JPH10330291A - Production of hetero element-containing oxide compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To directly produce-a hetero element-containing oxide compound such as a hetero element-containing epoxide compound, an N-oxide compound, etc., from a corresponding hetero element-containing compound such as a hetero element-containing compound, a nitrogen-containing compound, etc., more inexpensively than a conventional method using hydrogen peroxide or a hydroperoxide as an oxidizing agent. SOLUTION: A hetero element-containing compound is partially oxidized by using a catalyst comprising gold, titanium oxide, a carrier having >=50 m<2> /g specific surface area, optionally an alkali metal and/or an alkaline earth metal in the presence of hydrogen and oxygen, for example, in a vapor phase. Preferably the carrier contains silicon oxide and/or aluminum oxide. The content of gold in the catalyst is preferably >=0.01 wt.%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a hetero-element-containing oxide compound such as a hetero-element-containing epoxide compound or an N-oxide compound from a hetero-element-containing compound such as a hetero element-containing unsaturated compound or a nitrogen-containing compound. How to do it.

[0002]

2. Description of the Related Art Conventionally, a method for directly producing a corresponding hetero element-containing epoxide compound (hetero element-containing oxide compound) by oxidizing a hetero element-containing unsaturated compound (hetero element-containing compound) in a liquid phase has been known. Although many have been proposed, most are organic peracids such as peracetic acid, hydrogen peroxide,
An oxidizing agent such as a chlorine compound is used. For example, Japanese Patent Publication No. 4-5028 discloses a method for producing a hetero element-containing epoxide compound using hydrogen peroxide as an oxidizing agent. Also, for example, J. Org. Chem., Vol. 35, N
o. 6, 1970, pp. 1839-1843, describe a method for producing a hetero element-containing epoxide compound using a hydroperoxide such as cumene hydroperoxide as an oxidizing agent.

[0003]

However, in the above-mentioned conventional method, relatively expensive hydrogen peroxide or hydroperoxides must be used as an oxidizing agent, so that an epoxide compound containing a hetero element can be produced at low cost. There is a problem that cannot be done. In addition, a method for producing a hetero element-containing epoxide compound by oxidizing a hetero element-containing unsaturated compound in a gas phase, or a method for producing a hetero element-containing epoxide compound using molecular oxygen as an oxidizing agent has been proposed. Not done.
Therefore, a method for directly and inexpensively producing a hetero element-containing oxide compound such as a hetero element-containing epoxide compound from a hetero element-containing compound such as a hetero element-containing unsaturated compound has been desired.

The present invention has been made in view of the above-mentioned conventional problems, and has as its object to provide a method for directly and inexpensively producing a hetero element-containing oxide compound from a hetero element-containing compound. It is in.

[0005]

Means for Solving the Problems The inventors of the present invention have found that a compound containing a hetero element such as an unsaturated compound containing a hetero element or a compound containing nitrogen and a compound containing a hetero element such as an epoxide compound or an N-oxide compound containing a corresponding hetero element. The present inventors have intensively studied a method capable of producing an oxide compound directly and at a lower cost than the above-mentioned conventional method. As a result, the hetero element-containing compound is partially oxidized in the presence of hydrogen and oxygen using a catalyst containing gold, titanium oxide, and a carrier having a specific surface area of 50 m ² / g or more. The present inventors have found that a hetero element-containing oxide compound can be directly and inexpensively produced from a hetero element-containing compound, and have completed the present invention.

That is, in order to solve the above-mentioned problems, the method for producing a hetero element-containing oxide compound according to the first aspect of the present invention comprises gold, titanium oxide and a specific surface area of 50 m ² / g.
It is characterized in that a hetero element-containing compound is partially oxidized in the presence of hydrogen and oxygen using a catalyst containing the above-mentioned carrier.

According to a second aspect of the present invention, there is provided a method for producing a hetero element-containing oxide compound according to the first aspect of the present invention. It is characterized by oxidation.

According to a third aspect of the present invention, there is provided a method for producing a hetero element-containing oxide compound, the method comprising the steps of: Is a hetero element-containing unsaturated compound, and the hetero element-containing oxide compound is a hetero element-containing epoxide compound.

According to a fourth aspect of the present invention, there is provided a method for producing a hetero element-containing oxide compound, comprising the steps of: It is characterized by containing at least one element selected from the group consisting of nitrogen and halogen elements.

According to a fifth aspect of the present invention, there is provided a method for producing a hetero element-containing oxide compound according to the first or second aspect. Is a nitrogen-containing compound, and the hetero element-containing oxide compound is an N-oxide compound.

According to a sixth aspect of the present invention, there is provided a method for producing a hetero element-containing oxide compound according to any one of the first to fifth aspects. In the above, the carrier,
It is characterized by containing silicon oxide and / or aluminum oxide.

According to a seventh aspect of the present invention, there is provided a method for producing a hetero element-containing oxide compound according to any one of the first to sixth aspects. In the above, the catalyst is
It is characterized by further containing an alkali metal and / or an alkaline earth metal.

In order to solve the above-mentioned problems, a method for producing a hetero element-containing oxide compound according to the invention of claim 8 is a method for producing a hetero element-containing oxide compound according to any one of claims 1 to 7. Wherein the gold content in the catalyst is 0.01% by weight or more.

According to a ninth aspect of the present invention, there is provided a method for producing a hetero element-containing oxide compound according to the seventh or eighth aspect. The content is 0.1% by weight to 10% by weight, the content of titanium oxide is 0.1% by weight to 20% by weight, and the content of alkali metal and / or alkaline earth metal is 0.1% by weight. 01
% By weight to 3% by weight.

According to the above-mentioned method, a hetero element-containing oxide compound such as a hetero element-containing epoxide compound or an N-oxide compound is directly converted from a hetero element-containing unsaturated compound or a nitrogen-containing compound. In addition, it can be produced at lower cost than the conventional method using hydrogen peroxide or hydroperoxides as an oxidizing agent.

Hereinafter, the present invention will be described in detail. The method for producing a hetero element-containing oxide compound according to the present invention comprises a catalyst containing gold, titanium oxide, and a carrier having a specific surface area of 50 m ² / g or more, in the presence of hydrogen and oxygen,
This is a method of partially oxidizing a hetero element-containing compound. The catalyst comprises gold, titanium oxide (titania) and a specific surface area of 5
0 m ² / g or more of a carrier.

The gold is preferably a particle having a particle size of nanometer (nm) or less, that is, a so-called ultrafine particle. The supported amount (content) of gold in the catalyst is
0.001% by weight or more is preferable, 0.01% by weight or more is more preferable, and 0.1% by weight to 10% by weight is further preferable. If the amount of gold carried is less than 0.001% by weight, the activity of the catalyst is undesirably reduced. On the other hand, even if the supported amount of gold is more than 10% by weight, further improvement in the activity of the catalyst can hardly be expected as compared with the case where gold is supported within the above range, and gold is wasted. It is not preferable.

The crystal structure of the titanium oxide is not particularly limited, but is preferably amorphous or anatase. Further, titanium oxide may be present as a complex with another oxide. The supported amount (content) of titanium oxide in the catalyst is 0.1% by weight to 20% by weight.
Is more preferable, and the range of 0.5 to 10% by weight is more preferable. Therefore, the loading amount of gold is 0.1% by weight.
-10% by weight and the amount of titanium oxide supported is 0.1%.
It is particularly preferred that the content be 1% by weight to 20% by weight. If the amount of titanium oxide supported is less than 0.1% by weight, the activity of the catalyst is undesirably reduced. On the other hand, even if the supported amount of titanium oxide is larger than 20% by weight, further improvement in the activity of the catalyst can hardly be expected as compared with the case where titanium oxide is supported within the above range.

Gold and titanium oxide having a specific surface area of 50 m ²
By immobilizing (supporting) on a carrier of not less than / g, the activity of the catalyst is improved. As the above carrier, specifically,
For example, ceramics composed of silicon oxide (silica), aluminum oxide (alumina), magnesium oxide (magnesia), cordierite, zirconium oxide, and composites thereof; crystalline metallosilicates such as zeolite; foams composed of various metals A honeycomb carrier composed of various metals; a pellet composed of various metals; Among these, silicon oxide and / or aluminum oxide are more preferred, and silicon oxide is particularly preferred. The crystal structure, shape, size and the like of the carrier are not particularly limited, but the specific surface area is 50 m ² /
g or more, and more preferably 100 m ² / g or more. By setting the specific surface area to 50 m ² / g or more, the performance of the catalyst is further improved. That is, side reactions such as sequential oxidation are further suppressed, and the hetero element-containing compound can be efficiently partially oxidized, and the amount of burned hydrogen can be further reduced. In addition, when silicon oxide and aluminum oxide are used in combination, the ratio of both is not particularly limited. Further, in the present invention, "containing silicon oxide and aluminum oxide" includes the case where zeolite (aluminosilicate) or silica alumina is contained.

Further, the catalyst may further contain a carrier having a specific surface area of less than 50 m ² / g to the extent that its activity is not impaired. That is, the catalyst according to the present invention has gold and titanium oxide supported on a support having a specific surface area of 50 m ² / g or more (hereinafter simply referred to as a support). Note that titanium oxide such as a complex can be supported on a carrier and then calcined to support titanium oxide on the carrier.

Further, the catalyst may contain an alkali metal and / or an alkaline earth metal in addition to gold and titanium oxide. That is, the catalyst may contain at least one element selected from the group consisting of alkali metals and alkaline earth metals in addition to gold and titanium oxide. Examples of the alkali metal include Li, N
a, K, Rb, Cs, and Fr. Examples of the alkaline earth metal include Be, Mg, Ca, Sr, Ba, and R.
a. Among these alkali metals and alkaline earth metals, at least one element selected from the group consisting of K, Rb, Cs, Mg, Ca, Sr, and Ba is more preferable. Thereby, the performance of the catalyst is further improved. That is, side reactions such as sequential oxidation are further suppressed, and the hetero element-containing compound can be partially oxidized efficiently.

The alkali metal and / or alkaline earth metal may be present as a metal alone in the catalyst, or may be incorporated in other components, for example, in the crystal structure of titanium oxide. The alkali metal and / or alkaline earth metal may be contained in the carrier, but in such a case, the above effects cannot be expected.

The supported amount (content) of the alkali metal and / or alkaline earth metal in the catalyst is preferably in the range of 0.001% by weight to 20% by weight as a simple metal, and is preferably 0.005% by weight. It is more preferably in the range of from 5% by weight to 5% by weight, particularly preferably in the range of from 0.01% by weight to 3% by weight. Therefore, when the catalyst further contains an alkali metal and / or an alkaline earth metal, the supported amount of gold is 0.1% by weight to 10% by weight, and the supported amount of titanium oxide is 0.1% by weight to 20
It is particularly preferable that the amount of alkali metal and / or alkaline earth metal carried is 0.01% by weight to 3% by weight. If the amount of the alkali metal and / or alkaline earth metal carried is less than 0.001% by weight, the effect obtained by adding the alkali metal and / or alkaline earth metal becomes poor. On the other hand, even when the supported amount of the alkali metal and / or the alkaline earth metal is more than 20% by weight, as compared with the case where the alkali metal and / or the alkaline earth metal are supported within the above range, the alkali metal and / or the alkaline earth metal can be used. Further improvement in the effect obtained by the addition is hardly expected, and conversely, the performance of the catalyst is undesirably reduced.

As a method for preparing a catalyst, that is, a method for immobilizing gold and titanium oxide on a carrier, for example,
Examples include a precipitation method, a coprecipitation method, an impregnation method, and a chemical vapor deposition method, but are not particularly limited. Further, by performing an operation such as spraying a powder of gold and / or a gold compound and a powder of titanium oxide on the carrier, the gold and titanium oxide can be adhered to the carrier and immobilized. By the above fixing method, gold and titanium oxide are
It is firmly immobilized on the carrier with a relatively uniform distribution. In the case where gold and titanium oxide are separately supported on a carrier, a method of supporting gold after supporting titanium oxide is preferable. In addition, after gold is supported on titanium oxide, the titanium oxide-supported gold can be supported on a carrier. Further, titanium oxide can be carried on a carrier such as silicon oxide or aluminum oxide by so-called coating or by dispersing so as to form a so-called island-like structure.

As a method of immobilizing gold on a carrier, specifically, for example, after supporting titanium oxide on the carrier, the carrier is immersed in an aqueous solution containing a gold compound, and the gold is immobilized on the carrier. A method of depositing a precipitate can be employed. The gold compound described above may be water-soluble, and for example, chloroauric acid (tetrachloroaurate (III) acid) can be used, but is not particularly limited. The temperature of the aqueous solution is
Although not particularly limited, about 30 ° C. to 80 ° C. is preferable. In this case, if necessary, the pH of the aqueous solution may be adjusted within the range of 6 to 10, and further, the amount of gold supported on the catalyst may be increased, or the particle size of the ultrafine gold particles may be reduced. For this purpose, a surfactant, a carboxylic acid and / or a salt thereof may be added to the aqueous solution. Specific examples of the surfactant include long-chain alkyl (aryl) sulfonic acids having 8 or more carbon atoms and salts thereof, and long-chain alkyl (aryl) carboxylic acids and salts thereof. Further, specific examples of the carboxylic acid and its salt include citric acid and its sodium salt and magnesium salt.

The method for preparing a catalyst further containing an alkali metal and / or an alkaline earth metal includes:
For example, an alkali metal and / or a catalyst obtained by immobilizing gold and titanium oxide on a carrier by the above immobilization method are used.
Or a method for supporting an alkaline earth metal; a method for immobilizing titanium oxide on a carrier, then supporting an alkali metal and / or an alkaline earth metal, and then immobilizing gold on the carrier; immobilizing titanium oxide on the carrier. After the conversion, a method of immobilizing the gold on the carrier and simultaneously supporting the alkali metal and / or the alkaline earth metal; and the like are not particularly limited. Among the preparation methods exemplified above, the method shown by or is more preferable.

In the method described above, a method such as an impregnation method generally used conventionally can be adopted. When the impregnation method is adopted, an aqueous solution containing an alkali metal and / or an alkaline earth metal, specifically, for example, an aqueous solution of an alkali metal carbonate such as potassium carbonate, rubidium carbonate, or cesium carbonate, or
Gold and titanium oxide are added to aqueous solutions of alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide, or aqueous solutions of alkaline earth metal nitrates such as magnesium nitrate, calcium nitrate, strontium nitrate and barium nitrate. After the catalyst immobilized on the carrier is immersed, the alkali metal and / or alkaline earth metal may be forcibly carried on the catalyst by distilling off water.

In the above method, the alkali metal and / or alkaline earth metal may be supported on the carrier by immersing the carrier in an aqueous solution containing the alkali metal and / or alkaline earth metal.
The alkali metal and / or alkaline earth metal may be forcibly supported on the carrier by distilling off water. In the method described above, the titanium oxide may be immobilized on the carrier and, at the same time, the alkali metal and / or the alkaline earth metal may be supported.

By the above-mentioned various preparation methods, a catalyst containing gold, titanium oxide, a carrier having a specific surface area of 50 m ² / g or more, and if necessary, an alkali metal and / or an alkaline earth metal can be obtained. .

The method for producing a hetero element-containing oxide compound according to the present invention is a method of partially oxidizing a hetero element-containing compound in the presence of hydrogen and oxygen using the catalyst having the above-mentioned structure. The hetero element-containing compound used as a raw material in the partial oxidation method is not particularly limited, but a hetero element-containing unsaturated compound and a nitrogen-containing compound are preferable. The hetero element-containing unsaturated compound is not particularly limited as long as it contains a hetero element and an olefinic double bond, and is not particularly limited, but includes an oxygen-containing unsaturated compound, a nitrogen-containing unsaturated compound, and a Halogen unsaturated compounds are preferred. That is, the hetero element-containing unsaturated compound more preferably contains at least one element selected from the group consisting of oxygen, nitrogen, and a halogen element as a hetero element. Further, the nitrogen-containing compound may further include at least one hetero element selected from the group consisting of oxygen and a halogen element.

According to the above method, the double bond of the hetero element-containing unsaturated compound is selectively oxidized, and the hetero element-containing epoxide compound is selectively produced. Further, according to the above method, nitrogen of the nitrogen-containing compound is selectively oxidized, and an N-oxide compound is selectively generated.

Specific examples of the oxygen-containing unsaturated compound include unsaturated alcohols such as allyl alcohol, 2-buten-1-ol and 3-buten-1-ol; α, acrolein and methacrolein; β-unsaturated aldehydes; unsaturated aldehydes such as crotonaldehyde; acrylic acid, acrylic acid ester, methacrylic acid, methacrylic acid ester, maleic acid, maleic acid ester, etc.
α, β-unsaturated carboxylic acids and esters thereof; vinyl carboxylate such as vinyl acetate; unsaturated ketone such as methyl vinyl ketone;

Specific examples of the nitrogen-containing unsaturated compound include α, β-unsaturated nitriles such as acrylonitrile and methacrylonitrile.

Specific examples of the halogen-containing unsaturated compound include, for example, vinyl chloride, vinyl bromide, allyl chloride,
Allyl bromide and the like.

Specific examples of the nitrogen-containing compound include tertiary amines such as trimethylamine; cyclic amines such as N-methylmorpholine; and heterocyclic aromatic compounds such as pyridine.

The reaction for partially oxidizing the hetero element-containing compound is preferably performed in a gas phase, but may be performed in a liquid phase. In the following description, a case where the above reaction is performed in a gas phase will be described as an example.

The amount of the catalyst to be used may be set according to, for example, the amount of gold and titanium oxide carried, the type of the hetero element-containing compound, the reaction conditions, etc., and is not particularly limited. Space velocity of compound containing hetero element (S
V) is from 100 hr ^-1 · ml / g to 100,000 g / g catalyst.
An amount within the range of 00 hr ^-1 · ml is preferred.

Hydrogen (molecular hydrogen) acts as a reducing agent. The amount of hydrogen used is not particularly limited, but is preferably an amount such that the volume ratio of hydrogen to the hetero element-containing compound (hydrogen / hetero element-containing compound) falls within the range of 1/10 to 100/1. is there. The reaction rate increases as the proportion of hydrogen increases.
A value closer to 0/1 is more preferable. If no hydrogen is present, the hetero element-containing compound is completely oxidized to carbon dioxide and water. Therefore, in this case, a hetero element-containing oxide compound cannot be obtained.

The reaction for partially oxidizing the hetero element-containing compound proceeds by bringing a raw material gas containing the hetero element-containing compound, oxygen (molecular oxygen) and hydrogen into contact with a catalyst. Therefore, as a reaction method, for example, a method in which a catalyst is filled in a reactor and the above-described raw material gas is circulated in the reactor is preferable. Thereby, a product gas containing a hetero element-containing oxide compound such as a hetero element-containing epoxide compound or an N-oxide compound can be obtained. The reaction system is not particularly limited, but a continuous system is preferable because the above reaction is a so-called gas phase heterogeneous catalytic reaction. Further, the source gas may contain an inert gas such as nitrogen, helium, argon, carbon dioxide, or the like, if necessary. That is, the hetero element-containing compound may be diluted with an inert gas, if necessary.

The reaction temperature may be set according to the type of the hetero element-containing compound, etc., and is not particularly limited. However, the hetero element-containing compound or the target hetero element-containing oxide compound is converted into a gas. Temperature that can exist,
For example, the temperature is preferably in the range of 0 ° C to 300 ° C,
Optimally, the temperature is in the range of from 250C to 250C. When the reaction temperature is extremely high, the combustion reaction of the hetero element-containing compound or the hetero element-containing oxide compound, that is, the generation of carbon dioxide and water is likely to occur, and the amount of hydrogen burned increases. Therefore, the hetero element-containing oxide compound cannot be efficiently produced. However, by maintaining the reaction temperature relatively high, the partial oxidation reaction also proceeds efficiently, and in the present invention, the reaction temperature is more preferably 100 ° C. or higher. In the present invention, even when the reaction temperature is as high as 100 ° C. or more, the combustion reaction of the hetero element-containing compound or the hetero element-containing oxide compound can be suppressed.

The reaction pressure may be set according to the reaction conditions such as the reaction temperature, and is not particularly limited. However, the pressure at which the hetero element-containing compound or the hetero element-containing oxide compound can exist as a gas is set. Desirable, 0.05
The range from MPa to 5 MPa is preferable. The reaction time is
What is necessary is just to set according to reaction conditions, such as reaction temperature and reaction pressure, and it is not specifically limited.

In the catalyst according to the present invention, a synergistic effect of gold, titanium oxide, a carrier, and an optional alkali metal and / or alkaline earth metal is used, that is, these components are specifically and synergistically effective. , The hetero element-containing compound can be easily and efficiently partially oxidized. In this way, the direct oxidation in the gas phase, that is, the gas phase oxidation reaction, makes the reaction process one step (one step) and converts the hetero element-containing epoxide compound from the hetero element-containing unsaturated compound into a high selectivity and high conversion. The N-oxide compound can be obtained from the nitrogen-containing compound at a high selectivity and a high conversion rate, and the amount of burned hydrogen can be reduced.

When the reaction for partially oxidizing the hetero element-containing compound is performed in a liquid phase, the reaction temperature is set to a temperature at which the hetero element-containing compound or hetero element-containing oxide compound can exist as a liquid, for example, 0 ° C. It is preferable that the temperature is in the range of -100 ° C. The reaction pressure may be a pressure at which the hetero element-containing compound or the hetero element-containing oxide compound can exist as a liquid. Alternatively, the above reaction can be carried out in a liquid phase using a solvent inert to the reaction. As a reaction method using a solvent, for example, a method of bubbling the raw material gas into a suspension obtained by suspending a catalyst in a solvent is preferable. Examples of the solvent include aromatic hydrocarbons such as benzene and halogenated hydrocarbons such as methylene chloride, but are not particularly limited.

As described above, the method for producing a hetero element-containing oxide compound according to the present invention comprises the steps of: gold, titanium oxide, a carrier having a specific surface area of 50 m ² / g or more, and optionally an alkali metal and / or This is a method of partially oxidizing a hetero element-containing compound in the presence of hydrogen and oxygen using a catalyst containing an alkaline earth metal.

According to the above method, gold,
The hetero-element-containing compound can be easily and efficiently partially oxidized by a synergistic effect of the titanium oxide, the carrier, and the optional alkali metal and / or alkaline earth metal used. Thereby, from a hetero element-containing compound such as a hetero element-containing unsaturated compound or a nitrogen-containing compound,
The corresponding hetero element-containing oxide compounds such as hetero element-containing epoxide compounds and N-oxide compounds are directly processed in one step (one step), and the conventional method using hydrogen peroxide or hydroperoxides as an oxidizing agent. Can also be manufactured at low cost.

The effect of the addition of an alkali metal and / or an alkaline earth metal in the above catalyst is particularly to improve the activity of forming a hetero element-containing oxide compound and the selectivity of the hetero element-containing oxide compound.

The principle of its operation is unknown at present, but as a result of investigations by the present inventors, for example, partial oxidation of a hetero element-containing unsaturated compound using a catalyst to which an alkali metal or an alkaline earth metal is not added is described. It has been found that the reaction tends to increase the rate of formation of compounds such as aldehydes and ketones, which are thought to have been generated by isomerization of the hetero element-containing epoxide compound, or increase the rate of hydrogen conversion. Have been. For this reason, the principle of action of alkali metals and alkaline earth metals is that the addition of these basic metals poisons the strong acid sites possessed by the carrier, and sequentially causes the isomerization reaction of the hetero element-containing epoxide compound, etc. It is conceivable that various side reactions are suppressed, and that the physical properties of the catalyst surface are modified by the presence of the metal to improve the reactivity of hydrogen. It is generally known that an epoxide isomerization reaction proceeds with a strong acid.

The effects obtained by adding an alkali metal or an alkaline earth metal include, in addition to the above effects, an effect of improving the life stability of the catalyst. That is, by the addition of the metal, the generation of by-products is suppressed, so that the accumulation of resin-like substances, which may be caused by the by-products, on the catalyst surface is suppressed, and as a result, the catalyst deteriorates with time. Is suppressed.

[0049]

The present invention will be described in more detail with reference to the following Examples and Comparative Examples, but the present invention is not limited thereto.

Example 1 A methyl alcohol solution 500 containing 1.96 g of titanium (II) acetylacetonate
ml of silicon oxide as a carrier (trade name: Silica Q-
10, manufactured by Fuji Silysia Chemical Ltd .; specific surface area 326m
² / g, 10 mesh to 20 mesh, particle size 840μ
After immersion of 60 g of m.about.1,700 .mu.m), methyl alcohol was distilled off using an evaporator. The obtained solid was dried at 120 ° C. for 12 hours, and then dried in air at 600 ° C.
The resultant was baked at a temperature of 3 ° C. for 3 hours to obtain a titanium oxide-supported silicon oxide. The amount of titanium oxide supported on the carrier is
It was 1% by weight.

Then, tetrachloroaurate (III) acid 0.344
g in water and the pH is adjusted using an aqueous sodium hydroxide solution.
By adjusting to 8.8, 500 ml of tetrachloroauric (III) acid aqueous solution was prepared. 70 ° C
Then, 10 g of the above-mentioned titanium oxide-supported silicon oxide is added,
The mixture was stirred for 1 hour to suspend the titanium oxide-supported silicon oxide, and immobilized the gold precipitate on the surface thereof.

Thereafter, the suspension was filtered, and the residue was washed with water and dried. Next, the dried product was washed with potassium hydroxide 0.1.
24 g was immersed in an aqueous solution prepared by dissolving in 50 ml of ion-exchanged water. After impregnating the dried product with potassium hydroxide, the aqueous solution was filtered. The obtained residue is filtered at 120 ° C.
After drying overnight at 400 ° C. in air for 3 hours.
By firing for a period of time, a silicon oxide supported on gold-containing titanium oxide was obtained as a catalyst. The content of gold and metal potassium in the catalyst was analyzed by X-ray fluorescence spectroscopy, and was found to be 0.36% by weight and 0.50% by weight.

Next, the performance of the above catalyst for the partial oxidation reaction of methacrolein as a hetero element-containing compound (hetero element-containing unsaturated compound) was evaluated. That is, 1 ml of the catalyst was filled in a stainless steel reaction tube having an inner diameter of 8 mm. On the other hand, methacrolein, hydrogen, oxygen, and helium are mixed such that their proportions are 7.9%, 18.8%, 18.8%, and 54.5% by volume, respectively. Source gas was prepared. Then, the above raw material gas was supplied into the reaction tube at a space velocity of 3,240 hr ^-1 , and methacrolein was reacted at 230 ° C.

After the start of the reaction, when a steady state was reached, the generated gas at the outlet of the reaction tube was collected and analyzed for its composition by gas chromatography (GC). As a result, the conversion of methacrolein was 8.1%, and the oxide compound containing a hetero element (epoxide compound containing a hetero element)
Of 2-methyl-2,3-epoxypropanal was 2.1%, and the conversion of hydrogen was 20.6%. From the above results, the space-time yield of 2-methyl-2,3-epoxypropanal per liter of catalyst was 20.6.
g / hr. The main reaction conditions are shown in Table 1, and
Table 2 shows the results.

Example 2 In the preparation operation of the catalyst in Example 1, the amount of tetrachloroauric acid (III) was reduced to 0.
A catalyst was obtained by performing the same operation as in the same example except that the amount was changed from 344 g to 7.2 g. When the content of gold in the catalyst was analyzed by a fluorescent X-ray analysis method, it was 7.00% by weight.

Then, the same reaction and analysis as in Example 1 were performed to evaluate the performance of the above catalyst with respect to the partial oxidation reaction of methacrolein.
As a result, the conversion of methacrolein was 5.1%,
The single stream yield of 2-methyl-2,3-epoxypropanal was 0.9% and the conversion of hydrogen was 17.1%. From the above results, 2-methyl- / L of the catalyst was obtained.
The space-time yield of 2,3-epoxypropanal is 8.8 g /
hr. The main reaction conditions are shown in Table 1, and the results are shown in Table 2.

Example 3 In the preparation of the catalyst in Example 1, the amount of titanium (II) oxide acetylacetonate used was changed from 1.96 g to 49.0 g.
A catalyst was obtained by performing the same operation as in the example. The content of titanium oxide, gold, and metal potassium in the catalyst was analyzed by X-ray fluorescence analysis.
23.7%, 0.75% and 0.41% by weight.

Then, the same reaction and analysis as those of Example 1 were performed to evaluate the performance of the above catalyst with respect to the partial oxidation reaction of methacrolein.
As a result, the conversion of methacrolein was 8.7%,
The single flow yield of 2-methyl-2,3-epoxypropanal was 1.1% and the conversion of hydrogen was 25.1%. From the above results, 2-methyl- / L of the catalyst was obtained.
Space-time yield of 2,3-epoxypropanal is 10.8 g
/ Hr. The main reaction conditions are shown in Table 1, and the results are shown in Table 2.

Example 4 The catalyst was prepared in the same manner as in Example 1 except that the step of impregnating the dried product with potassium hydroxide was omitted in the preparation operation of the catalyst in Example 1. Obtained. That is, after drying the titanium oxide-supported silicon oxide having the gold precipitate immobilized thereon, the dried product was calcined in air at 400 ° C. for 3 hours to obtain gold-containing titanium oxide-supported silicon oxide as a catalyst. .

Then, the same reaction and analysis as in Example 1 were performed to evaluate the performance of the above catalyst with respect to the partial oxidation reaction of methacrolein.
As a result, the conversion of methacrolein was 6.0%,
The single stream yield of 2-methyl-2,3-epoxypropanal was 0.9% and the conversion of hydrogen was 22.8%. From the above results, 2-methyl- / L of the catalyst was obtained.
The space-time yield of 2,3-epoxypropanal is 8.8 g /
hr. The main reaction conditions are shown in Table 1, and the results are shown in Table 2.

Example 5 The same operation as in Example 1 was carried out except that the amount of potassium hydroxide used was changed from 0.24 g to 1.20 g in the preparation operation of the catalyst in Example 1. As a result, a catalyst was obtained. When the content of potassium metal in the catalyst was analyzed by a fluorescent X-ray analysis method, it was 2.50% by weight.

Then, the same reaction and analysis as in Example 1 were carried out to evaluate the performance of the catalyst for the partial oxidation of methacrolein.
As a result, the conversion of methacrolein was 3.2%,
The single stream yield of 2-methyl-2,3-epoxypropanal was 1.0% and the conversion of hydrogen was 13.5%. From the above results, 2-methyl- / L of the catalyst was obtained.
The space-time yield of 2,3-epoxypropanal is 9.8 g /
hr. The main reaction conditions are shown in Table 1, and the results are shown in Table 2.

Comparative Example 1 The procedure of Example 1 was repeated except that tetrachloroauric acid was not used.
A catalyst for comparison was obtained. That is, titanium oxide-supported silicon oxide containing no gold was obtained as a comparative catalyst.

Then, the same reaction and analysis as in Example 1 were performed to evaluate the performance of the comparative catalyst with respect to the partial oxidation reaction of methacrolein. However, the comparative catalyst has no activity, and the conversion of methacrolein is a trace, and 2-methyl-2,
The single-stream yield of 3-epoxypropanal and the conversion of hydrogen were all 0%. The main reaction conditions are shown in Table 1, and the results are shown in Table 2.

Comparative Example 2 A comparative catalyst was prepared in the same manner as in Example 1 except that titanium (II) acetylacetonate was not used in the preparation of the catalyst in Example 1. I got That is, gold-supported silicon oxide was obtained as a comparative catalyst. When the content of gold in the comparative catalyst was analyzed by a fluorescent X-ray analysis method,
0.16% by weight.

Then, the same reaction and analysis as in Example 1 were performed to evaluate the performance of the comparative catalyst with respect to the partial oxidation reaction of methacrolein. As a result, the conversion of methacrolein was 3.6%, the single-stream yield of 2-methyl-2,3-epoxypropanal was 0.5%, and the conversion of hydrogen was 15.0%. there were. From the above results, it was found that 2-L per 1 L of the comparative catalyst was used.
The space-time yield of methyl-2,3-epoxypropanal was 4.9 g / hr. The main reaction conditions are shown in Table 1, and the results are shown in Table 2.

Example 6 By performing the same operation as in the preparation of the catalyst in Example 1, a titanium oxide-supported silicon oxide having a gold precipitate immobilized thereon was obtained as a dried product. Next, the dried product was immersed in an aqueous solution obtained by dissolving 0.06 g of sodium hydroxide and 0.12 g of rubidium hydroxide in 50 ml of ion-exchanged water. After impregnating the dried product with sodium hydroxide and rubidium hydroxide, the aqueous solution was filtered. The obtained residue was dried at 120 ° C. overnight, and the dried product was calcined in air at 400 ° C. for 3 hours to obtain silicon oxide supported on gold-containing titanium oxide as a catalyst. The content of metallic sodium and metallic rubidium in the catalyst was analyzed by X-ray fluorescence spectroscopy.
Met.

Then, the same reaction and analysis as those of Example 1 were performed to evaluate the performance of the catalyst for the partial oxidation of methacrolein.
As a result, the conversion of methacrolein was 8.7%,
The single stream yield of 2-methyl-2,3-epoxypropanal was 2.5% and the conversion of hydrogen was 19.7%. From the above results, 2-methyl- / L of the catalyst was obtained.
The space-time yield of 2,3-epoxypropanal is 24.6 g.
/ Hr. The main reaction conditions are shown in Table 1, and the results are shown in Table 2.

Example 7 By performing the same operation as that for preparing the catalyst in Example 1, a titanium oxide-supported silicon oxide having a gold precipitate immobilized thereon was obtained as a dried product. Next, the dried product was immersed in an aqueous solution obtained by dissolving 0.34 g of lithium hydroxide and 0.19 g of cesium hydroxide in 50 ml of ion-exchanged water. Then, after the dried product was impregnated with lithium hydroxide and cesium hydroxide, the aqueous solution was filtered. The obtained residue was dried at 120 ° C. overnight, and the dried product was calcined in air at 400 ° C. for 3 hours to obtain silicon oxide supported on gold-containing titanium oxide as a catalyst. When the contents of metallic lithium and metallic cesium in the catalyst were analyzed by X-ray fluorescence analysis,
0.31% by weight and 0.52% by weight.

Next, the performance of the above catalyst with respect to the partial oxidation reaction of acrolein as a hetero element-containing compound (hetero element-containing unsaturated compound) was evaluated. That is, the catalyst 1
ml was filled into a stainless steel reaction tube having an inner diameter of 8 mm.
Meanwhile, acrolein, hydrogen, oxygen, and helium,
These ratios are 9.8% by volume, 18.4% by volume, 1
The raw material gas was prepared by mixing 8.4% by volume and 53.4% by volume. Then, the raw material gas is supplied into the reaction tube at a space velocity of 3,300 hr ^-1 ,
Acrolein was reacted at 200 ° C.

After the reaction started, when a steady state was reached, the product gas at the outlet of the reaction tube was collected and analyzed for its composition by gas chromatography. As a result, the conversion of acrolein was 1.0%, and the hetero element-containing oxide compound (hetero element-containing epoxide compound) 2,3
The single-stream yield of epoxypropanal is 0.5%,
The conversion of hydrogen was 0.9%. From the above results, the space-time yield of 2,3-epoxypropanal per 1 L of the catalyst was 5.0 g / hr. The main reaction conditions are shown in Table 1, and the results are shown in Table 2.

Example 8 By performing the same operation as that for preparing the catalyst in Example 1, a titanium oxide-supported silicon oxide having a gold precipitate immobilized thereon was obtained as a dried product. Next, the dried product was treated with magnesium nitrate hexahydrate 0.70
g of calcium nitrate tetrahydrate and 0.50 g of calcium nitrate tetrahydrate were immersed in an aqueous solution prepared by dissolving 50 ml of ion-exchanged water. After the dried product was impregnated with magnesium nitrate and calcium nitrate, the aqueous solution was filtered. 1 residue obtained
After drying overnight at 20 ° C., the dried product is
By calcining at 3 ° C. for 3 hours, a silicon oxide supported on gold-containing titanium oxide was obtained as a catalyst. The content of metallic magnesium and metallic calcium in the catalyst was analyzed by X-ray fluorescence spectroscopy.
It was 30% by weight.

Next, the performance of the above catalyst for the partial oxidation reaction of crotonaldehyde as a hetero element-containing compound (hetero element-containing unsaturated compound) was evaluated. That is, 1 ml of the catalyst was filled in a stainless steel reaction tube having an inner diameter of 8 mm. On the other hand, crotonaldehyde, hydrogen, oxygen and helium were respectively 6.2% by volume and 19.
The raw material gas was prepared by mixing so as to be 2% by volume, 19.2% by volume, and 55.4% by volume. And
The raw material gas is introduced into the reaction tube at a space velocity of 3,190 hr.
^And crotonaldehyde was reacted at 210 ° C.

After the start of the reaction, when a steady state was reached, the gas produced at the outlet of the reaction tube was sampled, and its composition was analyzed by gas chromatography. As a result, the conversion of crotonaldehyde was 5.6%, and the single-stream yield of 2,3-epoxybutanal, which is a hetero element-containing oxide compound (hetero element-containing epoxide compound), was 0.9%. The conversion of hydrogen was 8.1%. From the above results, the space-time yield of 2,3-epoxybutanal per 1 L of the catalyst was 6.5 g / hr. Table 1 shows the main reaction conditions.
And the results are shown in Table 2.

Example 9 By performing the same operation as that for preparing the catalyst in Example 1, a titanium oxide-supported silicon oxide having a gold precipitate immobilized thereon was obtained as a dried product. Next, the dried product was immersed in an aqueous solution obtained by dissolving 0.10 g of strontium nitrate and 0.06 g of barium nitrate in 50 ml of ion-exchanged water. After impregnating the dried product with strontium nitrate and barium nitrate, the aqueous solution was filtered. The obtained residue was dried at 120 ° C. overnight, and the dried product was calcined in air at 400 ° C. for 3 hours to obtain silicon oxide supported on gold-containing titanium oxide as a catalyst. The content of metal strontium and metal barium in the catalyst was analyzed by X-ray fluorescence spectroscopy, and was found to be 0.12% by weight and 0.10% by weight.

Next, the performance of the above catalyst with respect to the partial oxidation reaction of allyl alcohol as a hetero element-containing compound (hetero element-containing unsaturated compound) was evaluated. That is, 1 ml of the catalyst was filled in a stainless steel reaction tube having an inner diameter of 8 mm. On the other hand, by mixing allyl alcohol, hydrogen, oxygen, and helium such that their proportions are respectively 6.7% by volume, 19.1% by volume, 19.1% by volume, and 55.1% by volume, Source gas was prepared. Then, the above-mentioned raw material gas was supplied into the reaction tube at a space velocity of 3,200 hr ^-1 , and allyl alcohol was reacted at 150 ° C.

After the start of the reaction, when a steady state was reached, the produced gas at the outlet of the reaction tube was collected and analyzed for its composition by gas chromatography. As a result, the conversion of allyl alcohol was 15.3%, the single stream yield of glycidol, which is a hetero element-containing oxide compound (hetero element-containing epoxide compound), was 3.8%, and the hydrogen conversion was 7%. 0.2%. From the above results, the space-time yield of glycidol per 1 L of the catalyst was 26.9 g / hr. The main reaction conditions are shown in Table 1, and the results are shown in Table 2.

Example 10 In the preparation operation of the catalyst in Example 1, the amount of tetrachloroauric acid was changed from 0.344 g to 1.00 g, and the amount of potassium hydroxide was changed to 0.1 g. A catalyst was obtained by performing the same operation as in the example except that the amount was changed from 24 g to 0.60 g. When the contents of gold and metal potassium in the catalyst were analyzed by X-ray fluorescence analysis,
00% and 1.20% by weight.

Next, the performance of the above catalyst for the partial oxidation reaction of methyl acrylate as a hetero element-containing compound (hetero element-containing unsaturated compound) was evaluated. That is, 1 ml of the catalyst was filled in a stainless steel reaction tube having an inner diameter of 8 mm. On the other hand, by mixing methyl acrylate, hydrogen, oxygen, and helium such that their proportions become 6.4% by volume, 19.1% by volume, 19.1% by volume, and 55.4% by volume, respectively. , A raw material gas was prepared. Then, the raw material gas was supplied into the reaction tube at a space velocity of 3,250 hr ^-1 , and methyl acrylate was reacted at 230 ° C.

After the start of the reaction, when a steady state was reached, the generated gas at the outlet of the reaction tube was collected and analyzed for its composition by gas chromatography. As a result, the conversion of methyl acrylate was 4.4%, and the single flow yield of methyl 2,3-epoxypropionate, which is a hetero element-containing oxide compound (hetero element-containing epoxide compound), was 0.4%.
The conversion of hydrogen was 18.3%. From the above results, the space-time yield of methyl 2,3-epoxypropionate per 1 L of the catalyst was 4.1 g / hr. The main reaction conditions are shown in Table 1, and the results are shown in Table 2.

Example 11 The procedure of Example 1 was repeated, except that the amount of tetrachloroauric acid used was changed from 0.344 g to 3.00 g. By performing the operation, a catalyst was obtained.
When the content of gold in the catalyst was analyzed by a fluorescent X-ray analysis method, it was 3.20% by weight.

Next, the performance of the above catalyst with respect to the partial oxidation reaction of methyl methacrylate as a hetero element-containing compound (hetero element-containing unsaturated compound) was evaluated. That is, 1 ml of the catalyst was filled in a stainless steel reaction tube having an inner diameter of 8 mm. On the other hand, methyl methacrylate, hydrogen, oxygen and helium were respectively 5.8% by volume and 19.
The raw material gas was prepared by mixing so as to be 3% by volume, 19.3% by volume, and 55.6% by volume. And
The raw material gas is introduced into the reaction tube at a space velocity of 3,200 hr.
^-1 , and reacted with methyl methacrylate at 150 ° C.

After the start of the reaction, when a steady state was reached, the gas produced at the outlet of the reaction tube was collected, and its composition was analyzed by gas chromatography. As a result, the conversion of methyl methacrylate was 1.0%, and the single stream yield of methyl 2-methyl-2,3-epoxypropionate, which is a hetero element-containing oxide compound (hetero element-containing epoxide compound), was 0%. The conversion of hydrogen was 3.7%. From the above results, 2-methyl- / L of the catalyst was obtained.
The space-time yield of methyl 2,3-epoxypropionate is 2.
It was 7 g / hr. The main reaction conditions are shown in Table 1, and the results are shown in Table 2.

Example 12 A catalyst was obtained by performing the same preparation operation as that of the catalyst in Example 1. Next, the performance of the above catalyst with respect to the partial oxidation reaction of vinyl acetate as a hetero element-containing compound (hetero element-containing unsaturated compound) was evaluated. That is, 1 ml of the catalyst was filled in a stainless steel reaction tube having an inner diameter of 8 mm. On the other hand, vinyl acetate, hydrogen, oxygen, and helium are mixed so that their proportions are 6.1% by volume, 19.6% by volume, 19.6% by volume, and 54.7% by volume, respectively.
Source gas was prepared. Then, the raw material gas was supplied into the reaction tube at a space velocity of 3,200 hr ^-1 , and vinyl acetate was reacted at 210 ° C.

After the start of the reaction, the gas produced at the outlet of the reaction tube was sampled at the time of the steady state, and the composition was analyzed by gas chromatography. As a result, the conversion of vinyl acetate was 44.0%, the single flow yield of epoxyethyl acetate, which is a hetero element-containing oxide compound (hetero element-containing epoxide compound), was 0.5%, and the hydrogen conversion was Was 19.6%. From the above results, the space-time yield of epoxyethyl acetate per liter of the catalyst was 4.4 g / hr.
Met. The main reaction conditions are shown in Table 1, and the results are shown in Table 2.

Example 13 A catalyst was obtained by performing the same preparation operation as that of the catalyst in Example 1. Next, the performance of the catalyst for the partial oxidation reaction of acrylonitrile as a hetero element-containing compound (hetero element-containing unsaturated compound) was evaluated. That is, 1 ml of the catalyst
Was filled in a stainless steel reaction tube having an inner diameter of 8 mm. On the other hand, acrylonitrile, hydrogen, oxygen, and helium are mixed so that their proportions are 3.8% by volume, 19.7% by volume, 19.7% by volume, and 56.8% by volume, respectively. Gas was prepared. Then, the above-mentioned raw material gas was supplied into the reaction tube at a space velocity of 3,100 hr ^-1 , and acrylonitrile was reacted at 260 ° C.

After the start of the reaction, when a steady state was reached, the product gas at the outlet of the reaction tube was collected and analyzed for its composition by gas chromatography. As a result, the conversion of acrylonitrile was 0.5%, and the single-stream yield of 2,3-epoxypropionitrile, which is a hetero element-containing oxide compound (hetero element-containing epoxide compound), was 0.1%.
% And the conversion of hydrogen was 30.2%. From the above results, the space-time yield of 2,3-epoxypropionitrile per liter of the catalyst was 0.36 g / hr. The main reaction conditions are shown in Table 1, and the results are shown in Table 2.

Example 14 A catalyst was obtained by performing the same preparation operation as in the preparation of the catalyst in Example 1. Next, the performance of the catalyst for the partial oxidation reaction of N-methylmorpholine as a hetero element-containing compound (nitrogen-containing compound) was evaluated. That is, 1 ml of this catalyst is
mm in a stainless steel reaction tube. On the other hand, N-methylmorpholine, hydrogen, oxygen, and helium were used in proportions of 9.1% by volume, 18.6% by volume, and 18.6%, respectively.
The raw material gas was prepared by mixing so as to be 53.7% by volume. Then, the above raw material gas was supplied into the reaction tube at a space velocity of 3,300 hr ^-1 , and N-methylmorpholine was reacted at 250 ° C.

After the start of the reaction, when a steady state was attained, the gas produced at the outlet of the reaction tube was collected, and its composition was analyzed by gas chromatography. As a result, the conversion of N-methylmorpholine was 19.8%, and the single stream yield of N-methylmorpholine-N-oxide, which is a hetero element-containing oxide compound (N-oxide compound), was 0.5%. And the conversion of hydrogen was 3.9%. From the above results, the space-time yield of N-methylmorpholine-N-oxide per liter of the catalyst was 5.4 g / hr. The main reaction conditions are shown in Table 1, and the results are shown in Table 2.

[Example 15] In the preparation operation of the catalyst in Example 1, the amount of tetrachloroauric acid (III) was changed from 0.344 g to 5.00 g, and the amount of potassium hydroxide was reduced to 0. A catalyst was obtained by performing the same operation as in the same example except that the amount was changed from 24 g to 0.96 g. The content of gold and metal potassium in the catalyst was analyzed by X-ray fluorescence analysis.
20% by weight and 2.10% by weight.

Next, the performance of the above catalyst with respect to the partial oxidation reaction of allyl chloride as a hetero element-containing compound (hetero element-containing unsaturated compound) was evaluated. That is, the catalyst 1m
was filled in a stainless steel reaction tube having an inner diameter of 8 mm. On the other hand, allyl chloride, hydrogen, oxygen and helium were used in proportions of 5.0% by volume, 19.4% by volume and 19.
The raw material gas was prepared by mixing so as to be 4% by volume and 56.2% by volume. Then, the above-mentioned raw material gas was supplied into the reaction tube at a space velocity of 3,150 hr ^-1 , and allyl chloride was reacted at 320 ° C.

After the start of the reaction, when a steady state was reached, the generated gas at the outlet of the reaction tube was collected and analyzed for its composition by gas chromatography. As a result, the conversion of allyl chloride was 0.9%, the single-stream yield of epichlorohydrin, which is a hetero element-containing oxide compound (hetero element-containing epoxide compound), was 0.3%, and the conversion of hydrogen was 0.3%. Rate was trace. From the above results, the space-time yield of epichlorohydrin per liter of the catalyst was 2.0 g / hr. The main reaction conditions are shown in Table 1, and the results are shown in Table 2.

[0093]

[Table 1]

[0094]

[Table 2]

[0095]

As described above, the method for producing a hetero element-containing oxide compound according to claim 1 of the present invention comprises a catalyst containing gold, titanium oxide, and a carrier having a specific surface area of 50 m ² / g or more. And partially oxidizing the hetero element-containing compound in the presence of hydrogen and oxygen.

The method for producing a hetero element-containing oxide compound according to claim 2 of the present invention is a method of performing partial oxidation in a gas phase as described above.

[0097] The method for producing a hetero element-containing oxide compound according to claim 3 of the present invention, as described above, is characterized in that the hetero element-containing compound is a hetero element-containing unsaturated compound and the hetero element-containing oxide compound is a hetero element-containing oxide compound. Epoxide compound.

In the method for producing a hetero element-containing oxide compound according to claim 4 of the present invention, as described above, the hetero element includes at least one element selected from the group consisting of oxygen, nitrogen, and a halogen element. That's the way you are.

As described above, the method for producing a hetero element-containing oxide compound according to claim 5 of the present invention is characterized in that the hetero element-containing compound is a nitrogen-containing compound and the hetero element-containing oxide compound is an N-oxide compound. There is one way.

The method for producing a hetero element-containing oxide compound according to claim 6 of the present invention is a method wherein the carrier contains silicon oxide and / or aluminum oxide as described above.

The method for producing a hetero element-containing oxide compound according to claim 7 of the present invention is a method as described above, wherein the catalyst further contains an alkali metal and / or an alkaline earth metal.

The method for producing a hetero element-containing oxide compound according to claim 8 of the present invention is a method in which the gold content in the catalyst is 0.01% by weight or more as described above.

According to the method for producing a hetero element-containing oxide compound according to the ninth aspect of the present invention, as described above, the content of gold in the catalyst is 0.1% by weight to 10% by weight, and the content of titanium oxide is Is 0.1% by weight to 20% by weight, and the content of alkali metal and / or alkaline earth metal is 0.01% by weight to 3% by weight.

As a result, a hetero element-containing oxide compound such as a hetero element-containing epoxide compound or an N-oxide compound is directly and directly converted from a hetero element-containing unsaturated compound or a nitrogen-containing compound such as a hetero element-containing compound. This has the effect that it can be manufactured at lower cost than the conventional method using hydrogen peroxide or hydroperoxides as an oxidizing agent.

Continued on the front page (72) Inventor Masahiro Wada 5-8 Nishiburi-cho, Suita-shi, Osaka Nippon Shokubai Co., Ltd. (72) Inventor Masatake Haruta 1-81-31 Midorigaoka, Ikeda-shi, Osaka Industrial Technology Osaka Within the Institute of Industrial Technology (72) Inventor Toshi Tsubota Inside the Osaka Institute of Technology, 1-8-31 Midorioka, Ikeda-shi, Osaka

Claims (9)

[Claims] (1) gold, titanium oxide, and a specific surface area of 50 m ^2;
A method for producing a hetero element-containing oxide compound, comprising partially oxidizing a hetero element-containing compound in the presence of hydrogen and oxygen using a catalyst containing at least / g of a carrier. 2. The method for producing a hetero element-containing oxide compound according to claim 1, wherein partial oxidation is performed in a gas phase. 3. The hetero element-containing oxide according to claim 1, wherein the hetero element-containing compound is a hetero element-containing unsaturated compound, and the hetero element-containing oxide compound is a hetero element-containing epoxide compound. A method for producing a compound. 4. The method for producing a hetero element-containing oxide compound according to claim 3, wherein the hetero element includes at least one element selected from the group consisting of oxygen, nitrogen, and a halogen element. 5. The method for producing a hetero element-containing oxide compound according to claim 1, wherein the hetero element-containing compound is a nitrogen-containing compound, and the hetero element-containing oxide compound is an N-oxide compound. . 6. The method for producing a hetero element-containing oxide compound according to claim 1, wherein the carrier contains silicon oxide and / or aluminum oxide. 7. The method for producing a hetero element-containing oxide compound according to claim 1, wherein the catalyst further contains an alkali metal and / or an alkaline earth metal. 8. The gold content of the catalyst is 0.01% by weight.
The method for producing a hetero element-containing oxide compound according to any one of claims 1 to 7, wherein: 9. The catalyst according to claim 1, wherein the content of gold is 0.1% by weight or more.
10% by weight, and the content of titanium oxide is 0.1% by weight
The hetero element-containing oxide compound according to claim 7 or 8, wherein the content of the alkali metal and / or the alkaline earth metal is 0.01% to 3% by weight. Manufacturing method.