JP3541448B2 - Method for producing acetamide - Google Patents
Method for producing acetamide Download PDFInfo
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- JP3541448B2 JP3541448B2 JP20091994A JP20091994A JP3541448B2 JP 3541448 B2 JP3541448 B2 JP 3541448B2 JP 20091994 A JP20091994 A JP 20091994A JP 20091994 A JP20091994 A JP 20091994A JP 3541448 B2 JP3541448 B2 JP 3541448B2
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- catalyst
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- 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
Description
【０００１】
【産業上の利用分野】
本発明は、アセトニトリルと水とを反応させてアセトアミドを製造する方法に関する。
【０００２】
【従来の技術】
アセトニトリルからアセトアミドを製造する方法は、現在までに多数のものが提案されている。例えば、▲１▼水とアルコールの共存下、アセトニトリルを高温で加熱する方法（ＵＳＰ５，１０３，０５５）、▲２▼ＮＨ3の存在下、アセトニトリルをメタノール水溶液とオートクレイブ中で加熱する方法（特開昭５６−３４６３５号）、▲３▼ＣｕとＣｒとを含む酸化物触媒の存在下でアセトニトリルを加水分解する方法（ＵＳＰ３，９９４９７３）、▲４▼Ｃｕ、Ｚｎ、Ａｇなどを含むカチオン交換樹脂の存在下でアセトニトリルを水和する方法（ＵＳＰ３，６７４，８４８）、▲５▼Ｒｕ触媒の存在下でアセトニトリルを水和する方法（Ｊ．Ｏｒｇ．Ｃｈｅｍ．，５７，２５２１−２５２３（１９９２））、▲６▼球状のラネー銅触媒の存在下でアセトニトリルを水和する方法（特開平５−２５５２１４号）などである。
【０００３】
【発明が解決しようとする課題】
しかしながら、これらの方法においては、▲６▼の方法を除けば収率、選択率が充分でなく、また▲６▼の方法を含めてそのほとんどが液相反応を行う方法であるため、反応生成物の分離精製工程を必要とする問題点があった。本発明は、アセトニトリルと水とを気相で反応させ、また副生成物の発生を抑制することができるアセトアミド製造法を提供するものである。
【０００４】
【課題を解決するための手段】
本発明者らは、上記課題を解決するために鋭意研究を行ってきた結果、周期律表の第８族の金属元素を含む有機金属化合物と酸化バナジウムとのクラスター錯体を、好適にはアルミナ、シリカなどの多孔質担体に担持させた触媒の存在下に、アセトニトリルと水とを気相反応させることにより、高選択率で収率良くアセトアミドを製造できることを見いだし、本発明を完成するに至ったものである。以下に本発明の詳細について、実施例とともに説明する。
【０００５】
本発明は、周期律表の第８族の金属元素を含む有機金属化合物と酸化バナジウムとのクラスター錯体を触媒として用いるものであり、該有機金属化合物を構成する第８族金属元素としてはロジウムもしくはイリジウムが、また有機基はペンタメチルシクロペンタジエニル基であることが好ましい。そして、該触媒はアルミナ、シリカなどの多孔質担体に担持させて用いることが特に好ましい。
【０００６】
この多孔質担体担持触媒は次のようにして調製する。すなわち、アルミナ、シリカなどの多孔質担体を、必要に応じて温度１５０〜３００℃で加熱しながら真空排気処理したものを、該クラスター錯体を低沸点の無極性溶媒に溶解した溶液に加えて撹拌し、しかる後減圧下に該溶媒を溜去することによって目的の多孔質担体担持触媒を得る。このままでも充分な触媒活性を有しているが、得られた多孔質担体担持触媒を温度１５０〜２５０℃で真空排気処理することにより更に活性を上げることができる。
【０００７】
該多孔質担体担持触媒中の有機金属含有酸化バナジウムクラスターの含有量は、特に限定されないが、担体の比表面積が１〜１０００ｍ2／ｇであることを考慮すると、０．０１〜６０重量％であることが好ましく、取り扱いの面から５〜３０重量％であることが更に好ましい。
【０００８】
本発明は、このようにして得た多孔質担体担持触媒の充填層にアセトニトリルと水の混合物の蒸気を通過させることによって、アセトニトリルの気相水和反応を行わせるものである。この際の反応温度は、０〜２５０℃、好ましくは２０〜２００℃、更に好ましくは７０〜１５０℃である。２５０℃を超える温度は有機金属含有酸化バナジウムクラスターが分解するため好ましくない。また、低温度域での反応は真空ポンプの機能が充分でありさえすれば反応にはなんら問題がないが、経済的観点から必要以上の低温度域で操作することは避けねばならない。
【０００９】
アセトニトリルと水のモル比は特に限定されない、およそ水１モルに対し、アセトニトリル０．１〜２モル、好ましくは０．５〜１．５モルである。未反応の成分が少ないに越したことはないが、水とアセトニトリルのどちらが過剰成分として残っていても分離精製に問題があるわけではない。
【００１０】
【実施例】
以下に本発明の実施例を示す。
【実施例１】
シリカ粉末１．２５ｇに対し、有機ロジウム含有酸化バナジウム 〔（ＲｈＣ5（ＣＨ3）5）4Ｖ6Ｏ19〕（以下、Ｒｈ−ＶＯと略記する。）クラスター０．２４ｇを適当量のジクロロメタンに溶解し，この溶液を上記シリカ粉末に加え撹拌した。撹拌混合後減圧してジクロロメタンを溜去し、更に２００℃で真空排気処理して、シリカ表面に固定化したＲｈ−ＶＯクラスター触媒を得た。
【００１１】
上記触媒０．１ｇをガラス製反応管に充填し、モル比１：１のアセトニトリルと水を減圧下、ガス状態で該反応管に導入して反応を行った。反応装置は閉鎖系とし、循環ポンプによって反応ガスの反応管への循環を行い、約２０時間接触反応を行わせた。反応温度は１００℃であった。生成したアセトアミドは反応装置内に捕集し、反応終了後装置から取り出してアセトアミド生成の確認を行った。また、ガスクロを用いて生成ガスの分析を行い、副生成物から選択率を、アセトニトリルの消費量から転換率を算出した。表１に反応時の転換率，選択率を示す。
【００１２】
【実施例２，３】
実施例１と同じ触媒を用い、反応温度のみを変えて同じように反応を行った。その結果を表１に示す。
【００１３】
【表１】
【実施例４】
シリカ粉末0.73ｇに対し、有機イリジウム含有酸化バナジウム〔（ＩｒＣ5（ＣＨ3）5）4Ｖ6Ｏ19〕（以下、Ｉｒ−ＶＯと略記する。） クラスター０．２２ｇを適当量のジクロロメタンに溶解し，この溶液を上記シリカ粉末に加え撹拌した。撹拌混合後減圧してジクロロメタンを溜去し、更に２００℃で真空排気処理して、シリカ表面に固定化したＩｒ−ＶＯクラスター触媒を得た。該触媒を用い、実施例１と同様にして反応を行った結果を表２に示す。
【００１５】
【実施例５〜７】
実施例４と同じ触媒を用い、反応温度のみを変えて同じように反応を行った。その結果を表２に示す。
【００１６】
【表２】
【比較例１〜３】
Ｒｈ−ＶＯクラスターをシリカに担持した触媒の代わりに、市販の五酸化バナジウム（０．１ｇ）を用いる他は実施例１と同様にして反応を行った。その結果を表３に示す。
選択性はそう悪くないが、反応性が実施例に比較して非常に低い。
【００１８】
【表３】
【比較例４〜７】
シリカ粉末１．００ｇに対し、第８族元素を含有しない酸化バナジウムクラスター〔（ｎ−Ｃ4Ｈ9）3Ｎ〕3（Ｖ10０28Ｈ3）（以下、ＶＯと略記する。） ０．１６ｇを適当量のジクロロメタンに溶解し，この溶液を上記シリカ粉末に加え撹拌した。撹拌混合後減圧してジクロロメタンを溜去し、更に２００℃で真空排気処理して、シリカ表面に固定化したＶＯクラスター触媒を得た。該触媒を用いて実施例１と同様にして反応を行った結果を表４に示す。アセトニトリルは消費されても、アセトアミドの生成は全く認められなかった。
【００２０】
【表４】
【発明の効果】
本発明により、高選択率で収率良くアセトアミドを製造することができる。[0001]
[Industrial applications]
The present invention relates to a method for producing acetamide by reacting acetonitrile with water.
[0002]
[Prior art]
Many methods for producing acetamide from acetonitrile have been proposed to date. For example, (1) a method of heating acetonitrile at a high temperature in the coexistence of water and alcohol (US Pat. No. 5,103,055), and (2) a method of heating acetonitrile in an aqueous methanol solution and an autoclave in the presence of NH 3 (particularly). (3) A method of hydrolyzing acetonitrile in the presence of an oxide catalyst containing Cu and Cr (US Pat. No. 3,994,973); (4) A cation exchange resin containing Cu, Zn, Ag, etc. (US Pat. No. 3,674,848), (5) Method of hydrating acetonitrile in the presence of Ru catalyst (J. Org. Chem., 57, 2521-2523 (1992)) And (6) a method of hydrating acetonitrile in the presence of a spherical Raney copper catalyst (JP-A-5-255214).
[0003]
[Problems to be solved by the invention]
However, in these methods, the yield and selectivity are not sufficient except for the method (6), and most of the methods, including the method (6), involve a liquid phase reaction. There is a problem that requires a step of separating and purifying the product. The present invention provides a method for producing acetamide, which allows acetonitrile and water to react in a gas phase and suppresses generation of by-products.
[0004]
[Means for Solving the Problems]
The present inventors have conducted intensive studies to solve the above problems, and as a result, a cluster complex of an organometallic compound containing a metal element of Group 8 of the periodic table and vanadium oxide, preferably alumina, In the presence of a catalyst supported on a porous carrier such as silica, it has been found that acetamide can be produced with a high selectivity and a high yield by performing a gas phase reaction between acetonitrile and water, thereby completing the present invention. Things. Hereinafter, details of the present invention will be described together with examples.
[0005]
The present invention uses, as a catalyst, a cluster complex of an organometallic compound containing a metal element belonging to Group 8 of the periodic table and vanadium oxide, and as the Group 8 metal element constituting the organometallic compound, rhodium or Preferably, iridium and the organic group are pentamethylcyclopentadienyl groups. It is particularly preferable to use the catalyst supported on a porous carrier such as alumina or silica.
[0006]
This catalyst supported on a porous carrier is prepared as follows. That is, a porous carrier such as alumina or silica, which is subjected to vacuum evacuation while heating at a temperature of 150 to 300 ° C. as necessary, is added to a solution in which the cluster complex is dissolved in a low-boiling nonpolar solvent, and stirred. Thereafter, the solvent is distilled off under reduced pressure to obtain a desired catalyst supported on a porous carrier. Although the catalyst has sufficient catalytic activity as it is, the activity can be further increased by subjecting the obtained porous carrier-supported catalyst to a vacuum exhaust treatment at a temperature of 150 to 250 ° C.
[0007]
The content of the organometallic-containing vanadium oxide cluster in the porous carrier-supported catalyst is not particularly limited, but is 0.01 to 60% by weight in consideration that the specific surface area of the carrier is 1 to 1000 m2 / g. It is more preferably 5 to 30% by weight from the viewpoint of handling.
[0008]
In the present invention, a vapor phase of a mixture of acetonitrile and water is caused to pass through the packed bed of the thus obtained porous carrier-supported catalyst, thereby causing a gas phase hydration reaction of acetonitrile. The reaction temperature at this time is 0 to 250 ° C, preferably 20 to 200 ° C, more preferably 70 to 150 ° C. A temperature exceeding 250 ° C. is not preferable because the organometallic vanadium oxide cluster is decomposed. Although there is no problem in the reaction in the low temperature range as long as the function of the vacuum pump is sufficient, it is necessary to avoid operating in a lower temperature range than necessary from an economic viewpoint.
[0009]
The molar ratio of acetonitrile to water is not particularly limited, and is about 0.1 to 2 mol, preferably 0.5 to 1.5 mol, of acetonitrile per 1 mol of water. Although the amount of unreacted components has never been smaller, it does not mean that there is no problem in separation and purification regardless of whether water or acetonitrile remains as excess components.
[0010]
【Example】
Examples of the present invention will be described below.
Embodiment 1
To 1.25 g of silica powder, 0.24 g of an organorhodium-containing vanadium oxide [(RhC 5 (CH 3 ) 5 ) 4 V 6 O 19 ] (hereinafter abbreviated as Rh-VO) cluster was added to an appropriate amount of dichloromethane. After dissolution, this solution was added to the silica powder and stirred. After stirring and mixing, the pressure was reduced and the dichloromethane was distilled off, followed by vacuum evacuation at 200 ° C. to obtain a Rh-VO cluster catalyst immobilized on the silica surface.
[0011]
0.1 g of the above catalyst was charged into a glass reaction tube, and acetonitrile and water at a molar ratio of 1: 1 were introduced into the reaction tube in a gaseous state under reduced pressure to carry out a reaction. The reactor was a closed system, and the reaction gas was circulated to the reaction tube by a circulation pump, and the contact reaction was performed for about 20 hours. The reaction temperature was 100 ° C. The generated acetamide was collected in the reactor, taken out of the reactor after the reaction was completed, and the formation of acetamide was confirmed. The product gas was analyzed using a gas chromatograph, and the selectivity was calculated from the by-products and the conversion was calculated from the consumption of acetonitrile. Table 1 shows the conversion and selectivity during the reaction.
[0012]
Embodiments 2 and 3
The same reaction was performed using the same catalyst as in Example 1 except for changing the reaction temperature. Table 1 shows the results.
[0013]
[Table 1]
Embodiment 4
Silica powder 0.73g respect, organic iridium-containing vanadium oxide [(IrC 5 (CH 3) 5 ) 4 V 6 O 19 ] (hereinafter, abbreviated as Ir-VO.) Dissolved in a suitable amount of dichloromethane cluster 0.22g This solution was added to the above silica powder and stirred. After stirring and mixing, the pressure was reduced and the dichloromethane was distilled off, followed by vacuum evacuation at 200 ° C. to obtain an Ir-VO cluster catalyst immobilized on the silica surface. Table 2 shows the results of a reaction performed in the same manner as in Example 1 using the catalyst.
[0015]
[Examples 5 to 7]
The same reaction was carried out using the same catalyst as in Example 4 except for changing the reaction temperature. Table 2 shows the results.
[0016]
[Table 2]
[Comparative Examples 1-3]
The reaction was carried out in the same manner as in Example 1 except that a commercially available vanadium pentoxide (0.1 g) was used instead of the catalyst in which the Rh-VO cluster was supported on silica. Table 3 shows the results.
The selectivity is not so bad, but the reactivity is very low compared to the examples.
[0018]
[Table 3]
[Comparative Examples 4 to 7]
To silica powder 1.00 g, vanadium oxide clusters containing no Group 8 element [(n-C 4 H 9) 3 N ] 3 (V 10 0 28 H 3 ) ( hereinafter, abbreviated as VO.) 0. 16 g was dissolved in an appropriate amount of dichloromethane, and this solution was added to the above silica powder and stirred. After stirring and mixing, the pressure was reduced and the dichloromethane was distilled off. Further, the mixture was evacuated at 200 ° C. to obtain a VO cluster catalyst immobilized on the silica surface. The reaction was carried out in the same manner as in Example 1 using the catalyst, and the results are shown in Table 4. Even though acetonitrile was consumed, no formation of acetamide was observed.
[0020]
[Table 4]
【The invention's effect】
According to the present invention, acetamide can be produced with high selectivity and high yield.
Claims (9)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20091994A JP3541448B2 (en) | 1994-08-25 | 1994-08-25 | Method for producing acetamide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20091994A JP3541448B2 (en) | 1994-08-25 | 1994-08-25 | Method for producing acetamide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0859583A JPH0859583A (en) | 1996-03-05 |
| JP3541448B2 true JP3541448B2 (en) | 2004-07-14 |
Family
ID=16432462
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20091994A Expired - Lifetime JP3541448B2 (en) | 1994-08-25 | 1994-08-25 | Method for producing acetamide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3541448B2 (en) |
-
1994
- 1994-08-25 JP JP20091994A patent/JP3541448B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0859583A (en) | 1996-03-05 |
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