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RU-2026101721-A - COMPOSITE OXIDE SUPPORT, SUPPORTED CATALYST AND HYDROGENATED NITRILE BUTADIENE RUBBER AND A METHOD FOR THEIR PRODUCTION AND THEIR APPLICATION

RU2026101721ARU 2026101721 ARU2026101721 ARU 2026101721ARU-2026101721-A

Inventors

  • ДУ, Чжоу
  • Сюй, Линь
  • ЛЮ, Яньхой
  • ДУН, Лися
  • ШАО, Минбо
  • ЧЖАН, Фучунь
  • ЖЭНЬ, Юймэй
  • Ян, Гуан

Assignees

  • ЧАЙНА ПЕТРОЛЕУМ ЭНД КЕМИКАЛ КОРПОРЕЙШН
  • СИНОПЕК (БЭЙЦЗИН) РИСЕРЧ ИНСТИТЬЮТ ОФ КЕМИКАЛ ИНДАСТРИ КО., ЛТД.

Dates

Publication Date
20260507
Application Date
20231123
Priority Date
20230803

Claims (20)

  1. 1. A composite oxide support characterized in that it contains SiO 2 and a group IVB metal oxide, wherein the group IVB metal oxide is TiO 2 and/or ZrO 2 , the composite oxide support has surface characteristics such that its IR spectrum shows three characteristic peaks in the range of 610-720 cm -1 and three characteristic peaks in the range of 2840-2970 cm -1 .
  2. 2. The composite oxide support according to claim 1, characterized in that the composite oxide support has such surface characteristics that its IR spectrum shows characteristic peaks at 620±1 cm -1 , 649±1 cm -1 and 708±1 cm -1 ; and/or the composite oxide support has such surface characteristics that its IR spectrum shows characteristic peaks at 2850±1 cm -1 , 2919±1 cm -1 and 2955±1 cm -1 .
  3. 3. The composite oxide support according to claim 1, characterized in that the composite oxide support is obtained by subjecting a precursor of the composite oxide support containing SiO2 and a Group IVB metal oxide to a surface treatment using an impregnation solution containing an organic cationic quaternary ammonium salt, preferably the surface treatment is impregnation and drying; preferably the organic cationic quaternary ammonium salt is a quaternary ammonium salt with a C6 + long-chain alkyl, preferably a halide quaternary ammonium salt with a C6 + long-chain alkyl, more preferably at least one salt selected from dimethyl-dioctadecylammonium chloride, cetyltrimethylammonium chloride and C12-14 -alkyldimethylethylbenzylammonium chloride.
  4. 4. The composite oxide carrier according to one of claims 1 to 3, characterized in that, based on the total weight of the composite oxide carrier, the content of the Group IVB metal oxide is 5~25 wt.%, and the content of SiO2 is 75~95 wt.%, preferably the content of the Group IVB metal oxide is 10~25 wt.%, and the content of SiO2 is 75~90 wt.%; and/or, the composite oxide carrier has a particle size of 5~30 μm; and/or an average pore diameter of 100~1200 nm; and/or a specific surface area of 30~200 m2 /g.
  5. 5. A method for producing a composite oxide carrier according to any one of paragraphs 1-4, characterized in that it includes the following stages:
  6. (1) first impregnating a carrier of SiO2 microspheres with a solution of a Group IVB metal compound, followed by first drying and first firing to obtain a precursor of an oxide composite carrier, wherein the Group IVB metal compound is a titanium-containing compound and/or a zirconium-containing compound;
  7. (2) carrying out surface treatment of the composite oxide carrier precursor using an impregnation solution containing an organic cationic quaternary ammonium salt to obtain a composite oxide carrier.
  8. 6. The method according to claim 5, characterized in that the impregnation solution containing the organic cationic quaternary ammonium salt contains the organic cationic quaternary ammonium salt, a solvent and an acid; preferably, the concentration of the quaternary ammonium salt in the impregnation solution containing the organic cationic quaternary ammonium salt is 0.1~10 wt.%
  9. 7. The method according to claim 6, characterized in that the organic cationic quaternary ammonium salt is a C6 + long chain alkyl quaternary ammonium salt, preferably a halide quaternary ammonium salt with C6 + long chain alkyl, more preferably at least one salt selected from dimethyldioctadecylammonium chloride, cetyltrimethylammonium chloride and C12-14_ alkyldimethylethylbenzyl ammonium chloride;
  10. and/or the solvent is at least a solvent selected from deionized water, methanol, ethanol, acetone, methyl ethyl ketone, tetrahydrofuran, o-xylene, p-xylene and pyridine, preferably at least a solvent selected from o-xylene, p-xylene and pyridine, more preferably o-xylene or pyridine; and/or
  11. the acid is at least an acid selected from hydrochloric acid, sulfuric acid, nitric acid and citric acid, preferably hydrochloric acid.
  12. 8. The method according to any one of paragraphs. 5-7, characterized in that the surface treatment is impregnation and drying; preferably, the impregnation conditions include a temperature of 20~60°C and a time of 0.5~8 hours; the drying conditions include a temperature of 50~120°C and a time of 2~10 hours.
  13. 9. The method according to any one of paragraphs. 5-8, characterized in that the carrier of SiO 2 microspheres has a particle size of 5~30 μm; and/or an average pore diameter of 100~1200 nm; and/or a specific surface area of 30~200 m 2 /g.
  14. 10. The method according to any one of paragraphs 5-9, characterized in that the titanium-containing compound is at least a compound selected from titanium sulfate, metatitanic acid, titanium tetrachloride and tetrabutyl titanate;
  15. and/or the zirconium-containing compound is at least a compound selected from zirconium tetrachloride, zirconium sulfate, zirconium nitrate, zirconyl chloride and zirconium oxalate;
  16. and/or the concentration of the titanium compound and/or the zirconium-containing compound in the solution of the titanium-containing compound and/or the zirconium-containing compound is 0.1~1.0 mol/l.
  17. 11. The method according to any one of paragraphs. 5-10, characterized in that the molar ratio of the carrier of SiO 2 microspheres to the compound containing a metal of group IVB is 3~40:1; and/or the first impregnation conditions include a temperature of 20~60°C and a time of 0.5~8 h; and/or the first drying conditions include a temperature of 105~130°C and a time of 2~8 h; and/or the first firing conditions include a temperature of 450~650°C and a time of 3~8 h.
  18. 12. A supported catalyst comprising a composite oxide support according to any one of claims 1-4 and an active component of Cu and its oxide supported on the support; wherein the particle size of the copper atomic clusters of the active component is no more than 5 nm; based on the total weight of the supported catalyst, the content of Cu and its oxide, in terms of CuO, is 5~25 wt.%
  19. 13. The supported catalyst according to claim 12, characterized in that the supported catalyst has a particle size of 5~30 μm; and/or an average pore diameter of 100~1200 nm; and/or a specific surface area of 30~200 m2 /g; and/or the particle size of the copper atomic clusters of the active component is 2~5 nm.
  20. 14. A method for producing a catalyst on a support according to claim 12 or 13, comprising the following steps: carrying out a second impregnation of the composite oxide support according to any of claims 1-4 or the composite oxide support obtained by the method according to any of claims 5-9, with a solution of a soluble copper salt, followed by a second drying and a second annealing.