# US 9,006,489 B2 · Method for pretreating and using copper-based catalyst > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 9,006,489 B2 - Document ID: US9006489B2 - Status: Granted - Kind: B2 - Application number: 13/161,447 - Filed: 2011-06-15 - Published: 2012-12-13 - Granted: 2015-04-14 - Earliest claimed: 2011-06-07 - Assignees: Jiangsu Sinorgchem Technology Co., Ltd. - Applicants: Shiming Gao - Inventors: Shiming Gao - Web page: https://patentgrep.com/patent/US9006489B2 ## CPC - C07C 209/24: by reductive alkylation of ammonia, amines or compounds having groups reducible to amino groups, with carbonyl compounds - B01J 23/72: Copper - B01J 23/80: with zinc, cadmium or mercury - B01J 23/83: with rare earths or actinides - B01J 37/08: Heat treatment {(B01J37/0009, B01J37/0018 take precedence)} - B01J 37/18: with gases containing free hydrogen - C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS - B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS ## Abstract 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. ## Claims ### Claim 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, and passivating 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 by reacting formic acid with aniline to form formanilide, reacting the formanilide with para-nitrochlorobenzene to form 4-nitrodiphenylamine, and reducing the 4-nitrodiphenylamine to the 4-aminodiphenylamine, optionally in presence of sodium sulfide as a reduction agent. ### Claim 2 (depends on 1) The method of claim 1, wherein the copper-based catalyst comprises about 10% to 70% copper oxide. ### Claim 3 (depends on 1) The method of claim 1, wherein the copper-based catalyst comprises about 30 to 50% copper oxide. ### Claim 4 (depends on 1) 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. ### Claim 5 (depends on 1) 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. ### Claim 6 (depends on 5) The method of claim 5, wherein the copper-based catalyst is dehydrated at about 120° C. to 150° C. ### Claim 7 (depends on 1) The method of claim 1, wherein time for dehydration is about 4 to 12 hours. ### Claim 8 (depends on 1) The method of claim 1, wherein the temperature is elevated at about 5° C. to 10° C. per hour during dehydration. ### Claim 9 (depends on 1) The method of claim 1, wherein the dehydrated copper-based catalyst is reduced with hydrogen in a liquid or gas phase. ### Claim 10 (depends on 1) 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. ### Claim 11 (depends on 1) The method of claim 1, wherein the temperature for reduction is elevated at about 1° C. to 15° C. per hour. ### Claim 12 (depends on 1) The method of claim 1, wherein the copper-based catalyst is dehydrated and reduced simultaneously. ### Claim 13 (depends on 1) The method of claim 1, wherein molar ratio of the 4-aminodiphenylamine to the ketone is about (1:1) to (1:4). ### Claim 14 (depends on 1) 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, and passivating 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, and reacting 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 by reacting formic acid with aniline to form formanilide, reacting the formanilide with para-nitrochlorobenzene to form 4-nitrodiphenylamine, and reducing the 4-nitrodiphenylamine to the 4-aminodiphenylamine, optionally in presence of sodium sulfide as a reduction agent. ### Claim 15 (depends on 14) 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. ### Claim 16 (depends on 14) 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. ### Claim 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, and passivating 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, and wherein the mixture made by the nitrobenzene method is prepared by reacting aniline with nitrobenzene to make 4-nitrodiphenylamine and 4-nitrosodiphenylamine, and reducing the 4-nitrodiphenylamine and 4-nitrosodiphenylamine to the 4-aminodiphenylamine. ### Claim 18 (depends on 17) 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. ### Claim 19 (depends on 17) 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. ### Claim 20 (depends on 17) 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. ### Claim 21 (depends on 1) The passivated copper-based catalyst prepared by the method of claim 1. ### Claim 22 (depends on 21) The passivated copper-based catalyst of claim 21, comprising metal copper in a reduced form. ### Claim 23 (depends on 21) 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. ### Claim 24 (depends on 17) The method of claim 17, wherein the copper-based catalyst comprises about 10% to 70% copper oxide. ### Claim 25 (depends on 17) The method of claim 17, wherein the copper-based catalyst comprises about 30 to 50% copper oxide. ### Claim 26 (depends on 17) 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. ### Claim 27 (depends on 17) 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. ### Claim 28 (depends on 27) The method of claim 27, wherein the copper-based catalyst is dehydrated at about 120° C. to 150° C. ### Claim 29 (depends on 17) The method of claim 17, wherein time for dehydration is about 4 to 12 hours. ### Claim 30 (depends on 17) The method of claim 17, wherein the temperature is elevated at about 5° C. to 10° C. per hour during dehydration. ### Claim 31 (depends on 17) The method of claim 17, wherein the dehydrated copper-based catalyst is reduced with hydrogen in a liquid or gas phase. ### Claim 32 (depends on 17) 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. ### Claim 33 (depends on 17) The method of claim 17, wherein the temperature for reduction is elevated at about 1° C. to 15° C. per hour. ### Claim 34 (depends on 17) The method of claim 17, wherein the copper-based catalyst is dehydrated and reduced simultaneously. ### Claim 35 (depends on 17) The passivated copper-based catalyst prepared by the method of claim 17. ### Claim 36 (depends on 35) The passivated copper-based catalyst of claim 35, comprising metal copper in a reduced form. ### Claim 37 (depends on 35) 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. ### Claim 38 (depends on 17) 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, and passivating 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, and reacting 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 by reacting aniline with nitrobenzene to make 4-nitrodiphenylamine and 4-nitrosodiphenylamine, and reducing the 4-nitrodiphenylamine and 4-nitrosodiphenylamine to the 4-aminodiphenylamine. ### Claim 39 (depends on 38) 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. ### Claim 40 (depends on 38) 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.