JP2017113747A - Film-like catalyst - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a film-like catalyst excellent in reaction selectivity, and having a small falling amount of the catalyst; and to provide a production method of the film-like catalyst.SOLUTION: There is provided a film-like catalyst having a catalyst layer formed on a support medium. In the film-like catalyst, the catalyst layer includes catalyst particles containing a powdery catalyst and a binder and having a particle size of 1.3 μm or larger and 3.3 μm or smaller, and a pore volume of the catalyst layer is 0.40 mL/g or more and 0.87 mL/g or less.SELECTED DRAWING: None

Description

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

  In chemical processes in the chemical industry, processes using solid catalysts have been widely adopted. In this method, a powdered catalyst having a fine particle shape is often used as the catalyst, and the catalyst is directly added to the reaction kettle to cause the reaction. In a reaction process using a powdered catalyst, a technique such as stirring for effectively mixing the reactant and the catalyst is required. In addition, after the reaction is completed, it is necessary to remove the catalyst from the product, and there is a problem that facilities and operation become complicated. In this system, a large amount of filter aid is added. However, since the catalyst is a particle, the filtration time is long, and the filter aid adsorbs a large amount of reactants and decreases the reaction yield. Yes.

  By supporting the powdered catalyst on a porous support such as zeolite and increasing the powder particle size, the filterability of the fine particle powder can be improved and the filtration time can be shortened. In addition, 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 mixing operation of the catalyst by stirring or the like and does not require filtration and separation of the catalyst. Patent Document 1 and Patent Document 2 disclose a film catalyst as a novel form of a solid catalyst used in a fixed bed system. 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 amine production method. Patent Document 2 discloses a method for producing a film catalyst in which reaction activity and reaction selectivity are increased by forming a catalyst layer having a specific pore size distribution on a support.

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

  The film-type catalyst disclosed in Patent Document 1 and Patent Document 2 is an excellent invention in that the catalytic activity is good and the amount of catalyst falling off is small.

  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 dropout, 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, the catalyst layer comprising catalyst particles having a particle size of 1.3 μm or more and 3.3 μm or less containing a powdered catalyst and a binder,
The catalyst layer has a pore volume of 0.40 mL / g or more and 0.87 mL / g or less.

Moreover, this invention relates to the manufacturing method of the said film-form catalyst including the following processes.
Step 1: A step of preparing a coating composition containing a powdered catalyst, a binder and a solvent, wherein the particle size of the catalyst particles containing the powdered catalyst and the binder in the coating composition is 1.3 μm or more and 3.3 μm or less. Step 2: Step of applying the coating composition on a support and forming a catalyst layer

  ADVANTAGE OF THE INVENTION According to this invention, while the reaction selectivity is favorable, the manufacturing method of the film-form catalyst with few drop-off amounts of a catalyst can be provided.

The schematic sectional drawing of the film-like catalyst obtained with the manufacturing method of this invention. The fragmentary sectional view of FIG. The fragmentary sectional view of FIG. The perspective view of one Embodiment of the film-like catalyst obtained with the manufacturing method of this invention. The perspective view of other embodiment of the film-like catalyst obtained with the manufacturing method of this invention. The perspective view of other embodiment of the film-like catalyst obtained with the manufacturing method of this 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 has a particle size of 1.3 μm or more and 3.3 μm or less including a powdered catalyst and a binder. And the catalyst layer has 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 powdered catalyst having catalytic activity. The “catalyst particles” mean particles having a specific particle diameter including a powdered catalyst and a binder. In addition, the “film catalyst” means that the shape of the support is not limited to a film shape, and the formed catalyst layer is thin.

[Powdered catalyst]
As the powdered 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 that is effective for the applied chemical reaction, such as Ag, Au, Cu, Ni, Fe, Al, the fourth periodic transition metal element, the platinum group element, and the 3A group element of the periodic table. And metal elements such as alkali metals and alkaline earth metals and metal oxides thereof.

  The porous material is a catalyst carrier that supports the catalytic active material, and can 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, known methods such as a normal impregnation method, a co-impregnation method, a co-precipitation method, and an ion exchange method can be applied.

The particle size of the powdered 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 catalyst filtration and separation, and preferably from the viewpoint of the reaction activity of the catalyst. Is 4.5 μm or less, more preferably 4.3 μm or less, and still more 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 powdered 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 the 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 diameter of the powdered catalyst can be measured by diluting the powdered catalyst in 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 has excellent binding properties to the powdered catalysts and the support surface, withstands the reaction environment, and does not adversely affect the reaction system. Examples of such binders include cellulose resins such as carboxymethyl cellulose and hydroxyethyl cellulose, fluorine resins such as polytetrafluoroethylene and polyvinylidene fluoride, polyvinyl alcohol, urethane resins, epoxy resins, polyamide resins, polyimide resins, and polyamideimides. Various thermoplastic resins and thermosetting resins such as resins, polyester resins, phenol resins, melamine resins, and silicone resins can be used. By introducing a cross-linking reaction with a curing agent to these synthetic resins, higher polymerization can be achieved. What is illustrated can also be used. Of these, thermosetting resins such as phenol resins, furan resins, and epoxy resins are preferred, and more preferred are thermosetting resins that involve a condensation reaction during curing.

  When a thermosetting resin is used as a binder, the film strength and binding properties are improved by improving the crosslinking density due to the curing reaction, and the catalytic activity of the powdered catalyst is effectively derived from the porous catalyst coating by the condensation reaction. be able to.

  When the film-like 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, an example of a preferable combination of a powdery catalyst and a binder is a copper-nickel-ruthenium ternary system. A combination of a powdered catalyst and a phenol resin can be mentioned.

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

  The solvent is not particularly limited as long as it does not adversely affect the catalytic activity of the powdered 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. The solvent preferably has good binder solubility, and two or more kinds of solvents may be used in combination. The pore structure of the catalyst layer is controlled by selecting the solvent in accordance with the binder used. be able to.

Solvents include water; alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol, and allyl alcohol; ketones such as acetone, methyl ethyl ketone (MEK), and methyl isobutyl ketone (MIBK); ethylene glycol, propylene glycol, and 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 and derivatives thereof; glycerol, glycerol monoethyl ether, glycerol monoallyl ether, etc. Glycerol or its derivatives; tetrahydrofuran, Ethers such as oxane; liquid paraffin, decane, decene, methylnaphthalene, decalin, kerosene, diphenylmethane, toluene, dimethylbenzene, ethylbenzene, diethylbenzene, propylbenzene, cyclohexane, partially hydrogenated hydrocarbons such as triphenyl; chlorobenzene , Halogenated hydrocarbons such as dichlorobenzene, bromobenzene, chlorodiphenyl, chlorodiphenylmethane; fluorides such as demnum (manufactured by Daikin Industries); ethyl benzoate, octyl benzoate, dioctyl phthalate, trioctyl trimellitic acid , Ester compounds such as dibutyl sebacate, ethyl (meth) acrylate, butyl (meth) acrylate, dodecyl (meth) acrylate; other dimethylformamide, N-methyl-pyro It can be exemplified Don, acetonitrile, ethyl acetate.
Among them, the solvent is preferably an alcohol or a ketone, more preferably a ketone, and still more preferably methyl ethyl ketone (MEK) from the viewpoint of the paintability of the powdery catalyst surface and the solubility of the binder.

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

  As coupling agents, those generally known as silane coupling agents, titanate coupling agents and aluminate coupling agents can be used, and a plurality of coupling agents may be combined to adjust the concentration. It may be used after diluting with an organic solvent compatible with.

  As the fibrous material, organic fiber or inorganic fiber is used. The organic fibers include polyamide nylon 6, nylon 66, aramid fiber, polyvinyl alcohol fiber, polyester polyethylene terephthalate, polybutylene terephthalate fiber, polyarylate fiber, and polyvinylidene chloride. And polyvinyl chloride, polyacrylonitrile, and polyolefin-based polyethylene and polypropylene fibers. Organic fibers include organic regenerated fibers, and examples thereof include cellulose-based rayon and acetate. As the inorganic fiber, glass fiber, carbon fiber, activated carbon fiber, ceramic fiber, or the like can be used. By blending the fibers, the mechanical strength (membrane strength) of the catalyst layer can be improved due to the manifestation of the aggregate effect.

[Support]
The support used in the present invention can be appropriately selected according to the form of the target film-like catalyst, and 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 thereto.

  The plate-like support may have any suitable processability and durability and does not adversely affect the reaction system in which the film 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, copper foil and stainless steel foil can be used from the viewpoint of workability and corrosion resistance.

  Also, honeycomb or monolithic supports include cordierite, carbon composite, mullite, clay, magnesia, talc, zirconia, spinel, alumina, silica, ceria, titania, tungsten, chromium, stainless steel, copper, aluminum and Although what contains nickel can be mentioned, it is not limited to these.

  Here, the honeycomb shape is a shape in which a large number of cells are accumulated, forming a honeycomb-like structure partitioned by thin walls, and is preferable as a support constituting a film-like catalyst because the surface area per unit volume can be increased. . In addition, it is preferable to use regular triangles, regular pentagons, and regular hexagons because the cells can be accumulated without gaps, and the cells can be configured by combinations of irregularly shaped object cells or polygonal cells. For example, as a honeycomb-shaped support, an integrated structure formed by extrusion molding, or a support formed by stacking multiple layers of corrugated materials (corrugated) obtained by shaping a flat plate material and a flat plate material The body can also be used preferably.

Furthermore, the surface of the support is preferably subjected to a roughening treatment or a coupling treatment from the viewpoint of improving the adhesion with the catalyst layer. The coupling agent described above can be used for this coupling treatment.
In the case of roughening the surface of the support, the surface roughness Rz of the support is preferably 1.0 μm or more from the viewpoint of improving adhesion with the catalyst layer and diffusibility of the reaction substrate in the catalyst layer. More preferably, it is 2.0 μm or more, more preferably 2.5 μm or more, still more preferably 3.0 μm or more, and from the viewpoint of ensuring the uniformity of the catalyst layer, it is preferably 30.0 μm or less, more preferably 25. It is 0 μm or less, more preferably 20.0 μm or less. Here, the surface roughness Rz is a roughness curve maximum height, which 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 Corporation). 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 and chemical roughening.

(Catalyst layer)
From the viewpoint of catalytic activity, the particle diameter of the catalyst particles containing the powdered catalyst and the binder in the catalyst layer formed on the support is 1.3 μm or more, preferably 1.5 μm or more, more preferably 1.8 μm or more. And from a viewpoint of ensuring the uniformity of the film thickness of a film catalyst layer, and film | membrane intensity | strength, it is 3.3 micrometers or less, Preferably it is 3.0 micrometers or less, More preferably, it is 2.8 micrometers or less.
Here, the particle diameter is defined as a median diameter calculated on a volume basis.

Examples of the catalyst particle diameter include a method of calculating from a cross-sectional image of the catalyst layer, and a method of calculating from a coating composition containing catalyst particles.
When calculating from a coating composition, it can be measured by using a laser diffraction / scattering particle size distribution measuring apparatus (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, from the viewpoint of diffusibility of the reaction substrate in the catalyst layer, and the catalyst 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 a method for measuring the pore volume, the pore volume can be measured by using a mercury intrusion dedicated measuring machine such as a mercury intrusion pore distribution measuring apparatus (manufactured by Shimadzu Corporation, Pore Sizer 9320).

The average macropore diameter of the catalyst layer is preferably 0.20 μm or more, more preferably 0.21 μm or more, further preferably 0.22 μm or more, from the viewpoint of increasing the reaction selectivity by diffusing the reaction substrate into the catalyst layer. 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, and 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 method for measuring the average macropore diameter is to determine the pore volume Vo and the pore area A by using a mercury intrusion measuring apparatus such as the above-mentioned mercury intrusion type pore distribution measuring device (manufactured by Shimadzu Corporation, Pore Sizer 9320). 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 still more preferably 64% by mass from the viewpoint of expressing high reaction activity and reducing the amount of by-products. More preferably, it is 66% by mass or more, and from the same viewpoint, it is preferably 91% by mass or less, more preferably 90% by mass or less, still more preferably 88% by mass or less, and 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, still more preferably 12% by mass or more, and still more preferably 17%, from the viewpoint of binding to the support surface. 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, and still more preferably 34% by mass or less.

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

[Structure of film catalyst]
The film-like catalyst of the present invention has a catalyst layer on one side or both sides of a 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-like catalyst obtained by the production method of the present invention when cut in the thickness direction, and FIG. 2 is a portion surrounded by a square in FIG. FIG. 3 is an enlarged view of a portion surrounded by a square in FIG.

  As shown in FIG. 1, the film-like catalyst 1 has catalyst layers 3 on both surfaces of the support 2 (the catalyst layer 3 may be only one surface of the support 2). As shown in FIG. 2, the catalyst layer 3 includes a powdered catalyst 4 and a binder 5 covering the periphery of the powdered catalyst 4 to form catalyst particles, and a plurality of powdered catalysts 4 (and powdered catalysts 4) are formed. Between the binders 5) covering the periphery, there are gaps 6 as shown surrounded by broken lines in the figure. Further, as shown in FIG. 3, the binder 5 covering the periphery of the powdered catalyst 4 has holes 7 as shown by being surrounded by a broken line in the figure. 5 is not covered 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, still more preferably 5 μm or more, from the viewpoint of expressing high reaction activity and reducing the amount of byproducts. Preferably it is 500 micrometers or less, More preferably, it is 100 micrometers or less, More preferably, it is 50 micrometers or less. In addition, the catalyst layer loading 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 from the same viewpoint. m ² or less, more preferably 50 g / m ² or less, and even more preferably 30 g / m ² or less. In addition, the catalyst layer carrying amount per unit area is a carrying amount when the catalyst layer is provided only on one side of the support. When catalyst layers are provided on both sides, the amount of catalyst layer supported per unit area is doubled.

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

<Method for producing film catalyst>
The manufacturing method of the film catalyst of this invention is a manufacturing method of the said film catalyst containing the following processes.
Step 1: A step of preparing a coating composition containing a powdered catalyst, a binder and a solvent, wherein the particle size of the catalyst particles containing the powdered catalyst and the binder in the coating composition is 1.3 μm or more and 3.3 μm or less. Step 2: Step of applying the coating composition on a support and forming a catalyst layer The method for producing a film catalyst of the present invention appropriately applies the matters described above. Can do.

[Step 1]
Step 1 is a step of preparing a coating composition containing a powdered catalyst, a binder and a solvent, and the particle size of the catalyst particles containing the powdered catalyst and the binder in the coating composition is 1.3 μm or more and 3.3 μm. It is the process of preparing so that it may become the following.

  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, and still more preferably 30% by mass from the viewpoint of developing high reaction activity and 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 still more 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, still more preferably 10% by mass or more, from the viewpoint of the binding property to the support surface. From the viewpoint, it is preferably 40% by mass or less, more preferably 25% by mass or less, and still more preferably 20% by mass or less.

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

  By making the content ratio of the powdered catalyst and the binder within the predetermined range, it becomes possible to control the degree of exposure of the powdered catalyst, and further to extract the catalytic activity ability inherent to the powdered catalyst. And the effect of preventing the catalyst layer from falling off can also be improved. Specifically, as shown in FIGS. 1 to 3, the surface of the powdered catalyst can be controlled so that there are a portion coated with a binder and a portion not covered with the binder. And the like, 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 powdered catalyst or the coating state of the binder as shown in FIG. 3 becomes appropriate, and the catalytic activity of the powdered 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 developed, and the binding force between the powdered catalysts or between the powdered catalyst and the support is improved, during the production process of the film catalyst and the reaction operation The amount in which the catalyst layer peels off or part of the catalyst layer falls off 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 preferably prepared using a media type mill or a paint shaker. By using a media type mill, it is possible to uniformly treat each component constituting the coating composition from the structure and mechanism, so that the particle size and dispersion state of the catalyst particles are 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 (registered trademark), AD mills, twin AD mills, basket mills, twin basket mills, handy mills, SC mills, Glen mills, dyno mills, apex mills, star mills (Ashizawa Finetech Co., Ltd., registered trademark), viscomill, sand grinder, paint shaker using beads, and the like. In the present invention, as a disperser other than the media type mill, a dissolver type mixing disperser may be used.

The coating composition consists of a media type mill preparation time time (sec.), A representative speed V (m / sec.), An apparent volume P (L) of media used for the preparation, and a blending mass G (kg) of the coating composition. , It is preferable to prepare it under the 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 unit in the rotary mill, and the speed obtained by dividing the moving stroke by the moving time in a mill having a reciprocating motion such as a paint shaker.

In general, 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.). It is difficult to determine the shear rate and to model the state of shear application. For this reason, it has been found that it is effective to determine the paint conditions by the formula (I) in the media type mill. In other words, in the formula (I), the paint preparation conditions are the typical speed (V) and preparation time (time) of the stirring unit applied per unit mass of the paint, and the apparent volume ratio of media per unit mass of the paint composition. It can be expressed as a 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 coating, and if the apparent volume of the media during dispersion is smaller than the unit mass of the coating composition If P / G is small, it means that sufficient representative speed (V) and preparation time (time) of the stirring section are required to obtain good dispersion. Conversely, when the apparent volume of the media is large (when P / G is large), the representative speed (V) and preparation time (time) of the stirring unit may be small. The effect of dispersing 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 has the apparent volume of the media when the adjustment solvent is the same as a precondition. We focused on being the most dominant.

  Further, when only the relationship between the representative speed of the stirring unit and the preparation time is observed, when the representative speed of the stirring unit is small, good coating conditions can be obtained by taking a long preparation time.

  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 pulverization efficiency, and a viewpoint of suppressing excessive pulverization. Therefore, it is preferably 30 m / sec or less, more preferably 25 m / sec or less, and still more preferably 20 m / sec or less.

The preparation time (time) is preferably 30 sec or more, more preferably 45 sec or more, still more preferably 60 sec or more, from the viewpoint of ensuring uniformity of the paint, and preferably 10,000 sec or less, more preferably 7000 sec from the viewpoint of production efficiency. Hereinafter, it is more preferably 5000 sec or less.

The apparent volume P (L) of the media used for the preparation and the blending 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 grinding efficiency, preferably 0.01 or more, more preferably 0.03 or more, still more 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 / g to 0.87 mL / g and the average macropore diameter can be brought close to 0.2 μm to 0.5 μm.
The preparation conditions represented by the formula (I) are preferably 100 <time · V · P / G <1500, more preferably 110 <time · V · P / G <1400, still more preferably 120 <time · V · P. This is a condition represented by / G <1300.

  The solid content in the coating composition is preferably 5% by mass or more, more preferably, 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 mass% or more, More preferably, it is 15 mass% or more, Preferably it is 70 mass% or less, More preferably, it is 65 mass% or less, More preferably, it is 60 mass% or less.

  The viscosity of the coating composition is selected within a preferable range depending on the coating method, 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, and still more preferably 80 mPa · s or less.

[Step 2]
Step 2 is a step of coating 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 Tech Seed, registered trademark), kiss, gravure, die coating and the like are listed. be able to.

The support is preferably subjected to a roughening treatment from the viewpoint of improving the adhesion to the catalyst layer.
When roughening the surface of the support, the surface roughness Rz of the support is preferably 1.0 μm or more from the viewpoint of improving the adhesion with the catalyst layer and the diffusibility of the reaction substrate in the catalyst layer. More preferably, it is 2.0 μm or more, more preferably 2.5 μm or more, still more preferably 3.0 μm or more, and from the viewpoint of ensuring the uniformity of the catalyst layer, it is preferably 30.0 μm or less, more preferably 25. It is preferable to coat the coating composition on a support of 0 μm or less, more preferably 20.0 μm or less, and form a catalyst layer.

[Drying and curing process]
In the present invention, a drying and curing step can be provided after the step 2, and a shape processing step and a final heating step can be provided following the drying and curing step. In addition, when it is dried (cured) at room temperature after coating and film formation, the drying and curing steps are not necessary.

  The drying and curing steps are intended to remove the solvent, unreacted monomers, etc. contained in the coating composition after coating and forming the coating composition on the support. In addition to the case where the curing reaction proceeds with drying, the curing reaction can be partially advanced in parallel with the drying by adjusting the heating temperature and the heating time according to the composition of the coating composition. .

  The drying and curing steps are preferably carried out in an atmosphere heated with an inert gas such as air, water vapor, nitrogen, or argon, or a method of spraying these heat media is used. In addition, radiant heat such as infrared rays or far infrared rays is used. Various methods such as a heating method using an induced current caused by electromagnetic waves, a method combining these methods, or a method using natural drying (air drying) at room temperature can also be used. Components that are eliminated in this step are a volatile component mainly composed of a solvent and a curing reaction product. Examples of volatile components other than the solvent include unreacted monomer components.

  The drying and curing conditions must be adjusted according to the physical properties of the volatile components, mainly the binder and solvent contained in the coating composition. The porous structure of the catalyst layer depends on the selection of the solvent and the setting of 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 components are detached from the catalyst layer and the larger the pore structure (pore diameter, capacity). Further, it is considered that the pore structure becomes smaller as the drying temperature is lower and the amount of drying air 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 diameter of the catalyst particles does not change.

  In addition to the elimination of volatile components, mainly solvents, from the coating composition, the formation of a crosslinked structure (network structure) formed by the progress of the curing / crosslinking reaction, and if there is a further condensation reaction, The pore structure is determined during the desorption stage.

  The drying and curing treatment employs a drying method and drying conditions that do not adversely affect the catalytic activity inherent in the powdered catalyst used in the present invention.

In the drying and curing treatment 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, it is 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 even more preferably 10 minutes or less.

  In the case where only the drying without a curing reaction is intended, it is preferable to dry the coating composition immediately after applying the coating composition to the support. By adjusting the drying conditions at this time, the coating film can be made porous. You can control the structure. Therefore, it is desirable that the time from the formation of the catalyst layer on the support to the elimination of the volatile component mainly composed of the solvent is shorter, preferably within 2 hours, more preferably within 30 minutes, and even more preferably. Is within 5 minutes.

[Catalyst intermediate shape processing and final heating step]
In the present invention, when the binder contains a thermosetting resin, the final shape of the catalyst intermediate is processed with the uncured product remaining in the catalyst layer obtained by coating and drying (prepolymer state). Heat treatment is desirable.

  The drying and curing treatment of the catalyst intermediate performed before the final heat treatment may be terminated in a state where an uncured product remains in the thermosetting resin. Part of it is cured until handling during shape processing can be carried out, and it is desirable that the retention and mechanical strength of the catalyst layer are improved compared to the time of film formation. May remain in 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 / s, 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 exhibiting catalytic activity, preferably 10 g / m ² · s or less, more preferably 9 g / m ^2. · S or less, 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 even more preferably 10 minutes or less.

  By processing the shape of the catalyst layer of the film catalyst before it completely cures, the catalyst layer follows the plastic deformation of the support, improving the shape processability and completely curing after the processing is completed. In this final stage, the cross-linked structure of the catalyst layer can be fixed, the residual stress in the catalyst layer is relaxed, and the influence of the film catalyst on the catalyst layer falling off can be improved.

  Moreover, in this invention, when a binder contains a thermoplastic resin, it is desirable to heat-treat the catalyst layer obtained by apply | coating and drying, after carrying out shape processing. When the catalyst layer contains a thermoplastic resin, there is a concern that residual stress is generated in the catalyst layer due to plastic deformation of the support when the shape processing is performed, and the retention of the catalyst layer is adversely affected. The Therefore, the final heat treatment can alleviate the stress, and the entangled structure of the thermoplastic resin can be strengthened to improve the influence of the film catalyst on the catalyst layer falling off.

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

  Although the final heat treatment conditions vary depending on the type of binder, in the present invention, the heat treatment temperature is preferably 80 ° C. or higher, more preferably 100 ° C. or higher, and preferably 400 ° C. or lower, more preferably 350 ° C. It is desirable to perform the heat treatment at a temperature of not higher than ° C. and a heat treatment time of preferably 5 minutes or longer, more preferably 10 minutes or longer, preferably 600 minutes or shorter, more preferably 100 minutes or shorter. In place of the heat curing method, radical polymerization, radiation polymerization, UV curing or the like can also be applied. When these methods are applied, various polymerization catalysts are included in the catalyst layer as necessary. be able to.

  The shape of the film catalyst can be processed into various shapes depending on the shape of the various reactors to which the catalytic reaction is applied, and trimming, shape processing, integration / assembly processing methods can be applied as necessary. The target shape can be obtained. In addition to a flat plate shape and a tubular shape, a honeycomb shape, a monolith shape, or the like can be used. Further, a unit as a structural body can be formed by being accommodated and filled in a holder or a case for incorporation into an actual reaction apparatus.

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

  In any case, it is preferable to adopt a structure that can easily supply the reactant to the catalyst layer and recover the product from the catalyst layer. In addition, it is desirable to increase the surface area of the catalyst layer of the film catalyst provided in the reactor as much as possible in order to advance the reaction efficiently. In order to achieve the above requirements, an assembly in which tubes having an inner diameter of several mm to several tens of mm are bundled, or a catalyst layer is provided on the inner wall surface of a honeycomb structure having a cell density of several to 200 cells per square centimeter, 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, and is obtained particularly when the powdery catalyst used for the reaction in the liquid phase is applied. Even if the film-like catalyst is applied to the reaction as it is, it is preferable because it does not impair the diffusibility of the reactants and products and can be adapted 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, hydrogenation reaction, these dehydrogenation reactions, The present invention can also be applied to an amination reaction in which a tertiary amine is produced from an alcohol accompanied by a hydrogenation reaction and a primary amine or secondary amine.

  As mentioned above, although this invention was demonstrated based on the preferable embodiment, this invention is not restrict | limited to the said embodiment. For example, the film-like catalyst of the present invention can be applied to a catalyst for a liquid-liquid reaction, a gas-gas reaction, and a solid-liquid reaction in addition to a catalyst for a gas-liquid reaction.

  In relation to the above-described embodiment, the present invention further discloses the following film catalyst and method for producing the film catalyst.

<1>
A film-like catalyst having a catalyst layer formed on a support,
The catalyst layer includes catalyst particles having a particle size of 1.3 μm or more and 3.3 μm or less containing a powdered 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 size of the powdered 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>, wherein

<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-like catalyst according to <1> or <2>, which is g or less, more preferably 100 m ² / g or less.

<4>
<1> to <3>, wherein the binder is one or more thermosetting resins selected from a phenol resin, a furan resin, and an epoxy resin, preferably a thermosetting resin with a condensation reaction at the time of curing. The film catalyst according to any one of the above.

<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>. 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. <5> The film-like catalyst according to any one of the above.

<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>, wherein

<8>
The mass ratio of the powdered catalyst to the binder in the catalyst layer (powdered catalyst / binder) is 1 or more, preferably 1.5 or more, more preferably 1.8 or more, still more preferably 2 or more, and 10 or less. Preferably, it is 9 or less, More preferably, it is 7.5 or less, More preferably, it is 5 or less, The film-form catalyst in any one of said <1>-<7>.

<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. In the following, the film catalyst according to any one of <1> to <9>, more preferably 20.0 μm or less.

<11>
Any one of the above items <1> to <10>, wherein the catalyst layer has a thickness of 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-like catalyst according to 1.

<12>
The supported amount per unit area of the catalyst layer 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. The film catalyst according to any one of <1> to <11>, which is ² or less, more preferably 30 g / m ² or less.

<13>
The manufacturing method of the film-form catalyst in any one of said <1>-<12> including the following processes.
Step 1: A step of preparing a coating composition containing a powdered catalyst, a binder and a solvent, wherein the particle size of the catalyst particles containing the powdered catalyst and the binder in the coating composition is 1.3 μm or more and 3.3 μm or less. Step 2: Step of applying the coating composition on a support and forming a catalyst layer

<14>
The particle size of the powdered 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. The method for producing a film catalyst according to <13>, wherein

<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 / g or less, More preferably, it is 100 m < ² > / g or less, The manufacturing method of the film catalyst as described in said <13> or <14>.

<16>
<13> to <15>, wherein the binder is one or more thermosetting resins selected from a phenol resin, a furan resin, and an epoxy resin, preferably a thermosetting resin that involves a condensation reaction during curing. The manufacturing method of the film catalyst in any one.

<17>
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. The method for producing a film catalyst according to any one of 13> to <16>.

<18>
The content ratio of the powdered catalyst in the coating composition is 10% by mass or more, preferably 20% by mass or more, more preferably 30% by mass or more, and 90% by mass or less, preferably 80% by mass or less, more preferably. Is 70 mass% or less, The manufacturing method of the film catalyst in any one of said <13>-<17>.

<19>
The content of the binder in the coating composition is 3% by weight or more, preferably 5% by weight or more, more preferably 10% by weight or more, and 40% by weight or less, preferably 25% by weight or less, more preferably 20%. The manufacturing method of the film-form catalyst in any one of said <13>-<18> which is the mass% or less.

<20>
The mass ratio of the powdered 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, still more preferably 2 or more, and 10 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, and 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. Preparation time time (sec.), Representative speed V (m / sec.) In the media-type mill, and apparent volume P (L of media used for the preparation) ), A film-like catalyst according to any one of the above <13> to <21>, which is prepared under a condition satisfying the following formula (I) when the blending mass G (kg) of the coating composition is used: Manufacturing method.
100 <time.V.P / G <1500 (m.L / kg) (I)

<23>
The representative speed (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 manufacturing method of the film-form catalyst as described in said <22>.

<24>
The preparation time (time) is 30 sec or more, preferably 45 sec or more, more preferably 60 sec or more, and 10,000 sec or less, preferably 7000 sec or less, more preferably 5000 sec or less, according to <22> or <23> above. A method for producing a film catalyst.

<25>
The apparent volume ratio (P / G) of the media per blending 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. .9 or less, more preferably 0.8 or less, The method for producing a film-like catalyst according to any one of <22> to <24>.

<26>
The preparation conditions represented by formula (I) are 100 <time · V · P / G <1500, preferably 110 <time · V · P / G <1400, more preferably 120 <time · V · The method for producing a film catalyst according to any one of <22> to <25>, wherein P / G <1300.

<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 forming the catalyst layer by applying the coating composition on a support of 25.0 μm or less, more preferably 20.0 μm or less. A method for producing a catalyst.

<28>
A drying step is included after step 2, 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 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 as follows.

<29>
The method for producing a film-like catalyst according to any one of <13> to <28>, comprising a shape processing 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, and a drying time of 30 minutes or less, preferably 20 minutes or less, more preferably 10 <29> The method for producing a film-like catalyst according to <29>, wherein

<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 , 600 minutes or less, preferably 100 minutes or less, The method for producing a film catalyst according to <29> or <31>.

[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.

  Synthetic zeolite (average particle size: 3 μm) is charged into a 1 L flask, and then copper nitrate, nickel nitrate and ruthenium chloride are added so that the molar ratio of each metal atom is Cu: Ni: Ru = 4: 1: 0.01. A solution dissolved in water was added to the flask and heated with stirring. A 10% by mass aqueous sodium carbonate solution was gradually added dropwise at 90 ° C. while controlling the pH at 9-10. 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 catalyst 1 was 3.6 μm. The particle diameter is a median diameter calculated on a volume basis, and was measured by diluting the powdered catalyst in water and using a laser diffraction / scattering particle size distribution analyzer (LA-950, manufactured by Horiba, Ltd.). .

Production example of catalyst 2 Production example of catalyst 2 was produced according to the production example of catalyst 1 except that a tank having a capacity of 300 L was used, and catalyst 2 was obtained. 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 catalyst 2 was 3.8 μm as measured by the same method as for 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 tank capacity.

Production Example of Catalyst 3 Production Example of Catalyst 3 was produced according to the production example of Catalyst 1 except that a tank having a capacity of 1000 L was used, and Catalyst 3 was obtained. 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 diameter of catalyst 3 was 4.5 μm as measured by the same method as for 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 tank capacity.

[Production Example of Film Catalyst]
Examples and Comparative Examples, which are production examples of a film catalyst, are shown below.

Example 1
Methyl ethyl ketone (MEK) as a solvent, novolac phenol resin and hexamethylenetetramine as a binder, and catalyst 1 as a powdery catalyst were placed in a 250 mL wide-mouth polyethylene bottle in this order. With respect to 75 parts by mass (70 g) of the powdered catalyst, the mixing ratio is such that the non-volatile content of the phenol resin is 22.5 parts by mass and the hexamethylenetetramine is 2.5 parts by mass, and the MEK content is the solid content of the formulation 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 blending 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 12. It is moving at a cycle of 5 times, and the representative speed was 0.05 × 2 (m) / [1 / 12.5] (s) = 1.25 m / s). The catalyst particle diameter in the coating composition was 2.9 μm.

A copper foil (thickness 40 μm, weighing 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 coated on both sides of the copper foil with a gravure coater ( After coating with Yasui Seiki Co., Ltd., the film was treated with a dryer at a drying rate of 0.5 g / m ² · s for 60 seconds to obtain a film-like catalyst intermediate.

  The obtained film-like catalyst intermediate (width 65 mm × length 160 mm) is bent into a corrugated plate, overlapped with a flat film-like catalyst of the same size and wound into a cylindrical shape, outer diameter 30 mm × height 65 mm 25 cylindrical film-shaped catalyst intermediates were prepared. This was cured with 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, novolac phenol resin and hexamethylenetetramine as a binder, and catalyst 1 as a powdery catalyst were placed in a 250 mL wide-mouth polyethylene bottle in this order. The blending ratio is such that 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 (70 g) of the powdered catalyst, and the compounding amount of MEK is the solid content of the compound 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 blending 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 16 minutes as a preparation time to obtain a coating composition (the paint shaker was 12. It is moving at a cycle of 5 times, and the representative speed was 0.05 × 2 (m) / [1 / 12.5] (s) = 1.25 m / s). The catalyst particle diameter in the coating composition was 2.5 μm.

A copper foil (thickness 40 μm, weighing 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 coated on both sides of the copper foil with a gravure coater ( After coating with Yasui Seiki Co., Ltd., the film was treated with a dryer at a drying rate of 0.5 g / m ² · s for 60 seconds to obtain a film-like catalyst intermediate.

  The obtained film-like catalyst intermediate (width 65 mm × length 160 mm) is bent into a corrugated plate, overlapped with a flat film-like catalyst of the same size and wound into a cylindrical shape, outer diameter 30 mm × height 65 mm 25 cylindrical film-shaped catalyst intermediates were prepared. This was cured with 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, novolac phenol resin and hexamethylenetetramine as a binder, and catalyst 1 as a powdery catalyst were placed in a 250 mL wide-mouth polyethylene bottle in this order. The blending ratio is such that 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 (70 g) of the powdered catalyst, and the compounding amount of MEK is the solid content of the compound 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 blending 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 40 minutes as a preparation time to obtain a coating composition (the paint shaker was 12. It is moving at a cycle of 5 times, and the representative speed was 0.05 × 2 (m) / [1 / 12.5] (s) = 1.25 m / s). The catalyst particle diameter in the coating composition was 1.6 μm.

A copper foil (thickness 40 μm, weighing 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 coated on both sides of the copper foil with a gravure coater ( After coating with Yasui Seiki Co., Ltd., the film was treated with a dryer at a drying rate of 0.5 g / m ² · s for 60 seconds to obtain a film-like catalyst intermediate.

  The obtained film-like catalyst intermediate (width 65 mm × length 160 mm) is bent into a corrugated plate, overlapped with a flat film-like catalyst of the same size and wound into a cylindrical shape, outer diameter 30 mm × height 65 mm 25 cylindrical film-shaped catalyst intermediates were prepared. This was cured with 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, novolak phenol resin and hexamethylenetetramine as a binder, and catalyst 2 as a powdery catalyst were placed in a 250 mL wide-mouth polyethylene bottle in this order. The blending ratio is such that 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 (70 g) of the powdered catalyst, and the compounding amount of MEK is the solid content of the compound 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 blending 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 the mixture was mixed and dispersed for 8 minutes as a preparation time to obtain a coating composition (the paint shaker was 12. It is moving at a cycle of 5 times, and the representative speed was 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, weighing 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 coated on both sides of the copper foil with a gravure coater ( After coating with Yasui Seiki Co., Ltd., the film was treated with a dryer at a drying rate of 0.5 g / m ² · s for 60 seconds to obtain a film-like catalyst intermediate.

  The obtained film-like catalyst intermediate (width 65 mm × length 160 mm) is bent into a corrugated plate, overlapped with a flat film-like catalyst of the same size and wound into a cylindrical shape, outer diameter 30 mm × height 65 mm 25 cylindrical film-shaped catalyst intermediates were prepared. This was cured with 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, novolak phenol resin and hexamethylenetetramine as a binder, and catalyst 2 as a powdery catalyst were placed in a 250 mL wide-mouth polyethylene bottle in this order. The blending ratio is such that 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 (70 g) of the powdered catalyst, and the compounding amount of MEK is the solid content of the compound 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 blending 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 16 minutes as a preparation time to obtain a coating composition (the paint shaker was 12. It is moving at a cycle of 5 times, and the representative speed was 0.05 × 2 (m) / [1 / 12.5] (s) = 1.25 m / s). The catalyst particle diameter in the coating composition was 2.5 μm.

A copper foil (thickness 40 μm, weighing 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 coated on both sides of the copper foil with a gravure coater ( After coating with Yasui Seiki Co., Ltd., the film was treated with a dryer at a drying rate of 0.5 g / m ² · s for 60 seconds to obtain a film-like catalyst intermediate.

  The obtained film-like catalyst intermediate (width 65 mm × length 160 mm) is bent into a corrugated plate, overlapped with a flat film-like catalyst of the same size and wound into a cylindrical shape, outer diameter 30 mm × height 65 mm 25 cylindrical film-shaped catalyst intermediates were prepared. This was cured with 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. 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, novolac phenol resin and hexamethylenetetramine as a binder, and catalyst 3 as a powdery catalyst were put in a 50 L container in this order. The blending ratio is such that 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 powdered catalyst, and the compounding amount of MEK is the solid content of the compound Was 55% by mass. The blending mass of the coating composition was 45 kg.

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

A copper foil (thickness 40 μm, weighing 310 g / m ² , surface roughness Rz: one side 10.2 μm) is used as a support, and the coating composition is coated with a gravure coater (manufactured by Yasui Seiki Co., Ltd.) on the surface roughness surface. The film-like catalyst intermediate was obtained by applying for 60 seconds at a drying rate of 0.5 g / m ² · s with a dryer.

  The obtained film-like catalyst intermediate (width 65 mm × length 160 mm) is bent into a corrugated plate, overlapped with a flat film-like catalyst of the same size and wound into a cylindrical shape, outer diameter 30 mm × height 65 mm 50 cylindrical film-shaped catalyst intermediates were prepared. This was cured with 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 mass of the catalyst layer per unit area in the obtained film catalyst was 11.9 g / m ² on one side. Further, the supported amount of the powdered catalyst per unit area was 8.9 g / m ² on one side, and the supported amount of the powdered catalyst in the 50 cylindrical film-shaped 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, novolac phenol resin and hexamethylenetetramine as a binder, and catalyst 3 as a powder catalyst were put in a 250 mL wide-mouth polyethylene bottle in this order. The blending ratio is such that 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 (70 g) of the powdered catalyst, and the MEK content is the solid content of the formulation 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 blending 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 12. It is moving at a cycle of 5 times, and the representative speed was 0.05 × 2 (m) / [1 / 12.5] (s) = 1.25 m / s). The catalyst particle diameter in the coating composition was 2.5 μm.

A copper foil (thickness 40 μm, weighing 310 g / m ² , surface roughness Rz: one side 4.1 μm) is used as a support, and the coating composition is coated on the surface roughness surface with a gravure coater (manufactured by Yasui Seiki Co., Ltd.). The film-like catalyst intermediate was obtained by applying for 60 seconds at a drying rate of 0.5 g / m ² · s with a dryer.

  The obtained film-like catalyst intermediate (width 65 mm × length 160 mm) is bent into a corrugated plate, overlapped with a flat film-like catalyst of the same size and wound into a cylindrical shape, outer diameter 30 mm × height 65 mm 50 cylindrical film-shaped catalyst intermediates were prepared. This was cured with 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 12.5 g / m ² on one side. In addition, the supported amount of the powdery catalyst per unit area was 9.3 g / m ² on one side, and the supported amount of the powdered catalyst in the 50 cylindrical film-shaped 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, novolac phenol resin and hexamethylenetetramine as a binder, and catalyst 3 as a powder catalyst were put in a 250 mL wide-mouth polyethylene bottle in this order. The blending ratio is such that 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 (70 g) of the powdered catalyst, and the compounding amount of MEK is the solid content of the compound 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 blending 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 12. It is moving at a cycle of 5 times, and the representative speed was 0.05 × 2 (m) / [1 / 12.5] (s) = 1.25 m / s). The catalyst particle diameter in the coating composition was 2.5 μm.

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

  The obtained film-like catalyst intermediate (width 65 mm × length 160 mm) is bent into a corrugated plate, overlapped with a flat film-like catalyst of the same size and wound into a cylindrical shape, outer diameter 30 mm × height 65 mm 50 cylindrical film-shaped catalyst intermediates were prepared. This was cured with 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 12.0 g / m ² on one side. Further, the supported amount of the powdered catalyst per unit area was 8.9 g / m ² on one side, and the supported amount of the powdered catalyst in the 50 cylindrical film-shaped 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, novolac phenol resin and hexamethylenetetramine as a binder, and catalyst 1 as a powdery catalyst were placed in a 250 mL wide-mouth polyethylene bottle in this order. The blending ratio is such that 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 (70 g) of the powdered catalyst, and the compounding amount of MEK is the solid content of the compound Was 55% by mass. Further, glass beads having a diameter of 1 mm (manufactured by AS ONE, model number BZ-1, apparent volume 64 mL) were placed in a wide-mouth polyethylene bottle as a dispersion medium. The blending 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 1 minute as a preparation time to obtain a coating composition (the paint shaker was 12. It is moving at a cycle of 5 times, and the representative speed was 0.05 × 2 (m) / [1 / 12.5] (s) = 1.25 m / s). The catalyst particle diameter in the coating composition was 3.4 μm.

A copper foil (thickness 40 μm, weighing 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 stock). After coating with No. 8 and No. 12), a film-like catalyst intermediate was obtained by performing a treatment with a hot air circulation thermostat (manufactured by Yamato Scientific Co., Ltd.) at a drying rate of 0.5 g / m ² · s for 60 seconds. . In addition, although Examples 1-5 differ from a coating device and a dryer, there is no change in a coating system and a drying speed.

  The obtained film-like catalyst intermediate (width 65 mm × length 160 mm) is bent into a corrugated plate, overlapped with a flat film-like catalyst of the same size and wound into a cylindrical shape, outer diameter 30 mm × height 65 mm 25 cylindrical film-shaped catalyst intermediates were prepared. This was cured with 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 porous agent, is added to 80 parts by mass (61 g) of MEK as a solvent, and a novolac phenol resin and hexamethylene as binders. Tetramine and catalyst 1 as a powder catalyst were put in a 250 mL wide-mouth polyethylene bottle in this order. The blending ratio is such that 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 (70 g) of the powdered catalyst, and the amount of the solvent is the solid content of the formulation 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 blending 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 the mixture was mixed and dispersed for 8 minutes as a preparation time to obtain a coating composition (the paint shaker was 12. It is moving at a cycle of 5 times, and the representative 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, weighing 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 stock). After coating with No. 8 and No. 12), a film-like catalyst intermediate was obtained by performing a treatment with a hot air circulation thermostat (manufactured by Yamato Scientific Co., Ltd.) at a drying rate of 0.5 g / m ² · s for 60 seconds. . In addition, although Examples 1-5 differ from a coating device and a dryer, there is no change in a coating system and a drying speed.

  The obtained film-like catalyst intermediate (width 65 mm × length 160 mm) is bent into a corrugated plate, overlapped with a flat film-like catalyst of the same size and wound into a cylindrical shape, outer diameter 30 mm × height 65 mm 25 cylindrical film-shaped catalyst intermediates were prepared. This was cured with 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 in advance by weighing the mass of the catalyst layer of each film-like catalyst obtained in Examples 1 to 8 and Comparative Examples 1 and 2 before evaluating the following reaction characteristics, and each film-like catalyst was placed in an acetone solvent. And was irradiated with ultrasonic waves with an ultrasonic cleaner (SU-6TH, manufactured by Shibata Kagaku) for 30 minutes. The remaining amount of the catalyst layer after the irradiation was weighed, and the remaining rate (%) of the catalyst layer in the film-like catalyst was calculated to obtain the film strength. The higher the residual rate, the higher the film strength.

[Method for measuring catalyst particle diameter]
Examples of the catalyst particle diameter include a method of calculating from a cross-sectional image of the catalyst layer, and a method of calculating from a coating composition containing catalyst particles. In Examples 1 to 8 and Comparative Examples 1 and 2 of the present application, measurement was performed by the latter.
Each coating composition of Examples 1 to 8 and Comparative Examples 1 and 2 was diluted with MEK, and the particle size was adjusted 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 film-like catalyst obtained in Examples 1 to 8 and Comparative Examples 1 and 2 was measured using a mercury intrusion pore distribution measuring device (manufactured by Shimadzu Corporation, Pore Sizer 9320). The pore volume of the catalyst layer is the pore volume per unit mass of the powdered catalyst in the catalyst layer.

[Measuring method of average macropore diameter]
The average macropore diameter of the catalyst layer of each of the film-like catalysts obtained in Examples 1 to 8 and Comparative Examples 1 and 2 is assumed that the pores in the catalyst layer are cylindrical pores, and the average macropore diameter is the pore diameter D. The pore volume Vo and pore area A of the catalyst layer of each film-like catalyst were measured using a mercury intrusion pore distribution measuring device (manufactured by Shimadzu Corporation, Pore Sizer 9320), and the following formula D = 4Vo / A.

(Evaluation of reaction characteristics)
As for the reaction characteristics, only the film catalysts of Examples 1 to 8 having a residual rate of 40% or more were evaluated in the evaluation of the film strength.
In the cylindrical film catalysts obtained in Examples 1 to 8, a plurality of channels having a cross-sectional area of about 0.1 cm ² communicated in the height direction are formed.

  Into a glass reactor having an inner diameter of 130 mm whose bottom surface is a glass filter (2G), 915 g of the cylindrical film catalyst and dodecyl alcohol (Calcoal (registered trademark) 2098, manufactured by Kao Corporation), which is a raw material alcohol, are placed. After performing the reduction activation of dimethylamine, the supply of dimethylamine was started while supplying hydrogen gas, and kept constant at 220 ° C.

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

  The reaction end point is defined as the time when the dodecyl alcohol concentration is reduced 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 × By-product concentration] TIME × M 2 was calculated. The results are shown in Table 2 below.

  Here, the shorter the reaction time and the fewer by-products in the reaction, the better the reaction characteristics. Therefore, the above-mentioned TIME × M2 is introduced as an index for judging the superiority or inferiority. In addition, the sum of the content rate of the powdery catalyst of Table 1, and the content rate of a binder is 100 mass%.

(Discussion)
In Table 1, since 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, the membrane strength is 85. %, Which is a favorable result as compared with Comparative Examples 1 and 2. Moreover, Examples 1-8 satisfy | fills the conditions 100 <time * V * P / G <1500 (m * L / kg) of a media type mill.
In Comparative Example 1, since the catalyst particle diameter was larger than 3.3 μm, the film strength was 32.3%, and the film strength was deteriorated as compared with Examples 1-8. Moreover, the comparative example 1 does not satisfy | fill the conditions 100 <time * V * P / G <1500 (m * L / kg) of a media type mill.
In Comparative Example 2, since the pore volume became larger than 0.87 mL / g by adding silicone oil to the catalyst particle preparation solvent, 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 Examples 6 and 7 have a surface roughness Rz of the support of 2.0 μm or more, the surface roughness Rz of the support is less than 2.0 μm. Compared with a certain example 8, the reaction characteristic was more excellent.

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

Claims (10)

A film-like catalyst having a catalyst layer formed on a support,
The catalyst layer includes catalyst particles having a particle size of 1.3 μm or more and 3.3 μm or less containing a powdered 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.   The film catalyst of Claim 1 whose average macropore diameter of the said catalyst layer is 0.2 micrometer or more and 0.5 micrometer or less.   The film catalyst of Claim 1 or 2 whose mass ratio (powder catalyst / binder) of the said powder catalyst and the said binder is 1-10.   The film catalyst according to any one of claims 1 to 3, wherein the support is a metal foil.   The film-form catalyst of any one of Claims 1-4 whose surface roughness Rz of the said support body is 1.0 micrometer or more and 30 micrometers or less. The manufacturing method of the film-form catalyst of any one of Claims 1-5 including the following processes.
Step 1: A step of preparing a coating composition containing a powdered catalyst, a binder and a solvent, wherein the particle size of the catalyst particles containing the powdered catalyst and the binder in the coating composition is 1.3 μm or more and 3.3 μm or less. Step 2: Step of applying the coating composition on a support and forming a catalyst layer Step 1 was prepared using a media-type mill. Preparation time time (sec.), Representative speed V (m / sec.) In the media-type mill, and apparent volume P (L of media used for the preparation) ), The method for producing a film-like catalyst according to claim 6, which is prepared under a condition satisfying the following formula (I) when the blending mass G (kg) of the coating composition is used.
100 <time.V.P / G <1500 (m.L / kg) (I)   The process 2 is a process of apply | coating the said coating composition on the support whose surface roughness Rz of the said support is 1.0 micrometer or more and 30 micrometers or less, and forming a catalyst layer into a film of Claim 6 or 7. A method for producing a film catalyst. The method for producing a film catalyst according to any one of claims 6 to 8, further comprising a drying step after step 2 and having a drying rate of 0.01 g / m ² · s to 10 g / m ² · s. . The method for producing a fill catalyst according to claim 9, comprising a shape processing step and a heating step after the drying step.