JPS6116251B2 - - Google Patents
Info
- Publication number
- JPS6116251B2 JPS6116251B2 JP54040048A JP4004879A JPS6116251B2 JP S6116251 B2 JPS6116251 B2 JP S6116251B2 JP 54040048 A JP54040048 A JP 54040048A JP 4004879 A JP4004879 A JP 4004879A JP S6116251 B2 JPS6116251 B2 JP S6116251B2
- Authority
- JP
- Japan
- Prior art keywords
- butene
- perfluoro
- oxygen
- present
- mol
- 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
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
本発明は、パーフルオロ−１−ブテンを酸化ア
ルミニウムに接触させてパーフルオロ−２−ブテ
ンを製造する方法の改良に関する。
パーフルオロ−２−ブテンは、噴射剤、重合体
の単量体、たとえばフルオロ炭化水素重合体の改
質単量体として有用であり、また、中間体とし
て、たとえば酸化してトリフルオロ酢酸フルオリ
ドとし、これよりトリフルオロ酢酸を製造する中
間体として有用である。
本発明者等は、パーフルオロ−１−ブテンを触
媒である酸化アルミニウム（シリカアルミナを包
含する）または酸化ニツケルに接触させてパーフ
ルオロ−２−ブテンを製造する方法を開発し、す
でに特許出願を行つている（昭和54年３月31日出
願の特許願(3)）。
しかしながら、この方法においては、反応の経
過とともに転化率が低下する、すなわち触媒の劣
化が認められることを知つた。
本発明の目的は、そのような触媒の劣化を抑
え、長時間反応を継続させる方法を提供すること
にある。
この目的は、パーフルオロ−１−ブテンを酸化
アルミニウム（シリカアルミナを包含する）また
酸化ニツケルに接触させてパーフルオロ−２−ブ
テンを製造するに際し、酸素を存在させることに
より達成される。
酸素の存在により、10時間以内で触媒が劣化す
るのが防止され、100時間以上も活性を持続させ
ることができる。
本発明において、酸素は、酸素自体として存在
させてもよく、また、不活性気体とともに、たと
えば空気の形で存在せしめてもよい。
存在させる酸素の量は、パーフルオロ−１−ブ
テンに対し、少くとも0.1モル％であればよく、
上限は限定されることはないが、200モル％を越
えるのは熱経済上無駄である。酸素の量は、好ま
しくはパーフルオロ−１−ブテンに対し１〜50モ
ル％である。
触媒として使用される酸化アルミニウムは、特
に制限はないが、市販品でもよく、活性化アルミ
ナが好ましい。またシリカアルミナも使用するこ
とができる。
接触に際しては、パーフルオロ−１−ブテンを
適宜のガス体、たとえば窒素、炭酸ガスなどの不
活性ガスで稀釈してもよい。
接触時の温度条件は、150〜400℃、好ましくは
200〜300℃である。150℃より低い場合には変化
率が低く、400℃より高い場合には選択率が低く
なる。
圧力条件は、本発明に係る反応が転位反応であ
るところから理解できるように、ほとんどこれを
考慮に入れる必要はないが、通常は0.1〜10気
圧、好ましくは0.5〜３気圧の圧力または全圧
（稀釈ガス体が存在する場合）が採用される。
パーフルオロ−１−ブテンの空間速度は、他の
条件、特に温度に依存し、他の一般の反応と同じ
く、高温では大きく、低温では小さくとるのがよ
い。一般に30〜1000hr-1が好ましい。
次に実施例および比較例を示し、更に詳しく本
発明の製造法を説明する。
実施例１〜３および比較例１
粒状活性化アルミナ（水沢化学製NeobeadC−
４）を20〜50メツシユに粉砕し、窒素気流中、
400℃で５時間加熱した。
加熱した活性化アルミナ５ｇを長さ0.5m、内
径３mmのガラス製反応管に充填し、電気恒温槽中
で250℃に加熱する。この反応管に、パーフルオ
ロ−１−ブテンを大気圧、空間速度100hr-1で通
じる。この際、パーフルオロ−１−ブテンに対し
酸素を第１表に示す割合で添加し（したがつて全
圧は酸素を添加した分だけ相応して加圧した）、
連続して100時間反応を行つた。排出ガスを所定
時間毎にガスクロマトグラフイで分析した。分析
結果は第１表に示す通りであつた。
The present invention relates to an improvement in a method for producing perfluoro-2-butene by contacting perfluoro-1-butene with aluminum oxide. Perfluoro-2-butene is useful as a propellant, a monomer in polymers, such as a modifying monomer in fluorohydrocarbon polymers, and as an intermediate, such as upon oxidation to trifluoroacetic acid fluoride. , which is useful as an intermediate for producing trifluoroacetic acid. The present inventors have developed a method for producing perfluoro-2-butene by bringing perfluoro-1-butene into contact with a catalyst such as aluminum oxide (including silica alumina) or nickel oxide, and have already filed a patent application for this method. (Patent application (3) filed on March 31, 1972). However, it has been found that in this method, the conversion rate decreases as the reaction progresses, that is, deterioration of the catalyst is observed. An object of the present invention is to provide a method for suppressing such catalyst deterioration and allowing the reaction to continue for a long time. This objective is achieved by the presence of oxygen when contacting perfluoro-1-butene with aluminum oxide (including silica alumina) or nickel oxide to produce perfluoro-2-butene. The presence of oxygen prevents the catalyst from deteriorating within 10 hours and allows it to remain active for more than 100 hours. In the present invention, oxygen may be present as oxygen itself or together with an inert gas, for example in the form of air. The amount of oxygen present may be at least 0.1 mol% based on perfluoro-1-butene,
There is no upper limit, but exceeding 200 mol% is wasteful from a thermoeconomic standpoint. The amount of oxygen is preferably 1 to 50 mol%, based on perfluoro-1-butene. Aluminum oxide used as a catalyst is not particularly limited, but commercially available products may be used, and activated alumina is preferred. Silica alumina can also be used. During the contact, perfluoro-1-butene may be diluted with an appropriate gas, for example, an inert gas such as nitrogen or carbon dioxide. The temperature condition during contact is 150-400℃, preferably
The temperature is 200-300℃. When the temperature is lower than 150°C, the rate of change is low, and when it is higher than 400°C, the selectivity is low. As can be understood from the fact that the reaction according to the present invention is a rearrangement reaction, there is almost no need to take pressure conditions into consideration, but it is usually a pressure of 0.1 to 10 atm, preferably 0.5 to 3 atm, or a total pressure. (if a diluting gas is present) is adopted. The space velocity of perfluoro-1-butene depends on other conditions, especially temperature, and as with other general reactions, it is best to set it high at high temperatures and low at low temperatures. Generally 30 to 1000 hr -1 is preferred. Next, Examples and Comparative Examples will be shown to explain the manufacturing method of the present invention in more detail. Examples 1 to 3 and Comparative Example 1 Granular activated alumina (NeobeadC- manufactured by Mizusawa Chemical)
4) was crushed into 20 to 50 meshes, and in a nitrogen stream,
It was heated at 400°C for 5 hours. A glass reaction tube with a length of 0.5 m and an inner diameter of 3 mm is filled with 5 g of heated activated alumina, and heated to 250°C in an electric constant temperature bath. Perfluoro-1-butene is passed through the reaction tube at atmospheric pressure and a space velocity of 100 hr -1 . At this time, oxygen was added to perfluoro-1-butene in the proportion shown in Table 1 (therefore, the total pressure was increased accordingly by the amount of oxygen added),
The reaction was carried out continuously for 100 hours. Exhaust gas was analyzed by gas chromatography at predetermined intervals. The analysis results were as shown in Table 1.
【表】【table】
【表】
実施例 ４
粒状シリカアルミナ（SiO2：Al2O3＝60：40
（重量比））を20〜50メツシユに粉砕し、窒素気流
中、400℃で５時間加熱した。
加熱したシリカアルミナ５ｇを長さ0.5m、内
径３mmのパイレツクスガラス管に充填し、250℃
に加熱する。このガラス管に、パーフルオロ−１
−ブテンおよびこれに対し３モル％の酸素を、大
気圧、空間速度50hr-1で100時間連続して通じ、
反応を行つた。
100時間後の排出ガスの組成は、CO22.2モル
％、パーフルオロ−２−ブテン97.8モル％および
パーフルオロ−１−ブテン痕跡であつた。[Table] Example 4 Granular silica alumina (SiO 2 :Al 2 O 3 =60:40
(weight ratio)) was pulverized into 20 to 50 meshes and heated at 400° C. for 5 hours in a nitrogen stream. Fill a Pyrex glass tube with a length of 0.5 m and an inner diameter of 3 mm with 5 g of heated silica alumina and heat at 250°C.
Heat to. Perfluoro-1
- passing butene and 3 mol% oxygen thereto continuously for 100 hours at atmospheric pressure and a space velocity of 50 hr -1 ;
The reaction was carried out. The composition of the exhaust gas after 100 hours was 2.2 mol% CO2 , 97.8 mol% perfluoro-2-butene, and traces of perfluoro-1-butene.
Claims (1)
ムに接触させてパーフルオロ−２−ブテンを製造
する際し、酸素を存在させることを特徴とするパ
ーフルオロ−２−ブテンの製造法。 ２ 酸素をパーフルオロ−１−ブテンに対し少く
とも0.1モル％存在させるものである特許請求の
範囲第１項記載の製造法。 ３ 酸素をパーフルオロ−１−ブテンに対し0.1
〜200モル％存在させるものである特許請求の範
囲第２項記載の製造法。[Claims] 1. A method for producing perfluoro-2-butene, characterized in that oxygen is present when producing perfluoro-2-butene by contacting perfluoro-1-butene with aluminum oxide. . 2. The method according to claim 1, wherein oxygen is present in an amount of at least 0.1 mol % based on perfluoro-1-butene. 3 Oxygen to perfluoro-1-butene 0.1
The manufacturing method according to claim 2, wherein the amount is present in an amount of ~200 mol%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4004879A JPS55133321A (en) | 1979-04-02 | 1979-04-02 | Preparation of perfluoro-2-butene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4004879A JPS55133321A (en) | 1979-04-02 | 1979-04-02 | Preparation of perfluoro-2-butene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS55133321A JPS55133321A (en) | 1980-10-17 |
| JPS6116251B2 true JPS6116251B2 (en) | 1986-04-28 |
Family
ID=12570022
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4004879A Granted JPS55133321A (en) | 1979-04-02 | 1979-04-02 | Preparation of perfluoro-2-butene |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS55133321A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0362727U (en) * | 1989-10-23 | 1991-06-19 |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7360055B2 (en) * | 2021-07-15 | 2023-10-12 | ダイキン工業株式会社 | Alkene production method |
| JP7799217B1 (en) * | 2024-12-20 | 2026-01-15 | ダイキン工業株式会社 | Method for producing perfluoroalkene compounds and compositions |
-
1979
- 1979-04-02 JP JP4004879A patent/JPS55133321A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0362727U (en) * | 1989-10-23 | 1991-06-19 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS55133321A (en) | 1980-10-17 |
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