JP4549802B2 - Film catalyst and method for producing film catalyst - Google Patents

Description

  The present invention relates to a film catalyst obtained by immobilizing a catalyst on a support and a method for producing the same.

  In the chemical reaction process in the chemical industry, a process using a solid catalyst is 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. In a reaction process using a powdered catalyst, a technique such as agitation 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. Since the catalyst is a fine particle, the filtration time is long, and the filter aid adsorbs a large amount of reactants, thereby reducing the reaction yield.

  In order to improve the filterability of the fine particle powder, the filtration time has been shortened by increasing the powder particle size by supporting the powdered catalyst on a porous support such as zeolite. However, the problem of complicated facilities and 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.

  As the form of the catalyst used in the fixed bed system, conventionally formed catalysts such as pellets, noodles or tablets are well known. A powdery substance having catalytic activity is molded into the above form by a method such as compression or extrusion so that it has both a bulk form and a high surface area as a structure having innumerable pores therein. .

  However, since this type of shaped catalyst has a relatively large pressure loss in the catalyst layer filled with it, it has been difficult to efficiently bring the reactants into contact with the catalyst active sites. If the thickness of the catalyst layer is reduced, the effect of an increase in pressure loss can be reduced, but there is a problem that the cross-sectional area of the catalyst layer increases and the reactor itself becomes large. Also, the diffusion rate inside the formed catalyst becomes slower than the reaction rate and becomes diffusion-dominated, and depending on the type of reaction, the occurrence of various side reactions sometimes becomes a big problem.

As another form of the catalyst used in the fixed bed system, for example, in Patent Document 1, a structure that is partitioned by a thin wall and has a large number of flow paths from the fluid inlet to the outlet, for example, a pipe, a honeycomb, a flat plate A catalyst such as a catalyst is disclosed. In the example of Patent Document 1, the supported amount of the catalyst active material is 8.6 to 35.8 mg / cm ² per surface area of the support, and olefins and the like are dehydrogenated by a gas phase reaction. Describes that the specific surface area of the active ingredient is desirably 8 m ² / g or less.

  However, there is no mention of a specific catalyst layer structure for expressing high reaction activity, and by using such a form of catalyst, it is possible to secure a flow path for the reactants, reduce pressure loss, and react. It only suggests that it is due to lowering the total pressure of the system.

Further, Patent Document 2 discloses a coated monolith substrate including a wash coat formed from a solution that forms a furfuryl alcohol-containing polymer or a prepolymer containing polymerized units of furfuryl alcohol, and a catalytic metal deposited thereon. Monolith catalysts have been disclosed, both described as having a surface area in the range of 0.1 to 25 m < ² > / g to provide reaction activity and catalytic metal retention.

  However, it is necessary to manufacture through complicated processes such as a wash coat deposition process and a catalyst metal loading process, and it is difficult to control the porous structure and surface properties due to the complicated processes. The expression of the activity is not easy.

  In recent years, many studies have been made to support a catalyst active material on a support, particularly in the field of photocatalysis. For example, Patent Document 3 discloses a method of supporting photocatalyst particles in which titanium oxide particles dispersed in water or a binder solution are applied to a support and dried, and then a binder solution is further applied to the catalyst layer and dried. Has been.

  However, although a catalyst coating film containing catalyst particles can be obtained by the first application / drying, there is a concern that troubles may occur in the production process such as low strength and easy peeling. In the second coating / drying step, the binder solution is further applied onto the catalyst coating film obtained by the first coating / drying step, so that the adhesion at the interface between the catalyst coating film and the binder is sufficient. Since it cannot be expressed and a large amount of binder is required to improve adhesion, there are problems such as low exposure of the catalyst and low catalytic activity.

Patent Document 4 discloses a porous thin film photocatalyst in which pores are formed by applying a coating liquid containing a photocatalytic active material and / or a precursor thereof and a sublimation agent to a support and then sublimating the sublimation agent. Has been.
However, in the catalyst layer in which the pores are generated by desorbing the sublimation agent, the pore diameter becomes larger than the thickness of the catalyst layer, and the support is locally exposed. It is difficult to obtain a stable and uniform film.

As described above, the reaction activity, the retention of the catalyst active material, or the suppression of falling off have been studied. However, in the method of fixing the catalyst particles on the support, the reaction rate of the catalyst particle surface coating depends on the presence of the binder. In addition, when the amount of the binder is excessively reduced, there is a problem in that the retention of the catalyst particles is lowered and the coating film comes off. In addition, in the method of supporting the washcoat layer and the catalyst metal on the support, it is essential to carry out a calcination treatment, in order to provide a complex operation and a suitable balance of appropriate catalytic activity and selectivity to the catalyst metal. Therefore, a great deal of study on the preparation conditions was required.
Japanese Examined Patent Publication No. 62-21574 JP 2002-355554 A Japanese Patent Laid-Open No. 9-271676 JP 2003-135972 A

  An object of the present invention is to provide a film catalyst having a sufficient catalytic activity and a small amount of catalyst dropping, and a method for producing the film catalyst.

As a means for solving the problems, the present invention
Claim 1 is a film-like catalyst having a catalyst layer having a pore volume of 0.5 to 30 ml / m ² on a support, and the catalyst layer is a synthetic resin based on 100 parts by mass of a powdery catalyst on a raw material basis. A film-like catalyst containing 20 to 80 parts by mass,
The film catalyst according to claim 1, wherein the synthetic resin contains a thermosetting resin.
The film-like catalyst according to claim 1 or 2, wherein the synthetic resin contains a phenol resin,
The film catalyst according to any one of claims 1 to 3, wherein the support is a metal foil.
The film catalyst according to any one of claims 1 to 4, wherein the support is a honeycomb structure.
The film catalyst according to any one of claims 1 to 5, wherein the film catalyst is a film catalyst for dehydrogenation and / or hydrogenation reaction.
As Claim 7, it is a manufacturing method of the film-form catalyst in any one of Claims 1-6, The coating material containing 20-80 mass parts of synthetic resins with respect to 100 mass parts of powdery catalysts is provided on a support body. A process for producing a film-like catalyst, comprising a step of forming a catalyst layer having a pore volume of 0.5 to 30 ml / m ² by coating and forming a film;
The method for producing a film-like catalyst according to claim 7, further comprising a step of drying and desorbing volatile components after coating the coating material on the support.
According to a ninth aspect of the present invention, there is provided each invention of the method for producing a film catalyst according to the seventh or eighth aspect, wherein after the coating and drying, the shape is processed and the final heat treatment is further performed.

  In the present invention, the “powdered catalyst” means a powdered catalyst having catalytic activity.

  The film-shaped catalyst of the present invention, that is, the film-shaped catalyst obtained by the production method of the present invention has a sufficient catalytic activity and has a small amount of catalyst falling off from the catalyst layer.

  The present invention relates to a film catalyst obtained by forming a coating containing a powdered catalyst and a synthetic resin used as a binder on a support, and a method for producing the film catalyst, and the blending ratio of the powdered catalyst and the synthetic resin is By adjusting to an appropriate range, it is possible to control the degree of exposure of the powdered catalyst and the bonding force between the powdered catalyst and between the support and the powdered catalyst.

20-80 parts by mass of the synthetic resin is in an appropriate blending ratio range with respect to 100 parts by mass of the powdered catalyst.
Furthermore, it has been found that by controlling the pore volume per area of the support within the range of 0.5 to 30 ml / m ² , it is possible to obtain a film-like catalyst with an effective reaction activity as a film-like catalyst and a small amount of coating film falling off. It was.

Hereafter, the manufacturing method of a film-like catalyst and a film-like catalyst is demonstrated for every process.
[Film catalyst]
The film catalyst of the present invention has a thin catalyst layer having a thickness of 1 mm or less on the support, and preferably has a catalyst layer of 100 μm or less, more preferably 50 μm or less. The process in which the reactant and product move inside the catalyst layer is diffusion-dominated, and by reducing the film thickness to 1 mm or less, the mass transfer between the catalyst layer and the outside is promoted, It is preferable because an overreaction of the intermediate reactant can be suppressed. The lower limit of the thickness of the catalyst layer is preferably 0.01 μm or more and more preferably 1 μm or more in order to ensure the strength of the catalyst layer and to obtain durability of the strength surface.

The internal structure of the catalyst layer is a state in which the entire surface or part of the powder catalyst is covered with a synthetic resin, and the powder catalyst forms a three-dimensional network structure via the synthetic resin, It is preferable that air layers are scattered in the gaps and the synthetic resin itself has a porous structure. The catalyst layer desirably has 1 to 1000 powdered catalysts deposited in the thickness direction, and preferably 1 to 500, more preferably 1 to 200 powdered catalysts are deposited. Further, the catalyst layer can take a so-called gradient structure in which the existence ratio of the powdered catalyst and the synthetic resin is changed in the thickness direction, and more than two catalyst layers or fine layers having different blending ratios of the powdered catalyst and the synthetic resin. A catalyst layer composed of two or more catalyst layers having different pore structures may be formed.

  The form of the film-like catalyst can be made into various forms according to the shape of various reactors to which the catalytic reaction is applied. After the catalyst layer is provided on the support, the trimming process and the shape are performed as necessary. Processing, integration / assembly processing can be performed to achieve the desired form. In addition to a flat plate shape and a tubular shape, a honeycomb shape, a monolith shape, or the like can be used.

For example, a plate-like film-like catalyst and a corrugated film-like catalyst obtained by shaping the same are stacked to form a structure, on the inner wall surface of a pipe that can be used in a flow reactor A catalyst layer formed, a catalyst layer formed on the surface of a thin plate-like structure that partitions the inside of the pipe into a plurality of axial flow passages, and an open chamber installed inside a tank reactor that can be used in a tank reactor This corresponds to a type in which a catalyst layer is formed on the surface of a mold fin-shaped flat plate. 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 honeycomb structure having a cell density of several to 200 cells per cm ² and a catalyst layer provided on the inner wall surface is used. It is done.

Since the catalyst layer in the film-like catalyst of the present invention contains 20 to 80 parts by mass of synthetic resin with respect to 100 parts by mass of the powdery catalyst, the catalyst activity and the connection between the powdery catalysts or between the powdery catalyst and the support are included. Appearance is expressed. Pore volume of the catalyst layer is a support surface area per 0.5~30ml / m ^2, preferably 1~20ml / m ^2, more preferably 1~4ml / m ^2. Pore volume 0.5ml / m ²
In the case described above, the diffusion rate inside the catalyst layer is increased, and a sufficient reaction rate can be obtained when the film-like catalyst is applied to the reaction process. If the pore volume becomes too large, the catalyst layer becomes highly porous, and the binding force between the powdered catalysts and / or the powdered catalyst-support is reduced more than necessary, and the mechanical strength as the catalyst layer is insufficient. However, when it is 30 ml / m ² or less, the porosity of the catalyst layer becomes appropriate, the adhesion between the powdered catalysts and / or the powdered catalyst and the support is strengthened, and the mechanical property as the catalyst layer is increased. Strength is maintained and mass mobility of reactants and products is maintained in a good state.
In addition, the catalyst layer has a porous structure that exists in the gap between the powdered catalyst particles and the synthetic resin itself as the film thickness increases. The resulting pore volume per support area is increased, and the reaction rate as a film catalyst is improved. However, if it is thicker than 1 mm, the mass mobility between the outside of the catalyst layer is lowered, the reaction rate cannot be improved, and the overreaction of the intermediate reactant inside the catalyst layer is promoted. Resulting in.

The pore structure of the film-like catalyst in the present invention is such that a coating containing 20-80 parts by mass of a synthetic resin is applied to a support with respect to 100 parts by mass of a powdery catalyst, and then the volatile components are desorbed. It is determined in the process and the formation process of the entangled structure of the synthetic resin. When the synthetic resin is a thermosetting resin, in the case of forming a crosslinked structure (network structure) formed by a curing / crosslinking reaction in addition to the desorption process of the volatile component, and with a condensation reaction The pore structure is also affected by the desorption process of the condensation product. As a result of earnest research, by setting the pore volume of the catalyst layer per surface area of the support to 0.5 to 30 ml / m ² as an index characterizing the formed pore structure, sufficient reaction as a film catalyst in the reaction process It was found that the speed and retention of the powdered catalyst could be maintained.

The film-like catalyst of the present invention can be applied to various reactions depending on the selection of the powdery catalyst to be applied, 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 since it does not impair the diffusibility of the reactants and products and can be adapted to the temperature environment in the reactor. For example, olefin oxidation, alcohol oxidation, olefin isomerization, aromatic isomerization, carbonylation, ester hydrogenation, preferably used in dehydrogenation and hydrogenation reactions. These dehydrogenation and hydrogenation reactions The present invention can also be applied to an amination reaction in which a tertiary amine is produced from an alcohol and a primary amine or secondary amine.

<Coating / film forming process>
In this step, a coating containing 20 to 80 parts by mass of a synthetic resin is applied on a support to form a film with respect to 100 parts by mass of the powdered catalyst.

[Powdered catalyst and synthetic resin]
As the powdered catalyst used in the present invention, a powdered catalyst having established performance for a suspended bed process in an applied chemical reaction can be used. Therefore, the reaction activity of the film-like catalyst obtained by the present invention is certain, and it is developed because the reaction characteristics in the reaction process can be ensured as compared with the method of supporting a catalytically active substance composed of a catalytic metal or metal oxide on a support. Since the time is shortened and a complicated manufacturing process for expressing the reaction activity such as baking treatment is not required, the manufacturing process can be simplified.

The powdered catalyst used in the present invention has an average particle size of 0.01 to 500 μm, preferably 0.1 to 100 μm.
m, more preferably 0.5 to 50 μm, and a sharp distribution is preferable, and a specific surface area by the BET method is 1 to 500 m ² / g, preferably 5 to 200 m ² / g, more preferably Is 10 to 100 m ² / g. For example, it can be prepared using the following catalyst carrier and catalyst active material.

  Examples of the catalyst carrier constituting the powdery catalyst include carriers such as activated carbon, alumina, silica, zeolite, titania, silica-alumina, and diatomaceous earth, and one or more carriers selected from these can be preferably used. More preferably, a porous support having a high surface area is used, and a catalyst support such as a molecular sieve 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 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.

  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 synthetic resin used in the present invention is preferably one that is excellent in binding properties to powdered catalysts and the support surface, withstands the reaction environment, and does not adversely affect the reaction system. Examples of such synthetic resins 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, polyimides Various thermoplastic resins and thermosetting resins such as amide resins, polyester resins, phenol resins, melamine resins, and silicone resins are used. By introducing a crosslinking reaction with a curing agent into these synthetic resins, higher polymerization is achieved. Can also be used. Among these, thermosetting resins such as phenol resins, furan resins, and epoxy resins are preferable, and more preferable are thermosetting resins that involve a condensation reaction during curing.

  Use of such a thermosetting resin improves the coating strength and binding properties by improving the crosslinking density due to the curing reaction, and further increases the catalytic activity of the powdered catalyst due to the porous catalyst coating due to the condensation reaction. Can be pulled out.

  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 synthetic resin is a copper-nickel-ruthenium ternary system. And a combination of a powdered catalyst and a phenol resin.

The blending ratio of the powdered catalyst and the synthetic resin is 20 parts by weight of the synthetic resin with respect to 100 parts by mass of the powdered catalyst.
It is -80 mass parts, Preferably it is 30-70 mass parts, More preferably, it is 40-60 mass parts.

  By setting the blending ratio of the powdered catalyst and the synthetic resin within the above range, the exposure degree of the powdered catalyst can be controlled, the catalytic activity ability inherent to the powdered catalyst can be extracted, and the coating film is removed. Can also improve. When the blending amount of the synthetic resin is 80 parts by mass or less, the thickness of the synthetic resin covering the surface of the powdered catalyst or the coverage with the synthetic resin becomes moderate, and the catalytic activity of the powdered catalyst is sufficiently exhibited. High catalytic activity can be exhibited. When the blending amount of the synthetic resin is 20 parts by mass or more, the catalytic activity is sufficiently developed, the binding force between the powdered catalysts or between the powdered catalyst and the support is improved, and during the production process of the film catalyst and the reaction The amount of catalyst layer peeling or part of the catalyst falling off during operation is suppressed.

  In addition to powdered catalysts and synthetic resins, when preparing paints, it is necessary to use a solvent to improve the wettability of the powdered catalyst surface, dissolve the synthetic resin, and promote mixing and homogenization of these blends. it can. The solvent may be any solvent 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 according to the type of synthetic resin used. The pore structure of the film catalyst can be controlled by selecting the solvent.

For example, water; alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol, and allyl alcohol; acetone, methyl ethyl ketone (MEK)
), Ketones such as 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, etc. Glycols or derivatives thereof; glycerol or derivatives thereof such as glycerol, glycerol monoethyl ether, glycerol monoallyl ether; ethers such as tetrahydrofuran, dioxane; liquid paraffin, decane, decene, methylnaphthalene, decalin, kerosene, diphenylmethane, Toluene, dimethylbenzene, ethylbenzene, diethylbenzene , Propylbenzene, cyclohexane, hydrocarbons such as partially hydrogenated triphenyl, polydimethylsiloxane, partially octyl-substituted polydimethylsiloxane, partially phenyl-substituted polydimethylsiloxane, silicone oils such as fluorosilicone oil, chlorobenzene, di- Halogenated hydrocarbons such as chlorobenzene, bromobenzene, chlorodiphenyl, chlorodiphenylmethane, fluorides such as Dylroll (Daikin Industries), Demnam (Daikin Industries), ethyl benzoate, octyl benzoate , Ester compounds such as dioctyl phthalate, trioctyl trimellitic acid, dibutyl sebacate, ethyl (meth) acrylate, butyl (meth) acrylate, dodecyl (meth) acrylate, dimethylformamide, N Methyl - pyrrolidone, acetonitrile, ethyl acetate, and the like.

  Those having good solubility of the synthetic resin are preferable, and two or more solvents may be used in combination. The pore structure can be controlled by selecting a solvent in accordance with the selection of the synthetic resin.

[Preparation of paint]
In the present invention, the coating material containing a powdered catalyst and a synthetic resin can be prepared by a conventional method, and can be prepared by variously selecting a kneading step, a dissolving step, a dispersing step, a filtering step, and the like. In the dispersion step, the paint is made using a paint shaker, basket mill, glen mill, dyno mill, agitate mill or the like.

  It has been found that the reaction characteristics, coating film (catalyst layer) strength, and coating film (catalyst layer or catalyst) drop-off property of the finally obtained film catalyst can be improved by selecting appropriate conditions such as dispersion time in the paint preparation process. ing. In particular, it is considered that the above characteristics can be controlled in relation to the degree of paint dispersion. As a measure of the degree of paint dispersion, it can be quantified by techniques such as glossiness, particle gauge, viscosity, and rheological properties.

  In the dispersion step, the dispersion treatment can be efficiently carried out by carrying out the coating composition with a high solid content. If the solid content of the paint is too high or the fluidity is too low, uniform mixing becomes difficult and the efficiency of the dispersion treatment is not good. Therefore, there is a preferred range for the solid content and viscosity (fluidity) of the paint, the solid content of the paint is 10 to 80% by mass, preferably 20 to 70% by mass, more preferably 25 to 65% by mass, and the viscosity is 5 -10,000 mPas, preferably 20-5000 mPas, more preferably 50-1000 mPas.

  For example, a powdered catalyst, synthetic resin, and solvent are added to a stainless steel vat, mixed and stirred in a dispaper until there are no lumps that can be visually confirmed, and transferred to a basket mill vessel. Then, a mixing and dispersing process is performed at a predetermined number of rotations (dispersing step), and aggregates or foreign matters are removed by microfiltration (filtering step) to prepare a desired coating material.

The dispersion treatment in the preparation of the paint is, for example, 30 to 800 to 3000 r / min when 10,000 g of the paint raw material (total amount of powdered catalyst, synthetic resin and solvent) is placed in a 20 liter basket mill mixing tank. It is desirable to stir for 600 minutes.

  In addition, when judging based on the glossiness, it is desirable to perform dispersion processing until, for example, the evaluation value confirmed over time takes the maximum value. When judging with a particle gauge, it is desirable to carry out a dispersion treatment until the secondary aggregation is reduced based on the primary particle diameter of the powdered catalyst.

  In the preparation of paints, in addition to powdered catalysts, synthetic resins, and solvents, surfactants and coupling agents as dispersion aids, inorganic particles and fibrous materials as aggregates, high-boiling solvents as porosity aids, etc. Can be blended. 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. Examples of organic fibers include polyamide nylon 6, nylon 66, aramid fiber, polyvinyl alcohol fiber, polyester polyethylene terephthalate, polybutylene terephthalate fiber, polyarylate fiber, and polyvinylidene chloride. Type, polyvinyl chloride type, polyacrylonitrile type, polyolefin type polyethylene, polypropylene fiber and the like. The organic fiber includes organic regenerated fiber, and examples thereof include cellulose-based rayon and acetate. As the inorganic fiber, glass fiber, carbon fiber, activated carbon fiber, ceramic fiber, asbestos, or the like is used, and the mechanical strength of the catalyst layer can be improved by manifesting 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 plate-like support may have any suitable workability and durability and does not adversely affect the reaction system in which the film catalyst of the present invention is used. For example, copper foil, stainless steel foil, aluminum A foil etc. are mentioned. 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 the thing containing nickel is mentioned, It is not limited to these. Here, the honeycomb shape is a shape in which a large number of cells are accumulated and has a honeycomb structure partitioned by thin walls. Since the surface area per unit volume can be increased, the honeycomb shape is preferable as a support constituting the film catalyst. 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. In this coupling treatment, the above-described coupling agent can be used, and preferably the same kind as that used for preparing the paint can be used.

[Coating / Filming process]
A method of coating and forming a coating containing a powdered catalyst on the above-mentioned support surface is mentioned. As this film forming method, a conventionally known method can be used, and various coating methods such as blade, roll, knife, bar, spray, dip, spin, comma, kiss, gravure, die coating and the like can be mentioned. The solid content of the paint at the time of film formation affects the formation of the pore structure because the pore structure is controlled when the solvent is desorbed from the formed catalyst layer, and is 10 to 80% by mass, preferably 20 -70 mass%, more preferably 25-65 mass%, and the viscosity at the time of film formation is selected in various preferred ranges depending on the coating method, for example, 5-10,000 mPas, preferably 20-5000 mPas, more preferably 50- 1000mPas.

  In the present invention, the drying and curing reaction step carried out after applying and forming a coating containing a powdered catalyst on the surface of the support is carried out in an atmosphere heated with an inert gas such as air, water vapor, nitrogen or argon. The method of performing or spraying these heat media is preferably used, in addition, various means such as a method of using radiant heat such as infrared rays or far infrared rays, a heating method using an induction current due to electromagnetic waves can be used, and a method combining these Alternatively, a method of 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. The volatile component other than the solvent includes unreacted monomer components.

  The drying and curing conditions must be adjusted according to the physical properties of the volatile components, mainly the synthetic resin and solvent contained in the paint, and the porous structure of the catalyst layer (by selecting the solvent and setting the drying and curing conditions) The pore volume can be controlled, that is, desorption of volatile components, mainly solvents, from the paint, as well as the formation of a cross-linked structure (network structure) formed by a curing / cross-linking reaction. When the reaction is involved, the pore structure is determined in the desorption stage of the condensation product. In general, in the heat treatment with hot air, the higher the drying temperature and the larger the amount of dry air, the faster the components are desorbed 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 drying and curing treatment employs a drying method and drying conditions that do not adversely affect the catalytic activity inherent to the powdered catalyst used in the present invention, and the pore volume can be controlled to 0.5 to 30 ml / m ² .

In the present invention, typical drying and curing conditions by hot air drying for obtaining the desired film-like catalyst are 60 to 400 ° C, preferably 70 to 250 ° C, more preferably 80 to 150.
Drying and curing treatment at a temperature of 0 ° C., preferably at a wind speed of 0.5-30 m / sec, more preferably 1-20 m / sec, preferably 1 second or longer, more preferably 10 minutes or longer, more preferably 30 minutes or longer. It is desirable to implement.

<Additional step 1>
In the present invention, it is preferable to dry quickly after coating the coating material on the support, and the porous structure of the coating film can be controlled by adjusting the drying conditions at this time. 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.

<Additional step 2>
In the present invention, when the synthetic resin contains a thermosetting resin, the catalyst layer obtained by coating and drying is subjected to shape processing with the uncured product remaining (prepolymer state), and then subjected to final heat treatment It is desirable to do.

  The drying process performed before the final heat treatment is completed with the synthetic resin remaining in an uncured product. 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.

As a typical condition by hot air drying, drying before the final heat treatment for obtaining the target film catalyst is performed at a temperature of 60 to 400 ° C, preferably 70 to 250 ° C, more preferably 80 to 150 ° C. The drying treatment is preferably performed at a wind speed of 0.5 to 30 m / sec, more preferably 1 to 20 m / sec, preferably 0.5 to 300 seconds, more preferably 1 to 100 seconds.

  Manufactured by forming the shape before the catalyst layer of the film catalyst undergoes a complete curing reaction, allowing the catalyst layer to follow the plastic deformation of the support, improving the shape workability, and completely curing after completion of processing. The cross-linked structure of the catalyst layer can be fixed at the final stage of the process, the residual stress in the catalyst layer is relieved, and the influence of the film-like catalyst on the coating film removal can be improved.

  In the present invention, when the synthetic resin contains a thermoplastic resin, it is desirable that the catalyst layer obtained by coating and drying is subjected to final heat treatment after 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 For this reason, 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-like catalyst on the coating film removal.

  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 corrugated film-like catalyst obtained by processing the plate can be stacked to form a structure, which can be heat-treated in a holder or cassette for attachment to a reactor. .

  The final heat treatment conditions vary depending on the type of the synthetic resin, but in the present invention, it is preferably 80 to 400 ° C, more preferably 100 to 200 ° C, preferably 5 to 600 minutes, more preferably 10 to 100 minutes. It is desirable to perform heat treatment.

Production Example 1 (Preparation of powdered catalyst)
A stainless steel container is charged with synthetic zeolite, and then copper nitrate, nickel nitrate, and ruthenium chloride dissolved in water so that the molar ratio of each metal atom is Cu: Ni: Ru = 4: 1: 0.01 is added and stirred. While raising the temperature. 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 a powdered catalyst. The ratio of the metal oxide in the obtained powdery catalyst was 50% by mass, and the ratio of the synthetic zeolite was 50% by mass.

Example 1
The powdered catalyst prepared in Production Example 1, MEK as the solvent, and phenol resin as the synthetic resin (PR-9480, manufactured by Sumitomo Bakelite, nonvolatile content: 58% by mass) were placed in an SUS vat in this order. The non-volatile content of the phenol resin is 25 parts by mass with respect to 100 parts by mass of the powdered catalyst A, and the amount of MEK is such that the solid content of the compound is 55% by mass.

The blend was mixed and stirred in a dispaper for 10 minutes, and it was confirmed that there was no lump that could be confirmed by visual observation of the powdered catalyst. 10 kg of the obtained coating material was transferred to a vessel of a basket mill (filled with SS-3 manufactured by Asada Steel Co., Ltd., 800 ml of 1.4-diameter titania beads, 1900 g), and mixed and dispersed at 1500 r / min for 70 minutes.

A copper foil (thickness 40μm, weighing 310g / m ² ) is used as a support, and the paint is applied to both sides of the copper foil with a bar coater and then dried at 150 ° C for 30 seconds in a dryer to form a film for amine reaction A catalyst intermediate was obtained.

The resulting amine reaction film catalyst intermediate (width 65 mm x length 180 mm) is folded into a corrugated plate, wound with a flat plate of amine reaction film catalyst of the same size and wound, with an outer diameter of 30 mm. × Ten cylindrical film reaction intermediates for amine reaction having a height of 65 mm were prepared. This was cured in a dryer at 150 ° C. for 90 minutes to obtain a film catalyst for amine reaction.

The supported amount of the catalyst layer in the obtained film catalyst for amine reaction was 10.8 g / m ^{2 on} one side,
Both sides were 21.6 g / m ² . The amount of powder catalyst supported is 8.6 g / m ^{2 on} one side and 17.2 on both sides.
g / m ² .

Examples 2-4 and Comparative Examples 1-2
A film-like catalyst for amine reaction was obtained in the same manner as in Example 1 except that the blending ratio of the powdered catalyst and the phenol resin was changed to the ratio shown in Table 1 below. Table 1 shows the supported amount of the catalyst layer and the supported amount per one side of the powdery catalyst in the film catalyst for amine reaction obtained.

(Evaluation of reaction rate constant and evaluation of coating film removal)
In the cylindrical amine reaction film catalysts obtained in Examples 1 to 4 and Comparative Examples 1 and 2, a plurality of flow paths having a cross-sectional area of about 0.1 cm ² communicated in the height direction are formed.

To the glass reactor with an inner diameter of 130 mm whose bottom is a glass filter (2G), the above-mentioned cylindrical amine reaction film catalyst and dodecyl alcohol as raw material alcohol (Kao Corporation)
(Calcole 2098) 1000 g was charged and the catalyst was subjected to reduction activation. Then, supply of dimethylamine was started while supplying hydrogen gas, and the temperature was kept constant at 220 ° C.

Samples are collected from the reactor over time and analyzed with a gas chromatograph. The concentration change of dodecyl alcohol with respect to the reaction time, the mass of dodecyl alcohol used in the reaction M = 1.0 [kg], and the film-like catalyst used in the reaction surface area S (m ²⁾ (example: width 65 mm × length 180 mm × 20 sheets, the surface area is 0.47 m ²⁾ was calculated reaction rate constant k ^{[/ Hr · (m 2 / kg} -ROH) ] from.

When the dodecyl alcohol concentrations at the sampling times T1, T2 (Hr) [T2> T1] were C1, C2 (%), respectively, the calculation was performed according to the following formula.

The end point of the reaction was the time when the dodecyl alcohol concentration decreased to 1%, and after collecting all the reaction solution, this was filtered with a pre-weighed filter paper (PTFE, 0.32 μm), washed with acetone, Was dried and weighed to determine the amount (mg) of the component remaining on the filter paper, which was divided by the surface area S (m ² ) of the amine-reactive film catalyst used in the reaction to remove the catalyst layer (mg / m ² ) Was calculated. These results are shown in Table 1 below.

(Measurement of pore volume)
The pore volume in the pore diameter range of 10 nm to 5 μm was measured using a mercury intrusion pore size distribution measuring device (pore sizer 9320) manufactured by Shimadzu Corporation. From the obtained pore volume V (ml) and the support surface area Sp (m ² ) of the film catalyst used for the measurement, the pore volume Vs (ml / m ² ) per support surface area in the present invention is Vs. = Calculated as V / Sp. For example, in the case of a film-like catalyst sample in which a catalyst layer is provided on both sides of a flat support having a size of 20 mm × 20 mm, the surface area Sp is 8 × 10 ⁻⁴ m ² , and the catalyst layer is provided on one side of a flat support having the same size. In the case of a film-like catalyst sample provided with a surface area Sp, 4 × 10 ⁻⁴ m ² is obtained.)

(Measurement of catalyst layer thickness)
Using a contact-type film thickness meter (laser holo gauge LGH-110) manufactured by Mitutoyo, measure the thickness of the support before providing the catalyst layer, and then measure the thickness after forming the catalyst layer. Find the thickness. The average value obtained at N = 5 was taken as the measured value.

Claims (5)

It is a film catalyst having a catalyst layer having a pore volume of 0.5 to 30 ml / m ² on a support, and the catalyst layer is 20 to 80 parts by mass of a synthetic resin with respect to 100 parts by mass of a powdery catalyst on a raw material basis. And a synthetic resin is a thermosetting resin . Film catalyst according to claim 1, wherein the synthetic resin comprises a phenolic resin. The film catalyst according to claim 1 or 2 , wherein the support is a metal foil. Film catalyst according to any one of claims 1 to 3 support is a honeycomb structure. Film catalyst is, film catalyst according to any one of claim 1 to 4, which is a film catalyst for dehydrogenation and / or hydrogenation reaction.