JPS6046096B2 - Method for producing cyclohexylbenzene - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing jig-headed hexylbenzene by hydrogenation condensation of benzene.

Conventionally, the method for producing cyclohexylbenzene is as follows:
A method using a catalyst in which a Group 8 metal is supported on a solid acid support (silica alumina or H-type zeolite) (J, Cal
alysls, J3, 385 (1969), Yukishikawa (1), 25 (1976) and Patent Publication 53-10895
2), and supported palladium and catalytic salt (NaC1-AI
CI0) as a catalyst (Chem, Pharm,
Bull, Plate (1) 15 (1981) is known.

Furthermore, a method using a catalyst in which a hydrogenation catalyst and a heteropolyacid are supported on a carrier (U, S, P, 3, 153, 678)
There is also. However, these have low catalytic activity and require a long reaction time to increase the benzene conversion rate.
Alternatively, the generated cyclohexylbenzene is further alkylated to form cyclohexylpentene (C, O), etc.
This method cannot be said to be satisfactory as an industrial method for producing cyclohexylbenzene, as it produces a large amount of cyclohexylbenzene.
In order to overcome the drawbacks of the method for producing cyclohexylbenzene by hydrogenation condensation of benzene, the present inventors have made various studies and found that a heteropolyacid selected from silicotungstic acid, phosphotungstic acid, and phosphomolybdic acid, By using at least one metal (Group 8 metal) selected from nickel, palladium, and ruthenium or a compound thereof as a catalyst, and adding a dehydration drying agent selected from zeolite and silica gel,
Extremely easily and suppressing the formation of C,8 compounds,
It has been found that cyclohexylbenzene can be produced with high selectivity.

The present invention has been made based on this knowledge. In the presence of a catalyst consisting of at least one heteropolyacid selected from silicotungstic acid, phosphotungstic acid and phosphomolybdic acid and at least one metal selected from nickel, palladium and ruthenium or a compound thereof. Another object of the present invention is to provide a method for producing cyclohexylbenzene, which is characterized in that at least one dehydrating and drying agent selected from zeolite and silica gel is present in the reaction system when hydrogenating and condensing benzene.

The catalyst system used in the method of the present invention requires only adding each catalyst component to the reaction system together with the reaction raw materials, and does not require any special preparation method.

Among the catalyst components, silicotungstic acid is preferred.

If the water content is high, the catalytic activity will be low. Excess moisture can be removed by a conventional method such as drying in a drying box at 110° C. until a constant weight is reached. One of the major features of the present invention is to use the above-mentioned heteropolyacid from which excess water has been removed. It is clear from Comparative Example 2 that the presence of the heteropolyacid is essential for the production of cyclohexylbenzene in this reaction system. When adding it to the reaction system, it is desirable to grind it into as fine particles (200 mesh or less) as possible. The appropriate concentration of this heteropolyacid is in the range of 0.01 to 5n1m01/20g benzene, and 0.05 to 1mm01/20g.
g of benzene is preferred. The Group 8 metal components can be added in the form of metals or organic acid salts such as formic acid and acetic acid, carbonates, chlorides, nitrates, hydroxides, oxides, etc., and other compounds can also be added under the reaction conditions. A compound that activates hydrogen and benzene either as it is or when reduced. Anything that changes can be used.

When used as a metal, these compounds may be converted into a ring and used as a metal powder, or supported on a suitable carrier. Furthermore, in order to control the activity of these metals, they may be used in a supported form together with other metals. In the reaction system. The concentration of the Group 8 metal salt is 0.01 to 5n1m01/2
A range of 0g benzene is suitable, preferably 0.0g benzene.
5-1mm01/20g benzene. When carrying out the method of the present invention, at least one dehydration, water and desiccant agent selected from zeolite and silica gel is added to the reaction system. For example, even if the reaction is carried out using only nickel acetate and zeolite as catalysts (excluding silicotungstic acid), cyclohexylbenzene will not be produced under these reaction conditions (Comparative Example 2); If silica gel is used as a dehydrating and desiccant agent during this process, the yield and selectivity of cyclohexylbenzene can be significantly improved (Example 1 and Comparative Example 1). As the dehydration desiccant, any desiccant that is used industrially can be used, but Molecular Sieve 10X
113X silica gel is particularly good.

The amount used is suitably in the range of 0.05 to 5 g/20 g benzene, preferably 0.1 to 2 g/20 g benzene.
The process of the invention can be carried out without a catalyst or in a solvent. Any solvent inert to the reaction, such as cyclohexane, can be used. It is desirable that the raw material benzene has as little water content as possible. In the method of the present invention, the reaction temperature is usually 50~
300℃, preferably 100-250℃, reaction hydrogen pressure is 1-300kg/Cltl, preferably 10-15
It is 0k9/Clt.

The lower the reaction temperature, the higher the selectivity of cyclohexane;
Moreover, if the reaction temperature is too high, decomposition of the reaction products will occur, which is disadvantageous. Next, the present invention will be explained in more detail based on examples.

Example 1 Internal volume 80 equipped with gas inlet, pressure gauge, and thermometer insertion tube
mt(7) SUS3l6 autoclave, 0.6620g (0.2rI1m01) (1
The reagent dried at 10°C until constant weight was added to SiO2.1
2W03・26H20=3310.64), nickel acetate 0.1245g (4). 5mm01), 1g of Molecular Sieve 13X (1/16 pellets), 20g of benzene, and a Teflon-coated stirrer were added, and after purging the inside with nitrogen, hydrogen gas was pressurized to 50k9/Crl at room temperature.

While stirring with a magnetic stirrer, the reaction temperature was 20°C.
Heated to 0°C. The reaction was started when the reaction temperature was reached. After a reaction time of 9 minutes, the reaction was stopped by water cooling and then ice cooling, and the reaction solution was filtered and quantitatively determined by gas chromatography using PEG2OM as a packing material to obtain 3.46 g of cyclohexylbenzene and 1.04 g of cyclohexane. C
The production of the 18 compound was minimal. Comparative Example 1 Using the method of Example 1, molecular sieve 13X (1/1
6 pellets) were reacted to obtain 1.60 g of cyclohexylbenzet and 0.60 g of cyclohexane.

Comparative Example 2 As a result of carrying out the reaction in the same manner as in Example 1 except for silicotungstic acid, 0.13 g of cyclohexane and 0.02 g of cyclohexene were produced, with only a trace of cyclohexylbenzene produced.

Example 2 Using the method of Example 1, 0.6620 g of silicotungstic acid 0.0567 g of basic nickel carbonate (
stomach). 2rT1m01), molecular sieve 13×(
1/16 pellets) Using 1 g of benzene, 20 g of benzene, reaction temperature of 200°C, reaction time of 6 particles, the result was 3.96 g of cyclohexylbenzene and 0.60 g of cyclohexane.
I got it.

The production of Cl8 compound was small (0.17 g of 1,4-dicyclohexylbenzene). Example 3 Using the method of Example 1, 0.6620 g of silicotungstic acid 1 0.0224 g of palladium acetate (a)
．． 1mm01), molecular sieve 13x, (1/1
6 pellets) using 1 g and 20 g of benzene at a reaction temperature of 1
80°C, reaction time: 1 drop of cyclohexylbenzene, 2.
37g/2.00g of cyclohexane was obtained.

Example 4 Using the method of Example 1, 0.4965 g of silicotungstic acid 1 0.1307 g of ruthenium chloride (0.4965 g)
Using 1 q1 20 y of benzene, the reaction temperature was 200.
℃, reaction time 32 minutes, cyclohexylbenzene 2.8
3g1 1.59g of cyclohexane was obtained.

Example 5 0.6139 g (0.1 m
m01), nickel formate 0.0370g (0.2mm0
Then, Silbeed N-4 (silica gel manufactured by Mizusawa Chemical Co., Ltd.) and 20 g of benzene were added, and 0.23 g of cyclohexylbenzene and 0.10 g of cyclohexane were obtained at a reaction temperature of 210° C. and a reaction time of 90 minutes.

Example 6 0.8453g (0.2rnm01) of phosphomolybdic acid dried at 110°C until constant weight according to the method of Example 1
, basic nickel carbonate 0.0567g (0.2rnm0
Molecular sieve 13 x (1/16 pellet) 0
．． Add 5g1 benzene 20g, reaction temperature 190°C, reaction time 90 minutes, cyclohexylbenzene 0.11g1
0.67 g of cyclohexane was obtained.

Example 7 0.6620 g of silicotungstic acid 1 0.5 g of nickel-tin diatomaceous earth (45:5:50) activated at 1400°C 1 silica gel 1 by the method of Example 1
g1 20g of benzene was added and the reaction temperature was increased to 2 under nitrogen atmosphere.
After heating to 00° C., hydrogen was introduced under pressure at 68k9/CFli to carry out the reaction, and in a reaction time of 30 minutes, 3.39 g of cyclohexylbenzene and 0.96 g of cyclohexane were obtained.

Claims (1)

[Claims] 1. Presence of a catalyst consisting of at least one heteropolyacid selected from silicotungstic acid, phosphotungstic acid, and phosphomolybdic acid and at least one metal selected from nickel, palladium, and ruthenium or a compound thereof. The following is a method for producing cyclohexylbenzene, which is characterized in that at least one dehydrating and drying agent selected from zeolite and silica gel is present in the reaction system when hydrogenating and condensing benzene.