JPH0688916B2 - Method for producing vinylcyclohexane - Google Patents
Method for producing vinylcyclohexaneInfo
- Publication number
- JPH0688916B2 JPH0688916B2 JP3318810A JP31881091A JPH0688916B2 JP H0688916 B2 JPH0688916 B2 JP H0688916B2 JP 3318810 A JP3318810 A JP 3318810A JP 31881091 A JP31881091 A JP 31881091A JP H0688916 B2 JPH0688916 B2 JP H0688916B2
- Authority
- JP
- Japan
- Prior art keywords
- vinylcyclohexane
- producing
- selectivity
- catalyst
- vch
- 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 - Fee Related
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
【０００１】[0001]
【産業上の利用分野】本発明はビニルシクロヘキサンの
製造方法に関するものである。更に詳しくは１−シクロ
ヘキシルエタノール（以下ＣＨＥと略す。）の脱水反応
によるビニルシクロヘキサンの製造方法に関するもので
ある。FIELD OF THE INVENTION The present invention relates to a method for producing vinylcyclohexane. More specifically, it relates to a method for producing vinylcyclohexane by dehydration reaction of 1-cyclohexylethanol (hereinafter abbreviated as CHE).
【０００２】[0002]
【従来の技術】本発明の目的は、耐熱性ポリマーの原
料、ポリオレフィン用のコモノマー等として有用なビニ
ルシクロヘキサンの安価な製造方法を提供することにあ
る。従来ビニルシクロヘキサン（以下ＶＣＨと略す）が
ＣＨＥの脱水反応により製造できることは公知である。
例えば、Ｚｈ Ｐｒｉｋｌ−Ｋｈｉｍ．，３９（１
２），２７６６（’６６）．，ｉｂｉｄ．，４３（１
２），２７６９（’７０）．，ｉｂｉｄ．，４５
（２），３９０（’７２）．，Ｎｅｆｔｅｋｈｉｍｉｙ
ａ，９（１），５６（’６９），ｉｂｉｄ．，９
（５），７５３（’６９）．，Ｎｅｆｔｅｐｅｒｅｒａ
ｂ Ｎｅｆｔｅｋｈｉｍ，１９６９（６），３３．等に
よれば各種の触媒を用いて検討されているが、いづれも
ＶＣＨ選択率が非常に低く、副生物としてエチリデンシ
クロヘキサン（以下ＥＤＣと略す）、メチルシクロヘキ
シルケトン（以下ＭＣＫと略す）等が多量に得られてい
る。又、トリウムオキサイドを触媒として用いた場合に
は、ＶＣＨ選択率の高い例が報告されているが、トリウ
ムオキサイドは放射性物質であり、工業触媒として使用
するには安全上非常に問題がある。BACKGROUND OF THE INVENTION An object of the present invention is to provide an inexpensive method for producing vinylcyclohexane which is useful as a raw material for heat resistant polymers, a comonomer for polyolefins, and the like. It is known that vinylcyclohexane (hereinafter abbreviated as VCH) can be produced by a dehydration reaction of CHE.
For example, Zh Prikl-Khim. , 39 (1
2), 2766 ('66). , Ibid. , 43 (1
2), 2769 ('70). , Ibid. , 45
(2), 390 ('72). , Neftekhimy
a, 9 (1), 56 ('69), ibid. , 9
(5), 753 ('69). , Nefteperera
b Neftekhim, 1969 (6), 33. According to et al., Various catalysts have been investigated, but in each case, VCH selectivity is very low, and by-products such as ethylidene cyclohexane (hereinafter abbreviated as EDC) and methyl cyclohexyl ketone (hereinafter abbreviated as MCK) are contained in large amounts. Has been obtained. When thorium oxide is used as a catalyst, it has been reported that the VCH selectivity is high, but thorium oxide is a radioactive substance and is very problematic in safety when used as an industrial catalyst.
【０００３】[0003]
【発明が解決しようとする課題】本発明者らは従来知ら
れていた触媒のこれらの欠点を克服すべく鋭意研究の結
果、酸化ジルコニウムを触媒として用いるとＶＣＨ選択
率が大巾に向上することを見出し、本発明に到達したも
のである。DISCLOSURE OF THE INVENTION The inventors of the present invention have conducted extensive studies to overcome these drawbacks of the conventionally known catalysts, and as a result, the use of zirconium oxide as a catalyst significantly improved the VCH selectivity. And has arrived at the present invention.
【０００４】[0004]
【課題を解決するための手段】すなわち本発明はＣＨＥ
の脱水反応によりＶＣＨを製造する際に触媒として酸化
ジルコニウムを使用することを特徴とするＶＣＨの製造
方法である。本発明で使用する酸化ジルコニウムは各種
の製法で得られるが、中でもジルコニウム化合物を３０
０〜１５００℃で焼成して得られるものが好ましい。こ
の場合、焼成に用いられるジルコニウム化合物の好まし
い例としては水酸化ジルコニウム、水酸化ジルコニル、
硝酸ジルコニウム、硝酸ジルコニル、炭酸ジルコニル、
ジルコニウムアルコキサイド等が挙げられる。これらの
化合物を適当な担体に担持して焼成してもよいし、又、
焼成後の酸化ジルコニウムを適当な担体に担持してもよ
い。もちろん担体を使用せずに焼成後の酸化ジルコニウ
ムそれ自身を触媒として使用するのも好ましい使用例で
ある。必要によっては適当な第二成分、例えばイットリ
ウム、カルシウム、イッテリビウム、マグネシウム化合
物等の共存下に触媒を調製することも可能である。That is, the present invention is CHE
In the method for producing VCH, zirconium oxide is used as a catalyst when VCH is produced by the dehydration reaction. The zirconium oxide used in the present invention can be obtained by various production methods.
The thing obtained by baking at 0-1500 degreeC is preferable. In this case, preferred examples of the zirconium compound used for firing are zirconium hydroxide, zirconyl hydroxide,
Zirconium nitrate, zirconyl nitrate, zirconyl carbonate,
Examples thereof include zirconium alkoxide. These compounds may be carried on a suitable carrier and baked, or
The calcined zirconium oxide may be supported on a suitable carrier. Of course, it is also a preferable example to use zirconium oxide itself as a catalyst without using a carrier. If necessary, the catalyst can be prepared in the coexistence of a suitable second component such as yttrium, calcium, ytterbium, or a magnesium compound.
【０００５】焼成温度は通常３００〜１５００℃である
が、好ましくは５００〜１１００℃が採用される。焼成
時間は通常０．１〜５０時間、好ましくは１〜１０時間
が採用される。一般に焼成温度が高くなると活性は低下
する傾向にあるが、ＶＣＨ選択率は逆に高くなる傾向に
ある。１５００℃を越えると十分な活性が出なくなり
又、３００℃より低いと十分な選択性が出ない。The firing temperature is usually 300 to 1500 ° C., preferably 500 to 1100 ° C. The firing time is usually 0.1 to 50 hours, preferably 1 to 10 hours. Generally, the activity tends to decrease as the firing temperature increases, but the VCH selectivity tends to increase. If it exceeds 1500 ° C, sufficient activity cannot be obtained, and if it is lower than 300 ° C, sufficient selectivity cannot be obtained.
【０００６】次に本発明の実施方法について説明する。
反応方法は特に限定されないが、通常は固定床方式又は
流動床方式の気相反応が採用される。反応温度は通常は
２００〜５００℃が、好ましくは３００〜４００℃が採
用される。又、反応圧力は特に限定されないが通常は常
圧ないし若干の加圧下で実施される。必要によっては原
料ＣＨＥを窒素等の不活性ガスで希釈して反応させる方
法も採用される。原料の供給速度は通常ＬＨＳＶで０．
１〜１５（１／時間）が、好ましくは０．５〜５（１／
時間）が採用される。Next, a method for implementing the present invention will be described.
The reaction method is not particularly limited, but a gas phase reaction of a fixed bed system or a fluidized bed system is usually adopted. The reaction temperature is usually 200 to 500 ° C, preferably 300 to 400 ° C. Although the reaction pressure is not particularly limited, it is usually carried out under normal pressure or slightly increased pressure. If necessary, a method may be adopted in which the raw material CHE is diluted with an inert gas such as nitrogen and reacted. The feed rate of the raw material is usually LHSV of 0.
1 to 15 (1 / hour), preferably 0.5 to 5 (1 / hour)
Time) is adopted.
【０００７】[0007]
【実施例】以下実施例によりさらに詳しく説明するが、
本発明はこれら実施例に限定される訳ではない。 実施例１ 内径１９ｍｍで中心に外径６ｍｍの温度測定用鞘管を有
する硬質ガラス製反応管に、１０〜２４メッシュにそろ
えた水酸化ジルコニウムを１０００℃で２時間焼成して
調製したジルコニア触媒２７ｍｌを充填し、反応管外側
より電気炉にて加熱した。この反応管にＣＨＥ２８ｍｌ
／時間（ＬＨＳＶ＝１．０４（１／時間）、窒素ガス
１．５ｌ／ｍｉｎを常圧にて電気炉で加熱された気化器
を経由して供給した。反応器より出てきた反応ガスをト
ラップして、ガスクロマトグラフで分析した。定常活性
となった時点で、ＣＨＥ転化率９０％、ＶＣＨ選択率９
０％、ＥＤＣ選択率４．５％、ＭＣＫ選択率５．５％で
あった。又、この時の触媒の中心温度は３７６℃であっ
た。約１００時間連続運転を続けたが、活性、選択性は
ほとんど変化しなかった。 実施例２〜９ 実施例１と同様にして各種の触媒、反応条件で実施した
結果を表１に示す。[Examples] The present invention will be described in more detail with reference to the following examples.
The invention is not limited to these examples. Example 1 27 ml of a zirconia catalyst prepared by firing zirconium hydroxide in a hard glass reaction tube having an inner diameter of 19 mm and an outer diameter of 6 mm in the center and a temperature measuring sheath tube, and firing zirconium hydroxide in an amount of 10 to 24 mesh at 1000 ° C. for 2 hours. Was charged and heated from the outside of the reaction tube in an electric furnace. 28 ml of CHE in this reaction tube
/ Hour (LHSV = 1.04 (1 / hour), 1.5 l / min of nitrogen gas was supplied at a normal pressure through a vaporizer heated in an electric furnace. The reaction gas discharged from the reactor was supplied. When trapped and analyzed by gas chromatography, when the activity became steady, CHE conversion was 90% and VCH selectivity was 9
The selectivity was 0%, the EDC selectivity was 4.5%, and the MCK selectivity was 5.5%. The central temperature of the catalyst at this time was 376 ° C. The continuous operation was continued for about 100 hours, but the activity and selectivity hardly changed. Examples 2 to 9 Table 1 shows the results of carrying out under various catalysts and reaction conditions in the same manner as in Example 1.
【０００８】[0008]
【表１】 ---------------------------------------------------------------- 実施例 2 3 4 5 6 7 8 9 触媒 Zr化合物 *1 *1 *1 *1 *1 *1 *2 *3 焼成温度℃ 360 405 510 610 800 900 400 400 焼成時間hr 2 2 2 2 2 2 2 2 CHE 供給量 2.7 2.7 2.8 2.9 1.4 1.3 1.6 2.2 LHSV(hr-1) N 2 供給量 1.5 1.5 1.5 1.5 1.5 1.5 5.3*4 1.5 l/min 触媒中心温度℃ 326 332 332 329 351 372 345 350 転化率% 94 93 87 83 81 93 90 92 選択率% VCH 78 79 80 80 85 87 81 81 EDC 15 15 16 15 9 4 13 15 MCK 7 5 4 5 5 9 5 4 ---------------------------------------------------------------- [Table 1] ---------------------------------------------- ------------------ Example 2 3 4 5 6 7 8 9 Catalyst Zr compound * 1 * 1 * 1 * 1 * 1 * 1 * 2 * 3 Firing temperature ° C 360 405 510 610 800 900 400 400 Baking time hr 2 2 2 2 2 2 2 2 2 CHE supply amount 2.7 2.7 2.8 2.9 1.4 1.3 1.6 2.2 LHSV (hr -1 ) N 2 supply amount 1.5 1.5 1.5 1.5 1.5 1.5 5.3 * 4 1.5 l / min Catalyst center temperature ℃ 326 332 332 329 351 372 345 350 Conversion% 94 93 87 83 81 93 90 92 Selectivity% VCH 78 79 80 80 85 87 81 81 EDC 15 15 16 15 9 4 13 15 MCK 7 5 4 5 5 9 5 4 -------------------------------------------- --------------------
【０００９】*1 Ｚｒ（ＯＨ）4 *2 ＺｒＯ（ＮＯ3 ）2 ・２Ｈ2 Ｏ *3 同上をアルミナに担持（硝酸ジルコニルを無水物換
算で２０ｗｔ％、α−アルミナに担持した） *4 内径２８ｍｍのパイレックス製反応管に触媒１００
ｍｌ充填して反応させた* 1 Zr (OH) 4 * 2 ZrO (NO 3 ) 2 .2H 2 O * 3 Same as above supported on alumina (zirconyl nitrate 20 wt% in terms of anhydride, supported on α-alumina) * 4 Inner diameter Catalyst 100 in a 28 mm Pyrex reaction tube
ml filled and reacted
【００１０】[0010]
【発明の効果】以上説明したとおり、本発明により、Ｖ
ＣＨ選択率を大巾に向上させることができた。As described above, according to the present invention, V
It was possible to greatly improve the CH selectivity.
Claims (2)
によりビニルシクロヘキサンを製造する際に、触媒とし
て酸化ジルコニウムを用いることを特徴とするビニルシ
クロヘキサンの製造方法。1. A method for producing vinylcyclohexane, which comprises using zirconium oxide as a catalyst when producing vinylcyclohexane by dehydration reaction of 1-cyclohexylethanol.
を３００〜１５００℃で焼成して調製したものであるこ
とを特徴とする請求項１記載のビニルシクロヘキサンの
製造方法。2. The method for producing vinylcyclohexane according to claim 1, wherein the zirconium oxide is prepared by calcining a zirconium compound at 300 to 1500 ° C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3318810A JPH0688916B2 (en) | 1991-12-03 | 1991-12-03 | Method for producing vinylcyclohexane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3318810A JPH0688916B2 (en) | 1991-12-03 | 1991-12-03 | Method for producing vinylcyclohexane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH054931A JPH054931A (en) | 1993-01-14 |
| JPH0688916B2 true JPH0688916B2 (en) | 1994-11-09 |
Family
ID=18103200
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3318810A Expired - Fee Related JPH0688916B2 (en) | 1991-12-03 | 1991-12-03 | Method for producing vinylcyclohexane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0688916B2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7999123B2 (en) | 2006-05-23 | 2011-08-16 | Jnc Corporation | 2-oxetanone derivative and process for production thereof |
| JP2011084550A (en) * | 2009-09-17 | 2011-04-28 | Sumitomo Chemical Co Ltd | Method for producing compound having double bond |
| JPWO2017002494A1 (en) * | 2015-07-02 | 2018-04-19 | 昭和電工株式会社 | Method for producing N-vinylcarboxylic acid amide |
| JP2020143018A (en) * | 2019-03-07 | 2020-09-10 | 三井化学株式会社 | Method of producing terminal double bond-containing compound |
| CN112707779B (en) * | 2020-12-26 | 2023-06-30 | 蚌埠中实化学技术有限公司 | Preparation method of vinylcyclohexane |
-
1991
- 1991-12-03 JP JP3318810A patent/JPH0688916B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH054931A (en) | 1993-01-14 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |