JPS62255438A - Method for partially hydrogenating nucleus of aromatic hydrocarbon - Google Patents

Abstract

PURPOSE:In partially hydrogenating an aromatic hydrocarbon by reacting the aromatic hydrocarbon with a H2 gas in the presence of water and a hydrogenating catalyst, the catalyst obtained by dispersing Ru and Cu as main components into a solid derived from metallic hydroxide colloid is used. CONSTITUTION:In partially hydrogenating nucleus of an anomatic hydrocarbon in the presence of water, a catalyst obtained by dispersing Ru and Cu as main components into a solid derived from metallic hydroxide colloid is used. The catalyst is prepared by blending a solution of the metallic hydroxide colloid (e.g. silicic acid sol, alumina sol or titania sol) with a solution of a Tu salt and a Cu salt in an organic solvent, subjecting the blend to spray drying and heat-treating the spray dried blend at 200-800 deg.C in a H2 atmosphere. A polar solvent (e.g. polyhydric alcohol or acetylacetone) having multiple coordination ability or crosslinking coordination ability is preferable as the organic solvent. The amount of water used is 0.01-20pts.wt based on 1pts.wt. raw material.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for partial nuclear hydrogenation of aromatic hydrocarbons.

Partial nuclear hydrides of aromatic hydrocarbons, e.g.

Cyclohexene, alkylcyclohexene, etc.

It is an important compound as a synthetic raw material, and it is desired to develop an industrially advantageous manufacturing method. However, it is difficult to produce such partial nuclear hydrides of aromatic hydrocarbons;
When aromatic hydrocarbons are hydrogenated by a conventional method, the aromatic nuclei are completely hydrogenated without being partially oxidized, and chromoparaffins are completely hydrogenated.

Hitherto, as a method for such partial nuclear dihydration, there has been known a method in which hydrogenation is carried out using liquid ammonia as a solvent in the presence of total alkali concentration (West German Patent Nos. 1443377 and 1793757). There is. Although this method provides a relatively good yield of partial nuclear hydrides, it is unsuitable as an industrial method because it requires complicated reaction procedures.

--On the other hand, a method of hydrogenation using a ruthenium catalyst in the presence of water is known as a relatively interesting method from an industrial perspective (Japanese Patent Application Laid-Open No. 53-48938, 5
3-85849, 53-83350, etc.), the ruthenium catalyst in this case is one in which ruthenium is supported on a porous carrier such as silica or alumina, but the yield of partial nuclear hydride is low and it is not suitable for industrial use. From my point of view, it was completely unsatisfactory.

The present inventors previously proposed a method for partial hydrogenation of aromatic hydrocarbons (Japanese Unexamined Patent Application Publication No. 59-111) using a catalyst in which ruthenium and copper were uniformly dispersed in silica gel derived from the hydrolysis product of silicon alkoxide. 155328). The catalyst used in this method is obtained by mixing a polar solvent containing a ruthenium compound and a copper compound with a silicon alkoxide solution to form a uniform solution, and then gelling the entire sol by hydrolysis. In contrast to the conventional catalyst preparation using the impregnation method, which involves a solid-liquid reaction in which catalyst components in a solution are supported on the solid surface of a support, this method allows the support and catalyst components to be uniformly supported in a solution. This can be said to be a supporting method based on a liquid-liquid reaction, in which the carrier component is gelled after the reaction, and the catalyst component is supported on the solid surface. Since it is a liquid-liquid reaction, it is characterized by the ability to obtain a uniformly supported catalyst, but from an industrial standpoint it also has drawbacks such as the high cost of silicon alkoxide and the difficulty in handling the gel obtained by hydrolysis. ing.

Therefore, the present inventors focused on supporting by this liquid-liquid reaction and found that supported ruthenium and copper catalysts obtained using a metal hydroxide colloidal solution of a compound serving as a support have high catalytic activity. , provides a method for partial nuclear hydrogenation of aromatic hydrocarbons characterized by using the catalyst.

The present invention will be explained in detail below.

The catalyst used in the present invention is produced as follows. That is, a metal hydroxide colloidal solution and an organic solvent solution in which a ruthenium compound and a copper compound are dissolved are mixed and heated and stirred. Here, as the organic solvent, a polar solvent having polydentate coordination ability is essential. That is, the hydroxyl groups on the surface of the metal hydroxide gel and the metal ions of ruthenium and copper are bonded together in a cross-linked manner by a polar solvent having multidentate coordination ability, and are uniformly dispersed on the surface of the gel. Then, by drying this mixed solution, a metal hydroxide-supported ruthenium/copper compound in which the ruthenium compound and the copper compound are uniformly dispersed on the surface of the solid metal hydroxide gel is obtained. As the metal water oxide colloidal solution, silicate sol, alumina sol, titania sol, etc. are selected, or it is also possible to select one of these or more. The dispersion medium of the sol may be aqueous or organic, and in the case of organic, it is required to be mutually dissolved with the polar solvent solution in which the ruthenium compound and copper compound are dissolved.

Examples of the organic solvent solution of the ruthenium compound include polyhydric alcohols such as ethylene glycol, propylene glycol, and glycerin, and polar organic solvents such as acetylacetate 7. Among these solvents, ruthenium chloride, ruthenium bromide, etc. In addition to ruthenium salts such as ruthenium acetylacetonate, ruthenium ammine complexes combined with chelating agents such as ethylenediamine, phenanthroline, and bipyridyl, organic ruthenium complexes such as carbonylruthenium complexes and ruthenocene, and ruthenium compounds such as ruthenium alkoxides. A dissolved solution can be used. Also, regarding the 8 copper compounds,
It can be obtained in the same manner as above.

In the ruthenium-m catalyst dispersed in the metal oxide hydride gel used in the present invention, the amount of supported ruthenium is 0.01 to 50%, preferably 0.1 to 20% in terms of metal.
Tonnage rate%, copper carrying rate is 2 to 2 of the ruthenium carrying rate in metal equivalent
It is 20% by weight. The method of mixing the metal hydroxide colloid solution and the organic solvent solution in which the ruthenium compound and the copper compound are dissolved is not particularly limited. The temperature during heating and stirring is room temperature to 100°C, preferably 40 to 8°C.
It is 0°C.

Before use, the catalyst used in 92 Ming was subjected to a reduction treatment using a conventional hydrogen gas flow reduction method.

Activate. The reduction treatment temperature in this case is 50-900℃
, preferably from 200 to 800°C. The catalyst of the present invention is charged into a reactor after this reduction treatment. The method described below is carried out by reacting aromatic hydrocarbons with hydrogen scum. In this case, the amount of water used is 0 for 1 part by weight of yJ Xiangjeong hydrocarbon.
．． 01 to 20 parts of heavy liquid, preferably 0.1 to 5 parts of heavy liquid, and the amount of catalyst used is 0.01 to 20 parts of heavy liquid relative to the aromatic hydrocarbon.
50% by weight, preferably 0.1-1% by weight. The reaction temperature is 0-300°C, preferably 50-220°C, and the reaction pressure is 0. O1 ~ 500kg/c 2. Preferably it is 1 to 200 kg/am;

In the case of the method of the present invention, the reaction can be carried out continuously or batchwise, and if necessary, extracting additives, such as cobalt phosphate, cobalt sulfur, nickel chloride, iron chloride, may be added. In the present invention, it is not particularly safe to use reaction solvents, but gold salts such as ethanol, alkalis such as NaOHlKOH, acids such as [l] can be added to the reaction system, but ethanol, inpropyl alcohol, Solvents such as dioxane, hexane methylformamide, dimethylsulfoquine, etc. can be used. Specific examples of aromatic hydrocarbons that are not yet invented and can be used as raw materials include benzene, toluene, xylene, and the like.

Next, the present invention will be explained in more detail with reference to Examples. It should be noted that the conversion rates and selectivities shown in the Examples are both values obtained by analyzing the organic liquid layer produced by the reaction by gas chromatography and using the following formula for each designated substance.

Conversion rate (mol%) = [1-(A/B)×100A・
...Number of moles of aromatic hydrocarbon in the reaction solution B...
Raw material aromatic hydrocarbon mole selectivity (mol%) = C/
DX100C...Number of moles of cycloolefin D.
...Total number of moles of reaction products Reference example 1 (catalyst preparation method) Ruthenium chloride 0.52 in a 300 ml Erlenmeyer flask
g Take 0.05 g of cupric chloride, add 5 g of ethylene glycol
Add 6g and stir at 60°C for 2 hours. 75.1 for this liquid
g of reprinted silicic acid sol (S-208 manufactured by Catalyst Kasei) was added and stirred for further 2 hours. The obtained black-rimmed mixed solution is spray-dried at -heat, &iL inlet temperature of 200°C and outlet temperature of 120°C to obtain 21 g of a black-green solid. This is a silica gel with a ruthenium content of 1% by weight and a copper content of 0.1% by weight.

Reference Example 2 (Catalyst Preparation Method) Ruthenium chloride 1. Og,
Take 0.085 g of cupric chloride and add 1 ethylene glycol
Add 11.8 g and stir at 60°C for 1 hour. Alumina sol (Alumina sol 100 manufactured by B-san Kagaku) is added to this liquid and stirred for 2 hours. The mixed solution changes from yellow to a pale line color. Thereafter, 80.1 g of ruthenium-containing HL (10% copper-containing,
7t.

Obtain ψ% alumina gel.

Example 1 Ruthenium content obtained in Reference Example 1 is 1! 2 g of silica gel containing rLj11 taro and 0.1% by weight of copper was activated by reduction treatment at 500° C. for 8 hours in a hydrogen stream of 6 hours at 14 hours.

Next, 160 ml of benzene and 100 ml of water were charged into an autoclave with a content of 500 ml, and 2 g of the activated ruthenium Φ copper-containing silica gel was added, and the internal space of the body was sufficiently replaced with water and keratin scum. , under the conditions of hydrogen pressure cuff 0 kg/cm2 and temperature 180°C.
I did a response. In this case, by electromagnetic induction rotation type, 8
After stirring at 00 revolutions/min, the reaction solution was appropriately extracted and analyzed by gas chromatography. The results showed that the reaction time was 1 hour, the conversion rate of benzene was 77.5 mol≦, the yield of cyclohexene 7 was 2 days, and the yield of 6 de 6 and obtained a bond.

Example 2 Ruthenium-containing obtained in Reference Example 2:,? -174 de5. Copper 0
．． 2 g of alumina gel containing 1ffC; J+C% was activated by mass treatment at 300° C. for 8 hours in a hydrogen flow of 61/hour.

Next, add benzene 180+a1. After charging 1,001 liters of water and adding 2 g of the activated ruthenium/copper-containing silica gel, the interior space of the container was sufficiently replaced with hydrogen gas, and the reaction was carried out under the conditions of a hydrogen pressure cuff of 0 kg/cm7 and a temperature of 180°C. went. In this case, the reaction solution was stirred at 800 rpm using an electromagnetic induction rotary system, and the reaction solution was extracted as needed and analyzed using gas chromatography.
Benzene conversion rate 40.3 mol%, cyclohexene yield J
A score of 21.0% was obtained.

Examples 3 to 6 Ruthenium content 1% by weight, copper 0, lli obtained in Reference Example 1
% silica gel at 400°C in a hydrogen flow of 61% per hour.
The mixture was treated and activated for 8 hours.

In place of benzene in the reaction solution of Example 1, toluene, ethylbenzene, cumene+t-phthylbenzene, etc. were used, and the reaction was carried out using the same apparatus and experimental conditions. The results are shown in Table-1.

(Margin below)

Claims (5)

[Claims] (1) aromatic hydrocarbon in the presence of water and a hydrogenation catalyst,
A method of partial hydrogenation by reaction with hydrogen gas, characterized in that the hydrogenation catalyst is a catalyst in which ruthenium and copper are dispersed as main components in a solid derived from a metal hydroxide colloid. Partial nuclear hydrogenation method for group hydrocarbons. (2) The hydrogenation catalyst is a mixed solution of a metal hydroxide colloidal solution and an organic solvent solution in which ruthenium salts and copper salts are dissolved, which is then dried and heat-treated at 200 to 800°C in a hydrogen atmosphere. Claim 1
The method for partial nuclear hydrogenation of aromatic hydrocarbons described in . (3) Partial nuclear hydrogenation of aromatic hydrocarbons according to claim 1 or 2, wherein the metal hydroxide colloidal solution is selected from one or more of silicic acid sol, alumina sol, and titania sol. Law. (4) The method for partial hydrogenation of aromatic hydrocarbons according to claim 2, wherein the organic solvent is selected from one or more polar solvents having polydentate or crosslinking coordination ability. (5) The method for partial nuclear hydrogenation of aromatic hydrocarbons according to claim 2, wherein the drying is a spray drying method.