JPS59199641A - Production of cyclohexylbenzene - Google Patents

Abstract

PURPOSE:To obtain the titled substance in high selectivity, by the presence of a dehydrating and drying agent in the reaction system in reacting benzene with hydrogen in the presence of a catalyst containing a heteropolyacid and a metal of Group VIII, etc. supported on a carrier, e.g. alumina, used usually for a hydrogenation catalyst. CONSTITUTION:Benzene is hydrogenated and condensed in the presence of a catalyst containing a heteropolyacid and a metal of Group VIII or a compound thereof as essential components supported on a carrier, e.g. alumina, diatomaceous earth or activated carbon, at 50-300 deg.C, preferably 100-250 deg.C under 1- 300kg/cm<2>, preferably 10-150kg/cm<2> reaction hydrogen pressure to give the aimed compound. ''Molecular sieve 10X or 13X'' or silica gel may be preferred for the dehydrating and drying agent, and the amount thereof to be used is preferably 0.1-2g/20g benzene. The concentration of the heteropolyacid in the catalyst components is preferably 1-200%, more preferably 5-150% based on the weight of the carrier depending on the carrier.

Description

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

Conventionally, methods for producing cyclohexylbenzene include methods using catalysts in which Group 8 metals are supported on solid acid carriers (silica alumina or H-type zeolite) (J, C,
, IαYLi, Le 385 (1969).

Petroleum Journal 18(1), 25 (1976) and Japanese Patent Application Publication No. 1976-
108952), supported palladium and molten salt (
A method using NtLCl-A1C1□) as a catalyst (Cmu\
P/1. ayr-, BJ2, 29 (IL 15 (1
981) is known. However, these have low catalytic activity and require a long reaction time to increase the benzene conversion rate, or the generated cyclohexylbenzene may be further alkylated to form synchlohexylbenzene etc. (C, , ). This method cannot be said to be satisfactory as an industrial method for producing cyclohexylbenzene, as a large amount is produced.

The present inventors first attempted to overcome the drawbacks of the method for producing cyclohexylbenzene by hydrogenation condensation of benzene.
As a result of various studies, we found that by using telopolyacid and Group 8 metal as a catalyst, C1
It was discovered that cyclohexylbenzene could be produced with high selectivity by suppressing the formation of fi compounds, and a patent application was filed (Japanese Patent Application No. 113299/1989).Furthermore, after repeated improvements,
- Invented a method using a catalyst in which the above two catalyst components were supported on silica gel, and filed a patent application (Japanese Patent Application No. 58°-1,0263).
)did. Subsequently, as a result of repeated inquiries into the preparation method of the catalyst, we devised a preparation method such as supporting the above-mentioned metal components on alumina, diatom, or activated carbon carriers, which are commonly used in hydrogenation catalysts, and then supporting -heteropolyacid. The difference is that supports other than silica gel that are normally used for hydrogenation catalysts can be used, and therefore the preparation of the catalyst is surprisingly simple, and
We have discovered a method for producing cyclohexylbenzene that is easy to handle. The present invention has been made based on this knowledge.

That is, the present invention is characterized in that, in reacting benzene with hydrogen, a heteropolyacid is reacted with a Group 8 metal or its compound in the presence of a catalyst supported on a carrier such as alumina, diatomaceous material, activated carbon, etc. The catalyst for the benzene production method of the present invention can be prepared according to various methods, but typical examples include using a commercially available hydrogenation catalyst, or dissolving or suspending a Group 8 metal in a solvent such as water or acetic acid. By immersing the carrier material described in - in the cloudy solution, the metal component is deposited on the carrier, and dried.
0° C. is used, preferably 25° C., by hydrogenation at high temperature or by immersing a catalyst made hydrogenated active by means such as thermal decomposition in a solution of the heteropolyacid.
0-500°C.

Among the catalyst components, as the heteropolyacid, commercially available heteropolyacids such as silicotungstic acid, phosphotungstic acid, and phosphomolybdic acid can be used, but silicotungstic acid and phosphotungstic acid are particularly preferred. It is clear from Comparative Example 1 that the presence of a heteropolyacid is essential for the production of cyclohexylbenzene in this catalyst system.

Although the concentration of the heteropolyacid varies considerably depending on the carrier, a range of 1 to 200% of the carrier weight is used, preferably 5 to 150%.

Also, other compounds can be dissolved in the catalyst preparation solution or
Those that suspend can be used. Furthermore, in order to control the activity of these metals, they may be supported together with other metals. $8
The concentration of the group metal compound varies significantly depending on the type of supported metal, but a range of 0.005 to 50% of the weight of the support is used,
Preferably it is 0.1 to 30%. Group 8 metal components include nickel, palladium, rhodicum, ruthenium,
Platinum and isodicum are used. When using noble metals with high benzene hydrogenation activity, lower the supported concentration and
Increasing the heteropolyacid concentration is preferred in order to improve the selectivity of cyclohexylbenzene.

As the catalyst carrier in the method of the present invention, any of the carriers normally used for hydrogenation catalysts, such as alumina, diatomaceous, and activated carbon, can be used.

When carrying out the method of the present invention, a dehydrating/desiccating agent such as zeolite, silica gel, alumina gel, etc. can be added to the reaction system. In this case, benzene brought into contact with a dehydrating/desiccating agent may be used. Even if the reaction is carried out with zeolite and a catalyst in which only the Group 8 metal is supported on the carrier under small flame, cyclohexylbenzene is not produced (Comparative Example 1), but when the heteropolyacid and the Group 8 metal component are supported on the carrier When a catalyst supported on a cyclohexylbenzene coexists with a dehydrating/desiccating agent such as zeolite, the yield and selectivity of cyclohexylbenzene can be significantly improved (comparison of Examples 1 and 2). As a dehydrating/desiccating agent, any desiccant that is used industrially can be used, but Molecule? Particularly preferred are 10x, 13x (or their equivalents), silica gel, alumina gel, and the like. The amount used is suitably in the range of 005 to 5 r/20 f benzene, preferably 01 to 2 fI/20 f benzene.

The method of the invention can be carried out without or in a solvent. A solvent inert to the reaction (11/) such as cyclohexane may also be used. jKyoryo uses as much benzene as possible.

Preferably one with low moisture content.

In the method of the present invention, the reaction temperature is usually 50 to 300°
C1 is preferably 100 to 250°C, and the reaction hydrogen pressure is 1 to 300 K9/crl, preferably 10 to 150 to
It is. If the reaction temperature is low, the selectivity of cyclohexane will be high, and if the reaction temperature is too high, decomposition of the reaction product will occur, which is disadvantageous.

Next, the present invention will be explained in more detail based on examples.

Example 1 0.275f of silicotungstic acid (using a reagent dried to a constant weight at 110°C) was dissolved in water, and commercially available 05% Pd-alumina (manufactured by Nippon Engelhard Co., Ltd., spherical) 17 was added, stirred for 30 minutes, evaporated with a rotary vacuum evaporator, and heated to 110°
After drying at
The catalyst was prepared by drying at °C for 30 minutes.

This catalyst 05g was placed in a benzene 20'? and Teflon Two 1 with a stirrer, and after purging the inside with nitrogen, hydrogen gas was added at room temperature for 5 minutes.
It was press-fitted to 0Yl. The mixture was heated to a reaction temperature of 200° C. while stirring with a magnetic stirrer. The reaction was started when the reaction temperature was reached. After 70 minutes of reaction time, cyclohexylbenzene 3.2]1, cyclohexane 1.4
2 j／ I got it. The formation of CI m compound was traced.

Example 2゜0.59 of the catalyst prepared in Example 1, 20 g of benzene and 13X (1/16-comb 7)) l of molecular sieve
fi' was added and reacted for 87 minutes under the reaction conditions of Example 1, resulting in 4907 cyclohexylbenzene and 0 cyclohexane.
．． 711- was obtained.

+1 Comparative Example 1 No silicotungstic acid was supported in Example 1, and commercially available 0
Using 5% Pd-alumina 05g as is, it was reacted for 65 minutes under the reaction conditions of Example 2, and cyclohexane 3J17
I got it. No formation of cyclohexylbenzene was observed.

Example 3 Silicotungstic acid 0357 was dissolved in water according to the method of Example 1, commercially available 05% Pi-alumina (manufactured by Nippon Engelhard Co., Ltd., in pellet form) was added, and nitrogen was added according to the method of Example 1. Catalyst 057 prepared by drying at 350°C for 1 hour in a stream of air was reacted with 20 g of benzene and 1.3X O.52 of molecular sieves at a reaction temperature of 210°C for 42 minutes according to the method of Example 1. , cyclohexylbenzene 3307, and cyclohexane [492 were obtained.

Example 4 By the method of Example], phosphotungstic acid 02757
is dissolved in water, and commercially available 05% Pd-alumina sphere 1 is added to it.
2 was added, stirred, dried, and further heated to 375 mL in a nitrogen stream.
Catalyst 057 dried at ℃ for 30 minutes and benzene 207,
Using molecular sieve 13X 1.51i',
The reaction was carried out according to the method of Example 1 at a reaction temperature of 2058C for 67 minutes, and the amount of cyclohexylbenzene was 4.91? , 0.757 cyclohexane was obtained.

Example 5 By the method of Example 1, tungstic acid 120'i
A reaction was carried out according to the method of Example 1 using a catalyst prepared from 17'' and commercially available 2% Pd-activated carbon particles (manufactured by Nippon Engelhard Co., Ltd.), molecular sieve 13X O,75?, and benzene 205'. 9 at 220℃ each time
React for 00 minutes, cyclohexylbenzene 3.12f,
Cyclohexa:/+597 was obtained.

Example 6 Catalyst 057 prepared by the method of Example 1 from 0.25 g of silicotungstic acid and a commercially available 05% Ru-alumina catalyst (manufactured by Nikki Engelhard) 17 and 200.degree.
Using 15 g of silica gel dried at C and 20'i of benzene, 35
The reaction was carried out for a minute to obtain 3.09 g of cyclohexylbenzene and 1752 g of cyclohexane.

Example 7 Phosphortungstic acid 02757 was prepared by the method of Example 1.
Example 1 was carried out using catalyst 057 prepared from a commercially available 05% Rh-alumina catalyst, 0.57 alumina spheres (manufactured by Mizusawa Chemical Co., Ltd., I-OBID C-4,) dried at 450°C, and 20 g of benzene. 2 at a reaction temperature of 215°C by the method of
After reacting for 7 minutes, the cyclohexylbenzene 2,671
, 471977 was obtained in cyclohe.

Example 8 Ni (pJo, ), 6I-(,04,9533f
was dissolved in water (2), diatomaceous earth 101 was added thereto, stirred for 1 hour, water was evaporated using a rotary vacuum evaporator, and transferred to a glass tube at 300 TLI/m.
2 of the catalyst reduced for 1 hour at 450°C in a hydrogen stream was added to an aqueous solution of 0.57 silicotungstic acid, stirred and dried in the same manner as in Example 1, and then reduced at 300°C in a nitrogen stream.
Catalyst 057 prepared by drying for 30 minutes at 450'C
Zeorum I"9 (manufactured by Toyo Soda) 057 and benzene 207, which had been dried in
The reaction was allowed to proceed at 95°C for 35 minutes, yielding 3717 cyclo-xylbenzene and 1237 cyclohexane.

Example 9 By the method of Example 8, Nj (NO,), 6]-1,0
From a catalyst prepared by adding diatomaceous earth 101 to an aqueous solution of 71,9533 γCz, ·H, 00,0458 g, stirring, drying, and hydrogenating]7, phosphomolyfdic acid 06
Using the catalyst 0.57 prepared in addition to the aqueous solution of 7, Zeolum F9 0.75f, and benzene 202, the reaction was carried out according to the method of Example 1 at a reaction temperature of 200°C for 300 minutes, and cyclohexylbenzene 0397 and cyclohexane 2.5
5L? I got it.

Procedural Amendment (Voluntary) 58 Chemical Technology IU No. 1240 Director of the Patent Office Kazuo Wakasugi 1 Displaying 1 per month Patent Application No. 73571 of 1988
No. 2 = Name of the invention Process for manufacturing Nkuroheki/Rubet/Sen 3, Patent applicant related to the amendment case (4: Address: 1-3 Kasumigaseki, Chiyo J'-ku, Tokyo)
No. 1 Kawada Michi A Name (114) Director Zhou of the Agency of Industrial Science and Technology 1) Wi
1. Name of the invention cyclohexylbenzene 2. Claims (1) A heteropolyacid and a Group 8 metal or its compound, alumina, diatomaceous earth, activated carbon, etc. 1. A method for producing cyclohexylbenzene, which comprises the step of hydrogenating and condensing benzene in the presence of a catalyst supported on a carrier.

3. Detailed Description of the Invention The present invention relates to a method for producing cyclohexylbenzene by hydrogenation condensation of benzene.

Conventionally, the method for producing cyclohexylbenzene has been a method using a catalyst in which a group 8 metal is supported on a solid acid support (Si1heka alumina or H-type zeolite) (J, Ca
tako3'5iEil 3, 385 (1969)
, Japan Petroleum Magazine 1.8 (1), 25 (1976) and Japanese Patent Application Laid-Open No. 1989-1.08952).

In addition, supported palladium and molten salt (NaC7-J=JC1
3) as a catalyst (Chem, Pharm,
)3ullSg 9(1,).

1.5 (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) are also available. However, these have low catalytic activity and require a long reaction time to increase the benzene conversion rate, or
The produced cyclohexylbenzene is alkylated to produce a large amount of dicyclohexylbenzene (C18), etc., so it cannot be said to be a satisfactory method as an industrial method for producing cyclohexylbenzene.

The present inventors first attempted to overcome the drawbacks of the method for producing cyclohexylbenzene by hydrogenation condensation of benzene.
As a result of various studies, we found that by using a heteropolyacid and a Group 8 metal as a catalyst and adding a dehydrating and desiccant agent, it was possible to easily produce a C18 compound while suppressing the formation of C18 compounds.
He discovered that cyclohexylbenzene could be produced with high selectivity, patented it (Japanese Patent Application No. 113299/1983), and after repeated improvements, invented a method using a catalyst in which the above two catalyst components were supported on silica gel. , patent application (%application 1975)
8-10263). Subsequently, as a result of repeated studies on the preparation method of the catalyst, we found that it is possible to devise a preparation method such as supporting the above-mentioned metal components on alumina, diatomaceous earth, or activated carbon carriers, which are usually used in hydrogenation catalysts, and then supporting the heteropolyacid. The present inventors have discovered a method for producing cyclohexylbenzene that allows use of carriers other than silica gel, such as carriers normally used for hydrogenation catalysts, and that allows for extremely simple preparation of the catalyst and ease of handling. The present invention has been made based on this knowledge.

That is, in the present invention, when reacting benzene with hydrogen, a heteropolyacid and a Group 8 metal or its compound are reacted in the presence of a catalyst supported on a carrier such as alumina, diatomaceous earth, or activated carbon. The present invention provides a method for producing cyclohexylbenzene, which is characterized by adding a dehydrating and drying agent to the system.

The catalyst for the process of the present invention can be prepared according to various methods, but typical examples include commercially available hydrogenation catalysts or
The above-mentioned carrier material is immersed in a solution in which the group metal is dissolved or suspended in a solvent such as water or acetic acid, so that the metal component is deposited on the carrier, and then dried and hydrogenated at high temperature, or Alternatively, by immersing a catalyst in which pears have been made hydrogenated by a method such as a bunker in a solution of heteropolyacid, the heteropolyacid component is attached to the catalyst, dried, and calcined in an inert gas. There is a way. The firing temperature used is 200 to 600"C, preferably 25"C.
0 to 500''C.

Among the catalyst components, as the heteropolyacid, commercially available heteropolyacids such as silicotungstic acid, phosphotungstic acid, and phosphomolyphthenic acid can be used, but silicotungstic acid and phosphotungstic acid are particularly preferred. It is clear from Comparative Example 2 that in this catalyst system, the presence of a heteropolyacid is essential for the production of cyclohexylbenzene. The concentration of heteropolyacid varies significantly depending on the carrier, but a range of 1 to 200% of the carrier weight is used.
Preferably (rJ is 15 to 150%).

Group 8 metal components include organic acid salts such as formic acid and acetic acid, carbonates,
Can be added in the form of nitrates, chlorides, hydroxides, etc.
Other compounds can also be used as long as they are dissolved or suspended in the catalyst preparation solution. Furthermore, in order to control the activity of these metals, they may be supported together with other metals. Although the concentration of the Group 8 metal compound varies significantly depending on the type of compatible metal, a range of 0.05 to 50% of the weight of the carrier is used, preferably 01 to 30%. As the Group 8 metal component, nickel, palladium, rhodium, ruthenium, platinum, and iridium are used. When using a noble metal having a high benzene hydrogenation activity, it is preferable to lower the supported concentration and increase the heteropolyacid concentration in order to improve the selectivity of cyclohexylbenzene.

As the catalyst carrier in the method of the present invention, any of those commonly used for hydrogenation catalyst carriers, such as alumina, diatomaceous earth, and activated carbon, can be used.

When carrying out the method of the present invention, a dehydrating/desiccating agent such as zeolite, silica gel, alumina gel, etc. is added to the reaction system.

In this case, benzene brought into contact with a dehydrating/desiccating agent may be used. Even if the reaction is carried out with a catalyst in which only a Group 8 metal is supported on the carrier and zeolite, cyclohexylbenzene is not produced (Comparative Example 2), but a catalyst in which a heteropolyacid and a Group 8 metal component are supported in the carrier is not produced. In addition, in the absence of a dehydrating/desiccating agent such as zeolite, the yield and selectivity of cyclohexylbenzene can be significantly improved (comparison of Example 1 and Comparative Example 1). Dehydration As a desiccant, any desiccant that is used industrially can be used, but Molecular Sieve IOX, 13X (or a similar product)
, silica gel, alumina gel, etc. are particularly good. Usage amount u:
o, a range of 05 to 59/209 benzene is suitable;
O] to 2 g/209 benzene is preferred.

The method of the invention can be carried out without 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 to 300°
C1 is preferably 100 to 250'C, and the reaction hydrogen pressure is 1 to 300 kg/CfIL2, preferably 10 to 15
0 kg/crIL2. If the reaction temperature is low, the selectivity of cyclohexane will be high, and if the reaction temperature is too high, decomposition of the reaction product will occur, which is disadvantageous.

Next, the present invention will be explained in more detail based on examples.

Example j.

Silicotungstic acid 0.275.9 (using a reagent dried to a constant weight at 110°C) was dissolved in water, and 1 g of commercially available 0.5% Pd-alumina (manufactured by Nippon Engelhard Co., Ltd., spherical) was dissolved in water. and stirred for 30 minutes.
・Vacuum evaporate water to evaporate, 11
After drying at 0°C, transfer to a glass tube and incubate for 32 hours in a nitrogen stream.
The catalyst was prepared by drying at 5°C for 30 minutes.

0.5 g of this catalyst was placed together with a gas inlet, a pressure gauge, and a temperature stirrer, and after purging the inside with nitrogen, hydrogen gas was pressurized to 50 kg/c7n2 at room temperature. Magnetic
The mixture was heated to a reaction temperature of 200° C. while stirring with a stirrer. The reaction was started when the reaction temperature was reached. After 87 minutes of reaction time, 4.90 g of cyclohexylbenzene, 0.71 g of cyclohexane kl'+c.

Formation of CI8 compound was traced.

Comparative Example 1 Using the method of Example 1 except for the molecular sieve 13x, the reaction was carried out for 70 minutes, and cyclohexylbenzene 3.2
1 g and 1.42 g of cyclohexane were obtained.

Comparative Example 2 In Example 1, silicotungstic acid was not supported, and commercially available 0
．． 51 P (1-alumina 0.19 was used as it was and reacted for 65 minutes under the reaction conditions of Example 1 to obtain cyclohexane 3.11.9. No formation of cyclohexylbenzene was observed.

Example 2: Dissolve 035 g of silicotungstic acid in water according to the method of Example J, add 1 g of commercially available 0.5% Pt-alumina (manufactured by Nippon Engelhardt Co., Ltd., in pellet form), and dissolve according to the method of Example 1. , 0.5 g of a catalyst prepared by drying at 350"C for 1 hour in a nitrogen stream, 20g of benzene, molecular sieves, 3 42 minute reaction time, cyclohexylbenzene 3.30! j, cyclohexane 1.
49.9 was obtained.

Example 3 Phosphortungstic acid Q, 275 was prepared by the method of Example 1.
．． 9 was dissolved in water, 1 g of commercially available 05% Pd-alumina spheres was added thereto, stirred and dried, and then dissolved in a nitrogen stream.
Using 0.5g of catalyst dried at 375°C for 730 minutes, 20g of benzene, and 13 x 1.5I of molecular sieves, a reaction was carried out at a reaction temperature of 205°C for 67 minutes according to the method of Example 1. 0.75.9 was obtained.

Example 4 By the method of Example 1, tungstic silicoic acid], 20
! 0.125.9 of a catalyst prepared from J and commercially available 2% Pd-activated carbon particles (manufactured by Nippon Engelhardt Co., Ltd.) Ig;
Molecular sieve 13X0.75,9. benzene 2
Using 0g, the reaction temperature was 220°C by the method of Example 1.
312 g of chlorohexylbencef
, cyclohexane] was obtained.

Example 5 0.5 g of a catalyst prepared from silicotungstic acid 025y and 1 g of a commercially available 0.5% l' (u-alumina catalyst (manufactured by Nippon Engelhard) by the method of Example 1 and 20
15 g of silica gel, dried at 0°C, 20.9 g of benzene
was reacted for 35 minutes at a reaction temperature of 225°C according to the method of Example 1, and cyclohexylbenzene 3.09
,9. cyclohexane], 75.9i was obtained.

Example 6゜By the method of Example 1, phosphotungstic acid 0.275
．． 9 and a commercially available 0.5% Rh-alumina catalyst, and alumina spheres dried at 450°C (Mizusawa Chemical Membrane, Neobead C-4) 0.5. ! 9. Using 20 g of benzene and the method of Example 1, the reaction temperature was 215
℃ for 27 minutes, cyclohexylbenzene 267
g, cyclohexane 1.97! ! I got it.

Example 7 4.9533 g of N1(N03)2.6 H□0 was dissolved in water, 10 g of diatomaceous earth was added thereto, stirred for 1 hour, water was evaporated using a rotary vacuum evaporator, and the solution was transferred to a glass tube. 300 m1. 1 g of the catalyst reduced at 450°C for 1 hour in a hydrogen flow of / min.
was added to an aqueous solution of 0.5!9 silicotungstic acid, stirred and dried in the same manner as in Example 1, and heated at 300°C in a nitrogen stream for 30 minutes.
0.5 g of a catalyst prepared by drying for 0 minutes, 05 g of Zeorum F9 (manufactured by Toyo Soda) dried at 450°C, and 20 g of benzene were added, and the reaction temperature was adjusted to 195° C. according to the method of Example 1.
At °C, react for 35 min and cyclohexylbenzene 3
．． 71,9. 1.23 g of cyclohexane was obtained.

Example 8 Using the method of Example 7, N1(NO3)26H204,95
0.57 of the catalyst prepared by adding 1 g of the catalyst prepared by adding 33 g and an aqueous solution of IrCl4.HzOO, 0458 g, stirring, drying, and hydrogenation to an aqueous solution of 0.6.9 of phosphomolybdic acid; Zeorum F9
0.7551 and 20 g of benzene were reacted for 30 minutes at a reaction temperature of 200°C according to the method described in the example.
5g was obtained.

Claims (2)

[Claims] (1) ~Production of cyclohexylbenzene characterized by hydrogenation condensation of benzene in the presence of a catalyst in which terobic acid and a Group 8 metal or its compound are supported on a carrier such as alumina, diatomaceous earth, or activated carbon. Method. (2) When hydrogenating and condensing benzene in the presence of a catalyst in which a heteropolyacid and a Group 8 metal or its compound are supported on a carrier such as alumina, diatomaceous earth, or activated carbon,
A method for producing cyclohexylbenzene, characterized in that a dehydrating and drying agent is present in the reaction system.