JPS598248B2 - Method for producing 1,4-cyclohexanedione - Google Patents
Method for producing 1,4-cyclohexanedioneInfo
- Publication number
- JPS598248B2 JPS598248B2 JP49086019A JP8601974A JPS598248B2 JP S598248 B2 JPS598248 B2 JP S598248B2 JP 49086019 A JP49086019 A JP 49086019A JP 8601974 A JP8601974 A JP 8601974A JP S598248 B2 JPS598248 B2 JP S598248B2
- Authority
- JP
- Japan
- Prior art keywords
- cyclohexanediol
- cyclohexanedione
- reaction
- copper oxide
- hydroquinone
- 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
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
- 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、１・４−シクロヘキサンジオンの製造方法に
関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing 1,4-cyclohexanedione.
さらに詳しくは、１・４−シクロヘキサンジオールの気
相脱水素による１・４−シクロヘキサンジオンの製造方
法に関する。１・４−シクロヘキサンジオンは、最近、
有機半導体の合成原料として注目されている７・７・８
・８−テトラシアノキノジメタンの製造原料として工業
上きわめて重要な化合物であり、その有効な製造方法は
また確立されていなかつた。More specifically, the present invention relates to a method for producing 1,4-cyclohexanedione by gas phase dehydrogenation of 1,4-cyclohexanediol. 1,4-cyclohexanedione has recently been
7, 7, 8 attracting attention as raw materials for the synthesis of organic semiconductors
- It is an extremely important compound industrially as a raw material for the production of 8-tetracyanoquinodimethane, and an effective method for its production has not yet been established.
本発明者らは、１・４−シクロヘキサンジオールの脱水
素反応により１・４−シクロヘキサンジオンを製造する
方法について鋭意検討を行つた結果、収率よく製造する
方法を見出し、本発明に到達した。すなわち本発明は、
ヒドロキノンの存在下に、１・４−シクロヘキサンジオ
ールを酸化銅、酸化銅−部化亜鉛、酸化銅一酸化クロム
、酸化銅一酸化マンガンから選ばれる脱水素触媒と気相
で接触させることを特徴とする１・４−シクロヘキサン
ジオンの製造方法である。The present inventors have conducted intensive studies on a method for producing 1,4-cyclohexanedione through a dehydrogenation reaction of 1,4-cyclohexanediol, and as a result, have found a method for producing 1,4-cyclohexanedione with good yield, and have arrived at the present invention. That is, the present invention
It is characterized by contacting 1,4-cyclohexanediol with a dehydrogenation catalyst selected from copper oxide, copper oxide-partial zinc oxide, copper chromium monoxide, and copper manganese monoxide in the presence of hydroquinone in the gas phase. This is a method for producing 1,4-cyclohexanedione.
本発明により、１・４−シクロヘキサンジオールの脱水
素反応にヒドロキノンを添加すると、１・４−シクロヘ
キサンジオンの収率が大巾に向上することが明らかにな
つた。According to the present invention, it has been revealed that when hydroquinone is added to the dehydrogenation reaction of 1,4-cyclohexanediol, the yield of 1,4-cyclohexanedione is greatly improved.
原料として使用される１・４−シクロヘキサンジオール
は、ヒドロキノンの水素添加あるいはｐ−ベンゾキノン
の水素添加によつて製造できるが、一般にはヒドロキノ
ンを水溶媒中で水素添加することにより製造される。1,4-Cyclohexanediol used as a raw material can be produced by hydrogenating hydroquinone or p-benzoquinone, but is generally produced by hydrogenating hydroquinone in an aqueous solvent.
１・４−シクロヘキサンジオールをこのような方法によ
つて製造する場合、ヒドロキノンの−部が残つた状態で
反応を止めて水素添加触媒を濾別除去した後、１・４−
シクロヘキサンジオールを単離することなく反応混合物
をそのまゝ脱水素反応の原料として使用することができ
る。When producing 1,4-cyclohexanediol by such a method, the reaction is stopped with - portion of hydroquinone remaining, and the hydrogenation catalyst is removed by filtration.
The reaction mixture can be used as it is as a raw material for the dehydrogenation reaction without isolating the cyclohexanediol.
本発明による１・４−シクロヘキサンジオールの脱水素
反応には、酸化銅、酸化銅−部化亜鉛、酸化銅一酸化ク
ロム、酸化銅一酸化マンガンから選ばれる脱水素触媒が
用いられる。In the dehydrogenation reaction of 1,4-cyclohexanediol according to the present invention, a dehydrogenation catalyst selected from copper oxide, copper oxide-partial zinc oxide, copper oxide chromium monoxide, and copper oxide manganese monoxide is used.
これらの触媒は単味で使用することもできるが、活性ア
ルミナ、シリカアルミナ、シリカゲル、活性炭あるいは
ケイソウ土などの担体に担持させ使用することもできる
。また、本反応では原料１・４−シクロヘキサンジオー
ルは、水、ベンゼン、シクロヘキサンなどの希釈剤ある
いは窒素、ヘリウム、アルゴンなどのような不活性ガス
で希釈して供給することができる。These catalysts can be used alone, but they can also be supported on a carrier such as activated alumina, silica alumina, silica gel, activated carbon or diatomaceous earth. Further, in this reaction, the raw material 1,4-cyclohexanediol can be supplied diluted with a diluent such as water, benzene, or cyclohexane, or an inert gas such as nitrogen, helium, or argon.
これらの希釈剤のなかでは水がとくに好ましい。反応は
通常１００ないし４００℃、とくに２００ないし３５０
℃で行うのれ゛好ましい。触媒との接触時間は反応温度
によつても異なるが、通常６分ないし０．４秒の範囲が
適当である。１・４−シクロヘキサンジオールに対する
ヒドロキノンの添加量は通常０．１ないし４０モル％、
とくに０．５ないし２０モル％が好ましい。Among these diluents, water is particularly preferred. The reaction is usually carried out at 100 to 400°C, especially 200 to 350°C.
Preferably, it is carried out at ℃. The contact time with the catalyst varies depending on the reaction temperature, but is usually in the range of 6 minutes to 0.4 seconds. The amount of hydroquinone added to 1,4-cyclohexanediol is usually 0.1 to 40 mol%,
Particularly preferred is 0.5 to 20 mol%.
本発明の方法において脱水素反応に添加したヒドロキノ
ンは、反応後常法により反応生成物から分離し、再使用
される。次に、実施例により本発明を具体的に説明する
。Hydroquinone added to the dehydrogenation reaction in the method of the present invention is separated from the reaction product by a conventional method after the reaction and reused. Next, the present invention will be specifically explained with reference to Examples.
実施例１〜３、比較例１石英製気相反応管（内径２８ｍ
ｍ、長さ５５０鼎内に、１２００℃で焼成した球状のα
−アルミナ（直径５７ｎ０３０ｙを充填し、４００℃で
焼成した酸化銅一酸化亜鉛触媒（酸化銅６０％と酸化亜
鉛４０％）６０ｙを充填した後、さらに上記のアルミナ
１５０ｙを充填した。Examples 1 to 3, Comparative Example 1 Quartz gas phase reaction tube (inner diameter 28 m
m, length 550mm, spherical α fired at 1200℃
- Filled with alumina (diameter 57n030y, filled with 60y of copper oxide zinc monoxide catalyst (60% copper oxide and 40% zinc oxide) fired at 400°C, and then filled with 150y of the above alumina.
この気相反応管を電気炉中で２６０℃に保ち、ＧＨＳＶ
５ＯＯｈｒ−１の反応条件で１・４−シクロヘキサンジ
オール５モル％、水４５モル％、１・４−シクロヘキサ
ンジオールに対して第１表に示した濃度のヒドロキノン
、および窒素からなる原料を送入し、８時間の連続運転
を行つた。This gas phase reaction tube was kept at 260°C in an electric furnace, and the GHSV
Under reaction conditions of 5OOhr-1, raw materials consisting of 5 mol% of 1,4-cyclohexanediol, 45 mol% of water, hydroquinone at the concentration shown in Table 1 relative to 1,4-cyclohexanediol, and nitrogen were introduced. It operated continuously for 8 hours.
流出液中の１・４−シクロヘキサンジオンの量をガスク
ロマトグラフイ一によつて定量し、供給した１・４−シ
クロヘキサンジオールに対する収率を第１Ｚ表に示した
。第１表の結果から、ヒドロキノンを添加することによ
り１・４−シクロヘキサンジオンの収率が向上すること
がわかる。The amount of 1,4-cyclohexanedione in the effluent was determined by gas chromatography, and the yield based on the supplied 1,4-cyclohexanediol is shown in Table 1Z. The results in Table 1 show that the addition of hydroquinone improves the yield of 1,4-cyclohexanedione.
実施例４〜５、比較例２〜３
実施例１において、酸化銅一酸化亜鉛系触媒の代わりに
第２表に示した触媒を使用し、１・４−シクロヘキサン
ジオールに対して第２表に示した量のヒドロキノンを添
加して同様に反応を行い、次に示した結果を得た。Examples 4 to 5, Comparative Examples 2 to 3 In Example 1, the catalyst shown in Table 2 was used instead of the copper oxide zinc monoxide catalyst, and the catalyst shown in Table 2 was used for 1,4-cyclohexanediol. A similar reaction was carried out by adding the indicated amount of hydroquinone, and the following results were obtained.
第２表の結果から、酸化銅一亜クロム酸銅あるいは酸化
銅一酸化マンガンの触媒系でも、ヒドロキノンを添加す
ることにより、１・４−シクロヘキサンジオンの収率が
向上することがわかる。From the results in Table 2, it can be seen that the yield of 1,4-cyclohexanedione is improved by adding hydroquinone even in the catalyst system of copper oxide copper monochromite or copper oxide manganese monoxide.
実施例６、比較例４触媒としてＣｕＯ触媒を用い、１・
４−シクロヘキサンジオール５モル％、水８５モル％、
窒素１０モル％の原料をＧＨＳＶ５ＯＯｈｒ−１、２６
０℃の条件で反応させた。Example 6, Comparative Example 4 Using a CuO catalyst as a catalyst, 1.
4-cyclohexanediol 5 mol%, water 85 mol%,
GHSV5OOhr-1, 26 raw material containing 10 mol% nitrogen
The reaction was carried out at 0°C.
Claims (1)
ジオールを酸化銅、酸化銅−酸化亜鉛、酸化銅−酸化ク
ロム、酸化銅−酸化マンガンから選ばれる脱水素触媒と
気相で接触させることを特徴とする１・４−シクロヘキ
サンジオンの製造方法。1. In the presence of hydroquinone, 1,4-cyclohexanediol is brought into contact with a dehydrogenation catalyst selected from copper oxide, copper oxide-zinc oxide, copper oxide-chromium oxide, and copper oxide-manganese oxide in the gas phase. A method for producing 1,4-cyclohexanedione.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP49086019A JPS598248B2 (en) | 1974-07-29 | 1974-07-29 | Method for producing 1,4-cyclohexanedione |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP49086019A JPS598248B2 (en) | 1974-07-29 | 1974-07-29 | Method for producing 1,4-cyclohexanedione |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5116643A JPS5116643A (en) | 1976-02-10 |
| JPS598248B2 true JPS598248B2 (en) | 1984-02-23 |
Family
ID=13874945
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP49086019A Expired JPS598248B2 (en) | 1974-07-29 | 1974-07-29 | Method for producing 1,4-cyclohexanedione |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS598248B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4229364A (en) * | 1979-05-14 | 1980-10-21 | The Procter & Gamble Company | Synthesis of 1,4-bis(dicyanomethylene) cyclohexane |
| JP2765695B2 (en) * | 1989-08-23 | 1998-06-18 | 三井化学株式会社 | Method for producing quinones |
-
1974
- 1974-07-29 JP JP49086019A patent/JPS598248B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5116643A (en) | 1976-02-10 |
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