Method for pretreating and using copper-based catalyst
원문보기
IPC분류정보
국가/구분
United States(US) Patent
등록
국제특허분류(IPC7판)
C07C-209/00
C07C-209/24
B01J-037/08
B01J-037/18
B01J-023/72
B01J-023/80
B01J-023/83
출원번호
US-0161447
(2011-06-15)
등록번호
US-9006489
(2015-04-14)
우선권정보
CN-2011 1 0151516 (2011-06-07)
발명자
/ 주소
Gao, Shiming
출원인 / 주소
Jiangsu Sinorgchem Technology Co., Ltd.
대리인 / 주소
Li, Manni
인용정보
피인용 횟수 :
0인용 특허 :
18
초록▼
Method for pretreating the copper-based catalyst having the steps of dehydrating the copper-based catalyst at an elevated temperature, reducing the dehydrated copper-based catalyst with hydrogen, and passivating the activated copper-based catalyst to obtain a catalyst suitable for N-alkylation. The
Method for pretreating the copper-based catalyst having the steps of dehydrating the copper-based catalyst at an elevated temperature, reducing the dehydrated copper-based catalyst with hydrogen, and passivating the activated copper-based catalyst to obtain a catalyst suitable for N-alkylation. The dehydration and reduction steps may be conducted simultaneously.
대표청구항▼
1. A method for pretreating a copper-based catalyst comprising dehydrating a copper-based catalyst at an elevated temperature,reducing the dehydrated copper-based catalyst with hydrogen to obtain an activated copper-based catalyst, andpassivating the activated copper-based catalyst by reacting the a
1. A method for pretreating a copper-based catalyst comprising dehydrating a copper-based catalyst at an elevated temperature,reducing the dehydrated copper-based catalyst with hydrogen to obtain an activated copper-based catalyst, andpassivating the activated copper-based catalyst by reacting the activated copper-based catalyst with a ketone and a mixture comprising 4-aminodiphenylamine, said mixture made by a formanilide method, in presence of hydrogen at a temperature of about 100° C. to 180° C. and a hydrogen gas pressure of about 2 MPa to 6 MPa for about 20 to 40 hours, to obtain a passivated copper-based catalyst,wherein the mixture made by the formanilide method is prepared byreacting formic acid with aniline to form formanilide,reacting the formanilide with para-nitrochlorobenzene to form 4-nitrodiphenylamine, andreducing the 4-nitrodiphenylamine to the 4-aminodiphenylamine, optionally in presence of sodium sulfide as a reduction agent. 2. The method of claim 1, wherein the copper-based catalyst comprises about 10% to 70% copper oxide. 3. The method of claim 1, wherein the copper-based catalyst comprises about 30 to 50% copper oxide. 4. The method of claim 1, wherein the copper-based catalyst comprises a carrier that is ZnO, Al2O3, SiO2, activated carbon, glass fiber net, ceramic ball, layered graphite, natural clay, cerium oxide, or a mixture thereof. 5. The method of claim 1, wherein the copper-based catalyst is dehydrated at the elevated temperature of more than about 100° C. and under pressure of an inert gas at about 1 MPa to 5 MPa. 6. The method of claim 5, wherein the copper-based catalyst is dehydrated at about 120° C. to 150° C. 7. The method of claim 1, wherein time for dehydration is about 4 to 12 hours. 8. The method of claim 1, wherein the temperature is elevated at about 5° C. to 10° C. per hour during dehydration. 9. The method of claim 1, wherein the dehydrated copper-based catalyst is reduced with hydrogen in a liquid or gas phase. 10. The method of claim 1, wherein the dehydrated copper-based catalyst is reduced at a temperature of about 110° C. to 280° C., hydrogen gas is fed at a volume concentration of about 0.1% to 100%, and reaction time is about 40 to 100 hours. 11. The method of claim 1, wherein the temperature for reduction is elevated at about 1° C. to 15° C. per hour. 12. The method of claim 1, wherein the copper-based catalyst is dehydrated and reduced simultaneously. 13. The method of claim 1, wherein molar ratio of the 4-aminodiphenylamine to the ketone is about (1:1) to (1:4). 14. The method for making alkylated derivatives of 4-aminodiphenylamine according to claim 1, comprising dehydrating a copper-based catalyst at an elevated temperature,reducing the dehydrated copper-based catalyst with hydrogen to obtain an activated copper-based catalyst, andpassivating the activated copper-based catalyst by treating the activated copper-based catalyst with a ketone and a mixture comprising 4-aminodiphenylamine, said mixture made by a formanilide method, in presence of hydrogen at a temperature of about 100° C. to 180° C. and hydrogen gas pressure of about 2 MPa to 6 MPa for about 20 to 40 hours, to obtain a passivated copper-based catalyst, andreacting 4-aminodiphenylamine with a ketone in presence of hydrogen and the passivated copper-based catalyst to obtain alkylated derivatives of 4-aminodiphenylamine,wherein the mixture made by the formanilide method is prepared byreacting formic acid with aniline to form formanilide,reacting the formanilide with para-nitrochlorobenzene to form 4-nitrodiphenylamine, andreducing the 4-nitrodiphenylamine to the 4-aminodiphenylamine, optionally in presence of sodium sulfide as a reduction agent. 15. The method of claim 14, wherein the reaction of 4-aminodiphenylamine and the ketone in the presence of hydrogen and the passivated catalyst for making the alkylated derivatives of 4-aminodiphenylamine is conducted at a temperature of about 110° C. to 240° C., a hydrogen pressure of about 2 MPa to 8 MPa. 16. The method of claim 14, wherein the reaction of 4-aminodiphenylamine and the ketone in the presence of hydrogen and the passivated catalyst for making the alkylated derivatives of 4-aminodiphenylamine is conducted continuously, and a total feed amount of 4-aminodiphenylamine and ketone is about 10 to 25% by weight per hour of the weight of the catalyst. 17. A method for pretreating a copper-based catalyst comprising dehydrating the copper-based catalyst at an elevated temperature,reducing the dehydrated copper-based catalyst with hydrogen to obtain an activated copper-based catalyst, andpassivating the activated copper-based catalyst by reacting the activated copper-based catalyst with a compound comprising sulfur or a halogen in a mixture comprising 4-aminodiphenylamine, said mixture made by a nitrobenzene method, and a ketone in presence of hydrogen gas,wherein the passivation reaction is conducted in the mixture having a molar ratio of the 4-aminodiphenylamine made by the nitrobenzene method to the ketone at about (1:1) to (1:4); reaction temperature is about 100° C. to 180° C.; reaction time is about 20 to 40 hours; pressure of the hydrogen gas is about 2 MPa to 8 MPa, andwherein the mixture made by the nitrobenzene method is prepared byreacting aniline with nitrobenzene to make 4-nitrodiphenylamine and 4-nitrosodiphenylamine, andreducing the 4-nitrodiphenylamine and 4-nitrosodiphenylamine to the 4-aminodiphenylamine. 18. The method of claim 17, wherein a ratio of the halogen-containing compound to the copper-based catalyst is about 0.05-1 mole halogen per kilogram catalyst. 19. The method of claim 17, wherein the sulfur-containing compound or the halogen-containing compound is selected from the group consisting of carbon disulfide, hydrogen sulfide, chlorophenylamine, 2-mercaptobenzothiazole, thiophene, and tetramethyl thiuram disulfide. 20. The method of claim 17, wherein the sulfur-containing compound or the halogen-containing compound is dissolved in an alcohol, ketone, or amine solvent to form the solution for passivating the catalyst. 21. The passivated copper-based catalyst prepared by the method of claim 1. 22. The passivated copper-based catalyst of claim 21, comprising metal copper in a reduced form. 23. The method for making alkylated derivatives of 4-aminodiphenylamine according to claim 21, comprising reacting 4-aminodiphenylamine with a ketone in presence of hydrogen and the passivated copper-based catalyst to obtain alkylated derivatives of 4-aminodiphenylamine. 24. The method of claim 17, wherein the copper-based catalyst comprises about 10% to 70% copper oxide. 25. The method of claim 17, wherein the copper-based catalyst comprises about 30 to 50% copper oxide. 26. The method of claim 17, wherein the copper-based catalyst comprises a carrier that is ZnO, Al2O3, SiO2, activated carbon, glass fiber net, ceramic ball, layered graphite, natural clay, cerium oxide, or a mixture thereof. 27. The method of claim 17, wherein the copper-based catalyst is dehydrated at the elevated temperature of more than about 100° C. and under pressure of an inert gas at about 1 MPa to 5 MPa. 28. The method of claim 27, wherein the copper-based catalyst is dehydrated at about 120° C. to 150° C. 29. The method of claim 17, wherein time for dehydration is about 4 to 12 hours. 30. The method of claim 17, wherein the temperature is elevated at about 5° C. to 10° C. per hour during dehydration. 31. The method of claim 17, wherein the dehydrated copper-based catalyst is reduced with hydrogen in a liquid or gas phase. 32. The method of claim 17, wherein the dehydrated copper-based catalyst is reduced at a temperature of about 110° C. to 280° C., hydrogen gas is fed at a volume concentration of about 0.1% to 100%, and reaction time is about 40 to 100 hours. 33. The method of claim 17, wherein the temperature for reduction is elevated at about 1° C. to 15° C. per hour. 34. The method of claim 17, wherein the copper-based catalyst is dehydrated and reduced simultaneously. 35. The passivated copper-based catalyst prepared by the method of claim 17. 36. The passivated copper-based catalyst of claim 35, comprising metal copper in a reduced form. 37. The method for making alkylated derivatives of 4-aminodiphenylamine according to claim 35, comprising reacting 4-aminodiphenylamine with a ketone in presence of hydrogen and the passivated copper-based catalyst to obtain alkylated derivatives of 4-aminodiphenylamine. 38. The method for making alkylated derivatives of 4-aminodiphenylamine according to claim 17, comprising dehydrating a copper-based catalyst at an elevated temperature,reducing the dehydrated copper-based catalyst with hydrogen to obtain an activated copper-based catalyst, andpassivating the activated copper-based catalyst by reacting the activated copper-based catalyst with a compound comprising sulfur or a halogen in a mixture comprising 4-aminodiphenylamine, said mixture made by a nitrobenzene method, and a ketone in presence of hydrogen gas, at a temperature of about 100° C. to 180° C. for about 20 to 40 hours, andreacting 4-aminodiphenylamine with a ketone in presence of hydrogen and the passivated copper-based catalyst to obtain alkylated derivatives of 4-aminodiphenylamine,wherein the mixture made by the nitrobenzene method is prepared byreacting aniline with nitrobenzene to make 4-nitrodiphenylamine and 4-nitrosodiphenylamine, andreducing the 4-nitrodiphenylamine and 4-nitrosodiphenylamine to the 4-aminodiphenylamine. 39. The method of claim 38, wherein the reaction of 4-aminodiphenylamine and the ketone in the presence of hydrogen and the passivated catalyst for making the alkylated derivatives of 4-aminodiphenylamine is conducted at a temperature of about 110° C. to 240° C., a hydrogen pressure of about 2 MPa to 8 MPa. 40. The method of claim 38, wherein the reaction of 4-aminodiphenylamine and the ketone in the presence of hydrogen and the passivated catalyst for making the alkylated derivatives of 4-aminodiphenylamine is conducted continuously, and a total feed amount of 4-aminodiphenylamine and ketone is about 10 to 25% by weight per hour of the weight of the catalyst.
연구과제 타임라인
LOADING...
LOADING...
LOADING...
LOADING...
LOADING...
이 특허에 인용된 특허 (18)
Schlitter, Stephan; Schubert, Olga; Hesse, Michael; Borchers, Sabine; Roesch, Markus; Pinkos, Rolf; Weck, Alexander; Windecker, Gunther, Catalyst extrudates based on copper oxide and their use for hydrogenating carbonyl compounds.
Bankmann Martin (Gelnhausen DEX) Ohmer Johannes (Gruendau DEX) Tacke Thomas (Friedrichsdorf DEX), Formed copper catalyst for the selective hydrogenation of furfural to furfuryl alcohol.
Busch Lloyd E. (Ashland KY) Palmeter Charles W. (Ashland KY) Henderson Gerald O. (Ashland KY) Rice William M. (Ashland KY), Method and apparatus for converting oil feeds.
Haese,Frank; Bottcher,Arnd; Stein,Bernd; Reif,Wolfgang; Melder,Johann Peter; Roβ,Karl Heinz; Rutter,Heinz; Liang,Shelue; Rittinger,Stefan, Method for the continuous production of an amine.
Courty Philippe (Houilles FRX) Chaumette Patrick (Bougival FRX) Durand Daniel (Rueil-Malmaison FRX) Verdon Catherine (Rueil-Malmaison FRX), Process for manufacturing a mixture of primary alcohols from a synthesis gas, in the presence of a catalyst containing c.
Mueller, Christoph; Wigbers, Christof Wilhelm; Melder, Johann-Peter; Haderlein, Gerd; Gutfrucht, Norbert, Process for preparing unsymmetric secondary tert-butylamines in the gas phase.
Chaumette Patrick (Bougival FRX) Courty Philippe (Houilles FRX) Durand Daniel (Rueil Malmaison FRX) Grandvallet Pierre (Marly FRX) Travers Christine (Rueil Malmaison FRX), Process for synthesizing a mixture of primary alcohols from a synthesis gas in the presence of a catalyst containing cop.
Chaudhari,Raghunath Vitthal; Jaganathan,Rengaswamy; Chaudhari,Sopan Tukaram; Rode,Chandrashekhar Vasant, Process for the preparation of copper chromite catalyst.
Immel Otto (Krefeld DEX) Schwarz Hans-Helmut (Krefeld DEX) Braden Rudolf (Odenthal DEX), Supported copper catalyst, process for its preparation and process for the preparation of N-alkylated aromatic amines us.
※ AI-Helper는 부적절한 답변을 할 수 있습니다.