JP2010099588A - Method for manufacturing supported catalyst - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing a supported catalyst in which the kind of a catalyst component to be supported is not limited, which has excellent catalytic activity, from which the supported catalyst component is restrained from being dissociated in use and which is separated/recovered easily from a reaction product after used. <P>SOLUTION: The method for manufacturing the supported catalyst having a particulate carrier consisting of a resin and the catalyst component to be supported on the surface of the carrier includes: a dispersion step of dispersing the catalyst component in an aqueous medium; a mixing step of mixing the catalyst component-dispersed aqueous medium with a water-soluble initial condensate of the resin constituting the carrier; and a polymerization step of further polymerizing the water-soluble initial condensate to obtain the particulate non-water-soluble condensate. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a method for producing a supported catalyst, and more particularly to a method for producing a supported catalyst in which a catalyst component is supported on the surface of a particulate carrier made of a resin.

  In general, a catalyst has a metal component having catalytic activity as a main component, and in particular, a noble metal is used as the metal component. A catalyst component composed of such a metal component is used by being supported on the surface of a carrier. By supporting the catalyst component on the surface of the carrier, the catalyst efficiency can be improved, and the supported amount can be reduced by the effective use of the catalyst component, especially when the catalyst component is an expensive noble metal. is there. Further, since the catalyst component is separated and recovered from the reaction product after completion of the reaction, the catalyst component is supported on the surface of the carrier, so that the separation and recovery from the reaction product after the reaction is facilitated.

As such a carrier, for example, finely powdered activated carbon is used. A palladium-activated carbon catalyst in which palladium is supported on activated carbon, which is a typical example of supporting a catalyst component on activated carbon, is obtained by treating activated carbon with an acid or a base in advance, and then an aqueous solution of a water-soluble palladium salt such as palladium chloride or palladium nitrate. Manufactured by evaporating to dryness and reducing treatment. As the reduction treatment, reduction with a liquid phase reducing agent such as hydrazine or sodium borohydride is performed in addition to normal H ₂ reduction. Those using platinum or ruthenium as an active metal are also produced in the same manner.

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

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

  On the other hand, those containing cellulose as a carrier have been proposed. Cellulose is produced, for example, by subjecting cellulosic raw materials such as linter, pulp, and regenerated fiber to chemical treatment (acid hydrolysis, alkali oxidative decomposition, etc.) and / or mechanical treatment (pulverization, grinding, etc.). Is used. For supporting a catalyst component on a cellulose carrier, for example, a method is known in which a cellulose carrier is used as a core and a catalyst component is coated around the cellulose carrier using a binding solution (see, for example, Patent Document 2).

In addition, as a method for supporting the catalyst component on the carrier, a method in which the catalyst component is dissolved or suspended in a solvent and then supported on a fine powder as a carrier has been proposed (see, for example, Patent Document 3). .
JP-A 64-85141 JP-A-5-329380 JP-A-8-89817

  However, in the case where activated carbon is immersed in an aqueous solution of a catalyst component salt and subjected to a reduction treatment, the catalyst component may be detached from the support during use, and separation and recovery may be difficult. In addition, with respect to a catalyst component supported on alumina or silica by adsorption, modification or the like, the types of catalyst components that can be supported are limited. Furthermore, for those in which the catalyst component is supported on a carrier containing cellulose, the adhesive force between the carrier and the catalyst component is weak, and the catalyst component may be detached from the carrier during use, making separation and recovery difficult. Sometimes. Further, a catalyst component dissolved or suspended in a solvent and supported on a fine powder as a carrier may be detached from the carrier, which may make it difficult to separate and recover.

  The present invention has been made in order to solve such problems, and the type of catalyst component that can be supported is not limited, and has excellent catalytic activity and suppresses desorption of the catalyst component during use. In addition, an object of the present invention is to provide a method for producing a supported catalyst that can be easily separated and recovered from a reaction product after use.

  The method for producing a supported catalyst according to the present invention is a method for producing a supported catalyst having a particulate carrier made of a resin and a catalyst component supported on the surface of the carrier, wherein the catalyst component is dispersed in an aqueous medium. A dispersion step, a mixing step of mixing the aqueous medium in which the catalyst component is dispersed and the water-soluble initial condensate of the resin constituting the carrier, and further polymerizing the water-soluble initial condensate to form a particulate water-insoluble solution And a polymerization step for forming a condensate.

  As the catalyst component, for example, at least one selected from metals, metal oxides, and organometallic compounds can be used. The water-soluble initial condensate may be composed of, for example, an amino group-containing compound and an aldehyde compound.

  The water-soluble initial condensate is obtained, for example, by reacting the amino group-containing compound and the aldehyde compound under basic conditions, and the polymerization step is performed by adding an acid catalyst, for example. By precipitating the water-soluble initial condensate, it is precipitated as the particulate water-insoluble condensate.

  The dispersion of the catalyst component in the aqueous medium in the dispersion step may be performed by, for example, a media type atomizing device, or may be performed by, for example, a high pressure type atomizing device.

  According to the production method of the present invention, the type of the catalyst component that can be supported is not limited, the catalytic activity is excellent, the desorption of the catalyst component during use is suppressed, the reaction product after use, etc. A supported catalyst that can be easily separated and recovered from the catalyst can be produced. In particular, by performing a dispersion step in which the catalyst component is dispersed in an aqueous medium prior to the mixing step or the polymerization step, the catalyst component is finely divided on the surface of the particulate water-insoluble condensate as a carrier obtained in the polymerization step. The particulate water-insoluble condensate can be prevented from agglomerating excessively, and a supported catalyst having excellent catalytic activity can be easily produced.

Hereafter, the manufacturing method of the supported catalyst of this invention is demonstrated in detail.
The method for producing a supported catalyst of the present invention is a method for producing a supported catalyst having a particulate carrier made of a resin and a catalyst component supported on the surface of the carrier, the dispersion step, the mixing step, and the polymerization It has the process.

  In the present invention, the dispersion step is first performed prior to the mixing step and the polymerization step. In the dispersion step, the catalyst component supported on the surface of the carrier is dispersed in an aqueous medium. By performing the dispersion step prior to the mixing step and the polymerization step in this way, the catalyst components can be agglomerated to form fine particles, and the particulate water-insoluble property as a carrier obtained in the subsequent polymerization step A catalyst component can be supported in the form of fine particles on the surface of the condensate, and excessive aggregation of the particulate water-insoluble condensate can be suppressed, and as a result, a supported catalyst having excellent catalytic activity can be easily produced. Will be able to.

  Although the mechanism of action of the dispersion step prior to the mixing step or the polymerization step is not necessarily clear, the particulate water-insoluble property obtained in the polymerization step can be obtained by dispersing the catalyst component in an aqueous medium in the dispersion step in advance. The catalyst component can be supported in the form of fine particles on the surface of the condensate, and excessive aggregation of the particulate water-insoluble condensate can be suppressed due to the presence of the fine particle catalyst component supported on the surface, As a result, it is considered that a supported catalyst having excellent catalytic activity can be easily produced.

  The catalyst component used in the dispersion step is not particularly limited as long as it has catalytic activity, and can be appropriately selected according to the type of catalytic reaction when finally used as a supported catalyst. As such a catalyst component, specifically, one composed of at least one selected from metals, metal oxides, and organometallic compounds is used. For example, titanium, chromium, cobalt, nickel, copper, ruthenium, A material comprising at least one selected from metals such as rhodium, palladium, rhenium, osmium, platinum and oxides and complexes thereof is used. Moreover, the composite_body | complex containing 2 or more types of these can also be used.

  Such a catalyst component preferably has a primary particle size of 1 μm or less, for example, preferably 1 nm or more and 100 nm or less, but is not necessarily limited thereto. Moreover, as a catalyst component, what is called a metal nanoparticle catalyst can also be used suitably, for example.

  Moreover, as an aqueous medium as a dispersion medium for dispersing the catalyst component, for example, distilled water, ion-exchanged water and the like can be suitably used, but a part of the organic solvent soluble in water may be included. Such an organic solvent is preferably one that can dissolve a water-soluble initial condensate to be mixed in the subsequent mixing step, an acid catalyst suitably added in the subsequent polymerization step, and the like, for example, methanol, ethanol , Alcohols such as isopropanol and propanol, ethers such as dioxane, tetrahydrofuran and 1,2-dimethoxyethane, and polar solvents such as dimethylformamide and dimethylsulfoxide can be used.

  It is necessary to appropriately disperse the catalyst component in the aqueous medium. For example, it is preferable to carry out such that no catalyst component having a maximum particle size exceeding 1 μm is observed in the aqueous medium. When the maximum particle size of the catalyst component exceeds 1 μm, it may be difficult to support the catalyst component in the form of fine particles on the surface of the particulate water-insoluble condensate in the polymerization step. There is a possibility that the ionic condensate is excessively aggregated, and as a result, a supported catalyst having excellent catalytic activity may not be obtained. The maximum particle size of the catalyst component in the aqueous medium is measured using a known laser diffraction / scattering particle size distribution measuring device, for example, LA950 (trade name, manufactured by Horiba, Ltd.).

  The method for dispersing the catalyst component in the aqueous medium is not necessarily limited. However, since the maximum particle size of the catalyst component is easily within the above range, for example, a media type atomizing device or a high-pressure type atomizing device is used. It is preferable.

  Examples of the media type atomizer include dyno mill (made by Shinmaru Enterprises, trade name), DCP mill (made by Eirich, trade name), SC mill (made by Mitsui Mining Co., trade name), super visco mill, nano mill. Fine mills (trade name, manufactured by Nippon Pneumatic Co., Ltd.) can be used. When using a media-type atomizing device, it varies depending on the capacity of the pot, the diameter of the medium filled in the pot, the filling rate, etc. When used, the maximum particle size of the catalyst component can be within the above range by setting the dispersion treatment to 12 hours or longer.

  Moreover, as a high pressure type atomizer, for example, HOMOGENIZER (trade name, manufactured by Sanwa Kikai Co., Ltd.), ultrahigh pressure homogenizer; (Mizuho Kogyo Co., Ltd., trade name), Nanomizer; YSNM-1500AR, YSNM-1500-0025N, etc. (Yoshida Kikai Kogyo Co., Ltd., trade name), Emulsi Flex; EmulsiFlex-C3, C5, C50 etc. Product name), Gorin homogenizer APV, etc. (trade name, manufactured by Runny), Microfluidizer, Microfluidics, etc. (trade name, manufactured by International Corporation), Ultimateizer (trade name, manufactured by Sugino Machine), Nanomizer (Nanomizer Corporation) Manufactured, trade name), NS type high pressure homogenizer (Niro-Soav) .S.p.A Co., Ltd., trade name), and the like HC3-5 (Sanmaru Machinery Co., Ltd., it is possible to use a trade name), and the like. Even when a high-pressure atomizer is used, depending on whether it is a continuous type or a non-continuous type, and depending on the processing pressure, for example, when a non-continuous type is used, the dispersion treatment is performed three times or more at a processing pressure of 50 MPa. By performing the above, the maximum particle size of the catalyst component can be within the above range.

  In the mixing step, the aqueous medium in which the catalyst component is dispersed in the dispersing step and the water-soluble initial condensate of the resin constituting the carrier are mixed. As the water-soluble initial condensate, for example, a product comprising an amino group-containing compound and an aldehyde compound can be used.

  The water-soluble initial condensate is, for example, an initial condensate obtained by a condensation reaction between an amino group-containing compound and an aldehyde compound, and is water-soluble because of a relatively low degree of polymerization. That is, when a compound containing an amino group and an aldehyde compound are subjected to a condensation reaction, the condensation reaction is repeated to gradually decrease the solubility, and finally become water-insoluble. However, those having a low degree of polymerization at the initial stage of the reaction become water-soluble compounds and become the water-soluble initial condensate referred to in the present invention. Here, water-soluble means that which can be visually confirmed to be transparent.

  Examples of the compound containing an amino group used for obtaining a water-soluble initial condensate include urea, melamine, guanamine, aniline, or these compounds, and these may be used alone or in combination of two kinds. The above may be used in combination.

［式中、置換基、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５およびＲ^６は各々互いに独立しており、それら置換基の１ないし５個は、Ｃ_１−２０のアルキル基、Ｃ_２−２０のアルケニル基（該アルキル基またはアルケニル基は、その構造中に任意に脂環式構造またはフェニル基を有していても良く、また２個の該アルキル基またはアルケニル基が同一窒素原子上にある場合はその窒素原子と一緒になって３〜８員の含窒素複素環を形成しても良い）またはフェニル基を表し、そして残りの置換基は水素原子を表す。］ For example, examples of the melamine compound include those obtained by substituting the hydrogen of the amino group of melamine with an alkyl group, an alkenyl group, or a phenyl group, and specifically those represented by the following general formula (1).

[Wherein, each of the substituents R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ is independent of each other, and 1 to 5 of the substituents are C _1-20 alkyl groups, C _2-20 alkenyl group (the alkyl group or alkenyl group may optionally have an alicyclic structure or a phenyl group in its structure, and the two alkyl groups or alkenyl groups may be the same nitrogen. When present on an atom, it may form a 3- to 8-membered nitrogen-containing heterocyclic ring together with the nitrogen atom) or a phenyl group, and the remaining substituents represent a hydrogen atom. ]

A substituent represented by a C _1-20 alkyl group, a C _2-20 alkenyl group or a phenyl group, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ include a methyl group, Ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, tert-butyl group, cyclopropylmethyl group, cyclobutyl group, n-pentyl group, iso-pentyl group , Sec-pentyl group, tert-pentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, cyclohexylmethyl group, 4-methylcyclohexylmethyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n- Decyl group, n-dodecyl group, n-hexadecyl group, n-octadecyl group, benzyl group, 1-phenethyl group, 2-phenethyl group 1-phenylpropyl group, 3-phenylpropyl group, vinyl group, allyl group, methallyl group, crotyl group, 2-pentenyl group, 3-hexenyl group, styryl group and phenyl group, and two on the same nitrogen atom Examples of the ring structure in the case where the above substituent together with the nitrogen atom forms a heterocyclic ring include an aziridine ring, an azetidine ring, a pyrrolidine ring and a piperidine ring.

［但し、Ｘ、Ｘ′およびＸ″は−ＮＨ_２、−ＮＨＲおよび−ＮＲＲ′からなる群から選択されるものであり、その場合Ｘ、Ｘ′およびＸ″は同時には−ＮＨ_２ではなく、ＲおよびＲ′はヒドロキシ−Ｃ_２−１０−アルキル、ヒドロキシ−Ｃ_２−４−アルキル−（オキサ−Ｃ_２−４−アルキル）_ｎ、（ｎ＝１〜５）およびアミノ−Ｃ_２−１２−アルキルからなる群から選択されるものである。］ Furthermore, as a melamine compound, what substituted the amino group of melamine with the hydroxyalkyl group, the hydroxyalkyl (oxaalkyl) _n group, and the aminoalkyl group can be used, for example. As such a thing, what is shown by following General formula (2) is mentioned, for example.

Wherein X, X ′ and X ″ are selected from the group consisting of —NH ₂ , —NHR and —NRR ′, in which case X, X ′ and X ″ are not simultaneously —NH ₂ , R and R ′ are hydroxy-C _2-10 -alkyl, hydroxy-C _2-4 -alkyl- (oxa-C _2-4 -alkyl) _n , (n = 1-5) and amino-C _2-12- It is selected from the group consisting of alkyl. ]

The hydroxy-C _2-10 -alkyl group is preferably 2-hydroxyethyl, 3-hydroxy-n-propyl, 2-hydroxyisopropyl, 4-hydroxy-n-butyl, 5-hydroxy-n-pentyl, 6- Hydroxy-C _2-6 -alkyl such as hydroxy-n-hexyl, 3-hydroxy-xy-2,2-dimethylpropyl, preferably 2-hydroxyethyl, 3-hydroxy-n-propyl, 2-hydroxyisopropyl and Examples include hydroxy- _C2-4 -alkyl such as 4-hydroxy-n-butyl, particularly preferably 2-hydroxyethyl and 2-hydroxyisopropyl.

Hydroxy- _C2-4 -alkyl- (oxa- _C2-4 -alkyl) The _n group is preferably such that n = 1 to 4, particularly preferably n = 1 or 2. For example, 5-hydroxy-3-oxa-pentyl, 5-hydroxy-3-oxa-2,5-dimethyl-pentyl, 5-hydroxy-3-oxa-1,4-dimethyl-pentyl, 5-hydroxy-3- Examples include oxa-1,2,4,5-tetramethyl-pentyl and 8-hydroxy-3,6-dioxa-octyl.

The amino-C _2-12 -alkyl group is preferably 2-aminoethyl, 3-aminopropyl, 4-aminobutyl, 5-aminopentyl, 6-aminohexyl, 7-aminoheptyl and 8-aminooctyl. Amino-C _2-8 -alkyl groups, particularly preferably 2-aminoethyl and 6-aminohexyl, very preferably 6-aminohexyl.

  On the other hand, formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde, furfural and the like can be used as the aldehyde compound, but usually formaldehyde or paraformaldehyde which is inexpensive and excellent in reactivity with a compound containing an amino group is preferably used.

  As the aldehyde compound, for example, an aldehyde compound that is 1.1 mol to 6.0 mol, particularly 1.2 mol to 4.0 mol per effective aldehyde group with respect to 1 mol of the compound containing an amino group may be used. preferable. When the blending amount of the aldehyde compound is too small with respect to the blending amount of the compound containing an amino group, it becomes difficult to finally make it water-insoluble by three-dimensional crosslinking and precipitate it. Moreover, when there are too many compounding quantities of an aldehyde compound with respect to the compounding quantity of the compound containing an amino group, it may remain in a system as an unreacted substance and may cause various pollution.

  The water-soluble initial condensate is prepared by, for example, mixing the above-described compound containing an amino group and an aldehyde compound at a predetermined ratio, and performing a condensation reaction using a basic catalyst such as sodium hydroxide, potassium hydroxide, aqueous ammonia, triethylamine or the like. Can be easily obtained.

In the polymerization step, the catalyst component and the water-soluble initial condensate are mixed in the mixing step, and the water-soluble initial condensate is further polymerized to precipitate as a particulate water-insoluble condensate. At this time, the catalyst component adheres to the surface of the particulate water-insoluble condensate, whereby a supported catalyst in which the catalyst component is supported in the form of fine particles on the surface of the particulate water-insoluble condensate can be obtained. Also,
A supported catalyst in which excessive aggregation of the particulate water-insoluble condensate is suppressed by the particulate catalyst component supported on the surface can be obtained.

  In addition, a water-insoluble condensate is a water-insoluble condensate that has been made water-insoluble due to a decrease in solubility as a result of further increasing the degree of polymerization by further proceeding with the condensation reaction of the water-soluble initial condensate. Here, “water-insoluble” is not limited as long as it cannot be visually confirmed to be transparent. Moreover, although the catalyst component is mainly supported on the surface of the particulate water-insoluble condensate, a part thereof may be taken into the particulate water-insoluble condensate.

  In the polymerization step, it is preferable to use an acid catalyst to further polymerize the water-soluble initial condensate and deposit it as a particulate water-insoluble condensate. For example, the acid catalyst is added so that the reaction system has a pH of 6 or less. In particular, it is preferable to add an acid catalyst so that the reaction system has a pH of 2 to 5. A pH higher than 6 is not preferable because the particle size distribution of the particulate water-insoluble condensate becomes wide and the particulate water-insoluble condensate easily aggregates.

  Examples of the acid catalyst used in the polymerization step include inorganic acids such as hydrochloric acid, and organic acids such as acetic acid, alkylbenzenesulfonic acid, naphthalenesulfonic acid, paratoluenesulfonic acid, polyoxyethylene and sulfonated derivatives thereof.

  As the acid catalyst, a polybasic acid containing 2 or more hydrogen atoms capable of neutralizing a base in one molecule can be used. Examples of such compounds include aliphatic saturated dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid, and maleic acid and fumaric acid. Examples thereof include dibasic acids such as aliphatic unsaturated dicarboxylic acids, aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid, and inorganic acids such as sulfuric acid. Examples of the polybasic acid include tribasic acids such as tricarboxylic acids such as tricarballylic acid and benzenetricarboxylic acid, and inorganic acids such as phosphoric acid, arsenic acid and boric acid. Furthermore, examples of the polybasic acid include tetrabasic acids such as benzenetetracarboxylic acid and hexabasic acids such as benzenehexacarboxylic acid.

  According to such a method for producing a supported catalyst of the present invention, the type of catalyst component that can be supported is not limited, and desorption of the catalyst component during use is suppressed, so that the reaction product after use can be used. A supported catalyst that can be easily separated and recovered can be produced. In particular, by carrying out the dispersion step prior to the mixing step or the polymerization step, the catalyst component can be supported in the form of fine particles on the surface of the particulate water-insoluble condensate as a carrier. Excessive aggregation of the functional condensate can be suppressed, and as a result, a supported catalyst having excellent catalytic activity can be easily produced.

  Specifically, according to the method for producing a supported catalyst of the present invention, a supported catalyst having an average particle size (median diameter D50) of 30 μm or more and 100 μm or less can be easily produced. Here, the supported catalyst is, for example, a cocoon-shaped tuft formed by agglomerating a plurality of particulate water-insoluble condensates having a catalyst component supported on the surface. The water-insoluble condensate has a particle size of about 1 μm to 20 μm. The average particle diameter (median diameter D50) of the supported catalyst means a particle diameter in which the cumulative volume from 0 μm is 50% in the particle size distribution, and is measured using, for example, a laser diffraction / scattering particle size distribution measuring device. It is what is done.

  Next, the production method of the supported catalyst of the present invention will be specifically described with reference to examples.

Example 1
Palladium catalyst-containing iron oxide fine particles (Pd amount 2.2%, specific surface area 26 m ² / g, average particle size 0) in a ball mill pot (media: 2 mm diameter zirconia balls, filling rate 60%) with a capacity of 250 ml .05 μm) 20 parts by mass and 80 parts by mass of water were charged and dispersed for 12 hours or more to prepare a dispersion of catalyst components. In addition, when the state of the nub was confirmed using a grind gauge, the presence of nub was not observed. Further, the maximum particle size of the catalyst component in the dispersion of the catalyst component was determined by a laser diffraction / scattering particle size distribution measuring apparatus [LA950. It was 0.77 micrometer when measured by (Horiba Seisakusho make, brand name)].

  A 300 ml separable flask equipped with a stirring motor, a reflux condenser, and a thermometer was charged with 7.6 g of melamine, 14.6 g of 37% formalin, 0.090 g of sodium sulfate, and 128.2 g of water, and 25% aqueous ammonia. The pH was adjusted to 8.5. The mixture was heated while stirring and reacted at 30 ° C. for 30 minutes to prepare an aqueous solution of an initial condensate of melamine resin as a water-soluble initial condensate.

  Thereafter, the temperature of the aqueous solution of the water-soluble initial condensate was lowered to 50 ° C., and 3.24 g of the previously prepared catalyst component dispersion was mixed. Next, while maintaining the mixed solution of the catalyst component and the water-soluble initial condensate at 50 ° C., a 10% by mass paraene toluenesulfonic acid aqueous solution was added to adjust the pH to 5.1, and then at 50 ° C. for 3 hours. Further, the temperature was raised to 90 ° C. and a condensation reaction was carried out for 1 hour to further polymerize the water-soluble initial condensate to precipitate particulate water-insoluble condensate and to attach and carry the catalyst component on the surface. . The reaction liquid obtained by this condensation reaction is filtered, washed and dried, and the surface of the particulate water-insoluble condensate (melamine resin) as a carrier is supported with iron catalyst fine particles containing palladium catalyst as a catalyst component. A supported catalyst was obtained.

  The average particle diameter (median diameter D50) of the supported catalyst was measured by a laser diffraction / scattering particle size distribution analyzer [LA950 (trade name, manufactured by Horiba, Ltd.)] and found to be 67.8 μm. Further, when this supported catalyst was observed in detail, it was observed that spherical particles having a particle size of about 5 μm gathered to form cocoon-like particles. Furthermore, when this supported catalyst was used in a model reaction system of the Suzuki coupling reaction, it was confirmed that the reaction proceeded at a practical rate.

(Example 2)
A supported catalyst was prepared in the same manner as in Example 1 except that in the preparation of the aqueous solution of the water-soluble initial condensate, the amount of melamine was 5.8 g and 1.7 g of benzoguanamine was added. The average particle diameter (median diameter D50) of the supported catalyst thus produced was 72.3 μm. Further, when this supported catalyst was observed in detail, it was observed that spherical particles having a particle size of about 5 μm gathered to form cocoon-like particles. Furthermore, when this supported catalyst was used in a model reaction system of the Suzuki coupling reaction, it was confirmed that the reaction proceeded at a practical rate.

(Example 3)
The condensation reaction after mixing the catalyst component and the water-soluble initial condensate and adjusting the pH was carried out in the same manner as in Example 1 except that the condensation reaction was carried out at 50 ° C. for 3 hours and further raised to 70 ° C. for 1 hour. A supported catalyst was prepared. The average particle diameter (median diameter D50) of the supported catalyst thus produced was 45.5 μm. Further, when this supported catalyst was observed in detail, it was observed that spherical particles having a particle size of about 5 μm gathered to form cocoon-like particles. Furthermore, when this supported catalyst was used in a model reaction system of the Suzuki coupling reaction, it was confirmed that the reaction proceeded at a practical rate.

Example 4
A supported catalyst was prepared in the same manner as in Example 1, except that the catalyst component dispersion was prepared using a high-pressure atomizer instead of using a ball mill. That is, 20 parts by mass of palladium catalyst-containing iron oxide fine particles as a catalyst component and 80 parts by mass of water were mixed and stirred for 5 minutes with a stirring motor, and then treated at 50 MPa using EmulsiFlex-C5 (Avestin, trade name). A catalyst component dispersion was prepared by passing three times under pressure, and thereafter a supported catalyst was prepared in the same manner as in Example 1. The maximum particle size of the catalyst component in the catalyst component dispersion was 0.4 μm.

  The average particle diameter (median diameter D50) of the supported catalyst thus produced was 65.7 μm. Further, when this supported catalyst was observed in detail, it was observed that spherical particles having a particle size of about 5 μm gathered to form cocoon-like particles. Furthermore, when this supported catalyst was used in a model reaction system of the Suzuki coupling reaction, it was confirmed that the reaction proceeded at a practical rate.

(Comparative Example 1)
A 300 ml separable flask equipped with a stirring motor, a reflux condenser, and a thermometer was charged with 0.65 g of palladium oxide-containing fine iron oxide particles and 128.2 g of water as catalyst components, and stirred and mixed for 10 minutes at a stirring speed of 100 rpm. . The maximum particle size of the catalyst component in this mixed solution was 3.3 μm.

  Next, 7.6 g of melamine, 14.6 g of 37% formalin, and 0.090 g of sodium sulfate were added to this mixed solution, and the pH was adjusted to 8.5 with 25% aqueous ammonia. Thereafter, a water-soluble initial condensate was produced under the same reaction conditions as in Example 1, and then this water-soluble initial condensate was polymerized. As a result, during the condensation reaction at 50 ° C. when further polymerizing the water-soluble initial condensate, the water-insoluble condensate was excessively aggregated and a supported catalyst could not be obtained.

  From the above results, by performing the dispersion step prior to the mixing step and the polymerization step, the catalyst component can be supported in the form of fine particles on the surface of the particulate water-insoluble condensate as a carrier. It can be seen that excessive aggregation of the water-insoluble condensate can be suppressed, and as a result, a supported catalyst having excellent catalytic activity can be easily produced.

Claims (6)

A method for producing a supported catalyst comprising a particulate carrier made of a resin and a catalyst component supported on the surface of the carrier,
A dispersion step of dispersing the catalyst component in an aqueous medium;
A mixing step of mixing an aqueous medium in which the catalyst component is dispersed and a water-soluble initial condensate of the resin constituting the carrier;
And a polymerization step of polymerizing the water-soluble initial condensate to form a particulate water-insoluble condensate.   The method for producing a supported catalyst according to claim 1, wherein the catalyst component is at least one selected from a metal, a metal oxide, and an organometallic compound.   The method for producing a supported catalyst according to claim 1 or 2, wherein the water-soluble precondensate comprises an amino group-containing compound and an aldehyde compound.   The water-soluble initial condensate is obtained by reacting the compound containing an amino group and the aldehyde compound under basic conditions, and the polymerization step is performed by adding an acid catalyst to the water-soluble initial condensate. The method for producing a supported catalyst according to claim 3, wherein the particulate water-insoluble condensate is precipitated by polymerizing the catalyst.   The method for producing a supported catalyst according to any one of claims 1 to 4, wherein the catalyst component is dispersed in the aqueous medium in the dispersion step using a media atomizer.   The method for producing a supported catalyst according to any one of claims 1 to 4, wherein the catalyst component is dispersed in the aqueous medium in the dispersion step by a high-pressure atomizer.