JPH04312537A - Production of cycloolefin - Google Patents

Abstract

PURPOSE:To produce a cycloolefin useful for industrial use, especially cyclohexene, on an industrial scale in high yield at a low cost by partially hydrogenating an aromatic hydrocarbon such as benzene. CONSTITUTION:An aromatic hydrocarbon such as benzene is partially hydrogenated with hydrogen gas in the presence of a catalyst consisting of ruthenium and manganese, water and, as necessary, an alcohol and/or an alkaline agent. The catalyst consisting of ruthenium and manganese exhibits the catalytic activity extremely stable with time compared with conventional catalyst and the objective compound can be selectively produced at reduced cost over a long period.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an improvement in a method for producing cyclic olefins, such as cyclohexene, from aromatic hydrocarbons. To be more specific,
The present invention relates to a method for producing cyclic olefins in high yield and industrially advantageously by partially hydrogenating aromatic hydrocarbons with hydrogen gas using a catalyst system with excellent activity.

[Prior Art] Cyclic olefins are industrially useful raw material intermediates. For example, cyclohexene is expected to have a wide range of uses as a raw material for polymers such as adipic acid, caprolactam, and maleic acid, and as an intermediate for other pharmaceuticals and agricultural chemicals. It is an industrial raw material.

Conventionally known methods for producing cyclohexene include dehydration reaction of cyclohexanol and dehydrohalogenation reaction of halogenated cyclohexane. Furthermore, recently, a method for producing cyclohexene from benzene in good yield through nuclear partial hydrogenation of aromatic hydrocarbon compounds has been attracting attention as an economical industrial process.

[0003] As a method for producing cyclohexene by partial hydrogenation of benzene, a method using the following catalyst is known.

(1) A method using a catalyst in which ruthenium is supported on an oxide of nickel, cobalt, chromium or zirconium in the presence of an alcohol or ester (Japanese Patent Publication No. 3933/1983), (2) Water and an alkaline agent; A method using a catalyst consisting of a reduced cation of at least one Group 8 element (Japanese Patent Publication No. 56-22850
(3) A pre-reduced solid catalyst containing at least one of ruthenium and rhodium as a main component is combined with at least one selected from the group consisting of Group IA metals, Group IIA metals, manganese, iron and zinc in the periodic table. A method of reacting in the presence of water using an aqueous solution containing a cationic salt (Japanese Patent Publication No. 56-3852), (4
) A method of reacting in the presence of water and a catalyst supporting at least one metal selected from the group consisting of iron, cobalt, silver and copper and ruthenium using barium sulfate as a carrier (Japanese Patent Application Laid-open No. 122231/1983) Public bulletin),
(5) A method in which metal ruthenium crystallites and/or aggregated particles thereof having an average crystallite diameter of 200 angstroms or less are used as a hydrogenation catalyst in the presence of water and a zinc compound, and alcohol is used as an additive (special (6) A catalyst in which metal ruthenium-based particles having an average crystallite diameter of 30-200 angstroms are supported on a ZrO2 or HfO2 carrier in the presence of water and a zinc compound. A method of reacting using (Japanese Unexamined Patent Publication No. 63-243038) has been proposed.

[0005]

[Problems to be Solved by the Invention] However, in the methods (1) and (2) above, it is necessary to significantly lower the conversion rate of the raw material in order to obtain a high cyclohexene selectivity, and it is difficult to adopt it as a practical method. It has a surface. Also, (3)
, (4) and (6) are characterized by the use of catalysts in which ruthenium, the main catalyst metal, is supported on various carriers, and the hydrogenation is carried out under high temperature and high pressure conditions in the presence of water. As a result of studies conducted by the inventors, it was found that the activity of the ruthenium catalyst is extremely unstable over time under such reaction conditions, making it impossible to use the catalyst continuously for a long period of time (see Reference Examples). Furthermore, in the method (5) above, ruthenium fine particles tend to aggregate during the reaction, and it is judged that it is difficult to maintain stable catalyst performance over time.

[0006]

[Means for Solving the Problems] As a result of extensive research into catalysts for cyclohexene synthesis that are industrially advantageous and stable over time, the present inventors have found that the above object can be achieved by using a catalyst consisting of ruthenium and manganese. We have discovered that this can be achieved, and based on this knowledge, we have completed the present invention.

That is, the present invention provides a method for producing cyclic olefins, which is characterized in that aromatic hydrocarbons are partially hydrogenated with hydrogen gas in the presence of a catalyst comprising ruthenium and manganese and water.

The present invention will be explained in detail below. Examples of the aromatic hydrocarbon in the present invention include benzene, toluene, xylene and other benzene derivatives having an alkyl group, naphthalene and its alkyl derivatives.

[0009] In the present invention, a catalyst consisting of ruthenium and manganese is used as a catalyst, water is required for use, and alcohol and/or an alkaline agent are used as necessary.

The catalyst composed of ruthenium and manganese used in the method of the present invention is composed of ruthenium metal and/or a ruthenium compound and a manganese metal and/or a manganese compound, and is immobilized on a carrier.

Examples of raw material compounds for ruthenium and manganese constituting the catalyst include these metals, oxides, hydroxides, halides, nitrates, sulfates, acetates, acetylacetonate compounds, carbonyl compounds, ammine complexes, Alkyl metal compounds and the like are used.

[0012] In preparing the catalyst, these catalyst components such as ruthenium and manganese are supported on a carrier, but there are no particular restrictions on the method, and conventional methods for supporting catalyst components on a carrier, such as Methods include preparing a mixed solution in which catalyst components are simultaneously dissolved in the same solvent and simultaneously supporting them on a carrier, and methods in which each catalyst component is supported sequentially or stepwise while performing treatments such as reduction and heat treatment as necessary. Can be used. Examples of the solvent used in the supporting treatment of the catalyst component include water, methanol, ethanol, tetrahydrofuran, dioxane, acetone, hexane, benzene, toluene, and methylene chloride.

Other preparation methods, such as a method of supporting a catalyst metal component by ion exchange utilizing the ion exchange ability of a carrier, and a method of preparing a catalyst by a coprecipitation method, are also employed as a preparation method for the catalyst used in the present invention. can.

[0014] The catalyst prepared by the above-mentioned method is usually immobilized on a carrier by reduction treatment, activated, and then subjected to reaction. The reduction is preferably carried out using a hydrogen-containing gas at an elevated temperature. The reduction treatment can be performed at a temperature of about 100°C, which is the temperature at which ruthenium is reduced, but preferably the reduction treatment is performed at a temperature of 100°C to 600°C. Further, reduction treatment can be performed using a reducing agent such as hydrazine, formalin, a borohydride compound, or an aluminum hydride compound.

The carrier used in the present invention preferably has a specific surface area of 10 to 2000 m2/g and an average pore diameter of 10 angstroms or more, such as silica,
Examples include silica-based carriers such as silicate, silica gel, molecular sieve, diatomaceous earth, and metal oxide carriers such as alumina, magnesia, titania, zirconia, zinc oxide, and manganese oxide. In addition, manganese chromate,
Also included are manganese-containing complex oxide supports such as manganese silicate, manganese titanate, manganese zirconate, manganese niobate, manganese vanadate, and manganese ferrite.

[0016] In the catalyst composed of ruthenium and manganese used in the present invention, the supported amount and composition ratio of each component in the catalyst can be varied within a wide range. The amount of ruthenium supported on the carrier is 0.0001 to 0.5 in weight ratio, preferably 0.001 to 0, considering the specific surface area of the carrier.
．． It is 3. The other component, manganese, has an atomic ratio of 0.01 or more, preferably 0.01 to ruthenium.
．． The amount added is 1 or more.

In the present invention, it is necessary to carry out the hydrogenation in the presence of water. The amount of water may be sufficient to form two phases, an organic phase consisting of the aromatic hydrocarbon raw material and the product, and an aqueous phase containing the catalyst during the hydrogenation reaction. It is used in a ratio of 1 to 10. In addition, alcohol and/or alkaline agents can be used as necessary, and these agents are effective additives that suppress the hydrogenation ability of the catalyst and increase the yield of cyclic olefins. , aliphatic alcohols such as propanol, butanol, ethanolamine, aminopropanol, aminobutanol,
Alcohol amines such as diethanolamine, 3-amino-1,2-propanediol, and bis(hydroxyethyl)ethylenediamine are preferred, and the amount of alcohol added is 10 to 300 times the amount of ruthenium. Further, as the alkaline agent, lithium hydroxide, sodium hydroxide, potassium hydroxide, etc. are preferable, and the amount of the alkaline agent added is 1 to 200 times that of ruthenium.

The partial hydrogenation reaction in the present invention is carried out batchwise or continuously in a liquid phase suspension method, but it can also be carried out in a fixed bed method. The reaction conditions are selected by organically combining various factors with the aim of producing a cyclic olefin in high yield and high selectivity. The reaction pressure is 1~
150 atm, preferably in the range of 10 to 100 atm, and the reaction temperature is 50 to 250 °C, preferably 100 to 20 °C.
It is in the range of 0°C.

[0019]

According to the present invention, a cyclic olefin can be obtained in high yield by using a catalyst that exhibits stable and high performance over time, and is an economical industrial production method.

The present invention will be explained in more detail below with reference to Examples and Reference Examples, but the present invention is not limited to these Examples in any way.

[Example] Example 1 Manganese nitrate (Mn(NO3)2.6H2O) 1.4
5 g of silica gel (Carryact-30, manufactured by Fuji Davison), which had been previously calcined and degassed under high vacuum at 300° C. for 2 hours, was added to a methanol solution in which 35 g of the gel was dissolved, and immersed therein. Next, methanol was distilled off using a rotary evaporator to dryness, followed by further vacuum drying. After that, the Pyrex reaction tube was filled with hydrogen gas (300 m
Reduction treatment was carried out at 600°C for 5 hours under ventilation (1/min).
A manganese-supported silica support (Mn/SiO2) was prepared. Then, ruthenium chloride (RuCl3) 0.20
5 g of Mn/SiO2 carrier was added to an aqueous solution in which 7 g of Mn/SiO2 was dissolved, and the mixture was dispersed for 1 hour under strong stirring, followed by 15 ml of an aqueous solution in which 0.17 g of potassium hydroxide (KOH) was dissolved.
was added and stirring was continued for 3 hours to deposit an insoluble ruthenium compound mainly consisting of Ru(OH)3 onto the Mn/SiO2 support. Disperse this again in 30ml of water,
It was charged into a 200ml autoclave made of SUS-316, and reduced at 180°C under 50 atmospheres of hydrogen gas for 20 hours, washed with water, and dried to produce 2% Ru/Mn/SiO2.
I got a catalyst.

[0021]

[Chemical formula 1] Next, 20 mg of the catalyst obtained above and 6 g of water were added to SUS-3
The mixture was placed in a 200 ml autoclave manufactured by No. 16, sealed with hydrogen gas under 50 atm, and subjected to catalytic treatment at 180° C. for 13 hours. Thereafter, the autoclave was cooled to room temperature, the filled gas was evacuated, the autoclave was opened to the atmosphere, 3 g of benzene was charged, and the inside of the autoclave was replaced with hydrogen. After that, hydrogen was filled in at 5 atm, and the reaction temperature was maintained at 180°C with strong stirring. Below, a partial hydrogenation reaction of benzene was performed. After the reaction was completed, the reactor was rapidly cooled to room temperature, the filled gas was exhausted, the reactor was opened to the atmosphere, all contents were taken out, and the organic phase was analyzed by gas chromatography. As a result, the benzene conversion rate was 40% in a reaction time of 15 minutes.
．． 6%, cyclohexene selectivity 43.1%, and ruthenium unit atomic specific activity turnover 6732 (h-1). The by-product was cyclohexane.

Example 2 Manganese nitrate (Mn(NO3)2.6H2O) 0.8
Add 610g of the mixture to a methanol solution at 300°C in advance.
5 g of silica gel (Davison #57, manufactured by Davison) which had been calcined and degassed under high vacuum for 2 hours was added and immersed. Then,
After methanol was distilled off to dryness using a rotary evaporator, the mixture was further dried in vacuum. After that, the Pyrex reaction tube was filled with hydrogen gas (300 ml/min) at normal pressure.
A reduction treatment was performed at 600° C. for 5 hours under ventilation to prepare a manganese-supported silica carrier (Mn/SiO2). Next, 5 g of the above Mn/SiO2 carrier was added and immersed in a methanol solution in which 0.207 g of ruthenium chloride (RuCl3) was dissolved. After removing methanol by the same treatment as above, hydrogen gas (300 ml/min) was added at normal pressure.
Reduction treatment was performed at 450°C for 5 hours under aeration of 2% Ru.
/Mn/SiO2 catalyst was prepared.

[0023] After pulverizing this 2% Ru/Mn/SiO2 catalyst in an agate mortar, 100 mg of this catalyst and 6 g of water were added.
and 10.5 mg of diethanolamine were placed in a 200 ml autoclave, hydrogen gas was introduced at 50 atm at room temperature, and the catalyst was treated at 180° C. for 61 hours with stirring. After treatment,
The autoclave was returned to room temperature, hydrogen gas was purged, 3 g of benzene was added, hydrogen gas was sealed at 50 atm, and reaction was carried out at 180° C. for 15 minutes with stirring. After the reaction, the autoclave was rapidly cooled, and gas phase components and organic phase components were analyzed by gas chromatography. The results were a benzene conversion rate of 70.9%, a cyclohexene selectivity of 37.9%, and a specific activity (turnover) of ruthenium unit atoms of 2063 (h-1).

Example 3 To an aqueous solution in which 0.207 g of ruthenium chloride (RuCl3) was dissolved, 5 g of manganese silicate (MnSiO3), which had been previously calcined and degassed under high vacuum at 300°C for 2 hours, was added and dispersed for 1 hour with strong stirring. and then potassium hydroxide (K
Add 15 ml of an aqueous solution containing 0.17 g of OH),
Stirring was continued for 3 hours, and an insoluble ruthenium compound consisting mainly of Ru(OH)3 was deposited on the MnSiO3 support. Disperse this again in 30 ml of water and make SUS-3
Prepared in a 200ml autoclave made in 16, 18
Reduction was performed for 20 hours at 0° C. under 50 atmospheres of hydrogen gas, washed with water, and dried to obtain a 2% Ru/MnSiO3 catalyst.

[0025] Next, 50 mg of the catalyst obtained above, 6 g of water, and 0.2 g of n-propanol were placed in a 200 g
The mixture was placed in an autoclave, filled with hydrogen gas under 50 atm, and subjected to catalyst treatment at 180° C. for 110 hours. Thereafter, the autoclave was cooled to room temperature, the filled gas was exhausted, the autoclave was opened to the atmosphere, 3 g of benzene was charged, and the inside of the autoclave was replaced with hydrogen. Hydrogen was then sealed at 50 atm, and the reaction temperature was 18
A partial hydrogenation reaction of benzene was carried out under strong stirring while maintaining the temperature at 0°C. After the reaction was completed, the reactor was rapidly cooled to room temperature, the filled gas was exhausted, the reactor was opened to the atmosphere, all contents were taken out, and the organic phase was analyzed by gas chromatography. As a result, the benzene conversion rate was 39.2% in 15 minutes of reaction time.
, cyclohexene selectivity was 53.1%, and ruthenium unit atomic specific activity turnover was 2132 (h-1). The by-product was cyclohexane.

Examples 4, 5, 6 A 0.5% Ru/Mn/SiO2 catalyst was prepared in the same manner as in Example 2, except that 2.296 g of manganese nitrate and 51.9 mg of ruthenium chloride were used in Example 2. Prepared.

0.5% Ru/Mn/SiO ground into powder
2 Using 100 mg of catalyst, the amount of water or 1-butanol, 3-amino-1,
The catalyst was treated for 13 hours under the same conditions as in Example 2, except that 2-propanediol and lithium hydroxide were used. Thereafter, partial hydrogenation of benzene was performed in the same manner as in Example 2. The reaction results are shown in Table 1.

Example 7 Ruthenium chloride 0.207g and manganese chloride 1.5g
5 g of the same silica gel (Carryact-30) as in Example 1 was added to an aqueous solution in which 83 g was dissolved, and the mixture was dispersed and immersed for 1 hour under strong stirring. Add 1.0% potassium hydroxide to this solution.
15 ml of an aqueous solution in which 173 g of Ru-Mn was dissolved was added, and then 2% Ru-Mn/SiO2 was added in the same manner as in Example 1.
I got a catalyst.

Next, this catalyst was crushed into powder, and 2% Ru-
Catalytic treatment was carried out in the same manner as in Example 1, except that 50 mg of Mn/SiO2 catalyst, 6 g of water, and 0.3 g of potassium hydroxide were used, and then benzene was partially hydrogenated under the same conditions as in Example 1. As a result, in a reaction time of 15 minutes, the benzene conversion rate was 48.5%, the cyclohexene selectivity was 47.8%, and the ruthenium unit atomic specific activity turnover was 2374 (h-1
) was obtained.

Example 8 Diethanolamine 10 was used as an additive in Example 2.
．． When a partial hydrogenation reaction of benzene was carried out in the same manner as in Example 2 except that 5 mg and 0.3 g of potassium hydroxide were added, the benzene conversion rate was 24.3% and the cyclohexene selectivity was 60.7 in a reaction time of 15 minutes. %, a ruthenium unit atomic activity turnover of 1131 (h-1) was obtained.

Example 9 In Example 2, 0.2 n-propanol was added as an additive.
Example 2 except that g and 0.3 g of potassium hydroxide were added.
When a partial hydrogenation reaction of benzene was carried out in the same manner as above, a benzene conversion rate of 14.6%, a cyclohexene selectivity of 77.4%, and a ruthenium unit atomic specific activity turnover of 866 (h-1) were obtained in a reaction time of 15 minutes. Ta.

Reference Example 1 2% R was prepared in the same manner as in Example 1 except that silica gel (Carryact-30, manufactured by Fuji Davison) was used instead of the manganese-supported silica carrier.
A u/SiO2 catalyst was prepared. A partial reduction reaction of benzene was carried out in the same manner as in Example 1, except that the amount of catalyst used in the reaction was 50 mg. As a result, the benzene conversion rate was 11.4%, the cyclohexene selectivity was 20.7%, and the reaction time was 15 minutes.
Ruthenium unit atomic specific activity turnover 242 (h-
1). In this 2% Ru/SiO2 catalyst, when the catalyst treatment time was 15 minutes, only a trace amount of cyclohexene was produced with a benzene conversion rate of 91.2% in a reaction time of 15 minutes. From these results, Ru/SiO2
It is clear that the activity of the catalyst deactivates significantly over time under the reaction conditions.

Claims (1)

[Claims] Claim 1: A method for producing cyclic olefins by hydrogenating aromatic hydrocarbons in the presence of a catalyst and water, optionally in the coexistence of an alcohol and/or alkali agent, comprising: a catalyst comprising ruthenium and manganese; A method for producing the cyclic olefin, which is characterized in that it is used.