JP2003103174A - Metallic particle carrier and method for producing unsaturated carbonyl compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a material useful as a catalyst for oxidation reaction. SOLUTION: A metallic particle carrier is obtained by depositing metallic particles on a carrier, and the metallic particles contain gold and copper and their average particle size is <=10 nm.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel metal particle carrier and a method for producing an unsaturated carbonyl compound.

[0002]

In the oxidation reaction of an olefin compound, the position of the carbon adjacent to the olefinic double bond is oxidized to give a corresponding unsaturated carbonyl compound (α, β-unsaturated aldehyde or α, β-unsaturated ketone). The resulting oxidation reaction is called allylic oxidation.

This allyl type oxidation reaction is useful as a method for producing an oxygen-containing compound using unsaturated hydrocarbon as a raw material.
For example, in the case of producing acrolein from propylene on an industrial scale, the allylic oxidation reaction is often used.

By the way, as catalysts used in the allyl-type oxidation reaction, copper-based catalysts such as Cu ₂ O (undiscovered in the 1930s) and Bi-Mo-based composite oxide catalysts (1950) are mainly used.
Two types (not yet discovered) are well known. The former has been partially industrialized, but has been replaced by the latter. The latter is the synthesis of acrolein from propylene,
It is used on an industrial scale for the synthesis of methacrolein from isobutylene.

On the other hand, as a method for producing an unsaturated carbonyl compound, gold and copper (Au / Cu atomic ratio of 0.25 to 4.
Method for producing an unsaturated carbonyl compound by oxygen-oxidizing an olefinic compound at a temperature of 300 to 700 ° F. using an alloy catalyst consisting of 0) (US Pat. No. 3,9,9).
89, 674) and the like have been proposed.

[0006]

However, the performance of the above alloy catalyst is still insufficient. Also, the above B
Although the i-Mo composite oxide catalyst is used for the synthesis of methacrolein from isobutylene, the selectivity is about 80 to 85%, and further improvement in performance is required.

In particular, none of the catalysts has sufficiently solved the problem of side reaction. In the allyl type oxidation reaction,
When an olefinic compound having a CH bond adjacent to an olefinic double bond and a C—H bond adjacent to another CH bond is used as a raw material, α, β, which are oxygen addition products, are used. Not only unsaturated ketones, but also dehydrogenated products α, β, γ, δ-dienes are likely to be by-produced.

In the Bi-Mo type composite oxide catalyst, dienes are mainly formed. Further, in the copper-based catalyst, α, β-unsaturated ketone is mainly used, but it is not yet satisfactory, and further improvement is required.

As described above, although it is necessary to improve the performance of the conventional material as an oxidation reaction catalyst, the present situation has not been realized yet.

Therefore, the main object of the present invention is to provide a material useful as a catalyst for an oxidation reaction.

[0011]

The present inventor has conducted extensive studies to solve the problems of the prior art, and as a result,
The inventors have found that a material supporting specific ultrafine metal particles can achieve the above object, and completed the present invention.

That is, the present invention relates to the following metal particle carrier and the method for producing an unsaturated carbonyl compound.

1. A carrier having metal particles supported on a carrier, the metal particles being particles containing gold and copper, and having an average particle diameter of 10 nm or less. .

2. An oxidation reaction catalyst comprising the metal particle-carrying member according to item 1.

3. Item 3. A method for producing an unsaturated carbonyl compound by oxidizing an olefin compound in the presence of the oxidation reaction catalyst according to Item 2.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION 1. Metal particle carrier The metal particle carrier of the present invention is a carrier in which metal particles are supported on a carrier, wherein the metal particles are particles containing gold and copper, and the average particle diameter thereof is It is characterized by being 10 nm or less.

The metal particles contain gold and copper. In particular,
It is preferable that it consists essentially of only two components, gold and copper. Further, in the present invention, it is preferable that each individual metal particle contains gold and copper. Gold and copper may partly or wholly form an alloy or an intermetallic compound as long as the effects of the present invention are not impaired.

The metal particles are present as ultrafine particles having an average particle size of 10 nm or less (preferably 6 nm or less). By defining the average particle size to be 10 nm or less, high catalytic activity can be achieved. The lower limit of the average particle size is not particularly limited, but from the viewpoint of physical stability, it is about 1 nm.
It should be about. The average particle size of the metal particles (ultrafine gold particles) in the present invention is arbitrarily selected by observing the metal particles on the carrier with a transmission electron microscope (TEM).
The arithmetic mean value of the particle size of 00 particles is shown.

As the carrier, a material used as a carrier for a conventional catalyst for synthesizing an unsaturated carbonyl compound (in particular, an allyl-type oxidation reaction) or a commercially available product can be used, and it is not particularly limited. Moreover, the thing obtained by a well-known manufacturing method can also be used. For example, metal oxides (silica, alumina, titania, zirconia, magnesia, etc.), composite metal oxides (silica-alumina, titania-silica, silica-magnesia, etc.), zeolites (ZSM-5, etc.), mesoporous silicates (MCM-). 41 etc.) and various carriers of natural minerals (clay, diatomaceous earth, pumice, etc.). Among these, metal oxides or composite metal oxides are preferable, and metal oxides or composite metal oxides containing silica are particularly preferable.

The carrier is preferably porous,
In particular, it is more preferable that the specific surface area (BET method) is usually 50 m ² / g or more, particularly 100 m ² / g or more. The shape and size of the carrier are not limited, and may be appropriately determined depending on the use of the final product.

The carrier of the present invention may contain other components as long as the effects of the present invention are not impaired. For example, alkali metal (Na, K, etc.), alkaline earth metal (Ca, M
g) may be included.

The amount of gold supported on the carrier of the present invention may be appropriately determined according to the intended use of the final product, the type of carrier, etc., but is usually about 0.01 to 20 parts by weight per 100 parts by weight of the carrier. And particularly preferably 0.1 to 10 parts by weight.

The amount of copper supported on the carrier of the present invention may be appropriately determined according to the intended use of the final product, the type of carrier, etc., but is usually about 0.01 to 20 parts by weight per 100 parts by weight of the carrier. And particularly preferably 0.1 to 10 parts by weight.

The supporting ratio of gold and copper is not particularly limited as long as it is within the above-mentioned supported amounts, but usually the atomic ratio of gold: copper is about 1: 0.02 to 50, preferably 1 :. 0.
1 to 10, most preferably 1: 0.2 to 5. By setting the amount within this range, it is possible to obtain a more excellent catalytic activity. 2. Method for producing metal particle carrier The method for producing the carrier of the present invention is not limited as long as the above carrier can be obtained. For example, it can be obtained by heat-treating a carrier containing at least one of gold and its compound and at least one of copper and its compound. Gold compounds or copper compounds are all hydroxides, chlorides, carboxylates, nitrates, alkoxides,
It may be any of acetylacetonate salts and the like.

The order of supporting gold and copper on the carrier is not limited, either may be first, or may be simultaneous. That is, the following production method (A)
Either method of (C) can be adopted.

That is, after (A) copper is supported on a carrier,
A method of supporting gold, (B) a method of supporting gold on a carrier and then supporting copper, and (C) a method of simultaneously supporting gold and copper on a carrier can be applied. Hereinafter, each method will be described.

Manufacturing Method (A) The above method (A) is a method of supporting copper on a carrier and then supporting gold. First, a copper carrier on which copper is supported is manufactured.

The method of supporting copper is not limited and can be carried out according to a conventional method. For example, an impregnation method, an ion exchange method, a vapor deposition method, etc. may be mentioned. Of these, the impregnation method can be preferably used. For example, copper can be favorably supported by preparing a mixture of a solution in which a compound containing copper is dissolved and a carrier, and then heat treating the solid content recovered from the mixture.

The compound containing copper is not particularly limited, but examples thereof include inorganic compounds such as nitrates, sulfates, hydroxides and chlorides, and organic compounds such as formates, acetates, acetylacetonates and alkoxides. be able to. More specifically, copper acetate, copper nitrate, etc. can be mentioned.

The solution containing the compound containing copper can be prepared by using a combination of the compound containing copper and the solvent in which it is dissolved. The solvent is not particularly limited,
Water, an organic solvent or the like can be used. The organic solvent is, for example, alcohol. Examples thereof include ketones, aromatic hydrocarbons, carboxylic acid esters, nitriles and the like. In particular, it is preferable to use at least one of water and alcohol (particularly methanol and ethanol). Therefore, it is preferable that the above-mentioned combination uses the above-mentioned compounds soluble in water or alcohol.

The copper concentration of the solution in which the compound containing copper is dissolved can be appropriately determined according to the kind of the above compound, the kind of the solvent, etc., but it is usually about 0.01 to 10 mmol / L.

Next, the above solution and the carrier are mixed. The mixing ratio of the carrier and the solution in which the compound containing copper is dissolved can be appropriately determined depending on the concentration of the solution, the desired amount of gold or copper supported, and the like.

After preparing a mixture of the carrier and a solution in which a compound containing copper is dissolved, the solid content is recovered from the mixture. The method for collecting the solid content is not limited, but, for example, a copper compound may be supported on the carrier. For example, it is preferable to remove the solvent by using an evaporator or the like.

Then, the solid content is baked. The firing temperature varies depending on the kind of the compound containing copper, etc., but is generally about 150 to 800 ° C., preferably 200 to 700.
C., more preferably 250 to 600.degree. The firing atmosphere may be in air (atmosphere) or an oxidizing atmosphere, or may be in an atmosphere of an inert gas such as nitrogen, argon gas, or helium, or in a reducing atmosphere such as hydrogen gas or carbon monoxide. . Moreover, the firing time may be appropriately determined depending on the firing temperature, the size of the solid content, and the like.

Subsequently, gold is carried on the copper carrier. The method of supporting gold is not limited, and for example, a precipitation-precipitation method, an impregnation method, a vapor deposition method or the like can be adopted. In the present invention, a precipitation-precipitation method or the like is preferable.

When the precipitation-precipitation method is used, for example, the above-mentioned carrier is allowed to coexist in an aqueous solution containing a gold compound, the gold-containing precipitate is precipitated and deposited on the surface of the carrier, and then the carrier on which the gold-containing precipitate is precipitated is deposited. Gold can be supported by firing the body. When the gold-containing precipitate is deposited on the surface of the carrier, various conditions such as the gold concentration, temperature, and pH of the aqueous solution may be appropriately controlled. Further, the support on which the gold-containing precipitate is deposited may be washed with water, dried, etc. prior to firing, if necessary.

The gold compound is not particularly limited as long as it is water-soluble. For example, tetrachloroauric (III) acid “H [Au
Cl ₄ ] ”, sodium tetrachloroaurate (III)“ Na
[AuCl ₄ ] ”, potassium dicyanogold (I)“ K [A
u (CN) ₂ ] ”, diethylamine gold (III) trichloride“ (C ₂ H ₅ ) ₂ NH [AuCl ₃ ] ”and other complexes; and gold compounds such as gold (I) cyanide. At least one of these compounds can be used.

The gold concentration of the above-mentioned aqueous solution varies depending on the kind of compound used and the like, but is usually 0.1 to 100 mmol.
It may be about / L. Further, the pH of the above-mentioned aqueous solution may be set usually within the range of about 5 to 10, preferably within the range of 6 to 9. The pH can be adjusted with alkali such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and ammonia. If necessary, an acid such as hydrochloric acid can be used. If necessary, these alkalis or acids may be used in the form of an aqueous solution.

If necessary, a surfactant can be added to the above aqueous solution. The surfactant may be appropriately selected from known ones or commercially available ones according to the aqueous solution.
For example, anionic surfactants such as long-chain alkyl sulfonic acids and salts thereof, long-chain alkylbenzene sulfonic acids and salts thereof, long-chain alkyl carboxylic acids and salts thereof, aryl carboxylic acids and salts thereof; long-chain alkyl quaternary ammonium salts And the like; cationic surfactants such as; nonionic surfactants such as polyalkylene glycol and polyoxyethylene nonylphenol; and the like. At least one of these surfactants can be used. In the present invention, anionic surfactants and nonionic surfactants are preferable, and anionic surfactants are particularly preferable. Among the anionic surfactants, among others, a long-chain alkylsulfonic acid having 8 or more carbon atoms and its salt, a long-chain alkylbenzenesulfonic acid having 8 or more carbon atoms and its salt, a long-chain alkylcarboxylic acid having 8 or more carbon atoms and its Salts, arylcarboxylic acids and salts thereof are more preferable.

The amount of the surfactant used can be appropriately determined depending on the desired dispersibility, the type of the surfactant used, etc., but the concentration of the surfactant is usually 0.1 to 10 mmol.
It may be about / L.

The copper carrier mixed with the above aqueous solution may be used in any form such as a granular form or a granulated form. The amount of the carrier used may be appropriately set according to the concentration of the aqueous solution and the like. When mixing the aqueous solution and the carrier, the aqueous solution may be heated if necessary. The temperature in this case may be usually about 10 to 100 ° C. The mixing time of the aqueous solution and the support can be changed depending on the type of the carrier, the constituent elements, etc., but usually about 1 minute to 24 hours,
Preferably, it is set within a range of 10 minutes to 3 hours so that the gold-containing precipitate is supported on the carrier as much as possible. The amount of the carrier to be used may be set appropriately so that the amount of the carrier may be a predetermined amount.

After mixing and stirring the aqueous solution and the carrier, the solid content is recovered. The solid content can be collected by collecting the supernatant or by a known solid-liquid separation method. The collected solid content is preferably washed with deionized water or the like until the residual ions are substantially eliminated.

Next, heat treatment of the solid content is performed. If necessary, prior to the heat treatment, it may be heated to a predetermined temperature and dried. The drying temperature may usually be less than 150 ° C. The heat treatment temperature may be a temperature at which each metal particle obtained is composed of gold and copper. That is, the heat treatment may be performed so that when the finally obtained metal particle-supported body is used as a catalyst, the catalytic activity due to the composite of gold and copper is exhibited. The heat treatment temperature is usually about 50 to 800 ° C, preferably 100 to 600 ° C, more preferably 15
The temperature may be 0 to 500 ° C. The heat treatment atmosphere is not particularly limited, and may be a reducing atmosphere, an oxidizing atmosphere, an inert atmosphere, or the like. In order to create a reducing atmosphere, for example, in addition to reducing gas such as hydrogen, carbon monoxide, alcohol,
A mixed gas obtained by diluting these reducing gases with an inert gas such as nitrogen, helium or argon may be used. Also,
A gas containing oxygen, air, or the like may be used to form an oxidizing atmosphere. To create an inert atmosphere, an inert gas such as nitrogen, helium or argon may be used. Further, after the heat treatment is performed in the oxidizing atmosphere, the heat treatment can be further performed in the reducing atmosphere. The heat treatment time can be appropriately changed depending on the temperature of the heat treatment and the like, but it is usually about 10 minutes to 24 hours. By such heat treatment, it is possible to obtain a predetermined gold carrier in which gold is firmly fixed on the surface of the carrier.

In order to further promote the complexation of gold and copper, the solid content may be reduced with a reducing agent such as formalin, hydrazine, sodium borohydride and formic acid prior to the above heat treatment. .

Method (B) In the method (B) , gold is first supported on the carrier, and then copper is supported. The method of supporting gold is not limited, and the same method as the above (A) can be used, for example. That is, after depositing gold by a precipitation method or the like, drying and firing may be performed in the same manner as in the above (A). Copper can be carried on the gold carrier thus produced by the same method as in the above (A). Further, similarly to the above (A), it is desirable to perform the same heat treatment as the above (A) in order to more sufficiently form the composite of gold and copper. Further, if necessary, reduction treatment using a reducing agent can be combined.

Method (C) The above method (C) is a method of simultaneously supporting gold and copper on a carrier. For example, gold and copper can be simultaneously loaded on a carrier by a precipitation-precipitation method. Specifically, when gold is supported on the carrier by the precipitation-precipitation method in the above (A), both can be supported by coexisting a compound containing copper in the system. Further, a material carrying both of them can be heat-treated in the same manner as in the above (A) and (B). 3. Oxidation Reaction Catalyst The carrier of the present invention is particularly useful as an oxidation reaction catalyst. It is useful for the oxidation reaction of hydrocarbons using molecular oxygen as an oxidant. In particular, it can be suitably used as a catalyst for use in a method for producing an unsaturated carbonyl compound by oxidizing an olefin compound. For example, it can be used in a method for producing methacrolein from isobutene, a method for producing acrolein from propylene, a method for producing methyl vinyl ketone from 1-butene, and the like. 4. Method for Producing Unsaturated Carbonyl Compound The method for producing an unsaturated carbonyl compound according to the present invention produces an unsaturated carbonyl compound by oxidizing an olefin compound (especially oxygen oxidation) in the presence of the catalyst for oxidation reaction of the present invention.

The olefin compound is not limited as long as it has an olefinic double bond. Generally, an aliphatic olefin having 2 to 10 carbon atoms and 6 carbon atoms
At least one of the alicyclic olefins of ~ 12 can be used. Specifically, propylene, isobutene (isobutylene), 1-butene, 2-butene, 2-methyl-
1-butene, 1-pentene, 2-pentene, 1-hexene, 2-hexene, 3-hexene, cyclohexene, 1
-Methylhexene etc. can be illustrated. These olefin compounds may be used alone or in combination of two or more. Among these, in the present invention, propylene, isobutene, 1
-Butene, cyclohexene and the like are preferred.

In the production method of the present invention, the above olefin compound may be appropriately selected depending on the kind of the target unsaturated carbonyl compound and the like. For example, when synthesizing acrolein, propylene may be used. When methacrolein is synthesized, isobutylene may be used.

In the production method of the present invention, when it is carried out as a gas phase reaction, the oxidation reaction (partial oxidation reaction) of the olefin compound is carried out by bringing the raw material gas containing the olefin compound and oxygen into contact with the catalyst of the present invention. You can proceed.

The method of contacting the raw material gas with the catalyst of the present invention is not limited, and for example, the reaction apparatus (reactor) is filled with the catalyst of the present invention (granule or granulated product), and the raw material gas is placed in the reaction apparatus. The method of distribution can be suitably adopted. As a result, a product gas containing the target oxygen-containing compound (unsaturated carbonyl compound) can be obtained.

The raw material gas may be diluted with an inert gas such as nitrogen, helium, argon or carbon dioxide, if necessary. The amount of the inert gas used is not limited and can be appropriately set depending on the composition of the raw material gas, the catalyst used, and the like. The reaction system is not particularly limited, but a continuous system is preferable because the above-mentioned oxidation reaction is a so-called gas phase heterogeneous reaction.

The amount of the catalyst of the present invention used may be set according to the supported amounts of gold and copper, the type of olefin compound, the reaction conditions and the like. In particular, the space velocity (SV) of the total gas supplied to the reaction system is 100 to 1000 hr ⁻¹ · ml / g · c.
It is desirable to be within the range of at (space velocity per 1 g of catalyst).

Although the amount of oxygen used is not particularly limited, it is generally preferable that the ratio of oxygen to the olefin compound (oxygen / olefin compound) is within the range of 1/10 to 10/1. Within this range, the yield or selectivity of the oxygen-containing compound can be further increased.

The reaction temperature can be appropriately set depending on the kind of the olefin compound, the combination of the catalyst to be used and the olefin compound, etc., but is generally 0 to 500 ° C., particularly 5
0-400 degreeC is more preferable. By setting such a reaction temperature, higher yield or selectivity can be realized.

The reaction pressure can be appropriately changed according to the reaction conditions such as reaction temperature and is not particularly limited. Generally, the pressure may be adjusted so that the olefin compound and the oxygen-containing compound can exist as a gas (for example, about 0.01 to 2 MPa).

On the other hand, the oxidation reaction of the present invention can also be carried out as a liquid phase reaction. In this case, the batch type,
Various reaction types such as a semi-batch type and a continuous flow type can be adopted. The reaction temperature and the reaction pressure in the liquid phase reaction can be set to a temperature and a pressure at which the olefin compound and the oxygen-containing compound can exist as a liquid (for example, the temperature is 200 ° C. or less, the pressure is 0.05 to 10 MPa).

In the case of liquid phase reaction, it is desirable to use a solvent. For example, a method of bringing the above-mentioned raw material gas into contact with a suspension obtained by suspending the catalyst of the present invention in a solvent by bubbling or the like can be suitably adopted. The solvent is not particularly limited as long as it does not interfere with the oxidation reaction of the present invention. Examples thereof include aromatic hydrocarbons such as benzene and toluene, and halogenated hydrocarbons such as methylene chloride. Further, the amount of the solvent used may be appropriately set according to the type of solvent used and the like.

The unsaturated carbonyl compound obtained by the production method of the present invention can be used for the same applications as the unsaturated carbonyl compound obtained by the prior art. For example, acrolein, methacrolein, etc. are useful as a raw material for producing methyl methacrylate.

[0059]

INDUSTRIAL APPLICABILITY The metal particle-supporting material of the present invention is superior to conventional ones when used as a catalyst for an oxidation reaction, in particular, because metal particles containing gold and copper are supported on the carrier. It can exhibit catalytic activity. Moreover, even after repeated use, the performance is not easily deteriorated as in the prior art, and a relatively high activity can be maintained.

It is particularly effective when used as a reaction catalyst for synthesizing an unsaturated carbonyl compound from an olefin compound. For example, the synthesis of acrolein from propylene, the synthesis of methacrolein from isobutylene, 1
-Suitable for the synthesis of methyl vinyl ketone from butene, the synthesis of cyclohexen-3-one from cyclohexene, etc.

[0061]

EXAMPLES Examples and comparative examples will be shown below to further clarify the features of the present invention. However, the scope of the present invention is not limited to the scope of the embodiments.

The conversion rate and selectivity in Examples and Comparative Examples were calculated based on the following equations.

Conversion (%) = (1−B / A) × 100 Selectivity (%) = {C / (A−B)} × 100 (In the above two formulas, A: reactor inlet feed olefin , B: the number of moles of the raw material olefin at the reactor outlet, C: the number of moles of the product α, β-unsaturated aldehyde or ketone at the reactor inlet, respectively.) Further, Table 1 and Table 2 show The raw materials, reaction temperature, olefin conversion, main product and selectivity used in Examples and Comparative Examples are shown together.

[0064]

[Table 1]

[0065]

[Table 2]

Example 1 (1) Preparation of Au—Cu / Silica First, commercially available silica (product name “Carriact Q-10”) was prepared.
20 g of Fuji Silysia Chemical Co., Ltd., and copper nitrate trihydrate 3.
50 ml of an aqueous solution containing 80 g was added, and water was removed as much as possible while stirring on a warm bath. 12 remaining solids
After drying at 0 ° C. for 10 hours, it was calcined in air at 600 ° C. for 4 hours to obtain Cu / silica in which copper was supported on a silica carrier.

Next, while maintaining 500 ml of an aqueous solution of chloroauric acid having a concentration of 10 mmol / L at 65 to 70 ° C., 0.5
The pH was adjusted to 7 with an aqueous solution of N sodium hydroxide.
10 g of the above Cu / silica was added to this aqueous solution with stirring, and stirring was continued for 1 hour while maintaining the temperature at 65 to 70 ° C.
After that, the supernatant liquid was removed by leaving it still, 0.8 L of ion-exchanged water was added to the remaining solid content, the mixture was stirred at room temperature for 5 minutes, and then the cleaning process of removing the supernatant liquid was repeated three times. The solid content obtained by filtration is dried at 100 ° C. for 10 hours,
Further, by firing in air at 400 ° C. for 3 hours, a supported material (Au-Cu /
Silica) was obtained.

The amounts of gold and copper supported on this carrier were measured by fluorescent X-ray analysis, and as a result, they were 3.6% by weight and 5.0% by weight, respectively, with respect to the carrier. In addition, the state analysis of the gold particles of this support is carried out by a transmission electron microscope (TEM).
(Apparatus name "HF-2000" Hitachi, accelerating voltage 20
0 kV) (the same applies hereinafter)). As a result, almost all gold and copper are highly dispersed with a particle size of 10 nm or less, exhibit a narrow particle size distribution with a maximum in the vicinity of a particle size of 3 to 5 nm, and the average particle size is clearly 10 nm or less. It could be confirmed. Furthermore, when the composition of each metal particle was analyzed, both gold and copper components were detected. (2) Synthesis of Acrolein by Oxidation Reaction of Propylene Acrolein was synthesized using the supported material (Au-Cu / silica) obtained in (1) above.

A glass U-shaped reaction tube (inner diameter: 10 mm) was filled with 2 g of the supported material to form a catalyst layer, and the temperature of the catalyst layer (reaction temperature) while flowing a mixed gas of nitrogen and oxygen.
Was heated in an electric furnace so as to be 300 ° C. Then, the gas composition is propylene / oxygen / helium = 27/18/5
5 (vol%) mixed gas was passed through the reaction tube at a flow rate of 73.3 ml / min. After 30 minutes from the start of the reaction, the reactor outlet gas was analyzed by gas chromatography and the reaction results were determined. As a result, the conversion rate of propylene was 24% and the selectivity of acrolein was 82%.

Example 2 Methacrolein was synthesized by the oxidation reaction of isobutylene.

The procedure of Example 1 (2) was repeated except that isobutylene was used instead of propylene and the reaction temperature was 280 ° C. Analysis of the reactor outlet gas 30 minutes after the start of the reaction by gas chromatography,
As a result of obtaining reaction results, the conversion of isobutylene was 20%,
The methacrolein selectivity was 83%.

Example 3 Methyl vinyl ketone was synthesized by the oxidation reaction of 1-butene.

1-butene was used in place of propylene,
The procedure of Example 1 (2) was repeated except that the reaction temperature was 270 ° C. After 30 minutes from the start of the reaction, the outlet gas of the reactor was analyzed by gas chromatography, and the reaction results were determined. As a result, the conversion of 1-butene was 30% and the selectivity of methyl vinyl ketone was 78%.

Example 4 Cyclohexene-3-by oxidative reaction of cyclohexene
On synthesis was performed.

The same as (2) of Example 1 except that cyclohexene was used instead of propylene, the reaction temperature was 280 ° C., and the gas composition was hexene / oxygen / helium = 12/18/70 (volume%). Was carried out. After 30 minutes from the start of the reaction, the gas at the outlet of the reactor was analyzed by gas chromatography, and the reaction results were obtained. As a result, the conversion of cyclohexene was 17%, and the selectivity of cyclohexen-3-one was 7
It was 1%.

Comparative Example 1 Oxidation reaction was carried out using a supported material carrying metal particles having an average particle size of more than 10 nm. This is US Pat.
It was prepared in accordance with the method for producing a catalyst described in No. 989674.

First, 50 ml of an aqueous solution containing 0.75 g of tetrahydrate of chloroauric acid was added to 10 g of Cu / silica obtained in Example 1 (1), and water was removed as much as possible while stirring on a warm bath. The remaining solid content was dried at 100 ° C. for 10 hours and then calcined in air at 400 ° C. for 4 hours to obtain Au—Cu / silica in which gold and copper were supported on a silica carrier. The amount of gold and copper supported on this carrier was measured by fluorescent X-ray analysis.
% And 5.0% by weight. In addition, the state analysis of the gold particles of this support was examined by a transmission electron microscope. As a result, it was confirmed that almost all gold and copper had a particle size of more than 10 nm, and the average particle size was clearly more than 10 nm.

Next, acrolein was synthesized by the oxidation reaction of propylene in the same manner as in Example 1 except that the above-mentioned supported material was used as a catalyst. Analysis of the reactor outlet gas 30 minutes after the start of the reaction by gas chromatography,
As a result of obtaining the reaction results, the conversion of propylene was 2% and the selectivity of acrolein was 58%.

Example 5 (1) Preparation of Au-Cu / Silica First, commercially available silica (product name "Carriact Q-15") was used.
50 g of Fuji Silysia Chemical) to copper acetate monohydrate 4.
150 ml of an aqueous solution containing 71 g was added, and water was removed as much as possible while stirring on a warm bath. 1 remaining solid
After drying at 20 ° C. for 10 hours, it was calcined in air at 500 ° C. for 4 hours to form Cu / Cu on which silica was supported on a silica carrier.
Obtained silica.

Next, while maintaining 500 ml of a chloroauric acid aqueous solution having a concentration of 3 mmol / L at 65 to 70 ° C., 0.5 N
The pH was adjusted to 7 with aqueous sodium hydroxide solution. 10 g of the above Cu / silica was added to this aqueous solution with stirring,
The stirring was continued for 1 hour while maintaining the temperature at 65 to 70 ° C. After that, the supernatant liquid was removed by leaving it still, 0.8 L of ion-exchanged water was added to the remaining solid content, the mixture was stirred at room temperature for 5 minutes, and then the cleaning process of removing the supernatant liquid was repeated three times. The solid content obtained by filtration is dried at 100 ° C. for 10 hours, and further calcined in air at 400 ° C. for 3 hours to obtain a supported material (Au-Cu / silica) in which gold and copper are supported on a silica carrier. Obtained.

The amounts of gold and copper supported on this carrier were measured by fluorescent X-ray analysis and found to be 2.5% by weight and 3.0% by weight, respectively, with respect to the carrier. In addition, the state analysis of the gold particles of this support was examined by a transmission electron microscope.
As a result, almost all gold and copper were highly dispersed with a particle size of 10 nm or less, showing a narrow particle size distribution with a maximum around a particle size of 3 to 5 nm, and the average particle size was clearly 10
It was confirmed that it was less than or equal to nm. Furthermore, when the composition of each metal particle was analyzed, both gold and copper components were detected. (2) Synthesis of Methyl Vinyl Ketone by Oxidation Reaction of 1-Butene Methyl vinyl ketone was synthesized using the supported material (Au-Cu / silica) obtained in (1) above.

A glass U-shaped reaction tube (inner diameter: 10 mm) was filled with 2 g of the supported material to form a catalyst layer, and the temperature of the catalyst layer (reaction temperature) while flowing a mixed gas of nitrogen and oxygen.
Was heated in an electric furnace so as to be 300 ° C. Next, the gas composition is 1-butene / oxygen / nitrogen = 107/10/80.
(Volume%) mixed gas was passed through the reaction tube at a flow rate of 90 ml per minute. After 30 minutes from the start of the reaction, the outlet gas of the reactor was analyzed by gas chromatography and the reaction results were determined. As a result, the conversion rate of 1-butene was 28% and the selectivity of methyl vinyl ketone was 77%.

Example 6 A carrier in which gold and copper were supported on a silica carrier (Au-Cu / silica) in the same manner as in Example 5 except that the firing temperature of the carrier containing Au and Cu was set to 600 ° C. ) Got. The amounts of gold and copper supported on this carrier were measured by fluorescent X-ray analysis, and as a result, they were 2.5% by weight and 3.0% by weight, respectively, relative to the carrier. In addition, the state analysis of the gold particles of this support was examined by a transmission electron microscope. As a result, almost all gold and copper were highly dispersed with a particle size of 10 nm or less, and showed a narrow particle size distribution with a maximum around 5 to 8 nm, and the average particle size was clearly 10 nm or less. It could be confirmed. Furthermore, when the composition of each metal particle was analyzed, both gold and copper components were detected.

Methyl vinyl ketone was synthesized by the oxidation reaction of 1-butene in the same manner as in Example 5 except that this supported material was used as a catalyst. After 30 minutes from the start of the reaction, the gas at the outlet of the reactor was analyzed by gas chromatography, and the reaction results were obtained. As a result, the conversion rate of 1-butene was 24
%, The selectivity of methyl vinyl ketone was 74%.

Comparative Example 2 A catalyst containing metal particles made of gold and copper (particles having an average particle size of more than 10 nm) was used in the same manner as in Comparative Example 1 except that the firing temperature of the support containing Au and Cu was 850 ° C. Prepared. The amount of gold and copper supported on this carrier was measured by fluorescent X-ray analysis, and as a result, it was 2.5 for each carrier.
% And 3.0% by weight. In addition, the state analysis of the gold particles of this support was examined by a transmission electron microscope. As a result, it was confirmed that almost all gold and copper were dispersed with a particle size exceeding 10 nm, and the average particle size was clearly above 10 nm. Furthermore, when the composition of each metal particle was analyzed, both gold and copper components were detected.

Methyl vinyl ketone was synthesized by the oxidation reaction of 1-butene in the same manner as in Example 5 except that this supported material was used as a catalyst. After 30 minutes from the start of the reaction, the gas at the outlet of the reactor was analyzed by gas chromatography to obtain the reaction results.
The selectivity of methyl vinyl ketone was 69%. From this, it can be seen that a carrier carrying metal particles having an average particle size of more than 10 nm can obtain low catalytic activity.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C07C 49/603 C07C 49/603 // C07B 61/00 300 C07B 61/00 300 (72) Inventor Masatake Haruta 1-1-1 Higashi, Tsukuba, Ibaraki Independent Administrative Law, F-Term in Tsukuba Center, National Institute of Advanced Industrial Science and Technology (Reference) 4G069 AA03 BA01A BA02A BA02B BA03A BA04A BA05A BA06A BA07A BA09A BA10A BA16A BA20A BB02A BB02B BC31A BC31B BC33A BC33B CB07B02B CB07 EC27 ZA11A ZA35A 4H006 AA02 AC12 AC44 AC45 BA05 BA55 BA60 BA81 BE30 4H039 CA29 CA62 CC10 CC30

Claims (3)

[Claims] 1. A carrier comprising metal particles supported on a carrier, the metal particles containing gold and copper, and having an average particle diameter of 10 nm or less. A metal particle carrier. 2. A catalyst for oxidation reaction comprising the metal particle-supporting material according to claim 1. 3. In the presence of the oxidation reaction catalyst according to claim 2,
A method for producing an unsaturated carbonyl compound by oxidizing an olefin compound.