JP2011000554A - Catalyst-deposited sheet and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a catalyst-deposited sheet in which the thickness uniformity of a catalyst layer and the control of a distribution of a catalytically active component are facilitated to improve a ratio of catalyst particles capable of contributing to a reaction and which is excellent in handleability.SOLUTION: The catalyst-deposited sheet includes: a fluorocarbon resin on which the particles each having catalytic activity are deposited and which is soluble in a polar organic solvent; and a fibrous base material for supporting the fluorocarbon resin.

Description

  The present invention relates to a catalyst-carrying sheet carrying particles having catalytic activity used for chemical reaction in a solution and a method for producing the same, and in particular, a resin sheet formed using a fluororesin that is soluble in a polar organic solvent. The present invention relates to a catalyst-carrying sheet and a method for producing the same.

  Currently, in the chemical industry, catalysts are used in almost all cases utilizing chemical reactions such as synthesis and decomposition of chemical products, decomposition and removal of waste and waste gas, and have achieved remarkable results.

  These catalysts are required not to lose activity even when used for a long time, to have little loss, to be easily separated from raw materials and reaction products after use, and to be easily regenerated after recovery, The economic effect of using such a catalyst is enormous.

  In general, the catalyst used for the above-mentioned use has a metal component having catalytic activity as a main component, and a noble metal is used as this metal component. Usually, such a metal catalyst component is used by being supported on the surface of a carrier. By supporting the catalyst component on the surface of the carrier, the catalyst efficiency can be improved, and the amount supported can be reduced by the effective use of the catalyst component, so it is applied especially when the catalyst component is an expensive noble metal Is done. The catalyst is introduced into the reaction solution in the form of a solution or a fine dispersion in an appropriate diluent, and separated and recovered from the reaction product after the reaction is completed, but the catalyst component is supported on the surface of the carrier. Even when the catalyst component is in the form of particles, the separation and recovery are facilitated.

  As the carrier material, for example, finely powdered activated carbon is used. A palladium-activated carbon catalyst in which palladium is supported on activated carbon, which is a typical example in which a catalyst component is supported on activated carbon, is obtained by treating activated carbon with an acid or a base in advance, and then forming a water-soluble palladium salt such as palladium chloride or palladium nitrate. It is prepared by dipping in an aqueous solution, evaporating to dryness, and reducing treatment. As the reduction treatment, reduction with a liquid phase reducing agent such as hydrazine or sodium borohydride is performed in addition to normal hydrogen reduction. Those using platinum or ruthenium as the active metal are also prepared in the same manner.

  Further, for example, alumina, silica or the like is also used as a carrier material. As the alumina carrier, those utilizing adsorption with metal ions are known, and the supported amount is controlled by coexisting ions such as acid or base. On the other hand, the silica support is difficult to control the location of metal ions because it does not have the ability to adsorb metal ions, especially complex ions, and the metal impregnates the support inside the normal impregnation method. You can only get what you lack.

  For this reason, the solvent to which the metal salt solution is added is instantly evaporated to forcibly adhere the metal salt to the surface of the silica support, or the silica support impregnated with the metal salt is treated with an alkaline solution to make it non-water-soluble. A method for precipitating a noble metal compound and supporting it on the surface of a silica carrier has been studied. Furthermore, since these methods do not necessarily satisfy dispersibility and uniformity, the silica support is modified by reacting with an amino group-containing silane compound, and then contacted with an aqueous solution of a noble metal salt to fix the noble metal ions on the silica surface. And the method of performing a reduction process is proposed (for example, refer patent document 1).

  In addition, one using a porous film made of a synthetic resin as a carrier has been proposed. As the film, a porous film of polyethylene film, tetrafluoroethylene film, vinyl chloride film or the like is used. Immobilization of the catalyst involves mixing and containing the catalyst in a synthetic resin to form a film, or introducing a catalyst on the surface of a carrier such as silica gel, zeolite, activated carbon, etc., and mixing and containing this in the resin to form a film. Alternatively, a method of supporting the catalyst by pressurizing and thermocompression bonding on the surface of the synthetic resin film has been proposed (for example, see Patent Document 2).

  Furthermore, the higher the reaction activity per weight, the better the catalyst. For this reason, it is desirable to increase the porosity of the film catalyst and make it thinner. However, when the porosity of the film-like catalyst is increased or the thickness thereof is reduced, the mechanical strength is lowered, and there is a problem in the possibility of breakage or handling.

  For this reason, a catalyst manufacturing method in which a catalyst dispersion solution is applied onto a support such as metal and dried to form a catalyst layer, or further processed into a honeycomb structure optimal for a fixed bed system Has also been proposed (see, for example, Patent Document 3).

JP-A 64-85141 Japanese Patent Laid-Open No. 1-110541 JP 2008-110341 A

  However, for a catalyst in which a catalyst component is supported by adsorption or modification on alumina or silica, the types of catalyst components that can be supported are limited. Therefore, the catalytic activity is naturally limited by the type of the catalyst component.

  In addition, the catalyst supported on the porous synthetic film is excellent in handleability if there is a sufficient film thickness, but by increasing the thickness, the ratio of the catalyst that cannot contribute to the reaction increases. The activity was not sufficient. On the other hand, when the film thickness is reduced, the ratio of the catalyst that can contribute to the reaction can be improved, but there is a problem that the handleability is deteriorated.

  Furthermore, in a method of forming a catalyst layer by applying a catalyst dispersion solution on a support such as activated carbon or a honeycomb structure and drying, it may be difficult to control the uniformity of thickness and the distribution of active ingredients.

  The present invention has been made to solve such problems, and facilitates control of the uniformity of the catalyst layer thickness and the distribution of the catalytically active component, and improves the ratio of the catalyst that can contribute to the reaction. Furthermore, an object of the present invention is to provide a catalyst-carrying sheet that is excellent in handleability.

In order to achieve the above object, the present invention provides:
The present invention relates to a catalyst-carrying sheet comprising: a fluororesin that is soluble in a polar organic solvent that carries particles having catalytic activity; and a fiber substrate that supports the fluororesin.

  As a result of intensive studies to achieve the above object, the present inventors have reinforced a catalyst carrier made of a fluororesin soluble in a polar organic solvent and particles having catalytic activity with a fiber substrate. The inventors have found that a catalyst-supporting film having a uniform thickness of the catalyst characteristic layer and a uniform distribution of the active component can be obtained even if the catalyst active layer is formed thin, without affecting the handleability.

  In one embodiment of the present invention, the fluororesin can be impregnated in the fiber base (first catalyst-carrying sheet).

  In one embodiment of the present invention, the fluororesin forms a film and can be attached to at least one main surface of the fiber base (second catalyst-carrying sheet).

  Furthermore, in one embodiment of the present invention, the catalyst-carrying sheet can be wound in a spiral shape (third catalyst-carrying sheet).

  Therefore, according to the present invention, it is possible to easily control the uniformity of the catalyst layer thickness and the distribution of the catalytically active component, to improve the ratio of the catalyst that can contribute to the reaction, and to further improve the handling property. Can be provided.

It is a figure which shows the state before winding of the 3rd catalyst support sheet. It is a schematic block diagram of a 3rd catalyst support sheet.

  Hereinafter, the details of the present invention and other features and advantages will be described based on embodiments for carrying out the invention.

(Catalyst carrying sheet)
The catalyst-carrying sheet of the present invention includes a fluororesin that is soluble in a polar organic solvent that carries particles having catalytic activity, and a fiber substrate that supports the fluororesin.

  The particles having catalytic activity are not particularly limited as long as they have known catalytic activity. Specific examples include solid catalysts such as metal catalysts and metal compound catalysts that can be fixed to a resin, but metal compound catalysts are preferred, and perovskite-type metal oxides are preferred because of their high reaction conversion rate. Particularly preferred.

  Examples of the metal compound catalyst include a plurality of kinds of metals selected from metals such as titanium, iron, chromium, cobalt, nickel, copper, ruthenium, rhodium, palladium, rhenium, osmium, iridium, silver, gold, platinum, and tin. The composite metal oxide containing is mentioned, The thing containing palladium like palladium acetate, palladium chloride, etc. is preferable.

As the perovskite type metal oxide, a general formula LaFe _(1-r) Pd _r O _{3 (0 <r <0.2)} may be mentioned. Specifically, LaFe _0.95 Pd _0.05 O _{3 and the} like It can be illustrated.

  The catalyst particles preferably have an average particle size of 1 μm or less. For example, nano-sized composite oxide particles having an average primary particle size of 1 nm to 100 nm are preferably used, and the average secondary particle size is 0. It is preferable that it is 1-10 micrometers.

  The mass ratio of the support and the catalyst particles can be appropriately determined depending on the combination of the materials used. For example, film support: catalyst particles = 1000: 1 to 1:10 can be used. A range of ˜1: 2 is preferred.

Examples of the catalyst particles that are perovskite-type metal oxides preferred above include LaFe _(1-r) Pd _r O _{3 (0 <r <0.2)} as a perovskite-type compound containing palladium. A catalyst carrier having catalytic activity can be obtained by dissolving and mixing catalyst particles having a perovskite structure with a fluororesin.

  Further, the fluororesin constituting the catalyst supporting sheet is not particularly limited as long as it is a fluororesin that is soluble in a polar organic solvent. For example, chlorotrifluoroethylene, perfluoroalkylene vinyl ether, vinylidene fluoride, fluorine A fluorinated monopolymer obtained by polymerizing a compound such as vinyl fluoride, a fluorinated copolymer, or a polymer of a mixture thereof is preferable.

  Among these, polyvinylidene fluoride is particularly preferable as a carrier, and as a bonding form of structural units in the main chain, those containing many Head to Tail bonds in the main chain are preferable.

  In the present invention, the fluororesin is used because the heat resistance and chemical resistance of the fluororesin are good, so it can be used in any environment, and the product life can be extended. This is because it is easy to form a conductive film, and thus a catalytic reaction by a supported catalyst can be efficiently performed.

  Among the fluororesins, polyvinylidene fluoride resin is particularly preferable. While the fluororesin is excellent in heat resistance and chemical resistance, it has a drawback that it is difficult to process. On the other hand, the polyvinylidene fluoride resin is excellent in processability and further has an advantage that it is excellent in the above-described effects specific to the fluororesin.

  As the polyvinylidene fluoride resin, a commercially available product can be used, and examples thereof include Kureha KF polymer (trade name, manufactured by Kureha Co., Ltd.), Kyner 720 (trade name, manufactured by Penwalt).

  In order to form a porous film from a fluororesin, as described below, the fluororesin is melted (swelled) in a polar organic solvent, and then applied onto a release film, followed by solvent drying. Can be obtained.

  The porosity is adjusted by controlling the amount of poor solvent contained in the polar organic solvent, as is generally known.

  The fluororesin may contain inorganic particles and the like as necessary and as long as not departing from the spirit of the present invention. Examples of inorganic particles include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, quartz sand, clay, mica, wollastonite, diatomaceous earth, Examples thereof include chromium oxide, cerium oxide, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride. As long as these inorganic particles are sufficiently smaller than the desired average particle size of the carrier, the average particle size is not particularly limited.

  Resin for catalyst carrier other than fluororesin, for example, polystyrene resin, poly (meth) acrylic resin, polyolefin resin, polyester resin, polyamide resin, polycarbonate resin, polyether resin, polysulfone resin, etc. The obtained films must be subjected to a porous treatment, and the catalyst supported on these films cannot obtain a sufficient catalytic activity (the above-mentioned known films described in Patent Document 3).

  Examples of polar organic solvents for dissolving the fluororesin include acetone, N-methyl-2-pyrrolidone (NMP), methylene dichloride, tetrahydrofuran (THF), N, N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), Polar solvents such as dimethylacetamide (DMAc), hexamethylphosphoric triamide (HMPA), trifluoroacetic acid and the like can be used, but when dissolved (swelled) in NMP solvent, a catalyst carrier having uniform pores can be obtained, which is preferable. . In addition, as above-mentioned, a poor solvent is added suitably for adjustment of porosity.

  As a fiber base material which comprises the catalyst carrying | support sheet | seat of this invention, what consists of organic fiber or an inorganic fiber is used. Organic fibers include polyamide nylon 6, nylon 66, aramid fiber, polyvinyl alcohol fiber, polyester polyethylene terephthalate, polybutylene terephthalate fiber, polyarylate fiber, polyvinylidene chloride, polyvinyl chloride, polyacrylonitrile. And polyolefin-based polyethylene, polypropylene fiber, fluorine-based polytetrafluoroethylene, polyvinylidene fluoride, ethylene / trifluoroethylene chloride copolymer, and the like. Organic fibers include organic regenerated fibers, and examples thereof include cellulosic rayon and acetate. As the inorganic fiber, glass fiber, carbon fiber, activated carbon fiber, ceramic fiber, or the like can be used.

  As these fiber base materials, for example, any of woven fabrics such as plain weave, twill weave and satin weave can be used, and a fiber fabric in which short fibers are converged to form a nonwoven fabric may be used.

  About the thickness of these fiber base materials, 25 micrometers or more and less than 500 micrometers are preferable. If the thickness of the fiber base material is less than 25 μm, or 500 μm or more, there are problems in handling properties, which is not preferable.

  The said fluororesin can be impregnated in the said fiber base material (1st catalyst support sheet).

  In one embodiment of the present invention, the fluororesin forms a film and can be attached to at least one main surface of the fiber base (second catalyst-carrying sheet). In this case, the thickness of the film-like fluororesin is preferably 1 μm or more and 50 μm or less, and more preferably 5 μm or more and 25 μm or less. When the film thickness is less than 1 μm, the film strength is lowered, and it may be difficult to support the catalyst particles on the surface. On the other hand, a carrier having a film thickness of more than 50 μm is not preferable because a large number of catalysts that are present in the carrier and not involved in the reaction increase and the catalyst efficiency decreases.

  In the case of this aspect, the film can be formed on both sides of the fiber base material, but it is more efficient to form the film only on one side. The fiber substrate can be applied to either woven or non-woven fabrics. By adjusting the thickness, filament properties, and fiber density, the diffusion state of the reaction solution and the arrangement of the catalyst-carrying sheet can be set. Can be supported.

  Furthermore, in one embodiment of the present invention, the catalyst-carrying sheet can be wound in a spiral shape (third catalyst-carrying sheet). FIG. 1 is a schematic configuration diagram illustrating an example of the catalyst-carrying sheet according to this embodiment. As shown in FIG. 2, when the catalyst-carrying sheet 10 is formed in a spiral shape, the fluororesin film 11 carrying the catalytically active particles constituting the sheet 10 and the fiber base material 13 are concentrically wound. Thus, the catalyst carrying sheet 10 is configured. Note that the catalyst-carrying sheet 10 before being wound has a configuration as shown in FIG. 2, for example. Note that the configuration shown in FIG. 2 corresponds to an example of a second catalyst-carrying sheet.

  Moreover, in this aspect, the release film 12 is provided between the fluororesin film 11 and the fiber base material 13 according to the manufacturing method demonstrated below.

  The third catalyst-carrying sheet can be incorporated into, for example, a reaction apparatus and accommodated / filled in a holder or case to form a unit as a structure. In this case, since the surface area of the catalyst layer of the catalyst body provided in the reactor can be increased as compared with the catalyst body having a honeycomb structure, it is desirable for the reaction to proceed efficiently.

(Method for producing catalyst-carrying sheet)
Next, the manufacturing method of the catalyst carrying | support sheet | seat of this invention is demonstrated. Here, the description will focus on the manufacturing method of the first catalyst carrying sheet and the second catalyst carrying sheet described above.

  First, after a fluororesin is melted (swelled) in a polar organic solvent, catalyst particles are mixed and dispersed to prepare a catalyst-containing resin solution. In addition, after mixing and dispersing the catalyst particles in the polar organic solvent, the catalyst-containing resin solution may be prepared by melting (swelling) the fluororesin. Mixing / dispersing of the fluororesin and the catalyst particles can be easily performed by a general mixing / dispersing method using a known stirring device or the like. The stirring can be normally performed at ordinary temperature, and the stirring speed is not particularly limited as long as the mixture of the carrier and the dispersion of the catalyst particles can be mixed uniformly.

  In addition, in order to sufficiently disperse or to disintegrate and disperse particles when they are likely to aggregate, using a media dispersion device such as a ball mill, a high-speed high shear mixer such as a high-pressure homogenizer, etc. An operation of uniformly dispersing the catalyst particles in the fluororesin may be performed.

  Next, when producing the first catalyst-carrying sheet, the fiber-based substrate is impregnated with the catalyst-containing resin solution obtained as described above. The method for impregnating the fiber base material with the catalyst-containing resin solution is not particularly limited, but it is preferable to use a vertical coating machine, and further, a roll for adjusting the speed, temperature, and resin impregnation amount. It is particularly desirable to have a device for controlling the gap.

  Next, after impregnating the fiber base material with the catalyst-containing resin solution, the solvent in the solution is dried and evaporated. The drying conditions vary depending on the coating thickness and the organic solvent used, but it is generally desirable to carry out at 130 to 200 ° C. for 10 to 60 minutes. If it is less than 130 ° C. or less than 10 minutes, the removal of the solvent is insufficient, and if it is 200 ° C. or more or 60 minutes or more, the production cost increases, which is not preferable.

  In order to satisfactorily perform the impregnation, when the catalyst-containing resin solution is applied on the fiber base material, the application amount is usually 10 to 80% by volume, more preferably 20 to 70% by volume in terms of resin Is preferred. If it is less than 10% by volume, it cannot be uniformly coated and the fiber base material may not be sufficiently impregnated with resin. On the other hand, if it exceeds 80% by volume, application and impregnation operations become difficult.

  When the second catalyst-carrying sheet is produced, for example, the catalyst-containing resin solution obtained as described above is applied onto a release film, and then dried to remove the solvent and form a film. . Any of the existing coating methods can be applied. Specifically, a coating film is formed by a coater such as a gravure coater, reverse roll coater, kiss coater, roll knife coater, rod coater, etc. There are a film forming method, a bar coating method, a screen printing method, and the like, which are selected according to the product form.

  As described above, the coating thickness (that is, the film thickness to be formed) is preferably 1 μm or more and 50 μm or less, and more preferably 5 μm or more and 25 μm or less. When the coating thickness is less than 1 μm, the film strength is lowered, and it may be difficult to support the catalyst particles on the surface. On the other hand, a coating thickness exceeding 50 μm is not preferable because there are many catalysts that are present in the support and do not participate in the reaction, and the catalyst efficiency is lowered.

  Next, the catalyst-containing resin film obtained as described above is deposited on at least one main surface of the fiber base material. Although it does not specifically limit as a method to adhere, For example, a thermocompression bonding method can be used. In this case, since the catalyst-containing resin film is softened, it can be easily applied onto the main surface of the fiber substrate.

  A general-purpose method can be used as the thermocompression bonding method, and preferred examples include thermal lamination and hot pressing. For example, when a heat laminating method is adopted, it can be suitably produced under conditions of a pressure of 1 to 10 MPa with a hot roll at a roll temperature of 100 to 200 ° C., and when a hot press is adopted, between hot plates at a temperature of 100 to 200 ° C. It can be suitably produced by hot pressing under a pressure of 1 to 10 MPa.

  If the temperature is lower than 100 ° C. or a pressure of 1 MPa, the adhesive strength is weak and there is a risk of peeling between layers, such being undesirable. There is no particular problem even if the temperature is higher than 200 ° C. or a pressure of 10 MPa, but it is not appropriate because the load on the applied equipment increases.

  The catalyst-carrying sheet produced as described above can be used after being cut into necessary dimensions, and can be easily separated and recovered after the reaction. The supported catalyst separated and recovered in this way can be repeatedly used for the catalytic reaction in the same manner as a normal catalyst.

  In the above description, the manufacturing method of the first catalyst supporting sheet and the second catalyst supporting sheet has been mainly described. However, the manufacturing method can be appropriately changed according to the configuration of the catalyst supporting sheet.

  Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. The present invention is not limited to these examples.

Example 1
25 parts by mass of a 12% by mass solution of polyvinylidene fluoride (manufactured by Kureha Co., Ltd .; mass average molecular weight 280,000) using N-methyl-2-pyrrolidone as a solvent and 0.07 mass of palladium acetate (manufactured by Kanto Chemical Co., Inc.) Partly weighed and mixed to obtain a catalyst particle dispersion. 100 parts of DMF was added to 100 parts of the catalyst particle dispersion to prepare a catalyst-containing resin solution 1.

Next, 40 polyarylate long fibers “Vectran HT type” (manufactured by Kuraray Co., Ltd.) are bundled into one yarn, and plain weave with a warp density of 35 per inch and a weft density of 35 per inch. A woven fabric 1 made of polyarylate continuous fibers having a thickness of 62 g / m ² and a thickness of 0.1 mm was obtained. Next, the catalyst-containing resin solution 1 was immersed and impregnated in the woven fabric 1 composed of the polyarylate long fibers, and then dried at 150 ° C. for 30 minutes to obtain a catalyst-carrying sheet having a resin content of 40% by mass.

(Example 2)
The catalyst-containing resin solution 1 obtained in Example 1 was applied to a polyester film (trade name: Lumirror, manufactured by Toray Industries, Inc.) with an applicator and dried at 70 ° C. for 30 minutes to form a catalyst-carrying film having a thickness of 10 μm. Manufactured. Next, it was placed on the woven fabric 1, sandwiched between mirror plates, sandwiched between 170 ° C. hot plates, and heated and pressurized at a pressure of 3.0 MPa for 60 minutes to obtain a catalyst-carrying sheet.

(Example 3)
Example 2 except that instead of palladium acetate (manufactured by Kanto Chemical Co., Inc.), 6 parts by mass of LaFe _0.95 Pd _0.05 O ₃ (manufactured by Hokuko Chemical Co., Ltd.) which is a perovskite type metal oxide. A catalyst-supporting film was produced by the same operation as described above.

Example 4
15.0 parts by mass of polytetrafluoroethylene (manufactured by Daikin Industries, Ltd., trade name: Polyflon M-392; [PTFE]) and 3.0 masses of LaFe0.95PD0.0503 (made by Hokuko Chemical Industries, Ltd.) The parts were weighed, mixed for 20 hours in a ball mill (diameter 2 mm zirconia balls, filling rate 60%), kneaded and rolled at 260 ° C. without using a solvent, and then formed into a film to produce a catalyst-carrying film having a thickness of 10 μm. .

(Comparative Example 1)
The catalyst-containing resin solution 1 obtained in Example 1 was applied to a polyester film (trade name: Lumirror, manufactured by Toray Industries, Inc.) with an applicator, dried at 70 ° C. for 30 minutes, and a catalyst support having a film thickness of 35 μm. A film was produced.

(Comparative Example 2)
15.0 parts by mass of polyethylene resin (average molecular weight 150,000) and 3.6 parts by mass of LaFe _0.95 Pd _0.05 O ₃ (made by Hokuko Chemical Co., Ltd.) are weighed and mixed, and kneaded without using a solvent. And then rolled into a film to produce a catalyst-carrying film having a thickness of 35 μm.

(Comparative Example 3)
15.0 parts by mass of polytetrafluoroethylene (manufactured by Daikin Industries, Ltd., trade name: Polyflon M-392; [PTFE]) and 3.0 masses of LaFe _0.95 Pd _0.0503 (manufactured by _Hokuko Chemical Co., Ltd.) Partly weighed and mixed, kneaded and rolled at 260 ° C. without using a solvent, and then formed into a film to produce a catalyst-carrying film having a thickness of 35 μm.

(Test example)
Next, the catalyst conversion films produced in Examples and Comparative Examples were evaluated for reaction conversion rate, catalyst particle detachment, catalyst film recoverability and film shape after recovery, and the results are shown in Table 1. It was. The catalyst-carrying film was used by being peeled off from the polyester film that is a release film. Moreover, each evaluation was implemented on the conditions as shown below.

[Reaction conversion rate]
2.24 g (0.012 mol) of 4-bromoanisole, 2.19 g (0.018 mol) of phenylboronic acid and 4.98 g (0.036 mol) of potassium carbonate were added to a 100 mL round bottom flask. In addition, 18 mL each of pure water and 1-methoxy-2-propanol were added as solvents and dissolved by stirring. The catalyst-carrying film obtained in Examples and Comparative Examples is brought into contact with this solution (at this time, a catalyst-carrying film containing an amount corresponding to 0.005 mol% of the catalyst component with respect to 4-bromoanisole is used). And allowed to react at room temperature for 24 hours.

After completion of the reaction, 20 mL each of toluene and pure water was added to the reaction solution to dissolve the product, and then the insoluble material was removed by suction filtration, then transferred to a separatory funnel, and the lower aqueous layer was separated. The upper toluene layer was analyzed by gas chromatography to determine the reaction conversion rate.
Reaction conversion rate (%) = 4-methoxybiphenyl (reaction product) / 4-bromoanisole + 4-methoxybiphenyl (reaction product) (previously measured in toluene solution of 4-methoxybiphenyl and 4-bromoanisole separately) Relative sensitivity was obtained and corrected.)

[Desorption of catalyst particles]
The surface of the catalyst-carrying film after the reaction conversion rate was evaluated was observed with an electron microscope and evaluated based on the presence or absence of catalyst particles.
○: No change, Δ: Slight change is observed, ×: Omission of components having clear catalytic activity is observed.

[Recoverability of catalyst]
The sample after the reaction conversion rate evaluation was collected by filtration, and the mass of the catalyst support was calculated and evaluated.
○: over 95%, Δ: 95% to 85%, x: less than 85%

[Film shape]
In the catalyst recovery evaluation, the film shape of the collected sample was visually evaluated. Those that did not change before and after the test were flat, and other abnormalities were described (cracking or dissolution deformation).

[Handling]
The reactor was evaluated for charging into the reactor, operating conditions in the reactor, separation, recovery, and washing after the reaction.
○: No problem, ×: Poor handling due to occurrence of twisting, etc.

[Tear strength]
The tear strength (N) by the trouser tear method was measured according to JIS K 7128/1.

  As can be seen from the results shown in Table 1, the catalyst-carrying sheet using the fiber base material of the present invention as a support is excellent in handleability and has a high reaction conversion rate and a high ratio of catalyst that can contribute to the reaction. . That is, it can be seen that the uniformity of the catalyst layer thickness and the uniformity of the distribution of the catalyst active component are excellent. Further, it can be seen that there is little separation of the catalyst, the catalyst recoverability is excellent, and the sheet strength is also excellent.

  While the present invention has been described in detail based on the above specific examples, the present invention is not limited to the above specific examples, and various modifications and changes can be made without departing from the scope of the present invention.

Claims (9)

A fluororesin soluble in a polar organic solvent carrying particles having catalytic activity;
A fiber base material supporting the fluororesin;
A catalyst-supporting sheet comprising:   The catalyst-carrying sheet according to claim 1, wherein the fluororesin is polyvinylidene fluoride.   The catalyst carrying sheet according to claim 1, wherein the fluororesin is impregnated in the fiber base material.   The catalyst-carrying sheet according to claim 1 or 2, wherein the fluororesin forms a film and is adhered to at least one main surface of the fiber base material.   The catalyst carrying sheet according to claim 3 or 4, wherein the catalyst carrying sheet is wound in a spiral shape. A step of melting a fluororesin in a polar organic solvent and mixing and dispersing particles having catalytic activity to prepare a catalyst-containing resin solution;
Applying and impregnating the catalyst-containing resin solution on a fiber base material, and drying;
A method for producing a catalyst-carrying sheet, comprising: A step of melting a fluororesin in a polar organic solvent and mixing and dispersing particles having catalytic activity to prepare a catalyst-containing resin solution;
Forming the catalyst-containing resin solution into a film and forming a catalyst-containing resin film;
Depositing the catalyst-containing resin film on at least one main surface of the fiber substrate;
A method for producing a catalyst-carrying sheet, comprising:   The catalyst according to claim 7, wherein the catalyst-containing resin solution is applied on a release film, and then dried to remove the solvent, thereby forming the catalyst-containing resin film on the release film. A method for producing a carrier sheet.   The method for producing a catalyst-carrying sheet according to claim 7 or 8, wherein the catalyst-containing resin film is adhered to the fiber base material by thermocompression bonding.

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