JPH092981A - Production of cycloolefin - Google Patents

Abstract

PURPOSE: To obtain a cycloolefin in high selectivity by using a specific catalyst in a partial hydrogenation reaction of a monocyclic aromatic hydrocarbon. CONSTITUTION: In this method for producing a cycloolefin by the partial hydrogenation reaction of a monocyclic aromatic hydrocarbon in the presence of a catalyst and water, a reduced substance comprising (1) rethenium and (2) a promotor containing at least one selected from the group consisting of manganese, cobalt, nickel, zinc, chromium and lanthanide is formed so as to previously reduce the weight ratio of the promotor component to ruthenium in the reduced substance and used as a catalyst.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for partially hydrogenating a monocyclic aromatic hydrocarbon to produce corresponding cycloolefins, particularly cyclohexene. Cycloolefin is a compound useful as a raw material for polyamide such as lactams and dicarboxylic acids, and as an important intermediate raw material for lysine, pharmaceuticals, agricultural chemicals and the like.

[0002]

2. Description of the Related Art As a method for producing cycloolefin,
Many methods such as partial hydrogenation reaction of monocyclic aromatic hydrocarbons, dehydration reaction of cycloalkanol, dehydrogenation reaction of cycloalkane, and oxidative dehydrogenation reaction have been known.
Among them, if the cycloolefin can be efficiently obtained by the partial hydrogenation of the monocyclic aromatic hydrocarbon, the reaction step becomes the most simplified, which is preferable in the process.

As a method for producing a cycloolefin by partial hydrogenation of a monocyclic aromatic hydrocarbon, ruthenium metal is mainly used as a catalyst, and a hydrogenation reaction is generally performed in the presence of water. Also, this ruthenium catalyst
Generally, in order to increase the selectivity of cycloolefin,
With ruthenium, manganese, iron, cobalt, nickel,
It is said that it is particularly preferable to use a cocatalyst component such as zinc in combination (JP-A-53-63350, JP-A-4-74).
141 etc.).

[0004]

However, all the conventional methods have some problems, and an industrially advantageous method is not always established. For example, when a catalyst comprising ruthenium and a co-catalyst is used, the cycloolefin selectivity is improved, but on the other hand, there is a problem that the activity tends to decrease and the cycloolefin cannot be efficiently produced.

[0005]

Means for Solving the Problems The present inventors have made a detailed study by paying attention to a cocatalyst component that coexists with ruthenium, and found that the above problem can be solved by using a specific catalyst composed of ruthenium and the cocatalyst component. They have found what they can do and have reached the present invention. That is, the gist of the present invention is (1) ruthenium and (2) manganese, iron, cobalt, nickel, zinc in a method for producing a cycloolefin in which a monocyclic aromatic hydrocarbon is partially hydrogenated in the presence of a catalyst and water. Characterized in that a reduced product of a cocatalyst component containing at least one selected from the group consisting of chromium, lanthanum and lanthanum is previously used as a catalyst by reducing the weight ratio of the cocatalyst component to ruthenium in the reduced product. And a method for producing cycloolefin.

Hereinafter, the present invention will be described in detail. The catalyst in the present invention includes (1) ruthenium and (2) manganese,
Iron, cobalt, nickel, zinc, chromium, which consists of a co-catalyst component containing at least one selected from the group consisting of lanthanum, the raw material compound of each metal component of the catalyst, halides of each metal, nitrates, Acetates, sulfates, complex compounds containing each metal and the like are used.

The ruthenium catalyst of each metal component in the raw material compound of the catalyst is usually the weight ratio of the promoter metal containing at least one selected from the group consisting of manganese, iron, cobalt, nickel, zinc, chromium and lanthanum to ruthenium. It is 0.01 to 10, preferably 0.05 to 5, and more preferably 0.1 to 2. As the promoter metal component, zinc is particularly preferable. In addition to the above promoter components, gold, silver, copper, platinum, tungsten, molybdenum, etc. may be used as the third promoter metal component.

As a conventional general ruthenium catalyst, one containing metal ruthenium obtained by reducing a mixture of the above-mentioned catalyst raw material compounds is used. As the reduction method, a catalytic reduction method using hydrogen gas or a chemical reduction method using formalin, sodium borohydride, hydrazine or the like is used. Of these, catalytic reduction with hydrogen gas is preferable, and is usually 80 to 500 ° C., preferably 100 to 450.
Reductively activated under conditions of ℃. When the reduction temperature is lower than 80 ° C., the reduction ratio of ruthenium is remarkably reduced, and
If the temperature exceeds ℃, agglomeration of ruthenium is likely to occur, which causes a decrease in the yield and selectivity of cycloolefin production.

The ruthenium catalyst may be used as it is as the reduced metal particles containing ruthenium, or may be used as a supported catalyst supported on a carrier. As the carrier, barium sulfate, metal salts such as calcium sulfate, silica, alumina, zirconia, titania, chromina, oxides of rare earth metals, or silica-alumina, silica-zirconia, composite oxides such as zirconium silicate, Examples include silica modified with a metal oxide such as zirconia. As a method for supporting the catalyst component, after dipping the carrier in the catalyst component liquid and then evaporating the solvent by stirring to evaporate the solvent to fix the active component, a spray method in which the catalyst active component liquid is sprayed while keeping the carrier in a dry state Or a known impregnation-supporting method such as a method of immersing the carrier in the catalytically active component liquid and then filtering. The cocatalyst metal component to be co-loaded may be loaded on the carrier at the same time as the ruthenium raw material, or may be loaded after ruthenium is loaded in advance, or after these metals are loaded in advance, ruthenium is loaded afterwards. You may. In addition, as a solvent used for supporting the active component at the time of catalyst preparation, water or an organic solvent such as alcohol, acetone, tetrahydrofuran, hexane, and toluene is used. The amount of ruthenium supported is usually 0.
It is 001 to 10% by weight, preferably 0.1 to 5% by weight.

The reduced product comprising a promoter component containing at least one selected from the group consisting of (1) ruthenium and (2) manganese, iron, cobalt, nickel, zinc, chromium and lanthanum obtained by the above method is Although it can be used as it is as a catalyst, the present invention is characterized in that a catalyst obtained by previously reducing the weight ratio of the promoter component to ruthenium in the reduced product is used in the reaction.

There are no particular restrictions on the method for reducing the weight ratio of the promoter component to ruthenium in the reduced product,
Usually, a method of bringing the reduced product into contact with a solvent to elute the promoter component is adopted. Examples of this solvent include polar solvents such as water, alcohols and organic acids, but water is preferable. Almost no ruthenium component (1) in the reduced product subjected to the reduction treatment was dissolved in water by the contact treatment with water, but (2) manganese, iron, cobalt, nickel, zinc, chromium, A considerable amount of the lanthanum co-catalyst component is eluted in water depending on the conditions of the contact treatment with water.

Reducing the content of co-catalyst in the catalyst appears to have a detrimental effect on its performance as a catalyst,
In fact, surprisingly, the effect of improving the catalytic activity and the selectivity is achieved. Conventionally, in order to increase the selectivity of the catalyst, a certain amount of the cocatalyst component is generally required with respect to ruthenium, but on the other hand, the problem of the deterioration of the catalytic activity has been a problem. This problem is solved.

Although the cause of the effect of the present invention is not clear, ruthenium is reduced even if it is desirable that a certain amount of the cocatalyst component is present in the step of initially reducing the ruthenium component during catalyst preparation. It is estimated that the cocatalyst component that contributes to the reaction at the given stage is limited to a part of the catalyst.

The weight ratio of the promoter component to ruthenium is usually 8 based on the weight ratio before the contact treatment.
It is desirable to reduce it to 0% or less, preferably 50% or less. The lower limit of the weight ratio of the cocatalyst component is not particularly limited, and the effect can be recognized even if a small amount of the cocatalyst component is present, but it is preferably 0.1% or more. The contact treatment is usually 0.01 to 100 times by weight, preferably 0.1 to 100 times the weight of the catalyst.
It is carried out by immersing in 10 times by weight of water. The processing conditions are usually from normal pressure to pressurized, room temperature to 250 ° C,
The reaction is preferably performed at room temperature to 200 ° C., usually for 10 minutes or more, preferably for 1 to 20 hours. The catalyst treatment atmosphere is usually an inert gas atmosphere or a hydrogen gas atmosphere, preferably a hydrogen gas atmosphere. The catalyst after the contact treatment is usually dried before use. Further, the catalytic activity can be further enhanced by performing a contact treatment in a hydrogen gas atmosphere after drying.

The water used in the above contact treatment may be not only pure water but also an aqueous solution of a metal salt. It is desirable to carry out contact treatment with the aqueous metal salt solution, because further improvement in catalytic activity can be expected. As the metal salt used,
Group 1 elements such as lithium, sodium and potassium, Group 2 elements such as magnesium, calcium and strontium,
And metal salts of manganese, iron, nickel, cobalt, zinc, etc., for example, weak acid salts such as carbonates, acetates, sulfates,
A strong acid salt such as nitrate is used. The concentration of the metal salt in the aqueous solution is usually 1 × 10 ^-5 to 1 with respect to water.
It is 1 times by weight, preferably 1 × 10 ^{−4 to} 0.2 times by weight.
The catalyst after the contact treatment is usually used after filtering a metal salt aqueous solution, washing with pure water, and drying. Further, the catalytic activity can be further enhanced by performing a reduction treatment in a hydrogen gas atmosphere after drying.

The present invention is characterized by using the above-mentioned ruthenium catalyst. When the present invention is carried out, benzene, toluene,
Xylene and lower alkyl group-substituted benzenes having about 1 to 4 carbon atoms are exemplified. Further, the reaction system of the present invention requires the presence of water. The amount of water varies depending on the reaction mode, but is generally 0.01 to 10 times by weight of the monocyclic aromatic hydrocarbon, preferably 0.1 to 5 times.
Weight times. Under these conditions, two phases are formed: an organic liquid phase (oil phase) containing the raw materials and products as main components, and a liquid phase (water phase) containing water. When the ratio between the oil phase and the aqueous phase is extreme, it is difficult to form two phases, and liquid separation is difficult. Further, if the amount of water is too small or too large, the effect of the presence of water is reduced, and if the amount of water is too large, it is necessary to enlarge the reactor, which is not preferable.

In addition, a metal salt may be present in the reaction system of the present invention for the purpose of increasing the selectivity of cyclohexene, and Group 1 metals such as lithium, sodium and potassium in the periodic table, magnesium and calcium. Such as 2
Group metals (group numbers are IUPAC inorganic chemical nomenclature revised version (1
989)), or nitrates, chlorides, sulfates, acetates and phosphates of metals such as zinc, manganese and cobalt, and it is particularly preferable to use zinc sulfate in combination. The amount of metal salt used is usually 1 × 10 ^{−5 with} respect to the water in the reaction system.
˜1 times by weight, preferably 1 × 10 ^{−4 to} 0.1 times by weight.

The reaction conditions of the present invention are as follows:
It is usually selected from the range of 50 to 250 ° C, preferably 100 to 220 ° C. When the temperature is 250 ° C or higher, the selectivity of cycloolefin is lowered, and when the temperature is 50 ° C or lower, the reaction rate is remarkably lowered, which is not preferable. The hydrogen pressure during the reaction is usually selected from the range of 0.1 to 20 MPa, preferably 0.5 to 10 MPa. When it exceeds 20 MPa, it is industrially disadvantageous, while when it is less than 0.1 MPa, the reaction rate remarkably decreases and it is uneconomical in terms of equipment. The reaction can be carried out in either a gas phase reaction or a liquid phase reaction, but is preferably a liquid phase reaction. The reaction system is not particularly limited, and it can be carried out batchwise or continuously using one or two or more reaction tanks.

[0019]

EXAMPLES Examples will be described below, but the present invention is not limited to these examples. The conversion rate and selectivity shown in Examples and Comparative Examples are defined by the following equations.

[0020]

[Equation 1]

Comparative Example 1 20 ml of 0.87 g of zirconium oxynitrate dihydrate
8.0 g of silica (manufactured by Fuji Silysia Chemical Ltd., trade name: CARIACT50) was added to the aqueous solution of pure water.
After immersion at room temperature, water was distilled off and the product was dried. Next, it was calcined at 1000 ° C. for 4 hours under air flow to prepare a silica carrier modified with 5% by weight of zirconia with respect to silica.

The above-mentioned zirconia-modified silica carrier was added to an aqueous solution containing a predetermined amount of ruthenium chloride and zinc chloride, and the mixture was immersed at 60 ° C. for 1 hour, water was distilled off, and it was dried. The thus-obtained catalyst supporting 0.5 wt% of ruthenium (Ru) and zinc (Zn) on the carrier was reduced and activated in a hydrogen stream at 200 ° C. for 3 hours. . The contents of ruthenium and zinc contained in the above catalyst were measured by the fluorescent X-ray method. Table 1 shows the analysis results of the weight ratio of zinc / ruthenium.

Next, in an autoclave having an internal volume of 500 ml, 150 ml of an aqueous solution containing 6% by weight of zinc sulfate, the catalyst 3.
75 g and 100 ml of benzene were charged. Reaction temperature 15
Under conditions of 0 ° C. and a pressure of 50 MPa, hydrogen gas was added at 57 Nl /
It was supplied at a flow rate of Hr and stirred at 1000 rpm to carry out a partial hydrogenation reaction of benzene. The reaction liquid was appropriately extracted from the nozzle installed in the reactor, and the oil phase was analyzed by gas chromatography. The results are shown in Table 1.

Example 1 5 g of the catalyst prepared in Comparative Example 1 and 100 ml of an aqueous solution containing 6% by weight of zinc sulfate were charged into a Ti autoclave having an internal volume of 500 ml, and the temperature was 200 ° C. and the pressure was 5.0 MPa. Then, the mixture was stirred at 600 rpm for 5 hours. After the treatment, the catalyst was taken out and washed with pure water. Washing was performed by adding 30 times the amount of pure water to the catalyst and mixing them sufficiently for 1 hour with stirring, etc., until the zinc concentration in the wash water at the time of substantially equilibrium became 0.1 ppm or less. Further, the catalyst was dried and then kept in a hydrogen stream at 200 ° C. for 3 hours. Table 1 shows the analysis results of the weight ratio of zinc / ruthenium contained in the catalyst.

A partial hydrogenation reaction of benzene was carried out in the same manner as in Comparative Example 1 except that the above catalyst was used. The reaction results are shown in Table 1.

[0026]

[Table 1]

Comparative Example 2 A catalyst was prepared in the same manner as in Comparative Example 1 except that commercially available zirconium silicate (manufactured by Daiichi Rare Elements Co., Ltd.) was used instead of the carrier used in Comparative Example 1. Table 1 shows the analysis results of the weight ratio of zinc / ruthenium contained in the catalyst. A partial hydrogenation reaction of benzene was carried out in the same manner as in Comparative Example 1 except that this catalyst was used. Table 2 shows the reaction results.

Example 2 A catalyst was prepared in the same manner as in Example 1 except that commercially available zirconium silicate (manufactured by Daiichi Rare Elements Co., Ltd.) was used in place of the carrier used in Example 1. Table 1 shows the analysis results of the weight ratio of zinc / ruthenium contained in the catalyst. A partial hydrogenation reaction of benzene was carried out in the same manner as in Comparative Example 1 except that this catalyst was used. Table 2 shows the reaction results.

[0029]

[Table 2]

Example 3 7.0 g of the catalyst prepared by the method of Comparative Example 1, 30 m of pure water
1, and 3.6 g of zinc sulfate heptahydrate were charged into an autoclave, and the temperature was 150 ° C. and the pressure was 5 (5.0 MPa) under hydrogen pressure.
Stir for a period of time. After the treatment, the present catalyst was taken out, and Example 1
After washing and drying in the same manner as above, the sample was held in a hydrogen stream. Table 3 shows the analysis results of the weight ratio of zinc / ruthenium contained in the catalyst. 6.0 g of this catalyst, 80 ml of benzene, 120 ml of pure water, and 14.4 g of zinc sulfate heptahydrate were charged into an autoclave, and the partial hydrogenation reaction of benzene was performed under the conditions of a temperature of 150 ° C. and a hydrogen pressure of 50 MPa. Was carried out. The reaction results are shown in Table-3.

Example 4 7.0 g of the catalyst prepared by the method of Comparative Example 1, 30 m of pure water
1, and 3.6 g of lithium sulfate monohydrate were placed in an autoclave, and stirred at a temperature of 150 ° C. under hydrogen pressure (5.0 MPa) for 5 hours. After the treatment, the catalyst was taken out, washed in the same manner as in Example 1, dried and then held in a hydrogen stream. Table 3 shows the analysis results of the weight ratio of zinc / ruthenium contained in the catalyst. A partial hydrogenation reaction of benzene was carried out in the same manner as in Example 3 except that this catalyst was used. The reaction results are shown in Table-3.

Example 5 7.0 g of the catalyst prepared by the method of Comparative Example 1 and 30 m of pure water
1, and 3.6 g of cobalt sulfate heptahydrate were placed in an autoclave, and stirred at a temperature of 150 ° C. under hydrogen pressure (5.0 MPa) for 5 hours. After the treatment, the present catalyst was taken out, washed and dried in the same manner as in Example 1, and then held in a hydrogen stream. Table 3 shows the analysis results of the weight ratio of zinc / ruthenium contained in the catalyst. A partial hydrogenation reaction of benzene was carried out in the same manner as in Example 3 except that this catalyst was used. The reaction results are shown in Table-3.

Comparative Example 3 The partial hydrogenation reaction of benzene was carried out in the same manner as in Example 3 except that the catalyst prepared by the method of Comparative Example 1 was used. The reaction results are shown in Table-3.

[0034]

[Table 3]

Example 6 7.0 g of the catalyst prepared by the method of Comparative Example 1 and 30 ml of pure water
Was charged into an autoclave, and stirred at a temperature of 150 ° C. under hydrogen pressure (5.0 MPa) for 5 hours. After the processing,
The catalyst was taken out, washed in the same manner as in Example 1, dried and then held in a hydrogen stream. Table 4 shows the analysis results of the weight ratio of zinc / ruthenium contained in the catalyst. A partial hydrogenation reaction of benzene was carried out in the same manner as in Example 3 except that 3.0 g of this catalyst was used. The reaction results are shown in Table-4.

Comparative Example 4 A partial hydrogenation reaction of benzene was carried out in the same manner as in Example 6 except that the catalyst prepared by the method of Comparative Example 1 was used. The reaction results are shown in Table-4. Comparative Example 5 Except that the catalyst obtained by adjusting the amount of zinc chloride used in the preparation method of Comparative Example 1 and supporting 0.5% by weight of ruthenium and 0.25% by weight of zinc on the carrier was used.
The partial hydrogenation reaction of benzene was carried out in the same manner as in Example 6. The reaction results are shown in Table-4.

[0037]

[Table 4]

Example 7 2 g of the same catalyst used in the reaction in Example 4, 80 ml of benzene and 120 ml of pure water were charged into an autoclave, and benzene was heated under the conditions of a temperature of 150 ° C. and a hydrogen pressure of 5.0 MPa. Was partially hydrogenated. The reaction results are shown in Table-5.

Comparative Example 6 2 g of the same catalyst used in the reaction in Comparative Example 4, 80 ml of benzene and 120 ml of pure water were charged into an autoclave, and benzene was heated at a temperature of 150 ° C. and a hydrogen pressure of 5.0 MPa. Was partially hydrogenated. The reaction results are shown in Table-5.

[0040]

[Table 5]

[0041]

According to the present invention, a cycloolefin can be efficiently produced with a high selectivity by a partial hydrogenation reaction of a monocyclic aromatic hydrocarbon.

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Claims (5)

[Claims] 1. A method for producing a cycloolefin in which monocyclic aromatic hydrocarbons are partially hydrogenated in the presence of a catalyst and water, wherein (1) ruthenium and (2) manganese, iron, cobalt, nickel, zinc, chromium, A reduced product comprising a cocatalyst component containing at least one selected from the group consisting of lanthanum, which is used as a catalyst by previously reducing the weight ratio of the promoter component to ruthenium in the reduced product. Process for producing olefin. 2. The method according to claim 1, wherein a catalyst is used in which the weight ratio of the promoter component to ruthenium in the reduced product is reduced to 80% or less. 3. The method according to claim 1, wherein the weight ratio of the promoter component to the ruthenium in the reduced product is reduced by the contact treatment with water. 4. The method according to claim 3, wherein an aqueous solution of a metal salt is used as the water used for the contact treatment. 5. The method according to claim 1, wherein the partial hydrogenation is carried out in the presence of a metal salt.