JPH0321527B2 - - Google Patents
Info
- Publication number
- JPH0321527B2 JPH0321527B2 JP60025056A JP2505685A JPH0321527B2 JP H0321527 B2 JPH0321527 B2 JP H0321527B2 JP 60025056 A JP60025056 A JP 60025056A JP 2505685 A JP2505685 A JP 2505685A JP H0321527 B2 JPH0321527 B2 JP H0321527B2
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- reaction
- silica alumina
- benzene
- cyclohexylbenzene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【発明の詳細な説明】
本発明はベンゼンを水素化縮合することにより
シクロヘキシルベンゼンを製造する方法に関す
る。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing cyclohexylbenzene by hydrogenation condensation of benzene.
従来、ベンゼンの水素化縮合によるシクロヘキ
シルベンゼンの製造方法としては、第８族金属を
固体酸系担体（シリカアルミナまたはHY型ゼオ
ライト）に担持する方法〔J.Catalysis、13，385
（1969）、石油誌18，(1)，25（1976）や特開昭53−
108952〕、また、担持パラジウムと熔融塩（NaCl
−AlCl3）を用いる方法〔CHem.Pharm.Bull.、
29，(1)，15（1981）〕、さらに、水素化触媒とヘテ
ロポリ酸を担体に担持した触媒を用いる方法
（U.S.P.3153678）、また、高価なHYゼオライト
をシリカアルミナで希釈した担体にコバルト、ニ
ツケル、パラジウムを担持した触媒を用いる方法
（U.S.P.3760017）等が知られている。しかし、こ
れらはシクロヘキサンやジシクロヘキシルベンゼ
ンの生成が多く、シクロヘキシルベンゼンの選択
率が低いとか、反応速度が小さいとか、さらに、
触媒の調製に高価な試薬を用いるなど、工業的な
シクロヘキシルベンゼンの製造方法としては満足
すべき方法とは言えない。 本発明者らは、これ
らの製造方法の欠点を克服するため、種々検討を
重ねた結果、高価なHY型ゼオライトをシリカア
ルミナで希釈した安価な市販のFCC用シリカア
ルミナに、ニツケルを担持させる際、これに鉄ま
たはマンガンを加えると、シクロヘキサンの生成
を抑え、シクロヘキシルベンゼンの選択率を著し
く向上させ得ることを見い出し、さらに改良を重
ねて、反応系に脱水・乾燥剤を共存させると、反
応速度、シクロヘキシルベンゼン選択率ともに著
しく改善されることを見い出した。本発明はこの
知見に基づいてなされるに到つたものである。 Conventionally, as a method for producing cyclohexylbenzene by hydrogenation condensation of benzene, a method in which a Group 8 metal is supported on a solid acid support (silica alumina or HY type zeolite) [J.Catalysis, 13, 385
(1969), Petroleum Magazine 18, (1), 25 (1976) and JP-A-53-
108952], supported palladium and molten salt (NaCl
−AlCl 3 ) [CHem.Pharm.Bull.,
29, (1), 15 (1981)], and a method using a catalyst in which a hydrogenation catalyst and a heteropolyacid are supported on a carrier (USP 3153678). , a method using a catalyst supporting palladium (USP 3760017), etc. are known. However, these produce a lot of cyclohexane and dicyclohexylbenzene, and the selectivity of cyclohexylbenzene is low, the reaction rate is low, and
This method cannot be said to be satisfactory as an industrial method for producing cyclohexylbenzene, as it uses expensive reagents to prepare the catalyst. In order to overcome the drawbacks of these production methods, the present inventors have conducted various studies and found that when nickel is supported on inexpensive commercially available silica alumina for FCC, which is made by diluting expensive HY type zeolite with silica alumina. discovered that adding iron or manganese to this can suppress the formation of cyclohexane and significantly improve the selectivity of cyclohexylbenzene.Further improvements were made, and when a dehydrating/drying agent was coexisted in the reaction system, the reaction rate was increased. It was found that both the cyclohexylbenzene selectivity and the cyclohexylbenzene selectivity were significantly improved. The present invention has been made based on this knowledge.
すなわち、本発明はベンゼンと水素を反応させ
るにあたり、HY型ゼオライトをシリカアルミナ
で希釈した担体に、ニツケルとともに鉄またはマ
ンガンの内から選ばれた少なくとも一種の金属を
担持した触媒の存在下に反応させることを特徴と
するシクロヘキシルベンゼンの製造方法を提供す
るものである。 That is, in the present invention, when reacting benzene and hydrogen, the reaction is carried out in the presence of a catalyst in which HY type zeolite is supported on a carrier prepared by diluting HY type zeolite with silica alumina, and at least one metal selected from iron or manganese is supported along with nickel. The present invention provides a method for producing cyclohexylbenzene characterized by the following.
本発明方法の触媒は、種々の方法に従つて調製
出来るが、代表的な例としては、ニツケル塩を鉄
塩またはマンガン塩とともに、水または酢酸等の
溶媒に溶解もしくは懸濁させた液に、上記担体物
質を浸漬することにより金属成分を担体上に付着
せしめ、乾燥し、高温で水素化するか、あるい
は、不活性ガス中で焼成することにより熱分解す
るなどの手段を用いてもよい。触媒の水素化・焼
成温度としては、200〜600℃が用いられ、好しく
は、250〜500℃である。 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 nickel salt together with an iron salt or a manganese salt in a solvent such as water or acetic acid. Means such as depositing the metal component onto the carrier by immersing the carrier material, drying and hydrogenating at high temperature, or thermally decomposing by firing in an inert gas may be used. The hydrogenation/calcination temperature of the catalyst is 200 to 600°C, preferably 250 to 500°C.
ニツケル成分およびこれに助触媒として加える
鉄、マンガン成分は、ギ酸、酢酸等の有機酸塩、
炭酸塩、硝酸塩、塩化物、水酸化物等の形で加え
ることが出来、その他の化合物でも、触媒調製液
に溶解するか、懸濁するものは使用出来る。ニツ
ケルの担持量は担体重量の0.5〜20wt％が用いら
れ、好ましくは、１〜10wt％であり、鉄または
マンガン成分はニツケル量の１〜50wt％が用い
られ、好ましくは、３〜30wt％である。 The nickel component and the iron and manganese components added thereto as promoters are organic acid salts such as formic acid and acetic acid,
It can be added in the form of carbonate, nitrate, chloride, hydroxide, etc. Other compounds can also be used if they are dissolved or suspended in the catalyst preparation solution. The supported amount of nickel is 0.5 to 20 wt% of the carrier weight, preferably 1 to 10 wt%, and the iron or manganese component is 1 to 50 wt% of the nickel weight, preferably 3 to 30 wt%. be.
本発明の方法における触媒の担体にはHY型ゼ
オライトをシリカアルミナで希釈したもの、例え
ば、市販のFCC用シリカアルミナ触媒は、いづ
れも用いられる。 As the catalyst carrier in the method of the present invention, a diluted HY type zeolite with silica alumina, such as a commercially available silica alumina catalyst for FCC, is used.
本発明の方法を実施する場合、反応系にゼオラ
イト、シリカゲル、アルミナゲル等の脱水・乾燥
剤を添加出来る。この場合、脱水・乾燥剤に接触
させたベンゼンを用いてもよい。触媒と脱水・乾
燥剤を共存させると、反応速度を上げたり、シク
ロヘキシルベンゼンの選択率を著しく向上させ得
る（実施例２，３と比較例１の比較）。脱水・乾
燥剤としては、工業的に乾燥剤として用いられる
ものはいづれも用いられるが、モレキユラー・シ
ーブ10X、13X（または、その相当品）、シリカゲ
ル、アルミナゲル等が特によい。使用量は0.05〜
５ｇ／20ｇベンゼンの範囲が用いられ、0.1〜２
ｇ／20ｇベンゼンが好ましい。 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. When a catalyst and a dehydrating/drying agent coexist, the reaction rate can be increased and the selectivity of cyclohexylbenzene can be significantly improved (comparison between Examples 2 and 3 and Comparative Example 1). As the dehydrating/desiccating agent, any desiccant that is used industrially can be used, but molecular sieves 10X, 13X (or their equivalents), silica gel, alumina gel, etc. are particularly preferred. Usage amount is 0.05~
A range of 5g/20g benzene is used, with 0.1 to 2
g/20g benzene is preferred.
本発明の方法は無溶媒でも溶媒中でも行われ得
る。シクロヘキサン等の反応に不活性な溶媒はい
づれも用いられる。原料のベンゼンは出来る限り
水分含量の少ないものが望ましい。 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.
本発明の方法において、反応温度は通常50〜
300℃、好ましくは100〜250℃であり、反応水素
圧は１〜300Kg／cm2、好ましくは、10〜150Kg／cm2
である。反応温度が低いとシクロヘキサンの選択
率が高くなり、また反応温度が高すぎると、反応
生成物の分解が起つて不利である。 In the method of the present invention, the reaction temperature is usually 50~
The temperature is 300°C, preferably 100 to 250°C, and the reaction hydrogen pressure is 1 to 300 Kg/cm 2 , preferably 10 to 150 Kg/cm 2
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.
次に、本発明を実施例に基づき、さらに詳細に
説明する。 Next, the present invention will be explained in more detail based on examples.
実施例 １
Ni（NO3）2・6H2O0.1486ｇとFeCl20.0113ｇを
約20ｇの水に均一に溶解し、これに市販のFCC
用シリカアルミナ（触媒化成、MRZ−204）１ｇ
を加え、30分間撹拌し、ロータリー・バキユー
ム・エバポレーターで水分を蒸発させ、110℃で
20分間乾燥した後、焼成管に移し、水素気流100
ml／min.、325℃で1hr還元して触媒を調製した。Example 1 0.1486 g of Ni(NO 3 ) 2・6H 2 O and 0.0113 g of FeCl 2 were uniformly dissolved in about 20 g of water, and a commercially available FCC was added to the solution.
Silica alumina (Catalyst Kasei, MRZ-204) 1g
was added, stirred for 30 minutes, evaporated with a rotary vacuum evaporator, and heated to 110°C.
After drying for 20 minutes, transfer to a firing tube and heat with a hydrogen stream of 100 ml.
The catalyst was prepared by reduction at 325°C for 1 hour at ml/min.
この触媒（３％Ni−0.5％Fe−シリカアルミ
ナ）0.5ｇを、ガス導入口、圧力計、温度計挿入
管を備えた内容積80mlのSUS316製オートクレー
ブに、ベンゼン20ｇとテフロンコート撹拌子と共
に入れ、内部を窒素で置換した後、水素ガスを室
温で50Kg／cm2まで圧入した。マグネチツク・スタ
ーラーで撹拌しながら、反応温度200℃まで加熱
し、反応温度到達時をもつて反応開始とした。反
応時間68分で反応圧22Kg／cm2まで低下した。反応
液を冷却し分析した結果、シクロヘキシルベンゼ
ン（CHB）5.88ｇ、シクロヘキサン（CH）0.60
ｇを得、CHB（ｇ）／CH（ｇ）は9.8であつた。 0.5 g of this catalyst (3% Ni-0.5% Fe-silica alumina) was placed in an 80 ml SUS316 autoclave equipped with a gas inlet, pressure gauge, and thermometer insertion tube, along with 20 g of benzene and a Teflon-coated stirring bar. After purging the inside with nitrogen, hydrogen gas was injected under pressure at room temperature up to 50 kg/cm 2 . While stirring with a magnetic stirrer, the mixture was heated to a reaction temperature of 200°C, and the reaction was started when the reaction temperature was reached. The reaction pressure decreased to 22 kg/cm 2 after a reaction time of 68 minutes. As a result of cooling and analyzing the reaction solution, 5.88 g of cyclohexylbenzene (CHB) and 0.60 g of cyclohexane (CH) were found.
g, and CHB(g)/CH(g) was 9.8.
比較例 １
実施例１でFeCl2を加えずに、Ni（NO3）2・
6H2O0.1734ｇだけをFCC用シリカアルミナに担
持し、同様に調製した触媒（3.5％Ni−シリカア
ルミナ）0.5ｇを用い、実施例１の方法で90分間
反応を行わせ、反応圧25Kg／cm2まで低下した。反
応液を分析した結果、CHB4.83ｇ、CH1.20ｇを
得、CHB（ｇ）／CH（ｇ）は4.0であつた。ニツ
ケル担持量3.0％でも反応速度及びCHBの選択率
に有意の差は認められなかつた。Comparative Example 1 Ni(NO 3 ) 2・ without adding FeCl 2 in Example 1
Only 0.1734 g of 6H 2 O was supported on silica alumina for FCC, and using 0.5 g of a similarly prepared catalyst (3.5% Ni-silica alumina), the reaction was carried out for 90 minutes by the method of Example 1, and the reaction pressure was 25 kg/ decreased to cm2 . As a result of analyzing the reaction solution, 4.83 g of CHB and 1.20 g of CH were obtained, and CHB (g)/CH (g) was 4.0. Even when the nickel loading was 3.0%, no significant difference was observed in the reaction rate and CHB selectivity.
実施例 ２
実施例１で調製した触媒（３％Ni−0.5％Fe−
シリカアルミナ）0.5ｇに、脱水・乾燥剤として
モレキユラー・シーブ13X1ｇを加え、実施例１
と同様に反応させ、反応時間35分で、反応圧22
Kg／cm2まで低下した。反応液を分析しCHB5.77
ｇ、CH0.69ｇを得、CHB（ｇ）／CH（ｇ）は8.4
であつた。Example 2 Catalyst prepared in Example 1 (3% Ni-0.5% Fe-
Example 1: To 0.5 g of silica alumina, 1 g of Molecular Sieve 13X was added as a dehydrating and desiccant agent.
The reaction was carried out in the same manner as above, reaction time was 35 minutes, reaction pressure was 22
It decreased to Kg/ cm2 . Analyze the reaction solution and find CHB5.77
g, CH0.69g was obtained, CHB(g)/CH(g) was 8.4
It was hot.
実施例 ３
Ni（NO3）2・6H2O0.1486ｇ、Mn（OCOCH3）・
6H2O0.0223ｇを実施例１と同様に担持させて調
製した触媒（３％Ni−0.5％Mn−シリカアルミ
ナ）0.5ｇと450℃で乾燥したゼオラムF9（東洋曹
達製）を用い、実施例１の方法で90分反応させ、
反応圧が23Kg／cm2まで低下した。反応液を分析
し、CHB4.90ｇ、CH0.73ｇを得、CHB（ｇ）／
CH（ｇ）は6.7であつた。Example 3 Ni(NO 3 ) 2・6H 2 O0.1486g, Mn(OCOCH 3 )・
Example 1 Using 0.5 g of a catalyst (3% Ni-0.5% Mn-silica alumina) prepared by supporting 0.0223 g of 6H 2 O in the same manner as in Example 1 and Zeolum F9 (manufactured by Toyo Soda) dried at 450°C, React for 90 minutes using method 1.
The reaction pressure decreased to 23Kg/cm 2 . The reaction solution was analyzed and CHB4.90g and CH0.73g were obtained, CHB (g)/
CH(g) was 6.7.
比較例１と比較して、反応速度の増加や、シク
ロヘキシルベンゼン選択率の向上に対し、鉄やマ
ンガンの効果、および脱水・乾燥剤の効果は明ら
かである。 Compared with Comparative Example 1, the effects of iron and manganese, and the effects of dehydration and desiccant agents on increasing the reaction rate and improving the cyclohexylbenzene selectivity are clear.
Claims (1)
た担体に、ニツケルと、さらに、助触媒として鉄
またはマンガンの内から選ばれた少くとも一種の
金属とを担持した触媒の存在下に、ベンゼンを水
素化縮合することを特徴とするシクロヘキシルベ
ンゼンの製造方法。 ２ HY型ゼオライトをシリカアルミナで希釈し
た担体に、ニツケルと、さらに、助触媒として鉄
またはマンガンの内から選ばれた少くとも一種の
金属とを担持した触媒の存在下に、ベンゼンを水
素化縮合させるにあたり、反応系に脱水乾燥剤を
存在させることを特徴とするシクロヘキシルベン
ゼンの製造方法。[Claims] 1. HY type zeolite diluted with silica alumina in the presence of a catalyst supporting nickel and at least one metal selected from iron or manganese as a co-catalyst. , a method for producing cyclohexylbenzene, which comprises hydrogenating and condensing benzene. 2 Benzene is hydrogenated and condensed in the presence of a catalyst that supports nickel and at least one metal selected from iron or manganese as a promoter on a carrier prepared by diluting HY type zeolite with silica alumina. A method for producing cyclohexylbenzene, characterized in that a dehydrating and drying agent is present in the reaction system.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60025056A JPS61186332A (en) | 1985-02-12 | 1985-02-12 | Production of cyclohexylbenzene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60025056A JPS61186332A (en) | 1985-02-12 | 1985-02-12 | Production of cyclohexylbenzene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61186332A JPS61186332A (en) | 1986-08-20 |
| JPH0321527B2 true JPH0321527B2 (en) | 1991-03-22 |
Family
ID=12155263
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60025056A Granted JPS61186332A (en) | 1985-02-12 | 1985-02-12 | Production of cyclohexylbenzene |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61186332A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8084648B2 (en) * | 2008-02-12 | 2011-12-27 | Exxonmobil Chemical Patents Inc. | Process for producing cyclohexylbenzene |
| EP2371937A1 (en) * | 2010-03-26 | 2011-10-05 | BASF Corporation | Process for the hydrogenation of fatty acids using a promoted supported nickel catalyst |
| JP5711393B2 (en) * | 2011-02-18 | 2015-04-30 | エクソンモービル ケミカル パテンツ インコーポレイテッド | Method for producing cyclohexylbenzene |
| CN108435234A (en) * | 2018-04-26 | 2018-08-24 | 郑州大学 | Application of the molecular sieve carried heteropolyacid catalyst in cyclohexyl benzene synthesis |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3760017A (en) * | 1971-05-17 | 1973-09-18 | Texaco Inc | Hydroalkylation catalyst and process |
| JPS6046098B2 (en) * | 1983-04-26 | 1985-10-14 | 工業技術院長 | Method for producing cyclohexylbenzene |
-
1985
- 1985-02-12 JP JP60025056A patent/JPS61186332A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61186332A (en) | 1986-08-20 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |