JP6740104B2 - Film catalyst - Google Patents

Description

The present invention relates to a film catalyst and a method for producing a film catalyst.

As a chemical process in the chemical industry, a process utilizing a solid catalyst has been widely adopted. In this method, a powdery catalyst in the form of fine particles is often used as the catalyst, and the catalyst is added directly to the reaction vessel for reaction. In a reaction process using a powdery catalyst, a technique such as stirring for effectively mixing a reactant and a catalyst is required. Further, there is a problem that after the reaction is completed, it is necessary to remove the catalyst from the product, which complicates the equipment and operation. Further, in this system, a large amount of filter aid is added, but since the catalyst is particles, the filtration time is long, and the filter aid adsorbs many reactants, which causes a decrease in reaction yield. There is.

By increasing the powder particle size by supporting the powdered catalyst on a porous carrier such as zeolite, the filterability of the fine particle powder can be improved and the filtration time can be shortened. Also, the problem of complicated operation and the problem of requiring a large amount of filter aid cannot be solved.

On the other hand, a fixed bed system can be mentioned as a process that does not require a mixing operation of the catalyst by stirring or the like and does not require the separation of the catalyst by filtration. A film catalyst as a novel form of a solid catalyst used in a fixed bed system is disclosed in Patent Document 1 and Patent Document 2. Patent Document 1 discloses a method for producing a tertiary amine having excellent reaction selectivity by using a film catalyst having a thickness of 100 μm or less in the method for producing an amine. Patent Document 2 discloses a method for producing a film catalyst in which a catalyst layer having a specific pore size distribution is formed on a support to enhance reaction activity and reaction selectivity.

International Publication No. 2005/035122 JP, 2008-110341, A

The film-type catalysts disclosed in Patent Document 1 and Patent Document 2 are excellent inventions in that they have good catalytic activity and a small amount of catalyst dropped out.

The present invention is a further improvement of the inventions disclosed in Patent Document 1 and Patent Document 2, and provides a film catalyst having good reaction selectivity and a small amount of catalyst loss, and a method for producing the same. Is an issue.

The present invention is a film catalyst having a catalyst layer formed on a support, wherein the catalyst layer contains catalyst particles having a particle diameter of 1.3 μm or more and 3.3 μm or less containing a powdered catalyst and a binder,
The present invention relates to a film catalyst, wherein the catalyst layer has a pore volume of 0.40 mL/g or more and 0.87 mL/g or less.

The present invention also relates to a method for producing the film catalyst, which comprises the following steps.
Step 1: A step of preparing a coating composition containing a powdery catalyst, a binder and a solvent, wherein the particle size of the catalyst particles containing the powdery catalyst and the binder in the coating composition is 1.3 μm or more and 3.3 μm or less. Step 2: Applying the coating composition onto a support to form a catalyst layer

According to the present invention, it is possible to provide a method for producing a film catalyst, which has a good reaction selectivity and a small amount of catalyst falling off.

The schematic sectional drawing of the film catalyst obtained by the manufacturing method of this invention. 1. The partial cross section figure of FIG. FIG. 3 is a partial sectional view of FIG. 2. The perspective view of one embodiment of the film catalyst obtained by the manufacturing method of the present invention. The perspective view of other embodiment of the film catalyst obtained by the manufacturing method of the present invention. The perspective view of further another embodiment of the film catalyst obtained by the manufacturing method of the present invention.

<Film catalyst>
The film catalyst used in the present invention is a film catalyst having a catalyst layer formed on a support, and the catalyst layer contains a powder catalyst and a binder and has a particle size of 1.3 μm or more and 3.3 μm or less. And a catalyst layer having a pore volume of 0.40 mL/g or more and 0.87 mL/g or less.

In the present invention, the "powdered catalyst" means a powdery catalyst having catalytic activity. The "catalyst particle" means a particle containing a powdery catalyst and a binder and having a specific particle diameter. Further, the "film catalyst" means that the support has a film shape .

[Powdered catalyst]
As the powdery catalyst, a catalyst active material or a catalyst active material supported on a porous material can be used.

The catalyst active material may be any component effective for the applied chemical reaction, such as Ag, Au, Cu, Ni, Fe, Al, the fourth period transition metal element, the platinum group element, and the 3A group element of the periodic table. , Metal elements such as alkali metals and alkaline earth metals, and metal oxides thereof.

The porous material serves as a catalyst carrier that carries a catalyst active material, and examples thereof include one or more porous materials selected from activated carbon, alumina, silica, zeolite, titania, silica-alumina, diatomaceous earth, and the like. More preferably, a porous material having a high surface area is used, and in addition, a molecular sieve or the like can be used.

As a method for supporting the catalyst active material on the catalyst carrier, a known method such as an ordinary impregnation method, co-impregnation method, co-precipitation method, or ion exchange method can be applied.

The particle diameter of the powdery catalyst is preferably 1.3 μm or more, more preferably 1.5 μm or more, still more preferably 1.8 μm or more, from the viewpoint of filtration separation of the catalyst, and preferably from the viewpoint of reaction activity of the catalyst. Is 4.5 μm or less, more preferably 4.3 μm or less, and further preferably 4.0 μm or less. Here, the particle diameter is defined as a median diameter calculated on a volume basis.
Further, the specific surface area of the powdery catalyst by the BET method is preferably 0.1 m ² /g or more, more preferably 1 m ² /g or more, further preferably 10 m ² /g or more, from the viewpoint of filtration separation of the catalyst, and From the viewpoint of reaction activity of the catalyst, it is preferably 500 m ² /g or less, more preferably 200 m ² /g or less, still more preferably 100 m ² /g or less.

The particle size of the powdery catalyst can be measured by diluting the powdery catalyst with a solvent and using a laser diffraction/scattering particle size distribution analyzer (LA-950, manufactured by Horiba, Ltd.).

〔binder〕
The binder is preferably one that is excellent in binding properties between the powdery catalysts and to the surface of the support, is resistant to the reaction environment, and does not adversely affect the reaction system. Examples of such a binder include cellulosic resins such as carboxymethyl cellulose and hydroxyethyl cellulose, fluororesins such as polytetrafluoroethylene and polyvinylidene fluoride, polyvinyl alcohol, urethane resins, epoxy resins, polyamide resins, polyimide resins, polyamideimides. Various thermoplastic resins and thermosetting resins such as resins, polyester resins, phenol resins, melamine resins, and silicone resins can be used, and by introducing a cross-linking reaction with a curing agent into these synthetic resins, higher polymerization can be achieved. What is designed can also be used. Of these, a thermosetting resin such as a phenol resin, a furan resin or an epoxy resin is preferable, and more preferably, a thermosetting resin that accompanies a condensation reaction during curing can be used.

When a thermosetting resin is used as a binder, the crosslinking density is improved by the curing reaction to improve the film strength and binding property, and the catalytic activity of the powdery catalyst is effectively derived from the porosity of the catalyst coating film by the condensation reaction. be able to.

When the film catalyst of the present invention is used in a reaction for producing a tertiary amine from an alcohol and a primary amine or a secondary amine, one example of a preferable combination of a powdery catalyst and a binder is a copper-nickel-ruthenium ternary system. A combination of powdered catalyst and phenolic resin may be mentioned.

〔solvent〕
In addition to the powdery catalyst and the binder, a solvent is used to improve the wettability of the surface of the powdery catalyst, dissolve the binder, and promote mixing and homogenization of these blends.

Any solvent may be used as long as it does not adversely affect the catalytic activity of the powdery catalyst, and various water-soluble or water-insoluble solvents can be selected depending on the type of binder used. The pore structure of the film catalyst can be controlled by selection. Further, the solvent preferably has good binder solubility, and two or more kinds of solvents may be used in combination, and the pore structure of the catalyst layer is controlled by selecting a solvent suitable for the binder used. be able to.

As the solvent, water; alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol, allyl alcohol; ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK); ethylene glycol, propylene glycol, diethylene glycol , Polyethylene glycol, polypropylene glycol, diethylene glycol monoethyl ether, polypropylene glycol monoethyl ether, polyethylene glycol monoallyl ether, polypropylene glycol monoallyl ether and other glycols or derivatives thereof; glycerol, glycerol monoethyl ether, glycerol monoallyl ether, etc. Glycerol or its derivatives; ethers such as tetrahydrofuran and dioxane; liquid paraffin, decane, decene, methylnaphthalene, decalin, kerosene, diphenylmethane, toluene, dimethylbenzene, ethylbenzene, diethylbenzene, propylbenzene, cyclohexane, partially hydrogenated tri Hydrocarbons such as phenyl; halogenated hydrocarbons such as chlorobenzene, dichlorobenzene, bromobenzene, chlorodiphenyl, chlorodiphenylmethane; fluorides such as demnum (manufactured by Daikin Industries, Ltd.); ethyl benzoate, octyl benzoate, Ester compounds such as dioctyl phthalate, trioctyl trimellitate, dibutyl sebacate, ethyl (meth)acrylate, butyl (meth)acrylate, and dodecyl (meth)acrylate; dimethylformamide, N-methyl-pyrrolidone, acetonitrile , Ethyl acetate and the like.
Among them, the solvent is preferably alcohols and ketones, more preferably ketones, and further preferably methyl ethyl ketone (MEK), from the viewpoint of wettability of the powdery catalyst surface and solubility of the binder.

[Other ingredients]
In addition to the above components, the catalyst layer may contain a surfactant or a coupling agent as a dispersion aid, inorganic particles as an aggregate, a fibrous substance or the like, and a high boiling point solvent or the like as a porosity aid. .. The coupling agent has the effect of performing molecular crosslinking at the interface between the inorganic filler and the organic polymer matrix and improving the physical properties.

As the coupling agent, those generally known as silane coupling agents, titanate-based coupling agents and aluminate-based coupling agents can be used. It may be used after diluting with an organic solvent compatible with.

Organic fibers or inorganic fibers are used as the fibrous substance. As the organic fibers, polyamide type nylon 6, nylon 66, aramid fiber, polyvinyl alcohol type fiber, polyester type polyethylene terephthalate, polybutylene terephthalate fiber, polyarylate fiber, polyvinylidene chloride type Examples thereof include polyvinyl chloride-based, polyacrylonitrile-based, and polyolefin-based polyethylene and polypropylene fibers. The 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. By blending each of the above fibers, the mechanical strength (membrane strength) of the catalyst layer can be improved due to the expression of the aggregate effect.

[Support]
The support used in the present invention can be appropriately selected depending on the intended form of the film catalyst, and a support that can be processed into a flat plate shape, a tubular shape, a honeycomb shape, a monolith shape or the like can be used. The thickness of the support is preferably 1 mm or less, but is not limited to this.

The flat plate-shaped support may have appropriate processability and durability and does not adversely affect the reaction system in which the film-shaped catalyst of the present invention is used. For example, as a metal foil, a copper foil, Examples thereof include stainless steel foil and aluminum foil. Preferably, a copper foil or a stainless foil can be used in terms of workability and corrosion resistance.

Further, as the honeycomb or monolith-shaped support, cordierite, carbon composite, mullite, clay, magnesia, talc, zirconia, spinel, alumina, silica, ceria, titania, tungsten, chromium, stainless steel, copper, aluminum and Examples thereof include nickel, but are not limited thereto.

Here, the honeycomb shape is a honeycomb-shaped structure partitioned by thin walls, and is a shape in which a large number of cells are integrated. Since a large surface area per unit volume can be obtained, it is preferable as a support constituting a film catalyst. .. It is preferable to use regular triangles, regular pentagons, and regular hexagons for the cells because they can be integrated without a gap, and cells with different shapes or polygonal cells can be combined. For example, as a support of honeycomb-shaped, flat plate-like material and a flat plate-like material shaped machined support resulting corrugated material a (corrugated) formed by stacking many layers also can be preferably used.

Further, the surface of the support is preferably roughened or coupled from the viewpoint of improving the adhesion to the catalyst layer. The coupling agent described above can be used for this coupling treatment.
When the surface of the support is roughened, the surface roughness Rz of the support is preferably 1.0 μm or more, from the viewpoint of improving the adhesion to the catalyst layer and the diffusibility of the reaction substrate in the catalyst layer. More preferably 2.0 μm or more, still more preferably 2.5 μm or more, still more preferably 3.0 μm or more, and preferably 30.0 μm or less, more preferably 25.m or more from the viewpoint of ensuring the uniformity of the catalyst layer. It is 0 μm or less, more preferably 20.0 μm or less. Here, the surface roughness Rz is the maximum height of the roughness curve and is defined in JIS B 0601 (2001).
The surface roughness of the support can be calculated, for example, by using a dedicated measuring machine such as a surface roughness measuring device (model number CS-3200 manufactured by Mitutoyo Co., Ltd.). The measuring method is the method described in JIS B 0601.

Examples of the method for roughening the support include, but are not limited to, physical roughening treatment and chemical roughening treatment.

[Catalyst layer]
The particle size of the catalyst particles containing the powdery catalyst and the binder in the catalyst layer formed on the support is 1.3 μm or more, preferably 1.5 μm or more, and more preferably 1.8 μm or more from the viewpoint of catalytic activity. And, from the viewpoint of ensuring the uniformity of the film thickness of the film catalyst layer and the film strength, it is 3.3 μm or less, preferably 3.0 μm or less, and more preferably 2.8 μm or less.
Here, the particle diameter is defined as a median diameter calculated on a volume basis.

Examples of the catalyst particle size include a method of calculating from the cross-sectional image of the catalyst layer and a method of calculating from the coating composition containing the catalyst particles.
When calculated from the coating composition, it can be measured by using a laser diffraction/scattering type particle size distribution measuring device (LA-950 manufactured by Horiba, Ltd.).

The pore volume of the catalyst layer is 0.40 mL/g or more, preferably 0.45 mL/g or more, more preferably 0.5 mL/g or more, and the catalyst from the viewpoint of diffusibility of the reaction substrate in the catalyst layer. From the viewpoint of ensuring the denseness of the layer and the film strength, it is 0.87 mL/g or less, preferably 0.85 mL/g or less, more preferably 0.83 mL/g or less.
Here, the pore volume of the catalyst layer is defined as the pore volume per unit mass of the powdery catalyst in the catalyst layer.

As the method for measuring the pore volume, the pore volume can be measured by using a mercury-penetration-type pore distribution measuring apparatus (manufactured by Shimadzu Corporation, Poisizer 9320) or the like for exclusive use with the mercury-penetration method.

The average macropore diameter of the catalyst layer is preferably 0.20 μm or more, more preferably 0.21 μm or more, still more preferably 0.22 μm or more, from the viewpoint of diffusing the reaction substrate into the catalyst layer and increasing the reaction selectivity. From the viewpoint of the denseness of the catalyst layer, it is preferably 0.50 μm or less, more preferably 0.49 μm or less, still more preferably 0.48 μm or less.
Here, the average macropore diameter is defined as the pore diameter D when the pores in the catalyst layer are assumed to be cylindrical pores. The pore diameter D can be calculated from the pore volume Vo and the pore area A by D=4Vo/A.

The average macropore diameter is measured by using a mercury press-fitting type pore distribution measuring device (manufactured by Shimadzu Corp., Poisizer 9320) or the like to measure the pore volume Vo and the pore area A by using a dedicated mercury press-fitting measuring machine. By measuring, it can be calculated from the above formula.

The content ratio of the powdery catalyst in the catalyst layer is preferably 50% by mass or more, more preferably 60% by mass or more, and further preferably 64% by mass from the viewpoint of expressing high reaction activity and reducing the amount of by-products. As described above, further preferably 66% by mass or more, and from the same viewpoint, preferably 91% by mass or less, more preferably 90% by mass or less, further preferably 88% by mass or less, still more preferably 83% by mass or less. is there.

The content ratio of the binder in the catalyst layer is preferably 9% by mass or more, more preferably 10% by mass or more, further preferably 12% by mass or more, still more preferably 17 from the viewpoint of binding property to the surface of the support. From the same viewpoint, it is preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 36% by mass or less, still more preferably 34% by mass or less.

The mass ratio of the powdery catalyst and the binder in the catalyst layer (powdered catalyst/binder) is preferably 1 or more, more preferably 1.5 or more, still more preferably 1.8 or more from the viewpoint of exhibiting high reaction activity. It is more preferably 2 or more, and from the viewpoint of binding to the surface of the support, preferably 10 or less, more preferably 9 or less, still more preferably 7.5 or less, still more preferably 5 or less.

[Structure of film catalyst]
The film catalyst of the present invention has a catalyst layer on one surface or both surfaces of the support. Hereinafter, the layer structure of the catalyst layer in the film catalyst of the present invention will be described with reference to the drawings.

FIG. 1 is a conceptual diagram showing a layer structure of a catalyst layer in a film catalyst obtained by the production method of the present invention when cut in a thickness direction, and FIG. 2 is a portion surrounded by a square in FIG. 3 is an enlarged view of FIG. 3, and FIG. 3 is an enlarged view of a portion surrounded by a square in FIG. 2.

As shown in FIG. 1, the film catalyst 1 has a catalyst layer 3 on both sides of a support 2 (the catalyst layer 3 may be only one side of the support 2). As shown in FIG. 2, the catalyst layer 3 includes the powdery catalyst 4 and the binder 5 that covers the periphery of the powdery catalyst 4 to form catalyst particles, and a plurality of powdery catalysts 4 (and powdery catalyst 4 Between the binders 5) that surround the periphery, there are gaps 6 surrounded by broken lines in the figure. Further, as shown in FIG. 3, the binder 5 covering the periphery of the powdery catalyst 4 has a hole 7 surrounded by a broken line in the figure, and at the portion of the hole 7, the powdery catalyst 4 is a binder. It is not covered with 5, and the surface is exposed.

In the film catalyst of the present invention, the thickness of the catalyst layer is preferably 1 μm or more, more preferably 3 μm or more, further preferably 5 μm or more, from the viewpoint of exhibiting high reaction activity and the viewpoint of reducing the amount of by-products, and It is preferably 500 μm or less, more preferably 100 μm or less, still more preferably 50 μm or less. From the same viewpoint, the amount of the catalyst layer supported per unit area is preferably 0.5 g/m ² or more, more preferably 1 g/m ² or more, still more preferably 5 g/m ² or more, and preferably 100 g/m ^2. m ² or less, more preferably 50 g/m ² or less, still more preferably 30 g/m ² or less. The catalyst layer loading amount per unit area is the loading amount when the catalyst layer is provided on only one surface of the support. When the catalyst layer is provided on both sides, the amount of catalyst layer supported per unit area is doubled.

The total thickness of the film catalyst of the present invention is preferably 1 μm or more and 200 μm or less, but is not limited to this.

<Method for producing film catalyst>
The method for producing a film catalyst of the present invention is the method for producing a film catalyst, which comprises the following steps.
Step 1: A step of preparing a coating composition containing a powdery catalyst, a binder and a solvent, wherein the particle size of the catalyst particles containing the powdery catalyst and the binder in the coating composition is 1.3 μm or more and 3.3 μm or less. Step 2: Applying the coating composition onto a support to form a catalyst layer into the film-like catalyst of the present invention. You can

[Step 1]
Step 1 is a step of preparing a coating composition containing a powdery catalyst, a binder and a solvent, wherein the catalyst particles containing the powdery catalyst and the binder in the coating composition have a particle diameter of 1.3 μm or more and 3.3 μm or more. It is a step of preparing as follows.

The content ratio of the powdery catalyst in the coating composition is preferably 10% by mass or more, more preferably 20% by mass or more, further preferably 30% by mass from the viewpoint of exhibiting high reaction activity and the viewpoint of reducing the amount of by-products. % Or more, and from the same viewpoint, it is preferably 90% by mass or less, more preferably 80% by mass or less, and further preferably 70% by mass or less.

The content ratio of the binder in the coating composition is preferably 3% by mass or more, more preferably 5% by mass or more, further preferably 10% by mass or more, and the same, from the viewpoint of binding property to the surface of the support. From the viewpoint, it is preferably 40% by mass or less, more preferably 25% by mass or less, and further preferably 20% by mass or less.

The mass ratio of the powdery catalyst to the binder (powdered catalyst/binder) in the coating composition is preferably 1 or more, more preferably 1.5 or more, and further preferably 1.8 from the viewpoint of exhibiting high reaction activity. Or more, more preferably 2 or more, and from the viewpoint of binding property to the surface of the support, preferably 10 or less, more preferably 9 or less, still more preferably 7.5 or less, still more preferably 5 or less. ..

By setting the content ratio of the powdery catalyst to the binder within a predetermined range, it becomes possible to control the degree of exposure of the powdery catalyst, and further to bring out the catalytic activity originally possessed by the powdery catalyst. Therefore, the effect of preventing the catalyst layer from falling off can be improved. Specifically, as shown in FIGS. 1 to 3, it is possible to control the surface of the powdery catalyst so that a portion coated with the binder and a portion not coated with the binder are present, and therefore, the catalyst activity described above is present. And the effect of dropping the catalyst layer can be exhibited.

When the content of the binder is 40% by mass or less, the thickness of the binder covering the surface of the powdery catalyst or the coating state of the binder as shown in FIG. 3 becomes appropriate, and the catalytic activity of the powdery catalyst is sufficiently exhibited. As a result, high catalytic activity can be exhibited. When the content ratio of the binder is 10% by mass or more, the catalytic activity is sufficiently exhibited, the binding force between the powdery catalysts or between the powdery catalysts and the support is improved, and during the production process of the filmy catalyst and the reaction operation. The amount in which the catalyst layer peels off or falls off partly is suppressed.

The method for preparing the coating composition is not particularly limited as long as each component can be uniformly mixed, but in the present invention, it is preferable to prepare using a media type mill or a paint shaker. By using a media type mill, each component constituting the above coating composition can be uniformly processed due to its structure and mechanism, so that the particle size and dispersion state of the catalyst particles can be controlled to form a film. It is suitable for controlling the pore size distribution of the catalyst layer of the catalyst.

Media type mills include ball mills, attritors (Mitsui Mining Co., Ltd., registered trademark), AD mills, twin AD mills, basket mills, twin basket mills, handy mills, SC mills, gren mills, dyno mills, apex mills, star mills (Ashizawa Fine Tech Co., Ltd.), Viscomill, sand grinder, paint shaker using beads, and the like. In the present invention, a dissolver type mixing/dispersing machine can be used as a dispersing machine other than the media type mill.

The coating composition has a preparation time time (sec.) in a media type mill, a representative speed V (m/sec.), an apparent volume P (L) of the media used for the preparation, and a blending mass G (kg) of the coating composition. In such a case, it is preferable to prepare under conditions satisfying the following formula (I).
100<time・V・P/G<1500 (m・L/kg) (I)

In the formula (I), the representative speed is the peripheral speed of the stirring section in the rotary mill, and is the speed obtained by dividing the moving stroke by the moving time in a mill having a mechanism that reciprocates like a paint shaker.

Generally, the preparation conditions required for coating are often expressed by the product of the shear rate (sec. ^-1 ) applied to the coating composition and the preparation time (sec.). However, it is difficult to determine the shear rate and model the state of applying shear. Therefore, it has been found that it is effective to determine the coating condition by the formula (I) in the media type mill. That is, in the formula (I), the preparation conditions of the paint are as follows: the typical speed (V) of the stirring section, the preparation time (time), and the apparent volume ratio of the media per unit mass of the paint composition, which are applied per unit mass of the paint. It can be expressed by the product of (P/G). The apparent volume ratio (P/G) of the media per unit mass of the coating composition refers to the apparent volume of the media involved in forming the coating, and if the apparent volume of the media when dispersed is smaller than the unit mass of the coating composition. If P/G is small, it means that sufficient representative speed (V) of the stirring section and preparation time (time) are required to obtain good dispersion. On the contrary, when the apparent volume of the media is large (when P/G is large), the representative speed (V) of the stirring section and the preparation time (time) may be small. The dispersion effect of the coating composition by the media is affected by the shape, density, material, etc. of the media to be used, but the inventor of the present invention, when the adjusted solvent is the same as a prerequisite, the apparent volume of the media is Focused on the most dominant.

Further, when only looking at the relationship between the representative speed of the stirring section and the preparation time, if the representative speed of the stirring section becomes small, it is possible to obtain good coating conditions if the preparation time is long.

The representative speed (V) is preferably 0.50 m/sec or more, more preferably 0.75 m/sec or more, still more preferably 1.0 m/sec or more from the viewpoint of crushing efficiency, and from the viewpoint of suppressing over-milling. Therefore, it is preferably 30 m/sec or less, more preferably 25 m/sec or less, still more preferably 20 m/sec or less.

The preparation time (time) is preferably 30 sec or more, more preferably 45 sec or more, further preferably 60 sec or more from the viewpoint of ensuring the uniformity of the coating, and preferably 10000 sec or less, more preferably 7000 sec from the viewpoint of production efficiency. Hereafter, it is more preferably 5000 sec or less.

The apparent volume P(L) of the medium used for the preparation and the compounding mass G(kg) of the coating composition are not particularly limited, but the apparent volume ratio (P/G) of the media per unit mass of the coating composition is From the viewpoint of pulverization efficiency, preferably 0.01 or more, more preferably 0.03 or more, further preferably 0.05 or more, and from the viewpoint of production efficiency, preferably 1 or less, more preferably 0.9 or less, More preferably, it is 0.8 or less.

By preparing the coating composition so as to satisfy the formula (I), the catalyst particle diameter in the catalyst layer of the film catalyst is 1.3 μm or more and 3.3 μm or less, and the pore volume of the catalyst layer is 0.40 mL/ It is possible to make the average macropore diameter closer to 0.2 μm or more and 0.5 μm or less, with g or more and 0.87 mL/g or less.
The preparation condition represented by the formula (I) is preferably 100<time·V·P/G<1500, more preferably 110<time·V·P/G<1400, and further preferably 120<time·V·P. The condition is /G<1300.

The solid content of the coating composition is preferably 5% by mass or more, more preferably 5% by mass or more, because the pore structure is controlled when the solvent is desorbed from the formed catalyst layer and affects the formation of the pore structure. It is 10% by mass or more, more preferably 15% by mass or more, and preferably 70% by mass or less, more preferably 65% by mass or less, still more preferably 60% by mass or less.

The viscosity of the coating composition is selected within a preferred range depending on the coating method, and is preferably 0.1 mPa·s or more, more preferably 0.5 mPa·s or more, still more preferably 1 mPa·s or more, and preferably Is 100 mPa·s or less, more preferably 90 mPa·s or less, still more preferably 80 mPa·s or less.

[Step 2]
Step 2 is a step of applying the coating composition on a support to form a catalyst layer.

As a coating method, a conventionally known method can be used, and various coating methods such as blade, roll, knife, bar, spray, dip, spin, comma (Hirano Techseed, registered trademark), kiss, gravure, die coating and the like can be mentioned. be able to.

From the viewpoint of improving the adhesion to the catalyst layer, the support is preferably roughened.
When the surface of the support is roughened, the surface roughness Rz of the support is preferably 1.0 μm or more from the viewpoint of improving the adhesion to the catalyst layer and the diffusibility of the reaction substrate in the catalyst layer. More preferably 2.0 μm or more, still more preferably 2.5 μm or more, still more preferably 3.0 μm or more, and preferably 30.0 μm or less, more preferably 25.m or more from the viewpoint of ensuring the uniformity of the catalyst layer. It is preferable to apply the coating composition to a support having a thickness of 0 μm or less, more preferably 20.0 μm or less to form a catalyst layer.

[Drying and curing process]
In the present invention, a drying and curing step can be provided after step 2, and a shape processing step and a final heating step can be provided after the drying and curing step. In addition, after coating and film formation, when drying (curing) at room temperature, the drying and curing steps are unnecessary.

The drying and curing steps are intended to remove the solvent, unreacted monomers, etc. contained in the coating composition after coating and film-forming the coating composition on the support. In addition to the case where the curing reaction proceeds along with the drying, it is also possible to partially proceed the curing reaction in parallel with the drying by adjusting the heating temperature and the heating time according to the composition of the coating composition. ..

Drying and curing steps are preferably carried out in a heated atmosphere of air, steam or nitrogen, an inert gas such as argon or the like, or a method of spraying these heat media is preferably used, and radiant heat such as infrared rays or far infrared rays is used. Various methods such as a heating method using a current induced by electromagnetic waves, a method combining these methods, or a method of natural drying (air drying) at room temperature can also be used. The components to be desorbed in this step are a volatile component mainly containing a solvent and a curing reaction product. Volatile components other than the solvent include unreacted monomer components and the like.

The drying and curing conditions need to be adjusted according to the physical properties of the volatile components, mainly the binder and solvent contained in the coating composition, and the porous structure of the catalyst layer can be adjusted by selecting the solvent and setting the drying and curing conditions. (Pore volume) can be controlled. In the heat treatment with hot air, it is considered that the higher the drying temperature and the larger the amount of dry air, the faster the desorption of the components from the catalyst layer and the larger the pore structure (pore diameter, volume). It is also considered that the pore structure becomes smaller as the drying temperature is lower and the drying air volume is smaller. The catalyst particles in the catalyst layer after the drying and curing steps are formed by the catalyst particles in the paint, and the particle size of the catalyst particles does not change.

In addition to desorbing volatile components, mainly solvent, from the coating composition, when a crosslinking structure (network structure) is formed by the progress of curing/crosslinking reaction, when a condensation reaction is involved, condensation products The pore structure is determined in the desorption step.

For the drying and curing treatment, a drying method and drying conditions that do not adversely affect the catalytic activity originally possessed by the powdery catalyst used in the present invention are adopted.

In the drying and curing treatments of the present invention, the drying rate is preferably 0.01 g/m ² ·s or more, more preferably 0.02 g/m ² ·s or more, from the viewpoint of the pore structure expressing the catalytic activity. More preferably 0.03 g/m ² ·s or more, and from the same viewpoint, preferably 10 g/m ² ·s or less, more preferably 9 g/m ² ·s or less, further preferably 8 g/m ² ·s. It is as follows.
From the viewpoint of productivity and energy required for drying, the drying time is preferably 30 minutes or less, more preferably 20 minutes or less, and further preferably 10 minutes or less.

In addition, when only the purpose of drying without curing reaction is intended, it is preferable to apply the coating composition to the support and then to dry immediately. By adjusting the drying conditions at this time, the porosity of the coating film can be improved. You can control the structure. Therefore, it is desirable that the time from the formation of the catalyst layer on the support to the removal of the volatile components mainly of the solvent is shorter, preferably 2 hours or less, more preferably 30 minutes or less, and further preferably Is within 5 minutes.

[Shape processing of catalyst intermediate and final heating step]
In the present invention, when the binder contains a thermosetting resin, after the catalyst intermediate is shaped in a state where the uncured material remains in the catalyst layer obtained by coating and drying (prepolymer state), the final Heat treatment is desirable.

The drying and curing treatment of the catalyst intermediate, which is performed before the final heat treatment, may be terminated in a state where the uncured product remains in the thermosetting resin. It is desirable that part of it is hardened until it can be handled during shape processing, and that the retention and mechanical strength of the catalyst layer are improved compared to during film formation. May remain on order.

The drying rate before the final heat treatment for obtaining the target film-like catalyst is preferably 0.01 g/m ² ·s or more, more preferably 0.02 g/m from the viewpoint of the pore structure expressing the catalytic activity. m ² ·s or more, more preferably 0.03 g/m ² ·s or more, and from the viewpoint of the pore structure that exhibits catalytic activity, preferably 10 g/m ² ·s or less, more preferably 9 g/m ² ·S or less, and more preferably 8 g/m ² ·s or less.
From the viewpoint of productivity and energy required for drying, the drying time is preferably 30 minutes or less, more preferably 20 minutes or less, and further preferably 10 minutes or less.

By performing shape processing before the catalyst layer of the film catalyst completely cures, the catalyst layer follows the plastic deformation of the support, improving the shape processability, and completely curing after processing completes the manufacturing process. In the final step of (3), the crosslinked structure of the catalyst layer can be fixed, the residual stress in the catalyst layer can be relaxed, and the influence of the film catalyst on the catalyst layer falling can be improved.

Further, in the present invention, when the binder contains a thermoplastic resin, it is desirable that the catalyst layer obtained by coating and drying is subjected to shape processing and then subjected to final heat treatment. When the catalyst layer contains a thermoplastic resin, residual stress is generated in the catalyst layer due to plastic deformation of the support when shape processing is performed, which may adversely affect the retention of the catalyst layer. It Therefore, the stress can be relaxed by the final heat treatment, and the entangled structure of the thermoplastic resin is strengthened, so that the influence of the film-shaped catalyst on the dropping of the catalyst layer can be improved.

Further, this final heat treatment can be carried out after being shaped into various forms according to the shapes of various reactors. For example, a flat plate and a corrugated film-shaped catalyst obtained by processing the flat plate can be heat-treated while being housed in a holder or a cassette for attachment to a reactor, which is a structure in which multiple layers are stacked. ..

The condition of the final heat treatment varies depending on the kind of the binder, but in the present invention, the temperature of the heat treatment is preferably 80° C. or higher, more preferably 100° C. or higher, and preferably 400° C. or lower, more preferably 350. It is desirable that the heat treatment is performed at a temperature of not higher than 0° C. and a heat treatment time of preferably 5 minutes or longer, more preferably 10 minutes or longer, preferably 600 minutes or shorter, and more preferably 100 minutes or shorter. Radical polymerization, radiation polymerization, UV curing, etc. can be applied instead of the heat curing method. When applying these methods, various polymerization catalysts are contained in the catalyst layer as needed. be able to.

The shape of the film catalyst can be processed into various shapes according to the shape of various reactors to which the catalytic reaction is applied, and trimming processing, shape processing, integration and assembly processing methods are applied as necessary. The desired shape can be obtained. The structure may be a flat plate, a tube, a honeycomb, a monolith, or the like. In addition, a unit as a structure can be formed by accommodating and filling in a holder, a case or the like for incorporation in an actual reaction device.

The film catalyst obtained by the production method of the present invention is a structure obtained by stacking a number of layers of a flat film catalyst and a corrugated film catalyst obtained by processing the flat film catalyst (Fig. 4), a catalyst layer is formed on the inner wall surface of a pipe that can be used in a flow reactor (see FIG. 6), and a catalyst layer is formed on the surface of a thin plate-like structure that divides the pipe into a plurality of axial flow passages. The catalyst may be formed, an open fin-shaped flat plate installed inside the tank that can be used in a tank reactor, and a catalyst layer formed on the surface thereof.

In any case, it is preferable to have a structure that allows easy supply of the reactant to the catalyst layer and recovery of the product from the catalyst layer. Further, it is desirable that the surface area of the catalyst layer of the film catalyst provided in the reactor is as large as possible in order to allow the reaction to proceed efficiently. In order to achieve the above requirements, an assembly obtained by bundling tubes having an inner diameter of several mm to several tens of mm, a honeycomb structure having a cell density of several to 200 cells per square cm, and a catalyst layer provided on the inner wall surface thereof, etc. Can be used.

The film-like catalyst of the present invention can be applied to various reactions depending on the selection of the powdery catalyst contained therein, and in particular, to the case where the powdery catalyst used for the reaction in the liquid phase is applied, it is obtained. Even if the film catalyst is applied to the reaction as it is, it is preferable because it does not impair the diffusivity of reactants and products and can adapt to the temperature environment in the reactor, and is particularly suitable as a catalyst for gas-liquid reaction. ..

For example, it can be used for olefin oxidation, alcohol oxidation, olefin isomerization, aromatic isomerization, carbonylation, ester hydrogenation, preferably dehydrogenation reaction and hydrogenation reaction. It can also be applied to an amination reaction for producing a tertiary amine from an alcohol and a primary amine or a secondary amine accompanied by a hydrogenation reaction.

Although the present invention has been described above based on its preferred embodiments, the present invention is not limited to the above embodiments. For example, the film catalyst of the present invention can be applied not only to a gas-liquid reaction catalyst but also to a liquid-liquid reaction, a gas-vapor reaction, and a solid-liquid reaction catalyst.

Regarding the above-described embodiment, the present invention further discloses the following film-like catalyst and a method for producing the film-like catalyst.

<1>
A film-shaped catalyst having a catalyst layer formed on a support,
The catalyst layer contains catalyst particles having a particle diameter of 1.3 μm or more and 3.3 μm or less, which includes a powdery catalyst and a binder,
The pore volume of the catalyst layer is 0.40 mL/g or more and 0.87 mL/g or less,
Film catalyst.

<2>
The particle diameter of the powdery catalyst is 1.3 μm or more, preferably 1.5 μm or more, more preferably 1.8 μm or more, and 4.5 μm or less, preferably 4.3 μm or less, more preferably 4.0 μm or less. The film catalyst according to <1> above.

<3>
The BET specific surface area of the powdery catalyst, 0.1 m ² / g or more, preferably 1 m ² / g or more, more preferably 10 m ² / g or more, and, 500 meters ² / g or less, preferably 200 meters ² / The film catalyst according to <1> or <2>, which is g or less, more preferably 100 m ² /g or less.

<4>
The binder is one or more thermosetting resin selected from phenol resin, furan resin and epoxy resin, preferably thermosetting resin accompanied by condensation reaction at the time of curing, in the above <1> to <3>. The film catalyst according to any one of claims.

<5>
The particle diameter of the catalyst particles is 1.5 μm or more, preferably 1.8 μm or more, and 3.0 μm or less, preferably 2.8 μm or less, according to any one of <1> to <4> above. Film catalyst.

<6>
The pore volume of the catalyst layer is 0.45 mL/g or more, preferably 0.5 mL/g or more, and 0.85 mL/g or less, preferably 0.83 mL/g or less, <1> to The film catalyst according to any one of <5>.

<7>
The average macropore diameter of the catalyst layer is 0.20 μm or more, preferably 0.21 μm or more, more preferably 0.22 μm or more and 0.50 μm or less, preferably 0.49 μm or less, more preferably 0.48 μm or less. The film catalyst according to any one of <1> to <6> above.

<8>
The mass ratio of the powdery catalyst and the binder in the catalyst layer (powdered catalyst/binder) is 1 or more, preferably 1.5 or more, more preferably 1.8 or more, further preferably 2 or more, and 10 or less. The film catalyst according to any one of <1> to <7>, which is preferably 9 or less, more preferably 7.5 or less, still more preferably 5 or less.

<9>
The film catalyst according to any one of <1> to <8>, wherein the support is a metal foil.

<10>
The surface roughness Rz of the support is 1.0 μm or more, preferably 2.0 μm or more, more preferably 2.5 μm or more, further preferably 3.0 μm or more, and 30.0 μm or less, preferably 25.0 μm. Hereinafter, the film catalyst according to any one of the above items <1> to <9>, which is more preferably 20.0 μm or less.

<11>
Any of the above <1> to <10>, wherein the thickness of the catalyst layer is 1 μm or more, preferably 3 μm or more, more preferably 5 μm or more, and 500 μm or less, preferably 100 μm or less, more preferably 50 μm or less. The film catalyst according to item 1.

<12>
The amount of the catalyst layer supported per unit area is 0.5 g/m ² or more, preferably 1 g/m ² or more, more preferably 5 g/m ² or more, and 100 g/m ² or less, preferably 50 g/m ^{2. 2} or less, more preferably 30 g / ^{m 2} or less, the film catalyst according to any one of <1> to <11>.

<13>
The method for producing a film catalyst according to any one of <1> to <12>, including the following steps.
Step 1: A step of preparing a coating composition containing a powdery catalyst, a binder and a solvent, wherein the particle size of the catalyst particles containing the powdery catalyst and the binder in the coating composition is 1.3 μm or more and 3.3 μm or less. Step 2: Applying the coating composition onto a support to form a catalyst layer

<14>
The particle diameter of the powdery catalyst is 1.3 μm or more, preferably 1.5 μm or more, more preferably 1.8 μm or more, and 4.5 or less, preferably 4.3 μm or less, more preferably 4.0 μm or less. <13> The method for producing a film catalyst according to <13>.

<15>
The BET specific surface area of the powdery catalyst, 0.1 m ² / g or more, preferably 1 m ² / g or more, more preferably 10 m ² / g or more, and, 500 meters ² / g or less, preferably 200 meters ² / The method for producing a film-like catalyst according to <13> or <14>, which is g or less, more preferably 100 m ² /g or less.

<16>
In the above <13> to <15>, the binder is one or more thermosetting resin selected from a phenol resin, a furan resin, and an epoxy resin, preferably a thermosetting resin accompanied by a condensation reaction during curing. The method for producing a film catalyst according to any one of claims.

<17>
The step 1 is prepared such that the particle size of the catalyst particles is 1.5 μm or more, preferably 1.8 μm or more, and 3.0 μm or less, preferably 2.8 μm or less. 13> to <16>, the method for producing a film catalyst.

<18>
The content ratio of the powdery catalyst in the coating composition is 10 mass% or more, preferably 20 mass% or more, more preferably 30 mass% or more, and 90 mass% or less, preferably 80 mass% or less, more preferably Is 70% by mass or less, and the method for producing a film catalyst according to any one of <13> to <17>.

<19>
The content of the binder in the coating composition is 3 mass% or more, preferably 5 mass% or more, more preferably 10 mass% or more, and 40 mass% or less, preferably 25 mass% or less, more preferably 20 mass% or less. The method for producing a film catalyst according to any one of <13> to <18>, which is at most mass%.

<20>
The mass ratio of the powdery catalyst to the binder (powdered catalyst/binder) in the coating composition is 1 or more, preferably 1.5 or more, more preferably 1.8 or more, further preferably 2 or more, and 10 Hereinafter, the method for producing a film catalyst according to any one of <13> to <19>, which is preferably 9 or less, more preferably 7.5 or less, still more preferably 5 or less.

<21>
The solid content in the coating composition is 5% by mass or more, preferably 10% by mass or more, more preferably 15% by mass or more, and 70% by mass or less, preferably 65% by mass or less, more preferably 60% by mass. The method for producing a film catalyst according to any one of <13> to <20>, which is as follows.

<22>
Step 1 was prepared using a media type mill, the preparation time time (sec.) in the media type mill, a representative speed V (m/sec.), and an apparent volume P(L) of the medium used for the preparation. ), when the blending mass G (kg) of the coating composition is used, the film catalyst according to any one of the above items <13> to <21>, which is prepared under conditions satisfying the following formula (I). Manufacturing method.
100<time・V・P/G<1500 (m・L/kg) (I)

<23>
The representative velocity (V) is 0.50 m/sec or more, preferably 0.75 m/sec or more, more preferably 1.0 m/sec or more, and 30 m/sec or less, preferably 25 m/sec or less, more preferably Is 20 m/sec or less, The method for producing a film catalyst according to <22>.

<24>
<22> or <23>, wherein the preparation time (time) is 30 sec or more, preferably 45 sec or more, more preferably 60 sec or more, and 10000 sec or less, preferably 7000 sec or less, more preferably 5000 sec or less. The method for producing a film catalyst according to claim 1.

<25>
The apparent volume ratio (P/G) of the media per blended mass of the coating composition is 0.01 or more, preferably 0.03 or more, more preferably 0.05 or more, and 1 or less, preferably 0. 0.9 or less, more preferably 0.8 or less, The manufacturing method of the film catalyst in any one of said <22>-<24>.

<26>
The preparation condition represented by the formula (I) is 100<time·V·P/G<1500, preferably 110<time·V·P/G<1400, and more preferably 120<time·V·. P/G<1300, The manufacturing method of the film-form catalyst in any one of said <22>-<25>.

<27>
In step 2, the surface roughness Rz of the support is 1.0 μm or more, preferably 2.0 μm or more, more preferably 2.5 μm or more, further preferably 3.0 μm or more, and 30.0 μm or less, preferably The film according to any one of <13> to <26>, which is a step of applying the coating composition onto a support having a thickness of 25.0 μm or less, more preferably 20.0 μm or less to form a catalyst layer. Of producing a particulate catalyst.

<28>
A drying step is included after the step 2, and a drying rate is 0.01 g/m ² ·s or more, preferably 0.02 g/m ² ·s or more, more preferably 0.03 g/m ² ·s or more, and 10 g/m ² ·s or less, preferably 9 g/m ² ·s or less, more preferably 8 g/m ² ·s or less, drying time is 30 minutes or less, preferably 20 minutes or less, more preferably 10 minutes The method for producing a film catalyst according to any one of <13> to <26>, which is the following.

<29>
The method for producing a film catalyst according to any one of <13> to <28>, which includes a shaping step and a heating step after the drying step.

<30>
A drying step is included before the heating step, and the drying rate is 0.01 g/m ² ·s or more, preferably 0.02 g/m ² ·s or more, more preferably 0.03 g/m ² ·s or more, and 10 g/m ² ·s or less, preferably 9 g/m ² ·s or less, more preferably 8 g/m ² ·s or less, drying time is 30 minutes or less, preferably 20 minutes or less, more preferably 10 The method for producing a film catalyst according to <29>, which is less than or equal to minutes.

<31>
The temperature of the heat treatment in the heating step is 80° C. or higher, preferably 100° C. or higher, and 400° C. or lower, preferably 350° C. or lower, the heat treatment time is 5 minutes or longer, preferably 10 minutes or longer, and The method for producing a film catalyst according to <29> or <31>, which is 600 minutes or less, preferably 100 minutes or less.

[Production Example of Powdered Catalyst]
Production Example of Catalyst 1 A powdery catalyst comprising a copper-nickel-ruthenium ternary catalyst active material supported on a synthetic zeolite was prepared as follows.

A 1 L flask was charged with synthetic zeolite (average particle size: 3 μm), and then copper nitrate, nickel nitrate and ruthenium chloride were added so that the molar ratio of each metal atom was Cu:Ni:Ru=4:1:0.01. What was melt|dissolved in water was put in, and it heated up, stirring. A 10 mass% sodium carbonate aqueous solution was gradually added dropwise at 90°C while controlling the pH to 9 to 10. After aging for 1 hour, the precipitate was filtered, washed with water, dried at 80° C. for 10 hours, and calcined at 600° C. for 3 hours to obtain catalyst 1. In the obtained powdery catalyst, the proportion of metal oxide was 50% by mass and the proportion of synthetic zeolite was 50% by mass. The particle size of the catalyst 1 was 3.6 μm. The particle diameter is a median diameter calculated on a volume basis, and was measured by diluting the powdery catalyst with water and using a laser diffraction/scattering particle size distribution analyzer (LA-950, manufactured by Horiba, Ltd.). ..

Production Example of Catalyst 2 In the production example of the catalyst 2, a catalyst 2 was obtained according to the production example of the catalyst 1 except that a tank having a capacity of 300 L was used. In the obtained powdery catalyst, the proportion of metal oxide was 50% by mass and the proportion of synthetic zeolite was 50% by mass. The particle size of the catalyst 2 was 3.8 μm as measured by the same method as the catalyst 1. The particle size of the catalyst 2 is different from that of the catalyst 1 due to the difference in the stirring state due to the change in the capacity of the tank.

Production Example of Catalyst 3 In the production example of the catalyst 3, a catalyst 3 was obtained according to the production example of the catalyst 1 except that a tank having a capacity of 1000 L was used. In the obtained powdery catalyst, the proportion of metal oxide was 50% by mass and the proportion of synthetic zeolite was 50% by mass. The particle size of the catalyst 3 was 4.5 μm as measured by the same method as the catalyst 1. The particle size of the catalyst 3 is different from that of the catalyst 1 due to the difference in the stirring state due to the change in the capacity of the tank.

[Production Example of Film Catalyst]
Examples and comparative examples which are production examples of the film catalyst are shown below.

Example 1
Methyl ethyl ketone (MEK) as a solvent, a novolac phenolic resin and hexamethylene tetramine as a binder, and a catalyst 1 as a powdery catalyst were placed in this order in a 250 mL wide-mouth polyethylene bottle. The non-volatile content of the phenol resin is 22.5 parts by mass and the hexamethylenetetramine is 2.5 parts by mass with respect to 75 parts by mass of the powdery catalyst (70 g), and the compounding amount of MEK is the solid content of the composition. Was 55% by mass. Further, glass beads having a diameter of 1 mm (manufactured by AS ONE Corporation, model number BZ-1, apparent volume 64 mL) were placed in a wide-mouth polyethylene bottle as a dispersion medium. The coating mass of the coating composition was 0.17 kg.

A wide-mouth polyethylene bottle was set in a paint shaker (manufactured by Toyo Seiki Co., Ltd.), and mixed and dispersed for 4 minutes as a preparation time to obtain a coating composition (the paint shaker had a moving stroke of 5 cm, 12. It is moving in a cycle of 5 times, and the typical speed was 0.05×2 (m)/[1/12.5](s)=1.25 m/s). The catalyst particle size in the coating composition was 2.9 μm.

A copper foil (thickness 40 μm, basis weight 310 g/m ² , surface roughness Rz: one side 8.0 μm, the other side 4.1 μm) was used as a support, and the coating composition was applied to both sides of the copper foil by a gravure coater ( After coating by Yasui Seiki Co., Ltd.), it was treated with a dryer at a drying rate of 0.5 g/m ² ·s for 60 seconds to obtain a film-shaped catalyst intermediate.

The obtained film-shaped catalyst intermediate (width 65 mm x length 160 mm) was bent into a corrugated plate shape, superposed with a flat film-shaped catalyst of the same size, and wound into a cylindrical shape, and the outer diameter was 30 mm x height 65 mm. Twenty-five cylindrical film-shaped catalyst intermediates were prepared. This was cured in a dryer at a resin curing temperature of 200° C. or higher for 90 minutes to obtain a film catalyst having the shape shown in FIG.

Catalyst layer weight per unit area in the obtained film catalyst one side 14.1 g / ^{m 2,} was double-sided 28.3 g / ^{m 2.} The loading amount of the powdery catalyst per unit area, one-sided 10.6 g / ^{m 2,} a double-sided 21.2 g / ^{m 2,} the supported amount of the powdered catalyst in the cylindrical film catalyst 25 present is 5. It was 5 g. The pore volume of the catalyst layer was 0.85 mL/g. The average macropore diameter of the catalyst layer was 0.33 μm.

Example 2
MEK as a solvent, a novolac-based phenol resin and hexamethylenetetramine as a binder, and a catalyst 1 as a powdery catalyst were placed in this order in a 250 mL wide-mouth polyethylene bottle. The non-volatile content of the phenolic resin is 22.5 parts by mass and the hexamethylenetetramine is 2.5 parts by mass with respect to 75 parts by mass (70 g) of the powdery catalyst, and the compounding amount of MEK is the solid content of the composition. Was 55% by mass. Further, glass beads having a diameter of 1 mm (manufactured by AS ONE Corporation, model number BZ-1, apparent volume 64 mL) were placed in a wide-mouth polyethylene bottle as a dispersion medium. The coating mass of the coating composition was 0.17 kg.

A wide-mouth polyethylene bottle was set on a paint shaker (manufactured by Toyo Seiki Co., Ltd.), and mixed and dispersed for 16 minutes as a preparation time to obtain a coating composition (the paint shaker has a moving stroke of 5 cm and a rate of 12. It is moving in a cycle of 5 times, and the typical velocity is 0.05×2 (m)/[1/12.5](s)=1.25 m/s). The catalyst particle size in the coating composition was 2.5 μm.

A copper foil (thickness 40 μm, basis weight 310 g/m ² , surface roughness Rz: one side 8.0 μm, the other side 4.1 μm) was used as a support, and the coating composition was applied to both sides of the copper foil by a gravure coater ( After coating by Yasui Seiki Co., Ltd.), it was treated with a dryer at a drying rate of 0.5 g/m ² ·s for 60 seconds to obtain a film-shaped catalyst intermediate.

The obtained film-shaped catalyst intermediate (width 65 mm x length 160 mm) was bent into a corrugated plate shape, superposed with a flat film-shaped catalyst of the same size, and wound into a cylindrical shape, and the outer diameter was 30 mm x height 65 mm. Twenty-five cylindrical film-shaped catalyst intermediates were prepared. This was cured in a dryer at a resin curing temperature of 200° C. or higher for 90 minutes to obtain a film catalyst having the shape shown in FIG.

Catalyst layer weight per unit area in the obtained film catalyst one side 14.0 g / ^{m 2,} was double-sided 28.0 g / ^{m 2.} The loading amount of the powdery catalyst per unit area, one-sided 10.5 g / ^{m 2,} a double-sided 21.0 g / ^{m 2,} the supported amount of the powdered catalyst in the cylindrical film catalyst 25 present is 5. It was 5 g. The pore volume of the catalyst layer was 0.72 mL/g. The average macropore diameter of the catalyst layer was 0.27 μm.

Example 3
MEK as a solvent, a novolac-based phenol resin and hexamethylenetetramine as a binder, and a catalyst 1 as a powdery catalyst were placed in this order in a 250 mL wide-mouth polyethylene bottle. The non-volatile content of the phenolic resin is 22.5 parts by mass and the hexamethylenetetramine is 2.5 parts by mass with respect to 75 parts by mass (70 g) of the powdery catalyst, and the compounding amount of MEK is the solid content of the composition. Was 55% by mass. Further, glass beads having a diameter of 1 mm (manufactured by AS ONE Corporation, model number BZ-1, apparent volume 64 mL) were placed in a wide-mouth polyethylene bottle as a dispersion medium. The coating mass of the coating composition was 0.17 kg.

A wide-mouth polyethylene bottle was set on a paint shaker (manufactured by Toyo Seiki Co., Ltd.), and mixed and dispersed for 40 minutes as a preparation time to obtain a coating composition (the paint shaker has a moving stroke of 5 cm, 12. It is moving in a cycle of 5 times, and the typical velocity is 0.05×2 (m)/[1/12.5](s)=1.25 m/s). The catalyst particle size in the coating composition was 1.6 μm.

A copper foil (thickness 40 μm, basis weight 310 g/m ² , surface roughness Rz: one side 8.0 μm, the other side 4.1 μm) was used as a support, and the coating composition was applied to both sides of the copper foil by a gravure coater ( After coating by Yasui Seiki Co., Ltd.), it was treated with a dryer at a drying rate of 0.5 g/m ² ·s for 60 seconds to obtain a film-shaped catalyst intermediate.

The obtained film-shaped catalyst intermediate (width 65 mm x length 160 mm) was bent into a corrugated plate shape, superposed with a flat film-shaped catalyst of the same size, and wound in a cylindrical shape, and the outer diameter was 30 mm and the height was 65 mm. Twenty-five cylindrical film-shaped catalyst intermediates were prepared. This was cured in a dryer at a resin curing temperature of 200° C. or higher for 90 minutes to obtain a film catalyst having the shape shown in FIG.

Catalyst layer weight per unit area in the obtained film catalyst one side 14.1 g / ^{m 2,} was double-sided 28.2 g / ^{m 2.} The loading amount of the powdery catalyst per unit area, one-sided 10.6 g / ^{m 2,} a double-sided 21.2 g / ^{m 2,} the supported amount of the powdered catalyst in the cylindrical film catalyst 25 present is 5. It was 5 g. The pore volume of the catalyst layer was 0.56 mL/g. The average macropore diameter of the catalyst layer was 0.21 μm.

Example 4
MEK as a solvent, a novolac phenolic resin and hexamethylenetetramine as a binder, and a catalyst 2 as a powdery catalyst were placed in this order in a 250 mL wide-mouth polyethylene bottle. The non-volatile content of the phenolic resin is 22.5 parts by mass and the hexamethylenetetramine is 2.5 parts by mass with respect to 75 parts by mass (70 g) of the powdery catalyst, and the compounding amount of MEK is the solid content of the composition. Was 55% by mass. Further, glass beads having a diameter of 1 mm (manufactured by AS ONE Corporation, model number BZ-1, apparent volume 64 mL) were placed in a wide-mouth polyethylene bottle as a dispersion medium. The coating mass of the coating composition was 0.17 kg.

A wide-mouth polyethylene bottle was set on a paint shaker (manufactured by Toyo Seiki Co., Ltd.), and mixed and dispersed for 8 minutes as a preparation time to obtain a coating composition (the paint shaker was moved at a stroke of 5 cm for 12. seconds per second). It is moving in a cycle of 5 times, and the typical velocity is 0.05×2 (m)/[1/12.5](s)=1.25 m/s). The catalyst particle size in the coating composition was 3.1 μm.

A copper foil (thickness 40 μm, basis weight 310 g/m ² , surface roughness Rz: one side 8.0 μm, the other side 4.1 μm) was used as a support, and the coating composition was applied to both sides of the copper foil by a gravure coater ( After coating by Yasui Seiki Co., Ltd.), it was treated with a dryer at a drying rate of 0.5 g/m ² ·s for 60 seconds to obtain a film-shaped catalyst intermediate.

The obtained film-shaped catalyst intermediate (width 65 mm x length 160 mm) was bent into a corrugated plate shape, superposed with a flat film-shaped catalyst of the same size, and wound into a cylindrical shape, and the outer diameter was 30 mm x height 65 mm. Twenty-five cylindrical film-shaped catalyst intermediates were prepared. This was cured in a dryer at a resin curing temperature of 200° C. or higher for 90 minutes to obtain a film catalyst having the shape shown in FIG.

Catalyst layer weight per unit area in the obtained film catalyst one side 14.1 g / ^{m 2,} was double-sided 28.2 g / ^{m 2.} The loading amount of the powdery catalyst per unit area, one-sided 10.6 g / ^{m 2,} a double-sided 21.2 g / ^{m 2,} the supported amount of the powdered catalyst in the cylindrical film catalyst 25 present is 5. It was 5 g. The pore volume of the catalyst layer was 0.74 mL/g. The average macropore diameter of the catalyst layer was 0.43 μm.

Example 5
MEK as a solvent, a novolac phenolic resin and hexamethylenetetramine as a binder, and a catalyst 2 as a powdery catalyst were placed in this order in a 250 mL wide-mouth polyethylene bottle. The non-volatile content of the phenolic resin is 22.5 parts by mass and the hexamethylenetetramine is 2.5 parts by mass with respect to 75 parts by mass (70 g) of the powdery catalyst, and the compounding amount of MEK is the solid content of the composition. Was 55% by mass. Further, glass beads having a diameter of 1 mm (manufactured by AS ONE Corporation, model number BZ-1, apparent volume 64 mL) were placed in a wide-mouth polyethylene bottle as a dispersion medium. The coating mass of the coating composition was 0.17 kg.

A wide-mouth polyethylene bottle was set on a paint shaker (manufactured by Toyo Seiki Co., Ltd.), and mixed and dispersed for 16 minutes as a preparation time to obtain a coating composition (the paint shaker has a moving stroke of 5 cm and a rate of 12. It is moving in a cycle of 5 times, and the typical velocity is 0.05×2 (m)/[1/12.5](s)=1.25 m/s). The catalyst particle size in the coating composition was 2.5 μm.

A copper foil (thickness 40 μm, basis weight 310 g/m ² , surface roughness Rz: one side 8.0 μm, the other side 4.1 μm) was used as a support, and the coating composition was applied to both sides of the copper foil by a gravure coater ( After coating by Yasui Seiki Co., Ltd.), it was treated with a dryer at a drying rate of 0.5 g/m ² ·s for 60 seconds to obtain a film-shaped catalyst intermediate.

The obtained film-shaped catalyst intermediate (width 65 mm x length 160 mm) was bent into a corrugated plate shape, superposed with a flat film-shaped catalyst of the same size, and wound into a cylindrical shape, and the outer diameter was 30 mm x height 65 mm. Twenty-five cylindrical film-shaped catalyst intermediates were prepared. This was cured in a dryer at a resin curing temperature of 200° C. or higher for 90 minutes to obtain a film catalyst having the shape shown in FIG.

Catalyst layer weight per unit area in the obtained film catalyst one side 13.1 g / ^{m 2,} was double-sided 26.2 g / ^{m 2.} The loading amount of the powdery catalyst per unit area, one-sided 9.8 g / ^{m 2,} a double-sided 19.6 g / ^{m 2,} the supported amount of the powdered catalyst in the cylindrical film catalyst 25 present is 5. It was 1 g. The pore volume of the catalyst layer was 0.57 mL/g. The average macropore diameter of the catalyst layer was 0.32 μm.

Example 6
MEK as a solvent, a novolac phenolic resin and hexamethylenetetramine as a binder, and a catalyst 3 as a powdery catalyst were placed in this order in a 50 L container. The non-volatile content of the phenol resin is 22.5 parts by mass and the hexamethylenetetramine is 2.5 parts by mass with respect to 75 parts by mass (15 kg) of the powdery catalyst, and the compounding amount of MEK is the solid content of the composition. Was 55% by mass. The blending mass of the coating composition was 45 kg.

Further, glass beads having a diameter of 1 mm (manufactured by As One Co., Ltd., model number BZ-1, apparent volume 0.83 L) were set in a bead mill crusher (manufactured by Nippon Coke Co., Ltd.) as a dispersion medium, and mixed and dispersed for 30 minutes as a preparation time. To obtain a coating composition (the bead mill crusher has a 20 cm rotor rotating 8 times per second, and a typical speed is 0.2 (m)×3.14/[1/8]( s)=5.0 m/s). The catalyst particle size in the coating composition was 2.5 μm.

A copper foil (thickness 40 μm, basis weight 310 g/m ² , surface roughness Rz: 10.2 μm on one side) was used as a support, and the coating composition was applied to the surface roughness surface by a gravure coater (produced by Yasui Seiki Co., Ltd.). After coating with (1), it was treated with a dryer at a drying rate of 0.5 g/m ² ·s for 60 seconds to obtain a film-shaped catalyst intermediate.

The obtained film-shaped catalyst intermediate (width 65 mm x length 160 mm) was bent into a corrugated plate shape, superposed with a flat film-shaped catalyst of the same size, and wound into a cylindrical shape, and the outer diameter was 30 mm x height 65 mm. 50 cylindrical film-shaped catalyst intermediates were prepared. This was cured in a dryer at a resin curing temperature of 200° C. or higher for 90 minutes to obtain a film catalyst having the shape shown in FIG.

The catalyst layer mass per unit area in the obtained film catalyst was 11.9 g/m ² on one side. The amount of the powdery catalyst carried per unit area was 8.9 g/m ² on one side, and the amount of the powdery catalyst carried by the 50 cylindrical film catalysts was 4.6 g. The pore volume of the catalyst layer was 0.77 mL/g. The average macropore diameter of the catalyst layer was 0.33 μm.

Example 7
MEK as a solvent, a novolac phenolic resin and hexamethylenetetramine as a binder, and a catalyst 3 as a powdery catalyst were placed in this order in a 250 mL wide-mouth polyethylene bottle. The non-volatile content of the phenolic resin is 22.5 parts by mass and the hexamethylenetetramine is 2.5 parts by mass with respect to 75 parts by mass (70 g) of the powdery catalyst, and the compounding amount of MEK is the solid content of the composition. Was 55% by mass. Further, glass beads having a diameter of 1 mm (manufactured by AS ONE Corporation, model number BZ-1, apparent volume 64 mL) were placed in a wide-mouth polyethylene bottle as a dispersion medium. The coating mass of the coating composition was 0.17 kg.

A wide-mouth polyethylene bottle was set in a paint shaker (manufactured by Toyo Seiki Co., Ltd.), and mixed and dispersed for 4 minutes as a preparation time to obtain a coating composition (the paint shaker was moved at a stroke of 5 cm for 12. seconds per second). It is moving in a cycle of 5 times, and the typical velocity is 0.05×2 (m)/[1/12.5](s)=1.25 m/s). The catalyst particle size in the coating composition was 2.5 μm.

A copper foil (thickness 40 μm, basis weight 310 g/m ² , surface roughness Rz: 4.1 μm on one side) was used as a support, and the coating composition was applied to the surface roughness surface by a gravure coater (produced by Yasui Seiki Co., Ltd.). After coating with (1), it was treated with a dryer at a drying rate of 0.5 g/m ² ·s for 60 seconds to obtain a film-shaped catalyst intermediate.

The obtained film-shaped catalyst intermediate (width 65 mm x length 160 mm) was bent into a corrugated plate shape, superposed with a flat film-shaped catalyst of the same size, and wound into a cylindrical shape, and the outer diameter was 30 mm x height 65 mm. 50 cylindrical film-shaped catalyst intermediates were prepared. This was cured in a dryer at a resin curing temperature of 200° C. or higher for 90 minutes to obtain a film catalyst having the shape shown in FIG.

The catalyst layer mass per unit area of the obtained film catalyst was 12.5 g/m ² on one side. The amount of the powdery catalyst carried per unit area was 9.3 g/m ² on one side, and the amount of the powdery catalyst carried by the 50 cylindrical film catalysts was 4.8 g. The pore volume of the catalyst layer was 0.46 mL/g. The average macropore diameter of the catalyst layer was 0.24 μm.

Example 8
MEK as a solvent, a novolac phenolic resin and hexamethylenetetramine as a binder, and a catalyst 3 as a powdery catalyst were placed in this order in a 250 mL wide-mouth polyethylene bottle. The non-volatile content of the phenolic resin is 22.5 parts by mass and the hexamethylenetetramine is 2.5 parts by mass with respect to 75 parts by mass (70 g) of the powdery catalyst, and the compounding amount of MEK is the solid content of the composition. Was 55% by mass. Further, glass beads having a diameter of 1 mm (manufactured by AS ONE Corporation, model number BZ-1, apparent volume 64 mL) were placed in a wide-mouth polyethylene bottle as a dispersion medium. The coating mass of the coating composition was 0.17 kg.

A wide-mouth polyethylene bottle was set in a paint shaker (manufactured by Toyo Seiki Co., Ltd.), and mixed and dispersed for 4 minutes as a preparation time to obtain a coating composition (the paint shaker was moved at a stroke of 5 cm for 12. seconds per second). It is moving in a cycle of 5 times, and the typical velocity is 0.05×2 (m)/[1/12.5](s)=1.25 m/s). The catalyst particle size in the coating composition was 2.5 μm.

A copper foil (thickness 40 μm, basis weight 310 g/m ² , surface roughness Rz: one side 1.5 μm) was used as a support, and the coating composition was applied to the surface roughness surface by a gravure coater (produced by Yasui Seiki Co., Ltd.). After coating by (1), it was treated with a dryer at a drying rate of 0.5 g/m 2 ·s for 60 seconds to obtain a film-shaped catalyst intermediate.

The obtained film-shaped catalyst intermediate (width 65 mm x length 160 mm) was bent into a corrugated plate shape, superposed with a flat film-shaped catalyst of the same size, and wound into a cylindrical shape, and the outer diameter was 30 mm x height 65 mm. 50 cylindrical film-shaped catalyst intermediates were prepared. This was cured in a dryer at a resin curing temperature of 200° C. or higher for 90 minutes to obtain a film catalyst having the shape shown in FIG.

The catalyst layer mass per unit area of the obtained film catalyst was 12.0 g/m ² on one side. The amount of the powdery catalyst carried per unit area was 8.9 g/m ² on one side, and the amount of the powdery catalyst carried by the 50 cylindrical film catalysts was 4.6 g. The pore volume of the catalyst layer was 0.46 mL/g. The average macropore diameter of the catalyst layer was 0.24 μm.

Comparative Example 1
MEK as a solvent, a novolac-based phenol resin and hexamethylenetetramine as a binder, and a catalyst 1 as a powdery catalyst were placed in this order in a 250 mL wide-mouth polyethylene bottle. The non-volatile content of the phenolic resin is 22.5 parts by mass and the hexamethylenetetramine is 2.5 parts by mass with respect to 75 parts by mass (70 g) of the powdery catalyst, and the compounding amount of MEK is the solid content of the composition. Was 55% by mass. Further, glass beads having a diameter of 1 mm (manufactured by As One Co., Ltd., model number BZ-1, apparent volume 64 mL) were placed in a wide-mouth polyethylene bottle as a dispersion medium. The coating mass of the coating composition was 0.17 kg.

A wide-mouth polyethylene bottle was set on a paint shaker (manufactured by Toyo Seiki Co., Ltd.), and mixed and dispersed for 1 minute as a preparation time to obtain a coating composition (the paint shaker was moved at a stroke of 5 cm for 12 seconds per 1 second). It is moving in a cycle of 5 times, and the typical velocity is 0.05×2 (m)/[1/12.5](s)=1.25 m/s). The catalyst particle size in the coating composition was 3.4 μm.

A copper foil (thickness 40 μm, basis weight 310 g/m ²⁺ , surface roughness Rz: 8.0 μm on one side, 4.1 μm on the other side) was used as a support, and the coating composition was applied to both sides of the copper foil with a bar coater (As One Co., Ltd.). After coating with No. 8 and No. 12 manufactured by the company), it was treated with a hot-air circulating thermostat (made by Yamato Scientific Co., Ltd.) at a drying rate of 0.5 g/m ² ·s for 60 seconds to obtain a film-shaped catalyst intermediate. .. Although the coating device and the dryer are different from those in Examples 1 to 5, the coating method and the drying speed are the same.

The obtained film-shaped catalyst intermediate (width 65 mm x length 160 mm) was bent into a corrugated plate shape, superposed with a flat film-shaped catalyst of the same size, and wound in a cylindrical shape, and the outer diameter was 30 mm and the height was 65 mm. Twenty-five cylindrical film-shaped catalyst intermediates were prepared. This was cured in a dryer at a resin curing temperature of 200° C. or higher for 90 minutes to obtain a film catalyst having the shape shown in FIG.

Catalyst layer weight per unit area in the obtained film catalyst one side 11.6 g / ^{m 2,} was double-sided 23.2 g / ^{m 2.} The loading amount of the powdery catalyst per unit area, one-sided 8.7 g / ^{m 2,} a double-sided 17.4 g / ^{m 2,} the supported amount of the powdered catalyst in the cylindrical film catalyst 25 present in 4. It was 5 g. The pore volume of the catalyst layer was 0.75 mL/g. The average macropore diameter of the catalyst layer was 0.39 μm.

Comparative example 2
20 parts by mass (15 g) of silicone oil (KF-96L-1cs, manufactured by Shin-Etsu Chemical Co., Ltd.), which is a porosification aid, was added to 80 parts by mass of MEK (61 g) as a solvent, and a novolac-based phenol resin and hexamethylene were used as a binder. Tetramine and catalyst 1 as powdered catalyst were placed in this order in a 250 mL wide-mouth polyethylene bottle. The non-volatile content of the phenolic resin is 22.5 parts by mass and the hexamethylenetetramine is 2.5 parts by mass with respect to 75 parts by mass of the powdery catalyst (70 g), and the compounding amount of the solvent is the solid content of the composition. Was 55% by mass. Further, glass beads having a diameter of 1 mm (manufactured by AS ONE Corporation, model number BZ-1, apparent volume 64 mL) were placed in a wide-mouth polyethylene bottle as a dispersion medium. The coating mass of the coating composition was 0.17 kg.

A wide-mouth polyethylene bottle was set in a paint shaker (manufactured by Toyo Seiki Co., Ltd.) and mixed and dispersed for 8 minutes as a preparation time to obtain a coating composition (the paint shaker was moved at a stroke of 5 cm for 12. seconds per second). It is moving in a cycle of 5 times, and the typical speed was 0.05×2 (m)/[1/12.5](s)=1.25 m/s). The catalyst particle size in the coating composition was 3.2 μm.

A copper foil (thickness 40 μm, basis weight 310 g/m ² , surface roughness Rz: 8.0 μm on one side, 4.1 μm on the other side) was used as a support, and the coating composition was applied to both sides of the copper foil with a bar coater (As One Co., Ltd.). After coating with No. 8 and No. 12 manufactured by the company), it was treated with a hot-air circulating thermostat (made by Yamato Scientific Co., Ltd.) at a drying rate of 0.5 g/m ² ·s for 60 seconds to obtain a film-shaped catalyst intermediate. .. Although the coating device and the dryer are different from those in Examples 1 to 5, the coating method and the drying speed are the same.

The obtained film-shaped catalyst intermediate (width 65 mm x length 160 mm) was bent into a corrugated plate shape, superposed with a flat film-shaped catalyst of the same size, and wound into a cylindrical shape, and the outer diameter was 30 mm x height 65 mm. Twenty-five cylindrical film-shaped catalyst intermediates were prepared. This was cured in a dryer at a resin curing temperature of 200° C. or higher for 90 minutes to obtain a film catalyst having the shape shown in FIG.

Catalyst layer weight per unit area in the obtained film catalyst one side 13.9 g / ^{m 2,} was double-sided 27.7 g / ^{m 2.} The loading amount of the powdery catalyst per unit area, one-sided 10.4 g / ^{m 2,} a double-sided 20.8 g / ^{m 2,} the supported amount of the powdered catalyst in the cylindrical film catalyst 25 present is 5. It was 4 g. The pore volume of the catalyst layer was 0.88 mL/g. The average macropore diameter of the catalyst layer was 0.57 μm.

[Evaluation of film strength]
The membrane strength was measured by preliminarily weighing the mass of the catalyst layer of each film catalyst obtained in Examples 1 to 8 and Comparative Examples 1 and 2 before evaluation of the following reaction characteristics, and each film catalyst in acetone solvent. And was exposed to ultrasonic waves for 30 minutes with an ultrasonic cleaner (SU-6TH, manufactured by Shibata Scientific Co., Ltd.). The residual amount (%) of the catalyst layer in the film catalyst was calculated by weighing the residual amount of the catalyst layer after irradiation to obtain the film strength. The higher the residual rate, the higher the film strength.

[Method of measuring catalyst particle size]
Examples of the catalyst particle size include a method of calculating from the cross-sectional image of the catalyst layer and a method of calculating from the coating composition containing the catalyst particles. In Examples 1 to 8 and Comparative Examples 1 and 2 of the present application, the latter measurement was performed.
Each coating composition of Examples 1 to 8 and Comparative Examples 1 and 2 was diluted with MEK and the particle size was measured by using a laser diffraction/scattering type particle size distribution measuring device (LA-950 manufactured by Horiba, Ltd.). It was measured.
The particle diameter is a median diameter calculated on a volume basis.

[Measurement method of pore volume]
The pore volume of the catalyst layer of each of the film catalysts obtained in Examples 1 to 8 and Comparative Examples 1 and 2 was measured using a mercury penetration type pore distribution measuring device (Shimadzu Corporation, Poisizer 9320). The pore volume of the catalyst layer is the pore volume per unit mass of the powdery catalyst in the catalyst layer.

[Measurement method of average macropore diameter]
The average macropore diameter of the catalyst layer of each of the film-shaped catalysts obtained in Examples 1 to 8 and Comparative Examples 1 and 2 is such that the pores in the catalyst layer are assumed to be cylindrical pores, and the average macropore diameter is the pore diameter D. The pore volume Vo and the pore area A of the catalyst layer of each film-shaped catalyst were measured using a mercury penetration type pore distribution measuring apparatus (Shimadzu Corporation, Poisizer 9320), and the following equation D =4Vo/A.

[Evaluation of reaction characteristics]
Regarding the reaction characteristics, only the film catalysts of Examples 1 to 8 having a residual rate of 40% or more in the evaluation of the above-mentioned membrane strength were evaluated.
The cylindrical film-shaped catalysts obtained in Examples 1 to 8 have a plurality of flow passages having a cross-sectional area of about 0.1 cm ² that communicate with each other in the height direction.

Into a glass reactor having an inner diameter of 130 mm with a bottom having a glass filter (2 G), 915 g of the cylindrical film catalyst and dodecyl alcohol (Calcor (registered trademark) 2098 manufactured by Kao Co., Ltd.), which is a raw material alcohol, were added to the catalyst. After the reduction activation of (1) was performed, the supply of dimethylamine was started while supplying hydrogen gas, and the temperature was kept constant at 220°C.

Samples were taken from the reactor over time, analyzed by gas chromatography, and the change in the concentration of dodecyl alcohol with respect to the reaction time was calculated.

In addition, the reaction end point is defined as the time point when the dodecyl alcohol concentration decreases to 1%, the reaction time TIME (h) from the reaction start to the reaction end point, and the by-product dilauryl monomethylamine concentration M2 (%) at the reaction end point by gas chromatography , [Reaction time×byproduct concentration] TIME×M2 was calculated. The results are shown in Table 2 below.

Here, in the reaction, the shorter the reaction time and the smaller the number of by-products, the better the reaction characteristics. Therefore, the above-mentioned TIME×M2 was introduced as an index for judging the superiority or inferiority. The sum of the content ratio of the powdery catalyst and the content ratio of the binder shown in Table 1 is 100% by mass.

(Discussion)
In Table 1, Examples 1 to 8 satisfy the conditions that the catalyst particle diameter is 1.3 μm or more and 3.3 μm or less and the pore volume is 0.40 mL/g or more and 0.87 mL/g or less, so that the membrane strength is 85. % Or more, which was a good result as compared with Comparative Examples 1 and 2. Further, Examples 1 to 8 satisfy the condition 100<time·V·P/G<1500 (m·L/kg) of the media type mill.
In Comparative Example 1, since the catalyst particle size was larger than 3.3 μm, the film strength was 32.3%, which resulted in a deterioration of the film strength as compared with Examples 1-8. Further, Comparative Example 1 does not satisfy the condition 100<time·V·P/G<1500 (m·L/kg) of the media type mill.
In Comparative Example 2, since the pore volume was larger than 0.87 mL/g by adding the silicone oil to the solvent for preparing the catalyst particles, the membrane strength was 6.5%, which was compared with Examples 1-8. As a result, the film strength deteriorated.

(Discussion)
In Table 2, in the reaction characteristic evaluation of Examples 6 to 8, since the surface roughness Rz of the support is 2.0 μm or more in Examples 6 and 7, the surface roughness Rz of the support is less than 2.0 μm. As a result, the reaction characteristics were better than those of Example 8.

DESCRIPTION OF SYMBOLS 1 Film catalyst 2 Support 3 Catalyst layer 4 Powder catalyst 5 Binder 6 Gap 7 Hole

Claims (10)

A film-shaped catalyst having a catalyst layer formed on a support,
The catalyst layer contains catalyst particles having a particle diameter of 1.3 μm or more and 3.3 μm or less, which includes a powdery catalyst and a binder,
Ri 0.87 mL / g der less pore volume 0.40 mL / g or more of the catalyst layer,
The binder is Ru synthetic resin der, film catalyst. The film catalyst according to claim 1, wherein the average macropore diameter of the catalyst layer is 0.2 μm or more and 0.5 μm or less. The film catalyst according to claim 1 or 2, wherein a mass ratio of the powder catalyst and the binder (powder catalyst/binder) is 1 or more and 10 or less. The film catalyst according to claim 1, wherein the support is a metal foil. The film catalyst according to claim 1, wherein the surface roughness Rz of the support is 1.0 μm or more and 30 μm or less. The method for producing a film catalyst according to any one of claims 1 to 5, comprising the following steps.
Step 1: A step of preparing a coating composition containing a powdery catalyst, a binder and a solvent, wherein the particle size of the catalyst particles containing the powdery catalyst and the binder in the coating composition is 1.3 μm or more and 3.3 μm or less. Step 2: Applying the coating composition onto a support to form a catalyst layer A method for producing a film catalyst, comprising the following step 1 and step 2.
Step 1: a step of preparing a coating composition containing a powdered catalyst, a binder and a solvent,
Using a media type mill, the preparation time time (sec.) in the media type mill, the representative speed V (m/sec.), the apparent volume P (L) of the media used for the preparation, and the compounding mass G of the coating composition (Kg), the coating composition is prepared under the condition that the following formula (I) is satisfied ,
100<time・V・P/G<1500 (m・L/kg) (I)
A step of adjusting the particle size of the catalyst particles containing the powdery catalyst and the binder in the coating composition to 1.3 μm or more and 3.3 μm or less.
Step 2: A step of applying the coating composition onto a support to form a catalyst layer having a pore volume of 0.40 mL/g or more and 0.87 mL/g or less The step 2 is a step of applying the coating composition onto a support having a surface roughness Rz of the support of 1.0 μm or more and 30 μm or less and forming a catalyst layer into a film. Method for producing film catalyst. The method for producing a film catalyst according to any one of claims 6 to 8, which includes a drying step after step 2, and a drying rate is 0.01 g/m ² ·s or more and 10 g/m ² ·s or less. .. The method for producing a filled catalyst according to claim 9, further comprising a shaping step and a heating step after the drying step.