JP6326588B2 - Active metal supported catalyst based on fiber sheet and method for producing the same - Google Patents

Description

  The present invention relates to an active metal supported catalyst based on a fiber sheet and a method for producing the same.

  In the hydrogen production and fuel production processes, a solid catalyst that can be easily separated from the product is used. In recent years, small fuel cell systems and on-site small fuel production processes have attracted attention, and the reactors equipped with them are extremely small compared to those used in conventional complexes, and are in the form of powder, spheres, granules, and pellets. When the current catalyst having a shape such as an extruded shape, a ring shape, or a four-leaf shape is used, there is a possibility that the packing density in the reactor becomes small, and problems such as drift and pressure loss may occur. As described above, there is a limit to applying a catalyst used in a conventional chemical process as it is to a small process.

  On the other hand, structural catalysts such as a monolith catalyst typified by a cordierite honeycomb and a gauze catalyst in which wires of active metal or alloy are knitted into a sheet shape have been devised. However, since the reactor of the small process has a complicated shape such as concentric circles and uneven portions, it is difficult to handle with a honeycomb monolith catalyst, and the gauze type catalyst has flexibility in shape, Since the specific surface area is small and the catalyst filling amount needs to be increased, it is not suitable for a small apparatus.

  In addition, attempts have been made to use organic polymer as a material that easily takes various shapes and forms, and to utilize characteristics that are not found in inorganic catalyst carriers. For example, a technology for fixing catalyst particles to cloth using starch, polyvinyl alcohol, or a synthetic resin adhesive on a fiber sheet (Patent Document 1), or a polymer that causes phase separation from this polymer in a fiber-forming polymer. And a technique of making catalyst particles kneaded and spinning and then making them porous by stretching (Patent Document 2) is disclosed.

JP-A-56-1333029 JP-A-3-270718

  In the catalyst described in Patent Document 1, when the amount of the pressure-sensitive adhesive used is small, the catalyst particles fall off. When the amount of the pressure-sensitive adhesive used is large, the catalyst particles are buried in the pressure-sensitive adhesive, resulting in a decrease in catalyst performance. End up. In addition, when the reaction temperature is high, the pressure-sensitive adhesive is melted or thermally decomposed. As a result, not only the catalyst performance is lowered, but there is a concern that impurities are mixed due to generation of decomposition gas. Furthermore, there is a concern that the air permeability of the catalyst layer becomes non-uniform due to the thermal contraction of the fiber sheet, and the contact frequency between the catalyst and the reaction fluid decreases.

  In the catalyst described in Patent Document 2, only the active metal exposed on the surface exhibits the catalytic performance, and the active metal buried in the fiber cannot exhibit the catalytic performance. In addition, when the reaction temperature is high, the active metal exposed on the surface before the reaction is buried in the fiber due to the melting of the fiber, so that not only the catalytic performance is deteriorated, but also pyrolysis gas generated from the fiber is generated. There is a concern that it will be mixed into the reaction fluid. Further, as with the catalyst described in Patent Document 1, there are concerns that the air permeability of the catalyst layer becomes non-uniform due to thermal contraction of the fiber sheet, and the contact frequency between the catalyst and the reaction fluid decreases.

  Accordingly, an object of the present invention is to provide a novel catalyst having flexibility that can be used for a small apparatus and having high catalytic activity, and a method for producing the same.

According to the present invention, an active metal supported catalyst based on the following fiber sheet can be provided.
1. An active metal-supported catalyst based on a fiber sheet, wherein a layer containing a metal oxide is formed on the surface of the fiber sheet, and the active metal is supported on at least one of the surface and the inside of the metal oxide layer. Catalyst.
2. An active metal-supported catalyst for water gas shift reaction based on a fiber sheet, wherein a layer containing a metal oxide is formed on the surface of the fiber sheet, and the active is provided on at least one of the surface and the inside of the metal oxide layer A catalyst in which a metal is supported and the active metal is one to three metals selected from the group consisting of ruthenium, iron, copper, nickel, and cobalt.
3. The active metal is 0.5 wt% or more and 30 wt% or less based on the total weight of the catalyst, and the metal oxide layer is 0.1 wt% or more and 10 wt% or less based on the total weight of the catalyst, 3. The catalyst according to 2, wherein the remainder is the fiber sheet.
4). An active metal-supported catalyst for Fischer-Tropsch reaction based on a fiber sheet, wherein a layer containing a metal oxide is formed on the surface of the fiber sheet, and at least one of the surface and the inside of the metal oxide layer An active metal is supported, and the active metal is one or two selected from the group consisting of ruthenium, cobalt, and iron.
5. The active metal is 5 wt% or more and 25 wt% or less based on the total weight of the catalyst, the metal oxide layer is 0.1 wt% or more and 10 wt% or less based on the total weight of the catalyst, and the balance 5. The catalyst according to 4, which is the fiber sheet.
6). The fiber sheet is phenol resin, aramid, epoxy resin, polytetrafluoroethylene, polychlorotrifluoroethylene, polyphenylene sulfide, polyarylate, polysulfone, polyethersulfone, polyetherimide, polyamideimide, polyetheretherketone, polycarbonate. Including at least one fiber selected from the group consisting of urea resin, melamine resin, diallyl phthalate, silicone resin, furan resin, cellulose acetate, nitrocellulose, cellulose propionate, alumina fiber, basalt fiber, and glass fiber, The catalyst in any one of 1-5.
7). The catalyst according to any one of 1 to 6, wherein the fiber sheet is in the form of a fiber nonwoven fabric, a woven fabric, or a knitted fabric.
8). The catalyst according to any one of 1 to 7, wherein the metal oxide is silica, titania, alumina, zirconia, silica-alumina, silica-titania, silica-zirconia, titania-alumina, or silica-titania-zirconia.
9. A method for producing an active metal supported catalyst based on a fiber sheet,
100% of the total weight of the solution, 10 to 40% by weight of metal alkoxide, 10 to 50% by weight of alcohol, 0.1 to 0.5% by weight of 1-15 N mineral acid, and the remaining water A step of immersing the fiber sheet in the solution containing,
Heating the soaked fiber sheet;
Immersing the heated fiber sheet in an active metal salt solution;
Heating the soaked fiber sheet;
Including methods.
10. A method for producing an active metal supported catalyst based on a fiber sheet,
In a solution containing metal alkoxide 10 to 40%, alcohol 10 to 50%, 1 to 15 N mineral acid 0.1 to 0.5%, and the balance water with the total weight of the solution as 100% Adding an active metal salt to the fiber sheet and immersing the fiber sheet;
Heating the soaked fiber sheet;
Including methods.
11. The fiber sheet is phenol resin, aramid, epoxy resin, polytetrafluoroethylene, polychlorotrifluoroethylene, polyphenylene sulfide, polyarylate, polysulfone, polyethersulfone, polyetherimide, polyamideimide, polyetheretherketone, polycarbonate. Including at least one fiber selected from the group consisting of urea resin, melamine resin, diallyl phthalate, silicone resin, furan resin, cellulose acetate, nitrocellulose, cellulose propionate, alumina fiber, basalt fiber, and glass fiber, The method according to 9 or 10.
12 The method according to any one of 9 to 11, wherein the fiber sheet is in the form of a fiber nonwoven fabric, a woven fabric, or a knitted fabric.
13. The method according to any one of 9 to 12, wherein the metal alkoxide includes at least one selected from the group consisting of tetraethoxysilane, tetraethoxytitanium, and aluminum isopropoxide.
14 The alcohol is at least one selected from the group consisting of methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, and 2-methyl-2-propanol. The method in any one of 9-13 containing.
15. An active metal-supported catalyst carrier comprising a fiber sheet as a base material, wherein the fiber sheet has a layer containing a metal oxide formed on the surface thereof.

  ADVANTAGE OF THE INVENTION According to this invention, it has the softness | flexibility which can be used for a small apparatus, and can provide the novel catalyst and its manufacturing method with high catalyst activity.

It is a schematic diagram of an example of a cyclic reactor made of Pyrex (registered trademark) glass that can be used when performing a WGS reaction using the catalyst of the present invention. It is a graph showing the time-dependent change of a composition of hydrogen, methane, carbon monoxide, and a carbon dioxide at the time of performing WGS reaction using the catalyst prepared in Example 1. FIG. It is a graph showing the time-dependent change of a composition of hydrogen, methane, carbon monoxide, and a carbon dioxide at the time of performing WGS reaction using the catalyst prepared in Example 2. FIG. It is a graph showing the time-dependent change of a composition of hydrogen, methane, carbon monoxide, and a carbon dioxide at the time of performing WGS reaction using the catalyst prepared in Example 3. FIG. It is a graph showing the time-dependent change of a composition of hydrogen, methane, carbon monoxide, and a carbon dioxide at the time of performing WGS reaction using the catalyst prepared in the comparative example 1.

(Catalyst of the present invention)
The catalyst of the present invention is an active metal-supported catalyst based on a fiber sheet, wherein a layer containing a metal oxide is formed on the surface of the fiber sheet, and is formed on at least one of the surface and the inside of the metal oxide layer. The active metal is supported on the catalyst.

The fiber sheet that is the base material of the catalyst is flexible and flexible, and can be bent and bent freely. Therefore, the catalyst of the present invention is not limited to the size and shape of the apparatus to be used and can be used in a wide range of applications. Can be used. Since it can take any shape and form, it can be suitably used particularly in a small reactor. For example, a plurality of the catalysts of the present invention can be laminated on the catalyst layer, or the catalyst of the present invention can be spread on the reactor wall surface.
In addition, since the fiber sheet is used as a base material, it has excellent air permeability as compared with a solid catalyst of a conventional powder or molded product, so that pressure loss and reaction fluid drift in a catalyst layer of a reactor, particularly a small reactor Can be suppressed.

  The fiber sheet used as the base material of the catalyst of the present invention refers to a fiber sheet formed into a thin plate shape. Since fiber is used as a material, it has flexibility and flexibility, and can be bent and bent freely. The fiber sheet can be in the form of, for example, a nonwoven fabric, a woven fabric, or a knitted fabric. The fiber sheet may be in the form of a woven fabric because the air permeability can be controlled by adjusting the fabric density in the warp direction and the weft direction. preferable.

The fiber constituting the fiber sheet is not particularly limited, but a polymer material having high heat resistance is preferable. Examples of relatively high heat-resistant polymer materials include phenol resin, aramid, epoxy resin, polytetrafluoroethylene, polychlorotrifluoroethylene, polyphenylene sulfide, polyarylate, polysulfone, polyethersulfone, polyetherimide, Polyamideimide, polyether ether ketone, polycarbonate, urea resin, melamine resin, diallyl phthalate, silicon resin, furan resin, cellulose acetate, nitrocellulose, cellulose propionate, alumina fiber, basalt fiber, glass fiber, and the like. Phenolic resins, aramids, and polycarbonates are more preferable because techniques for weaving and knitting into woven fabrics and knitted fabrics in addition to yarns are established, and phenolic resins are particularly preferable.
The fiber sheet may be composed of only one kind of the above-listed fibers, or may be composed of a plurality of kinds of fibers.
The fiber sheet preferably includes at least one fiber selected from the group consisting of the above-mentioned fibers. Moreover, it is more preferable that the fiber of a phenol resin, an aramid, or a polycarbonate is included, and it is especially preferable that a phenol resin fiber is included.

  As the yarn constituting the fiber sheet, either a filament yarn or a spun yarn can be used. When the fiber sheet is a woven fabric or a knitted fabric, a spun yarn that has a high resistance to slipping and prevents slipping is preferable. The yarn may be a single yarn or may be a single yarn formed by twisting or the like, but the total fineness of the yarn is preferably 20d (denier) to 2000d, preferably 50d to 500d is more preferable, and 75d to 200d is particularly preferable. If the fineness is less than 20d, the strength of the yarn becomes low, and even if a fiber sheet is formed from the yarn, there is a concern that the yarn is likely to break when forming a metal oxide layer or during a catalytic reaction. On the other hand, when the yarn has a fineness of more than 2000d, there is a concern that the flexibility of the formed fiber sheet is impaired and deformation such as bending becomes difficult.

  The yarn may be twisted for the purpose of improving strength and making the thickness uniform. The twist direction may be either the S direction or the Z direction, and the number of twists is, for example, 5 to 200 T / inch, preferably 15 to 50 T / inch, more preferably 20 to 25 T / inch. is there. If the number of twists is less than 5 T / inch, it is easily untwisted and its practical significance is sparse. If the number of twists is more than 200 T / inch, the flexibility of the fiber sheet is low, and deformation such as bending may be difficult. is there.

  When the form of the fiber sheet is a woven fabric or a knitted fabric, the fabric density in the warp direction and the weft direction is preferably 20 to 200 / inch, more preferably 30 to 150 / inch, and 60 to 100. Particularly preferred is book / inch. When the fabric density is lower than 20 / inch, the strength of the fiber sheet is low, and the fiber sheet may be easily broken when a metal oxide layer is formed or during a catalytic reaction. May become non-uniform. If the fabric density is higher than 200 / inch, the air permeability of the fiber sheet is lowered, and there is a concern that the effect of suppressing the pressure loss when using the catalyst expected for the fiber sheet is reduced.

When the form of the fiber sheet is a nonwoven fabric, the weight per unit area of the nonwoven fabric is preferably 10 to 500 g / m ² , more preferably 50 to 250 g / m ² , and even more preferably 100 to 200 g / m ^2. m ² , particularly preferably 100 to 150 g / m ² . When the weight per unit area is less than 10 g / m ² , the strength of the fiber sheet is lowered, and there is a possibility that the fiber sheet is easily broken when the metal oxide layer is formed or during the catalytic reaction. When the weight per unit area is heavier than 500 g / m ^2, there is a concern that the air permeability of the fiber sheet is lowered, and the effect of suppressing the pressure loss when using the catalyst expected for the fiber sheet is reduced.

  The layer containing a metal oxide formed on the surface of the fiber sheet has a function of supporting the active metal on the fiber sheet. Therefore, the metal oxide layer may be continuously formed on the fiber sheet or discontinuously on the condition that it supports an active metal sufficient to exhibit the catalytic activity of the target catalyst. It may be formed. Further, the thickness of the layer is not particularly limited.

  Further, since the metal oxide layer also functions as a reinforcing material for the fiber sheet, it contributes to the improvement of strength and heat resistance, and the catalyst life is also improved. Furthermore, since the metal oxide layer is unlikely to melt or thermally decompose during activation of the active metal or during the catalytic reaction, it is difficult for the catalytic activity to decrease due to inclusion of decomposition products or burying of the active metal.

  The metal oxide is not particularly limited, and examples thereof include silica, titania, alumina, zirconia, silica-alumina, silica-titania, silica-zirconia, titania-alumina, silica-titania-zirconia and the like. The metal oxide layer should just contain said metal oxide, and may contain other arbitrary components.

  The weight ratio of the metal oxide layer to the total catalyst is not particularly limited, but is preferably 0.1% by weight or more and 10% by weight or less based on the total weight of the catalyst.

  In the catalyst of the present invention, an active metal is supported on at least one of the surface and the inside of the metal oxide layer. The active metal is preferably present on the fiber sheet through the metal oxide layer. The active metal may be supported continuously on the surface of the metal oxide layer, or may be supported discontinuously. The active metal may be present inside the metal oxide layer and supported on the fiber sheet together with the metal oxide.

The active metal used in the catalyst of the present invention is not particularly limited, and can be appropriately determined depending on the target reaction using the catalyst. An active metal may be used individually by 1 type, and may be used in combination of multiple types.
Examples of the active metal include ruthenium, iron, cobalt, nickel, copper, and the like. Ruthenium, iron, cobalt, and nickel, which are widely used for reactions that proceed even at temperatures lower than the fiber weight reduction starting temperature (for example, 250 ° C. to 350 ° C.), preferably have high catalytic activity and also have a carbon precipitation reaction. Ruthenium, which hardly occurs, is particularly preferable.
The active metal preferably includes at least one selected from the group consisting of ruthenium, iron, copper, nickel, and cobalt.
The amount of the active metal supported is not particularly limited, and can be appropriately determined depending on the target reaction using the catalyst. For example, when the catalyst of the present invention is used as a catalyst for water gas shift reaction, it is preferably 0.5% by weight or more and 30% by weight or less, more preferably 0.5% by weight or more and 25% by weight or less, based on the total weight of the catalyst. Preferably, 0.5 wt% or more and 15 wt% or less is more preferable. When the catalyst of the present invention is used as a catalyst for the Fischer-Tropsch reaction, it is preferably 5% by weight or more and 25% by weight or less, more preferably 7% by weight or more and 20% by weight or less, based on the total weight of the catalyst. More preferably, it is more than 20% by weight.

When using the catalyst of this invention for a water gas shift reaction, it is preferable that an active metal contains 1-3 types selected from the group which consists of ruthenium, iron, copper, nickel, and cobalt.
When using the catalyst of this invention for a Fischer-Tropsch reaction, it is preferable that an active metal contains 1-2 types selected from the group which consists of ruthenium, cobalt, and iron.
In the catalyst of the present invention, in addition to these active metals, a promoter may be fixed for the purpose of improving the catalyst performance.

The catalyst of the present invention can be used for various reactions by appropriately changing the supported active metal. For example, it can be suitably used for water gas shift reaction, Fischer-Tropsch reaction and the like.
One aspect of the catalyst of the present invention is an active metal-supported catalyst for water gas shift reaction based on a fiber sheet, wherein a layer containing a metal oxide is formed on the surface of the fiber sheet, The active metal is supported on at least one of the surface and the inside, and the active metal is a catalyst that is one to three metals selected from the group consisting of ruthenium, iron, copper, nickel, and cobalt.
In this embodiment, preferably, the active metal is 0.5 wt% or more and 30 wt% or less based on the total weight of the catalyst, and the metal oxide layer is 0.1 wt% or more and 10 wt% based on the total weight of the catalyst. % Or less, and the balance is a fiber sheet.

Another embodiment of the catalyst of the present invention is a Fischer-Tropsch active metal-supported catalyst based on a fiber sheet, wherein a layer containing a metal oxide is formed on the surface of the fiber sheet, and the metal The active metal is supported on at least one of the surface and the inside of the oxide layer, and the active metal is one or two kinds of catalysts selected from the group consisting of ruthenium, cobalt, and iron.
In this embodiment, preferably, the active metal is 5 wt% or more and 25 wt% or less based on the total weight of the catalyst, and the metal oxide layer is 0.1 wt% or more and 10 wt% or less based on the total weight of the catalyst. The remainder is a fiber sheet.

  The catalyst of this invention can be manufactured according to the catalyst manufacturing method of this invention mentioned later.

(Catalyst carrier of the present invention)
The catalyst carrier of the present invention is an active metal-supported catalyst carrier based on a fiber sheet, and is a catalyst carrier in which a layer containing a metal oxide is formed on the surface of the fiber sheet.
By using a fiber sheet as a base material, it has flexibility and flexibility and can be used in a wide range like the catalyst of the present invention described above, and can be suitably used particularly in a small reactor. it can. By using a fiber sheet having a metal oxide layer formed on the surface as a catalyst carrier, the active metal can be easily supported only by impregnation in the active metal salt solution without using an adhesive.

The fiber sheet and metal oxide layer constituting the catalyst carrier of the present invention are as described above for the catalyst of the present invention.
The catalyst carrier of the present invention can be produced according to the first to third steps of the first catalyst production method of the present invention described later.
In order to use the catalyst carrier of the present invention as a catalyst, an active metal suitable for the target catalytic reaction is supported according to the fourth to fifth steps of the first catalyst production method of the present invention described later. You can do it. Moreover, you may perform the ammonia treatment process which is an additional process suitably.

(Catalyst production method of the present invention)
The first catalyst production method of the present invention is a method for producing an active metal-supported catalyst based on a fiber sheet, and (1) 10 to 40% by weight of a metal alkoxide, based on the total weight of the solution, A step of immersing a fiber sheet in a solution containing 10 to 50% by weight of alcohol, 0.1 to 0.5% by weight of a mineral acid of 1 to 15 N, and the balance of water, and (2) the immersion Heating the fiber sheet, (3) immersing the heated fiber sheet in an active metal salt solution, and (4) heating the soaked fiber sheet.

  First, as the first step, the total weight of the solution is 100%, the metal alkoxide is 10 to 40% by weight, the alcohol is 10 to 50% by weight, and 1 to 15 N mineral acid is 0.1 to 0.5% by weight. % And the fiber sheet is immersed in a solution containing the remaining water. Thereby, the solution containing a metal oxide can be impregnated in the fiber sheet.

The fiber sheet is as described above for the catalyst of the present invention.
The solution for immersing the fiber sheet contains metal alkoxide, alcohol, water, and mineral acid.
The weight ratio of the metal alkoxide is preferably 10 to 40%, more preferably 20 to 40%, and particularly preferably 25 to 30%, assuming that the entire solution in which the fiber sheet is immersed is 100%. When the weight ratio of the metal alkoxide is less than 10%, there is a concern that the active metal is not sufficiently supported by dropping off or the like, and when it exceeds 40%, the gap between the fiber sheets is blocked by the metal oxide layer formed on the fiber sheet surface. As a result, there is a concern that the air permeability of the fiber sheet is impaired.

  The metal alkoxide includes at least one selected from the group consisting of tetraethoxysilane, tetraethoxytitanium, aluminum isopropoxide, magnesium diethoxide, zinc ethoxide, and zirconium ethoxide. Tetraethoxysilane and aluminum isopropoxide are preferable because they become silica and alumina that are generally used as catalyst carriers by hydrolysis, respectively, and tetraethoxysilane is more preferable.

When the total weight of the solution in which the fiber sheet is immersed is 100%, the weight ratio of the alcohol is preferably 10 to 50%, more preferably 30 to 50%, and particularly preferably 40 to 45%. . When the weight ratio of the alcohol is less than 10%, the hydrolysis of the metal alkoxide proceeds rapidly, and there is a concern that the metal oxide layer may not be uniformly formed on the fiber sheet surface. Since the hydrolysis of the alkoxide is slow and it takes time to form the metal oxide layer, the practical significance of the present invention is diminished.
The alcohol is at least one selected from the group consisting of methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, and 2-methyl-2-propanol. Including. Methanol and ethanol are preferred and methanol is more preferred because of their higher hydrophilicity than other alcohols.

  It is preferable that the water contained in the solution in which the fiber sheet is immersed does not contain impurities or is small. For example, pure water, distilled water, deionized water, or the like can be used.

When the total weight of the solution in which the fiber sheet is immersed is 100%, the weight ratio of the mineral acid is preferably 0.1 to 0.5%, more preferably 0.2 to 0.5%, and It is especially preferable that it is 3 to 0.35%. When the weight ratio of the mineral acid is less than 0.1%, the hydrolysis of the metal alkoxide is slow, and it takes time to form the metal oxide layer. In many cases, the mineral acid acts as a catalyst poison, and there is a concern that the catalyst performance is lowered.
As the mineral acid, for example, hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, or hydrofluoric acid can be used. The concentration of the mineral acid is, for example, preferably 1 to 15 N, more preferably 5 to 15 N, and particularly preferably 8 to 12 N. When the concentration of the mineral acid is lower than 1N, the hydrolysis rate of the metal alkoxide is slow and the formation of the metal oxide becomes insufficient. Moreover, even if the concentration is higher than 15N, there is no difference in the formation of the metal oxide, and the practical significance is diminished.

  The weight ratio of the fiber sheet immersed in the metal alkoxide solution to the metal alkoxide solution is preferably 1: 1 to 1: 100, more preferably 1:10 to 1:30, and 1:15 to 1:20. Most preferably. When the bath ratio is less than 1: 1, the metal alkoxide solution cannot be sufficiently immersed on the entire surface of the fiber sheet. When the bath ratio is greater than 1: 100, the ratio of the metal oxide not formed on the fiber sheet increases. There is a concern that the supported amount decreases and the catalyst performance decreases accordingly.

  As for immersion time, 30 minutes or more are preferable, for example. Although the upper limit of immersion time is not specifically limited, It is desirable to finish an immersion process within 12 hours from viewpoints of productivity.

Next, as the second step, the fiber sheet immersed in the first step is heated. By the heating process which is the second process, the fiber sheet can be dried and the degree of polymerization of the metal oxide can be increased.
By drying the fiber sheet, an excess solution can be removed from the fiber sheet, and a metal oxide layer can be formed on the surface of the fiber sheet. Moreover, the effect that the solution containing an active metal spreads uniformly in a metal oxide layer increases by drying.
Heating for drying can be appropriately performed using means known in the art, and conditions such as temperature and time can be appropriately set.

  Moreover, by heating a fiber sheet at 250-350 degreeC, the unreacted OH group and OR group in a metal oxide layer remove | deviate, and the polymerization degree of a metal oxide becomes higher. The temperature range of 250 to 350 ° C is a preferable temperature range for the water gas shift reaction and the Fischer-Tropsch reaction, and heating in this temperature range suppresses changes in the physical properties of the catalyst by giving a thermal history in advance. In addition, the effect of stabilizing the activity exhibited by the catalyst can be expected.

The heating temperature for increasing the degree of polymerization of the metal oxide is 250 to 350 ° C, preferably 280 to 320 ° C, more preferably 295 to 305 ° C. If the temperature is lower than 250 ° C., the formation of the metal oxide layer becomes insufficient, and the amount of active metal supported is reduced, and there is a concern that the catalyst performance may be lowered accordingly. At a temperature higher than 350 ° C., there is a concern that decomposition gas is generated due to thermal decomposition of the fiber sheet.
The heating time is 15 to 240 minutes, preferably 45 to 120 minutes, and more preferably 50 to 70 minutes. There is a concern that the polymerization does not proceed sufficiently in a time shorter than 15 minutes. Moreover, in the time longer than 240 minutes, there exists a concern about the embrittlement by decomposition | disassembly of a fiber sheet.
In addition, the heating process which is a 2nd process may distinguish and perform the process of drying and the process of heating at 250-350 degreeC, or it is drying by performing only the process of heating at 250-350 degreeC. It may also serve as a process.

  Next, as a third step, the fiber sheet heated in the second step is immersed in the active metal solution. Thereby, the active metal solution can be impregnated into the fiber sheet on which the metal oxide layer is formed.

The active metal solution is obtained by dissolving a salt of an active metal in a suitable solvent. The active metal is as described above for the catalyst of the present invention. The active metal salt is not particularly limited as long as it is soluble in the solvent used.
The solvent of the active metal solution is not particularly limited as long as it can dissolve the salt of the active metal to be used. In order to increase the dispersibility of the active metal with respect to the fiber sheet having a metal oxide layer formed on the surface, it is necessary to improve the wettability of the fiber sheet. For this purpose, the solvent of the active metal solution is 1 An aqueous alcohol solution having a concentration of at least% is preferred. If the concentration of the aqueous alcohol solution is less than 1%, the wettability of the fiber sheet is insufficiently improved, and the dispersibility of the active metal may be reduced. The alcohol used in the aqueous alcohol solution as the active metal solution is composed of methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, and 2-methyl-2-propanol. It is preferable to include at least one selected from the group. Methanol and ethanol are more preferable, and methanol is particularly preferable because of its higher hydrophilicity than other alcohols.

  The weight ratio of the fiber sheet heated in the second step to the active metal solution is preferably 1: 1 to 1:20, more preferably 1: 3 to 1:10, and 1: 4 to 1: 7. Most preferably. If the weight ratio is less than 1: 1, the active metal solution cannot be sufficiently immersed on the entire surface of the fiber sheet. If the weight ratio is greater than 1:20, the proportion of active metal not supported on the fiber sheet increases. There is a concern that the catalyst performance will decrease with the decrease.

  The amount of active metal dissolved in the active metal solution is not particularly limited. For example, when the catalyst of the present invention is used as a catalyst for the water gas shift reaction, the active metal is 0.1% relative to the fiber sheet heated in the second step. It is preferable to dissolve at a weight ratio of 5 to 30%. If the amount is less than 0.5%, the active metal loading is small, so there is a concern that the reaction activity is low, and if more than 30% is loaded on the fiber sheet, the active metal may be peeled off, which is practical. The above significance is sparse. Moreover, when using the catalyst of this invention as a catalyst for Fischer-Tropsch reaction, it is preferable that the active metal is melt | dissolving in the weight ratio of 5 to 30% with respect to the fiber sheet heated in the 2nd process. . If the amount is less than 5%, the amount of active metal supported is small, so there is a concern that the reaction activity is low. If more than 30% of the active metal is supported on the fiber sheet, the active metal may be peeled off, which is practical. Significance is sparse.

  For example, the immersion time is preferably 1 to 60 minutes, more preferably 20 to 45 minutes, and most preferably 35 to 40 minutes. When the immersion time is less than 1 minute, there is a concern that the active metal is not sufficiently supported on the fiber sheet. Moreover, even if it soaks for more than 1 hour, there is no difference in the amount of active metal supported on the fiber sheet, and practical significance is diminished.

Next, as a fourth step, the fiber sheet immersed in the third step is heated. The heating step, which is the fourth step, can dry the fiber sheet, remove the excess active metal solution from the fiber sheet, and carry the necessary active metal.
Heating for drying can be appropriately performed using means known in the art, and conditions such as temperature and time can be appropriately set.

As an additional step, when chloride is used as the raw material for preparing the active metal solution, it is preferable to perform an ammonia treatment step in order to dechlorinate the metal chloride adhering to the fiber sheet. The ammonia treatment step can be performed by immersing the fiber sheet in an aqueous ammonia solution and repeating the steps of heating, washing and drying as necessary.
The ammonia concentration is preferably 1 mol / l or more, and the weight ratio of the fiber sheet immersed in the aqueous ammonia solution to the aqueous ammonia solution is preferably 1: 1 to 1: 100. When an aqueous ammonia solution having a concentration lower than 1 mol / l is used, dechlorination may be insufficient. When the bath ratio is less than 1: 1, the fiber sheet cannot be sufficiently immersed in the aqueous ammonia solution, so that dechlorination becomes insufficient. When the bath ratio is greater than 1: 100, the effect of dechlorination is not changed, and practical significance is diminished.
Other conditions for the ammonia treatment step can be set as appropriate.

Moreover, in order to improve the activity of the produced catalyst, it is preferable to further perform an activation treatment step. The activation treatment step can be performed by heat treatment under vacuum conditions in a rare gas atmosphere, a nitrogen atmosphere, a carbon dioxide atmosphere, or a hydrogen atmosphere. Moreover, heat processing can be performed at 300 degreeC for 1 hour, for example.
The activation treatment step may be performed separately from the heating step that is the fourth step, or the fourth drying step and the activation treatment are performed by performing the fourth drying step in the absence of oxygen. It may also serve as a process.

  The second catalyst production method of the present invention is a method for producing an active metal-supported catalyst based on a fiber sheet, wherein (1) the total weight of the solution is 100%, the metal alkoxide is 10 to 40%, Adding an active metal salt to a solution containing 10 to 50% alcohol, 0.1 to 0.5% mineral acid of 1 to 15 N, and the balance water, and immersing the fiber sheet; 2) heating the soaked fiber sheet.

  The first catalyst production method of the present invention is performed by separately performing a dipping step for forming a metal oxide layer as a first step and a dipping step for supporting an active metal as a third step. However, in the second catalyst production method of the present invention, in the first step, the metal oxide layer raw material and the active metal salt are included in the solution, thereby forming the metal oxide layer and the active metal. Is carried out simultaneously. This saves work and saves time.

The first step can be performed in the same manner as the first step of the first catalyst production method of the present invention. For example, when the catalyst of the present invention is used as a catalyst for a water gas shift reaction, the active metal salt is used in an amount of 0.5 to 30% by weight in terms of the total catalyst weight metal, and the present invention. When the above catalyst is used as a catalyst for the Fischer-Tropsch reaction, it may be added to the solution so as to be 5% by weight or more and 25% by weight or less in terms of metal based on the total weight of the catalyst.
The second step can be performed in the same manner as the second step of the first catalyst production method of the present invention. Specifically, the step of drying and the step of heating at 250 to 350 ° C may be performed separately, or the drying step may be performed by performing only the step of heating at 250 to 350 ° C.
Moreover, you may perform the ammonia process process and activation process which are an additional process suitably. The activation treatment step may be performed separately from the heating step, which is the second step, or the second drying step is performed under a vacuum condition under a rare gas atmosphere, a nitrogen atmosphere, a carbon dioxide atmosphere, or hydrogen. By performing in an atmosphere, you may serve as a 2nd heating process and an activation process process.

(Catalytic reaction using the catalyst of the present invention)
In the catalytic reaction using the catalyst of the present invention, the reaction temperature is preferably 350 ° C. or lower, more preferably 300 ° C. or lower. When the reaction temperature is higher than 350 ° C., there is a concern that decomposition gas is generated due to thermal decomposition of the fiber sheet.
The pressure is preferably 100 atm or less, more preferably 10 atm or less, and particularly preferably 1 atm or less. When the reaction pressure is higher than 100 atm, the fiber sheet is significantly embrittled, and there is a concern that its practicality as a catalyst carrier becomes dilute.

When the reaction is performed in a flow system, the flow rate of the raw material gas is GHSV (number obtained by dividing the volume through which the feed for one hour passes is divided by the volume of the catalyst; gas hourly space velocity) is 200 (vol / vol) h ⁻¹ or more and 30000. preferably (vol / ^vol) it is ^{h -1} or less, more preferably 800 (vol / ^{vol) h -1} or 25000 (vol / ^{vol) h -1} or less, 1200 (vol / vol) h - It is particularly preferably ¹ or more and 5000 (vol / vol) h ⁻¹ or less. If it is less than 200 (vol / vol) h ⁻¹ , the space-time yield becomes small and uneconomical, and if it exceeds 30000 (vol / vol) h ⁻¹ , the conversion rate reaches its peak and there is a concern that the separation process becomes difficult.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the scope of the present invention is not limited to the description of these examples.

Example 1
(1) Manufacture of catalyst for water gas shift (WGS) reaction Novoloid fiber (Kinol (registered trademark) KF-01551HCRC, Gunei Chemical Industry Co., Ltd.), which is a phenol resin fiber, and aramid fiber (Twaron (registered trademark), Teijin Ltd.) Was made at a rate of 8: 2 and then twisted in the Z direction at a rate of 22.8 T / inch so that the fineness of the blended yarn was 106d. Further, using a rapier loom (Model 735, manufactured by Ishikawa Seisakusho), plain weave fabric (hereinafter referred to as “NA fabric”) so that the yarn density in the warp and weft directions is 100 / inch and 70 / inch, respectively. Was woven.

10 g of NA fabric was immersed in a mixed solution of 50.0 g of tetraethyl orthosilicate (TEOS), 75.2 g of ethanol, 57.0 g of distilled water and 0.6 g of 10 N hydrochloric acid for 1 hour, and then air-dried for 12 hours (hereinafter referred to as the following). referred to as _"SiO 2 -NA fabric".). After 5 g of this SiO ₂ -NA fabric was heat-treated at 300 ° C. for 1 hour using an electric furnace, 30 ml of a solution in which distilled water and methanol were mixed at a volume ratio of 2: 1 was used as a reference based on the total weight of the catalyst. It was immersed in a solution in which ruthenium chloride n-hydrate (special grade reagent, Wako Pure Chemical Industries, Ltd., Ru assay 40%) was dissolved so that the weight ratio of ruthenium was 2.0% by weight.

  Next, the soaked fabric was placed in a rotary evaporator, and the evaporator was rotated in a water bath set at 50 ° C. for 30 minutes at a rotation speed of 20 rpm, and then dried under reduced pressure using an aspirator to remove moisture. . Further, dechlorination is performed by dipping the dried fabric in 250 ml of 7% ammonia water, placing the soaked fabric in a rotary evaporator, and rotating the evaporator in a water bath set at 50 ° C. for 30 minutes at a rotation speed of 20 rpm. The process was repeated twice. The fabric after the dechlorination step was sufficiently washed with water and dried in a dryer at 60 ° C. for 4 hours to obtain Catalyst 1.

(2) WGS reaction The catalyst 1 was used and WGS reaction was performed. A Pyrex (registered trademark) glass circulation reactor as shown in FIG. 1 was used for the reaction. The circulation section is composed of a glass tube having an inner diameter of 8 mmφ, and includes a U-shaped reactor and an electromagnet-driven piston circulation pump (manufactured by Misuzu Co., Ltd.). The driving electromagnet was manufactured using about 500 g of 0.6 mmφ enameled wire, a pulse current for driving was applied, and the piston was moved up and down to circulate the gas.
During the reaction, 1.0 g of catalyst 1 is placed in the catalyst bed, and an activation treatment step is performed in which heat treatment is performed at 300 ° C. for 1 hour under vacuum conditions. At the same temperature, water vapor and carbon monoxide are each 3.33 kPa (25 torr). ) Were introduced into the system one by one and a WGS reaction was carried out.

A thermal conductivity detector gas chromatograph (TCD-GC) (GC-8A, manufactured by Shimadzu Corporation) was used for analysis of the inorganic gas in the reaction apparatus. The column oven temperature was 80 ° C. to 100 ° C., and the temperature was raised with a temperature gradient of 10 ° C./min. As the column, a separation column of 4 mm × 3 m packed with Unibeads C (80 to 100 mesh, manufactured by GL Sciences Inc.) was used.
For analysis of lower hydrocarbons, a flame ionization detector gas chromatograph (FID-GC) (GC-9A, manufactured by Shimadzu Corporation) was used. The column oven temperature was 50 ° C. to 150 ° C., and the temperature was raised with a temperature gradient of 5 ° C./min. The column used was a 4 mm × 2 m separation column packed with Unipak S (100-150 mesh, manufactured by GL Sciences Inc.).
As a carrier gas, argon was used for both gas chromatographs.

  FIG. 2 shows the change over time in the gas composition when the total amount of dry gas of hydrogen, methane, carbon monoxide and carbon dioxide is 100%. The compositions of hydrogen, methane, carbon monoxide and carbon dioxide after the reaction for 4 hours were 10.9%, 16.0%, 0.7% and 72.4%, respectively. The conversion of carbon monoxide was 99.3%.

(3) Breaking stress of the catalyst The catalyst 1 is cut into a size of 50 mm in the warp direction and 25 mm in the weft direction (hereinafter referred to as “longitudinal sample”), and cut into a size of 25 mm in the warp direction and 50 mm in the weft direction. (Hereinafter referred to as “weft direction sample”). About these samples, the breaking stress was measured on the conditions of the distance between chuck | zippers of 30 mm, and the crosshead speed of 30 mm / min using the screw type universal testing machine (LSC-1 / 30-2, Tokyo Test Instruments Co., Ltd.). As a result, the breaking stress in the warp direction and the weft direction of the catalyst 1 was 0.396 MPa and 0.106 MPa, respectively.

(4) Thermal contraction rate of catalyst carrier The SiO ₂ -NA woven fabric was cut into a size of 10 cm square and subjected to heat treatment at 300 ° C. for 1 hour using an electric furnace. Then, by measuring the size of the SiO 2 _-NA fabrics were calculated warp direction and weft direction of shrinkage by the following equation (1).
Shrinkage rate (%) = {(length before heat treatment) − (length after heat treatment)} / (length before heat treatment) × 100 (1)
As a result, the shrinkage rates in the warp direction and the weft direction of the SiO ₂ -NA fabric were 4.8% and 5.0%, respectively.
From the results of Example 1 above, the overall evaluation of the catalyst 1 was appropriate.

Example 2
(1) Production of catalyst for WGS reaction In a mixed solution of 25.0 g of TEOS, 37.6 g of ethanol, 23.5 g of distilled water and 0.3 g of 10 N hydrochloric acid, the weight ratio of ruthenium is 1. Ruthenium chloride n-hydrate and NA woven fabric were added so as to be 2% by weight, soaked for 1 hour, and then naturally dried for 12 hours (hereinafter referred to as “Ru (1.2) Cl ₃ / SiO ₂ -NA woven fabric”. "). The Ru (1.2) Cl ₃ / SiO ₂ —NA fabric was heat-treated at 300 ° C. for 1 hour using an electric furnace. Thereafter, 5 g of the fabric after the heat treatment was immersed in 250 ml of 7% ammonia water, the immersed fabric was put into a rotary evaporator, and the evaporator was rotated in a water bath set at 50 ° C. for 30 minutes at a rotation speed of 20 rpm. This dechlorination step was repeated twice. The fabric after the dechlorination step was sufficiently washed with water and dried in a dryer at 60 ° C. for 4 hours to obtain Catalyst 2.

(2) WGS reaction A WGS reaction and gas analysis were performed in the same manner as in Example 1 except that the catalyst 2 was used as the catalyst. During the reaction, 1.0 g of catalyst 2 is placed in the catalyst bed, and an activation treatment step is performed in which heat treatment is performed at 300 ° C. for 1 hour under vacuum conditions. Water vapor and carbon monoxide are each 3.33 kPa at the same temperature. Each (25 torr) was introduced into the system to carry out WGS reaction.
FIG. 3 shows changes over time in the gas composition when the total amount of dry gas of hydrogen, methane, carbon monoxide and carbon dioxide is 100%. The compositions of hydrogen, methane, carbon monoxide and carbon dioxide after reacting for 4 hours were 30.2%, 4.7%, 10.3% and 54.8%, respectively. The conversion of carbon monoxide was 89.7%.

(3) Breaking stress of catalyst The breaking stress in the warp direction and the weft direction was measured in the same manner as in Example 1 except that the catalyst 2 was used as a sample. As a result, the breaking stress in the warp direction and the weft direction of the catalyst 2 was 0.402 MPa and 0.103 MPa, respectively.

(4) Thermal contraction rate of catalyst The contraction rate was calculated in the same manner as in Example 1 except that Ru (1.2) Cl ₃ / SiO ₂ -NA fabric was used as a sample. As a result, the shrinkage in the warp and weft directions of the Ru (1.2) Cl ₃ / SiO ₂ -NA fabric was 4.9% and 4.9%, respectively.
From the results of Example 2 above, the overall evaluation of the catalyst 2 was appropriate.

Example 3
(1) Production of catalyst for WGS reaction In a mixed solution of 25.0 g of TEOS, 37.6 g of ethanol, 23.5 g of distilled water, and 0.3 g of 10N hydrochloric acid, the weight ratio of ruthenium was 0.00 based on the total weight of the catalyst. Ruthenium chloride n-hydrate and NA woven fabric were added so as to be 8% by weight, soaked for 1 hour, and then naturally dried for 12 hours (hereinafter referred to as “Ru (0.8) Cl ₃ / SiO ₂ -NA woven fabric”). Call it.) 5 g of this Ru (0.8) Cl ₃ / SiO ₂ -NA fabric was immersed in 250 ml of 7% ammonia water, the immersed fabric was placed in a rotary evaporator, and the evaporator was heated in a water bath set at 50 ° C. The dechlorination step of rotating for 30 minutes at a rotation speed of 20 rpm was repeated twice. The fabric after the dechlorination step was thoroughly washed with water and dried in a dryer at 60 ° C. for 4 hours (hereinafter referred to as “Ru (0.8) (OH) ₃ / SiO ₂ -NA fabric”). Thereafter, heat treatment was performed at 300 ° C. for 1 hour using an electric furnace to obtain a catalyst 3.

(2) WGS reaction A WGS reaction and gas analysis were performed in the same manner as in Example 1 except that the catalyst 3 was used as a catalyst. During the reaction, 1.0 g of catalyst 3 was placed in the catalyst bed, and an activation treatment step was performed in which heat treatment was performed at 300 ° C. for 1 hour under vacuum conditions. Water vapor and carbon monoxide were each 3.33 kPa at the same temperature. Each (25 torr) was introduced into the system to carry out WGS reaction.
FIG. 4 shows the change over time in the gas composition when the total amount of dry gas of hydrogen, methane, carbon monoxide and carbon dioxide is 100%. The compositions of hydrogen, methane, carbon monoxide and carbon dioxide after reacting for 4 hours were 18.0%, 1.2%, 24.6% and 56.3%, respectively. Further, the conversion of carbon monoxide was 75.4%.

(3) Breaking stress of catalyst The breaking stress in the longitudinal direction and the weft direction was measured in the same manner as in Example 1 except that the catalyst 3 was used as a sample. As a result, the breaking stress in the warp direction and the weft direction of the catalyst 3 was 0.391 MPa and 0.110 MPa, respectively.

(4) Thermal contraction rate of catalyst The contraction rate was calculated in the same manner as in Example 1 except that Ru (0.8) (OH) ₃ / SiO ₂ -NA fabric was used as a sample. As a result, the shrinkage ratios in the warp and weft directions of the Ru (0.8) (OH) ₃ / SiO ₂ -NA fabric were 4.8% and 5.1%, respectively.
From the results of Example 3 above, the overall evaluation of the catalyst 3 was appropriate.

Comparative Example 1
(1) Production of catalyst for WGS reaction 0.25 g of ruthenium chloride n-hydrate was dissolved in 30 ml of a solution in which distilled water and methanol were mixed at a volume ratio of 2: 1. In this solution, 5 g of NA fabric was added. Soaked. Next, the soaked fabric was placed in a rotary evaporator, and the evaporator was rotated in a water bath set at 50 ° C. for 30 minutes at a rotation speed of 20 rpm, and then dried under reduced pressure using an aspirator to remove moisture. . Further, dechlorination is performed by dipping the dried fabric in 250 ml of 7% ammonia water, placing the soaked fabric in a rotary evaporator, and rotating the evaporator in a water bath set at 50 ° C. for 30 minutes at a rotation speed of 20 rpm. The process was repeated twice. At this time, the ruthenium content was significantly removed from the NA fabric. Thereafter, the fabric after the dechlorination step was sufficiently washed with water, dried in a dryer at 60 ° C. for 4 hours, and heat-treated at 300 ° C. for 1 hour using an electric furnace. In this way, catalyst 4 was obtained.

(2) WGS reaction A WGS reaction and gas analysis were performed in the same manner as in Example 1 except that the catalyst 4 was used as the catalyst. FIG. 5 shows the change over time in the gas composition when the total amount of hydrogen, methane, carbon monoxide and carbon dioxide is 100%. The compositions of hydrogen, methane, carbon monoxide and carbon dioxide after reacting for 4 hours were 7.1%, 0.4%, 85.8% and 6.7%, respectively. The catalyst performance was low as compared with the catalysts 1 to 3 used in the above.

(3) Breaking stress of catalyst The breaking stress in the warp direction and the weft direction was measured in the same manner as in Example 1 except that the catalyst 4 was used as a sample. As a result, the breaking stress in the warp direction and the weft direction of the catalyst 4 was 0.054 MPa and 0.036 MPa, respectively, which was lower than those of the catalysts 1 to 3 prepared in Examples 1 to 3.

(4) Thermal shrinkage rate of catalyst The shrinkage rate was calculated in the same manner as in Example 1 except that NA fabric was used as a sample. As a result, the shrinkage ratios of the warp direction and the weft direction of the catalyst 4 were 26.1% and 23.5%, respectively. Compared with the sample which measured the shrinkage rate in Examples 1-3, the shrinkage rate by heat processing was large.
From the results of Comparative Example 1 described above, the overall evaluation of the catalyst 4 was inappropriate.

The results of Examples 1 to 3 and Comparative Example 1 are shown in Table 1 below.

  From the above results, it has been clarified that by forming a metal oxide film on the NA fabric surface, the amount of active metal supported is increased, and the WGS reaction activity is improved accordingly.

  The catalyst of the present invention can be used in a wide range of applications without being limited by the size and shape of the apparatus to be used, and can be suitably used particularly in a small reactor. For example, it can be suitably used for water gas shift reaction and Fischer-Tropsch reaction.

DESCRIPTION OF SYMBOLS 1 ... TCD-GC, 2 ... FID-GC, 3 ... Diffusion pump, 4 ... Vacuum pump, 5 ... Glass gas reservoir filled with carbon monoxide, 6 ... Electric furnace, 7 ... Catalyst bed, 8 ... Distilled water , 9 ... Circulation pump, 10 ... Manometer, 11a-11l ... Stop valve

Claims (21)

An active metal-supported catalyst based on a fiber sheet, wherein a layer containing a metal oxide is formed on the surface of the fiber sheet, and the active metal is supported on at least one of the surface and the inside of the metal oxide layer. A catalyst ,
The said fiber sheet is the said catalyst containing the fiber of a phenol resin, an aramid, or a polycarbonate . An active metal-supported catalyst for water gas shift reaction based on a fiber sheet , wherein the fiber sheet contains a fiber of phenol resin, aramid, or polycarbonate, and a layer containing a metal oxide is formed on the surface of the fiber sheet The active metal is supported on at least one of the surface and the inside of the metal oxide layer, and the active metal is selected from the group consisting of ruthenium, iron, copper, nickel, and cobalt. Is a catalyst.   The active metal is 0.5 wt% or more and 30 wt% or less based on the total weight of the catalyst, and the metal oxide layer is 0.1 wt% or more and 10 wt% or less based on the total weight of the catalyst, The catalyst according to claim 2, wherein the remainder is the fiber sheet. An active metal-supported catalyst for a Fischer-Tropsch reaction based on a fiber sheet , wherein the fiber sheet contains phenol resin, aramid, or polycarbonate fibers, and a layer containing a metal oxide on the surface of the fiber sheet The catalyst which is formed, the active metal is supported on at least one of the surface and the inside of the metal oxide layer, and the active metal is one or two selected from the group consisting of ruthenium, cobalt and iron.   The active metal is 5 wt% or more and 25 wt% or less based on the total weight of the catalyst, the metal oxide layer is 0.1 wt% or more and 10 wt% or less based on the total weight of the catalyst, and the balance The catalyst according to claim 4, which is the fiber sheet. The catalyst according to any one of claims 1 to 5, wherein the fiber sheet includes phenol resin fibers and aramid fibers. The catalyst according to any one of claims 1 to 6, wherein the phenol resin fiber is a novoloid fiber. The fiber sheet, e epoxy resins, polytetrafluoroethylene, polychlorotrifluoroethylene, polyphenylene sulfide, polyarylate, polysulfone, polyether sulfone, polyetherimide, polyamideimide, polyetheretherketone, Yu rear resins, melamine including resin, diallyl phthalate, silicone resin, furan resin, cellulose acetate, nitrocellulose, cellulose propionate, alumina fiber, at least one fiber selected from the group consisting of basalt fibers, and glass fibers, according to claim 1 to 7 The catalyst in any one of. The catalyst according to any one of claims 1 to 8 , wherein the fiber sheet is in the form of a fiber nonwoven fabric, a woven fabric, or a knitted fabric. Wherein the metal oxide is silica, titania, alumina, zirconia, silica - alumina, silica - titania, silica - zirconia, titania - alumina, or silica - titania - catalyst according to any one of claims 1 to 9, which is a zirconia . A method for producing an active metal supported catalyst based on a fiber sheet,
100% of the total weight of the solution, 10 to 40% by weight of metal alkoxide, 10 to 50% by weight of alcohol, 0.1 to 0.5% by weight of 1-15 N mineral acid, and the remaining water A step of immersing a fiber sheet containing a fiber of phenolic resin, aramid, or polycarbonate in a solution containing,
Heating the soaked fiber sheet;
Immersing the heated fiber sheet in an active metal salt solution;
Heating the soaked fiber sheet;
Including methods. A method for producing an active metal supported catalyst based on a fiber sheet,
In a solution containing metal alkoxide 10 to 40%, alcohol 10 to 50%, 1 to 15 N mineral acid 0.1 to 0.5%, and the balance water, with the total weight of the solution being 100% Adding an active metal salt to and immersing a fiber sheet containing a fiber of phenolic resin, aramid, or polycarbonate ; and
Heating the soaked fiber sheet;
Including methods. The method according to claim 11, wherein the fiber sheet includes phenol resin fibers and aramid fibers. The method according to claim 11, wherein the phenol resin fiber is a novoloid fiber. The fiber sheet, e epoxy resins, polytetrafluoroethylene, polychlorotrifluoroethylene, polyphenylene sulfide, polyarylate, polysulfone, polyether sulfone, polyetherimide, polyamideimide, polyetheretherketone, Yu rear resins, melamine including resin, diallyl phthalate, silicone resin, furan resin, cellulose acetate, nitrocellulose, cellulose propionate, alumina fibers, basalt fibers, and at least one fiber selected from the group consisting of glass fibers, according to claim 11 to 14 The method in any one of. The method according to claim 11 , wherein the fiber sheet is in the form of a fiber nonwoven fabric, a woven fabric, or a knitted fabric. The method according to claim 11 , wherein the metal alkoxide includes at least one selected from the group consisting of tetraethoxysilane, tetraethoxytitanium, and aluminum isopropoxide. The alcohol is at least one selected from the group consisting of methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, and 2-methyl-2-propanol. The method according to claim 11 , comprising: An active metal-supported catalyst carrier based on a fiber sheet containing phenol resin, aramid, or polycarbonate fibers , wherein a layer containing a metal oxide is formed on the surface of the fiber sheet. The catalyst carrier according to claim 19, wherein the fiber sheet includes a phenol resin fiber and an aramid fiber. The catalyst carrier according to claim 19 or 20, wherein the phenol resin fiber is a novoloid fiber.