JPS61186332A - Production of cyclohexylbenzene - Google Patents
Production of cyclohexylbenzeneInfo
- Publication number
- JPS61186332A JPS61186332A JP60025056A JP2505685A JPS61186332A JP S61186332 A JPS61186332 A JP S61186332A JP 60025056 A JP60025056 A JP 60025056A JP 2505685 A JP2505685 A JP 2505685A JP S61186332 A JPS61186332 A JP S61186332A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- nickel
- silica alumina
- benzene
- reaction
- 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.)
- Granted
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)
Abstract
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りｉぞ 一、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 can be achieved by hydrogenation condensation of benzene. 1. A method for producing cyclohexylbenzene.
）パ従来、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 。) Conventionally, as a method for producing cyclohexylbenzene by hydrogenation condensation of benzene, a method of supporting a Group 8 metal on a solid acid support (silica alumina or HY type zeolite) (J, Catalysis, 13).
３８５ （１９６９）、石油誌１８．（ＩＪ、２５ （
１９７６）や特開昭５３−１０８９５２）、また、担持
パラジウムと熔融塩（ＮａＣ６−ＡＩｃＩ３） ｔ”用
いる方法（Ｃｈｅｍ、 Ｐｈａ−ｒｍ、 Ｂｕｌｌ、
、２９ 、（１）、 １５ （１９８１） ）、さらに
、水素化触媒とへテロポリ酸を担体に担持した触媒を用
いる方法（Ｕ、 Ｓ、 Ｐ、 ３，１５３，６７８）
、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、ニッケル、パラジウムを担持した
触媒を用いる方法（Ｕ、 Ｓ、 Ｐ、 ３，７６０，０
１７）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ヲ用いるなど
、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。385 (1969), Petroleum Magazine 18. (IJ, 25 (
1976) and JP-A-53-108952), and a method using supported palladium and molten salt (NaC6-AIcI3) (Chem, Pha-rm, Bull,
, 29, (1), 15 (1981)), and a method using a catalyst in which a hydrogenation catalyst and a heteropolyacid are supported on a carrier (U, S, P, 3,153,678)
, and a method using a catalyst in which cobalt, nickel, and palladium are supported on a carrier prepared by diluting expensive HY zeolite with silica alumina (U, S, P, 3,760,0
17) etc. are known. However, these methods produce a large amount of cyclohexane and dicyclohexylbenzene, have low selectivity for cyclohexylbenzene, have a slow reaction rate, and use expensive reagents to prepare the catalyst. cannot be said to be a satisfactory method.
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、ニッケルを担持させる際、こｎ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ったものである。In order to overcome the drawbacks of these manufacturing 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. It was 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 co-existed in the reaction system, the reaction It was found that both speed and 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、ニッ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、種々の方法に従って調製出来るが
、代表的な例としては、ニッケル塩を鉄′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
け、２５０〜５００℃である。The catalyst of the present invention can be prepared according to various methods, but as a typical example, a nickel salt is dissolved or suspended together with an iron salt or a manganese salt in a solvent such as water or acetic acid, and then the above-mentioned method is added. Means such as depositing the metal component on the carrier by immersing the carrier material, drying and hydrogenating at high temperature, or pyrolyzing 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.
るか、懸濁するものは使用出来る。ニッケルの担持量は
担体重量の０．５〜２０ｗｔ％が用いられ、好ましくは
、１〜ｌＱｗｔ％であり、鉄またはマンガン成分はニッ
ケル量の１〜５０ ｗｔ％が用いられ、好ましくは、３
〜３Ｑｗｔチである。or suspension can be used. The amount of nickel supported is 0.5 to 20 wt% of the carrier weight, preferably 1 to 1Qwt%, and the iron or manganese component is 1 to 50 wt% of the nickel amount, preferably 3
~3Qwt Chi.
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、モレキュラー・シーブＩＯＸ、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゜０５〜５ ｆｉ／２０１７ベン
ゼンの範囲が用いられ、０，１〜２ｇ／２０９ベンゼン
が好ましい。The catalyst carrier in the method of the present invention is HY type zeolite diluted with silica alumina. For example, 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/desiccant agent coexist, the reaction rate can be increased,
The selectivity of cyclohexylbenzene can be significantly improved (comparison of Example 2.3 and Comparative Example 1). As a dehydrating/desiccating agent, any desiccant that is used industrially can be used, but Molecular Sieve IOX, 13X (
or its equivalent), silica gel, alumina gel, etc. are particularly good. The amount used is in the range of 0.05 to 5 fi/2017 benzene, preferably 0.1 to 2 g/209 benzene.
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〜に９／ａ
ｎ２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
分解が起って不利である。In the method of the present invention, the reaction temperature is usually 50 to 9/a
It is n2. 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 ・６Ｈ２００，１４８６ｇとＦｅ
Ｃｌ２０．０１１３ｇを約２０．９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、Ｍ
ＲＺ−２０４）１ｇを加え、３０分間攪拌し、ロータリ
ー・バキューム・エバポレーターで水分を蒸発させ、１
１０℃で２０分間乾燥した後、焼成管に移し、水素気流
１００ｍＡ！／ｍｉｎ 、 、３２５℃でｌ ｈｒ還元
して触媒を調製した。Example 1゜Ni (NO3)2 6H200, 1486g and Fe
20.0113 g of Cl was uniformly dissolved in approximately 20.9 g of water, and commercially available silica alumina for FCC (Catalyst Kasei, M
Add 1 g of RZ-204), stir for 30 minutes, evaporate water using a rotary vacuum evaporator,
After drying at 10°C for 20 minutes, transfer to a firing tube and apply a hydrogen flow of 100mA! The catalyst was prepared by reduction at 325° C./min for 1 hr.
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８０ ｍｌの５ＵＳ３１６製オートクレーブ
に、ベンゼン２０ｇとテフロンコート攪拌子と共に入ト
楔、内部を窒素で置換した後、水素ガスを室温で一３０
ｋｇ／ｃＩｒＬ２まで圧入した。マグネチック・スター
ラ・−で攪拌しながら、反応温度２００℃まで加熱し、
反応温度到達時をもって反応開始とした。反応時間６８
分で反応圧２２ｋｇ／ｃＩｒＬ２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（ＣＨ
Ｂ） ５．８８．！ｉ’、シクロヘキサン（ＣＨ） ０
．６０ ｇを得、ＣＨＢＵ”）／ＣＨＵ）は９．８であ
った。0.5 g of this catalyst (3% Ni-0.5% Fe-silica alumina) was placed in a 5US316 autoclave with an internal volume of 80 ml equipped with a gas inlet, a pressure gauge, and a thermometer insertion tube, and 20 g of benzene and Teflon coated. After replacing the inside of the wedge with a stirrer with nitrogen, hydrogen gas was heated at room temperature for 30 minutes.
It was press-fitted up to kg/cIrL2. While stirring with a magnetic stirrer, heat to a reaction temperature of 200°C,
The reaction was started when the reaction temperature was reached. reaction time 68
The reaction pressure decreased to 22 kg/cIrL2 in minutes. As a result of cooling and analyzing the reaction solution, cyclohexylbenzene (CH
B) 5.88. ! i', cyclohexane (CH) 0
．． 60 g was obtained, and CHBU'')/CHU) was 9.8.
比較例１゜
実施例１でＦｅＣ６ｚを加えずに、Ｎｉ（ＮＯ３）２
’ ６ Ｈ２Ｏ０，１７３４ｇだけをＦ’ＣＣ用シリカ
シリカアルミナし、同様に調製した触媒（３，５％Ｎ１
−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２５ ｋｌｉｌ／ｃｍ２
まで低下した。反応液を分析した結果、ＣＨＢ４．８３
，９．ＣＨｌ、２１を得、ＣＨＢ（ｇ） ／ＣＨ（、ｆ
）は４．０であった。ニッケル担持量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った
。Comparative Example 1゜Ni(NO3)2 without adding FeC6z in Example 1
'6 Only 1734 g of H2O was treated with silica silica alumina for F'CC, and a similarly prepared catalyst (3.5% N1
- 0.5 g of silica alumina) was reacted for 90 minutes according to the method of Example 1, and the reaction pressure was 25 klil/cm2.
It dropped to . As a result of analyzing the reaction solution, CHB4.83
,9. CHl, 21 was obtained, CHB(g) /CH(,f
) was 4.0. Even when the amount of nickel supported 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
リ力アルミナ）０．５ｇに、脱水・乾燥剤としてモレキ
ュラー・シープ１３Ｘ１．９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２２ｋｇ／ｃＷＬ
２まで低下した。反応液を分析しＣＨＢ５．７７、Ｖ、
ＣＨｏ、６９ｇを得、ＣＨＢ Ｃｇ＞ ／ＣＨＵ’）は
８．４であった。Example 2゜To 0.5 g of the catalyst prepared in Example 1 (3% Ni-0.5% Fe-silicate alumina), Molecular Sheep 13X1.9 was added as a dehydrating and desiccant agent, and the same procedure as in Example 1 was carried out. The reaction time was 35 minutes, and the reaction pressure was 22 kg/cWL.
It dropped to 2. The reaction solution was analyzed and CHB5.77, V,
69 g of CHo was obtained, and CHB Cg>/CHU') was 8.4.
実施例３゜
Ｎ’ （ＮＯ３）２ ・６ Ｈ２Ｏ０，１４８６ｆｉ、
Ｍｎ （ＯＣＯＣＨ３） −６Ｈ，ＯＯ，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チ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／ｃｒｎ
２まで低下した。反応液を分析し、ＣＨＢ４．９０，９
．ＣＨｏ、７３ｇを得、ＣＨＢ Ｃｆ！＞ ／ＣＨＣｌ
！’）は６．７であった。Example 3゜N' (NO3)2 ・6 H2O0,1486fi,
A catalyst (3% Ni
-0.5g of Mn-silica alumina) and 450℃
Using Zeolum F9 (manufactured by Toyo Soda) dried in
It dropped to 2. The reaction solution was analyzed and CHB4.90.9
．． CHo, obtained 73g, CHB Cf! ＞ /CHCl
! ') was 6.7.
比較例１．２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 1.2, 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 obvious.
Claims (2)
体に、ニッケルと、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。(1) Benzene is hydrogenated in the presence of a catalyst that supports nickel and at least one metal selected from iron or manganese as a co-catalyst on a carrier prepared by diluting HY type zeolite with silica alumina. A method for producing cyclohexylbenzene, which comprises chemical condensation.
体に、ニッケルと、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。(2) Benzene is hydrogenated 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. 1. A method for producing cyclohexylbenzene, which is characterized in that a dehydrating and drying agent is present in the reaction system during chemical condensation.
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 true JPS61186332A (en) | 1986-08-20 |
| JPH0321527B2 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) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011511836A (en) * | 2008-02-12 | 2011-04-14 | エクソンモービル・ケミカル・パテンツ・インク | Method for producing cyclohexylbenzene |
| JP2013523631A (en) * | 2010-03-26 | 2013-06-17 | ビーエーエスエフ コーポレーション | Fatty acid hydrogenation process using promoted supported nickel catalyst |
| JP2014513050A (en) * | 2011-02-18 | 2014-05-29 | 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 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3760017A (en) * | 1971-05-17 | 1973-09-18 | Texaco Inc | Hydroalkylation catalyst and process |
| JPS59199641A (en) * | 1983-04-26 | 1984-11-12 | Agency Of Ind Science & Technol | Production of cyclohexylbenzene |
-
1985
- 1985-02-12 JP JP60025056A patent/JPS61186332A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3760017A (en) * | 1971-05-17 | 1973-09-18 | Texaco Inc | Hydroalkylation catalyst and process |
| JPS59199641A (en) * | 1983-04-26 | 1984-11-12 | Agency Of Ind Science & Technol | Production of cyclohexylbenzene |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011511836A (en) * | 2008-02-12 | 2011-04-14 | エクソンモービル・ケミカル・パテンツ・インク | Method for producing cyclohexylbenzene |
| JP2013523631A (en) * | 2010-03-26 | 2013-06-17 | ビーエーエスエフ コーポレーション | Fatty acid hydrogenation process using promoted supported nickel catalyst |
| JP2014513050A (en) * | 2011-02-18 | 2014-05-29 | 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0321527B2 (en) | 1991-03-22 |
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