JPH0535135B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a method for producing α,β-ethylenically unsaturated carbonyl compounds in the presence of a titanium-containing catalyst which is extremely easy to prepare. [Prior art] Methyl vinyl ketone (1-buten-3-one), which is one of α,β-ethylenically unsaturated carbonyl compounds, has conventionally been produced by a condensation reaction of acetone and formaldehyde (or methylal). However, since a strong alkali such as caustic soda is used as a catalyst at this time, undesirable problems arise such as the cost of concentrating the spent alkali and the need to neutralize the waste liquid. Further, there are other problems such as formaldehyde being unstable and the method of preparing the catalyst being a coprecipitation method, which makes the process of preparing the catalyst complicated. In addition, a production method using a hydration reaction of vinyl acetylene is also known, but this method requires the use of harmful mercury as a catalyst,
Vinyl acetylene itself is easily polymerized and is therefore difficult to handle, which is not industrially advantageous. Furthermore, a method for producing methyl vinyl ketone using methanol and acetone as raw materials is also known [Chemistry Letters 333 (1973)/Chem.Lett.333
(1973), JC Chemical Communication 39 (1984); JCSChem
Commun. 39 (1984) and Japanese Unexamined Patent Publication No. 59-36635]. This method is industrially advantageous because it uses cheap methanol as a raw material, but on the other hand, since it does not use oxygen, the by-product hydrogen is used to hydrogenate the product methyl vinyl ketone or the raw material acetone. However, there are problems such as large amounts of methyl ethyl ketone and isopropanol being produced as by-products. [Problems to be Solved by the Invention] The present invention solves the above-mentioned conventional problems and produces α,β-ethylenically unsaturated carbonyl compounds in high yield using a titanium-containing catalyst that is extremely easy to prepare. The purpose is to provide a method for manufacturing. [Means and effects for solving the problem] The method for producing an α,β-ethylenically unsaturated carbonyl compound of the present invention includes a method for producing an α,β-ethylenically unsaturated carbonyl compound using a titanium compound supported on fluorine tetrasilicon mica, sepiolite, taeniolite, hectorite or silica gel; titanium It is characterized by reacting methanol, ketones, and oxygen with at least one catalyst selected from the group of ion-exchanged fluorine tetrasilicon mica, sepiolite, taeniolite, hectorite, or siliga gel; or titanium oxide. First, one of the ketones used as raw materials in the present invention is acetone,
Methyl ethyl ketone, methyl-n-propyl ketone, methyl-iso-propyl ketone, methyl-n
-butyl ketone, acetophenone, benzylmethyl ketone, cyclohexanone, cyclopentanone, etc. The titanium-containing catalyst used in the present invention includes fluorine tetrasilicon mica (NaMg ₂₅ Si ₄ O ₁₀ F ₂ ), sepiolite (Mg ₈ H ₂ (Si ₄ O ₁₁ ) _{3-8H 2} O), and taeniolite (NaMg ₂ LiSi ₄ O ₁₀ F ₂ ), hectorite (Na _1/3
A layered material such as Mg _8/3 Li _1/3 Si ₄ O ₁₀ F ₂ ) or silica gel is used as a carrier, and a titanium compound is supported on these, and a part of the interlayer cations of the above carrier are ion-exchanged with titanium. , and even titanium oxide itself. At this time, in the case of a carrier ion-exchanged with titanium, titanium is ion-exchanged and supported as Ti ³⁺ and Ti ⁴⁺ . In addition, Zn ²⁺ , Cr ³⁺ , Mn ²⁺ ,
There is no problem even if metal ions such as Fe ³⁺ , Ni ²⁺ , Co ²⁺ are supported. The amount of the titanium compound supported on the carrier or the rate of ion exchange of titanium is unique because it is necessary to vary it depending on the type and amount of the α,β-ethylenically unsaturated carbonyl compound to be produced. However, in the case of loading, the amount should be adjusted to 0.01 to 60% by weight based on the carrier, and in the case of ion exchange, it should be adjusted to 0.1 to 100% by weight based on the amount of interlayer cations to be exchanged. is preferred. Particularly preferably, the amount is 1 to 30% by weight in the case of support, and 5 to 100% by weight in the case of ion exchange. If it is outside this range, the ability of the resulting catalyst to produce an α,β-ethylenically unsaturated carbonyl compound will not be fully exhibited, which is not preferable. The catalyst according to the present invention is produced, for example, as follows. That is, first, purified fluorine tetrasilicon mica,
A carrier suspension is prepared by dispersing a layered material such as sepiolite, taeniolite, hectorite, or silica gel powder in water. Next, a predetermined amount of an aqueous solution of a titanium compound having a predetermined concentration is added thereto, and the mixture is stirred at room temperature or left to stand to exchange interlayer cations of the carrier with titanium ions. At this time, the titanium compounds used include titanium trichloride,
Examples include titanium tetrachloride, titanium sulfate, and titanium oxyacetylacetonate. Since the amount of supported titanium compound or the ratio of ion exchange of titanium is determined by the concentration of the aqueous titanium compound solution, the stirring time, or the length of the standing time, these conditions are set appropriately in consideration of the relationship with the amount supported above. . Thereafter, the suspension is filtered and washed repeatedly, and the resulting solid cake is dried to obtain the catalyst of the present invention.
The catalyst prepared in this way is a powder,
When used, it may be used as a powder or, if necessary, may be formed into an appropriate shape such as a tablet or sphere. The reaction is carried out by filling a reaction tube with a catalyst and introducing nitrogen/
A mixture of oxygen gas and methanol/ketones may be flowed as a gas. The molar ratio of nitrogen/oxygen mixed gas is 0/1 to 100/1, preferably 1/20.
~20/1. The molar ratio of the methanol/ketone mixture is from 0.01 to 100, preferably from 0.1 to 100.
It is 10. The flow rate of the nitrogen/oxygen gas mixture is preferably 1 to 1000 ml/min per unit weight of the catalyst, and the flow rate of the methanol/ketone mixture gas is preferably 0.1 to 500 ml/min. The reaction temperature is set at 200-500°C. Preferably it is 250-450°C. The pressure may be reduced pressure, normal pressure, or increased pressure, but it is usually preferably carried out at 0.1 to 50 atmospheres. In addition, the contact time of nitrogen/oxygen mixed gas and methanol/ketones mixed gas with the catalyst is 0.01 to 100 seconds,
Preferably it is 0.1 to 50 seconds. In this way, there are many kinds of α,β-ethylenically unsaturated carbonyl compounds produced depending on the type of raw materials, but examples include methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, butyl vinyl ketone. , phenyl vinyl ketone, benzyl vinyl ketone, 2-methylidenecyclohexanone, 2-methylidenecyclopentanone, and the like. [Example] Example 1 1 Preparation of catalyst 2 g of purified fluorine tetrasilicon mica powder was added to water.
A carrier sol was prepared by dispersing in 800 g and stirring at room temperature for 2.5 hours. Add a solution of 2ml of 20% titanium trichloride aqueous solution diluted with 200ml of water,
The mixture was further stirred at room temperature for 2 hours to perform ion exchange. Thereafter, the entire cake was filtered and washed repeatedly, and the obtained solid cake was dried at 120° C. overnight to obtain a catalyst powder. 2 Production of Methyl Vinyl Ketone 1 g of the above catalyst was filled into a glass reaction tube and first calcined at 350° C. for 2 hours in a nitrogen stream. At that temperature, a mixed gas of nitrogen/oxygen = 3/1 (molar ratio) is mixed with methanol/acetone at a flow rate of 20 ml/min.
3ml/1/1 (molar ratio) mixture as a gas
It was supplied to the catalyst layer at a flow rate of min. The results of analysis of the obtained reaction products are shown in the table. Example 2 1 Preparation of catalyst 2 g of purified fluorine tetrasilicon mica and 800 g of water
and stirred at room temperature for 2.5 hours to prepare a carrier sol. To this were added 2 ml of a 20% titanium trichloride aqueous solution and a solution of 9.78 mg of zinc chloride diluted with 200 ml of water, and the mixture was further stirred at room temperature for 3 hours to perform ion exchange. Thereafter, the entire cake was filtered and washed repeatedly, and the obtained solid cake was dried at 120°C to obtain a catalyst powder. 2 Production of Methyl Vinyl Ketone The reaction was carried out in the same manner as in Example 1, except that 1 g of the catalyst in 1 above was used. The results obtained are shown in the table. Example 3 A reaction was carried out in the same manner as in Example 1, except that the catalyst of Example 2 was used and the methanol/acetone molar ratio was 9/1. The results obtained are shown in the table. Example 4 Instead of zinc chloride in Example 2, chromium chloride.
A catalyst was prepared using 19.1 mg of hexahydrate. A reaction was carried out in the same manner as in Example 1 using the above catalyst. The results obtained are shown in the table. Example 5 In place of zinc chloride in Example 2, 14.2 mg of manganese chloride tetrahydrate was used to prepare a catalyst. A reaction was carried out in the same manner as in Example 1 using the above catalyst. The results obtained are shown in the table. Example 6 Instead of zinc chloride in Example 2, ferric chloride
A catalyst was prepared using 19.4 mg of hexahydrate. A reaction was carried out in the same manner as in Example 1 using the above catalyst. The results obtained are shown in the table. Example 7 In place of zinc chloride in Example 2, 17.1 mg of nickel chloride hexahydrate was used to prepare a catalyst. A reaction similar to that in Example 1 was carried out using the above catalyst. The results obtained are shown in the table. Example 8 A catalyst was prepared in the same manner as in Example 1, except that 2.1 g of a 30% titanium sulfate aqueous solution was used instead of the titanium trichloride aqueous solution in Example 1. A reaction was carried out in the same manner as in Example 1 using the above catalyst. The results obtained are shown in the table. Example 9 A catalyst was prepared in the same manner as in Example 2, except that the amount of zinc chloride in Example 2 was increased to 76.1 mg. A reaction was carried out in the same manner as in Example 1 using the above catalyst. The results obtained are shown in the table. Example 10 A catalyst was prepared in the same manner as in Example 1, except that 2 g of fluorine tetrasilicon mica in Example 1 was replaced with 2 g of hectorite. A reaction was carried out in the same manner as in Example 1 using the above catalyst. The results obtained are shown in the table. Example 11 A reaction was carried out in the same manner as in Example 1, except that 1 g of commercially available titanium oxide (anatase type) was used as a catalyst and the reaction temperature was 300°C. The results obtained are shown in the table. Comparative Example 1 A reaction was carried out in the same manner as in Example 1, except that the catalyst of Example 2 was used and nitrogen gas was supplied at 20 ml/min instead of the nitrogen/oxygen mixed gas. The results obtained are shown in the table.

[Table] [Effects of the Invention] As is clear from the above explanation, the catalyst used in the method of the present invention is extremely easy to prepare. Further, according to the present invention, various α,β-ethylenically unsaturated carbonyl compounds can be produced in extremely high yields, and the industrial value thereof is great.

Claims (1)

[Claims] 1. A method for producing an α,β-ethylenically unsaturated carbonyl compound, which comprises reacting methanol, ketones, and oxygen in the presence of a titanium-containing catalyst. 2 The titanium-containing catalyst is fluorine-tetrasilicon mica, sepiolite, taeniolite, hectorite, silica gel supporting a titanium compound; fluorine-tetrasilicon mica, sepiolite, taeniolite, hectorite, silica gel ion-exchanged with titanium; or titanium oxide. 2. The method according to claim 1, wherein the catalyst is at least one catalyst selected from the group consisting of: