same-diameter and close-contact coil shape, and is mounted in the stock solution reaction pipe or housing container in the flow direction of the supplied stock solution. Therefore, the catalytic reaction is likely to be a reaction on a very limited part of the surface, such as the coil portion on the tip side of the coil wire body of the feed stock solution, and the length of the coil wire body is reduced. The accompanying length effect is not sufficient. For this reason, for example, the fluid to be processed flowing in the space inside the central portion of the coil wire body or the outer gap with the piping container is discharged without causing a catalytic reaction, and the generated fluid and the untreated fluid are further separated. There is a need for devices that increase reaction efficiency, such as the need to perform work.

  Therefore, the present invention improves the catalyst performance by improving the above-described disadvantages of the proposed conventional coil wire, and more effectively utilizes the piping space for housing the housing and the flow path space of the housing container. As a result, it has been concluded that it is effective to obtain an irregular coil shape with an increased projection width when projected in the axial direction, and the present invention has been completed here.

Solutions to confront challenges

That is, the invention according to claim 1 of the present application is a catalyst carrier for supporting a catalyst substance,
A virtual outer diameter (D1) drawn by the metal wire, which is composed of a coil wire continuously wound from one side to the other by a metal wire, and the winding projects the coil wire in the axial direction. And an imaginary inner diameter (D2), the carrier width for the catalyst is formed into a deformed coil shape amplified to be twice or more the equivalent wire diameter (d) of the metal wire It is.

  In the invention according to claim 2 of the present application, the coil wire body is formed by decentering the coil center point from the first coil portion along the axial direction toward the Nth coil portion. In the invention according to claim 3, the coil wire body is formed in a non-circular shape and the non-circular shape is provided. By changing the winding azimuth angle (α) from the first coil portion toward the Nth coil portion, the shape of the coil wire body is formed with spiral grooves or spiral ridges, In the invention according to claim 4 of the present application, the non-circular shape is an ellipse or a flat shape having a ratio (Cw / Ch) of the coil forming width (Cw) to the coil height (Ch) of 1.5 to 10 times. Further, the invention according to claim 5 is the eccentricity or winding of the coil center point. An inclination angle (θ) of the spiral groove or spiral ridge of the spiral groove or spiral ridge formed by winding with a change in the angle (α) with respect to the axis of the coil wire body is 20 to 80 °. The catalyst carrier is characterized by the above.

    Further, the invention according to claim 6 is such that the opening width (H) is amplified to 3 to 15 times the equivalent wire diameter (d) of the metal wire, and the invention according to claim 7 is the coil The wire is closely wound at a pitch of 1.3 times or less the equivalent wire diameter (d) of the metal wire, and the invention according to claim 8 is characterized in that the metal wire is self-heated by energization or electromagnetic induction. In the invention according to claim 9, wherein the metal wire has a composite rate of the second metal sheathing material in the transverse section thereof. In the invention according to claim 10, wherein the metal core wire has an electrical resistivity at room temperature of 5 μΩ・ Nickel or nickel alloy, chrome or chromium alloy, titanium The catalyst carrier as described above, comprising at least one of titanium, a titanium alloy, iron, and an iron alloy.

  The invention according to claim 11 relating to the catalyst product is such that predetermined catalyst particles are supported on the catalyst carrier according to any one of these, and the invention according to claim 12 is characterized in that the catalyst particles In the invention according to claim 13, wherein the oxide layer is formed of an aluminum alumite layer and is supported in at least one of the catalyst carriers. The catalyst product is formed by encapsulating the entire surface except for a portion to be a connecting portion for electrical wiring.

  Furthermore, the invention according to claim 14 is configured such that the catalyst product is incorporated in a pipe or a housing container having one opening leading to an internal flow path through which the fluid to be treated flows down along the longitudinal direction thereof and the other opening. The catalyst module is configured to be capable of self-heating the metal core wire by supplying electricity to the metal wire through the connection portion for wiring. The invention according to claim 15 is directed to an aromatic compound. The catalyst module as described above, which is used for hydrogenation reaction or dehydrogenation reaction of a hydrogenated derivative of the aromatic compound.

Effect of the invention

  According to each invention of the catalyst carrier of the present invention, the catalyst product using the catalyst carrier, and the catalyst module, the catalyst carrier as the constituent material has an opening width drawn by the metal wire when projected in the axial direction. Since (H) is a coiled wire with a deformed coil shape that has been amplified more than twice the equivalent wire diameter of the metal wire, when using it as a catalyst product or further as a catalyst module, In the cross section of the piping container, etc., the distribution density of the metal wire of the coil wire body and the catalyst substance supported on the coil wire is improved, and the contact opportunity of the fluid to be treated is increased, so that the catalytic reaction is greatly improved. You can plan.

  Moreover, the shaping | molding can also be implemented with a various method and form, and since the obtained coil wire can be handled similarly to the conventional coil goods, the special design change accompanying the use is not required. Accordingly, the increased surface area of the metal wire and the performance improvement due to the response of the reaction is brought about by heating the surface by means such as direct current heating.

    FIG. 1A is an external view showing an example of a catalyst carrier according to the present invention, FIG. 1A is a perspective view thereof, FIG. 1B is a plan view seen from the BA direction of FIG. 1A, and FIG. 1B is a side view seen from the Bb direction. is there.     It is a side view of what is based on the said catalyst support | carrier of the coil wire body by another form as an example of the catalyst product which concerns on this invention.     It is an expanded sectional view which shows the A-A 'cross section of FIG.     It is a microscope picture which shows an example of the metal wire of composite structure.     It is a microscope picture which shows the longitudinal cross-section of a metal wire provided with an oxide layer.     It is an enlarged view which shows the porous structure formed in an oxide layer.     It is a microscope picture which shows an example of the porous surface state by an Example.     1 is a schematic configuration diagram of an example of a hydrogen storage / generation system using a platinum-supported alumite clad metal fine wire catalyst for hydrogenation / dehydrogenation reaction.     It is sectional drawing of one form explaining the effect | action of a catalyst module.     It is a cross-sectional view which shows the other form of a catalyst module.

DESCRIPTION OF SYMBOLS 1 Catalyst support | carrier 2 Metal wire 2A Metal core wire 2B Metal exterior material 3 (13) Coil wire 4 Spiral groove 4a Spiral protrusion 5 (5A, 5B) Electrical connection part 8 Oxide layer A1 Catalyst product A2 Catalyst module D1 Virtual outside Diameter D2 Virtual inner diameter X Catalytic substance Y Axis H Opening width

Hereinafter, preferred embodiments of the present invention will be described with reference to the accompanying drawings.
The catalyst carrier (hereinafter also simply referred to as carrier) 1 according to the present invention is composed of the coil wire 3 of the metal wire 2 as described above, and the coil shape is projected in the direction of the axis Y of the coil wire 3. Amplifying the opening width (H) between the virtual outer diameter (D1) and the virtual inner diameter (D2) drawn by the metal wire 2 to be twice or more the wire diameter (d) of the metal wire 2 Features.

As an example, in FIGS. 1A to 1C, each coil shape of the coil wire 3 is continuously wound in an elliptical shape or a flat non-circular shape, and the winding direction is a predetermined azimuth angle (α). FIG. 1A is a perspective view thereof, FIG. 1B is a plan view seen from the direction of the arrow Ba in FIG. 1A, and FIG. 1C is seen in the axis Y direction of the arrow Bb direction. It is a side view.

  And in the coil wire body of each of the figures, the drawn opening width (H) is shown to be amplified to about 5 times the equivalent wire diameter (d) of the metal wire 2, and the formed coil shape is It is a non-circular shape that is substantially flattened as if a normal circular coil is slightly crushed, and the molding direction is the second, third,... Nth from the first coil portion. By changing with the azimuth angle (α), the spiral outer surface (D1), the virtual inner diameter (D2), and the coil body have a spiral stepped spiral groove 4 over its entire length, and a spiral ridge formed by its overhang. 4a is formed.

  In order to have such a spiral stepped surface shape and the azimuth angle (α), in this embodiment, as shown in FIG. 1C, each coil shape is, for example, a wide chestnut shape close to an elliptical shape or a flat shape. A flat shape having a slight roundness and a slight divergence angle, and having a coil width (Cw), a coil height (Ch), and a predetermined curvature bend r. The adjustment of the coil shape can be arbitrarily set. For example, in order to increase the opening width (H), the Cw / Ch ratio of the coil shape is preferably at least twice, for example, about 2 to 20 times, more preferably It is recommended to flatten at a ratio of 3 to 15 times. Conversely, in addition to such a flat shape, for example, a shape having a relatively small ratio of coil width Cw / coil height Ch, such as a slightly rounded triangular shape, square shape, pentagonal shape, etc., can be used. In such a case, it is desirable that the number of sides be as small as possible.

  Here, with respect to the opening width (H), for example, when the arbitrary cross section of the coil wire body 3 is viewed as shown in FIG. 1C, that is, when projected (perspectively) in the axis Y direction, It is indicated by a width dimension (H) between the outermost imaginary line (D1) to be drawn and the innermost imaginary line (D2) obtained on the same axis. However, when the opening width is not constant, an average value of several points arbitrarily measured is used.

  In the present invention, the opening width (H) differs depending on the wire diameter (d) of the metal wire 2 used for it and the size of the coil shape to be formed and the shape ratio, but is more than twice the wire diameter d of the metal wire 2. Yes. If it is 2 times or less, it is difficult to expect a sufficient effect for the fluid to be treated to use effectively when it is used, and it is usually set to about 2 to 20. In particular, in the case of a flat coil body as shown in FIG. 1C, the ratio can be set larger. However, in the case where the size is increased to exceed 20 times, the carrier 1 itself is increased in diameter and increased in size, and conversely, in order to reduce the size of the coil, the curvature diameter of the coil bending portion is reduced. As r is reduced, the metal wire 2 is also broken. In order to prevent such breakage, it is preferable to set the radius of curvature r of the coil-formed bent portion to be at least 5 times the wire diameter d of the metal wire 2. Further, in the case of a coil shape that does not substantially have a virtual inner diameter (D2) as shown in FIG. 2, the opening width (H) is indicated by a width dimension to the center point of the coil wire body.

The metal wire 2 used for the coil wire 3 finally carries the catalyst substance X on its surface, and its cross-sectional shape and wire diameter can be arbitrarily set, but in general, like a normal wire wire A wire with a circular cross section is adopted. However, any other non-circular wire rod such as an elliptical elliptical line, a triangular line, a strip line, a square line, or a star line can be used. In particular, a multi-sided wire rod such as a round wire shape, an ellipse, or a star shape has a remarkable effect of increasing the surface area, and as a result, the efficiency of accommodating the catalytic substance X can be increased. Thus, in the present invention, since the metal wire includes a deformed wire having a non-circular cross section, the wire diameter display in that case is based on, for example, an equivalent conversion wire diameter (d) calculated from the cross-sectional area. The equivalent wire diameter (d) is, for example, 1 mm or less, more preferably a thin wire of about 0.2 to 0.8 mm. However, the present invention is not limited to this.

  The coil wire body 3 of this embodiment is a non-circular coil shape flattened as described in FIGS. 1A to 1C, and by changing the direction of each coil shape by a predetermined azimuth angle (α), The coil body is formed of a deformed coil wire body having a spiral groove 4 extending in a spiral staircase shape along the axis Y direction of the coil wire body and a protrusion 4a formed therewith.

  By setting the azimuth angle (α) to about 5 to 60 °, for example, a gap Cs is formed between the metal wires 2 as shown in FIG. 1C, for example. The gap Cs promotes free inflow of the fluid to be treated, and the spiral groove 4 is formed with an inclination angle (θ) of, for example, 20 to 80 ° in a plan view with respect to the axis Y. Such spiral grooves 4 and spiral ridges 4a are formed in the cross section of the metal wire 2 when the spiral grooves 4 and the spiral ridges 4a are set inside a predetermined pipe or housing container as shown in FIGS. The apparent occupied volume ratio occupied by can be increased. And when the to-be-processed fluid supplied flows down, more effective contact is aimed at by the multistage spiral groove 4 or the spiral protrusion 4a, and as a result, the catalytic reaction is promoted, and the to-be-processed fluid Can circulate between the gaps Cs to achieve smooth processing. In addition, when a plurality of coil wire bodies 13A, 13B,... Are arranged side by side, positioning (arbitrarily rotates) so that they partially overlap each other, thereby promoting overall reduction in the amount of space as a catalyst module. There are also advantages. The preferable said intersection angle ((theta)) is designed by 30-70 degrees, More preferably, it is 40-60 degrees.

Next, the 2nd form of such a coil wire 3 is shown in FIG.
In this form, the shape of the formed coil is circular, but the coil center point is wound while sequentially decentering so as to draw a circle, for example, so that the same spiral groove as in the case of the coil wire of the first form is used. 4 and spiral ridges 4a are formed. In this embodiment, the virtual outer diameter (D1) is approximately twice the coil diameter of each coil portion, so that the virtual inner diameter (D2) is not substantially seen. In this case, the opening width (H) is ½ of the virtual outer diameter (D1). If necessary, a virtual inner diameter (D2) can be provided in the same manner as in the first embodiment by adjusting the diameter of the formed coil to be decentered, and can be set by arbitrary dimensional adjustment as necessary. The size and shape of the eccentric dimension are arbitrary, and other than circular shapes are possible. As in the second embodiment, the coil wire configured to shift the center point of each coil is an eccentric type coil wire. Call it.

  The catalyst carrier 1 according to the present invention is according to the first embodiment of the system in which the coil shape is changed to a non-circular shape and the winding azimuth angle (α) is changed. Although the coil shape is circular, there are various types, such as a second form using an eccentric coil wire body that decenters the center point, and (3) a combination form that combines the first form and the second form as appropriate. Provided is a support for carrying the catalyst which can be implemented in the form and which has improved properties.

  Such an irregularly shaped coil wire can be directly formed by a fine pin adjustment by a spring forming machine such as a normal coil spring, a method by winding around a predetermined shaped tool, and a normal same diameter. The coil wire-shaped coil wire 3 can be partially pressed and deformed in a spiral shape with a roller, a press or the like. In addition, when the coil wire is relatively short, for example, it is not such a deformed shape, and its winding diameter is simply changed to a conical shape, a drum coil shape, or a bellows coil shape along its longitudinal direction. It can also consist of things. However, when there are a plurality of them, it is necessary to make the coil shape in which the height position of the uneven shape is adjusted in advance. However, the spiral coil wire body has an advantage that it can be freely set by rotation adjustment. .

  The specification design of the coil wire body 3 such as the winding method, its configuration, and dimensions can be appropriately set according to the purpose of use, the device used, the installation space, the design performance, and the like. For example, as shown in FIG. 9 and FIG. 10, when one or more are incorporated in a predetermined pipe, the outer diameter D1 is 30 mm or less, for example, about 5 to 15 mm, and the length is 5 to 500 mm. It is wound with a molding dimension of about. In addition, the winding pitch (P) is usually 1.3 times or less of the equivalent wire diameter (d) of the metal wire 2 as a closely wound coil wire body, so that the handling and multiple wires are adjacent to each other. In the arrangement, the coil wire on the other side can be prevented from being entangled, the assembly workability in the apparatus is improved, and the thermal efficiency associated with the heat generation is also improved in terms of performance.

Further, as the metal wire 2 in the case where the catalyst product by the coil wire body 3 is self-heated to a predetermined use temperature by, for example, electrical conduction or electromagnetic induction, for example, the electrical resistivity at room temperature is 5 μΩ · A low expansion material having an electric characteristic of cm or more (about 5 to 200 μΩ.cm) and a thermal expansion coefficient of 20 × 10 ⁻⁶ / ° C. or less (however, a temperature of 0 to 100 ° C.) is selected. As a result, the use performance is improved, and specifically, a single metal wire made of the following metal material or a composite wire as illustrated in FIGS. it can.

    The composite wire is composed of the metal core wire 2A having the characteristics selected for the self-heating, and the surface covered with the second metal sheathing material 2B, and the coil itself as a whole. It is adjusted to have a predetermined elastic strength that enables the shape of the wire body to be maintained. The metal core wire 2A (in the case of a single wire, metal wire 2) includes, for example, a metal material such as stainless steel, nickel or nickel alloy, chromium or chromium alloy, titanium or titanium alloy, aluminum or aluminum alloy, tungsten or tungsten alloy, etc. Is used.

  As a more preferable alloy composition, for example, Cr: 15 to 25 wt%, Ni + Co: 55% or more, C: 0.15% or less, Si: 0.5 to 1.5%, Mn: 2.5% or less JIS-NCH1 to NCH2 containing 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 In addition to JIS-FCH1 and FCH2 made of Al: 2 to 6% and the balance Fe and inevitable impurities, the nickel material is, for example, Ni: 99 wt% or more of N200 material, in particular, aluminum whose heat generation characteristic is an exterior material In addition, it is excellent in workability of small diameter machining. The strength is preferably that having a tensile strength of about 300 to 600 MPa, for example.

    On the other hand, the case where, for example, an aluminum metal layer (also simply referred to as an aluminum layer) 7 is used as the metal sheathing material 2B covering these metal core wires 2A will be described. The aluminum is anodized to form an alumite (oxide layer) layer 8 having a porous structure as shown in FIGS. 5 to 7 on the surface. In particular, this is suitable for supporting a predetermined catalytic substance X in the porous structure.

    An alumite layer is formed by, for example, electrochemical treatment in a predetermined electrolytic solution and heating and baking at, for example, about 350 to 600 ° C., as disclosed in, for example, JP-A-2-144154 and JP-A-8-246190. Implemented in the process. Although the details of the generation phenomenon are omitted, it is said that 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 a porous structure. .

  FIG. 6 is an enlarged schematic view of an example of the porous structure, for example, a mesoporous structure in which a number of fine bottomed pores As distributed in a turtle shell shape are formed in the thickness direction. For example, it has a bottomed cylindrical shape having a fine opening with an inner diameter of about 10 to 100 nm, preferably 30 to 50 nm, and a predetermined length (L) of 500 μm 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 As and post-plowing treatment.

  The alumite layer 8 thus obtained functions as an electrically non-conductive insulating coating, and the catalyst carrier 1 covered with this insulating coating is used for other members (other coil wire bodies and housings) at the time of use. Electrical short circuit due to contact with containers, etc.) can be prevented. For this reason, the convenience that can be used without taking special insulating means, and the porous structure is very fine and hard, and the catalyst substance X is supported on the inner surface of the pore As as shown in FIG. Therefore, it has the advantage that it can be detached by contact with other members or friction in its use, or deformation or sealing of the pores can be prevented.

  These anodized layers 8 can be formed, for example, by oxidizing the exterior material 2B such as aluminum. The aluminum is combined with the surface of the metal core wire 2A by, for example, plating or clad technology, for example, the core wire 2 It can also be formed by forming itself with a metal material containing aluminum, and laminating aluminum elements on the surface thereof by, for example, precipitation heat treatment, which is not exemplified.

  The composite ratio of the metal sheathing material 2B (including the alumite layer) in the metal wire 2 is, for example, a ratio of [volume of (alumite layer + aluminum layer) / volume of metal wire] is 5 in consideration of the variation. It is preferable to set it to be ˜40%. When the volume ratio is less than 5%, it is difficult to obtain a sufficient thickness of the alumite layer. Conversely, when the volume ratio is set to be larger than 40%, the production efficiency is lowered, and there is a problem caused by the thermal influence during use. It tends to cause deterioration of strength characteristics. More preferably, the composite rate is 8 to 20%, and the thickness of the exterior material 2B (aluminum layer 7) is preferably adjusted to be, for example, 0.2 mm or less, preferably about 10 to 100 μm. .

    By the way, since the alumite layer 8 is generally inferior in toughness and easily cracked due to bending deformation or the like, the metal wire 2 is usually formed in advance into a coil wire 3 having a desired shape prior to the forming process. It is preferable. Thereby, cracks and crack peeling of the alumite layer (oxide layer) accompanying bending can be prevented.

FIG. 2 not only shows the shape of the coil as the carrier 1 but also includes the structure as the catalyst product A1, and the metal wire material is substantially formed without providing the alumite layer 8 at both ends of the coil wire 3. 2 are provided, and the alumite layer 8 further carries a catalyst material X.
These connecting portions 5A and 5B are portions for wiring connection for self-heating by the external power source V via the conducting wire 6 when they are used, and the exterior material 2B or metal over the necessary length as shown in FIG. The core wire 2A is exposed, and the treatment is performed by, for example, a method of masking so that the portion is not treated during the alumite treatment, or by removing by a polishing process after the treatment. In the present embodiment, the case where the metal sheathing material 2B is mainly made of aluminum has been described. However, the present invention is not limited to this, and various metal materials such as Mg, Ti, Ta, and Zn that form a similar oxide layer can also be used. In FIG. 1, only the wound state of the formed coil is described as the catalyst carrier, but this is treated in the same manner as in FIG. 2 and used as a catalyst product.

  Next, the carrier 1 thus obtained becomes a catalyst product A1 by carrying a predetermined catalyst substance X on the surface thereof, and the type and amount of the catalyst substance X are variously selected according to the purpose of use. For example, platinum, rhodium, rhenium, nickel, zirconium, titanium, zinc, magnesium, molybdenum or tungsten salts are selected, and water, ethanol or methanol solutions using their hydrochlorides, nitrates, oxalates and oxyacid salts From the above, the carrier having a porous alumina surface layer can be impregnated and supported in the same or sequential steps. Further, the present invention includes the catalyst material X supported directly on the metal wire 2 without the alumite layer 8 interposed therebetween.

  As for the catalyst material loading technology, various methods have been known and widely implemented. For example, when a platinum solution containing platinum is applied, a supporting method in which it is applied to the porous anodized layer 8 and pressed into the bottomed pores As can be recommended. Examples of the platinum solution used in this step include haxachloroplatinum (IV) acid hexahydrate, dinitrodiammineplatinum (II) nitric acid solution, hexaammineplatinum (IV) chloride solution, tetraammineplatinum (II) hydrochloride solution, and the like. Are preferably used. In addition, platinum or a transition metal salt solution is prepared by simultaneously immersing platinum or transition metal salt by a method such as immersion, dropping, coating or spraying in a predetermined temperature range while energizing an alumite clad metal wire or heating an electromagnetic dielectric. Or it can carry | support sequentially.

In addition, metal carbonyl compounds such as Pt (CO) ₂ Cl, Rh ₄ (CO ₁₂ , Ni (CO) ₄ , Re ₂ (CO) ₇ , CpTiCl ₂ (Cp = cyclopentadienyl), Mo (CO ) It can be supported by a chemical vapor deposition method using _6, etc. After supporting, stepwise firing in a temperature range of 250 to 600 ° C. in an oxygen-containing atmosphere, and further in a hydrogen gas atmosphere The activation treatment is preferably carried out by raising the temperature stepwise in the temperature range of 100 to 450 ° C. Platinum and / or transition metal by hydrogen activation treatment or reduction treatment with a reducing agent such as hydrazine or boron hydride. It is possible to prepare an aluminum clad metal fine wire catalyst supporting platinum, platinum and transition metal alloys. For example, the supported amount with respect to the metal clad metal wire is 0.01 to 10% by weight, and preferably 0.1 to 5% by weight. It is 1 to 10, preferably 0.1 to 0.5, and 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 product A1 thus configured is used as a catalyst module 10 accommodated in predetermined piping or a housing container 11 as shown in FIGS. 9 and 10, for example. The catalyst module 10 can be widely employed as various catalyst devices for other reactions, for example, for exhaust gas, for example, for hydrogenation reaction to an aromatic compound or for dehydrogenation of a hydrogenated derivative of the aromatic compound. .

  In the hydrogen reaction product, for example, methylhexane (MCH) sprayed fluid supplied from the introduction side is heated by some method, or inside the coiled catalyst product configured to be self-heated to a predetermined temperature. By flowing in, the fluid to be treated is converted into hydrogen gas by the catalyst substance X on the metal wire and taken out, and the reaction is performed as follows.

CH ₃ C ₆ H ₁₁ ＣＨ CH ₃ C ₆ H ₅ + 3H ₂

  In the catalyst module A2 of FIG. 9, two catalyst products 13A and 13B are set at a predetermined arrangement interval in a predetermined pipe 10, for example, and both ends thereof are connected by an electrical connection portion 5 having no anodized layer as shown in FIG. By connecting to the external power supply V via the wiring 16 to be configured, it can be adjusted to a target use temperature (for example, 200 to 600 ° C.). The catalyst products 13A and 13B are rotationally arranged so that the spiral grooves 4 and the spiral ridges 4a are fitted, and are held between the upper and lower perforated plates 12A and 12B, and the external wiring 16 is the wall surface of the container 10 It is considered that the fluid to be treated and the generated hydrogen do not leak by sealing with a predetermined filler through the extraction hole 11 provided in the container. Similarly, in FIG. 10, five catalyst products are arranged so as to partially overlap each other and are electrically connected to each other.

    According to the performance comparison by the present inventors, the opening width (H) can be freely set by selecting the formation method as compared with the catalyst product using the coil wire body of the conventional close contact coil of the same diameter. In addition, a high effective area ratio of several to several tens of times can be provided even by simple comparison within a certain cross section. For this reason, the supplied fluid to be treated is subjected to an effective contact reaction while freely flowing through the formation gap Cs of the coil wire body having a wide and porous distribution in the cross section of the predetermined container 10. Thus, the unreacted fluid (that is, the supply fluid) that is released while the fluid to be treated is in an untreated state is greatly reduced to, for example, 50% → 5% or less of the conventional type. At the same time, even when a plurality of coil wire bodies are used by such a coil structure, the spiral grooves 4 can be arranged so as to overlap each other by rotational fitting between the spiral grooves 4, thereby reducing the overall arrangement area and saving the module. Therefore, it is possible to provide a small catalyst module excellent in catalyst reactivity and operability without causing a substantial increase in flow resistance.

The performance evaluation of the carrier product and the catalyst module of the present invention is performed, for example, by the hydrogen storage / hydrogen generation system 20 shown in FIG.
The system 20 adds hydrogen to an aromatic compound (eg, toluene) to store the hydrogen as a hydrogenated derivative, organic hydride (eg, methylcyclohexane), and dehydrogenates the organic hydride to form an aromatic compound. It is an apparatus that can decompose hydrogen into hydrogen. The system 20 mainly includes a reactor 22, a tank 23 containing an aromatic compound, a tank 24 containing an organic hydride, and a tank 25 for storing a reaction product generated in the reactor 22. I have.

  The reactor 22 carries a predetermined platinum catalyst for hydrogenation / dehydrogenation, for example, on a heating means 26 (for example, an electromagnetic dielectric heater) and a catalyst carrier that is configured to be self-heated and formed in a coil wire. The coil-shaped catalyst product (hereinafter simply referred to as “coil catalyst”) 27 is provided and stored in a predetermined container. As the coil catalyst 27, for example, a flat coil wire or an eccentric coil wire is used, which is modularized as shown in FIG. 9. A pipe 28 for supplying a liquid raw material is provided above the reactor 22. The fluid to be processed is supplied from the spray nozzle 29 penetrating through the tip, and the fluid to be processed is supplied from the tank 23 or 24 via each pipe 28, the three-way valve 32, and the variable valve 30.

  The three-way valve 32 and the bottom of the tank 23 are connected by a pipe 31, and a liquid feed pump 33 is connected in the middle of the pipe 31. The three-way valve 32 and the bottom of the tank 24 are connected by a pipe 34, and a liquid feed pump 35 is connected in the middle of the pipe 34. The three-way valve 32 opens only between the tank 23 and the reactor 22, opens only between the tank 24 and the reactor 22, or closes between the reactor 22 and the tanks 23, 24. It is a valve that can be switched to.

  A hydrogen supply pipe 36 passes through the reactor 22. A valve 37 is connected in the middle of the pipe 36. A hydrogen supply means (not shown) is connected to the tip of the pipe 36 outside the reactor 22. A pipe 38 is connected between the vicinity of the bottom of the reactor 22 and the top of the tank 25. A pump 39 and a cooler 40 are connected in the middle of the pipe 38. A pipe 41 for exhausting a gas such as hydrogen is connected above the tank 25.

  When hydrogen is stored in the form of organic hydride, the operation is performed in the following procedure. For heating, for example, the heating means 26 or the coil catalyst 27 made of platinum-supported anodized clad metal wire by self-heating is energized and heated. Next, the valve 37 is opened, and hydrogen is introduced into the reactor 22 via the pipe 36. At this time, it is preferable that the pump 39 is turned on and hydrogen is allowed to flow from the reactor 22 to the outside through the pipe 41. Next, the three-way valve 32 is adjusted to open only the path between the tank 23 and the reactor 22, the liquid feed pump 33 is turned on, and the aromatic compound in the tank 23 is directed to the reactor 22. send. The valve 30 is opened at regular intervals, and the aromatic compound is sprayed from the spray nozzle 29 at regular intervals. Along with this, a hydrogenation reaction between the atomized aromatic compound and hydrogen occurs on the surface of the coil catalyst 27 in the fluid to be treated, and organic hydride is generated. The organic hydride enters the tank 25 through the pump 39. The gaseous product passing through the pipe 38 is cooled by the cooler 40 and stored as a liquid in the tank 25. Since hydrogen does not liquefy even when cooled by the cooler 40, it is exhausted to the outside through the pipe 41.

  On the other hand, when hydrogen is generated by dehydrogenation of organic hydride, the operation is performed according to the following procedure. First, the platinum-supported alumite clad fine wire catalyst 27 is heated using the heating means 26. Next, the pump 39 is turned on.

Only the path between the tank 24 and the reactor 22 is opened through the three-way valve 32, the liquid feed pump 35 is turned on, and the organic hydride in the tank 24 is sent toward the reactor 22. The valve 30 is opened at regular intervals, and the organic hydride is sprayed from the spray nozzle 29 at regular intervals. Along with this, a dehydrogenation reaction of the sprayed organic hydride occurs on the surface of the coil catalyst 27, thereby generating hydrogen and an aromatic compound. Aromatic compounds enter the tank 25 through the pump 39. The gaseous aromatic compound passing through the pipe 38 is cooled by the cooler 40 and stored as a liquid in the tank 25. Hydrogen is discharged outside through the pipe 41.

  In this embodiment, the coil catalyst is formed by a platinum-supported alumite clad wire for hydrogenation reaction of aromatic hydrocarbon / dehydrogenation of hydrogenated derivative, but only hydrogenation reaction of aromatic hydrocarbon is performed. It can also be used for the dehydrogenation of hydrogenated derivatives (organic hydrides). In addition, a plurality of the composite catalysts 1 in the system are housed in, for example, a pipe or widened housing container 12 as shown in FIG. 7 so that the raw material fluid flows into the internal flow path. It is used as a self-heatable module by connecting to an external power supply, and such modularization allows easy handling.

  Thus, the fluid to be treated (MCH pulse spray) causes a catalytic reaction by the coil catalyst while being supplied from one opening on the supply side, for example, in a sprayed state, and is discharged out of the system from the other discharge port 15b. The catalyst module is arbitrarily configured as necessary. Moreover, when applying this as hydrogen fuel of an internal combustion engine, it is also preferable that the side surface of the reactor vessel 12 is connected by piping so as to be indirectly heated by, for example, exhaust gas heated by the engine.

Hereinafter, although the more optimal example of the composite catalyst which concerns on this invention is further demonstrated, this is an example and does not limit this invention at all.
<< Product 1 >>

(Manufacture of aluminum clad coil wire)
An aluminum clad wire (12 mm diameter) encapsulated in a nickel (purity 99%) wire having an electric heating function and encapsulated with an aluminum (purity 99.9%) strip is used as a base material, and this is drawn at a temperature of 600 ° C. The aluminum clad metal fine wire having an aluminum layer with a wire diameter of 0.45 mm and an average thickness of 30 μm was obtained while repeating the heat treatment. FIG. 4 shows an enlarged covering state of the cross section of the clad fine wire.

    This thin clad wire has sufficient strength with a tensile strength of 420 MPa, and is set in a coil spring molding machine. The coil shape has a coil width (w) of 12 mm and a coil height (h) of 5 mm as shown in FIG. 1C. By forming a flat chestnut-shaped close-contact coil wire having a curvature on both sides and displacing the azimuth angle (α) of each coil portion by 25 °, the coil body portion has an inclination angle with the axis Y ( Spiral grooves (spiral ridges) having a θ) of 55 ° were formed.

The coil wire has an imaginary outer diameter of 12 mm, an imaginary inner diameter of 3 mm, and an overall length of the coil body of 120 mm. With this configuration, the clad fine wire with respect to the opening width (H) of the imaginary inner and outer diameters The ratio of to the wire diameter d was about 10 times, and a total of 20 spiral protrusions were formed by the spiral groove over the entire length of the coil wire. The substantial volume ratio of the thick cylindrical body due to the opening width within a predetermined volume formed by the virtual outer diameter of the coil wire body is 93.8%, and the metal wire material is distributed over a substantially wide area and in many stages. As a result, a more reliable contact of the fluid to be treated flowing down the interior is possible.
<Product 2>

As shown in FIG. 2, the center point is set so that the coil diameter of each coil portion is 7 mm and the overall configuration outer diameter (virtual outer diameter D1) is 12 mm by the aluminum clad thin wire used in the product 1. An eccentric coil having an opening width (H) of 4 mm was obtained by performing eccentricity. The ratio of the wire diameter of the clad fine wire to the opening width (H) is 8.8 times, and in the same manner as in the first embodiment, the clad fine wire is formed in the coil body portion in the form of spiral ridges in total 24 pieces. Could be formed. Moreover, the area ratio which the said opening width part occupies in the predetermined cross section of the cylindrical body by the virtual outer diameter D1 of the coil wire body is 97%, and a very high thing was obtained.
<Product 3>

  Using a soft metal thin wire of an iron-chromium alloy (FCH1 / wire diameter of 0.40 mm) for electric heating, this was wound around a twisted rod-shaped tool having a cross section ellipse shape of width 7 mm and thickness 2.3 mm, and a virtual outer diameter of 8 mm, A coil wire body having a virtual inner diameter of 2 mm and a spiral protrusion having a tilt angle θ of 58 ° and a length of 100 mm was obtained. There is no disconnection of the thin wire in the forming process, the opening width H is 3 mm, 7.5 times the wire diameter of the metal thin wire, and the predetermined cross section of the cylindrical body by the virtual outer diameter D1 of the coil wire body The area ratio occupied by the opening width portion was 93%.

Then, the coil wire was subjected to a precipitation treatment in which the Al element in the fine metal wire was deposited in a layered manner on the surface thereof by a predetermined precipitation heat treatment. The obtained coiled wire was covered with an Al coating layer in which Al gradually increased toward the surface side, and had a good surface state without peeling.
<Comparative product 1>

  As a comparative coil wire, a general close-contact coil wire having a coil outer diameter of 8 mm and a coil total length of 120 mm was manufactured from the aluminum clad fine wire used in the product 1. This comparative coil wire is a cylindrical coil-shaped product that does not have the spiral groove or spiral ridge, and the opening width (H) is substantially the wire diameter itself of the clad wire, and the coil outer diameter. The area ratio occupied by the thin clad wire in a predetermined cross section with a cylindrical body is as low as 21% because the inner area of the coil shape is not reflected, which is significantly inferior to the above-mentioned respective products. .

Next, each coil wire was subjected to an alumite treatment. In the treatment, an alumite layer having a thickness of about 10 to 30 μm was formed on the entire surface excluding both ends of each linear body to obtain a total of four types of catalyst carriers. In the anodizing treatment, each coil wire was anodized under a condition of a current density of 50 to 70 A / m ² at 35 ° C. in a 4% wt oxalic acid aqueous solution, and then immersed in the same kind of oxalic acid treatment solution for 6 hours. The acid treatment was carried out as it was, and the pore size widening treatment was carried out, followed by drying in the atmosphere. Next, after baking at 300-450 ° C. for about 1 hour, hydration at 80 ° C. or higher for about 2 hours, drying, and further baking at 500 ° C. for 3 hours. A heat resistant porous alumina film was formed. 5 and 7 show micrographs of the aluminum clad wire according to Example 1 as an example.

The apparent area ratio of each catalyst carrier thus obtained was as follows: Example 1 (A): 93.8%, Example 2 (B): 97%, Example 3 (C): 93.0%, Comparative product 1 (D): 21%, and each of the implemented products had a larger volume occupancy rate than the comparative product, and the effect could be increased. In addition, the coil wire bodies of the respective products are formed with pores As that allow the fluid to be treated to flow sufficiently by the distribution of the fine metal wires in the structure, and there is no problem of increasing the flow resistance of the fluid to be treated. It was not possible.
(Catalyst loading adjustment)

Next, for the coil wires of the products A and B and the comparative product D, a catalyst supporting treatment for making a catalyst product was performed.
The catalyst material was platinum, and 0.02 gr of chloroplatinic acid H ₂ PtCl ₆ 6H ₂ O was dissolved in 10 cc ethanol to prepare a chloroplatinic acid solution. Each coil wire was immersed in this, and platinum was supported in the porous structure on its surface, and then heated to a predetermined temperature and dried to obtain three types of target supported catalyst products.

The catalyst products A, B, and D thus supported on the catalyst were incorporated as modules of the hydrogenation reaction and dehydrogenation reaction apparatus shown in FIG. 8, respectively, and methylcyclohexane was dehydrogenated. A predetermined temperature of 310 ° C. at a spray cycle of 10 and 20 seconds for methylcyclohexane in a nitrogen stream (flow rate 150 ml / min) spray cycle 0.5 seconds (single spray amount 0.39 gr) from a pulse type spray nozzle provided in the reactor The hydrogen generation rate and the toluene conversion rate of methylcyclohexane in the experiment using each catalyst heated in the same manner were analyzed and measured by gas chromatography.
<< Test Example 1 >>

Each of the test bodies A, B, and D was directly energized and heated with a predetermined amount of electricity to each coil wire body by a current / voltage stable power source outside the system. As a result, the catalyst products A and B, which are platinum-supported deformed coil products, had a methylcyclohexane conversion of 80 to 90% and a toluene selectivity of 80 to 100%, whereas the comparative products of the conventional type. In C, only about 1/2 or less performance was obtained, and the effectiveness of the deformed coil product according to the present invention was confirmed.
<< Test Example 2 >>

  Three catalyst products A using the coil wire body of the product 1 were prepared, and these were set in a pipe-made housing container having an inner diameter of 26 mm, and wired and assembled so that they could be heated in series. In the assembled state, the area ratio occupied by the catalyst product per cross-sectional area of the container is 68%, and in order to set three points in the same manner as the conventional comparative product C, the pipe has a large diameter of about 30 mm. As a result, the area ratio was greatly reduced to 4.5%. As described above, the distribution area ratio in which the carrier exists in the substantial flow-down direction of the fluid to be treated has an effect of about 15 times.

  The catalyst carrier, catalyst product, and catalyst module of the present invention bring about high functionality by increasing their constituent density, and are widely used in automobiles, ships, locomotive industries and chemical industries that use hydrogen as a fuel. Can be used.

Claims (15)

A catalyst carrier for supporting a catalyst substance,
A virtual outer diameter (D1) drawn by the metal wire, which is composed of a coil wire continuously wound from one side to the other by a metal wire, and the winding projects the coil wire in the axial direction. And an imaginary inner diameter (D2), the carrier width for the catalyst is formed into a deformed coil shape amplified to be twice or more the equivalent wire diameter (d) of the metal wire .     In the coil wire body, the coil center point is decentered from the first coil portion along the axial direction toward the Nth coil portion, so that a spiral groove or a spiral ridge is formed in the body portion of the coil wire body. The catalyst carrier according to claim 1, wherein     The coil wire is formed in a non-circular shape, and the non-circular shape has a winding azimuth angle (α) from the first coil portion toward the N-th coil portion. The catalyst carrier according to claim 1, wherein a spiral groove or a spiral ridge is formed in a body portion of the coil wire body by changing     The catalyst carrier according to claim 3, wherein the non-circular shape is an ellipse or a flat shape having a ratio (Cw / Ch) of a coil width (Cw) to a coil height (Ch) of 1.3 to 10 times. .     The inclination angle (θ) of the spiral groove or spiral ridge formed by the eccentricity of the center point or the winding with the winding azimuth angle (α) changed with respect to the axis Y of the coil wire body is 20 to 80 °. The catalyst carrier according to any one of claims 2 to 4.     The catalyst carrier according to any one of claims 1 to 5, wherein the opening width (H) is 3 to 15 times the equivalent wire diameter (d) of the metal wire.     The catalyst carrier according to any one of claims 1 to 6, wherein the coil wire is tightly wound at a pitch (P) that is 1.3 times or less the equivalent wire diameter (d) of the metal wire.     The catalyst carrier according to any one of claims 1 to 7, wherein the metal wire is a composite wire of a metal core wire that self-heats by energization or electromagnetic induction and a second metal sheathing material that covers the surface of the metal core wire.     The metal wire is compounded with a composite ratio of the second metal sheathing material in the cross section of 5 to 40%, and further provided with a porous structure made of an oxide of the metal sheathing material on the outer surface. The catalyst carrier according to claim 8.     The metal wire includes at least one of nickel or a nickel alloy, chromium or a chromium alloy, titanium or a titanium alloy having an electrical resistivity at room temperature of 5 μΩ · cm or more. A catalyst carrier as described in 1. above.     A catalyst product comprising predetermined catalyst particles supported on the catalyst carrier according to any one of claims 1 to 10.     The catalyst product according to claim 11, wherein the catalyst particles are supported in a porous structure of an oxide layer formed on an outer surface of the catalyst carrier.     13. The catalyst product according to claim 12, wherein the oxide layer is formed of an aluminum alumite layer, and encapsulates the entire surface except for at least a part of the catalyst carrier used as a connection part for electric wiring.     The catalyst product according to claim 13 is incorporated in a pipe or housing container provided with one opening leading to an internal flow path through which a fluid to be treated flows along the longitudinal direction thereof, and the other opening, and the wiring A catalyst module, wherein the metal wire is configured to be capable of self-heating by supplying electricity to the metal wire via a connecting portion.   The catalyst module according to claim 14, wherein the catalyst module is used for a hydrogenation reaction to an aromatic compound or a dehydrogenation reaction of a hydrogenated derivative of the aromatic compound.