JPS6161644A - Preparation of porous and highly dispersed metallic catalyst using silica as carrier - Google Patents

Abstract

PURPOSE:To disperse uniformly and highly catalystic metals and to enhance the porosity of the catalyst by mixing alkoxysilane and the metallic salt to be deposited in a soln. of a polar compd. having multidentate or cross-linking ligand formability to obtain a homogeneous soln., and hydrolyzing the soln. CONSTITUTION:Alkoxysilane, a catalytic metallic salt, and a polar compd. are uniformly mixed, and warmed at 10-75 deg.C at which the catalytic metallic salt is not precipitated. At this time, 1-10mole polar compd. is added to 1mole alkoxysilane. The mixed soln. is hydrolyzed under heating, and the formed gelatinous or agar-like gel is crushed in appropriate size. The gel is dried under reduced pressure for 10-30hr at 80-110 deg.C at which the combined polar compd. contained in the gel is not substantially volatilized. Then the polar compd. remaining in the gel is scattered by heat treatment to complete the porous and highly dispersed catalyst using silica as the carrier.

Description

Detailed Description of the Invention The present invention involves chemically mixing an alkoxysilane and a supported metal salt to form a homogeneous solution in a solution of a polar compound having polydentate or bridging coordination ability, and then forming a homogeneous sol by hydrolysis. It is characterized by utilizing the gelation process of solidifying into agar or jelly and the cross-linking coordination ability of a polar compound to uniformly and highly disperse the supported metal, and by utilizing the cross-linking coordination ability to make the catalyst porous. The present invention relates to a method for preparing a supported metal catalyst.

For metal catalysts, metal-supported catalysts in which the catalytic active component is supported on a carrier are usually used for reactions in order to increase the thermal stability and efficiency of the catalyst and to prevent deterioration due to melting, but the reaction proceeds on the surface of the metal particles. Therefore, if the surface area of the catalytic gold particles (4+7) is increased, the catalytic activity will be increased.

In order to increase the surface area, it is sufficient to produce a catalyst supporting fine gold particles with a smaller particle diameter, that is, a catalyst with a high dispersion coefficient. Such catalysts have high activity per unit metal weight and are resource-saving, and are extremely economical, especially for noble metal catalysts.

The most commonly used methods for preparing supported catalysts are impregnation and coprecipitation. The impregnation method is a method of making a supported catalyst by immersing a carrier in a solution containing a supported metal salt, adsorbing the dissolved gold/acid, and then drying it. Although this is a simple method, dAe distribution tends to occur during adsorption and drying depending on the supported silicon, and it is not necessarily recommended as a method for preparing a homogeneous and highly dispersed supported catalyst. The coprecipitation method is a method for producing a catalyst by simultaneously precipitating a carrier and a supported metal salt. This method is said to be easier to obtain a uniform texture than the impregnation method, but it has the disadvantage that t, type 4, which is heavily used in F to generate precipitate 11Q, is incorporated as an impurity during precipitate+C precipitation.

In addition, since the precipitation of the precipitate often occurs as minute nuclei, the concentration distribution of the supported gold Fli 4 tends to occur during the growth of the precipitate, making it impossible to obtain a satisfactory homogeneous and highly dispersed supported metal catalyst. Hateful. Furthermore, in both the impregnation method and the coprecipitation method, it is difficult to make the catalyst porous during catalyst preparation.

In recent years, impregnation method and new catalyst (different from coprecipitation method! 11)
As W m, a method of dissolving and mixing a carrier metal alkoxide and a carrier metal salt in ethylene glycol, heating and then hydrolyzing the mixture is described in Catalyst Vol. 24, p. 58 (1982) and Vol. 25, 3.
11 N (1983). This method is said to produce relatively uniform silica-supported disokel, cobalt and rhodium catalysts and titania-supported nickel catalysts, but due to the high temperature during molding, it has various drawbacks and drawbacks as shown below. There are differences with the invention. That is, in this method, ethylene glycol turns into dialkyl chloride (Catalyst, Vol. 25, 311β) and loses polydentate and bridging coordination ability, making it impossible to bind the silicon carrier and the supported metal, or to bind the silicon monomers. Sill.

Therefore, the supported metal moves easily during firing, resulting in a large amount of gold.
As ts particles are generated and the dispersion t(C) becomes worse, there is less ethylene glycol remaining until the heat treatment, so less ethylene glycol is scattered during the heat treatment, making it difficult to become porous.In addition, in this method, the supported metal M is (J-8i
Because it is immobilized by bonding and incorporated into the network structure of silica (Catalyst Vol. 24, 58@), even if a highly dispersed silica-supported metal catalyst is created, only a small amount of the catalytic metal appears on the silica surface, and therefore the catalyst It's great to see that metal is being used effectively. Historically, in this method, the preparation temperature is high, so the supported metal species forms insoluble matter and precipitates, and it is often not possible to obtain a homogeneously-highly dispersed catalyst.In addition, since the amount of ethylene glycol is too large relative to the alkoxysilane, the entire solution may not gel into agar-like or jelly-like form.

The present inventors conducted various studies to improve these points, and as a result, they arrived at the present invention.

The present invention produces a gel by hydrolyzing a polar compound solution containing an alkoxysilane, a catalytic metal salt, and a polar compound having multidentate coordination or crosslinking coordination ability. After drying under conditions in which the bonds contained in the gel are not substantially volatilized, a high temperature heat treatment is performed,
A method for preparing a porous highly dispersed metal catalyst is provided, which comprises scattering the bonded polar compound remaining in the gel to form pores.

In other words, the first step in preparing a homogeneous and highly dispersed catalyst is to create a homogeneous solution, so the alkoxysilane, catalyst metal salt, and polar compound are mixed uniformly and the catalyst metal salt does not precipitate. It is preferable to heat at a low temperature of 75°C or lower, preferably between 20°C and 70°C. Also,
In the case of polar compounds with diol hydroxyl groups, such as ethyl cernolp, excessive heating should be avoided in order to prevent their etherification and to prevent the formation of catalytic siloxane (8/f-0-8i) bonds. This is important, and from this perspective as well, it is appropriate to heat the temperature between 20°C and 70°C.

Etherification of the hydroxyl group causes a decrease in the coordination ability of the diol, and significantly reduces the ability of the diol to immobilize the catalyst metal and the crosslinking ability, so it is necessary to avoid etherification as much as possible, and at the same time reduce the amount of diol due to etherification. It is important to determine the amount of diol when preparing the catalyst by taking this into account. If the amount of diol for 1 liter is too large for 7 strands of alcoquine, the entire sol will not solidify during hydrolysis, and jelly or agar will form in the diol solution. The substance appears to be floating. In such a case, most of the catalyst metal salt has been dissolved in the diol, so even if the gel and diol solution are separated, it is essentially the same as the impregnation method, and a homogeneous and highly dispersed catalyst cannot be obtained. I can't get it.

~10 mol, preferably I'i 1.5-5 mol, is suitable.

Polar compounds generally have a boiling point of 10 at normal pressure.
Temperatures above 0°C are applicable.

Diols with low alkyl substituents often form insoluble complexes with certain catalyst metal salts resulting in precipitation. For example, when ethoxysila/and rhodium chloride are mixed under heating in ethylene glycol in order to prepare a silica-supported rhodium catalyst, fine precipitates occur and the solution becomes opaque, that is, becomes non-uniform. In such cases, diols that do not cause precipitation, generally highly branched diols such as pinacol and 2-°methyl-2,4-pentanediol (hexylene glycol), are used, but keto alcohols, amino alcohols, Homogeneous and porous highly dispersed silica can be produced by using polar compounds with polydentate or crosslinking coordination ability that do not cause precipitation other than diols, such as oxycarbo/acids, ketocarboxylic acids, dicarboxylic acids, and in special cases diketones. A supported metal catalyst (supported metal particle size of 2oA or less, surface area of 150 to 1000 m'/7, pore volume of 0.01 to 0.4 cm3/g) can be prepared. Therefore, it is necessary to change the polar compound or use a mixture of two or more types depending on the supported metal situation.The catalyst metal salts used in this Qing include titanium, vanadium, chromium, mankan, iron, Cobalt, nickel, fIIi1, Ill! Lead, gallium l1, germanium, arsenic, selenium, niobium, molybdenum, technetium, rhodium, palladium, silver, cadmium, indium, tin, antimony, tellurium, lanthanide, hafnium, tantalum, tungsten, rhenium, osmium,
Examples include salts of iridium, platinum, gold, water SR, thallium lead, bismuth, boronium, astatine, or actinides. These materials may be used alone or in a mixture.

The amount of catalyst metal supported in the product is generally 011 to 10
It is preferably about 0.5 to 5% by weight per liter.

Hydrolysis accelerators such as acids and alkalis may be used when preparing at low temperatures to prevent precipitation during the chemical mixing process, or when hydrolysis does not proceed quickly due to the nature of the alkoxide and requires a long time for hydrolysis. Hydrolysis can be carried out smoothly by using . The hydrolysis accelerator may be any of ordinary inorganic acids, organic acids, yH alkali absorbers, and organic bases, but the most preferred ones are organic acids with polydentate or crosslinking coordination ability (carphonic acid, ketol carbonate, certain organic bases (amines, aminoalcohols), such as formic acid, oxalic acid, tartaric acid, malonic acid, succinic acid,
Ethanolamine, propatoolamine, etc. are good.

The jelly-like or agar-like gel produced by hydrolysis is pulverized to an appropriate size, and the gel is heated under conditions such that the bound polar compounds contained in the gel are not substantially volatilized, for example, from 80°C to 110°C.
Dry at a temperature of 10 to 30 hours under reduced pressure. This drying process removes volatile water and polar compounds contained in the gel, but the polar compounds bonded to the silicon carrier and catalyst metal are not substantially volatilized and remain in the gel.

Next, a porous highly dispersed silica-supported catalyst is completed by performing a heat treatment after this drying and scattering the polar compounds. All conventional heat treatment methods can be used, and it is also possible to combine several heat treatment methods.For example, heat treatment can be performed in a hydrogen atmosphere alone, or in oxygen or air. Alternatively, after heat treatment in oxygen, air, or inert gas, further heat treatment in a hydrogen stream can be performed.

The catalyst prepared by the method described above did not show clear diffraction lines in powder X-ray diffraction, and electron microscopy confirmed that the supported metal particle size was 20λ or less and highly dispersed. Although it varies depending on the polar compound used during preparation, the surface area is 150 to 1000 i/9, the pore size is 40 A or less, and the pore volume is 0.01 to 0.
．． (l cm3/j9. It is generally extremely difficult to prepare catalysts with such high dispersion and small pore volume by impregnation methods or coprecipitation methods. Since the catalytic metal or catalytic metal bioxide is uniformly distributed in the phosphoric acid-supported catalyst, the catalytic activity is high (hydrogenation, catalytic acid, isomerism, or water utilization reaction).
This is something that can be effectively used as a starting point.

Next, the present invention will be explained in more detail by the fruit 0 and 11 rζ theory: 1
do.

Put 1g of hyosmium into a 1°200 meter beaker, add 50g of ethylene glycol, and heat at 65℃ for 30 minutes.
Dissolve completely while warming for a few minutes. Add 109I tetranidoxin run and warm at the same temperature for 3 hours. Next, by adding 19.9 water and stirring at the same temperature, the sol gradually becomes viscous, and within 1 to 2 hours after adding water, the entire solution solidifies into an agar-like gel. The gel was left at the same temperature for 1 hour, and then left at room temperature overnight. Next, crush the gel to an appropriate size and place it in a 300 ml eggplant-shaped flask.
Dry on a rotary evaporator at 100° C. under reduced pressure for 24 hours. Yield 25.8 g (5iOz total nm I)
Approximately 1.4).

The dry gel was pulverized and spread in a quartz tube at 400° in a hydrogen stream.
C for 8 hours to obtain a 2 wt% Os SiO□ catalyst. Surface area 794 m”/g, pore volume 0.1
0cmV9゜Example 2゜Pour 10ml of ethanol into a 20QmJ beaker,
To this, 0.01152 g of chloride 111 hydrate and 0.
．． 912I cobalt chloride hexahydrate was dissolved at 25°C, 5C17 ethylene gelcol was added, and the mixture was boiled at 65°C.
Add 63.3 g of tetraethquinofuran to this solution, which is heated for 0 minutes, and stirred at the same 1'KA K for 3 hours. Next, an aqueous solution of 1.0 g of tartaric acid dissolved in tt and sg of water was added, stirred at the same temperature for 50 minutes, and 1.0 g of tartaric acid was added again to 12.1. ! When the aqueous solution of No. 17 is added and stirred at the same temperature, it solidifies after about 10 minutes. Yield l: 29.2
．． 9. Heat treatment was performed in the same manner as in Experiment 111.

Example 3 10 me of ethanol is placed in a 200 m beaker, and 0.75 g of nickel chloride hydrate is stirred therein at 30°C. After adding 50y of 2,3-butadiol to this solution and warming it at 60°C for 1 hour, 63.4g of tetraethoxy7-norane was added and stirred while heating at the same temperature for 3 hours. Next, 22 parts of water is added to this solution and stirred while heating at the same temperature, resulting in gelation in about 2 hours under hydrogenation force. Yield after drying 32. ．． 1. @. The heat treatment was performed in the same manner as in the example.

Example 4 Put 80.9 ethanol in a 300ml beaker and
Then, I took a cup of palladium, a glass of 7aa, and 8 cups of palladium.
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Toshi Kasumi Industrial Director General Yotafu-gun ゛'' Geicho Ko 1 sentence ゛ Management Y7 circle Ahi danhei 1 Shiba Ore Milk ``N ξ door narrowed (Mi condolence: Kerita procedure amendment (self-motivated) 60 Kagiken No. tge February 27, 1985 3, Affiliate person o'Ai party" Patent applicant address related to the case Address: 13-1 Kasumigaseki ITr, Chiyoda-ku, Tokyo Trap "sya (nri Kogyo) Technical Director Tatsu Todoroki (Delivery date: Showa 1999, Month, Day) Details
Book 1, Title of the invention: A method for preparing a porous highly dispersed metal catalyst using silica as a carrier.

2. Claims (1) Using an alkoxysilane, a catalytic metal salt, and a polar compound having multidentate coordination ability or bridging coordination ability.
molar ratio of C and alkoxysilane polar compound l: 1 to 100 After hydrolyzing a polar compound solution containing an alkoxysilane and a catalyst metal base to gel it, A method for preparing a porous highly dispersed metal catalyst, characterized in that the bound polar compounds contained in the gel substantially scatter the bound polar compounds remaining in the gel to form pores.

(2) The catalyst metal salt is titanium, vanadium, chromium,
Manganese, iron, cobalt, nickel, copper, salivary lead, gallium, germanium, arsenic, selenium, niobium, molybdenum, technetium, rhodium, radium, silver, cadmium, inodium, tin, antimony, tellurium, lanthanoids, rhenium , tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, mercury, thallium, lead, bismuth, polonium, astatine, or an actinide salt.

(3) The polar compound is a monohydric alcohol, a dihydric alcohol,
Amino alcohols, keto alcohols, ketones, molecarboxylic acids, ketocarboxylic acids, ox7carboxylic acids, and cicarboxylic acids. 2. The method according to claim 1, wherein I ((Ii) or a mixture of two or more of the phosphoric acids.

(4) A diol whose dihydric alcohol has 14 or less carbon atoms
Claim 3 which is a mixture of species or d2fi or more
Section method.

f5) The dihydric alcohol is ethylene glycol, 1
．． 2-propanediol, 1,3-propanediol,
1,2-butanediol, 2,3-butanediol, 1
．． 3-buta/diol, 1,=1-butanediol, 1
, 2-pentanediol, 1゜4-pentanediol,
2.4-pentanediol, 1,2-hexanediol, 1.5-hexanediol, 1.6-hexanediol, 2,5-hexanediol, 2-methyl-2,4-
Pentanediol, 3-methyl-1,3-buta/diol, 2,5-dimethyl-2,5-hexanediol, Hynacol, 1,2-cyclohexanediol, 1,3-
5. The method of claim 4, wherein the mixture is a mixture of cyclohexanediol and 1°4-7 chlorohexanediol or more than 2a+.

(6) Alkoxysilane has an alkoxy group with 1 carbon number (calkoxysilane is methoxysilane, ethoxysilane,
n-propoxysilane, 1sO-propoquine silane, n
-) The method according to claim 1, wherein one or a mixture of 21 m or more of ethoxysilane, 180-phytoxysilane and 5ec-butoxysilane is used.

(8) The method according to claim 1, wherein the solution formation temperature and the hydrolysis γ temperature are from 20°C to 70°C.

(9) The molar ratio of alkoxysilane and polar compound Z is 1
Claim 3: 1.5 to 5 Detailed explanation of @Ai The present invention involves mixing an alkoxysilane and a supported gold with a salt in a solution of a polar compound having polydentate or crosslinking coordination ability. A homogeneous solution is formed, and then a gelation process is carried out in which the homogeneous sol is solidified into agar or jelly-like form by hydrolysis, and the crosslinking coordination ability of the polar compound is utilized to uniformly and highly disperse the supported metal and to make the catalyst porous. The present invention relates to a method for preparing a metal-supported catalyst characterized by the following.

Regarding metal catalysts, Shinfu I! is a metal catalyst supported on a metal catalyst that supports IJy of catalytic activity on a carrier for the purpose of increasing the thermal stability and efficiency of the catalyst and preventing deterioration due to melting. Although it is used in Li reactor cores, the reaction proceeds on the surface of the metal particles, so increasing the surface area of the catalytic metal particles will increase the catalytic activity. In order to increase the surface area, it is sufficient to make a catalyst that supports sigma particles, such as fine particles with a smaller particle size, that is, a catalyst with a high fractionation rate. The activity of such catalysts per unit amount of metal is as high as Akane (11), especially for Aogane (4).
It is the most economical catalyst.

The four most commonly used methods for preparing supported catalysts are the impregnation method and the coprecipitation method. The impregnation method is a method of preparing a supported catalyst by immersing a support in a solution in which a supported gold 4.1 salt is dissolved, allowing the dissolved metal salt to absorb, and then drying. Although this is a simple method, it is not necessarily recommended as a method for preparing a homogeneous and highly dispersed supported catalyst, as it tends to produce a strawberry distribution during adsorption and drying depending on the supporting structure. The coprecipitation method is a method for preparing a catalyst by simultaneously precipitating a carrier and a compatible metal salt. Although this method is said to be easier to obtain a homogeneous IIIJ+ medium than the impregnation method, it has the disadvantage that the salt used to generate the precipitate is incorporated as an impurity during precipitation.

However, since the precipitation of precipitates often occurs with microscopic precipitates as the core, the supported metal salt tends to undergo four-dimensional distribution during the growth of the precipitate, making it difficult to obtain a satisfactory homogeneous and highly dispersed supported metal catalyst. Rarenigui. In addition, even if the impregnation method is used or the coprecipitation method is used, 1.l! l! It is difficult to make the medium porous.

In recent years, an attractive catalyst preparation method, which is different from both the impregnation method and the coprecipitation method, has been discovered. In other words, a method of dissolving and mixing 4 [1 body Kinji salt] with the carrier Kinjo alkoxy/do in ethylene glycol, and hydrolyzing it after heating is described in Catalyst Vol. 24, p. 58 (1982) and Vol. 25, 311 Sada (1983). has been reported.

This method is said to yield relatively uniform silica-supported nickel, cobalt, and rhodium catalysts and titania-supported nickel catalysts, but due to the high temperature during preparation, there are various drawbacks and differences with the present invention as shown below. There are differences. In other words, with this method, ethylene glycol is converted to dialkyl sesolsolve! 11 (Catalyst, Vol. 25, p. 311) Since polydentate and bridging coordination abilities are lost, it becomes impossible to bind the silicon support and the supported metal, or to bind silicon molecules together.

Therefore, during firing, the supporting metals tend to move easily, producing large metal particles, resulting in poor dispersion, and since there is little ethylene glycol remaining until heat treatment, less ethylene glycol is scattered during heat treatment, making it difficult to form porosity. Also,
In this method, the supporting metals 1 to 1 are fixed and incorporated into the network structure of silica through M-0-8 bonding (Catalyst Vol. 211, p. 58). Even if a medium is formed, there is little catalytic gold (J3) appearing on the silica surface, so the catalytic metal is not used effectively. This often results in the formation of insoluble matter and precipitation, making it impossible to obtain a homogeneous and highly dispersed catalyst. In addition, because the amount of ethylene glycol is too large relative to the alkoxysilane, the entire solution may not gel into an agar-like or jelly-like state.

The present inventors conducted extensive research to improve these points, and as a result, they arrived at the present invention. The present invention uses an alkoxysilane, a catalytic metal salt, and a polar compound having multidentate coordination ability or crosslinking coordination ability, at a temperature of IO to 75'C, and at a molar ratio of alkoxysilane and polar compound of 1:1-1o. Alcogine/Ran formed under the conditions of W gold, a polar compound solution containing a salt, a trowel prepared by hydrolyzing the solution to form a gel, and the bound polar compounds contained in the gel are substantially volatilized. A method for preparing a porous polymer Vk@jj4, which is characterized by drying under harsh conditions and then subjecting it to high-temperature heat treatment to scatter the bonded polar compounds remaining in the gel to form pores. This is what we provide.

In other words, since the first step in preparing a homogeneous and highly dispersed catalyst is to prepare a homogeneous solution, it is necessary to uniformly mix the alkoxysilane, the catalyst metal salt, and the polar compound, and to precipitate the catalyst gold salt. A medium metal siloxane (M-0
-8i) In order to prevent the formation of bonds, it is important to avoid excessive heating, and from this point of view,
``Heating at C is appropriate.

The ether content of the hydroxyl group causes an extreme decrease in the coordinating ability of the diol, and significantly reduces the catalytic metal immobilization ability and crosslinking ability of the diol, so it is necessary to avoid etherification as much as possible, and at the same time, the amount of diol decreases due to etherification. In consideration of this, the geo-response will be determined when the catalyst crystal is produced. Since most of these catalyst metal salts have been dissolved into the diol,
Even if the gel and diol solution are separated, it is essentially the same as the impregnation method, and a homogeneous and highly fractionated catalyst cannot be obtained.

The amount of the polar compound and the alcoquine to be used is generally determined per 1 mole of the alcoquine to form an insoluble complex with the inertial compound 'P/I' and a certain type of solubilizing agent, resulting in a precipitate. For example, in order to prepare a silica-supported rhodium catalyst, when ethoxylate and chlorinated rhodium are mixed under heating in ethylene glycol, a slight precipitate occurs, making the solution opaque and non-uniform. come. Such a threat is caused by the use of non-precipitating diols, generally less branched diols such as pinacol and 2-methyl-2,4-diols.
1-pencunediol (hequinlenoglycol) Total I
吏') Keto alcohol, amino alcohol, oxygen/carboxylic acid, ketocarboxylic acid, carboxylic acid 7) In special cases, polar f that has polydentate or crosslinking coordination ability that does not cause precipitation of other than diols such as diketones. By using all the hybrids, a homogeneous and porous field-dispersed Norica-supported metal catalyst (supported metal particle size of 20A or less, surface area of 150 to 100
0mf/,! li, pore volume 0.01-0.・l r：
mJ/9) can be prepared. Therefore, it is necessary to change the polar compound or use a mixture of two or more kinds depending on the situation of the compatible metals.

Catalytic metal salts used in the present invention include titanium, vanadium, chromium, mankanium, cobalt, nickel, copper, scolded lead, gallium, germanium, arsenic, selenium, niobium, molybdenum, technetium, rhodium, palladium, silver, Salts of cadmium, indium, tin, antimony, tellurium, lanthanides, hafnium, lithium/tal, tungsten, rhenium, osmium, iridium, platinum, gold, mercury, thallium, lead, bismuth, polonium, astatine, or actinides may be mentioned. These substances may be used alone or in a mixture. The amount of catalyst metal supported in the product is generally 0.1 to 1O heavy soft metal,
Preferably it is about 0.05 to 5.00 cm.

In order to prevent the precipitation of precipitates during the mixing process, hydrolysis with acids or alkalis may be used, or if hydrolysis does not proceed quickly due to the nature of the alkoxide and takes a long time to complete, hydrolysis with acids or alkalis may be used. Hydrolysis can be carried out smoothly by using an accelerator. The hydrolysis accelerator may be any of ordinary inorganic acids, organic acids, inorganic alkalis, and organic bases. carboxylic acids, oxy/carboxylic acids, etc.) or organic bases (amines, aminoalcohols, etc.), such as formic acid,
Oxalic acid, tartaric acid, malonated acid, succinic acid, ethanolamine, glopanolamine, etc. are good.

The jelly-like or agar-like gel produced by hydrolysis is pulverized to an appropriate size, and the gel is heated under conditions such that the bonded polar compound contained in the gel does not substantially volatilize, for example from 80°C to 11°C.
Dry for 10 to 30 hours at a temperature of 0°C under reduced pressure. This drying process removes volatile water and polar compounds contained in the gel, completing the O'L-dispersed silica-supported catalyst, but the temperature and atmosphere for the heat treatment must be set according to the intended use of the catalyst. Good. In this case, all conventional heat treatment methods can be used, and some
It is also possible to combine treatment methods. For example, heat treatment can be carried out in a hydrogen atmosphere alone, in arsenic or air, or in air or inert gas for just one minute, followed by further heat treatment in a hydrogen stream. can.

The catalyst prepared by the method described above is powder Xf.
! Diffraction shows no clear diffraction lines, and electron microscopy confirms that the supported metal particle size is 20A or less and is highly dispersed.Although it varies depending on the polar mixture used when preparing sea bream, the surface area is 150-1000 i/g
The pore diameter is distributed below 40A, and the pore volume is 0.01~
It was 0.4 ramJ/, ji+.

It is generally extremely difficult to prepare catalysts with such high dispersion and small pore volume using impregnation methods or coprecipitation methods. In addition, in the porous/liquid-supported catalyst obtained in this way, the catalytic metal or catalytic metal oxide is uniformly distributed, so the catalytic activity is increased. Drunk,
It can be used for bamboo effects as a catalyst for isomerization or water utilization reactions.

Next, the present invention will be explained in detail by way of examples.

Example 1 Row 1 Add 1.9 osmium trichloride and 50 g of ethylene glycol to a 200 me beaker and completely dissolve while heating at 65° C. for 30 minutes. Next, 109 g of tetraethoxysilane was added and heated at the same temperature for 3 hours, and 19.9 g of water was added to the resulting homogeneous solution and as it was stirred at the same temperature, it gradually became a viscous sol. After addition 1-2
In time, the entire solution solidifies into an agar-like gel. The gel was left at the same temperature for 1 hour, and then left at room temperature overnight.

Next, the gel is crushed into a suitable size, placed in a 300 ml eggplant-shaped flask, and dried in a rotary evaporator at 100° C. under reduced pressure for 24 hours. Yield 57.39 (5i (approximately 1.8 times the weight calculated as J2). Heat treatment was performed at 400°C for 8 hours to obtain 32.5 g of 2wt% Qs-8in2 catalyst. Surface area 794 m/!?, pores Volume Q, l Or
yn2/ 9゜Example 2゜Pour 10=/ of ethanol into a 200ml beaker,
To this is added 0.065:l of cupric chloride dihydrate and Q, 91
2 g of cobalt chloride hexahydrate was dissolved at 25°C and 50
, p of ethylene glycol and heated at 65"C for 30 minutes. Add 63.3g of tetraethoxy 7 run to this solution and stir at the same temperature for 3 hours. Next, it will solidify after about 10 minutes. Yield 29.2.90 When heat treated under the same conditions as Example 1, surface area 7) Q of 2rrt/g,
1wt%Cu-1wt%Co-8iQ2 catalyst is 18,8
J was obtained.

After heating at 60°C for 1 hour, tetraethoxysilane 63.4j9 was added and stirred while heating at the same temperature for 3 hours. Next, add 22.9 of water to this solution,
When stirred while heating at the same temperature, the mixture becomes a gel in about 2 hours after addition of water. Yield after drying: 32.4.90 When the heat treatment is carried out in the same manner as in Example 1, the surface area is 537 m''
/g of 1 wt% Ni-8in2 catalyst was obtained.

Practical Mfi Example 11 50 g of ethanolamine is placed in a 300 ml beaker, and 0.5 g of rhodium trichloride is dissolved therein at 60°C. Tetraethoxysilane No. 73.8.9 is added to this solution and stirred while warming at 60°C for 2 hours.

Next, when 14p of water was added to this solution, it solidified into an agar-like state. Drying and heat treatment were carried out in the same manner as in Example 1.
1.5g was obtained.

Example 5 Put 1 Q me of ethanol in a 300 ml beaker, dissolve 1.5 g of large chloroplatinic acid, add 100.9 of 1,4-butanediol, and stir at 55°C.
After heating for 0 minutes, 63.3 g of tetraethoxysilane was added, and the mixture was stirred while heating at the same temperature for 4 hours. Next, 22 g of water is added to this solution, and when the solution is stirred while being heated at the same temperature, it becomes a gel within 2 to 3 hours after the addition of water.

When drying and heat treatment are performed in the same manner as in Example 1, the surface area is 959 @, / I, and the pore volume is IV = t 0.2 cmj.
/g of 3wt% Pt-8in□ catalyst was obtained.

Claims (9)

[Claims] (1) Using an alkoxysilane, a catalytic metal salt, and a polar compound having multidentate coordination ability or crosslinking coordination ability, at a temperature of 10 to
A polar compound solution containing an alkoxysilane and a catalyst metal salt formed under conditions of 75°C and a molar ratio of alkoxysilane and polar compound of 1:1 to 10 is hydrolyzed to form a gel, and then in the gel A porous highly dispersed metal characterized in that the gel is dried under conditions in which the bound polar compound contained therein is not substantially volatilized, and then subjected to high temperature heat treatment to scatter the bound polar compound remaining in the gel to form pores. Method for preparing catalyst. (2) The catalyst metal salt is titanium, vanadium, chromium,
Manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, arsenic, selenium, niobium, molybdenum, technetium, rhodium, palladium, silver, cadmium, indium, tin, antimony, tellurium, lanthanoids, hafnium, tantalum, tungsten, The method of claim 1, wherein the salt is rhenium, osmium, iridium, platinum, gold, mercury, thallium lead, bismuth, polonium, astatine, or actinide. (3) The polar compound is monohydric alcohol, dihydric alcohol,
2. The method of claim 1, wherein the alcohol is one or a mixture of two or more of amino alcohols, keto alcohols, diketones, monocarboxylic acids, ketocarboxylic acids, oxycarboxylic acids, and zocarboxylic acids. (4) A diol whose dihydric alcohol has 14 or less carbon atoms
4. The method of claim 3, which is a species or a mixture of two or more species. (5) The dihydric alcohol is ethylene glycol, 1,
2-propanediol, 1,3-propanediol, 1
, 2-butanediol, 2,3-butanediol, 1,
3-butanediol, 1,4-butanediol, 1,2
-pentanediol, 1,4-pentanediol, 2,
4-pentanediol, 1,2-hexanediol, 1
, 5-hexanediol, 1,6-hexanediol,
2,5-hexanediol, 2-methyl-2,4-pentanediol, 3-methyl-1,3-butanediol,
The claim is one or a mixture of two or more of 2,5-dimethyl-2,5-hexanediol, pinacol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, and 1,4-cyclohexanediol Method of Section 4. (6) Claims 1, 3, 4, or 5, wherein the alkoxysilane is one type or a mixture of two or more types of alkoxysilanes having an alkoxy group having 1 to 6 carbon atoms. Method. (7) A patent claim in which the alkoxysilane is one or a mixture of two or more of methoxysilane, ethoxysilane, n-propoxysilane, iso-propoxysilane, n-butoxysilane, iso-butoxysilane and sec-butoxysilane. The method according to any one of the ranges 1 to 5. (8) Solution formation temperature and hydrolysis temperature range from 20℃ to 7
The method according to claims 1 to 7, wherein the temperature is 0°C. (9) The molar ratio of alkoxysilane and polar compound is 1:
1.5 to 5. The method according to any one of claims 1 to 7.