JPH078805A - Metal-containing catalyst and catalytic reactor - Google Patents

Abstract

PURPOSE:To accelerate catalytic reaction by depositing a catalytic metal on a pellet like carrier made of a porous fluororesin and tightly bonding the catalytic metal onto at least the surface part to the pellet like carrier with high percentage content through a hydrophilic high polymer. CONSTITUTION:The metal-containing catalyst is constituted by depositing the catalytic metal on the pellet like carrier made of the porous fluororesin. And the catalytic metal is bonded onto at least the surface part of the pellet like carrier through the hydrophilic high polymer. The hydrophilic high polymer is defined as a copolymer of a fluorine-containing monomer and a hydrophilic group-containing monomer. Further, the porous fluororesin is a one made of polytetrafluoroethylene. And catalytic metal is distributed in the range of 0.01-0.1mm depth. The other hand the catalytic reactor is constituted by filling the metal-containing catalyst F in a vessel 1 provided with a raw material supply opening 2 and a treated-material discharge opening 3.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a metal-containing catalyst and a catalytic reactor.

[0002]

2. Description of the Related Art A catalyst having a structure in which a porous fluororesin is used as a carrier and a catalyst metal is supported on the carrier is known (Japanese Patent Publication Nos. 57-45614 and 59-19732).
No. 60-83042, JP-A-3-27693.
No. 4). By the way, in such a catalyst, the catalyst metal is bonded to the fluororesin which is the catalyst carrier by a method such as a chemical plating method, a metal colloid attachment method, a metal salt solution impregnation method or the like. However, since the fluororesin is surface-inert and rich in water repellency and oil repellency, it is very difficult to firmly bond a large amount of catalyst metal to the resin carrier. Further, in the conventional catalyst, the catalyst metal has a structure deposited on the surface of the resin carrier, and is not distributed deep inside the carrier from the surface.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a catalyst and a catalytic reaction apparatus in which a catalytic metal is firmly bound to a pellet-shaped carrier made of a porous fluororesin at a high content. .

[0004]

The present inventors have completed the present invention as a result of intensive studies to solve the above problems. That is, according to the present invention, a catalyst carrier is supported on a pellet carrier made of a porous fluororesin, and the catalyst metal is present on at least a surface portion of the carrier pellet through a hydrophilic polymer. Provided is a metal-containing catalyst characterized by being bound. Further, according to the present invention, there is provided a catalytic reaction device in which a container having a raw material supply port and a processed product discharge port is filled with the catalyst.

The porous fluororesin used as the catalyst carrier in the present invention may be any one having continuous fine pores (through holes), and the means for forming the fine pores is not particularly limited, and stretching, expansion and foaming are possible. , Extraction, etc. are adopted. Also,
The type of fluororesin is not particularly limited, and various types can be used. The preferred fluororesin for use in the present invention is polytetrafluoroethylene, but tetrafluoroethylene / hexafluoropropylene copolymer, polyvinyl fluoride, polyvinylidene fluoride, etc. may also be used.
In the present invention, it is preferable to use porous polytetrafluoroethylene, particularly stretched porous polytetrafluoroethylene.

The porous fluororesin preferably used as a catalyst carrier in the present invention comprises a stretched product of polytetrafluoroethylene and has an average pore diameter of 50 μm or less, preferably 0.1 to 10 μm, and a porosity of 15 to 95. %, Preferably 50 to 95%. Regarding such a fluororesin, Japanese Examined Patent Publication No. 56-45773 and Japanese Examined Patent Publication 56
-17216, U.S. Pat. No. 4,187,390. The catalyst carrier has a pellet shape. The pellet-shaped carrier includes, for example, various shapes such as a cylindrical shape, a prismatic shape, a cylindrical shape, a rectangular shape, and a spherical shape. The dimensions of the carrier are usually diameter: 1-10 mm, preferably 3
~ 5 mm, length: 2-20 mm, preferably 4-10 m
It is about m.

In the carrier resin used in the present invention, a hydrophilic polymer is adhered and bound in the pores, and as the hydrophilic polymer in this case, various polymers having a hydrophilic group can be used. As the hydrophilic group, a hydroxyl group, a carboxyl group, a sulfone group, a cyano group, a pyrrolidone group,
Examples thereof include an isocyanate group, an imidazole group, a phosphoric acid group, an N-substituted amide group, an N-substituted amino group, and a sulfonamide group. Further, alkylene oxides such as ethylene oxide and propylene oxide may be added to the active hydrogens of the hydrophilic groups.

As the hydrophilic polymer, a water-soluble one can be used, but in particular, it is soluble in an organic solvent and is somewhat soluble in water or an aqueous solution, preferably substantially. It is preferable to use those which show water insolubility. Further, it is preferable that it has excellent heat resistance, alkali resistance and acid resistance.

As the hydrophilic polymer, polyvinyl alcohol, polyacrylic acid, polyacrylonitrile, polyvinyl sulfone, polyurethane, polyethylene oxide,
Various synthetic and natural polymers having hydrophilicity such as starch, carboxymethyl cellulose, ethyl cellulose, sodium alginate, gluten, collagen, and casein can be used, but especially from the viewpoint of adhesive bond to the carrier resin, fluorine-containing hydrophilicity The use of macromolecules is advantageous. Such a fluorine-containing hydrophilic polymer can be obtained by copolymerizing a fluorine-containing ethylenically unsaturated monomer and a fluorine-free hydrophilic group-containing vinyl monomer. Examples of the fluorine-containing monomer include tetrafluoroethylene, vinyl fluoride, vinylidene fluoride, monochlorotrifluoroethylene, dichlorodifluoroethylene, hexafluoropropylene and the like.

Preferred fluorine-containing monomers can be represented by the general formula: CXY = CFZ (1) In the formula, Z is a fluorine or hydrogen, X and Y are hydrogen, fluorine, chlorine and trifluoromethyl (-CF ₃₎
Chosen from among.

Further, other preferable fluorine-containing monomers can be represented by the following general formula. In the above formula, R is hydrogen, fluorine, a methyl group, an ethyl group, a trifluoromethyl group (CF ₃ ) or a pentafluoroethyl (C ₂ F ₅ ). Rf represents a perfluoroalkyl group having 4 to 21 carbon atoms.

On the other hand, as the hydrophilic group-containing monomer, vinyl monomers having various hydrophilic groups as described above and monomers obtained by addition reaction of alkylene oxides such as ethylene oxide and propylene oxide with active hydrogen of the hydrophilic groups are also preferable. is there. Also used are those which give a hydrophilic group-containing copolymer by hydrolysis after copolymerization, such as vinyl acetate.

Specific examples of hydrophilic monomers include vinyl.
Alcohol, acrylic acid, methacrylic acid, fumaric acid,
In addition to unsaturated carboxylic acids such as rain acid and itaconic acid,
Acrylic acid or methacrylic acid alkylene as shown below
An oxide adduct is mentioned. In the above formula, R is hydrogen or a methyl group, and n and m are 1
It is an integer above the above. Fluorine-containing monomer and hydrophilic group-containing model
Each of the nomers may be one kind or two or more kinds. Well
Further, the fluorine-containing monomer and the hydrophilic group-containing monomer,
If desired, other vinyl monomers, such as
Acrylic and methacrylic acid alkyl esters, trimethyl
Polyhydric alcohol such as roll propane and acrylic acid or
An ester or the like with methacrylic acid can be used in combination.

The copolymer of vinyl alcohol and a fluorine-containing monomer used as the preferred hydrophilic polymer in the present invention saponifies the copolymer of vinyl acetate and a fluorine-containing monomer, and converts the acetate group contained in the copolymer into a hydroxyl group. Can be obtained. In this case, it is not always necessary to convert all the acetate groups contained in the copolymer into hydroxyl groups, and conversion of the acetate groups into hydroxyl groups may be carried out to the extent that the copolymer has hydrophilicity.

The fluorine content of the fluorine-containing hydrophilic copolymer preferably used in the present invention is, on a weight basis,
It is usually 2% to 60%, preferably 10% to 60%, and more preferably 20% to 60%. When the fluorine content of the fluorinated hydrophilic copolymer is too high, the heat resistance is improved but the hydrophilicity of the polymer is reduced. On the other hand, if the fluorine content is too low, the adhesiveness of the fluorine-containing hydrophilic copolymer to the carrier resin becomes small and the heat resistance also becomes small. In the fluorine-containing hydrophilic copolymer preferably used in the present invention, the hydrophilic group equivalent is generally 45 to 700, preferably 60 to 500, more preferably 60 to 450. When the hydrophilic group equivalent is less than 45, the solubility of the fluorinated hydrophilic copolymer becomes very large, and the copolymer is easily eluted from the carrier resin by water, while when the hydrophilic group equivalent is larger than 700, the hydrophilicity becomes small. As a result, the carrier resin cannot be made hydrophilic.

Tables 1 and 2 show some copolymers in terms of mol% of fluorine-containing monomer units in the copolymer, fluorine weight% (F-wt%) and hydrophilic group equivalent (Eq).
-W) is shown. VOH is vinyl alcohol.

The hydrophilic group equivalent (Eq
-W) is the molecular weight of the copolymer divided by the number of hydrophilic groups. The hydrophilic group equivalent shown below is calculated by the following formula. In the formula, A · x is a value obtained by multiplying the molecular weight of the fluorine-containing monomer by its mole number x, while B · y is a value obtained by multiplying the molecular weight of the hydrophilic group-containing monomer by its mole number y.

[0017]

[Table 1] Copolymer Copolymer molar ratio Fluorine-containing monomer F-wt% Eq-W mol% (CF ₂ = CF ₂ ) x / (VOH) y X = 1, Y = 40 2.4 4.2 45.5 1, 30 3.2 5.5 46.4 1, 20 4.8 7.9 48.0 1, 10 9.1 14.3 53 1, 4 20 27.5 68 1, 1 50 53.1 143 10, 1 91 72.8 1043 (CF ₂ = CFH) x / (VOH) y X = 1, Y = 40 2.4 2.1 44.6 1, 30 3.2 2.8 45.2 1, 20 4.8 4.1 46.2 1, 10 9.1 7.5 49 1, 4 20 − − 1, 1 50 33.6 107 10, 1 91 55.6 683 (CFH = CH ₂ ) x / (VOH) y X = 1, Y = 40 2.4 1.1 44.2 1, 30 3.2 1.4 45.6 1, 20 4.8 2.1 45.3 1, 10 9.1 4.0 47.6 1, 4 20 − − 1, 1 50 21.3 89 10, 1 91 37.8 503

[0018]

[Table 2] Copolymer Copolymer molar ratio in the copolymer Fluorine-containing monomer F-wt% Eq-W mol% (CF ₂ = CFCl) x / (VOH) y X = 1, Y = 40 2.4 3.1 46.0 1 , 30 3.2 4.0 46.9 1, 20 4.8 5.8 48.9 1, 10 9.1 10.4 54.6 1, 4 20 − − 1, 1 50 35.8 159 10, 1 91 47.2 1208 (CF ₂ = CCl ₂ ) x / (VOH) y X = 1, Y = 40 2.4 2.0 46.6 1, 30 3.2 2.7 47.7 1, 20 4.8 3.8 50.0 1, 10 9.1 6.7 57 1, 4 20 − − 1, 1 50 20.8 183 10, 1 91 26.3 1442 (CF ₂ = CFCF ₃ ) x / (VOH) y X = 1, Y = 40 2.4 6.1 46.8 1, 30 3.2 7.9 48.0 1, 20 4.8 11.3 50.5 1, 10 9.1 19.6 58 1, 4 20 − − 1, 1 50 59.0 193 10, 1 91 73.9 1543

In order to adhere and bond the hydrophilic polymer to the inner surface of the pores of the carrier resin, for example, the fluorine-containing hydrophilic copolymer is dissolved in an organic solvent such as alcohol, ketone, ester, amide or hydrocarbon. The carrier resin is immersed in the solution, or the solution is impregnated into the carrier resin by a coating method using a spray or a roller, and then dried. The hydrophilic polymer that is adhered and bonded to the carrier resin does not necessarily have to be the entire carrier resin, and may have a depth of about 0.01 to 0.1 mm from the surface of the carrier resin, for example, the surface of the carrier resin. . In this way, the hydrophilic polymer adheres to the inner surface, and the hydrophilic carrier resin that allows water to penetrate into the fine pores is obtained. The amount of the hydrophilic polymer attached to the carrier resin may be an amount sufficient to increase the hydrophilicity of the carrier resin and varies depending on the porosity of the carrier resin used, etc. It is 1.5 to 10% by weight, preferably 2 to 6% by weight, based on the weight of the carrier resin.

The hydrophilic carrier resin is impregnated with a solution of a fluorine-containing monomer and a copolymer of a hydrophobic monomer such as vinyl acetate that can be converted into a hydrophilic group in an organic solvent, dried, and then the acetate thereof. It can also be produced by converting at least a part of the groups into hydrophilic groups.

The hydrophilic carrier resin obtained as described above has a structure in which the hydrophilic polymer is bonded to the inner surfaces of the pores in the form of a film or particles. This allows water and various aqueous solutions to enter the pores. Elution of the polymer itself from the carrier resin can be prevented by defining the hydrophilic group equivalent of the hydrophilic polymer in an appropriate range and controlling the solubility of the polymer in water. The adhesive bond strength of the fluorinated hydrophilic copolymer to the carrier resin is stronger than that of other hydrophilic polymers due to the action of the fluorine atom in the copolymer, and its durability is stable for a long period of time. Maintained over.

In the catalyst of the present invention, the catalyst metal is bonded to the supporting resin having the hydrophilic polymer adhered and bonded to the inner surfaces of the pores obtained as described above through the hydrophilic polymer.
As the method of binding the catalytic metal, a conventionally known catalytic metal supporting method such as a chemical plating method, a method of impregnating with a metal colloid solution and then drying, a method of impregnating with a metal solution and then drying can be adopted. Since the inner surface of the pores of the catalyst carrier of the present invention is hydrophilic, a conventionally known method can be easily adopted. The metal is preferably bound to the catalyst carrier of the present invention by a chemical plating method, and this method will be described in detail below.

In order to bond the metal to the carrier resin to which the hydrophilic polymer is adhered and bonded by the chemical plating method, the carrier resin is subjected to a pretreatment for chemical plating and then a chemical plating treatment. Each step of these pretreatment and chemical plating treatment may be performed according to a conventionally known method. That is, in the pretreatment step, a noble metal serving as a catalyst for chemical plating is attached to the inner surface of the pores of the carrier resin. As the noble metal, palladium, platinum, gold or the like is used, but palladium is preferable. As a method of depositing the noble metal, for example, a method of immersing the carrier resin in an aqueous solution of tin (II) chloride, rinsing with water, immersing in a palladium chloride aqueous solution, and then rinsing with water can be adopted. Such pretreatment for chemical plating is a well known technique.

Next, the carrier resin preliminarily treated for chemical plating as described above is immersed in a chemical plating solution for chemical plating treatment. The chemical plating solution generally contains a metal, a reducing agent, a complexing agent, a buffer, a stabilizer and the like. In this case, as the reducing agent, sodium hypophosphite, sodium borohydride, aminoborane, formalin, hydrazine and the like are adopted, and as the complexing agent and the buffer, formic acid, acetic acid, succinic acid, citric acid, tartaric acid. , Malic acid, glycine, ethylenediamine, EDTA, triethanolamine, sodium / potassium tartrate, etc. are adopted.

The metal for plating acts as a catalyst metal, and various kinds of metals described later can be mentioned as such a metal. Preferred metal for plating is, for example, gold,
Various metals such as silver, platinum, rhodium, nickel, cobalt, tungsten, copper, zinc and iron, and alloys thereof can be mentioned. When the alloy is bonded to the carrier resin, a metal salt having a component composition corresponding to the desired alloy may be used as the metal salt added to the plating solution. In order to bond platinum or gold, their alloys, or other metals that are difficult to bond by chemical plating to the carrier resin, the carrier resin can be easily chemically plated with cobalt, nickel, copper, or the like. It is preferable to preliminarily bond metals that can be bonded and then subject the carrier resin to chemical plating or electroplating.

When platinum or an alloy containing platinum is bonded to the carrier resin by chemical plating, chemical plating can be easily carried out by using hydrazine hydrochloride as a reducing agent. When hydrazine hydrochloride is used as the reducing agent, a platinum alloy, for example, a metal such as platinum-iridium or platinum-rhodium can be easily bonded. The typical composition of the chemical plating solution containing platinum ions is as follows. Chloroplatinic acid: 3 × 1/10 ^{3 to} 7 × 1/10 ³ mol /
l Hydrazine hydrochloride: 0.1 to 0.3 mol / l pH: 3 to 4 Temperature: 30 ° C to 40 ° C

As the chemical plating method used in the present invention, a composite plating method can be adopted. This composite plating method is a method of adhering a metal containing fine powders such as metal oxides, nitrides, and carbides, and a plating solution in which the fine powders are uniformly dispersed is used.

As the catalyst metal, various conventionally known metals are used, and transition metals are generally used. Examples of such catalytic metals include Cu, Ag, Zn and C.
d, In, Ti, Zr, Sn, Sb, Bi, V, Nb,
Cr, Mo, W, Mn, Re, Fe, Co, Ni, R
Various metals such as u, Rh, Pd, Os, Ir and Pt can be used. These metals or alloys thereof can be bonded to the carrier resin by a metal supporting method such as the chemical plating method described above. Further, the catalyst metal can be in a metallic state, and can be in the form of various compounds such as oxides and sulfides. The catalytic metal in compound form is
It can be obtained by reacting the metal bound to the carrier resin with a gaseous or liquid reactant corresponding to the desired compound form. The supported amount of the catalyst metal is 0.005 to 5 wt%, preferably 0.1 to 1 wt%, based on the total amount of the catalyst, in terms of metal. The catalyst metal is at least the surface portion of the carrier resin, preferably 0.01 to 0.1 from the surface.
It is preferable to distribute in the depth range up to mm. When the catalyst metal is present only on the surface of the carrier resin, the catalyst metal is easily desorbed from the surface of the carrier resin. On the other hand, when the catalyst metal is present too deeply from the surface of the carrier resin, the catalytic activity is not particularly improved. The average pore diameter of the catalyst is 0.01 to 10 μm,
The porosity of the catalyst can range from 10 to 95%.

The metal-containing catalyst of the present invention is usually packed and used in a fixed bed type reactor. For example, by filling the catalyst of the present invention in a container having a raw material supply port and a processed product discharge port, a catalytic reaction device having a simple structure can be obtained. Further, by filling the catalyst in the porous container, a catalytic reaction device having a simple structure can be obtained. In the case of such an apparatus, the catalytic reaction can be carried out by immersing the apparatus in the liquid to be treated, allowing the liquid to be treated to permeate the inside of the porous container wall, and contact with the catalyst. The material of the reaction vessel is preferably made of a fluororesin, a plastic whose surface is coated with a fluororesin, a metal, or a material having corrosion resistance such as ceramics or stainless steel. The catalyst and the catalytic reaction device of the present invention can be applied to various catalytic reactions, particularly in water,
Advantageously applied to catalytic reaction in a mixture of water and organic solvent in hydrophilic organic solvent, catalytic reaction in steam / water system, catalytic reaction in steam, catalytic reaction in gas, etc. .

[0030]

EXAMPLES Next, the present invention will be described in more detail by way of examples. The characteristics relating to the carrier resin were determined as follows. (1) Porosity The porosity of the carrier resin before the hydrophilic polymer was adhered and bonded was obtained by measuring its density. The density of the carrier resin (polyteftrafluoroethylene) is 2.2 g / cm ³ . The porosity was calculated using the following formula. Porosity = (2.2−Sample Density) ÷ 2.2 × 100 In the calculation of the porosity of the carrier resin after the hydrophilic polymer was adhered and bonded, the density was changed to 2.2 g / cm ³ . 2.1 g / cm ³ was adopted. (2) Heat resistance The heat resistance is determined by placing the carrier resin in an air oven controlled at a test temperature for a predetermined time and then measuring the hydrophilicity according to the following. (3) Acid resistance, alkali resistance, and solvent resistance The hydrophilicity of the carrier resin after being immersed in a liquid and dried is measured according to the following. (4) Hydrophilicity The initial hydrophilicity is determined by dropping water droplets from a height of 5 cm on the surface of the carrier resin and measuring the time taken until the water droplets are absorbed. The hydrophilicity is evaluated as follows. A: Absorbed within 1 second B: Absorbed naturally C: Absorbed only by pressurizing D: Not absorbed but contact angle decreased E: Not absorbed That is, it repels water. This E rating is unique to porous fluororesins.

Reference Example 1 Tetrafluoroethylene / vinyl alcohol copolymer (saponification compound of tetrafluoroethylene / vinyl alcohol copolymer; saponification degree 100%; fluorine content 27% by weight; hydroxyl group content 14.5 mmol / g) Was dissolved in 1 liter of methanol to prepare a 0.2 wt% methanol solution. Cylindrical pellets (diameter: 3) made of porous fluororesin (polytetrafluoroethylene) with a porosity of 80%
mm, length: 5 mm) was immersed in the above methanol solution for impregnation, and then dried at 50 ° C. for 5 minutes. The same process was repeated 5 times to obtain hydrophilic porous resin pellets whose hydrophilicity was evaluated as A. This product has a porosity of 70% and a pore diameter of 0.
It was 2 μm. At the heat resistance temperature of 120 ° C., this good hydrophilicity was maintained after 24 hours, but at 135 ° C., the hydrophilicity was lost.

When the pellets were immersed in water, the substance did not dissolve in water (no elution of the copolymer). No change was observed when immersed in boiling water. The above pellets are 12N hydrochloric acid (room temperature) or 1
Shows high acid resistance against acids such as normal hydrochloric acid (80 ° C),
It also showed high alkali resistance against alkali such as 5N sodium hydroxide (room temperature) and 1N sodium hydroxide (80 ° C).

Reference Example 2 Tetrafluoroethylene / vinyl acetate copolymer was dissolved in methyl ethyl ketone to prepare a 0.3 wt% solution.
The resin pellets shown in Reference Example 1 were impregnated with the above solution and then dried at 60 ° C. for 5 minutes. The same process was repeated 5 times. The obtained pellets were immersed in ethanol containing sodium methoxide and heat-treated for 30 minutes for saponification, and then the saponified hydrophilic pellets were washed with water. The pellets showed similar properties to the pellets of Example 1.

Reference Comparative Example 1 The pellets shown in Example 1 were treated with 5% by weight of isopropanol (FC-93 manufactured by 3M Co.) as a surfactant to prepare 20 pellets.
Impregnation for a minute and then drying at room temperature gave hydrophilic pellets. The stability of this pellet was poor, and its hydrophilicity was lost only by immersing the pellet in water.

(Heat resistance) The hydrophilic pellets obtained in Reference Example 1 were heat-treated at the following temperature and time and then subjected to a hydrophilicity test. The following results were obtained. Temperature Time Hydrophilicity test result 100 ° C. 30 hours A 120 ° C. 5 hours B (absorption after 60 seconds) 120 ° C. 24 hours B (absorption after 60 seconds) 120 ° C. 48 hours B (absorption after 120 seconds) 120 ° C. 2 hours C or D 150 ° C 24 hours D 200 ° C 1 hour D

(Oxidation resistance) The hydrophilic pellets obtained in Reference Example 1 were immersed in the oxidizing conditions shown below for the times shown below, and then subjected to a hydrophilicity test to obtain the following results. Oxidizer temperature time hydrophilicity test result 1N hydrochloric acid 80 ° C 2 hours A 3N nitric acid room temperature 350 hours A 12N nitric acid room temperature 1 hour A

(Alkali resistance) The hydrophilic pellets obtained in Reference Example 1 were immersed under the alkaline conditions shown below for the times shown below, and then subjected to a hydrophilicity test. The following results were obtained. Alkali temperature Time hydrophilicity test result 1N sodium hydroxide 80 ° C 1 hour A 1N sodium hydroxide 80 ° C 5 hours D 6N sodium hydroxide room temperature 36 hours A

Example 1 Porous fluororesin pellets (polytetrafluoroethylene pellets, diameter 3 mm, length: 5 mm) having a porosity of 80% and an average pore diameter of 0.2 μm were immersed in acetone for 5 minutes for degreasing and washing. To do. Tetrafluoroethylene / vinyl alcohol copolymer (saponified tetrafluoroethylene / vinyl acetate copolymer, saponification degree: 100%, fluorine content: 27% by weight, hydroxyl group content: 14.5 mmol /
2 g of g) was dissolved in 1 liter of methyl alcohol, and this solution was impregnated into the above degreased and washed pellets, and the temperature was raised to 60 °
It was dried for 5 minutes and then immersed in water. The pellet is immersed in an aqueous solution of tin (II) chloride SnCl ₄ acidified with hydrochloric acid for 2 minutes at room temperature to adsorb Sn (II) ions on the surface and washed with water. Next, the pellet is immersed in an acidic aqueous solution of palladium chloride PdCl ₅ for 2 minutes at room temperature to deposit a trace amount of palladium on the surface and wash with water. Then, the pellet was nickel-plated by immersing it in an inorganic electrolytic nickel plating bath (Ni-201, manufactured by Kojundo Chemical Laboratory Co., Ltd.) kept at 80 ° C. for 1 minute. The nickel content in this pellet was 1.0 wt%.

Example 2 The pellet shown in Example 1 is immersed in acetone for 5 minutes to be degreased and washed. Tetrafluoroethylene / vinyl alcohol copolymer (saponified tetrafluoroethylene / vinyl acetate copolymer, saponification degree: 100%, fluorine content:
27% by weight, hydroxyl group content 14.5 mmol / g) 2
g was dissolved in 1 liter of methyl alcohol, this solution was impregnated into the above degreased and washed pellets, dried at 80 ° C. for 5 minutes, and then immersed in water. The pellets were immersed in an aqueous solution of tin (II) chloride SnCl ₄ acidified with hydrochloric acid at room temperature for 2 hours.
Immerse for a minute to adsorb Sn (II) ions on the surface and wash with water. Next, this pellet is immersed in an acidic aqueous solution of palladium chloride PdCl ₄ for 2 minutes at room temperature to deposit a trace amount of palladium on the surface and wash with water. The pellets were placed at 40 ° C. in a plating solution prepared by adding 0.26 g of chloroplatinic acid hexahydrate to 100 ml of an aqueous solution containing 0.9 g of hydrazine hydrochloride.
It was soaked for 120 minutes for platinum plating. The platinum content in this pellet was 0.5 wt%.

Example 3 The nickel-plated pellets obtained in Example 1 were
It was immersed in an electroless gold plating bath (K-24N, manufactured by Kojundo Chemical Laboratory Co., Ltd.) kept at 85 ° C. for 30 minutes for gold plating.
The gold content in this pellet was 0.1 wt%,
The nickel content was 0.1 wt%.

Next, the heat resistance, alkali resistance and acid resistance of the platinum-plated pellets obtained in Example 2 were evaluated as follows. (Heat resistance) No change was observed in plating adhesion strength and pellets even after heating at 260 ° C for 5 hours. (Alkali resistance) 80 ℃ in 1N sodium hydroxide, 1
Even after heating for 2 hours, no change was observed in plating adhesion strength and pellets. (Acid resistance) No change was observed in the plating adhesion strength and pellets even when kept in 12N nitric acid at room temperature for 12 hours.

Example 4 A catalytic cracking reaction of ammonia contained in water was carried out using the catalyst device shown in FIG. The catalytic reactor shown in FIG. 1 is made of polytetrafluoroethylene, and the container body 1
And a raw material supply pipe 2 attached thereto and a treated product discharge pipe 3, and the inside of the container was filled with the platinum-plated pellets F obtained in Example 2 in a net bag. An aqueous solution containing 10 wt% of ammonia was introduced into this catalytic reactor in the state of a gas / liquid mixture heated to 200 ° C. via line 4, and the treated product was discharged via line 5. The reaction conditions in this case are as follows. (1) Reaction temperature: 200 ° C. (2) Reaction pressure: 1.5 kg / cm ² G (3) Reaction time: 10 minutes When ammonia in the aqueous solution was decomposed as described above, treatment at the 48th hour The ammonia concentration in the liquid is 0.
It was 001 wt%.

[0043]

The catalyst of the present invention has a structure in which a large amount of catalytic metal is firmly attached and bonded to at least the surface portion of a porous fluororesin carrier through a hydrophilic polymer, and the inside of the pores is It has hydrophilicity. Therefore, by using the catalyst of the present invention, the catalytic reaction of the reaction components contained in water, the hydrophilic organic solvent, or the vapor of these liquids can smoothly proceed. Moreover, the catalyst of the present invention is
It has excellent alkali resistance and acid resistance, and its catalyst life is long.

[Brief description of drawings]

FIG. 1 shows a structural diagram of a catalytic reactor.

[Explanation of symbols]

 1 Container body 2 Raw material supply pipe 3 Treated product discharge pipe F Catalyst

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Koichi Okino 1-42-5-5 Akakutsumi, Setagaya-ku, Tokyo Inside Japan Gopantex Co., Ltd.

Claims (5)

[Claims] 1. A pellet-shaped carrier made of a porous fluororesin carrying a catalyst metal, wherein the catalyst metal is bound to at least the surface of the pellet-shaped carrier through a hydrophilic polymer. A metal-containing catalyst characterized by being present. 2. The catalyst according to claim 1, wherein the hydrophilic polymer is a copolymer of a fluorine-containing monomer and a hydrophilic group-containing monomer. 3. The catalyst according to claim 1, wherein the porous fluororesin comprises polytetrafluoroethylene. 4. The catalyst metal is 0.01 to 0.01% from the surface of the carrier.
Distributing in a depth range of up to 0.1 mm.
The catalyst of any one of 3. 5. A catalytic reaction apparatus comprising a container having a raw material supply port and a processed product discharge port, filled with the catalyst according to any one of claims 1 to 4.