JP2002154990A - Method for producing cycloolefin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To efficiently produce a cycloolefin with a high selectivity and a high yield by a partial hydrogenation reaction of a monocyclic aromatic hydrocarbon. A monocyclic aromatic hydrocarbon is partially hydrogenated in the liquid phase in the presence of water using a ruthenium-supported silica mesopore molecular sieve catalyst. [Effect] (1) High selectivity from monocyclic aromatic hydrocarbons,
The desired cycloolefin per unit weight of ruthenium can be efficiently obtained in high yield.
(2) Easy handling with respect to extraction and separation of the catalyst. (3) High loading of ruthenium as a supported catalyst becomes possible, the activity per catalyst is increased, the metal poisoning is deteriorated, and the industrial stability is excellent. It has the advantage of being extremely valuable.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for producing a cycloolefin by partially hydrogenating a monocyclic aromatic hydrocarbon. Specifically, in the production of cycloolefins by partially hydrogenating monocyclic aromatic hydrocarbons, the monocyclic aromatic hydrocarbons are partially hydrogenated in the liquid phase in the presence of water using a ruthenium-supported silica mesopore molecular sieve catalyst. And a method for producing a cycloolefin.

[0002]

2. Description of the Related Art Cycloolefin production methods include:
Conventionally, methods such as a partial hydrogenation reaction of a monocyclic aromatic hydrocarbon, a dehydration reaction of a cycloalkanol and a dehydrogenation reaction of a cycloalkane have been known. Among them, a method based on partial hydrogenation of a monocyclic aromatic hydrocarbon is preferred as the most simplified process.

As a method for producing 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 and a metal salt. is there. As the ruthenium catalyst, a method using metal ruthenium fine particles as they are (Japanese Patent Application Laid-Open Nos. 61-50930 and 62-45541,
JP-A-62-45544, etc.) and a method of adding at least one metal oxide in addition to metal ruthenium fine particles to carry out a reaction (JP-A-62-201830, JP-A-63-178).
34, JP-A-63-63627), silica, alumina,
A method using a catalyst in which ruthenium is supported on a carrier such as silica or zirconia (JP-A-57-130926;
1-404026, JP-A-4-74141, JP-A-7-2
Many proposals have been made.

[0004]

However, all of the known methods have some problems and cannot be said to be necessarily industrially advantageous. When the metal ruthenium fine particles are used as they are, the fine particle catalyst agglomerates in the reaction system, and the productivity of the target cycloolefin per unit weight of ruthenium decreases due to the reduction of the reaction active site due to the aggregation. In addition, when the additive is added to the ruthenium fine particles, the reaction system becomes complicated, and the handling property relating to the extraction of the catalyst and the separation operation becomes difficult.

[0005] On the other hand, a catalyst in which ruthenium is supported on a carrier has a high activity per supported metal, but the selectivity of a target cycloolefin is extremely low. For this reason, in order to improve the selectivity, measures such as adding a second component and an additive different from the main metal have been devised, but the activity has to be remarkably reduced, and the high selectivity and the yield are not necessarily high. Not obtained. In addition, the catalyst in which ruthenium is supported on the carrier affects the activity, selectivity, and catalyst deterioration depending on the supporting rate of the main metal supported on the carrier. At low loadings, catalysts elute from the reactor over time, such as metals
Poisoning deterioration due to iron, nickel, chromium, molybdenum, etc. is liable to occur, and the activity and selectivity decrease over time, making it difficult to become an industrially stable catalyst. On the other hand, when the loading rate is high, there is a problem that the metal is aggregated on the surface of the carrier or in the bulk of the carrier, and the activity and the selectivity are reduced.

[0006]

Means for Solving the Problems The present inventors have made intensive studies in order to solve such a problem. As a result, a catalyst in which ruthenium is highly dispersed and supported using a silica mesopore molecular sieve carrier has the following advantages. This led to the present invention. (1) The desired cycloolefin per unit weight of ruthenium can be efficiently obtained with high selectivity and high yield from monocyclic aromatic hydrocarbons.
(2) Easy handling with respect to extraction and separation of the catalyst. (3) As a supported catalyst, ruthenium can be supported at a high level, the activity per catalyst is increased, the metal poisoning is deteriorated, and the industrial stability is excellent. That is, the present invention relates to a method for producing a cycloolefin, which comprises partially hydrogenating a monocyclic aromatic hydrocarbon in a liquid phase in the presence of water using a silica mesopore molecular sieve catalyst supporting ruthenium. is there.

Hereinafter, the present invention will be described in detail. The catalyst support used in the present invention is a silica mesopore molecular sieve. The silica mesopore molecular sieve used for the catalyst support of the present invention is a metal oxide having a metal oxide skeleton containing silicon oxide as a main component, and having a mesopore region, in particular, monodisperse pores having a diameter of 1.5 to 10 nm. It is a porous material. As a method for synthesizing these mesopore molecular sieves, US Pat.
No. 8684, No. 5102643, No. 5108725
And JP-A-5-503499 discloses a method of synthesizing a compound by hydrothermal synthesis using a quaternary ammonium salt or a phosphonium salt having a long-chain alkyl group as a template. In addition, Japanese Patent Application Laid-Open No. Hei 4-23881
No. 0 discloses a method of synthesizing a layered silica by ion exchange using a long-chain alkylammonium cation. In addition, as an organic hybrid mesopore molecular sieve, an organic component bonded to silicon has 1 to 60 equivalent% with respect to silicon. The organic component is a hydrocarbon group, and the organic component is based on silicon atoms in the catalyst. 1
It is also known that they contain 60 equivalent%, preferably 5 to 50 equivalent%. Such an inorganic-organic hybrid mesopore molecular sieve can be synthesized according to a known method such as JP-A-10-72212.

As the catalyst used in the present invention, such an organic hybrid mesopore molecular sieve having excellent hydrophobicity can also be used. The mesopore molecular sieve of the present invention is
In addition to silicon, aluminum, boron, tin and transition metal elements such as titanium, iron, zinc, rare earth elements and zirconium can be used. The ratio of these metal oxides to silicon in the mesopore molecular sieve, when the metal group is represented by M, has a silicon / M atomic ratio of 10 or more, and preferably 10 to 100.

The catalyst can be prepared according to a commonly used method for preparing a supported metal catalyst. That is, after the mesopore molecular sieve serving as a carrier is immersed in the catalyst component liquid, the solvent is evaporated while stirring to immobilize the active ingredient, or an evaporation to dryness method, or the mesopore molecular sieve carrier is immersed in the catalyst active ingredient liquid, followed by filtration. A known impregnation-supporting method such as is used. As the ruthenium raw material of the catalytically active component, ruthenium halides, nitrates, hydroxides, and complexes such as ruthenium carbonyl and ruthenium ammine complexes are used. Water or an organic solvent such as alcohol, acetone, hexane, or benzene is used as a solvent for the support.

[0010] Ruthenium, which is the active component of the catalyst, can be used alone, but it is effective to co-support other metal components. As a component co-supported with ruthenium, zinc, nickel, iron, copper, cobalt, manganese, alkaline earth, and the like are used, and among them, zinc is most preferable. As these compounds which are co-supporting components, halides, nitrates, acetates, sulfates, complex compounds containing the respective metals, etc. of the respective metals are used. These co-supported components may be supported on the carrier at the same time as ruthenium, or may be pre-supported and then supported on ruthenium, or may be supported on these metals first and then on ruthenium. The catalyst thus prepared is usually used by reducing and activating ruthenium in a gas phase or a liquid phase. Known reducing agents such as hydrogen, hydrazine, formalin, and sodium borohydride can be used as the reducing agent. Preferably, hydrogen is used. It is activated usually at 80 to 450 ° C, preferably at 100 to 400 ° C. Further, the catalyst used in the present invention is preferably used after being subjected to a preliminary reduction treatment in water before the reaction.

The loading amount of ruthenium is usually 0.1 to 40% by weight, preferably 1 to 30% by weight, based on the mesopore molecular sieve support. When a co-supporting component is used, the atomic ratio to ruthenium is about 0.01 to 20, preferably about 0.05 to 10. The reason why the catalyst of the present invention exhibits an effective effect as a partial hydrogenation catalyst is that, by using a mesopore molecular sieve carrier, the catalyst is in the form of a ruthenium fine particle supported uniformly and highly dispersed even under a high supported condition. Is presumed to have an effect. Compared with a conventionally used carrier, the mesopore molecular sieve carrier has a very large specific surface area (on the order of 1000 m ² / g), and the pores are uniformly present in the mesopore region. It is possible to use a supported catalyst dispersed in a fine particle state. On the other hand, conventionally used supports have a wide pore distribution or a large pore size as compared with the mesopore molecular sieve, and the supported ruthenium is not uniformly dispersed in the pores during catalyst preparation, and the selectivity is low. Low high activity sites and aggregating extremely low activity parts are mixed,
It is thought that this is due to a decrease in catalyst performance.

The reason why the metal poisoning resistance is increased is as follows.
It is presumed that it was possible to increase the loading of ruthenium. Those with a low loading ratio have many hydrogenation active sites per ruthenium and are susceptible to metals that have a poisoning effect per ruthenium. On the other hand, in the case of high loading, ruthenium is uniformly dispersed, but each fine particle is close to each other, there are fewer hydrogen active sites per ruthenium than in the low loading ratio, and there is a poisoning effect per ruthenium We believe that it will be less affected by metal.

As a mode of using the catalyst of the present invention, a method using a solid catalyst, such as a slurry suspension system or a fixed bed flow system as a molded catalyst, can be applied. In the present invention, it is necessary that water is present in the reaction system,
The amount of water is usually 0.01 to 0.01% relative to the aromatic hydrocarbon.
-100 weight times is used. However, under the reaction conditions, it is preferable that the organic phase containing the raw materials and the product as main components and the liquid phase containing water form two liquid phases, and more preferably 0.5 to 20 times by weight.

Further, in the present invention, a method is used in which a metal compound other than the catalyst component is present in the reaction system.
Examples of the metal compound include Group 1 elements of the periodic table such as lithium, sodium, and potassium, Group 2 elements such as magnesium, calcium, and strontium, and metal compounds such as manganese, iron, cobalt, zinc, and copper. As the kind of the metal compound, carbonate, acetate, hydrochloride, sulfate, nitrate, oxide, and hydroxide can be used. As particularly effective metal compounds, zinc sulfate, zinc hydroxide and zinc oxide are preferred, and among them, zinc sulfate is most preferred.

The amount of these salts to be added is 1 × 10 ^{−5 to} 1.0 times by weight, preferably 1 × 10 ^{−4 to} 0.5 times by weight, based on the water present in the reaction system. It is not necessary that all of these compounds used be dissolved in water coexisting in the reaction system. These metal compounds may be used alone or in combination of two or more. In the present invention, it is preferable that the coexisting aqueous phase is reacted under neutral or acidic conditions. When the aqueous phase becomes alkaline, the reaction rate is particularly remarkably reduced, which is not preferable. Preferably, the pH of the aqueous phase is from 0.5 to less than 7, more preferably from 2 to 6.5.

The monocyclic aromatic hydrocarbon used as a raw material in the present invention refers to benzene, toluene, xylenes and lower alkylbenzenes. The conditions for the partial hydrogenation reaction are appropriately selected depending on the type and amount of the catalyst and additives used, but the hydrogen pressure is usually 0.1 to 20 MPa, preferably 1 to 10 MPa.
MPa, and the reaction temperature is in the range of 50 to 250 ° C, preferably 100 to 200 ° C. Further, the reaction time may be selected as appropriate, by setting a substantial target of the selectivity and yield of the target cycloolefin, and is not particularly limited, but is usually about several seconds to several hours.

[0017]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be specifically described below with reference to examples, reference examples and comparative examples, but the present invention is not limited to these examples. In the following examples, the catalytic metal composition was determined by X-ray fluorescence analysis. Specific surface area of mesopore molecular sieve using elemental analysis for analysis of silicon and organic groups bonded to silicon,
The pore diameter was measured by a nitrogen adsorption method. The average crystallite diameter was determined from the spread of the diffraction peak of the ruthenium metal diffraction angle (2θ) around 44 degrees by powder X-ray diffraction analysis according to Scherrer's formula. For the reaction evaluation, a batch method using an autoclave was employed, and the reaction solution withdrawn over time was subjected to F
Gas chromatograph with ID detector (G from Shimadzu Corporation)
C-14A).

The conversion of benzene and the selectivity of cyclohexene described below are calculated by the following formulas based on the concentration analysis values of the experiment. Benzene conversion (%) = (moles of benzene consumed by reaction) * 100 / (moles of benzene supplied to reaction) Cyclohexene selectivity (%) = (moles of cyclohexene produced by reaction) * 100 / P where P (mole number) = (mole number of cyclohexene formed by the reaction) + (mole number of cyclohexane formed by the reaction) The activity per ruthenium is defined as per Ru (g) contained in the catalyst. The conversion rate (g / Hr) of the benzene was calculated by the following formula based on the conversion rate of 50%. Activity per Ru = Amount of benzene used (g) * 1/2
* 1 / Time required for conversion to 50% (Hr)
* 1 / weight of ruthenium used (g) On the other hand, the catalytic activity represents the activity per used catalyst.

[0019]

[Reference Example 1] Synthesis of silica mesopore molecular sieve Ethanol was added to 200 g of distilled water using a beaker of 1000 ml.
160 g of ethanol and 20 g of dodecylamine were added and dissolved.
And then, with stirring, tetraethylorthosilicate
Add 83g and stir for about 30 minutes to form a slurry
Become. This was left to react at room temperature for 20 hours. Reaction mixing
The product was filtered, washed with water and dried at 110 ° C for 5 hours to give a white powder.
37.2 g of the product were obtained. Then at 300 ° C for 2 hours,
Calcium in the air at 550 ° C for 4 hours, and the template (Ami
) And remove 24.4 g of silica mesopore molecular sieve.
Obtained. (Referred to as MP-1) The powder X-ray diffraction pattern shows a strong peak at d value = 40.3.
showed that. Measure specific surface area and pore distribution by nitrogen adsorption / desorption method
As a result, the specific surface area was 950 m ^Two/ G, pore size is 3.
It was 2 nm.

2. Catalyst Preparation Using a 300 cc evaporating dish, MP-1 was added to a solution prepared by dissolving 15 g of ruthenium chloride aqueous solution (manufactured by Tanaka Kikinzoku, containing 8.39 wt% of Ru) and 0.25 g of zinc chloride in a mixed solution of 5 g of ethanol and 10 g of water. 5 g was added, and the mixture was sufficiently evaporated to dryness on a water bath with stirring. Then, the mixture was charged into a Pyrex (registered trademark) glass tube and subjected to a reduction treatment in a hydrogen stream at 300 ° C. for 3 hours. Subsequently, a process of dispersing in 200 cc of a 0.01 N aqueous solution of caustic soda, stirring at room temperature for 30 minutes, filtering and washing with water was repeated three times. Next, vacuum drying was performed at 150 ° C. to obtain a Ru—Zn-supported silica mesopore molecular sieve catalyst. The Ru content of the catalyst thus obtained was 19.7 wt%, and the atomic ratio of Zn / Ru was 0.11. The average crystallite size of Ru determined by X-ray diffraction is 2
It was an extremely small value of 4 °.

[0021]

[Reference Example 2] Silica / alumina mesopore molecular sieve
Ethanol was added to 300 g of distilled water using a 1000 ml beaker.
And 240 g of ethanol and 30 g of dodecylamine.
And then, with stirring, tetraethylorthosilicate
125 g are added, followed by aluminum isopropoxa
When 8.1 g of amide was added and stirring was continued, a slurry was formed.
You. This was left to react at room temperature for 20 hours. Reaction mixture
Is filtered, washed with water and dried at 110 ° C for 5 hours to give a white powder
61.2 g of the product were obtained. Then at 300 ° C for 2 hours, 5
Calcium in the air at 50 ° C for 4 hours.
) And remove the silica-alumina mesopore molecular sieve 3
6.7 g were obtained. (Referred to as MP-2) The powder X-ray diffraction pattern shows a strong peak at d value = 40.5.
showed that. Measure specific surface area and pore distribution by nitrogen adsorption / desorption method
As a result, the specific surface area was 900m ^Two/ G, pore size is 3.
It was 2 nm. Further, the Si / Al ratio was 13.

2. Catalyst Preparation Using a 300 cc evaporating dish, MP-2 was dissolved in a solution prepared by dissolving 30 g of ruthenium chloride aqueous solution (manufactured by Tanaka Kikinzoku, containing 8.39 wt% of Ru) and 0.5 g of zinc chloride in a mixed solution of 15 g of ethanol and 15 g of water. 10 g was added, and the mixture was sufficiently evaporated to dryness on a water bath with stirring. Next, the mixture was charged into a Pyrex glass tube and subjected to a reduction treatment in a hydrogen stream at 300 ° C. for 3 hours. Next, a 0.01N aqueous solution of caustic soda 2
A process of dispersing in 00 cc, stirring at room temperature for 30 minutes, filtering and washing with water was repeated three times. Then, vacuum drying at 150 ° C.
A Ru-Zn supported silica / alumina mesopore molecular sieve catalyst was obtained. The Ru content of the catalyst thus obtained was 19.0% by weight, and the Zn / Ru atomic ratio was 0.10. The average crystallite size of Ru determined by X-ray diffraction is 2
It was an extremely small value of 8 °.

[0023]

[Reference Example 3] Silica-zirconia mesopore molecular sieve
The synthesis was performed in the same manner as in Reference Example 2 except that tetraethylorthosilicate
Replaced with aluminum propoxide for 1125g
Zirconium propoxide propanol solution (70
%) Was added and reacted. Treated as in Reference Example 2
60.9 g of a dried white powdery product were obtained. Then 3
Calcination in air at 550 ° C for 4 hours at 00 ° C.
39 g of Rica-zirconia mesopore molecular sieve were obtained.
(Referred to as MP-3) The powder X-ray diffraction pattern showed a strong peak at d value = 35.3.
showed that. Measure specific surface area and pore distribution by nitrogen adsorption / desorption method
As a result, the specific surface area was 740 m ^Two/ G, pore size is 3.
It was 2 nm. Further, the Si / Zr ratio was 10.

2. Preparation of Catalyst A catalyst was prepared in the same manner as in Reference Example 2, except that the carrier was changed to a silica-zirconia mesopore molecular sieve (MP-3). The Ru content of the catalyst thus obtained is 1
8.6 wt%, and the Zn / Ru atomic ratio was 0.15.
The average crystallite size of Ru determined by X-ray diffraction was 30 °.
It was an extremely small value.

[0025]

Example 1 In a 1 liter Hastelloy autoclave, 280 ml of an aqueous solution containing 10 wt% of zinc sulfate and Ru-Zn / MP- prepared in Reference Example 1 as a catalyst were used.
One catalyst (0.5 g) was charged and replaced with hydrogen under stirring.
After raising the temperature to ℃, 140 cc of benzene was injected.
The reaction was carried out at a total pressure of 5 MPa under high-speed stirring. The reaction solution was withdrawn over time, and the composition of the oil phase was analyzed by gas chromatography. The by-product was cyclohexane.
Further, when the average crystallite size of ruthenium in the catalyst after the reaction was measured, it was found that there was almost no change in the crystal diameter of 25 ° and the catalyst was stable. Table 1 shows the reaction results.

[0026]

COMPARATIVE EXAMPLE 1 A 300 cc evaporating dish was used to prepare a solution prepared by dissolving 15 g of a ruthenium chloride aqueous solution (manufactured by Tanaka Kikinzoku, containing 8.39 wt% of ruthenium), 0.25 g of zinc chloride and 5 g of water into commercially available silica gel ( 5 g of Carrieract Q50 manufactured by Fuji Silysia (pore diameter: 500 °) was added, and the mixture was sufficiently evaporated to dryness on a water bath with stirring. Next, the mixture was charged into a Pyrex glass tube and subjected to a reduction treatment in a hydrogen stream at 300 ° C. for 3 hours. Subsequently, a process of dispersing in 400 cc of a 0.01 N aqueous sodium hydroxide solution, stirring at room temperature for 30 minutes, filtering and washing with water was repeated three times. Then, at 120 ° C, 3
After vacuum drying for an hour, a Ru-Zn supported silica catalyst was obtained. The specific surface area of the catalyst thus obtained is 47 m ² / g.
The Ru content was 19.7 wt% and the Zn / Ru atomic ratio was 0.12. The average crystallite size of Ru determined from X-ray diffraction was 170 °. This catalyst was subjected to the partial hydrogenation reaction of benzene in the same manner as in Example 1 except that the amount of the catalyst was 1 g. When the withdrawn reaction liquid after 6 hours was analyzed, the benzene conversion was 2.5%, indicating that there was almost no reaction activity, and the reaction was stopped.

[0027]

Comparative Example 2 In the same manner as in Comparative Example 1, except that the catalyst reduction treatment temperature during catalyst preparation was set to 200 ° C., reduction treatment was performed in a hydrogen stream for 3 hours to obtain a Ru—Zn-supported silica catalyst. The specific surface area of the catalyst thus obtained is 48 m ² / g, and R
The u content is 20.9 wt%, and the Zn / Ru atomic ratio is 0.1
It was 0. The average crystallite size of Ru determined from X-ray diffraction was 86 °. This catalyst was subjected to a partial hydrogenation reaction of benzene in the same manner as in Example 1, except that the amount of the catalyst was 3.5 g. Table 1 shows the reaction results.

[0028]

[Table 1] From Table 1 and Comparative Example 1, it can be said that those not using the mesopore molecular sieve have low selectivity, yield and activity per ruthenium (catalytic activity).

[0029]

Example 2 As in Reference Example 1, except that the catalyst was prepared.
The amount of zinc chloride added was 0.5 g and the catalyst was adjusted in the same manner.
Made. The specific surface area of the catalyst thus obtained is 49
0m ^Two/ G, Ru content is 19.1 wt%, Zn / R
The u atomic ratio was 0.28. In addition, we obtain from X-ray diffraction
The average crystallite diameter of the obtained Ru was 30 °. This catalyst
In the same manner as in Example 1, except that the amount of the catalyst was 1.36 g.
To carry out a partial hydrogenation reaction of benzene. Table 2 shows the reaction results.
Shown in

[0030]

Example 3 A catalyst was prepared in the same manner as in Reference Example 1, except that the amount of zinc chloride added in the preparation of the catalyst was 1.66 g. The specific surface area of the catalyst thus obtained is 5
20 m ² / g, Ru content 19.2 wt%, Zn /
The Ru atomic ratio was 0.40. The average crystallite size of Ru determined by X-ray diffraction was 31 °. This catalyst was subjected to the partial hydrogenation reaction of benzene in the same manner as in Example 1 except that the amount of the catalyst was 1 g. Table 2 shows the reaction results.

[0031]

Example 4 As in Reference Example 1, except that a ruthenium chloride aqueous solution (Tanaka Kikinzoku, Ru
The catalyst was prepared in the same manner, except that 3.75 g of 8.39 wt%) and 0.25 g of zinc chloride were added. The specific surface area of the catalyst thus obtained was 600 m ² / g, the Ru content was 6.5 wt%, and the atomic ratio of Zn / Ru was 0.46. The average crystallite size of Ru determined by X-ray diffraction was 24 °. This catalyst was subjected to a partial hydrogenation reaction of benzene in the same manner as in Example 1 except that the amount of the catalyst was 3 g. Table 2 shows the reaction results.

[0032]

Comparative Example 3 A catalyst was prepared in the same manner as in Comparative Example 1. Was
However, ruthenium chloride aqueous solution (made by Tanaka Kikinzoku, Ru
3.2g, zinc chloride 0.15g,
10 g of water, commercially available silica gel (Fuji Silysia carrier)
To 50 g, to obtain a Ru—Zn-supported silica catalyst.
Was. The specific surface area of the catalyst thus obtained is 60 m ^Two
/ G, Ru content is 6.1 wt%, Zn / Ru atomic ratio
Was 0.33. In addition, Ru of X-ray diffraction
The average crystallite size was 140 °. Implement this catalyst
As in Example 1, but with a catalyst amount of 2 g and
A partial hydrogenation reaction was performed. After 7 hours, withdraw the reaction solution
Analysis showed that the benzene conversion was 2.5%,
The reaction was found to be inactive and the reaction was stopped.

[0033]

Comparative Example 4 The same procedure as in Comparative Example 2 was carried out except that the catalyst was subjected to a reduction treatment in a hydrogen stream for 3 hours at a catalyst reduction temperature of 200 ° C. during the preparation of the catalyst to obtain a Ru—Zn supported silica catalyst. The specific surface area of the catalyst thus obtained was 63 m ² / g, the Ru content was 5.5 wt%, and the atomic ratio of Zn / Ru was 0.34. The average crystallite size of Ru determined from X-ray diffraction was 45 °. This catalyst was subjected to a partial hydrogenation reaction of benzene in the same manner as in Example 1 except that the amount of the catalyst was 3 g. Table 2 shows the reaction results.

[0034]

Comparative Example 5 A catalyst was prepared in the same manner as in Comparative Example 1, except that zinc chloride was not used. However, a Ru-supported silica catalyst was obtained at a reduction treatment temperature of 200 ° C. for 3 hours during catalyst preparation. The specific surface area of the catalyst thus obtained is 68 m ² / g, and the Ru content is 5.6.
wt%. The average crystallite diameter of Ru determined from X-ray diffraction was 54 °. This catalyst was subjected to a partial hydrogenation reaction of benzene in the same manner as in Example 1, except that the amount of the catalyst was 3.5 g. Table 2 shows the reaction results.

[0035]

Comparative Example 6 As in Comparative Example 1, except that the amounts of ruthenium chloride and zinc chloride were changed, and the Ru content was 0.53 wt.
%, And a Zn / Ru atomic ratio of 0.43 was obtained. In addition,
The carrier is a commercially available silica gel (Carrieract Q50, manufactured by Fuji Silysia) previously calcined at 1000 ° C. for 4 hours.
Was used. This catalyst was used as in Example 1, except that
The catalyst was used in an amount of 10.5 g to perform a partial hydrogenation reaction of benzene. Table 2 shows the reaction results.

[0036]

[Table 2] From Table 2 and Comparative Example 3, it can be said that those without the mesopore molecular sieve have low selectivity, yield and activity per ruthenium (catalytic activity).

[0037]

Example 5 As in Example 3, except that the amount of catalyst was 5
g, Ni (OH) as a metal poisoning substance _Two10mg
Then, a partial hydrogenation reaction of benzene was performed. The reaction result
It is shown in Table 3.

Comparative Example 7 A partial hydrogenation reaction of benzene was carried out in the same manner as in Example 5, but using the same catalyst as used in Comparative Example 6. Table 3 shows the reaction results.

[0038]

[Table 3] Catalysts using mesopore molecular sieves show little decrease in selectivity, yield and activity, whereas those using commercially available silica gel as the support have significantly reduced selectivity, yield and activity. .

[0039]

Example 6 A partial hydrogenation reaction of benzene was carried out in the same manner as in Example 1 except that 0.5 g of the catalyst prepared in Reference Example 2 was used as the catalyst. The selectivity of cyclohexene is 78.
The activity per ruthenium was 3475 (at a benzene conversion rate of 50%), and was 1475.

Example 7 A partial hydrogenation reaction of benzene was carried out in the same manner as in Example 1 except that 0.5 g of the catalyst prepared in Reference Example 3 was used as the catalyst. Cyclohexene selectivity 73.1%
(At a benzene conversion of 40%), the activity per ruthenium was 1,845.

[0040]

According to the method of the present invention, it is possible to (1) efficiently obtain a desired cycloolefin per unit weight of ruthenium from a monocyclic aromatic hydrocarbon with a high selectivity and a high yield. Can be. (2) Easy handling with respect to extraction and separation of the catalyst. (3) High loading of ruthenium as a supported catalyst becomes possible, the activity per catalyst is increased, the metal poisoning is deteriorated, and the industrial stability is excellent. It has the advantage of being extremely valuable.

Continuation of the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) // C07B 61/00 300 C07B 61/00 300 (72) Inventor Yohei Fukuoka 649-6 Sachikawa, Omiya City, Saitama Prefecture Foundation Noguchi Research Laboratories (72) Inventor Aki Fukuzawa 2767-11 Fukuta 2767-11 Shinhama, Kojima Shioike, Kurashiki-shi, Okayama F-term (reference) ZE09 4H006 AA02 AC11 BA07 BA23 BA28 BA29 BA55 BA56 BB31 BC14 BE20 4H039 CA40 CB10

Claims (3)

[Claims] When producing a cycloolefin by partially hydrogenating a monocyclic aromatic hydrocarbon, the monocyclic aromatic hydrocarbon is partially converted into a liquid phase in the presence of water using a silica mesopore molecular sieve catalyst supporting ruthenium. A method for producing a cycloolefin, comprising hydrogenating. 2. The method for producing cycloolefin according to claim 1, wherein the hydrogenation catalyst is a silica mesopore molecular sieve catalyst pre-supported with ruthenium and zinc. 3. The method for producing a cycloolefin according to claim 1, wherein a zinc compound is present in the liquid phase.