JP2008110341A - Manufacturing method of filmy catalyst - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method of a filmy catalyst which has high reactivity and reaction selectivity. <P>SOLUTION: The manufacturing method of the filmy catalyst having a catalyst layer on the substrate, which comprises the preparation step of a coating composition containing a powdery catalyst, a binder and a solvent and the step of obtaining a catalyst intermediate by forming the catalyst layer on the substrate using the coating composition, is characterized in that the obtained filmy catalyst satisfies formula (I): 0.55T<SB>1</SB><t<SB>1</SB><2T<SB>1</SB>(I), wherein T<SB>1</SB>is the maximum mode value (measured by the mercury porosimetry) of the pore size distribution of the powdery catalyst itself used as a raw material, which is included in the catalyst layer of the filmy catalyst and t<SB>1</SB>is the maximum mode value (measured by the mercury intrusion porosimetry) among the pore size distribution of the catalyst layer of the filmy catalyst. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a method for producing a film catalyst suitable as a catalyst for gas-liquid reaction and the like.

  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 discloses a film catalyst as a novel form of a solid catalyst used in a fixed bed system. In this method for producing an amine, a film-like catalyst having a thickness of 100 μm or less is used, so that an amine having excellent reaction selectivity is tertiaryized.
WO2005 / 035122

  The film-type catalyst disclosed in Patent Document 1 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 invention disclosed in Patent Document 1, and an object of the present invention is to provide a method for producing a film-like catalyst having high reaction activity and a small amount of catalyst falling off.

As a means for solving the problems, the present invention
Claim 1 includes a step of preparing a coating composition containing a powdered catalyst, a binder and a solvent, and a step of using the coating composition to form a catalyst layer on a support to obtain a catalyst intermediate. A method for producing a film catalyst having a catalyst layer on the support,
Provided is a method for producing a film-like catalyst, wherein the obtained film-like catalyst satisfies the following formula (I).

0.55T ₁ <t ₁ <2T ₁ (I)
T ₁ : Maximum mode value of the pore size distribution of the powder catalyst used as a raw material contained in the catalyst layer of the film catalyst (measured by mercury intrusion method)
t ₁ : Maximum mode value (measured by mercury intrusion method) in the pore size distribution of the catalyst layer of the film catalyst
Furthermore, the present invention provides a solution for the problem,
As a second aspect, the catalyst layer of the film-like catalyst has a mode value t ₂ having a pore size distribution different from the t ₁ measured by the mercury intrusion method, and t ₂ ≦ 0.2 × t ₁ A method for producing a film catalyst according to claim 1, wherein
The method for producing a film catalyst according to claim ₂ , wherein the mode value t2 is ₄ to 50 nm.
The method for producing a film-like catalyst according to any one of claims 1 to 3, wherein the coating composition is prepared using a media mill.
As a fifth aspect of the present invention, the coating composition includes a preparation time time (sec.), A representative speed V (m / sec.), An apparent volume P (L) of the medium used for the preparation, and a coating composition. Any one of claims 1 to 4 prepared under conditions satisfying the following formula: 500 <time · V · P / G <5000 (m · L / kg). A method for producing a film catalyst according to claim 1;
The method for producing a film catalyst according to any one of claims 1 to 5, comprising a drying and / or curing step as claim 6.
The method for producing a film catalyst according to claim 6, further comprising a shape processing step and a heating step after the drying and / or curing step.
The method for producing a film catalyst according to claim 8, wherein the shape processing step is a step of processing into a honeycomb structure.
The powdered catalyst contained in the coating composition according to claim 9 is the film-shaped catalyst according to any one of claims 1 to 8, wherein the catalyst active material is supported on a porous material. Production method;
As Claim 10, the manufacturing method of the film-form catalyst of any one of Claims 1-9 whose ratio of the binder contained in the said coating composition is 10-40 mass%;
The method for producing a film catalyst according to any one of claims 1 to 10, wherein the thickness of the catalyst layer of the film catalyst is 100 µm or less.
As a twelfth aspect of the invention, there is provided each invention of the method for producing a film-like catalyst according to any one of the first to eleventh aspects, wherein the film-like catalyst is used as a catalyst for gas-liquid reaction.

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

In the present invention, the “mode value” is a pore size (for example, the peak value PT ₁ ) corresponding to each peak value (for example, PT ₁ , Pt ₁ , Pt _2, etc. in FIG. 4) of the pore size distribution (for example, FIG. 4). relative Further _{t 1,} for _T 1, Pt ₁ is, for Pt ₂ means _{t 2).} Here, each peak value is obtained without including data clearly indicating noise of the measuring instrument (for example, when the pore diameter is 0.03 to 0.05 μm and 0.6 μm or more in FIG. 4).

  The film-like catalyst obtained by the production method of the present invention has sufficient reaction activity, a small amount of by-products, and a large peel strength of the catalyst layer from the support, so that the amount of catalyst falling off from the catalyst layer is also small. Few.

  Hereinafter, the manufacturing method of the film-shaped catalyst of this invention is demonstrated for every process. In addition, within the range which can solve the subject of this invention, another process process can be added besides the process demonstrated below.

<Process for preparing a coating composition>
In this step, a powdery catalyst, a binder, a solvent, and other components blended as necessary are mixed uniformly to prepare a coating composition.

[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 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 activated carbon, alumina, silica, zeolite, titania, silica-alumina, diatomaceous earth, and the like, and one or more porous materials selected from these materials Can be preferably used. 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 powdered catalyst preferably has an average particle diameter of 0.01 to 500 μm, more preferably 0.5 to 150 μm, and still more preferably 1 to 1, from the viewpoint of expressing high reaction activity and reducing the amount of by-products. A particle having a particle size of 50 μm and a sharp distribution is preferable. Further, from the same viewpoint of the specific surface area according to the BET method, a surface area of 1 to 500 m ² / g is preferable, more preferably 5 to 200 m ² / g, and still more preferably 10 to 100 m ² / g.

  The content ratio of the powdered catalyst in the coating composition is preferably 60 to 90% by mass, more preferably 60 to 85% by mass, and still more preferably, from the viewpoint of expressing high reaction activity and reducing the amount of by-products. It is 70-85 mass%.

〔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 the binder, the coating strength and binding properties are improved by improving the crosslinking density due to the curing reaction, and the catalyst activity of the powdered catalyst is effectively improved by making the catalyst coating porous by the condensation reaction. It can be pulled out.

  When the film-like catalyst obtained by the production method 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 copper-nickel. -A combination of a ruthenium ternary powder catalyst and a phenol resin can be mentioned.

  The content ratio of the binder in the coating composition is preferably 10 to 40% by mass, more preferably 15 to 40% by mass, and still more preferably 15 to 30% by mass.

  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 blending 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.

  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.

〔solvent〕
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, dioxane Ethers such as liquid paraffin, decane, decene, methylnaphthalene, decalin, kerosene, diphenylmethane, toluene, dimethylbenzene, ethylbenzene, diethylbenzene, propylbenzene, cyclohexane, partially hydrogenated hydrocarbons such as triphenyl, polydimethyl Silicone oils such as siloxane, partially octyl-substituted polydimethylsiloxane, partially phenyl-substituted polydimethylsiloxane, fluorosilicone oil, halogenated hydrocarbons such as chlorobenzene, dichlorobenzene, bromobenzene, chlorodiphenyl, chlorodiphenylmethane, Dylroll (Daikin Industries) ), Demnum (Daikin Kogyo Co., Ltd.), etc., ethyl benzoate, octyl benzoate, dioctyl phthalate, trimellitic acid tri List ester compounds such as cutyl, dibutyl sebacate, ethyl (meth) acrylate, butyl (meth) acrylate, dodecyl (meth) acrylate, dimethylformamide, N-methyl-pyrrolidone, acetonitrile, ethyl acetate, etc. Can do.

  In addition to the above-mentioned components, the coating composition 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. it can. 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. As organic fibers, polyamide nylon 6, nylon 66, aramid fiber, polyvinyl alcohol fiber, polyester polyethylene terephthalate, polybutylene terephthalate fiber, polyarylate fiber, 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 (coating film strength) of the catalyst layer can be improved due to the manifestation of the aggregate effect.

[Preparation method of coating composition]
The film-like catalyst obtained by the production method of the present invention has a catalyst layer on one or both sides of the support, and satisfies the production conditions of the following formula (I) due to the layer structure of the catalyst layer. is there.

0.55T ₁ <t ₁ <2T ₁ (I)
T ₁ : Maximum mode value of the pore size distribution of the powder catalyst used as a raw material contained in the catalyst layer of the film catalyst (measured by mercury intrusion method)
t ₁ : The maximum mode value in the pore size distribution of the catalyst layer of the film catalyst (measured by mercury porosimetry)
Hereinafter, the relationship between the layer structure of the catalyst layer in the film-like catalyst obtained by the production method of the present invention and the formula (I) 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.

FIG. 4 is a diagram showing the pore size distribution measured by the mercury intrusion method (the details of the measurement method are described in the examples), and each of the aforementioned mode values T ₁ , t ₁ , and t ₂ are shown. . FIG. 5 is a diagram for explaining how to obtain the mode value.

  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 powder catalyst 4 and a binder 5 that covers the periphery of the powder catalyst 4, and a plurality of powder catalysts 4 (and a binder 5 that covers the periphery of the powder catalyst 4). There is a gap 6 between them as shown by a broken line 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.

Then, _(of the pore size distribution of the catalyst layer of the film catalyst, the maximum value of mode) t ₁ shown in FIG. 4 is a peak derived from the porous structure (gap 6) existing between the powdery catalyst particles in the catalyst layer Yes, t ₂ (mode value different from t ₁ ) is considered to be a peak derived from the pore structure (hole 7) in which the resin (binder) present on the surface of the powdery catalyst is partially missing.

In the film-like catalyst obtained by the production method of the present invention, the catalyst layer has a layer structure as shown in FIGS. Furthermore, T ₁ (the maximum mode value of the pore size distribution of the powdered catalyst itself used as a raw material contained in the catalyst layer of the film-like catalyst) and t ₁ are approximate values, that is, satisfy the formula (I). Will be able to. The fact that T ₁ and t ₁ are approximate values means that when a film catalyst is used as a catalyst for a certain reaction, the particle shape of the powder catalyst as a raw material, that is, before the step of adjusting the coating composition is determined. Since it exists in the catalyst layer in a substantially retained state, the void structure of the powdered catalyst as a raw material is close to the void structure formed by the catalyst particles in the catalyst layer via a binder. is there. Therefore, it can exist also in a catalyst layer, without impairing performance as a powdery catalyst established with the raw material.
In addition, since a void structure exists between the powdery catalyst particles, the mobility of the reactants up to the deepest part of the catalyst layer can be ensured. Furthermore, the presence of a pore structure in which the resin (binder) present on the surface of the powdered catalyst is partially missing, dramatically improves the contact of the reactants that have been exposed and moved at the active site. , Chemical reaction on the surface is promoted. In addition, it allows the reaction product to move smoothly from the pore surface structure where the resin (binder) is partially missing from the vicinity of the exposed catalyst surface to the void structure between the powdered catalyst particles and further to the outside of the catalyst layer. In addition, the mobility of reaction products can be dramatically improved. By ensuring such smooth substance mobility, it is possible to suppress overreaction of reaction products in the catalyst layer, and to improve selectivity. In other words, the inventor of the present application has clarified a method for producing a film catalyst having a layer structure capable of maintaining the inherent reaction performance of a powdered catalyst as a raw material and highly capable of extracting the reaction performance.
For the above reason, it means that the contact property between the powdery catalyst contained in the catalyst layer of the film catalyst and the reactant is very good. As a result, it is considered that high reaction activity and reaction selectivity can be expressed as clarified in the examples.

In the film-like catalyst obtained by the production method of the present invention, the relationship represented by the formula (I) is preferably 0.7T ₁ <t ₁ <2T ₁ , more preferably 0.8T ₁ <t ₁ <1. by a 5T _1, it can exhibit a higher reaction activity.

From the viewpoint of expressing a high reaction activity, the mode value T ₁ is preferably ₁₀ nm to 250,000 nm (250 μm), more preferably 200 nm to 50,000 nm (50 μm), still more preferably 400 nm to 25, 000 nm (25 μm).

From the viewpoint of expressing high reaction activity, the mode value t ₁ is preferably 20 nm to 250,000 nm (250 μm), more preferably 100 nm to 100,000 nm (100 μm), still more preferably 200 nm to 50, 000 nm (50 μm).

Furthermore, in the film-like catalyst obtained by the production method of the present invention, the catalyst layer of the film-like catalyst has a mode value t different from the maximum mode value t ₁ among the mode values of the pore size distribution measured by the mercury intrusion method. ₂ and preferably t ₂ ≦ 0.2 × t ₁ , more preferably t ₂ ≦ 0.15 × t ₁ . Further, from the viewpoint of capable of expressing high reaction activity, the mode value _{t 2} is preferably 4 to 50 nm, more preferably 4～30Nm.

The lower limit of t ₂ / t ₁ is 1.6 × 10 ⁻⁵ considering that the preferable upper limit of t ₁ is 250 μm and the preferable lower limit of t ₂ is 4 nm.

  When the mode value cannot be clearly recognized as shown in FIG. 5, the intersection of the tangent lines of the plot is set as the mode value.

The film-like catalyst obtained by the production method of the present invention preferably has a catalyst layer thickness of 500 μm or less, preferably 100 μm or less from the viewpoint of expressing high reaction activity and reducing the amount of by-products. More preferably, the thickness is 50 μm or less. From the same viewpoint, catalyst loading per unit area is preferably from 0.5 to 100 g / m ^2, more preferably 1~60g / m ^2, more preferably 10 to 30 g / m ^2.

  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 pent 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 powdered catalyst are controlled, and the film It is suitable for controlling the pore size distribution of the catalyst layer of the catalyst.

  Media type mills include ball mills, attritors, AD mills, twin AD mills, basket mills, twin basket mills, handy mills, glen mills, dyno mills, apex mills, star mills, visco mills, sand grinders, paint shakers using beads, etc. Can be mentioned. In the present invention, a dissolver type mixing and dispersing machine can also be used as a dispersing machine other than the media type mill.

  The coating composition consists of a preparation time time (sec.), A representative speed V (m / sec.), An apparent volume P (L) of the media used for the preparation, and a blending mass G (kg) of the coating composition. It is preferable to prepare it under the conditions satisfying the following formula (II): 500 <time · V · P / G <5000 (m · L / kg) (II).

  In the formula (II), 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 paint and the preparation time (sec). It is difficult to determine the shear rate and to model the state of applying shear. For this reason, it has been found that it is effective to determine the paint conditions by the formula (II) in the media type mill. In other words, in the formula (II), the preparation conditions of the paint 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 paint (P / G). The apparent volume ratio (P / G) of media per unit mass of paint refers to the apparent volume of the media involved in coating, and if the apparent volume of media during dispersion is smaller than the paint weight (P / G is If it 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 paint by the media is affected by the shape, density, material, and the like of the media used, but the inventors of the present invention have noted that the apparent volume of the media is 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 from 0.1 to 20 m / sec, more preferably from 0.5 to 10 m / sec. The preparation time is 10 to 180 minutes, preferably 10 to 90 minutes. 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 media per unit mass of the coating is 1 to 9, preferably 2-8.

By preparing the coating composition so as to satisfy the formula (II), the maximum mode value (measured by the mercury intrusion method) t ₁ in the pore size distribution of the catalyst layer of the film catalyst is defined as the catalyst layer of the film catalyst. The maximum mode value (measured by the mercury intrusion method) T ₁ of the pore size distribution of the powdered catalyst itself used as a raw material contained in ₁ can be brought to a state (see FIG. 4). The preparation conditions represented by the formula (II) are preferably 700 <time · V · P / G <4000, more preferably 1000 <time · V · P / G <3000.

  The solid content in the coating composition is preferably 10 to 80% by mass, and more preferably 10 to 80% by mass, because the pore structure is controlled at the time of desorption of the solvent from the formed catalyst layer and affects the formation of the pore structure. Is 20-70 mass%, More preferably, it is 25-65 mass%. The viscosity of the coating composition is selected within a preferable range depending on the coating method, and is, for example, 5 to 10,000 mPas, preferably 20 to 5000 mPas, and more preferably 50 to 1000 mPas.

<Step of forming a catalyst layer on a support to obtain a catalyst intermediate>
In this step, the above-described coating composition is used to form a catalyst layer on the support.

[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 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. can be 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 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. 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.

[Method of forming catalyst layer]
As a method of forming the catalyst layer on the surface of the support described above, a method of applying and forming the coating composition on the support can be applied.

  A conventionally known method can be used as the coating method, and examples thereof include various coating methods such as blade, roll, knife, bar, spray, dip, spin, comma, kiss, gravure, and die coating.

<Drying and curing process>
In the present invention, a coating composition can be applied to the surface of the support and formed into a film, and then a drying and curing step can be provided. Following the drying and curing step, a shape processing step and a final heating step can be provided. . 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. The volatile component other than the solvent includes unreacted monomer components and the like.

  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.

  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 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 ° C. The drying and curing treatment is performed at a wind speed of preferably 0.5 to 30 m / sec, more preferably 1 to 20 m / sec, preferably 1 second or more, more preferably 10 minutes or more, and further preferably 30 minutes or more. It is desirable to do.

  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 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 before the final heat treatment for obtaining the target film-like catalyst is typically performed at a temperature of 60 to 400 ° C., preferably 70 to 250 ° C., more preferably 80 to 150 ° C. by hot air drying. 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.

  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 film-like catalyst obtained by shaping the same can be used as a structure in which multiple layers are stacked, and heat treatment can be performed in a state of being stored in a holder or cassette for attachment to a reactor. .

  The final heat treatment conditions vary depending on the type of the binder, 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, Heat treatment is desirable. 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. 6), a catalyst layer formed on the inner wall surface of a pipe that can be used in a flow reactor (see FIG. 8), and a catalyst layer on the surface of a thin plate-like 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 obtained by the production method of the present invention can be applied to various reactions depending on the selection of the contained powder-like catalyst, especially when the powder-like catalyst used for the reaction in the liquid phase is applied. Therefore, even if the obtained 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. Suitable as a catalyst for the 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 obtained by the production method 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.

Production Example 1 (Production of powdered catalyst)
A powdered catalyst made of a copper / nickel / ruthenium ternary catalytic active material supported on a synthetic zeolite was prepared as follows.

Synthetic zeolite (average particle size: 6 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 a powdered catalyst. In the obtained powdery catalyst, the proportion of metal oxide was 50% by mass, and the proportion of synthetic zeolite was 50% by mass. Powdery catalyst pore size distribution mode value T ₁ by the mercury porosimetry was 515 nm.

Production Examples 2 and 3 (Production of powdered catalyst)
In Production Example 2, the average particle diameter of the synthetic zeolite was 3 μm. In Production Example 3, the average particle diameter of the synthetic zeolite was 3 μm, and the dropping temperature of the 10 mass% sodium carbonate aqueous solution was 80 ° C. 1 was produced. Further, a powdered catalyst made of a copper-nickel-ruthenium ternary catalytic active material supported on a synthetic zeolite was obtained. The pore size distribution mode value T ₁ of the powdery catalyst by mercury porosimetry was 230 nm in Production Example 2 and 258 nm in Production Example 3.

Production Example 4 (Phenolic resin production)
A resole type phenolic resin was prepared as follows. Paraformaldehyde (F), phenol (P), and zinc acetate (CAT) as a reaction catalyst were added to a 4 L flask so that the molar ratio was F / P / CAT = 1.8 / 1.0 / 0.015. The mixture was reacted at 80 ° C. for 16 hours with stirring to obtain a resol type phenol resin.

  Examples and comparative examples are shown below. Here, Examples 1-4 and Comparative Examples 1-4 are methods for producing a film-like catalyst that can be applied to the production of tertiary amines, and Examples 5 and Comparative Example 5 are methods for producing a film-like catalyst that can be applied to the production of aldehydes. Is illustrated.

Example 1
MIBK as a solvent, phenol resin as a binder (PR-9480 manufactured by Sumitomo Bakelite), and powdered catalyst prepared in Production Example 1 were placed in this order in a 250 ml wide-mouth polyethylene bottle. The blending ratio was such that the nonvolatile content of the phenol resin was 20 parts by weight with respect to 80 parts by weight (65 g) of the powdered catalyst, and the amount of MIBK was such that the solid content of the blend was 60% by weight. Further, glass beads having a diameter of 1 mm (apparent volume of 65 ml) were placed in a wide-mouth polyethylene bottle as a dispersion medium.

  A wide-mouth polyethylene bottle was set in a paint shaker and mixed and dispersed for 30 minutes as a preparation time to obtain a coating composition. (The paint shaker moved at a rate of 12.5 times per second with a moving stroller of 5 cm. The representative speed was 0.05 × 2 (m) / [1 / 12.5] (s) = 1.25 m / s).

A copper foil (thickness 40 μm, weighing 310 g / m ² ) is used as a support, the coating composition is applied to both sides of the copper foil with a bar coater, and then treated at 130 ° C. for 30 seconds with a hot air circulating thermostat. A catalyst intermediate was obtained.

  The obtained film-like catalyst intermediate (width: 65 mm × length: 160 mm) is bent into a corrugated plate, overlapped with a flat plate-like film-like catalyst of the same size and wound into a cylindrical shape, outer diameter 30 mm × height 65 mm 14 cylindrical film-shaped catalyst intermediates were prepared. This was subjected to a curing treatment at 150 ° C. for 90 minutes with a dryer to obtain a film-like catalyst having the shape shown in FIG.

The catalyst layer mass per unit area in the obtained film catalyst was 17.9 g / m ^{2 on} one side and 35.8 g / m ² on both sides. The loading amount of the powdery catalyst per unit area, one-sided 14.3 g / m ^2, a double-sided 28.6 g / m ^2, the supported amount of the powdered catalyst in the cylindrical film catalyst 14 present 8. 2g. The average thickness (one side) of the catalyst layer was 10 μm.

Example 2
MIBK as a solvent, phenol resin (PR-9480 manufactured by Sumitomo Bakelite) as a binder, and the powdered catalyst prepared in Production Example 1 were put in a 500 ml beaker in this order. The blending ratio was such that the nonvolatile content of the phenol resin was 20 parts by weight with respect to 80 parts by weight (350 g) of the powdered catalyst, and the amount of MIBK was such that the solid content of the blend was 60% by weight.

  Using a tabletop dissolver, the above composition was mixed and dispersed for 30 minutes to prepare a coating composition.

A copper foil (thickness 40 μm, weighing 310 g / m ² ) is used as a support, and the coating composition is applied by a bar coater and then treated at 130 ° C. for 30 seconds with a hot air circulating thermostat to form a catalyst layer. A catalyst intermediate was obtained. The catalyst layer was formed on both sides of the copper foil by the same method.

  The obtained film-like catalyst intermediate (width 65 mm × length 150 mm) is bent into a corrugated plate, is overlapped with a flat film-like catalyst of the same size and wound into a cylindrical shape, and has an outer diameter of 30 mm × height of 65 mm. 14 cylindrical film-shaped catalyst intermediates were prepared. This was subjected to a curing treatment at 150 ° C. for 90 minutes with a dryer to obtain a film-like catalyst having the shape shown in FIG.

Catalyst layer weight per unit area in the obtained film catalyst one side 18.0 g / m ^2, was double-sided 36.0 g / m ^2. The loading amount of the powdery catalyst per unit area, one-sided 14.4 g / m ^2, a double-sided 28.8 g / m ^2, the supported amount of the powdered catalyst in the cylindrical film catalyst 14 present 8. 0 g. The average thickness (one side) of the catalyst layer was 12 μm.

Example 3
MIBK as a solvent, phenol resin prepared in Production Example 4 as a binder, and powdered catalyst prepared in Production Example 2 were placed in this order in a 250 ml wide-mouth polyethylene bottle. The mixing ratio was such that the nonvolatile content of the phenol resin was 32 parts by mass with respect to 68 parts by mass (65 g) of the powdered catalyst, and the amount of MIBK was such that the solid content of the formulation was 60% by mass. Further, zirconia beads having a diameter of 2 mm (apparent volume: 65 ml) were placed in a wide-mouth polyethylene bottle as a dispersion medium.

  A wide-mouthed polyethylene bottle was set in a paint shaker, and the mixture was mixed and dispersed for 110 minutes as a preparation time to obtain a coating composition (typical speed was 1.25 m / s as in Example 1).

A copper foil (thickness 40 μm, weighing 310 g / m ² ) is used as a support, and the coating composition is applied by a bar coater and then treated at 130 ° C. for 30 seconds with a hot air circulating thermostat to form a catalyst layer. A catalyst intermediate was obtained. The catalyst layer was formed on both sides of the copper foil by the same method.

  The obtained film-like catalyst intermediate (width 65 mm × length 150 mm) is bent into a corrugated plate, is overlapped with a flat film-like catalyst of the same size and wound into a cylindrical shape, and has an outer diameter of 30 mm × height of 65 mm. 12 cylindrical film-like catalyst intermediates were prepared. This was subjected to a curing treatment at 150 ° C. for 90 minutes with a dryer to obtain a film-like catalyst having the shape shown in FIG.

The catalyst layer mass per unit area in the obtained film catalyst was 9.6 g / m ^{2 on} one side and 19.3 g / m ² on both sides. The loading amount of the powdery catalyst per unit area, 6.6g / m ^2, a double-sided 13.2 g / m ^2, the amount of supported powder catalyst at 12 the cylindrical film catalyst 3.1g Met. The average thickness (one side) of the catalyst layer was 4 μm.

Example 4
MIBK as a solvent, phenol resin (PR-9480 manufactured by Sumitomo Bakelite) as a binder, and the powdered catalyst prepared in Production Example 3 were put in a 1 L vessel in this order. With respect to 65 parts by mass (350 g) of the powdered catalyst, the blending ratio was such that the nonvolatile content of the phenol resin was 35 parts by mass, and the amount of MIBK was such that the solid content of the formulation was 60% by mass.

  Using a desktop dissolver, the above-mentioned composition was preliminarily mixed and stirred for 10 minutes, and it was confirmed that there was no lump that could be visually confirmed in the powdered catalyst, and further mixed and stirred for 30 minutes. Using a basket mill (Asada Tekko SS-L, filling a 150 ml basket with 1.4 mm diameter titania beads (apparent volume 120 ml)) at a typical speed of 3000 rpm and a peripheral speed of 7 m / s, a preparation time of 60 Mixing and dispersing was performed for a minute.

A copper foil (thickness 40 μm, weighing 310 g / m ² ) was used as a support, the coating composition was applied to both sides of the copper foil with a bar coater, and then treated with a hot air circulating thermostat at 130 ° C. for 30 seconds. A film-like catalyst intermediate having a shape indicated by 7 was obtained.

  The obtained film-like catalyst intermediate (width 65 mm × length 150 mm) is bent into a corrugated plate, is overlapped with a flat film-like catalyst of the same size and wound into a cylindrical shape, and has an outer diameter of 30 mm × height of 65 mm. 15 cylindrical film-shaped catalyst intermediates were prepared. This was subjected to a curing treatment at 150 ° C. for 90 minutes with a dryer to obtain a film-like catalyst having the shape shown in FIG.

The catalyst layer mass per unit area in the obtained film catalyst was 29.2 g / m ^{2 on} one side and 58.4 g / m ² on both sides. The loading amount of the powdery catalyst per unit area, one-sided 19.0 g / m ^2, a double-sided 38.0 g / m ^2, the supported amount of the powdered catalyst in the cylindrical film catalyst 15 present 11. 1 g. The average thickness (one side) of the catalyst layer was 12 μm.

Example 5
MIBK as a solvent, phenol resin as a binder (PR-9480 manufactured by Sumitomo Bakelite), and powdered catalyst prepared in Production Example 1 were put in a 250 ml wide-mouth polyethylene bottle in this order. The blending ratio was such that the nonvolatile content of the phenol resin was 20 parts by weight with respect to 80 parts by weight (65 g) of the powdered catalyst, and the amount of MIBK was such that the solid content of the blend was 60% by weight. Further, glass beads having a diameter of 1 mm (apparent volume 65 ml) were placed in a wide-mouth polyethylene bottle as a dispersion medium.

  A wide-mouth polyethylene bottle was set in a paint shaker, and mixed and dispersed for 30 minutes as a preparation time to obtain a coating composition.

A copper foil (thickness 40 μm, basis weight 310 g / m ² ) is used as a support, and the coating composition is applied to both sides of the copper foil with a bar coater and then treated at 130 ° C. for 30 seconds with a hot air circulating thermostat. A film-like catalyst intermediate was obtained (the same intermediate as in Example 1).

  The obtained film-like catalyst intermediate (130 mm × 840 mm) was bent into a flat plate and a corrugated plate, and then alternately stacked and filled into a stainless steel cylindrical reaction vessel having an inner diameter of 21.4 mm and a length of 390 mm. (FIG. 9) A curing treatment was carried out at 150 ° C. for 90 minutes with a hot-air circulating thermostat to obtain a film catalyst.

The catalyst layer mass per unit area in the obtained film catalyst was 17.9 g / m ^{2 on} one side and 35.8 g / m ² on both sides. The loading amount of the powdery catalyst per unit area, one-sided 14.3 g / m ^2, a double-sided 28.6 g / m ^2, the powdery catalyst contained has been film catalyst packed into the tubular reactor The mass of was 3.1 g. The average thickness (one side) of the catalyst layer was 10 μm.

Comparative Example 1
MIBK as a solvent, phenol resin (PR-9480 manufactured by Sumitomo Bakelite) as a binder, and a powdered catalyst prepared in Production Example 3 were put in a 15 L vessel in this order. With respect to 65 parts by mass (4500 g) of the powdered catalyst, the blending ratio was such that the non-volatile content of the phenol resin was 35 parts by mass, and the MIBK content was such that the solid content of the formulation was 60% by mass.

  Using a desktop dissolver, the above composition was preliminarily mixed and stirred for 30 minutes (rotation speed: 800 rpm, peripheral speed: 4 m / s), and the resulting coating composition was added to a basket mill (Asada Tekko SS-3, 1 L basket) And 1.4 mm diameter titania beads (with an apparent volume of 800 ml, 1900 g) were used, and the mixture dispersion process was performed for 325 minutes as a preparation time at 1500 rpm and a representative speed, that is, a peripheral speed of 4.8 m / s.

A copper foil (thickness 40 μm, weighing 310 g / m ² ) is used as a support, the coating composition is applied to both sides of the copper foil with a bar coater, and then treated at 130 ° C. for 30 seconds with a hot air circulating thermostat. A catalyst intermediate was obtained.

  The obtained film-like catalyst intermediate (width 65 mm × length 150 mm) is bent into a corrugated plate, is overlapped with a flat film-like catalyst of the same size and wound into a cylindrical shape, and has an outer diameter of 30 mm × height of 65 mm. 12 cylindrical film-like catalyst intermediates were prepared. This was subjected to a curing treatment at 150 ° C. for 90 minutes with a dryer to obtain a film-like catalyst having the shape shown in FIG.

Catalyst layer weight per unit area in the obtained film catalyst one side 14.9 g / m ^2, was double-sided 29.7 g / m ^2. The loading amount of the powdery catalyst per unit area, one-sided 9.7 g / m ^2, a double-sided 19.4 g / m ^2, the supported amount of the powdered catalyst in the cylindrical film catalyst 12 is 4. It was 5 g. The average thickness (one side) of the catalyst layer was 6 μm.

Comparative Example 2
MIBK as a solvent, phenol resin as a binder (PR-9480 manufactured by Sumitomo Bakelite), and powdered catalyst prepared in Production Example 2 were placed in this order in a 250 ml wide-mouth polyethylene bottle. The mixing ratio was such that the nonvolatile content of the phenol resin was 32 parts by mass with respect to 68 parts by mass (65 g) of the powdered catalyst, and the amount of MIBK was such that the solid content of the formulation was 60% by mass. Further, an apparent volume of 65 ml of zirconia beads having a diameter of 2 mm was placed in a polybin as a dispersion medium.

  A wide-mouth polyethylene bottle was set on a paint shaker and subjected to a mixing and dispersion treatment for 180 minutes as a preparation time to obtain a coating composition (typical speed is 1.25 m / s as in Example 1).

A copper foil (thickness 40 μm, weighing 310 g / m ² ) is used as a support, the coating composition is applied to both sides of the copper foil with a bar coater, and then treated at 130 ° C. for 30 seconds with a hot air circulating thermostat. A catalyst intermediate was obtained.

  The obtained film-like catalyst intermediate (width 65 mm × length 150 mm) is bent into a corrugated plate, is overlapped with a flat film-like catalyst of the same size and wound into a cylindrical shape, and has an outer diameter of 30 mm × height of 65 mm. 12 cylindrical film-like catalyst intermediates were prepared. This was subjected to curing treatment at 210 ° C. for 180 minutes with a dryer to obtain a film-like catalyst having the shape shown in FIG.

Catalyst layer weight per unit area in the obtained film catalyst one side 12.9 g / m ^2, was double-sided 25.9 g / m ^2. The loading amount of the powdery catalyst per unit area, one-sided 8.8 g / m ^2, a double-sided 17.6 g / m ^2, the supported amount of the powdered catalyst in the cylindrical film catalyst 12 is 4. 1 g. The average thickness (one side) of the catalyst layer was 6 μm.

Comparative Example 3
MIBK as a solvent, phenol resin as a binder (PR-9480 manufactured by Sumitomo Bakelite), and powdered catalyst prepared in Production Example 1 were placed in this order in a 250 ml wide-mouth polyethylene bottle. The blending ratio was such that the nonvolatile content of the phenol resin was 5 parts by weight with respect to 95 parts by weight (65 g) of the powdered catalyst, and the amount of MIBK was such that the solid content of the blend was 60% by weight. Further, as a dispersion medium, glass beads having a diameter of 1 mm (apparent volume 65 ml) were placed in a wide-mouth polyethylene bottle.

  A wide-mouth polyethylene bottle was set on a paint shaker, and the mixture was mixed and dispersed for 5 minutes as a preparation time to obtain a coating composition (typical speed was 1.25 m / s as in Example 1). The obtained coating composition was in a state with many grains (aggregates).

A copper foil (thickness 40 μm, weighing 310 g / m ² ) is used as a support, the coating composition is applied to both sides of the copper foil with a bar coater, and then treated at 130 ° C. for 30 seconds with a hot air circulating thermostat. A catalyst intermediate was obtained.

  The obtained film-like catalyst intermediate (width 65 mm × length 150 mm) is bent into a corrugated plate, is overlapped with a flat film-like catalyst of the same size and wound into a cylindrical shape, and has an outer diameter of 30 mm × height of 65 mm. 14 cylindrical film-shaped catalyst intermediates were prepared. This was subjected to curing treatment at 210 ° C. for 180 minutes with a dryer to obtain a film-like catalyst having the shape shown in FIG.

The catalyst layer mass per unit area in the obtained film catalyst was 9.0 g / m ^{2 on} one side and 18.0 g / m ² on both sides. The loading amount of the powdery catalyst per unit area, one-sided 8.6 g / m ^2, a double-sided 17.2 g / m ^2, the supported amount of the powdered catalyst in the cylindrical film catalyst 14 present in 4. It was 6 g. The average thickness (one side) of the catalyst layer was 8 μm. The catalyst layer of the obtained film-like catalyst was in a very fragile state and lacked strength. Although it was applied to the reaction evaluation by the following procedure, it was not able to be evaluated well as a fixed bed reaction because of many membrane dropouts.

Comparative Example 4
MIBK as a solvent, phenol resin as a binder (PR-9480 manufactured by Sumitomo Bakelite), and powdered catalyst prepared in Production Example 3 were put in a 250 ml wide-mouth polyethylene bottle in this order. The blending ratio was such that the nonvolatile content of the phenol resin was 50 parts by mass with respect to 50 parts by mass (65 g) of the powdered catalyst, and the amount of MIBK was such that the solid content of the blend was 50% by mass. Further, as a dispersion medium, zirconia beads having a diameter of 2 mm (apparent volume 65 ml) were placed in a wide-mouth polyethylene bottle.

  A wide-mouth polyethylene bottle was set on a paint shaker, and the mixture was mixed and dispersed for 250 minutes as a preparation time to obtain a coating composition (typical speed was 1.25 m / s as in Example 1).

A copper foil (thickness 40 μm, weighing 310 g / m ² ) is used as a support, the coating composition is applied to both sides of the copper foil with a bar coater, and then treated at 130 ° C. for 30 seconds with a hot air circulating thermostat. A catalyst intermediate was obtained.

  The obtained film-like catalyst intermediate (width 65 mm × length 150 mm) is bent into a corrugated plate, is overlapped with a flat film-like catalyst of the same size and wound into a cylindrical shape, and has an outer diameter of 30 mm × height of 65 mm. 13 cylindrical film-shaped catalyst intermediates were prepared. This was subjected to a curing treatment at 150 ° C. for 90 minutes with a dryer to obtain a film-like catalyst having the shape shown in FIG.

The catalyst layer mass per unit area in the obtained film catalyst was 15.9 g / m ² on one side and 31.6 g / m ² on both sides. The supported amount of the powdery catalyst per unit area is 7.9 g / m ^{2 on} one side and 15.8 g / m ² on both sides. The supported amount of the powdered catalyst on the 13 cylindrical film catalysts is 4. 0 g. The average thickness (one side) of the catalyst layer was 11 μm.

Comparative Example 5
MIBK as a solvent, phenol resin as a binder (PR-9480 manufactured by Sumitomo Bakelite), and powdered catalyst prepared in Production Example 2 were placed in this order in a 250 ml wide-mouth polyethylene bottle. The mixing ratio was such that the nonvolatile content of the phenol resin was 32 parts by mass with respect to 68 parts by mass (65 g) of the powdered catalyst, and the amount of MIBK was such that the solid content of the formulation was 60% by mass. Further, zirconia beads having a diameter of 2 mm (apparent volume: 65 ml) were placed in a polyethylene bottle as a dispersion medium.

  A wide-mouth polyethylene bottle was set on a paint shaker, and the mixture composition was mixed and dispersed for 180 minutes to obtain a coating composition.

A copper foil (thickness 40 μm, weighing 310 g / m ² ) is used as a support, the coating composition is applied to both sides of the copper foil with a bar coater, and then treated at 130 ° C. for 30 seconds with a hot air circulating thermostat. A catalyst-like intermediate was obtained (the same intermediate as in Comparative Example 2).

  The obtained film-like catalyst intermediate (130 mm × 840 mm) was bent into a flat plate and a corrugated plate, and then alternately stacked and filled into a stainless steel cylindrical reaction vessel having an inner diameter of 21.4 mm and a length of 390 mm. (FIG. 9) A curing treatment was carried out at 150 ° C. for 90 minutes with a hot-air circulating thermostat to obtain a film catalyst.

Catalyst layer weight per unit area in the obtained film catalyst one side 12.9 g / m ^2, was double-sided 25.9 g / m ^2. The loading amount of the powdery catalyst per unit area, one-sided 8.8 g / m ^2, a double-sided 17.6 g / m ^2, the supported amount of the powdered catalyst in the cylindrical film catalyst 12 is 1. It was 9 g. The average thickness (one side) of the catalyst layer was 6 μm.

(Evaluation of reaction characteristics 1)
In the cylindrical film catalysts obtained in Examples 1 to 4 and Comparative Examples 1 to 4, a plurality of flow paths 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 is a glass filter (2G), 1000 g of the cylindrical film catalyst and raw alcohol dodecyl alcohol (Calcoal 2098 manufactured by Kao Co., Ltd.) are placed to reduce the catalyst. Then, the 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 = 1000 [g], and the film-like catalyst used in the reaction The reaction rate constant k [/ Hr · (m ² / kg−ROH)] was calculated from the amount G (g) of the powdered catalyst in the mixture.

  When the dodecyl alcohol concentrations at the sampling times Time1, Time2 (Hr) [Time2> Time1] were C1 and C2 (%), respectively, the calculation was performed according to the following formula.

  Also, the reaction end point is the time when the dodecyl alcohol concentration is reduced to 1%, the reaction time TIME (Hr) from the reaction start to the reaction end point, and the by-product dilauryl monomethylamine concentration M2 (%) at the reaction end point by gas chromatograph [Reaction time × By-product concentration] TIME × M2 was calculated. The results are shown in Table 1 below.

  Here, the shorter the reaction time and the fewer by-products in the reaction, the better the reaction characteristics. Therefore, TIME × M2 is introduced as an index for judging the superiority or inferiority. The smaller this value, the better the reaction characteristics. 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%. In Table 1, the coating strength is evaluated as “peeling strength”, “×” indicates a state in which film peeling occurs and the reaction liquid becomes cloudy due to the peeled material, and “◯” indicates that the peeling cannot be visually recognized after the reaction evaluation. It shows a state in which liquid turbidity is not generated.

(Evaluation of reaction characteristics 2)
To the film-shaped catalyst packed in the cylindrical reaction vessel obtained in Example 5, dodecyl alcohol (Kalco, Inc., Calcoal 2098) at a flow rate of 73.9 g / Hr, hydrogen gas at 33.6 NL / Hr. The catalyst was reduced and activated while flowing at a flow rate.

Thereafter, the supply of hydrogen gas was stopped, the temperature was raised while supplying N ₂ gas at 9 NL / Hr and dodecyl alcohol at 73.9 g / Hr, the temperature was kept constant at 220 ° C., and the dehydrogenation reaction was carried out continuously. It was. The pressure was normal pressure.

The obtained reaction solution sample was analyzed with a gas chromatograph. The concentration of dodecyl alcohol was 58.4%, and the concentration of the produced aldehyde was 16.1%. The concentration of dodecyl alcohol used as a raw material was 98.6%. From this result,
Reaction rate (%) = raw material dodecyl alcohol concentration−post-reaction dodecyl alcohol concentration = 98.6-58.4 = 40.2 (%)
Selectivity (%) = post-reaction aldehyde concentration (%) / reaction rate (%) × 100
= 16.1 / 40.2 × 100 = 39.9 (%). The results are shown in Table 2 below. In addition, the sum of the content rate of the powdery catalyst of Table 2, and the content rate of a binder is 100 mass%. Further, the peel strength in Table 2 shows the same contents as in Table 1.

  Here, the higher the reaction rate and the higher the selectivity in the reaction, the better the reaction characteristics. Therefore, the reaction rate × selectivity is introduced as an index for judging the superiority or inferiority. Show. The reason for using an index different from the above-mentioned “Evaluation of Reaction Characteristics 1” is that the reaction system is different and the evaluation cannot be performed with the TIME × M2.

(Evaluation of reaction characteristics 3)
In the same manner as in Evaluation 2 of the above reaction characteristics, 73.9 g / Hr of dodecyl alcohol (Calcoal 2098 manufactured by Kao Corporation) was added to the film-like catalyst filled in the cylindrical reaction vessel obtained in Comparative Example 5. The catalyst was reduced and activated while flowing hydrogen gas at a flow rate of 33.6 NL / Hr.

Thereafter, the supply of hydrogen gas was stopped, the temperature was raised while supplying N ₂ gas at 9 NL / Hr and dodecyl alcohol at 73.9 g / Hr, the temperature was kept constant at 220 ° C., and the dehydrogenation reaction was carried out continuously. It was. The pressure was normal pressure.

The obtained reaction liquid sample was analyzed with a gas chromatograph. The concentration of dodecyl alcohol was 95.3% and the concentration of the produced aldehyde was 0.8%. The concentration of dodecyl alcohol used as a raw material was 98.6%. From this result,
Reaction rate (%) = raw material dodecyl alcohol concentration-post-reaction dodecyl alcohol concentration = 98.6-95.3 = 3.3 (%)
Selectivity (%) = post-reaction aldehyde concentration (%) / reaction rate (%) × 100
= 0.8 / 3.3 × 100 = 24.2 (%). The results are shown in Table 2 below.

(Measurement method of pore size distribution)
The pore size distribution is measured according to the measurement method (mercury intrusion method) described in “Functionality of Substance (4th edition, Experimental Chemistry Course 12, edited by The Chemical Society of Japan, published by Maruzen Co., Ltd., page 486)”. Specifically, the pore size distribution can be measured by using a mercury intrusion measuring device such as a mercury intrusion type pore distribution measuring device (pore sizer 9320) manufactured by Shimadzu Corporation.

  The film-form catalyst measured the basic weight, the copper foil basic weight before application | coating, and an area beforehand, measured the catalyst layer mass, and measured the pore size distribution of the catalyst layer by the mercury intrusion method. The measurement of the pore diameter by the mercury intrusion method was calculated using the following formula.

D = -4γCOSθ / P
In the formula, D: pore diameter, γ: mercury surface tension, θ: contact angle, and P: pressure, respectively. The surface tension of mercury was 482.536 dyn / cm, the contact angle used was 130 °, and the mercury pressure was measured at 0 to 30000 psia.

  The pore size distribution uses the above principle to gradually change the pressure applied to mercury, measure the volume of mercury that has entered the pores at that time, that is, the pore volume V, The relationship with the pore volume was drawn, and the differential coefficient dV / d (log D) of this relationship curve was determined and plotted on the vertical axis, and the pore diameter D was plotted on the horizontal axis (see FIG. 4). This method is called mercury intrusion method. The pore size distribution was measured for a pore size range of 6 nm to 10,000 nm. In addition, (ml) which is a unit of the pore volume shown in FIG.4 and FIG.5 shows the penetration | invasion amount of the mercury to the pore, (g) shows the mass of the catalyst layer sample used for the measurement. NO DETECT means that the mode value cannot be confirmed visually from the graph.

Of the pore size distributions having different mode values (curve peaks shown in the graph) of the catalyst layer measured by this measurement method, the pore size distribution having the maximum mode value is the mode value t ₁ , which is smaller than the t _1. a large mode value of the most frequent value of the pore size distribution having a mode value is a hole diameter is t _2.

As shown in Table 1, Examples 1-4 are those in which the mode value T ₁ of the pore size distribution of the powdered catalyst and the mode value t ₁ of the pore size distribution of the catalyst layer of the film-like catalyst satisfy the formula (I). The reaction activity was high, the amount of by-products was small, good characteristics were obtained, and sufficient peel strength was obtained.

On the other hand, Comparative Example 1-4, and a state where the mode value t ₁ of the pore diameter distribution of the catalyst layer of powdered pore size distribution of catalysts mode value T ₁ and the film catalyst is very different, the reaction activity is low, There were also many by-products.

As shown in Table 2, in Example 5, the mode value T ₁ of the pore size distribution of the powder catalyst and the mode value t ₁ of the pore size distribution of the catalyst layer of the film catalyst satisfy the formula (I), and the reaction The characteristics (reaction rate × selectivity) were high, and the peel strength was sufficient.

  The aldehyde reaction, which is an equilibrium reaction, is known to be difficult to achieve both a reaction rate and a selectivity, but excellent reaction characteristics were obtained in the reaction using the film catalyst according to the present invention.

On the other hand, in Comparative Example 5, the mode value T ₁ of the pore size distribution of the powder catalyst and the mode value t ₁ of the pore size distribution of the catalyst layer of the film catalyst do not satisfy the formula (I), and the reaction characteristics (reaction rate × selectivity) was low.

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 graph which shows the hole diameter distribution for demonstrating Formula (I). Explanatory drawing of the method of calculating | requiring the mode value in Formula (I). 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 further another embodiment of the film-like catalyst obtained with the manufacturing method of this invention. The perspective view of the cylindrical reaction container used in Example 5 and Comparative Example 5. FIG.

Claims (12)

A step of preparing a coating composition comprising a powdered catalyst, a binder and a solvent; and a step of forming a catalyst layer on the support and using the coating composition to obtain a catalyst intermediate on the support. A method for producing a film catalyst having a catalyst layer,
The film-like catalyst obtained satisfies the following formula (I): A method for producing a film-like catalyst.
0.55T ₁ <t ₁ <2T ₁ (I)
T ₁ : Maximum mode value of the pore size distribution of the powder catalyst used as a raw material contained in the catalyst layer of the film catalyst (measured by mercury intrusion method)
t ₁ : The maximum mode value in the pore size distribution of the catalyst layer of the film catalyst (measured by mercury porosimetry) The catalyst layer of the film catalyst is from said t ₁ as measured by mercury porosimetry has a mode value t ₂ of different pore size distribution, a t ₂ ≦ 0.2 × t _1, claim 1 The manufacturing method of the film-form catalyst of description. The method for producing a film catalyst according to claim 2, wherein the mode value t2 is ₄ to 50 nm.   The method for producing a film catalyst according to any one of claims 1 to 3, wherein the coating composition is prepared using a media mill.   The coating composition has a 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 ( It is prepared under conditions satisfying the following formula: 500 <time · V · P / G <5000 (m · L / kg). A method for producing a film catalyst.   The manufacturing method of the film-form catalyst of any one of Claims 1-5 including a drying and / or hardening process.   The manufacturing method of the film-form catalyst of Claim 6 which has a shape processing process and a heating process after the said drying and / or hardening process.   The method for producing a film catalyst according to claim 8, wherein the shape processing step is a step of processing into a honeycomb structure.   The method for producing a film catalyst according to any one of claims 1 to 8, wherein the powdered catalyst contained in the coating composition is a catalyst active material supported on a porous material.   The manufacturing method of the film-form catalyst of any one of Claims 1-9 whose ratio of the binder contained in the said coating composition is 10-40 mass%.   The manufacturing method of the film catalyst of any one of Claims 1-10 whose thickness of the catalyst layer of the said film catalyst is 100 micrometers or less.   The manufacturing method of the film-form catalyst of any one of Claims 1-11 which uses the said film-form catalyst as a catalyst of a gas-liquid reaction.

Images