JPH0541619B2 - - Google Patents
Info
- Publication number
- JPH0541619B2 JPH0541619B2 JP31386986A JP31386986A JPH0541619B2 JP H0541619 B2 JPH0541619 B2 JP H0541619B2 JP 31386986 A JP31386986 A JP 31386986A JP 31386986 A JP31386986 A JP 31386986A JP H0541619 B2 JPH0541619 B2 JP H0541619B2
- Authority
- JP
- Japan
- Prior art keywords
- isopropenyl acetate
- reaction
- acetylacetone
- water
- yield
- 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 - Lifetime
Links
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 20
- HETCEOQFVDFGSY-UHFFFAOYSA-N Isopropenyl acetate Chemical compound CC(=C)OC(C)=O HETCEOQFVDFGSY-UHFFFAOYSA-N 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 230000009466 transformation Effects 0.000 claims description 2
- 238000000034 method Methods 0.000 description 15
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 230000008707 rearrangement Effects 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000001247 metal acetylides Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- 229910001182 Mo alloy Inorganic materials 0.000 description 1
- WDJHALXBUFZDSR-UHFFFAOYSA-M acetoacetate Chemical compound CC(=O)CC([O-])=O WDJHALXBUFZDSR-UHFFFAOYSA-M 0.000 description 1
- 150000001361 allenes Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000002611 lead compounds Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000006462 rearrangement reaction Methods 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000010512 thermal transition Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
〔産業上の利用分野〕
本発明は、イソプロペニルアセテートの気相熱
転移によりアセチルアセトンを製造する方法の改
良に関するものである。
〔従来の技術及び問題点〕
アセチルアセトンを製造する方法として、無水
酢酸とアセト酢酸エステルを反応させる方法、ア
セトンと無水酢酸を反応させる方法、アセトンと
酢酸エチルを縮合させる方法、アセトンとケトン
との反応により得られるイソプロペニルアセテー
トを熱転移させる方法等が挙げられる。この中
で、原材料費の問題、或いはカーボン収支の面か
らイソプロペニルアセテートを原料として熱転位
させる方法が有利であると考えられる。
イソプロペニルアセテートの熱転位によるアセ
チルアセトンの製造法として、空のクロム／鉄
管、ニツケル／クロム管、又は陶製管よりなる反
応器を用いる方法（米国特許第2395800号明細書）
があるが、この方法には低い転化率でしか高い選
択率を得られない他、反応器へ激しく炭化状物が
付着する問題があつた。
この改良法として、金属モリブデンを担体へ担
持した触媒又はモリブデン／鉄よりなる合金の旋
削屑を触媒とし、反応させる方法（ドイツ特許第
1001249号）が提案され、この方法により収率が
高められる結果となつた。しかしながら、こうし
たた固体触媒を用いた場合、炭化状物の付着が緩
和されるとはいえ、触媒壁への付着の問題が残り
活性が著しく失われることとなる。
また、添加剤として鉛化合物を用いる方法（特
公昭50−30604号公報）が提案された。しかしな
がら、こうした添加剤は強い毒性があり、その添
加方法、或いは反応液精製の際の残渣処理方法に
問題があつた。
〔問題点を解決するための手段〕
而して本発明者は、イソプロペニルアセテート
の熱転位によりアセチルアセトンを製造する方法
に於いて、収率を改善し、炭化物の付着を防止
し、かつ取り扱いの容易な添加剤を探索すべく鋭
意検討を重ねた。この結果全く意外なことに、水
が非常に効果のあることを発見するに至つた。
即ち本発明は、イソプロペニルアセテートを
400〜600℃で気相熱転移させ、アセチルアセトン
を製造するに当たり、イソプロペニルアセテート
に対し重量基準で１％以上の水を添加して反応を
行うことを特徴とするアセチルアセトンの製造方
法に関するものである。
イソプロペニルアセテートの熱転位反応は分子
内転位機構であると考えられ、イソプロペニルア
セテート濃度に関する一次反応速度式が成立す
る。この一次反応速度定数に関し、イソプロペニ
ルアセテートに対して重量基準で５％の水を添加
した場合と、添加しなかつた場合の比較を表−１
に示した。
[Industrial Field of Application] The present invention relates to an improvement in a method for producing acetylacetone by vapor phase thermal transformation of isopropenyl acetate. [Prior art and problems] Methods for producing acetylacetone include a method of reacting acetic anhydride and acetoacetate, a method of reacting acetone and acetic anhydride, a method of condensing acetone and ethyl acetate, and a method of reacting acetone with ketone. Examples include a method of thermally transferring isopropenyl acetate obtained by. Among these, a method of thermally rearranging isopropenyl acetate using isopropenyl acetate as a raw material is considered to be advantageous from the viewpoint of raw material cost or carbon balance. A method for producing acetylacetone by thermal rearrangement of isopropenyl acetate using a reactor made of an empty chromium/iron tube, nickel/chromium tube, or ceramic tube (U.S. Pat. No. 2,395,800)
However, in addition to being able to obtain high selectivity only at low conversion rates, this method also had the problem of severe adhesion of char to the reactor. As an improved method, a reaction is carried out using a catalyst in which metal molybdenum is supported on a carrier or turning scraps of a molybdenum/iron alloy as a catalyst (German patent No.
No. 1001249) was proposed, and this method resulted in an increased yield. However, when such a solid catalyst is used, although the adhesion of charred substances is alleviated, the problem of adhesion to the catalyst wall remains, resulting in a significant loss of activity. Furthermore, a method using a lead compound as an additive (Japanese Patent Publication No. 30604/1983) was proposed. However, these additives have strong toxicity, and there are problems with the method of adding them or the method of treating the residue during purification of the reaction solution. [Means for Solving the Problems] Therefore, the present inventor has developed a method for producing acetylacetone by thermal rearrangement of isopropenyl acetate, which improves the yield, prevents the adhesion of carbides, and reduces handling. We conducted extensive research to find a simple additive. This led to the discovery, quite unexpectedly, that water was extremely effective. That is, the present invention uses isopropenyl acetate.
This invention relates to a method for producing acetylacetone, which is characterized in that the reaction is carried out by adding 1% or more water on a weight basis to isopropenyl acetate in producing acetylacetone through gas phase thermal transition at 400 to 600°C. . The thermal rearrangement reaction of isopropenyl acetate is considered to be an intramolecular rearrangement mechanism, and a first-order reaction rate equation regarding the isopropenyl acetate concentration is established. Regarding this first-order reaction rate constant, Table 1 shows a comparison between when 5% water is added to isopropenyl acetate on a weight basis and when it is not added.
It was shown to.
本発明の方法、即ちイソプロペニルアセテート
と共に水を供給して反応させる方法により収率が
著しく向上する他、炭化物の付着も全くなくなつ
た。更に空時収率を向上させることが可能となつ
た。
〔実施例〕
以下、実施例により本発明を説明するが、本発
明はこれらの実施例に限定されるものではない。
実施例 １
ステンレス製の蒸発器、内径10mmで長さ50cmの
電気的に加熱できるステンレス製予熱器、及び電
気的に保温できる内径10mmで長さ２ｍのステンレ
ス製反応器、更に球面形及びび蛇管形の組み合わ
せよりなる冷却器、反応液受容器からなる実験装
置を用い、イソプロペニルアセテート400ｇ／Ｈ、
水20ｇ／Ｈを蒸発器へ供給した。反応温度を530
℃に保ちながら運転を行つたところ、反応液406
ｇ／Ｈを得た。またCO、CO2、アレン、メタン
等からなるガス生成物が14ｇ／Ｈ得られた。
反応液中、未反応イソプロペニルアセテートは
38ｇ／Ｈであり、アセチルアセトン含量は302
ｇ／Ｈであつた。このことから、反応の転化率は
90.5％、選択率83.4％、収率75.5％であつた。
実施例 ２
実施例１と同じ装置を用い、イソプロペニルア
セテート500ｇ／Ｈ、水25ｇ／Ｈを蒸発器へ供給
した。反応温度を530℃に保ちながら運転を行つ
たところ、反応液513ｇ／Ｈを得た。ガス生成物
は12ｇ／Ｈ得られた。
反応液中未反応イソプロペニルアセテートは94
ｇ／Ｈであり、アセチルアセトン含量は346ｇ／
Ｈであつた。このことから、反応の転化率は81.2
％、選択率85.3％、収率69.3％であつた。
実施例１の条件と併せて、約２週間の運転でも
閉塞等のトラブルは全く起きなかつた。
比較例 １
水の供給を止めたこと以外、実施例１と同様の
処理を行つた。反応液396ｇ／Ｈの他、ガス生成
物20ｇ／Ｈを得た。
反応液中未反応イソプロペニルアセテートは82
ｇ／Ｈであり、アセチルアセトン含量は231ｇ／
Ｈであつた。このことから、反応の転化率は79.5
％であり、選択率72.6％、収率57.7％であつた。
この運転を始めて、半日後に蒸発器内圧力が
徐々に上昇を始めた。１日後に運転を停止し、反
応器から冷却器を点検したところ、反応器内部に
約１mmの炭化物が付着しており、反応器出口付近
から冷却器の間の配置に固い炭化状物がぎつしり
と詰まつていた。
By the method of the present invention, that is, the method of supplying water together with isopropenyl acetate for reaction, not only the yield was significantly improved, but also the adhesion of carbides was completely eliminated. Furthermore, it became possible to improve the space-time yield. [Examples] The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples. Example 1 A stainless steel evaporator, an electrically heated stainless steel preheater with an internal diameter of 10 mm and a length of 50 cm, a stainless steel reactor with an internal diameter of 10 mm and a length of 2 m that can be electrically insulated, and a spherical and serpentine tube. Using an experimental device consisting of a condenser with a combination of shapes and a reaction liquid receiver, 400 g/h of isopropenyl acetate,
20 g/H of water was fed to the evaporator. Reaction temperature 530
When the operation was carried out while keeping the temperature at ℃, the reaction solution was 406
g/H was obtained. Additionally, 14 g/h of gas products consisting of CO, CO 2 , allene, methane, etc. was obtained. In the reaction solution, unreacted isopropenyl acetate is
38g/H, and the acetylacetone content is 302
g/H. From this, the conversion rate of the reaction is
The selectivity was 83.4%, and the yield was 75.5%. Example 2 Using the same equipment as in Example 1, 500 g/H of isopropenyl acetate and 25 g/H of water were supplied to the evaporator. When the operation was carried out while maintaining the reaction temperature at 530°C, 513 g/H of reaction liquid was obtained. 12 g/h of gas product was obtained. Unreacted isopropenyl acetate in the reaction solution was 94
g/H, and the acetylacetone content is 346 g/H.
It was H. From this, the conversion rate of the reaction is 81.2
%, selectivity was 85.3%, and yield was 69.3%. Under the conditions of Example 1, no troubles such as blockages occurred even after about two weeks of operation. Comparative Example 1 The same treatment as in Example 1 was carried out except that the water supply was stopped. In addition to 396 g/H of reaction liquid, 20 g/H of gas product was obtained. Unreacted isopropenyl acetate in the reaction solution is 82
g/H, and the acetylacetone content is 231 g/H.
It was H. From this, the conversion rate of the reaction is 79.5
%, selectivity was 72.6%, and yield was 57.7%. Half a day after starting this operation, the pressure inside the evaporator started to rise gradually. When the operation was stopped one day later and the cooler was inspected, it was found that about 1 mm of char had adhered inside the reactor, and there was hard char in the area between the reactor outlet and the cooler. It was tightly packed.
Claims (1)
相熱転移させ、アセチルアセトンを製造するるに
当たり、イソプロペニルアセテートに対し重量基
準で１％以上の水を添加して反応を行うことを特
徴とするアセチルアセトンの製造方法。1. A method for producing acetylacetone, which is characterized in that when producing acetylacetone by subjecting isopropenyl acetate to gas phase thermal transformation at 400 to 600°C, the reaction is carried out by adding 1% or more water on a weight basis to isopropenyl acetate. Production method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31386986A JPS63159337A (en) | 1986-12-24 | 1986-12-24 | Production of acetylacetone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31386986A JPS63159337A (en) | 1986-12-24 | 1986-12-24 | Production of acetylacetone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63159337A JPS63159337A (en) | 1988-07-02 |
| JPH0541619B2 true JPH0541619B2 (en) | 1993-06-24 |
Family
ID=18046482
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP31386986A Granted JPS63159337A (en) | 1986-12-24 | 1986-12-24 | Production of acetylacetone |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63159337A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19938341A1 (en) | 1999-08-13 | 2001-02-22 | Wacker Chemie Gmbh | Production of 1,3-diketone, especially acetyl-acetone, involves thermal rearrangement of enol-ester in a special tubular reactor which is only heated over part of its length and insulated over the rest |
-
1986
- 1986-12-24 JP JP31386986A patent/JPS63159337A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63159337A (en) | 1988-07-02 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313532 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| EXPY | Cancellation because of completion of term |