JP2011225502A5 - - Google Patents
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- JP2011225502A5 JP2011225502A5 JP2010099198A JP2010099198A JP2011225502A5 JP 2011225502 A5 JP2011225502 A5 JP 2011225502A5 JP 2010099198 A JP2010099198 A JP 2010099198A JP 2010099198 A JP2010099198 A JP 2010099198A JP 2011225502 A5 JP2011225502 A5 JP 2011225502A5
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上記課題を解決するための本発明は、以下の技術手段から構成される。
(1)超臨界二酸化炭素を反応媒体として、水素と、Pd担持触媒又はRh担持触媒を用いて、脂肪族又は芳香族のニトリル又はジニトリルから選択される有機ニトリル化合物を水素化してその水素化物を製造する方法。
(2)Pd/MCM−41触媒を用いて、ベンゾニトリルを水素化してベンジルアミンを製造する、前記(1)に記載の方法。
(3)Rh/Al2O3触媒を用いて、アジポニトリルを水素化して、6−アミノカプロニトリルを製造する、前記(1)に記載の方法。
(4)CO2圧が、8〜10MPaの範囲である、前記(1)から(3)のいずれかに記載の方法。
(5)CO2圧を6〜14MPaの範囲で調整することにより、ベンジルアミン又はジベンジルアミンを製造する、前記(1)又は(2)に記載の方法。
(6)CO2圧6〜14MPaの範囲のうち、6〜8MPaの範囲のより低い圧力領域で、保護剤としてのCO2の作用により、第1級アミンを生成させ、8〜14MPaの範囲のより高い圧力領域で、CO2中へのイミン中間体の溶解性を増大させて、ジベンジルアミンを生成させる、前記(1)又は(2)に記載の方法。
(7)H2圧が、1〜4MPaの範囲である、前記(1)から(6)のいずれかに記載の方法。
The present invention for solving the above problems comprises the following technical means.
(1) Hydrogenation of an organic nitrile compound selected from aliphatic or aromatic nitriles or dinitriles using hydrogen and a Pd- supported catalyst or Rh- supported catalyst using supercritical carbon dioxide as a reaction medium and the hydride thereof How to manufacture.
(2) using Pd / MCM-41 catalyst, to produce a benzylamine benzonitrile and water hydrogenation method according to (1).
(3) The method according to (1) above, wherein adiponitrile is hydrogenated using a Rh / Al 2 O 3 catalyst to produce 6-aminocapronitrile.
(4) The method according to any one of (1) to (3), wherein the CO 2 pressure is in the range of 8 to 10 MPa.
(5) The method according to (1) or (2) above, wherein benzylamine or dibenzylamine is produced by adjusting the CO 2 pressure in the range of 6 to 14 MPa .
(6) A primary amine is produced by the action of CO 2 as a protective agent in a lower pressure range of 6 to 8 MPa in the range of CO 2 pressure of 6 to 14 MPa, and the range of 8 to 14 MPa. at higher pressure range, it increases the solubility of the imine intermediate into CO 2, dibenzylamine to generated and method according to (1) or (2).
(7) The method according to any one of (1) to (6), wherein the H 2 pressure is in a range of 1 to 4 MPa.
次に、本発明について更に詳細に説明する。
本発明では、材料として、ベンゾニトリル、アジポニトリルなどの脂肪族及び芳香族系ニトリルやジニトリル化合物、二酸化炭素が用いられ、また、触媒としては、Pd/C、Pd/Al2O3、Pt/SiO2、Rh/C、Rh/Al2O3、Pd/MCM−41、Pt/MCM−41、及びRh/MCM−41触媒が用いられる。ニトリル化合物は、一般式
Next, the present invention will be described in more detail.
In the present invention, aliphatic and aromatic nitriles such as benzonitrile and adiponitrile, dinitrile compounds, and carbon dioxide are used as materials, and Pd / C, Pd / Al 2 O 3 , Pt / SiO are used as catalysts. 2 , Rh / C, Rh / Al 2 O 3 , Pd / MCM-41, Pt / MCM-41, and Rh / MCM-41 catalysts are used. Nitrile compounds have the general formula
触媒及び反応物を、反応器内に導入し、所要の温度に達した後、H 2 を導入し、それに続いて高圧液体ポンプを用いてCO2を反応器内に仕込み、所望の圧力に調整する。生成物の液体を単に濾過により触媒から分離して、NMR及びGC−MSにより同定し、続いて、キャピラリーカラムとフレームイオン化検出器とを備えたGC(HP6890)を用いて定量分析を行い、選択率は、以下により算出する。
選択率%=(生成物濃度/全生成物濃度)×100
The catalyst and reactant are introduced into the reactor and, after reaching the required temperature, H 2 is introduced , followed by charging CO 2 into the reactor using a high pressure liquid pump, to the desired pressure. Adjust . The product liquid is simply separated from the catalyst by filtration and identified by NMR and GC-MS, followed by quantitative analysis using a GC (HP6890) equipped with a capillary column and flame ionization detector to determine selectivity. Is calculated as follows.
Selectivity% = (product concentration / total product concentration) × 100
さらには、CO2圧は、また、アジポニトリルの転化率を増大させる効果的な役割も果たす。CO2圧及び温度に依存して、Rh/Al2O3触媒を用いて、アジポニトリルから6−アミノカプロニトリル(ナイロン66に非常に重要な化合物;100%)への完全転化が達成される。触媒は、両方とも、リサイクルして好結果を得ることが可能である。ここに提示された本発明の方法は、ベンゾニトリル、アジポニトリルなどの脂肪族及び芳香族系ニトリルやジニトリル化合物などの有機ニトリル化合物を水素化するためのクリーンな化学プロセスのさらなる改良を行うのにきわめて好適なものとして有用である。 Furthermore, the CO 2 pressure also plays an effective role in increasing the conversion of adiponitrile. Depending on the CO 2 pressure and temperature, complete conversion of adiponitrile to 6-aminocapronitrile (a very important compound for nylon 66; 100%) is achieved using Rh / Al 2 O 3 catalyst. . Both catalysts can be recycled for good results. The method of the present invention presented here is extremely useful for further improvement of clean chemical processes for hydrogenating aliphatic and aromatic nitriles such as benzonitrile, adiponitrile and organonitrile compounds such as dinitrile compounds. It is useful as a suitable one.
0.1gの触媒及び1.0gの反応物を、反応器内に導入した。所要の温度に達した後、H 2 を導入し、それに続いて高圧液体ポンプを用いてCO2を反応器内に仕込み、次に、所望の圧力に調整した。生成物の液体を単に濾過により触媒から分離して、NMR及びGC−MSにより同定し、続いて、キャピラリーカラムとフレームイオン化検出器とを備えたGC(HP6890)を用いて定量分析を行った。本明細書に記載したすべての結果に関して、選択率は、以下により算出した。
選択率%=(生成物濃度/全生成物濃度)×100
0.1 g catalyst and 1.0 g reactant were introduced into the reactor. After reaching the required temperature, H 2 was introduced , followed by charging the CO 2 into the reactor using a high pressure liquid pump and then adjusting to the desired pressure. The product liquid was separated from the catalyst by simple filtration and identified by NMR and GC-MS followed by quantitative analysis using GC (HP6890) equipped with a capillary column and flame ionization detector. For all results described herein, the selectivity was calculated as follows .
Selectivity% = (product concentration / total product concentration) × 100
Claims (7)
Priority Applications (1)
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JP2010099198A JP5565799B2 (en) | 2010-04-22 | 2010-04-22 | Method for producing hydrides of organic nitrile compounds in supercritical carbon dioxide |
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JP2010099198A JP5565799B2 (en) | 2010-04-22 | 2010-04-22 | Method for producing hydrides of organic nitrile compounds in supercritical carbon dioxide |
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JP2011225502A JP2011225502A (en) | 2011-11-10 |
JP2011225502A5 true JP2011225502A5 (en) | 2013-07-04 |
JP5565799B2 JP5565799B2 (en) | 2014-08-06 |
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JP2010099198A Expired - Fee Related JP5565799B2 (en) | 2010-04-22 | 2010-04-22 | Method for producing hydrides of organic nitrile compounds in supercritical carbon dioxide |
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Families Citing this family (4)
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JP5659860B2 (en) * | 2011-02-28 | 2015-01-28 | エヌ・イーケムキャット株式会社 | Palladium-containing catalyst for hydrogenating nitrile compound and method for hydrogenating nitrile compound using the catalyst |
CN102924286B (en) * | 2012-10-31 | 2014-06-11 | 万华化学集团股份有限公司 | Preparation method of N1-(2-aminoethyl)-1,2-ethylenediamine |
CN104258874A (en) * | 2014-08-19 | 2015-01-07 | 华南理工大学 | Catalyst for use in one-step preparation of imine through selective hydrogenation coupling of cyanophenyl and preparation method and application |
CN110922605B (en) * | 2019-12-09 | 2022-03-08 | 海南大学 | Method for preparing covalent organic framework material by using supercritical carbon dioxide |
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JPS5663944A (en) * | 1979-10-26 | 1981-05-30 | Takeda Chem Ind Ltd | Reduction of aromatic nitrile |
US4389348A (en) * | 1981-10-26 | 1983-06-21 | Allied Corporation | Selective hydrogenation of dinitrile to omega-aminonitrile and supported rhodium-containing catalyst therefor |
GB9607917D0 (en) * | 1996-04-17 | 1996-06-19 | Swan Thomas & Co Ltd | Supercritical hydrogenation |
GB2374071A (en) * | 2001-04-06 | 2002-10-09 | Swan Thomas & Co Ltd | Hydrogenation reactions using supercritical fluids |
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