JP6450247B2 - Catalyst carrier and catalyst member using the same - Google Patents

Description

  The present invention relates to a catalyst carrier and a catalyst member using the same, and more specifically, to increase the chance of contact between a fluid to be treated and a catalyst substance, and thus to efficiently promote a catalytic reaction, and to use the catalyst carrier. The present invention relates to a catalyst member.

  In the following Patent Document 1, the present applicant has proposed a catalyst member for hydrogenation reaction or dehydrogenation reaction. The catalyst member includes a coiled portion in which a metal core wire is formed in a coil shape, and a catalyst material supported on the surface of the coiled portion. Such a coil-shaped catalyst member is expected to have an effect of increasing the contact opportunity between the fluid to be treated and the catalyst substance, and thus enhancing the catalytic reaction due to the large surface area of the metal core wire.

  Further, when the metal core wire is simply coiled, the inside of the coil becomes a complete cavity, and the amount of catalyst supported per unit volume is limited. In Patent Document 2 below, a multi-layer catalyst member is proposed in which a second coil body is further inserted into the coil cavity.

JP 2011-245475 A International Publication No. 2012/90326

  In recent years, further improvement in catalyst efficiency has been demanded. For example, when used in a system for extracting hydrogen from a fluid to be treated as disclosed in Patent Document 1, in the case where the metal core wire is simply formed in a coil shape, the substantial catalyst loading is performed on the surface portion of the wound metal wire. However, the central portion is in a completely hollow state, so there is a limit to increasing the amount of catalyst supported. Moreover, in the close-contact coil product in which the coil wires to be wound are in close contact with each other, the flow of the fluid to be treated is hindered at the contact portion between the coil wires, and as a result, the fluidity of the fluid to be treated is reduced, which is favorable. It is difficult to obtain catalyst efficiency. In particular, when the catalyst members are arranged in multiple stages perpendicular to the flow direction of the fluid to be treated, the fluid flow becomes uneven between the upper stage side and the lower stage side, and it is difficult to obtain a stable catalytic reaction.

  Further, in the case of a multi-structure in which two or more types of coil bodies are inserted as in Patent Document 2, it is necessary to prepare each coil wire separately, which causes inventory management and cost increase.

  The present invention has been devised in view of the above circumstances, and a catalyst carrier that can further improve the efficiency of a catalytic reaction by further improving the contact opportunity between a fluid to be treated and a catalyst substance, and a catalyst member using the same. The main purpose is to provide

  The present invention is a catalyst carrier for supporting a catalytic substance on the surface, and has a main body portion in which a metal wire is wound in a coil shape, and the main body portion is adjacent to the coil wire in the coil axial direction. A contact portion that is in contact with each other and a non-contact portion that is spaced apart from each other are included.

In another aspect of the present invention, a spirally extending ridge portion and a spirally extending groove portion may be provided on the outer surface of the metal wire.

  In another aspect of the present invention, the metal wire may be a stranded wire in which at least two wires are twisted together.

  In another aspect of the present invention, the stranded wire may be twisted at a twist angle of 10 to 50 ° with respect to the axis of the stranded wire.

  In another aspect of the present invention, the stranded wire may have a length that is not more than 0.9 times the original length of each wire.

  In another aspect of the present invention, the wire may be formed from a non-straight single wire that has been previously two-dimensionally or three-dimensionally kneaded.

  In another aspect of the present invention, the metal wire may include a first wire serving as a core wire and a second wire wound spirally on the surface thereof.

  In another aspect of the present invention, at least one of the wires may include an aluminum metal wire having an alumite layer on the surface.

  In another aspect of the present invention, the aluminum metal wire may have a heating wire having an electric resistance of 5 Ω / m or more inside.

  In another aspect of the present invention, the catalyst carrier according to any one of the above and a catalyst material supported on at least a part of the surface thereof, the catalyst material supported on the surface of the metal wire. It can also be configured as a catalyst member.

  The catalyst carrier according to the present invention can efficiently distribute the fluid to be treated into the internal space of the coil main body extending in the coil axis direction. The catalyst carrier and the catalyst member according to the present invention include contact portions that are in contact with each other and non-contact portions that are separated from each other between coil wires adjacent in the coil axial direction. The contact portion serves to increase the winding density of the coil wire to increase the surface area per unit axial length of the main body, and thus to provide a large surface area for supporting the catalytic material in the catalytic reaction space. . On the other hand, the fluid to be treated can flow between the internal space and the external space of the coil through the non-contact portion. By such an action, the catalyst carrier and the catalyst member of the present invention can increase the chance of contact between the supplied fluid to be treated and the catalyst substance, and thus can greatly improve the catalytic reaction.

  Further, when the catalyst member is used by being arranged in multiple stages in a direction crossing the flow direction of the fluid to be treated, the fluid to be treated can freely flow through the non-contact portion. On the other hand, the contact portion achieves a constant winding pitch between the coil wires and provides a stable catalyst member.

Further, the contact portion and to a catalyst member comprising a non-contact portion, than those helically along the ridge and the groove in the twisted structure in its longitudinal direction, in comparison with those made of conventional single wire , The surface area can be further increased.

It is a perspective view of the catalyst member which shows one Embodiment of this invention. It is the principal part enlarged view. It is a top view of a metal wire. It is sectional drawing explaining an example of the one wire which comprises the metal wire of FIG. It is a perspective view of a catalyst member arranged in a planar shape It is a perspective view of the catalyst member of other embodiments of the present invention. (A) is a perspective view of the catalyst member which shows other embodiment of this invention, (b) is sectional drawing along the plane containing the axial centerline. It is a perspective view of the catalyst member which shows other embodiment of this invention. It is a schematic block diagram of the dehydrogenation reaction system of an Example.

Hereinafter, an embodiment of the present invention will be described with reference to the drawings.
FIG. 1 is a perspective view showing an example of the catalyst member 1 of the present embodiment. The catalyst member 1 of the present embodiment includes a catalyst carrier 2 and a catalyst material 3 supported on at least a part of the surface thereof. The catalyst carrier 2 of this embodiment uses a metal wire 10 made of a stranded wire in which two wires 11 and 12 are twisted at a predetermined pitch, and is coiled by winding this to a predetermined winding diameter. The main body 4 is shown.

  The catalyst member 1 is stacked and installed in multiple stages, for example, in a chamber (for example, see reference numeral 31 in FIG. 5) to which a fluid to be processed is supplied. As a result, the fluid to be treated is provided with an opportunity to come into contact with the supported catalyst material 3, and a predetermined catalytic reaction is performed. The application of the catalyst member 1 (and the catalyst carrier 2) of the present invention is not particularly limited, and is suitable for chemical reactions of all fluids to be treated (gas and liquid). In a preferred embodiment, the present invention, as shown in Patent Documents 1 and 2 above, is used for hydrogenation reaction of a fluid to be treated made of an aromatic compound or dehydration of a fluid to be treated made of a hydrogen derivative of an aromatic compound. Used for elementary reactions.

  A catalyst material 3 selected in advance is supported on the surface of the catalyst carrier 2. The catalyst material 3 is appropriately selected according to the chemical reaction of the fluid to be treated, and is not particularly limited. As the catalyst material 3 for the hydrogenation or dehydrogenation reaction, for example, one or more of platinum, rhodium, rhenium, nickel, zirconium, titanium, zinc, magnesium, molybdenum, tungsten salt and the like are preferable. The specific loading method and loading amount of the catalyst substance 3 can also be arbitrarily set with reference to, for example, Patent Documents 1 and 2.

  As shown in FIG. 1, the catalyst carrier 2 includes at least a main body 4 around which a metal wire 10 is wound in a coil shape. In the present embodiment, the one further including the non-coiled end portion 5 continuously on at least one side of the main body portion 4 is shown. For example, when the catalyst member 1 is energized and heated and used, the end portion 5 can be used as a wiring connection portion so that a predetermined electric circuit is formed.

  As shown in FIG. 2, the main body 4 includes a contact portion 7 in which the coil wires 6 are adjacent to each other and a non-contact portion 8 that is substantially spaced apart to form a gap in the coil axial direction X. It is formed including. Through the non-contact portion 8, the fluid to be treated is promoted to flow in and out of the coil (in the radial direction of the catalyst member 1), thereby contributing to improvement in catalyst efficiency. In the present embodiment, the coil shape is formed in a circular shape having the same outer diameter, but the present invention is not limited to this, and the coil shape may be wound in various modes.

  Patent Documents 1 and 2 propose supplying a fluid to be processed along the coil axis direction as a conventional coil-shaped catalyst member. However, in such a catalyst member, the helical pitch of the coil is made as small as possible from the viewpoint of increasing the surface area per unit volume and increasing the density of the catalyst material. In this case, the coil wires are in close contact with each other, and the flow between the internal space and the external space of the coil is substantially blocked. On the other hand, when the coil pitch is larger than necessary, it becomes difficult to arrange the catalyst material at a high density in a limited space. Further, if the coil wires are too far apart, for example, the heat generation efficiency is lowered and the heating temperature is likely to be uneven.

  This embodiment improves such a conventional coil-shaped catalyst member, and the coil wires 6 and 6 adjacent to each other in the coil axial direction X are formed while the metal wire 10 is coiled at a substantially small pitch. Are provided with an uneven surface having a contact portion 7 and a non-contact portion 8 in contact with each other. The contact portion 7 contributes to an increase in the surface area per unit length of the catalyst carrier 2 in the catalytic reaction space, and thus provides a large surface area for supporting the catalytic material 3 in the catalytic reaction space. On the other hand, the non-contact portion 8 can communicate fluids to be processed between the internal space and the external space of the coil.

As for the metal wire 10, the ridge part and groove part which make the said unevenness | corrugation are formed spirally along the longitudinal direction. Therefore, the surface area can be increased and the permeability of the fluid to be processed flowing in the orthogonal direction can be increased as compared with the case of using an ordinary metal single wire.

  In particular, when the main body 4 includes the contact portions 7 and the non-contact portions 8 alternately and repeatedly, the flow of the fluid to be treated is more complicated, and as a result, the fluid to be treated and the catalytic material 3 are effectively brought into contact with each other. It becomes possible. Particularly preferably, the contact portion 7 and the non-contact portion 8 are repeatedly arranged at equal intervals.

  As described above, the catalyst member 1 of the present embodiment greatly increases the chance of contact between the supplied fluid to be treated and the catalyst material while allowing the catalyst material 3 to be arranged at a high density, and thus efficiently catalyzes the catalyst. The reaction can be promoted.

As shown in FIG. 2, the metal wire 10 of the present embodiment forms a circumscribed cylinder 14 configured by twisting two wires 11 and 12, and the spiral ridges and A groove is provided. Further, the apparent diameter D substantially corresponds to the total dimension of the wire diameters of the wires 11 and 12. Although the stranded wire of this embodiment is comprised by the two wire rods 11 and 12, it is not restricted to this, Three or more may be sufficient and also about the twist structure, a single twist, a layer twist, Various structures such as double twist are not particularly limited, and various structures can be adopted.

  Such a stranded wire is coiled with a helical pitch P substantially equal to the wire diameter D (specifically, the outer diameter of the circumscribed cylinder 14) D, for example, and has a contact portion 7 and a non-contact portion 8. 4 is formed. The coil shape, coil diameter, and pitch P are not limited to this, and are arbitrarily set.

  For each of the wires 11 and 12 constituting the stranded wire, for example, a single wire (monofilament) is used. The single wire material of the present embodiment has a circular cross section, for example, like a general wire, but may have a cross sectional shape such as an ellipse, a triangle, a quadrangle, or a star, for example. good. The wire diameter of the single wire is not particularly limited, and can be variously changed according to demand. For example, for a hydrogenation reaction or a dehydrogenation reaction, a fine wire having an equivalent wire diameter of, for example, 1 mm or less, more preferably about 0.2 to 0.8 mm is particularly suitable. Note that the “equivalent wire diameter” for a wire is a wire diameter of a round wire having a cross-sectional area of the wire.

  Further, the single wire material may be, for example, a straight straight line, or a non-straight line that has been two-dimensionally or three-dimensionally kneaded in advance. In the latter case, since a gap is also formed inside the stranded wire, a more complicated distribution path can be provided.

  The front view of the metal wire 10 which consists of a twisted wire is shown by FIG. As shown in FIG. 3, it is desirable that the metal wire 10 is formed by twisting the wires 11 and 12 at a twist angle α of 10 to 60 ° with respect to the axis CL.

  The total length of the stranded wires in which the single wires are twisted together at the twist angle α is shorter than the initial length of each single wire used. In particular, the larger the twist angle α, the smaller the overall length of the stranded wire, and the greater the surface area per unit length. This means that the supported area of the catalyst material, and hence the supported amount, increases. From such a viewpoint, when the twist angle α is less than 10 °, the effect is not sufficient. When the twist angle α exceeds 60 °, the twist processing cannot be endured and causes troubles such as disconnection. More preferably, the twist angle α is 20 to 50 °, and the twisted wires are preferably twisted so as to be shortened to 0.9 times or less the original length of each of the wires 11 and 12. .

  FIG. 4 shows a typical cross section of a wire 11 constituting the metal wire 10 of the catalyst member 1 of FIG. Although not shown, the wire 12 is similar in cross section. In the present embodiment, at least the surfaces of the wires 11 and 12 are made of an aluminum metal 21 so that, for example, a predetermined alumite layer (oxidized compound layer) 22 for supporting a predetermined catalyst substance 3 is formed on the surface. Composed. In addition to what is entirely composed of aluminum metal, as shown in each of the above-mentioned patent documents and seen in FIG. 4, a composite structure including a core portion 20 made of a metal material that can further generate heat inside the aluminum metal 21. You may be comprised with a wire. A large number of pores s are formed on the surface of the alumite layer 22, and the catalyst material 3 is supported thereon.

  The core portion 20 preferably has an electrical characteristic capable of generating heat to a predetermined temperature by energization, for example. As such a core part 20, a stainless steel wire, nickel or a nickel alloy wire, chromium or a chromium alloy wire, titanium or a titanium alloy wire, tungsten or a tungsten alloy wire, etc. are employ | adopted, for example. In particular, the core 20 is preferably made of a material having an electrical resistivity of 5 (Ω · cm) or more, more preferably 5 to 200 (Ω · cm). Particularly, nickel, a nickel alloy wire, and a chromium alloy wire are It generates heat to a working temperature of 200 to 600 ° C. easily by direct energization or electromagnetic induction. This is useful for supplying large amounts of reaction heat to endothermic reactions such as those for dehydrogenation of aromatic hydrogen derivatives.

  More preferable nickel alloy wire for the core 20 is, for example, mass%, Cr: 15 to 25%, Ni + Co: 55% or more, C: 0.15% or less, Si: 0.5 to 1.5%, and Mn: Nickel alloy of JIS-NCH1 and NCH2 containing 2.5% or less and the balance being composed of Fe and inevitable impurities. As another example for the core part 20, N200 material of Ni: 95% or more, preferably 98% or more, and more preferably 99% or more is mentioned by mass%, for example. The core portion 20 made of a nickel material is preferable in terms of excellent workability at the time of a small diameter because the heat generation characteristics are similar to those of the outer aluminum metal 21.

  Moreover, as the core part 20, for example, in mass%, Cr: 15 to 25%, C: 0.10% or less, Si: 1.5% or less, Mn: 1.0% or less, and Al: 2 to 6% It is also possible to use a chromium alloy of JIS-FCH1, FCH2, which contains Fe and the balance of Fe and inevitable impurities.

  On the other hand, in the case of using an aluminum wire without using the core portion 20, the temperature required for the catalytic reaction when using the aluminum wire as the catalyst member 1 can be secured by, for example, various conventional external heating methods. it can.

  Next, the manufacturing method of the catalyst carrier 2 according to the present embodiment will be described. For example, in the former composite wire using the core portion 20, an aluminum metal 21 having a predetermined thickness is applied to the core material by plating, cladding, or the like. The composite wire is formed, and the composite wire is reduced to a desired wire diameter. The thinned wire is twisted as shown in FIG. 3, and then coiled as shown in FIG. Thereby, the catalyst carrier 2 is obtained. The catalyst carrier 2 is then subjected to anodization treatment and firing treatment, whereby a porous anodized layer 22 having a large number of pores s is formed on the surfaces of the wires 11 and 12. Thereafter, the catalyst substance 3 is fixed to the pores S formed on the surfaces of the wires 11 and 12.

  The porous alumite layer 22 formed on each of the wires 11 and 12 is not particularly limited and is arbitrarily set. For example, it is set to have a thickness of 5 μm or more. In Patent Documents 1 and 2, for example, [(volume of alumite layer + aluminum layer) / total volume of wire] is exemplified. However, in the case involving twisting as in this embodiment, the volume ratio is It is preferable to make it as large as possible. That is, when the volume ratio is small, there is a risk that the twisting process may cause cracking or fatigue failure of the aluminum metal. Therefore, the volume ratio is preferably 30% or more, more preferably 42% or more, and further preferably 45 to 65%.

  FIG. 5 shows an example of a catalytic reactor 30 as one usage form of the catalyst member 1 of the present embodiment. The catalytic reactor 30 includes, for example, a chamber 31 and a planar element 33 disposed in the chamber 31.

  The chamber 31 is a closed space having an inlet 31a and an outlet 31b, for example. The shape of the chamber 31 is not particularly limited, and any form can be adopted.

  The element 33 is, for example, a planar shape in which a plurality of catalyst members 1 are arranged side by side on a plane, and forms an apparent plane H that extends on an arbitrary plane. In the present embodiment, the linear catalyst members 1 are arranged substantially in parallel to form the planar element 33. For example, the catalyst member 1 can be meandered in a wavy or zigzag shape on a plane. . In any embodiment, whether or not the adjacent catalyst members 1 are in contact with each other in the element 33 is not particularly a problem. In a preferred embodiment, the planar elements 33 are arranged in multiple stages, and the basic flow of the fluid to be processed is in a direction perpendicular to the apparent plane H of the elements 33.

  The fluid to be processed supplied into the chamber 31 from the inlet 31a comes into contact with the catalyst material of the element 33, and a predetermined chemical reaction is promoted. Thereafter, the fluid to be processed is sent to the outside of the chamber 31 from the outlet 31b. As shown in FIG. 2, each catalyst member 1 constituting the element 33 includes a contact portion 7 in which adjacent coil wires 6 and 6 are in contact with each other, and a non-contact portion 8 in which the coil wires 6 and 6 are separated from each other. Therefore, it is possible to arrange the catalyst material 3 in the chamber 31 at a high density, while greatly increasing the chance of contact between the supplied fluid to be treated and the catalyst material, thereby efficiently performing the catalytic reaction. Can be promoted.

  FIG. 6 shows another embodiment of the metal wire 10 used in the catalyst member 1 (and the catalyst carrier 2) of the present invention. Throughout all the following embodiments, the same or common elements as those described in the previous embodiment are denoted by the same reference numerals, and description thereof is omitted.

The metal wire 10 according to the embodiment of FIG. 6 includes a first wire 41 serving as a core wire and a second wire 42 wound spirally with a slightly small diameter on the surface thereof. The first wire 41 has substantially straightness before coiling. Thereby, the metal wire 10 has a spiral ridge 43 formed by the second wire 42 and a groove 44 formed between the second wires 42, 42. By coiling the metal wire 10, the catalyst carrier 2 as shown in FIG. 1 can be obtained.

  In FIG. 6, the second wire 42 is wound at a relatively large spiral pitch P <b> 1, and this pitch P <b> 1 is larger than the outer diameter of the first wire 41, for example. In the main body portion 4 of the catalyst member 1 using such a metal wire 10, a relatively long non-contact portion is formed between the coil wires adjacent in the coil axis direction, and consequently, the continuous space between the internal space and the external space of the coil. Sex can be provided more reliably.

  FIG. 7A shows still another embodiment of the metal wire 10. The metal wire 10 includes a first wire 41 and a second wire 42 wound around the first wire 41 with a relatively small helical pitch P2. The pitch P2 is equal to the wire diameter of the second wire 42, whereby the second wire 42 is tightly wound so as to be in contact with each other. In this embodiment, the first wire 41 is a wire for core wire when energized and heated, while the second wire 42 wound around the surface is made of the aluminum wire for forming an alumite layer. Both wires may be different metal wires.

FIG. 7B shows a cross-sectional view along a plane including the axial center line of the metal wire rod 10 of FIG. As is clear from FIG. 7B, the metal wire 10 of the present embodiment also has a spiral ridge 43 formed by the second wire 42 and a groove 44 formed between the second wires 42 and 42. And have. By coiling the metal wire 10, the catalyst carrier 2 as described in FIG. 1 can be obtained. Such a catalyst carrier is preferable in that the space of the groove portion 44 is smaller than that of the previous embodiment, and consequently, a high-density arrangement of the catalyst material is possible. A spiral groove 46 is formed between the adjacent second wire rods 42 and 42 and the first wire rod 41. The catalytic reaction of the fluid to be treated is further promoted by supporting the catalyst substance also in the groove 46.

FIG. 8 shows still another embodiment of the metal wire 10. The metal wire 10 of this embodiment is a non-twisted wire, in which a spiral or ring-shaped groove 44 is formed on the surface of a round wire having a circular cross section. Thus, a ridge portion 43 extending in the circumferential direction and a groove portion 44 extending in a spiral manner are formed on the outer surface of the metal wire 10 in FIG.

  Although the embodiments of the present invention have been described in detail above, the present invention is not limited to the above-described embodiments, and can be implemented with various modifications.

  The effect of the catalyst member of the present invention was evaluated using a dehydrogenation reaction system 50 as shown in FIG. The dehydrogenation reaction system 50 uses, for example, an organic hydride of a hydrogenated derivative of an aromatic compound such as toluene (for example, methylcyclohexane, MCH) as a main raw material fluid, and dehydrogenates while adding an accompanying gas to the raw material fluid. Hydrogen is decomposed and produced by the reaction.

  The dehydrogenation reaction system 50 includes a storage tank 51 that stores, for example, an MCH solution that is a fluid to be treated, a pump 52 that pumps the MCH solution in the storage tank 51, a vaporizer 53 that vaporizes the MCH solution pumped by the pump 52, A catalytic reactor 54 that is arranged downstream of the vaporizer 53 and separates into an aromatic compound and hydrogen by a dehydrogenation reaction, and a cooler 55 that cools the reaction gas and enables gas / liquid separation. The gas content in the product is taken out as hydrogen, and the liquid is taken out as toluene. In addition, this toluene can be returned to the said raw material methylcyclohexane by making the dehydrogenation reaction of the reverse reaction to the said hydrogenation reaction if necessary.

  The supply of the fluid to be treated to the catalytic reactor 54 is preferably made into a gas by heating to a predetermined temperature in advance, but the fluid to be treated may be sprayed under pressure while in a liquid state. Thus, the vaporizer 53 is selectively used according to the purpose.

  The catalyst reactors 54 are arranged in multiple stages as elements in which the catalyst members are arranged in a plane, as described with reference to FIG. Each catalyst member 1 is connected to a power source so as to be heated to a predetermined temperature by energization. Use of the catalyst members of Examples and Comparative Examples is as follows.

[Example 1]
The catalyst carrier of the example had a main body portion in which a metal wire obtained by twisting two wires was wound in a coil shape. Each wire is made of a clad material having a circular cross section including a core part made of a nickel alloy having a purity of 99.9% and an aluminum layer made of aluminum having a purity of 99.9% covering the core part. For example, the wire diameter was reduced to 0.5 mm by wire drawing and heat treatment as necessary. And after making these wires into the twisted wire twisted on the conditions of Table 1, coiling processing was carried out so that it might have a close-contact coil-like main-body part with an outer diameter of 7 mm, and the predetermined | prescribed catalyst carrier was obtained.

  The coil winding is provided with spiral irregularities so that a contact portion and a non-contact portion are alternately provided between the next coil winding by the twisted wire processing, and the twisted wire is not yet twisted. It has a length that is 0.81 times shorter than the initial length of the clad fine wire. The surface area per unit length of the stranded wire increases with the twist angle α °.

  Next, the obtained catalyst carrier was further alumite-treated to form an alumite layer having a thickness of about 10 to 30 μm on the surface of the aluminum layer. The alumite layer is provided with a concave porous structure having fine openings on the surface, and the details of the treatment method and the subsequent catalyst material loading treatment are performed based on each of the above-mentioned patent documents. A uniform alumite layer was formed.

Specifically, in the catalyst loading treatment, 0.01, 0.015, 0.02 gr of chloroplatinic acid H ₂ PtCl ₆ 6H ₂ O was used as a platinum salt serving as a catalyst substance, and dissolved in 10 cc ethanol. A chloroplatinic acid solution was prepared. The catalyst carrier is immersed in this solution, platinum is supported in the pores on the surface, and then heated to a predetermined temperature and dried to obtain a target catalyst member.

[Example 2]
In this embodiment, an example of using a thin aluminum wire having a wire diameter of 0.5 mm and a purity of 99.5% as a wire of a metal wire is shown. It is a twisted wire made of aluminum metal. In addition, the holding length is similarly set to 0.81 times by adjusting the twist angle α ° of the twisted wire (20 to 45 °).

  The aluminum metal stranded wire is wound tightly to form a catalyst carrier having a main body having an outer diameter of 10 mm and a coil length of 20 cm. Further, the same alumite treatment and catalyst material loading treatment with a platinum salt are performed. And a predetermined catalyst member was obtained. When the peripheral surface of the catalyst member was observed with a magnifying glass, contact portions where the stranded wires contact each other and non-contact portions separated from each other were alternately formed, and the fluid to be treated sufficiently circulated on the peripheral surface of the coil body. It was provided with a gap opening to obtain.

[Comparative example]
The catalyst carrier of the comparative example had a main body wound in a coil shape using a metal wire made of one wire. This metal wire is a clad member having a circular cross section including a core portion made of a nickel alloy having a purity of 99.9% and an aluminum layer made of aluminum having a purity of 99.9% covering the core portion, as in Example 1. And their wire diameter was 0.7 mm. Using this wire, a coiling process was performed without forming the stranded wire, and an alumite process and a catalyst supporting process were further performed.

Since the surface of this catalyst member is substantially a 0.7 mm cross-section circular wire, the substantial surface area is 2.2 mm ² (per 1 mm length), which is a comparative catalyst. It was set as a member.

[Example 3]
The catalyst members of Examples and Comparative Examples were incorporated into the catalytic reactor 30 shown in FIG. 5 (indicated by reference numeral 54 in FIG. 9), and methylcyclohexane (MCH) was dehydrogenated. As shown in FIG. 9, each of the catalyst members is set in multiple stages in a predetermined holder as shown in FIG. 5 and is supplied in a gaseous state with a vaporizer in advance from a predetermined nozzle. The hydrogen production process was performed by the system device.

  The hydrogen evolution rate and the toluene conversion rate of methylcyclohexane were analyzed and measured by gas chromatography. In the experiment, methylcyclohexane was flowed in a nitrogen stream from a pulse type spray nozzle provided in the reactor, a flow rate of 150 ml / min, a spray cycle of 0.5 seconds (a single spray amount of 0.39 gr), and a spray interval of 10 seconds or 20 seconds. , Using each catalyst member heated to 310 ° C.

  The temperature required for the catalytic reaction is the same as that for the catalyst member of Example 1 by the energization heating method and the aluminum catalyst member of Example 2 by the method of heating the fluid to be treated to the reaction temperature in advance. In the catalyst member of each Example according to the present invention, the surface area increased by the twisted structure and the good flowability of the fluid to be treated were confirmed, and the catalyst efficiency was improved. On the other hand, the catalyst member of the comparative example using the normal wire coil system has a limited surface area, and also has a high flow resistance and a high supply pressure.

  It was confirmed that the methylcyclohexane conversion rate and hydrogen generation rate when using the catalyst member of the example were improved as compared with those of the comparative example. Further, it was confirmed that the catalyst member of the present invention can be used in various other fields including the hydrogen production field.

DESCRIPTION OF SYMBOLS 1 Catalytic member 2 Catalytic support 3 Catalytic substance 4 Body part 6 Coil wire 7 Coil wire contact part 8 Coil wire non-contact part 10 Metal wire

Claims (8)

A catalyst carrier for supporting a catalyst substance on the surface,
A metal wire has a main body wound in a coil shape,
The body portion between the coil wire adjoining each other in the coil axis direction, seen including a contact portion in contact with each other, and a non-contact portion spaced from each other,
The metal wire of the main body is a stranded wire in which at least two wires are twisted together,
On the outer surface of the stranded wire, a ridge portion extending in a spiral shape and a groove portion extending in a spiral shape are provided.
Catalyst carrier. 2. The catalyst carrier according to claim 1, wherein the stranded wire is formed by twisting the wire at a twist angle of 10 to 50 ° with respect to the axis of the stranded wire . The catalyst carrier according to claim 1 or 2, wherein the stranded wire has a length of 0.9 times or less of an original length of each wire . The catalyst carrier according to any one of claims 1 to 3, wherein the wire is formed from a non-straight single wire that has been previously two-dimensionally or three-dimensionally kneaded . The catalyst carrier according to any one of claims 1 to 4, wherein at least one of the wires includes an aluminum metal wire having an alumite layer on a surface thereof . The catalyst carrier according to claim 5, wherein the aluminum metal wire has a heating wire having an electric resistance of 5 Ω / m or more inside . A catalyst carrier for supporting a catalyst substance on the surface,
A metal wire has a main body wound in a coil shape,
The main body portion includes contact portions that are in contact with each other between coil wires adjacent in the coil axis direction, and non-contact portions that are separated from each other.
The metal wire has a first wire comprising a core wire, the second wire and the including wound helically on its surface,
Catalyst carrier. A catalyst carrier according to any one of claims 1 to 7, and a catalyst substance supported on at least a part of the surface thereof,
A catalyst member in which the catalyst substance is supported on the surface of the metal wire.

Images