JPS6221338B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing a carbonyl compound from butene, and more particularly to a method for efficiently producing a carbonyl compound by oxidizing butene in the presence of a specific catalyst. As a method for producing carbonyl compounds by oxidizing olefins, the so-called Hoechst-Watzker process is known (Japanese Patent Publication No. 7869/1983). but,
This method has drawbacks such as a considerable amount of halides being produced as by-products and a low conversion rate when oxidizing olefins having 4 or more carbon atoms. Furthermore, in conventional Watzker type catalysts, the reactivity of internal olefins was extremely poor compared to that of unterminated olefins. Since then, various proposals have been made as catalysts for use in the production of carbonyl compounds. For example, there are catalysts that combine palladium or rhodium with iron, cobalt, nickel, or manganese. There are few by-products, but the activity is low (Japanese Patent Publication No. 51-6643, Japanese Patent Publication No. 53
-43686). The present inventors have repeatedly conducted research on various catalysts or supports for the production of olefins, particularly methyl ethyl ketone by catalytic oxidation of butene, which has few problems as an industrial production method and has low reactivity. As a result, it has already been found that methyl ethyl ketone can be efficiently produced without the need for a reoxidizing agent by using a specific catalyst containing a rhodium compound, but the present invention further improves this method to further produce carbonyl compounds. The purpose is to provide an efficient manufacturing method. The present invention provides a method for producing a carbonyl compound by reacting butene, water, and oxygen or an oxygen-containing gas in the presence of a catalyst, in which the catalysts include (a) rhodium, (b) manganese, and (c) cobalt, iron, and nickel. , bismuth, and tin, as a catalyst in which γ-alumina supports at least one element selected from the group consisting of bismuth and tin. The catalyst used in the present invention is a system of rhodium and manganese to which metals such as cobalt, iron, nickel, bismuth, tin, and zinc are added as a third component. Component (a) rhodium can be made from various compounds, including halides, sulfates, chlorates, formates, acetates, monochloroacetates, benzoates, naphthenates, oxides, There are hydroxides, etc. Component (a) is used in an amount of 0.2 to 5 parts by weight as an element per 100 parts by weight of γ-alumina of the carrier. Next, various types of manganese can be used as raw materials for the component (b), such as halides, sulfates, nitrates, carbonates, acetates, oxalates, and hydroxides. This (b) component is carrier 100
The element is used in an amount of 0.5 to 30 parts by weight per part by weight. Further, as for component (c), halides, nitrates, sulfates, carbonates, acetates, oxalates, perchlorates, hydroxides, oxides, etc. of the above metals can be mentioned. Component (c) is used in an amount of 0.5 to 30 parts by weight as an element per 100 parts by weight of the carrier. The γ-alumina of the carrier is preferably treated with hydrochloric acid. To support the catalyst component on the carrier, methods such as ordinary impregnation method and adsorption method, or method of mixing an aqueous solution of the catalyst component with a colloidal carrier, concentrating and solidifying it, and then forming it, can be applied. Or carry it in several stages. The carrier supporting the catalyst component has a molecular weight of 100 to 800 after drying.
℃, preferably 200 to 600℃ in air or under an atmosphere of inert gas, nitrogen gas, etc. 1 to 10
By calcining for a period of time, preferably 3 to 8 hours, a highly active and stable catalyst can be obtained. Here, an example of a catalyst preparation method is shown in which γ-alumina is used as a carrier, impregnated with a solution of the metal of component (c), and after drying, 200 to 500
C. for 3 to 5 hours, then impregnated with solutions of rhodium as component (a) and manganese as component (b), dried, and then heat treated at 200 to 500 DEG C. for 3 to 5 hours. In the present invention, butenes include butene-1,
Butene-2 and mixtures thereof can be used. In the present invention, the above-mentioned butene is reacted with oxygen or an oxygen-containing gas in the presence of water, and the mixing ratio of these is olefin:oxygen:water=1:1 to 40:1.
40 (capacity ratio). The reaction temperature is 50 to 400°C, preferably 80 to 300°C, and the reaction pressure is not particularly limited and is usually carried out at atmospheric pressure to 50 Kg/cm ² , and for reacting butene-2, it is 1 to 5 Kg/cm ² G is preferred. There are no restrictions on contact time, but in general
0.5-20 seconds is sufficient. Further, this reaction can be carried out using any fixed bed, fluidized bed, or moving bed method, and is carried out using a gas phase method, a gas-liquid mixing method, or a liquid phase method, but preferably a gas phase reaction is carried out using a flow-through method. By doing so, it becomes easy to separate and purify the product. Here, the oxygen-containing gas includes, in addition to air, a mixed gas of oxygen and an inert gas (such as nitrogen), and water is desirably vaporized through a preheating layer and introduced into the reaction system as water vapor. According to the present invention, methyl ethyl ketone can be produced in high yield from an olefin with low reactivity such as butene, and a major advantage of the present invention, which is not found in conventional methods, is that methyl ethyl ketone can be produced in high yield, and there is little by-product of halides such as 2-chloroethyl methyl ketone. It is a special feature. Furthermore, the catalyst used in the method of the present invention has excellent strength and stability,
It is industrially very advantageous. Next, the present invention will be explained in detail using examples. Example 1 2.3 g of anhydrous iron chloride (FeCl ₃ ) was dissolved in 80 ml of distilled water, and γ-Al ₂ O ₃ (specific surface area 200 m ² /
78.2 g (3 mm φ x 3 mm) was immersed and then evaporated to dryness. This was baked at 500° C. for 4 hours under air circulation. Next, manganese chloride (MnCl ₂
4H ₂ O) and 2.8 g of rhodium chloride (RhCl ₃ .
2.0 g of 3H ₂ O) was dissolved in 80 ml of distilled water, and the above support was impregnated with this solution, dried, and then heated at 200° C. for 3 hours under air circulation. As a result, a catalyst was obtained in which 1 part by weight of each of rhodium, manganese and iron was supported per 100 parts by weight of the carrier. A glass reaction tube with a diameter of 25 mm was filled with 30 ml of the above catalyst, and a mixed gas consisting of 17.5% by volume of butene, 5% by volume of oxygen, and 87.5% by volume of water was heated at 135°C and normal pressure.
The reaction was carried out under conditions of a contact time of 9 seconds. The results are shown in Table 1. Example 2 2.8 g of manganese chloride (MnCl ₂ 4H ₂ O) and 9.5 g of cobalt chloride (CoCl ₂ 6H ₂ O) were dissolved in 80 ml of distilled water, and γ-Al ₂ O ₃ (same as Example 1) was dissolved. After impregnating 78.2g, it was dried. Next, 2 g of rhodium chloride (RhCl ₃ .3H ₂ O) was dissolved in 80 ml of distilled water, impregnated into the above support, and then calcined at 200°C for 4 hours under air circulation to dissolve 1 part by weight of rhodium per 100 parts by weight of the support. A catalyst was obtained in which 1 part by weight of manganese and 3 parts by weight of cobalt were supported. Using 30 ml of this catalyst, the same procedure as in Example 1 was carried out.
The reaction was carried out at 160°C. The results are shown in Table 1. Comparative Example 1 2.3 g of anhydrous iron chloride (FeCl ₃ ) was dissolved in 80 ml of distilled water, and this was dissolved in 78.2 g of γ-Al ₂ O ₃ (same as Example 1).
After impregnation and drying, it was baked at 500°C for 4 hours under air circulation. Then rhodium chloride (RhCl _{3.3H 2} O)
Dissolve 2g in 80ml of distilled water, impregnate the above support with this solution, dry and heat at 200°C under air circulation.
The catalyst was calcined for 3 hours to obtain a catalyst in which 1 part by weight of each of rhodium and iron was supported per 100 parts by weight of the carrier. Example 1 Using 30 ml of the catalyst thus obtained
reacted in the same way. The results are shown in Table 1. Comparative Examples 2 to 4 Manganese chloride (MnCl ₂ .
4H ₂ O) (Comparative Example 2), cobalt chloride (CoCl ₂ 6H ₂ O) 9.5 g (Comparative Example 3), or vanadyl oxalate 7.8 g (Comparative Example 4). I did the same thing. The results are shown in Table 1. Comparative Example 5 4.1 g of cupric chloride (CuCl ₂ ) was dissolved in 80 ml of distilled water, impregnated with 78.2 g of γ-Al ₂ O ₃ (same as in Example 1), dried, and then heated at 200°C under air circulation. It was baked for 4 hours. Then rhodium chloride (RhCl _{3.3H 2} O)
2 g was dissolved in 80 ml of distilled water, impregnated with the above support, dried, and fired at 200°C for 3 hours under air circulation to obtain 1 part by weight of rhodium and 2.5 parts by weight of copper per 100 parts by weight of the support.
A catalyst was obtained in which parts by weight were supported. A reaction was carried out in the same manner as in Example 1 using 30 ml of this catalyst. The results are shown in Table 1. Comparative Example 6 The same procedure as Comparative Example 5 was carried out except that 1.3 g of palladium chloride (PdCl ₂ ) was used instead of rhodium chloride and the amount of cupric chloride (CuCl ₂ ) was changed to 9.9 g. A catalyst supporting 1 part by weight of palladium and 6 parts by weight of copper was obtained. A reaction was carried out in the same manner as in Example 1 using 30 ml of this catalyst. The results are shown in Table 1.

[Table] Examples 3 to 6 30 ml of the catalyst of Example 1 was filled into a stainless steel reaction tube with a diameter of 25 mm, and a mixed gas consisting of 17.5% butene, 5% oxygen, 17.5% nitrogen, and 70% water (by volume) was prepared. The reaction was carried out at various reaction temperatures and pressures with a contact time of 9 seconds. The results are shown in Table 2. Comparative Examples 7-8 Catalyst of Comparative Example 1 (Rhodium (1 part by weight) - Iron (1 part by weight)/γ-Al ₂ O ₃ (100 parts by weight)) or Catalyst of Comparative Example 2 (Rhodium (1 part by weight) - Manganese (1 part by weight)/γ-Al ₂ O ₃ (100 parts by weight)) was used to react in the same manner as in Example 6. The results are shown in Table 2.

[Table] Example 7 The same operation as in Example 6 was performed except that the contact time was 6 seconds, and the results shown below were obtained. Conversion rate of butene-1 63 mol% Selectivity of methyl ethyl ketone 88 mol% Yield of methyl ethyl ketone 55 mol% Examples 8 to 11 Catalysts with various metal loading ratios were prepared using the catalyst preparation method of Example 1, The reaction was carried out in the same manner as in Example 1. The results are shown in Table 3.

[Table] Examples 12 to 13 Using the catalyst preparation method of Example 2, catalysts with various metal loading rates were prepared and reacted in the same manner as in Example 1. The results are shown in Table 4.

[Table] Example 14 Using the catalyst preparation method of Example 2, a catalyst was prepared in which 1 part by weight of rhodium, 3 parts by weight of manganese, and 1 part by weight of cobalt were supported per 100 parts by weight of the carrier.
30 ml of the obtained catalyst was packed into a stainless steel reaction tube with a diameter of 25 mm, and the mixture was filled with 17.5% butene, 5% oxygen, and nitrogen.
A mixed gas consisting of 17.5% water and 70% water (volume composition)
The reaction was carried out at 210° C., 3 Kg/cm ² G, and a contact time of 9 seconds, and the results shown below were obtained. Conversion rate of butene-1 73 mol% Selectivity of methyl ethyl ketone 80 mol% Yield of methyl ethyl ketone 58 mol% Example 15 Catalyst of Example 1 (rhodium (1 part by weight) - manganese (1 part by weight) - iron (1 part by weight) part)/γ−Al ₂ O ₃
(100 parts by weight)) was filled into a stainless steel reaction tube with a diameter of 25 mm, and a mixed gas consisting of 27.5% trans-butene, 5% oxygen, 17.5% nitrogen, and 70% water (volume composition) was added at 200℃, 3 kg. /cm ² G and a contact time of 9 seconds to cause the reaction. The results are shown in Table 5. Example 16 Catalyst of Example 2 (rhodium (1 part by weight) - manganese (1 part by weight) - cobalt (3 parts by weight)/γ-
The same operation as in Example 15 was carried out using Al ₂ O ₃ (100 parts by weight). The results are shown in Table 5.

[Table] Comparative Examples 7 to 12 Using 30 ml of each of the catalysts of Comparative Examples 1 to 6, trans-butene - 27.5%, oxygen 5%, water 87.5%
Mixed gas consisting of (volume composition) at 200℃, 3Kg/cm ²
G, reaction was allowed to flow for a contact time of 9 seconds. The results are shown in Table 6.

【table】

[Table] Examples 17 to 24 Catalysts with various metal loading rates were prepared using the catalyst preparation method of Example 2, and 30 ml of each catalyst was used to prepare trans-butene-27.5%, oxygen 5%, and nitrogen.
A mixed gas consisting of 17.5% water and 70% water was flowed for a contact time of 9 seconds to cause a reaction. The results are shown in Table 7.

[Table] Comparative Examples 13 to 20 Catalysts with various metal loading rates were prepared using the catalyst preparation method of Example 2, and trans-butene-27.5 was prepared using 30 ml of each of the various catalysts shown in Table 8.
%, oxygen 5%, nitrogen 17.5%, and water 70% for a contact time of 9 seconds to cause a reaction. The results are shown in Table 8.

【table】

[Table] Example 25 58.6g of γ-Al ₂ O ₃ (specific surface area 200m ² /g, 3mm
φ×3 mm) was immersed in 250 c.c. of 2N hydrochloric acid for 4 hours, washed with distilled water three times, and dried at 80° C. overnight. This carrier was calcined at 500° C. for 4 hours under air circulation to obtain hydrochloric acid-treated γ-Al ₂ O ₃ . Next, 1.5 g of rhodium chloride (RhCl ₃ 3H ₂ O),
7.1 g cobalt chloride (CoCl ₂ 6H ₂ O) and 6.3
g of manganese chloride (MnCl ₂ 4H ₂ O) was dissolved in 80 ml of distilled water, and 58.6 g of the above hydrochloric acid treatment γ-Al ₂ O ₃ was dissolved.
After impregnation, the catalyst was dried and calcined at 200° C. for 4 hours under air circulation to obtain a catalyst in which 1 part by weight of rhodium, 3 parts by weight of manganese, and 3 parts by weight of cobalt were supported per 100 parts by weight of the carrier. Example 18 using 30 ml of the obtained catalyst
reacted in the same way. The results are shown below. Conversion rate of trans-butene-2 70 mol% Selectivity of methyl ethyl ketone 60 mol% Yield of methyl ethyl ketone 42 mol% Example 26 65.3 g of γ-Al ₂ O ₃ instead of 78.2 g of γ-Al ₂ O ₃
(5 mmφ x 5 mm, specific surface area 200 m ² /g) was operated in the same manner as in Example 2, and per 100 parts by weight of the carrier, 1.2 parts by weight of rhodium, 3.6 parts by weight of manganese,
A catalyst on which 3.6 parts by weight of cobalt was supported was obtained. Using 30 ml of this catalyst, trans-butene-27.5%,
A mixed gas consisting of 17.5% oxygen, 5% nitrogen, and 70% water was flowed at 200° C., 3/cm ² G, and a contact time of 9 seconds to cause a reaction. The results are shown below. Conversion rate of trans-butene-2 74 mol% Selectivity of methyl ethyl ketone 59 mol% Yield of methyl ethyl ketone 44 mol% Example 27 0.9 g of bismuth chloride (BiCl ₃ ) was dissolved in 60 ml of distilled water, and 58.6 g of γ- Al ₂ O ₃ (3mmφ×3mm,
After impregnation to a specific surface area of 200 m ² /g) and drying, it was fired at 400° C. for 4 hours under air circulation. Next, 1.5 g of rhodium chloride (RhCl ₃ .3H ₂ O) and 4.2 g of manganese chloride (MnCl ₂ .4H ₂ O) were dissolved in 60 ml of distilled water, impregnated onto the above supported catalyst, dried, and then cooled under air circulation.
The catalyst was calcined at 200° C. for 4 hours to obtain a catalyst in which 1 part by weight of rhodium, 2 parts by weight of manganese, and 1 part by weight of bismuth were supported per 100 parts by weight of the carrier. A reaction was carried out in the same manner as in Example 18 using 30 ml of this catalyst. The result is the 9th
Shown in the table. Example 28 The same operation as in Example 27 was carried out except that 2.6 g of nickel chloride (NiCl ₂ ) was used instead of bismuth chloride, and 1 part by weight of rhodium, 2 parts by weight of manganese, and 2 parts by weight of nickel were added per 100 parts by weight of support. A catalyst was obtained in which part was supported. Example using 30ml of this catalyst
The reaction was carried out in the same manner as in 18. The results are shown in Table 9. Example 29 2.3g of tin chloride ( _SnCl4.5H2O ) was dissolved in 80ml of distilled water, and _{78.2g of} γ- _Al2O3 (3mmφ×3
mm, specific surface area 200 m ² /g) and dried.
Next, add 14.1g of manganese oxide (MnCl ₂ 4H ₂ O).
After dissolving in 80 ml of distilled water and impregnating the above supported catalyst,
Dry. Then, 2 g of rhodium chloride (RhCl ₃ 3H ₂ O) was dissolved in 80 ml of distilled dry water,
After impregnating the catalyst on which tin and manganese were supported, it was calcined at 200° C. under air circulation to obtain a catalyst on which 1 part by weight of rhodium, 5 parts by weight of manganese, and 1 part by weight of tin were supported per 100 parts by weight of the carrier. A reaction was carried out in the same manner as in Example 18 using 30 ml of this catalyst. The results are shown in Table 9. Example 30 1.5 g rhodium chloride (RhCl _{3.3H 2} O), 1.2 g
of zinc chloride (ZnCl ₂ ) and 10.6 g of manganese chloride (MnCl ₂ 4H ₂ O) were dissolved in 60 ml of distilled water, and 58.6
g of γ-Al ₂ O ₃ (3mmφ×3mm, specific surface area 200
m ² /g), dried, and calcined for 4 hours at 200°C under air circulation to obtain a catalyst in which 1 part by weight of rhodium, 5 parts by weight of manganese, and 1 part by weight of zinc were supported per 100 parts by weight of the carrier. . Example 18 using 30 ml of this catalyst
reacted in the same way. The results are shown in Table 9.

[Table] Comparative Examples 21 to 24 Catalysts were prepared by removing manganese from the catalyst components of Examples 27 to 30, and reacted in the same manner as in Example 18.
The results are shown in Table 10.

【table】

Claims (1)

[Claims] 1. A method for producing a carbonyl compound by reacting butene, water, and oxygen or an oxygen-containing gas in the presence of a catalyst, in which (a) rhodium, (b)
A method for producing a carbonyl compound, comprising using a catalyst in which manganese and (c) at least one element selected from cobalt, iron, nickel, bismuth, zinc and tin are supported on γ-alumina. 2 The catalyst contains (a) component 0.2 to 5 parts by weight, (b) component 0.5 to 30 parts by weight, and (c) as an element per 100 parts by weight of carrier.
The method according to claim 1, which contains 0.5 to 30 parts by weight of the ingredient.