JPH0621085B2 - Method for producing 2,5-dimethyl-2,4-hexadiene - Google Patents
Method for producing 2,5-dimethyl-2,4-hexadieneInfo
- Publication number
- JPH0621085B2 JPH0621085B2 JP61145563A JP14556386A JPH0621085B2 JP H0621085 B2 JPH0621085 B2 JP H0621085B2 JP 61145563 A JP61145563 A JP 61145563A JP 14556386 A JP14556386 A JP 14556386A JP H0621085 B2 JPH0621085 B2 JP H0621085B2
- Authority
- JP
- Japan
- Prior art keywords
- hexadiene
- dimethyl
- catalyst
- producing
- 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.)
- 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
- 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】 ＜産業上の利用分野＞ 本発明はイソブチレンおよび／またはターシャリーブチ
ルアルコールとイソブチルアルデヒドから2,5-ジメチル
-2,4-ヘキサジエンを製造する方法に係るものである。
2,5-ジメチル-2,4-ヘキサジエンは農薬、殺虫剤、医薬
あるいは各種有機合成の中間体として非常に有用なもの
である。DETAILED DESCRIPTION OF THE INVENTION <Industrial field of application> The present invention relates to 2,5-dimethyl from isobutylene and / or tertiary butyl alcohol and isobutyraldehyde.
It relates to a method for producing -2,4-hexadiene.
2,5-Dimethyl-2,4-hexadiene is very useful as a pesticide, an insecticide, a medicine or an intermediate for various organic syntheses.
＜従来の技術＞ イソブチレンおよび／またはターシャリーブチルアルコ
ールとイソブチルアルデヒドから2,5-ジメチル-2,4-ヘ
キサジエンを製造する方法としては鉱酸、スルホン酸、
ヘテロポリ酸等を触媒として液相加圧下に反応させる方
法が知られている （特開昭48-34108号公報）。<Prior Art> As a method for producing 2,5-dimethyl-2,4-hexadiene from isobutylene and / or tertiary butyl alcohol and isobutyraldehyde, mineral acid, sulfonic acid,
A method is known in which a reaction is carried out under pressure in a liquid phase using a heteropoly acid or the like as a catalyst (JP-A-48-34108).
しかしながらこの方法では2,5ジメチル-2,4-ヘキサジエ
ンの収率は40％以下と低く、多量の副生物が生成する。
また鉱酸、スルホン酸等は材質に対する腐食性が強く、
材質腐食によるトラブルに常に注意して運転しなければ
ならない欠点があった。However, with this method, the yield of 2,5 dimethyl-2,4-hexadiene is as low as 40% or less, and a large amount of by-products are produced.
In addition, mineral acids, sulfonic acids, etc. are highly corrosive to materials,
There was a drawback in that the driver had to always pay attention to troubles due to material corrosion.
＜本発明が解決しようとする問題点＞ 本発明はイソブチレンおよび／またはターシャリーブチ
ルアルコールとイソブチルアルデヒドから2,5-ジメチル
-2,4-ヘキサジエンを製造する方法において、従来の技
術の欠点、即ち副生成物が多量に生成し収率が低いこ
と、装置の材質に対する腐食性が強いこと等の問題点を
解決し、収率よく2,5-ジメチル-2,4-ヘキサジエンを得
る工業的に有利な方法を提供しようとするものである。<Problems to be Solved by the Present Invention> The present invention uses 2,5-dimethyl from isobutylene and / or tertiary butyl alcohol and isobutyraldehyde.
In the method of producing -2,4-hexadiene, the drawbacks of the conventional technology, namely, the problem that the yield is low and a large amount of by-products are produced, and that the material of the device is highly corrosive, It is intended to provide an industrially advantageous method for obtaining 2,5-dimethyl-2,4-hexadiene in good yield.
＜問題点を解決するための手段＞ 本発明者らはイソブチレンおよび／またはターシャリー
ブチルアルコールとイソブチルアルデヒドから2,5-ジメ
チル-2,4-ヘキサジエンを収率よく得るための工業的に
有利な方法について鋭意研究を行ない本発明に到達した
ものである。すなわち本発明は イソブチレンおよび／またはターシャリーブチルアルコ
ールとイソブチルアルデヒドを触媒の存在下に反応させ
2,5-ジメチル-2,4-ヘキサジエンを製造する方法におい
て150〜350℃の温度範囲、気相条件下で、触媒としてニ
オブ酸と炭素から構成される成型粒状触媒を用いること
を特徴とする2,5-ジメチル-2,4-ヘキサジエンの製造方
法である。<Means for Solving Problems> The present inventors have an industrial advantage for obtaining 2,5-dimethyl-2,4-hexadiene in good yield from isobutylene and / or tertiary butyl alcohol and isobutyraldehyde. The present invention has been achieved through intensive research on the method. That is, the present invention involves reacting isobutylene and / or tertiary butyl alcohol with isobutyraldehyde in the presence of a catalyst.
A method for producing 2,5-dimethyl-2,4-hexadiene is characterized by using a molded granular catalyst composed of niobic acid and carbon as a catalyst under a temperature range of 150 to 350 ° C. under a gas phase condition. This is a method for producing 2,5-dimethyl-2,4-hexadiene.
本発明方法に用いられる原料はイソブチレンおよび／ま
たはターシャリーブチルアルコールとイソブチルアルデ
ヒドである。イソブチレンはその純度について特に制約
を受けることはなく、純度の高いイソブチレンをそのま
ま用いてもよく、あるいはいわゆるスペントＢ−Ｂ留分
として取得されるものを用いてもよい。ターシャリーブ
チルアルコールについても同様に純度について特に制約
を受けることはない。また原料としてイソブチレンとタ
ーシャリーブチルアルコールの混合物を使用することも
できる。イソブチルアルデヒドについてもその純度につ
いて特に制約を受けることはない。The raw materials used in the method of the present invention are isobutylene and / or tertiary butyl alcohol and isobutyraldehyde. The purity of isobutylene is not particularly limited, and high-purity isobutylene may be used as it is, or may be obtained as a so-called spent BB fraction. Similarly, there is no particular restriction on the purity of tertiary butyl alcohol. It is also possible to use a mixture of isobutylene and tertiary butyl alcohol as a raw material. Isobutyraldehyde is not particularly limited in its purity.
イソブチレンまたはターシャリーブチルアルコールとイ
ソブチルアルデヒドとの比率あるいはイソブチレンとタ
ーシャリーブチルアルコールの混合物とイソブチルアル
デヒドとの比率は任意に選択することができるが、イソ
ブチルアルデヒドに対するイソブチレンまたはターシャ
リーブチルアルコールあるいはイソブチレンとターシャ
リーブチルアルコールの混合物がモル比１〜10の範囲が
もっとも有効に用いられる。The ratio of isobutylene or tertiary butyl alcohol to isobutyraldehyde or the ratio of a mixture of isobutylene and tertiary butyl alcohol and isobutyraldehyde can be arbitrarily selected. A mixture of butyl alcohol is most effectively used in a molar ratio range of 1-10.
本発明方法に用いられる触媒はニオブ惨と炭素から構成
される成型粒状触媒である。我々は先にニオブ酸を触媒
として用いることにより2,5-ジメチル-2,4-ヘキサジエ
ンが収率よく得られることを見いだしたが、このニオブ
酸と炭素とを混合して成型した成型粒状触媒を用いるこ
とにより2,5-ジメチル-2,4-ヘキサジエンの収率がさら
に向上することを見い出したものである。The catalyst used in the method of the present invention is a molded granular catalyst composed of niobium and carbon. We previously found that 2,5-dimethyl-2,4-hexadiene can be obtained in good yield by using niobic acid as a catalyst.However, a molded granular catalyst formed by mixing niobic acid and carbon was molded. It has been found that the yield of 2,5-dimethyl-2,4-hexadiene is further improved by using.
炭素としては、好ましくはグラファイトが用いられる。
また炭素の含有率は、ニオブ酸に対して０．２〜５重量
％の範囲が好ましい。炭素の含有率がニオブ酸に対して
０．２重量％以下では2,5-ジメチル-2,4-ヘキサジエン
生成選択率の向上効果はそれほど大きくない。また炭素
の含有率がニオブ酸に対して５重量％以上では強度のあ
る成型触媒が得難くなるという欠点が発生する。Graphite is preferably used as carbon.
Further, the carbon content is preferably in the range of 0.2 to 5% by weight with respect to niobic acid. When the carbon content is 0.2% by weight or less with respect to niobic acid, the effect of improving the selectivity for forming 2,5-dimethyl-2,4-hexadiene is not so large. On the other hand, if the carbon content is 5% by weight or more with respect to niobic acid, it becomes difficult to obtain a molded catalyst having high strength.
触媒の調製方法は通常粉末状のニオブ酸と炭素とを混合
した後、打錠成型機、圧縮成型機、ペレタイザーなどに
よって調製される。この成型粒状触媒は、いかなる形状
のものでも差支えがないが、通常錠剤状、ペレット状、
班状などに成型されており、その粒径は通常0.5mm、以
上好ましくは１〜10mmの範囲である。The catalyst is usually prepared by mixing powdery niobic acid and carbon and then using a tabletting machine, a compression machine, a pelletizer or the like. The molded granular catalyst may be of any shape, but is usually in the form of tablets, pellets,
It is formed into a plaque or the like, and the particle size thereof is usually 0.5 mm, preferably 1 to 10 mm.
本発明方法は気相で反応が行なわれる。反応温度は150
〜350℃の温度範囲が有効に用いられ、好ましくは200〜
300℃の温度範囲が用いられる。反応温度が350℃以上に
なると重合物等の高沸点物の生成が多くなり、また反応
温度が150℃以下になると反応速度が非常に遅くなる。
反応応力は反応系が気相に保たれる圧力であれば特に限
定されないが、通常は大気圧ないし加圧条件下で反応が
行なわれ、好ましくは２〜10絶対気圧の圧力範囲で反応
が行なわれる。In the method of the present invention, the reaction is carried out in the gas phase. Reaction temperature is 150
~ 350 ℃ temperature range is effectively used, preferably 200 ~
A temperature range of 300 ° C is used. When the reaction temperature is 350 ° C. or higher, the amount of high-boiling substances such as polymers is increased, and when the reaction temperature is 150 ° C. or lower, the reaction rate becomes very slow.
The reaction stress is not particularly limited as long as it is a pressure at which the reaction system is kept in a gas phase, but usually the reaction is carried out under atmospheric pressure or pressurized conditions, preferably in the pressure range of 2 to 10 absolute atmospheres. Be done.
反応形式としては成型粒状触媒が充填された充填層に原
料を連続的に供給するいわゆる固定床流通反応型の形式
が一般的に採用される。As a reaction system, a so-called fixed bed flow reaction system in which the raw materials are continuously supplied to a packed bed filled with a molded granular catalyst is generally adopted.
以下に実施例によって本発明方法をさらに具体的に説明
するが、本発明の範囲はこれによって制限を受けるもの
ではない。Hereinafter, the method of the present invention will be described more specifically with reference to Examples, but the scope of the present invention is not limited thereto.
＜実施例＞ 実施例１ ニオブ酸（CBMM社製）に対して１．０重量％のカーボン
グラファイトを混合した後、打錠機で成型し、直径3m
m、高さ3mmの円柱状成型触媒を製作した。<Example> Example 1 1.0% by weight of carbon graphite was mixed with niobic acid (manufactured by CBMM), followed by molding with a tableting machine to obtain a diameter of 3 m.
A cylindrical molded catalyst with m and height of 3 mm was manufactured.
この触媒40mlを反応管径23mmのSUS製反応管に充填し、
反応管を電気炉で270℃に加熱した。この反応管にイソ
ブチレン44.8g/hrで、イソブチルアルデヒドを14.4g/hr
で通じ、反応応力３kg/cm2（ゲージ圧）で反応を行っ
た。反応器を出たガスは常圧に減圧した後、ドライアイ
ス−メタノールで冷却した。このようにして得られた反
応液をガスクロマトグラフィーで分析した。40 ml of this catalyst was filled in a SUS reaction tube with a reaction tube diameter of 23 mm,
The reaction tube was heated to 270 ° C. in an electric furnace. Isobutylene 44.8 g / hr and isobutyraldehyde 14.4 g / hr in this reaction tube.
The reaction was performed with a reaction stress of 3 kg / cm 2 (gauge pressure). The gas leaving the reactor was depressurized to normal pressure and then cooled with dry ice-methanol. The reaction liquid thus obtained was analyzed by gas chromatography.
反応開始８時間後のイソブチルアルデヒドの転化率は9
3.2％、2,5-ジメチル-2,4-ヘキサジエンの選択率は78.4
％、収率は73.1であった。The conversion of isobutyraldehyde 8 hours after the start of the reaction was 9
3.2%, the selectivity of 2,5-dimethyl-2,4-hexadiene is 78.4
%, And the yield was 73.1.
実施例２〜４、比較例１ ニオブ酸に対するカーボングラファイトの含有率を第１
表に記載した値にする以外は実施例１に記載したのと同
じ方法で円柱状成型触媒は調製しかつ、実施例１に記載
したのと同じ条件で反応及び分析を行い、第１票成績欄
に記載した結果を得た。Examples 2 to 4 and Comparative Example 1 The content ratio of carbon graphite to niobic acid was first
A cylindrical molded catalyst was prepared by the same method as described in Example 1 except that the values shown in the table were used, and the reaction and analysis were performed under the same conditions as described in Example 1, and the results of the first vote The results given in the column were obtained.
なお第１表に示す反応成績は反応開始８時間後の値であ
り、また転化率はイソブチルアルデヒドの転化率、選択
率および収率は2,5-ジメチル-2,4-ヘキサジエンの選択
率と収率である。The reaction results shown in Table 1 are the values after 8 hours from the start of the reaction, and the conversion is the conversion of isobutyraldehyde, the selectivity and the yield are those of 2,5-dimethyl-2,4-hexadiene. The yield.
＜発明の効果＞ ニオブ酸触媒の担体として、グラファイトを用いること
により、一層選択率が向上し高い収率が得られるように
なった。 <Effects of the Invention> By using graphite as the carrier of the niobate catalyst, the selectivity is further improved and a high yield can be obtained.
Claims (3)
ブチルアルコールとイソブチルアルデヒドを触媒の存在
下に反応させ２，５−ジメチル−２，４−ヘキサジエン
を製造する方法において150〜350℃の温度範囲、気相条
件下で、触媒としてニオブ酸と炭素から構成される成型
粒状触媒を用いることを特徴とする２，５−ジメチル−
２，４−ヘキサジエンの製造方法。1. A method for producing 2,5-dimethyl-2,4-hexadiene by reacting isobutylene and / or tertiary butyl alcohol with isobutyraldehyde in the presence of a catalyst, in the temperature range of 150 to 350 ° C., gas phase 2,5-dimethyl-characterized by using a molded granular catalyst composed of niobic acid and carbon as a catalyst under the conditions
A method for producing 2,4-hexadiene.
徴とする特許請求の範囲第１項に記載の２，５−ジメチ
ル−２，４−ヘキサジエンの製造方法。2. The method for producing 2,5-dimethyl-2,4-hexadiene according to claim 1, wherein graphite is used as carbon.
て0.2〜５重量％の範囲にある成型粒状触媒を用いるこ
とを特徴とする特許請求の範囲第１項または第２項に記
載の２，５−ジメチル−２，４−ヘキサジエンの製造方
法。3. A molded granular catalyst having a carbon content in the range of 0.2 to 5% by weight with respect to niobic acid is used as the catalyst, according to claim 1 or 2. Method for producing 2,5-dimethyl-2,4-hexadiene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61145563A JPH0621085B2 (en) | 1986-06-20 | 1986-06-20 | Method for producing 2,5-dimethyl-2,4-hexadiene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61145563A JPH0621085B2 (en) | 1986-06-20 | 1986-06-20 | Method for producing 2,5-dimethyl-2,4-hexadiene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS632936A JPS632936A (en) | 1988-01-07 |
| JPH0621085B2 true JPH0621085B2 (en) | 1994-03-23 |
Family
ID=15388029
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61145563A Expired - Fee Related JPH0621085B2 (en) | 1986-06-20 | 1986-06-20 | Method for producing 2,5-dimethyl-2,4-hexadiene |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0621085B2 (en) |
-
1986
- 1986-06-20 JP JP61145563A patent/JPH0621085B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS632936A (en) | 1988-01-07 |
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