JP2011225502A5 - - Google Patents

Download PDF

Info

Publication number
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
Authority
JP
Japan
Prior art keywords
mpa
pressure
range
catalyst
produce
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.)
Granted
Application number
JP2010099198A
Other languages
Japanese (ja)
Other versions
JP2011225502A (en
JP5565799B2 (en
Filing date
Publication date
Application filed filed Critical
Priority to JP2010099198A priority Critical patent/JP5565799B2/en
Priority claimed from JP2010099198A external-priority patent/JP5565799B2/en
Publication of JP2011225502A publication Critical patent/JP2011225502A/en
Publication of JP2011225502A5 publication Critical patent/JP2011225502A5/ja
Application granted granted Critical
Publication of JP5565799B2 publication Critical patent/JP5565799B2/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Description

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/Al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)CO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)CO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)CO6〜14MPaの範囲のうち、6〜8MPa範囲のより低い圧力領域で、保護剤としてのCO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、CO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)H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/Al、Pt/SiO、Rh/C、Rh/Al、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、 を導入し、それに続いて高圧液体ポンプを用いてC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、CO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。CO圧及び温度に依存して、Rh/Al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、 を導入し、それに続いて高圧液体ポンプを用いてC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)

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。 Method of hydrogenating 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 to produce a hydride thereof . 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、請求項1に記載の方法。 Using Pd / MCM-41 catalyst, to produce a benzylamine benzonitrile and water hydrogenation process according to claim 1. Rh/Al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、請求項1に記載の方法。 The method of claim 1, wherein adiponitrile is hydrogenated to produce 6-aminocapronitrile using a Rh / Al 2 O 3 catalyst. CO圧が、8〜10MPaの範囲である、請求項1から3のいずれかに記載の方法。 The method according to claim 1, wherein the CO 2 pressure is in the range of 8 to 10 MPa. CO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、請求項1又は2に記載の方法。 The method according to claim 1 or 2, wherein benzylamine or dibenzylamine is produced by adjusting the CO 2 pressure in the range of 6 to 14 MPa . CO6〜14MPaの範囲のうち、6〜8MPa範囲のより低い圧力領域で、保護剤としてのCO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、CO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、請求項1又は2に記載の方法。 In the range of 6 to 14 MPa of CO 2 pressure, primary amine is generated by the action of CO 2 as a protective agent in a lower pressure range of 6 to 8 MPa, and higher pressure in the range of 8 to 14 MPa. area, increase the solubility of the imine intermediate into CO 2, the dibenzylamine to generated and method according to claim 1 or 2. 圧が、1〜4MPaの範囲である、請求項1から6のいずれかに記載の方法。 H 2 pressure ranges from 1 to 4 MPa, the method according to any one of claims 1 to 6.
JP2010099198A 2010-04-22 2010-04-22 Method for producing hydrides of organic nitrile compounds in supercritical carbon dioxide Expired - Fee Related JP5565799B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2010099198A JP5565799B2 (en) 2010-04-22 2010-04-22 Method for producing hydrides of organic nitrile compounds in supercritical carbon dioxide

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2010099198A JP5565799B2 (en) 2010-04-22 2010-04-22 Method for producing hydrides of organic nitrile compounds in supercritical carbon dioxide

Publications (3)

Publication Number Publication Date
JP2011225502A JP2011225502A (en) 2011-11-10
JP2011225502A5 true JP2011225502A5 (en) 2013-07-04
JP5565799B2 JP5565799B2 (en) 2014-08-06

Family

ID=45041354

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2010099198A Expired - Fee Related JP5565799B2 (en) 2010-04-22 2010-04-22 Method for producing hydrides of organic nitrile compounds in supercritical carbon dioxide

Country Status (1)

Country Link
JP (1) JP5565799B2 (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Similar Documents

Publication Publication Date Title
JP5409393B2 (en) Method for producing ethyleneamine
US8877976B2 (en) Process for preparing 3-aminomethyl-3,5,5-trimethylcyclohexylamine
JP5399270B2 (en) Method for producing ethylenediamine
Coetzee et al. The First Continuous Flow Hydrogenation of Amides to Amines.
Artiukha et al. One-pot reductive amination of aldehydes with nitroarenes over an Au/Al 2 O 3 catalyst in a continuous flow reactor
JP6997175B2 (en) Methods for nitrile hydrogenation in the presence of ruthenium catalysts supported on ZrO2
JP6704896B2 (en) Method for producing aromatic primary diamine
JP2013514309A (en) Catalytic phenol hydrogenation
JP2010520167A (en) Method for producing ethyleneamine from raw material AAN
US6951959B2 (en) Low pressure process for manufacture of 3-dimethylaminopropylamine (DMAPA)
CA2444442A1 (en) Environmentally friendly process for the hydrogenation of dinitriles
JP2017197566A (en) Process for preparing eda using so2-free hydrocyanic acid
JP2011225502A5 (en)
EP1857434B1 (en) Method for producing xylylenediamine
JP2007099771A (en) Method for reductively aminating ketone and aldehyde with aqueous amine and suitable catalyst
RU2153489C2 (en) Method of preparing aliphatic alpha and omega aminonitriles
RU2010134416A (en) METHOD FOR PRODUCING NITRILES
JP5565799B2 (en) Method for producing hydrides of organic nitrile compounds in supercritical carbon dioxide
BRPI0415819B1 (en) HYDROGENING PROCESS OF A DINITRIL
JP5531961B2 (en) Method for producing xylylenediamine
JP5125771B2 (en) Method for producing alicyclic amines
JP2007332135A (en) Method for producing xylylenediamine
Chatterjee et al. Selective Hydrogenation in Supercritical Carbon Dioxide Using Metal Supported Heterogeneous Catalyst
JP2011512327A (en) Method for treating hydrocarbon compounds having nitrile functional groups or amine functional groups
JP6140826B2 (en) Continuous process for the production of primary aliphatic amines from aldehydes