JPS59137426A - Production of cyclohexylbenzene - Google Patents

Abstract

PURPOSE:To produce the titled compound economically, by the hydrogenative condensation of benzene using a catalyst obtained by supporting a heteropolyacid and a VIII-group metal or its compound to silica gel in combination with a dehydrating and drying agent. CONSTITUTION:Cyclohexylbenzene is produced extremely easily, in high selectivity, by the hydrogenative condensation of benzene in the presence of (A) a catalyst obtained by supporting a heteropolyacid, especially silicotungstic acid and a VIII-group metal (Ni, Pd, Rh, Ru, Pt or Ir) to silica gel and (B) a dehydrating and drying agent such as zeolite, silica gel, alumina gel, etc., especially molecular sieve 10X13X(or a material corresponding thereto), silica gel, alumina gel, etc. The use of the catalyst in combination with the dehydration and drying agent enables the reduction of the amount of the catalyst component and remarkably facilitates the handling of the catalyst, and accordingly, results in the economical production of the objective compound.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a method for producing chlorohexylbenzene by hydrogenation condensation of benzene.

Conventionally, as a method for producing cyclohexylbenzene, a method using a catalyst in which a Group 8 metal is supported on a solid acid support (Nrica alumina 11 type zeolite) (J, Cat.
lysis, 13.385 (1969),
Petroleum U-JilsQ), 25 (1976) and JP-A-53-108952), and a method using supported paranrum and molten salt (NaCIAlCl5) as a catalyst (C
nem, Pharm, Bull, 29(1), 1
5 (1981)) is known. However, these have low catalytic activity, and in order to increase the benzene conversion rate, a long reaction time is required, or (d) The generated shitacyclohexylbenzene is further alkylated. As a result of various studies to overcome the drawbacks of cyclohexylbenzene, we have found that by using a heteropolyacid and a Group 8 metal as a catalyst, cyclohexylbenzene can be produced extremely easily and with high selectivity while suppressing the formation of C18 compounds. I found 44 octopuses, and found 1 octopus (Tokusho 57-).
113299) I did. As a result of various studies on improving this catalyst, the inventors of the present invention found that by using a catalyst in which the above two catalyst components are supported on silica gel, the amount of catalyst components used can be significantly reduced. We have discovered a method for producing cyclohexylbenzene that allows for extremely easy handling of the catalyst. The present invention has been made based on this knowledge.

That is, the present invention involves the production of cyclohexylbenzene by reacting benzene and hydrogen with a heteropolyacid and a group 8 gold PA or its compound in the presence of a catalyst supported on a silica gel carrier. The present invention provides a method.

The catalyst of the method of the present invention can be prepared according to various methods, but typically, a compound of a heteropolyacid as a component and a metal as a component is suspended in water, By immersing the carrier material in the liquid,
There is a method in which a catalyst component is deposited on a carrier, dried, and calcined in an inert slag. Alternatively, (d) means such as thermal decomposition may be used. Furthermore, it is preferable to reduce the catalyst before using it in the reaction, since high activity can be obtained from the initial stage of the reaction.

As the ring formation method, for example, a method in which the catalyst is maintained at high temperature in a hydrogen stream for several hours, etc. is used. The reduction temperature is 2
00~4,50''C is used, preferably 250~3
The temperature is 75°C.

Among the catalyst components, as the heteropolyacid, any commercially available heteropolyacid such as silicotungstic acid, phosphotungstic acid, phosphomorubdic acid, etc. can be used, but silicotungstic acid is particularly preferred. It is clear from Comparative Example 1 that in this catalyst system, the presence of a heteropolyacid is essential for the production of 7 clo-xylbenzene. The concentration of heteropolyacid is 0.005 to 0.5 mm01/, 9
J Kakeru (7) He has a range of 4, and he is a disciple,
It is 0.01-0.2 mm○1/g of licagel.

Group 8 metal components include organic acid salts such as formic acid and acetic acid, and charcoal 1!
4+ Can be added in the form of chlorides, nitrates, hydroxides, etc., and other compounds can also be added to the heterobo IJ during catalyst preparation.
Any substance that dissolves uniformly or mixes with m can be used. Furthermore, in order to control the activity of these metals, they may be supported together with other metals. The concentration of the Group 8 metal compound is in the range of 0.001 to 2 mmol/9 silica gel, preferably 0.01 to 1 mmol/9 silica gel.
1/'i silica gel range. As the Group 8 metal component, nickel, palladium, rhodium, ruthenium, platinum, and iridium are used. When using a noble metal that has a high benzene hydrogenation activity, it is preferable to lower the carrier concentration and increase the heteropoly(n) concentration in order to improve the selection rate of cyclohexylbenzene.

Preferably, silica gel is used as the carrier for the catalyst in the method (1) of the present invention.Even if a carrier other than silica gel that is normally used as a catalyst phase is used, the activity or selectivity is extremely low.This is the method of the present invention. This is one of the major features of

When carrying out the method of the present invention, zeolite,
When dehydrating silica gel, alumina gel, etc., dehydrating dry β-olide, etc., and coexisting with a drying agent, the yield and selectivity of cyclohexylbenzene can be significantly improved (Example 1)
(comparison between Especially good. Usage amount is 0.0
A range of 5 to 53/2 (J,!9 benzene is appropriate;
01-2β/20g benzene is preferred.

The method of the invention can be carried out without or in a solvent. /An inert solvent such as chlorohexane is also used.The raw material benzene should contain as much water as possible. One with a small jl is desirable.

In the method of 1IJ1 of the present invention, the reaction temperature tri is usually 50
~300°C, preferably 100~250°C, and the reaction hydrogen pressure is 1~300 to 9/CTL2, preferably 74
．． It is 10 to 150 kg/cm2. If the reaction temperature IW 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.

Fruit lI Jusili 1 Silicotungstic acid 0.0828. ? (0,025m
mol) (1) The reagent dried at 0'C until constant weight was mixed with Sin□, 12WO3,26H20=3310.
64 (assumed) and nickel acetate 0.0467g (0,
Dissolve 1875 mmol) in water, add FprL, add 1 ounce of gel (32-42 mesh of Dabin'I'' M 57 crushed), (add 1 hour of IHJ stirring L,
Evaporate the moisture using a rotary, vacuum, or evaporator and dry at 110'C until it reaches a constant weight.
．． 5.9 into a glass tube, ], OQ rn, i/
The sample was reduced with hydrogen at 325° C. for 1 hour in a hydrogen stream of 100 min to prepare a hydrogen-rich solution.

This catalyst was placed in a 5US316 autoclave with an internal volume of 8.0 ml, equipped with a gas inlet, a pressure gauge, and a thermometer insertion tube, along with benzene 20.9 and a Teflon-coated stirrer, and after purging the inside with nitrogen, hydrogen Gas at room temperature 50k
It was press-fitted at g/cm21. Magnetic.

The mixture was heated to a reaction temperature of 200'C while stirring with a stirrer. The reaction started when the reaction temperature was reached, and after 90 minutes of initial reaction time, cyclohexylbenzene 1.32,9,
0.94 g of cyclohexane was obtained. The production of C18 compounds was cross-sectional.

Example 2 0.5 g of the catalyst prepared in Example 1, 20 g of benzene, and 1 g of molecular 7-bu 13 ．． ! 56.9. Cyclohexane 0
．． 509't[7v.

Comparative Example 1 A catalyst was prepared in Example 1 except for silicotungstic acid,
The reaction was carried out for 90 minutes under the conditions of Example 2, and 2.64% of cyclohexane was used. ．． I got a 9. The production of cyclohexylbenzene was cross-sectional.

Example Using the method of Example 1, palladium acetate 0.0071. ! 9
(0,025 mmol), tungstic acid Q, 24
84.9 (0,5625 mmol) was suspended in water for a sufficient amount of time, 1 g of silica gel was added, and the mixture was stirred.
0.5 from dry. Catalyst prepared by hydrogenating F, benzene 20,9, molecular sieve 13X19
, the reaction temperature was 210°C according to the method of Example 1-1].
/Chlohexylbenzene 309
11/Cucohexane 1.35.9 was obtained.

Actual addition 11 Ri 14 By the method of Act 1 Ri, rhodium chloride 0.0066,! 9
(0,025 mmol), silicotungstic acid 0165
6jl (0,,281,3mmol)%-Soluble in water+
4, then add 1 g of silica gel (manufactured by Kanto Kagaku, for chromatography, 100 meth/U or more) for D days, stir and dry, 0.51 'k] O0rne/m
A catalyst hydrogenated at 250°C for 1 hour in a hydrogen stream of
Using 1 g of 4-8 mesh), the reaction was carried out according to the method of Example 1 (each time the reaction was carried out at 190° C. for 60 minutes to obtain 1.51 g of cyclohexylbenzene and 238 g of cyclohexane).

Example 5 Platinum chloride @o, 0065 g (0,0
125 mmol), silicotungstic acid 0.1656
9 (0,2813 mmo4) was dissolved in water, silica gel (Kanto Kagakureki) 19 was added thereto, stirred, dried, and hydrogenated for 1 hour at 350°C in a hydrogen flow of 0.5 gf: 100 ml/min. catalyst and benzene 20
Using 0.5 g of Zeorum A5 (Toyo Usutatsuge, spherical, 4-6 mesh), the reaction temperature was set to 2 according to the method of Example 1.
Heat the reaction at 30°C for 48 minutes, and cyclohexylbenzene 13
79, cyclohexane 2.1.1.9 (i= (4'
S.

Example By the method of Example 1, 0.0868j of phosphotungstic acid
;? (0,0125 mrno1), acetic acid di:, 7 kel O, Q467, F (0,1875 m body 1) was dissolved in water, silica gel (Kanto Kagaku/Bin)] g was added, and the mixture was stirred.
0.5g from the dried one at I 00〃l(!/min
A reaction was carried out at 205°C by the method of Example 1 using a catalyst hydrogenated at 300'Cf for 1 hour in a hydrogen stream of
0 minute reaction, cyclohexylbenzene 1.94. p,
103 g of cyclohexane was obtained.

Example 7 By the method of Example 1, 0.0994 silicotungstic acid
j7 (0.03 mmol), nickel acetate 0.037
49 (0,1,5mm01), ruthenium hydrideoo
o13g (0,005mmol), iridium chloride o
oo18g (Q, QQ5mmol) 'c water Vc solution m
Add L, Norikikeru (manufactured by Tabin 7) Li, stir, dry, then 0.5 g was hydrogenated in a hydrogen stream of 10 Q + ul/min at 315°C for 1 hour, and the catalyst was hydrogenated, and 20 g of Hensen, molecular sieve], 3X (1/16
Using 3.89.9 g of cyclohexylbenzene and 7129 g of cyclohexane, 3.89.9 g of cyclohexylbenzene and 7129 g of cyclohexane were obtained by reacting for 65 minutes at a reaction temperature of 215° C. using the method of Example 1.

Procedural amendment (spontaneous) No. 58 Hi Giken Division No. 248 1983 Month/Date 58 3 -1 Commissioner of the Patent Office Aio Wakasugi 1゜: 'J1 case (y) display Patent application No. 10 of 1988
263 No. 2- Name of Ja Mei Method for manufacturing cyclohexylbenzene 3 □ Person making amendment Patent applicant address 1-3-1 Kasumigaseki, Chiyoda-ku, Tokyo 4 (114) Director of the Agency of Industrial Science and Technology Makoto Ishizaka -8
, Contents of the amendment (1) In the bottom five lines of the first page of the specification, "・°°・To the method for producing benzene..." will be corrected to "...to the method for producing benzene..." .

(2) Correct "..., application..." in the fourth line from the bottom of the second page to "..., patent application...°".

(3) On page 6, line 3 of the same page, "Can be increased. (Comparison of Examples 1 and 2) Dehydration..." has been changed to "Can be stopped (Comparison of Examples 1 and 2). Dehydration..." Please correct it.

(4) On page 8, line 6, "... put 1 g" in "..."
・Corrected to ``Add 1g and perform 1.''

Procedural amendment (voluntary) 58 Kagiken No. 108T July 211, 1980 Kazuo Wakasugi, Commissioner of the Patent Office 1, Indication of the case Patent application No. 10263 of 1988
No. 2, Title of the invention Process for producing cyclohexylbenzene 3, Person making the amendment 1 I/1 Related patent applicant address Kawa, 1-3-1 Kasumigaseki, Chiyoda-ku, Tokyo (114) Director, Agency of Industrial Science and Technology Kawa 1) Contents of Hakama Part 8 Amendment Correction as per the attached full text correction specification ■ Name of the invention Cyclohexylbenzene (7) j; * How to use y12,
Claims (1) In 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 7-lica gel, a dehydrating and drying agent is present in the reaction system. Characteristic method for producing cyclohexylbenzene.

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

Conventionally, the method for producing rubenzene has been to use a catalyst in which a Group 8 metal is supported on a solid acid support (Shisoroki Alumina Ushitaba I (type theolite)): (J,
Catalysis, 13, 385 (196
9), Petroleum Journal (1), 25 (1976), JP-A-53-108952), and a method using supported palladium and molten salt (NaC1-A1C13) as a catalyst (Ch.
em, pharmBull, 29(1), 15(19
81) is known. Furthermore, a method using a hydrogenation catalyst and a catalyst in which telopolyacid is supported on a carrier ([J, S
, l', 3,1.53,678). but,
These have low catalytic activity, and in order to increase the benzene conversion rate, a long reaction time is required, or the generated cyclohexylbenzene is further alkylated/many cyclohexylbenzenes (C+s) etc. (d) cannot be said to be a satisfactory method for industrially producing cyclohexylbenzene.

In order to overcome the shortcomings of the method for producing cyclohexylbenzene by hydrogenation condensation of benzene, the present inventors (d) have conducted extensive research and found that a heteropolyacid and a Group 8 metal are used as a catalyst. At the same time, it was discovered that cyclohexylbenzene could be produced with high selectivity by dehydration and drying: by adding a chestnut agent, it was possible to produce cyclohexylbenzene very easily and with high selectivity while suppressing the formation of the compound. 113299)
l,ta. As a result of various studies on improving the present catalyst, the inventors of the present invention have found that by using the catalyst supported on the above-mentioned two-component all-phosphorus silica gel together with a dehydrating/desiccating agent, the use area of the catalyst components can be significantly reduced. discovered a method for producing cyclohexylbenzene that allows for extremely easy handling of the catalyst. 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 and a group 8 metal compound (d) are used as catalysts supported on a silica gel carrier, and the reaction can be filtered in the presence of a dehydrating and drying agent. The present invention provides a method for producing cyclohexylbenzene.

The catalyst for the method of the present invention can be prepared according to various methods, but a typical example is to dissolve or suspend a compound of a heteropolyacid as a component and a component metal in water or acetic acid and add a carrier material to the solution. There is a method in which catalyst components are deposited on a carrier by immersion, dried, and calcined in an inert gas.Alternatively, means such as thermal decomposition may be used.Furthermore, before using this catalyst in a reaction, It is preferable to reduce to °C is used, preferably 250-375 °C.

Among the catalyst components, as the heteropolyacid, any commercially available heteropolyacid such as silicotungstic acid, phosphotungstic acid, phosphomolybdic acid, etc. can be used, but silicotungstic acid is 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 is 0.005 to 0.5 mmol/ji'
/ ') Kakeru F) Range is appropriate, preferably,
0.01-0.2 mmol/g silica gel.

Group 8 metal components include organic acid salts such as formic acid and acetic acid, carbonates,
Can be added in the form of chlorides, nitrates, hydroxides, etc.
Other compounds can also be used as long as they are uniformly dissolved or mixed with the heteropolyacid during catalyst preparation.

Furthermore, in order to control the activity of these metals, they may be supported together with other metals. The concentration of the Group 8 metal compound is as follows. As the Group 8 metal component, nickel, palladium, rhodium, ruthenium, platinum, and iridium are used. When using a noble metal that has a high benzene hydrogenation activity, it is preferable to lower its coexisting concentration and increase the heteropolyacid concentration in order to improve the selectivity of cyclohexylbenzene.

The catalyst support in the process of the invention has a significantly low content of lyka. This is one of the key features of the present invention.

When carrying out the method of the present invention, cyclohexylbenzene U is not produced even if zeo is added to the reaction system (Comparative Example 2)
However, when a heteropolyacid and a dehydrating/desiccating agent made of a Group 8 metal coexist, the yield and selectivity of cyclohexylbenzene can be significantly improved (comparison between Example 1 and Comparative Example 1). As a dehydrating/desiccating agent, any desiccant that is used industrially can be used, but Molecular Lube 10
x, 13x (or equivalent), silica gel, alumina gel, etc. are particularly good. Usage amount is 0.05-5p/20
The range of g benzene is suitable, 01-2 g720
G Bentsen is good.

The method of the invention can be carried out without or in a solvent. 7. Any solvent inert to the reaction, such as chlorohexane, 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°C.
, preferably 100 to 250°C, and the reaction hydrogen pressure is 1
~300kg/school 2, preferably 10-150kg/
It is CrrL2. 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 detail based on examples.

Example 1 Silicotungstic acid 0.082 i (0,025 mm
ol) (dry the reagent to a constant weight at 110°C,
5102・12WO,・261-120=331064
) and vinegar I'1% - 0.0467,!l
' (0,1875 mmol) was dissolved in water, and silica gel (Davison 'I' M57 was crushed into it and 32-42
Add 1g of Metsushi's) and stir 1f1g for 1 hour.
, Evaporate the water using a rotary vacuum evaporator, 1], Transfer 05I from the dried material to a glass tube, which reaches a constant weight at 0°C, and 100 m1'! /min
A catalyst was prepared by reduction in a hydrogen stream at 325°C for 1 hour.

This catalyst was placed in a 5US316 autoclave with an internal volume of 80 m1, which had a gas inlet, pressure gauge, and thermometer insertion tube.
7”/C, benzene 20g, molecular sieve]
1 g of 3x (1/16 pellets) and a Teflon-coated stirrer were placed in the reactor, the inside was replaced with nitrogen, and then hydrogen gas was pressurized at room temperature to 50 kg/'cx2. 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 55 minutes of reaction time, cyclohexylbenzene was 3.56. ! 7. Cyclohexane 0.50. I got r. The production of C1g compound was sideways.

Comparative Example 1 A reaction was carried out in the same manner as in Example 1 except for the regular sieve 13X. After a reaction time of 90 minutes, 1.32.9 g of cyclohegysylbenzene and 094 g of cyclohexane were obtained.

Comparative Shio 112 A catalyst was prepared by removing silicotungstic acid in Example 1,
The reaction was carried out for 90 minutes under the conditions of Example 1, and 2.64 g of cyclohexane was obtained. The production of cyclohexylbenzene was a sidetrack.

Example 2゜ Palladium acetate 0.0071.9 (
0.025 mmol), silicotungstic acid 0.248
4!9 (0,5625 mmol) was suspended in water over a sufficient period of time, 1 g of silica gel was added, stirred and dried, and 0.5 g of the catalyst was hydrogenated, 20 g of benzene, and a molecular sieve. Using 13×1.9e, the reaction temperature was 210°C for 90 minutes 1 according to the method of Example 1.
jj Reaction sequence, cyclohexylbenzene 3.09g,
135 g of cyclohexane was obtained.

Example 3 Rhodium chloride 0.0066.5' (
0,025 mmol), silica tungstearic acid 0.1
Dissolve 6569 (0,28], 3 mmol) in water, add 1 g of silica gel (manufactured by Kanto Kagaku, for chromatography, 100 ml or more), stir, and dry. The catalyst was hydrogenated for 1 hour at 250°C in a hydrogen flow of
J9, Ceorum F9 (manufactured by Toyo Soda, spherical, 4 to 8 mesh) 1,! 7 using the reaction temperature 1 according to the method of Example 1.
The reaction was carried out at 90°C for 60 minutes to obtain 51 g of cyclohexylbenzene and 238 g of cyclohexane.

Example 4 Using the method of Example 1, 0.0065 g of chloroplatinic acid (0.0
125 mmol), silicotungstic acid 0.16569
(0.2813mm01) was dissolved in water, 1g of silica gel (manufactured by Kanto Kagaku) was added thereto, stirred, and dried. ! 7 was hydrogenated at 350'C for 1 hour in a hydrogen flow of 100 rnl/min using the catalyst Tobe/Cen 20,9 and 05 g of Ceorum A5 (manufactured by Toyo Soda, spherical, 4-6 mesh), and the method of Example 1. Cyclohexylbenzene was reacted for 48 minutes at a reaction temperature of 230°C. Cyclohexane 2.119k fc
.

Example 5 Using the method of Example 1, phosphotungstic acid 0.08687
? (0,0], 25 mmol), nickel acetate Q, O467,9 (O1B75mmO1) f: water 11c
Dissolve and add 1g of 0.5.9 to 100 m6 of the dried material.
A catalyst hydrogenated at 300°C for 1 hour in a 7mln hydrogen stream, benzene 20.9, Neobead C4 (Mizusawa Chemical Division) 1. ! 9', and the reaction 205 was carried out by the method of Example 1.
℃ for 90 minutes, cyclohexylbenzene 1.94
,9. 103 g of cyclohexane was obtained.

Example 6 By the method of Example 1, 0.0994 tungstic acid
g (0.03mm01), nickel acetate #0.037
4g (0.15mm○1), Ruthenium chloride 0.001
．． 3. ! 9 (0,005 mm01), iridium chloride O, O61sy (Q, O005 mmol) k Dissolve in water, add Shitsuka Gel (manufactured by Ribbison) 17, stir,
The method of Example 1 was carried out using a catalyst obtained by hydrogenating dried material, 20 g of benzene, and 1 g of molecular sieve 13 According to the method, 3.89 g of cyclohexylbenzene and 129 g of cyclohexane were obtained after a 65 minute reaction at a reaction temperature of 215°C.

Claims (2)

[Claims] (1) A method for producing cyclohexylbenzene, which comprises hydrogenating and condensing benzene in the presence of a catalyst in which a heteropolyacid and a Group 8 metal (PA) or its compound are supported on silica gel. (2) When hydrogenating and condensing benzene in the presence of a catalyst consisting of a heteropolyacid and a compound of Group 8 metal i' supported on silica gel, a dehydrating and drying agent is present in the reaction system. A method for producing cyclohexylbenzene.