JPS6140226A - Method for producing cycloolefin - Google Patents

Abstract

PURPOSE:To improve the yield easily without corrosion of apparatuses in partially hydrogenating an aromatic hydrocarbon in the presence of a supported rutheniumcatalyst and water to give the titled compound which is an intermediate raw material for medicines, etc., by using specific compounds as a catalyst carrier and additive. CONSTITUTION:An aromatic hydrocarbon is partially hydrogenated in the presence of a supported catalyst containing barium sulfate as a carrier and ruthenium supported thereon as a catalyst and at least one or more metal sulfates selected from the group consisting of lithium, cobalt, iron and zinc as an additive added thereto at 0-250 deg.C, preferably 100-200 deg.C to give the corresponding cycloolefin. The ratio of the supported ruthenium in the above-mentioned catalyst is 0.01-20wt%, preferably 0.1-10wt%. The concentration of the metal sulfate which is an additive used is preferably within 1:5-1:250 atomic ratio range of the metal species to the ruthenium in the catalyst to be used for the reaction.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention provides the following methods:
The present invention relates to a method for producing a corresponding cycloolefin.

(Prior Art) Cycloolefins are useful compounds as important intermediate raw materials for lysine, caprolactam, adipic acid, pharmaceuticals, agricultural chemicals, dyes, and the like.

Conventionally, there are many methods for producing cycloolefins, such as dehydration reaction of cyclohexanols, dehydrohalogenation reaction of halogenated cyclohexanes, cranking reaction of cyclohexylarenes, and dehydrogenation or oxidative dehydrogenation reaction of cyclohexanes. method is known.

It is well known that the production of cycloolefins by partial hydrogenation of aromatic hydrocarbon compounds is difficult to carry out because the resulting cycloolefins are usually reduced more easily than the raw aromatic hydrocarbon compounds. It is.

However, since the starting material for both methods is an aromatic hydrocarbon compound, if cycloolefins can be obtained in good yield through the partial hydrogenation reaction of aromatic hydrocarbon compounds, it is possible to obtain cycloolefins using the simplest reaction process. It is also preferred from an industrial standpoint.

The following methods are known as methods for producing cycloolefins by partial hydrogenation of aromatic compounds.

(1) in the presence of a catalyst consisting of water and an alkaline agent and at least one reduced cation of a group II element;
How to partially hydrogenate.

(Japanese Patent Publication No. 56-22850) (2) A method in which ruthenium glycoxide and ethyl silicate are hydrolyzed and then partially hydrogenated in the presence of water and a ruthenium-silica catalyst prepared by hydrogen reduction at 400°C. (Chemical Society of Japan, 47th Spring Annual Meeting, 4DO2) (
3) A method of partially hydrogenating a metal oxide such as silica or alumina in the presence of a catalyst mainly supporting ruthenium, water and cobalt sulfate. (Unexamined Japanese Patent Publication No. 57-13092
6)(4) A method of partially hydrogenating a solid catalyst containing at least one of ruthenium and rhodium as a main component in the presence of water and a catalyst previously treated with an aqueous solution containing a cationic salt. (Unexamined Japanese Patent Publication No. 51-98243) Although the method (1) has a relatively good yield of cyclohexene, it not only requires an extremely complicated reaction system, but also requires separation of the reaction products and corrosion of the reaction equipment due to chlorine ions. There are problems, and it cannot be said that it is necessarily satisfactory from an industrial perspective.

Method (2) requires a complicated catalyst preparation process and has problems in terms of reproducibility of catalyst performance, and +3), +4
It was difficult to put the + method into practical use industrially, as a dramatic improvement in selectivity and yield was desired.

(Problems to be Solved by the Invention) An object of the present invention is to improve the drawbacks of these conventional techniques and to provide an industrially advantageous method for producing cycloolefins. In order to achieve this object, the present inventors conducted extensive studies and invented a new catalyst suitable for partially hydrogenating aromatic hydrocarbons to produce corresponding cycloolefins, resulting in the present invention.

(Means for Solving the Problems) That is, the present invention provides a method for producing a corresponding cycloolefin by partially hydrogenating an aromatic hydrocarbon in the presence of a catalyst having ruthenium supported on a carrier, water and an additive. This is a method for producing a cycloolefin, characterized in that barium sulfate is used as the additive, and at least one metal sulfate selected from lithium, cobalt, nickel and zinc is used as the additive.

The method of the present invention will be explained in more detail below.

The aromatic hydrocarbons targeted by the present invention are benzene, toluene, xylene, and lower alkylbenzene, and the purity of the aromatic hydrocarbons does not need to be particularly high. However, there is no problem.

The catalyst used in the present invention is a catalyst in which ruthenium is supported using barium sulfate as a carrier. The catalyst is prepared according to a commonly used method for preparing supported metal catalysts. That is, the evaporation-drying method involves immersing barium sulfate in a catalytic active ingredient liquid and then evaporating the solvent while stirring to fix the active ingredient; the spraying method involves spraying a catalytic active ingredient liquid while keeping the barium sulfate in a dry state; Known impregnating and supporting methods, such as a method in which barium sulfate is immersed in a catalyst active component liquid and then filtered, are preferably used.

Raw materials for ruthenium used as a catalytic active component include ruthenium genides, nitrates, hydroxides and oxides, as well as ruthenium carbonyl and ruthenium ammine i! , complex compounds with metals, ruthenium alkoxide, etc. are used.

As a solvent for the active component during catalyst preparation, water or an organic solvent such as alcohol, acetone, or tetrahydrofuran is used.

The catalyst prepared by the above method is activated by further reducing ruthenium before use. As the reducing agent, hydrogen, carbon oxide, alcohol vapor, hydrazine, sodium borohydride, and other known reducing agents can be used.

When hydrogen is used, the reduction temperature is selected to be in the range of 150 to 450°C, preferably 180 to 300°C.

When the hydrogen reduction temperature is below 150°C, the reduction rate of the active ingredient decreases, and when it is above 400°C, the metal surface area decreases due to aggregation of supported ruthenium and the catalyst surface is modified, resulting in a decrease in the activity and selectivity of cycloolefin production. Cause.

The ruthenium loading rate is selected from the range of 0.01 to 20% by weight, preferably 0.1 to 10% by weight.

The additive used in the present invention is at least one metal sulfate selected from the group consisting of lithium, cobalt, iron, and zinc. The metal sulfate concentration is the atomic ratio of the metal species to ruthenium in the catalyst used for the reaction, which is 1:
It is used in a range of 1:500 to 1:500, preferably 1:5 to 1:250.

In the method of the present invention, water is added into the reaction system. Since the catalyst is suspended in water, not only is the reaction product in the organic layer easily separated from the catalyst, but water has a significant effect on increasing the selectivity to cycloolefins. The amount of water added is usually 0.01 to 1 in terms of volume ratio to aromatic hydrocarbons.
It is selected from the range of 0 times, preferably 0.1 to 5 times.

The hydrogen pressure during the reaction is usually selected from the range of 0.1 to 20 MPa, preferably 0.5 to 10 MPa. 29M
A high pressure of more than 0.1 MPa is uneconomical from an industrial standpoint, and a pressure of less than 0.1 MPa reduces the reaction rate and is uneconomical in terms of equipment.

The reaction temperature is usually 50-250°C, preferably 100-250°C.
The temperature is selected from the range of 00°C. At temperatures above 250°C, the selectivity of cycloolefins decreases, while at temperatures below 50°C, the reaction rate is slow, which is disadvantageous.

The reaction format of the present invention is not particularly limited, and can be carried out batchwise or continuously using one or more reaction tanks.

(Effects of the Invention) According to the method of the present invention, cycloolefins can be obtained in high yield, the reaction operation is simple, corrosion of equipment is less likely to occur, and cycloolefins can be produced industrially advantageously. Become.

In order to explain the present invention more clearly, Examples and Comparative Examples are described below, but the present invention is not limited only by these Examples.

In addition, the conversion rate, yield, and selectivity shown in an Example and a comparative example are defined by the following formula.

Example 1 RuC1!3.3H in an eggplant-shaped flask with a capacity of 500 W
200,190 g was added, and 200 ct- of water was added to dissolve it. Next, commercially available BaSO43-6F was added thereto, and then the mixture was placed in a rotary evaporator. After impregnation for 1 hour at room temperature and 1 hour at 60°C under stirring, 80°C under reduced pressure.
℃ and the water was evaporated.

The obtained evaporated product was filled into a Pyrex glass tube with an inner diameter of 5 yxtn, heated to 200° C. while flowing hydrogen at a rate of 100 ml/min, and kept at this temperature for 4 hours to activate the catalyst. The composition of the catalyst obtained is 2% mu/Ba SO4.

I, iso,
, 15 cc of water in which 0.5 f of H2O was dissolved were charged, and then 100 to 100 of the above catalyst and 15 ω of benzene were added in this order.

Furthermore, hydrogen gas was introduced, and the reaction was carried out under stirring at a reaction pressure of 4.9 MPa and a temperature of 180° C. for 3 hours.

After the reaction was completed, the oil layer was taken out and the product was analyzed by gas chromatography, and the benzene conversion rate was 59.1.
%, cyclohexene selectivity was 23.0%, and cyclohexene yield was 13.6%.

Note that the only reaction product other than cyclohexene was cyclohexane.

Comparative Example 1 A partial hydrogenation reaction of benzene was carried out for 15 minutes using the catalyst of Example 1 and performing the same operations as in Example 1 except that no metal sulfate was added. The benzene conversion rate was 69.7. H. The cyclohexene selectivity was 2.3%, and the cyclohexene yield was 1°6q6.

Comparative Example 2 In the process of manufacturing the catalyst of Example 1, the same operations as in Example 1 were performed except that T-type alumina was used instead of Ba S04, and 2% Ru
/r AZ2q catalyst was produced.

Using this catalyst, a partial hydrogenation reaction of benzene was carried out for 15 minutes in the same manner as in Example 1 except that Li 5o4-H2O was not added. The benzene conversion rate was 84.8%, and the cyclohexene Selection rate 0.8%
, the cyclohexene yield was 0.7%.

Comparative Example 3 L x S04, H
15 heads of water in which 200-5j' was dissolved, 100 ml of the catalyst prepared in Comparative Example 2, and 150 H of benzene were added in this order. Furthermore, hydrogen gas was introduced to increase the reaction pressure to 4.0 MPa.
When the reaction was carried out at a temperature of 180°C with stirring for 3 hours,
Benzene & conversion rate 87.8%, cyclohexene selected tFU
K8.9%, cyclohexene yield a, (1).

Example 2 Using the catalyst prepared in Example 1 and using L i 5 as an additive
04- Instead of H2O-(Fe50., 5H,00,
A partial hydrogenation reaction of benzene was carried out for 3 hours in the same manner as in Example 1 except that 5y was used, and the benzene conversion was 60.6% and the cyclohexene selectivity was 23.9%.
H. The yield of cyclohexene was 14.5%.

Comparative Example 4 A partial hydrogenation reaction of benzene was carried out for 2 hours in the same manner as in Example 2 except that the catalyst produced in Comparative Example 2 was used, and the Hensen conversion rate was 6o. 8chi, cyclohexene R selectivity x3. s%, cyclohexene yield 8.2
%Met.

Example 3 Using the catalyst produced in Example 1, CoS was added as an additive.
The partial hydrogenation reaction of benzene was carried out for 3 hours in the same manner as in Example 1 except that 04.7H200.5f was used. Yield 29.0%
Met.

Comparative Example 5 A partial hydrogenation reaction of benzene was carried out for 3 hours in the same manner as in Example 3 except that the catalyst prepared in Comparative Example 2 was used. 6%, cyclohexene yield 23
It was 5%.

Example 4 Using the catalyst produced in Example 1, Zn50 was added as an additive.
4-7H200, all Example 1 except for using 5f
When a partial hydrogenation reaction of benzene was carried out for 3 hours in the same manner as above, the benzene conversion rate was 64.6%, the cyclobexene selectivity was 32.8%, and the cyclohexene yield was 21.2%.

Comparative Example 6 A partial hydrogenation reaction of benzene was carried out for 2 hours in the same manner as in Example 4 except that the catalyst produced in Comparative Example 2 was used. The benzene conversion rate so, ss and the cyclohexene selectivity were 9°. 8, cyclohexene yield 5,. 0
%Met.

Examples 5 to 8 In the process of manufacturing the catalyst of Example 1, Ru CI! A catalyst was produced in the same manner as in Example 1, except that the amount of 3.3H20 used was changed. Co S 04/7H in a stainless steel autoclave with a content of 1A100-1, which was thoroughly replaced with argon in advance.
Pour 150C of water in which ,01,Of was dissolved, and then
100 η of the above catalyst and 15 cr of benzene were charged in this order.

Further, hydrogen gas was introduced and the reaction was carried out at a reaction pressure of 4.0 MPa and a temperature of 180° C. for 3 hours with stirring.

After the reaction was completed, the oil layer was taken out and the product was analyzed by gas chromatography, and the results shown in Table 1 were obtained.

Comparative Examples 7 to 13 All the same as in Example 1 except that the catalyst of Example 1 was used and 0.5 f of the metal sulfate in Table 2 was used in place of 0.5 g of L*SO4.H2O in Example 1. The reaction was carried out.

The results are shown in Table 2.

Claims (1)

[Claims] A method for producing a corresponding cycloolefin by partially hydrogenating an aromatic hydrocarbon in the presence of a catalyst having ruthenium supported on a carrier, water and an additive, using barium sulfate as a catalyst carrier, and as an additive, A method for producing a cycloolefin, the method comprising using at least one metal sulfate selected from the group consisting of lithium, cobalt, iron and zinc.