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RU2011131292A - METHOD FOR PRODUCING CATALYST OR PROCATALIZER CONTAINING ZIRCONIUM DIOXIDE, CATALYTIC COMPOSITION AND METHOD FOR PRODUCING ALKENYLALKANOATES USING SUCH COMPOSITION - Google Patents

METHOD FOR PRODUCING CATALYST OR PROCATALIZER CONTAINING ZIRCONIUM DIOXIDE, CATALYTIC COMPOSITION AND METHOD FOR PRODUCING ALKENYLALKANOATES USING SUCH COMPOSITION Download PDF

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RU2011131292A
RU2011131292A RU2011131292/04A RU2011131292A RU2011131292A RU 2011131292 A RU2011131292 A RU 2011131292A RU 2011131292/04 A RU2011131292/04 A RU 2011131292/04A RU 2011131292 A RU2011131292 A RU 2011131292A RU 2011131292 A RU2011131292 A RU 2011131292A
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carrier material
material containing
palladium
range
surface area
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Тао ВАН
Лесли Э. УЭЙД
Виктор ВОН
Дэвид М. ЛОУ
Альфред ХЕЙДЖМЕЙЕР
Цзюнь ХАНЬ
Валерий СОКОЛОВСКИЙ
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Селаниз Интернэшнл Корпорейшн
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    • B01J37/0009Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00Preparation of carboxylic acid esters
    • C07C67/04Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
    • C07C67/05Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds with oxidation
    • C07C67/055Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds with oxidation in the presence of platinum group metals or their compounds
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    • B01J35/397Egg shell like
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Abstract

1. Способ получения катализатора или прокатализатора, подходящих для содействия получению алкенилалканоатов, включающий:введение палладий- и золотосодержащих предшественников в контакт с материалом носителя, содержащим диоксид циркония причем материал носителя, содержащий диоксид циркония, обладает площадью удельной поверхности по БЭТ между примерно 10 м/г до примерно 135 м/г;необязательно стадию фиксации с использованием фиксирующего вещества; ивосстановление, по меньшей мере, палладийсодержащего предшественника в результате введения восстанавливающей среды в контакт с материалом носителя, содержащим диоксид циркония.2. Способ по п.1, где материал носителя, содержащий диоксид циркония, характеризуется площадью удельной поверхности в диапазоне от приблизительно 10 м/г до приблизительно 60 м/г согласно измерениям по методу БЭТ.3. Способ по п.2, где материал носителя, содержащий диоксид циркония, характеризуется площадью удельной поверхности по методу БЭТ в диапазоне от приблизительно 37 м/г до приблизительно 60 м/г.4. Способ по пп.1-3, где материал носителя, содержащий диоксид циркония, характеризуется площадью удельной поверхности по методу БЭТ приблизительно 42 м/г.5. Способ по пп.1-3, где материал носителя, содержащий диоксид циркония, характеризуется площадью удельной поверхности по методу БЭТ приблизительно 55 м/г.6. Способ по п.1, где материал носителя, содержащий диоксид циркония, характеризуется объемом пор в диапазоне от приблизительно 0,1 мл/г до приблизительно 0,6 мл/г.7. Способ по п.1, где стадия введения в контакт включает импрегнирование палладий- и золотосодержащим предшественниками материала носителя, содер1. A method of preparing a catalyst or procatalyst suitable for facilitating the production of alkenyl alkanoates, comprising: contacting palladium and gold-containing precursors with a support material containing zirconia, wherein the support material containing zirconia has a BET specific surface area of between about 10 m2 / g up to about 135 m / g; optionally a fixation step using a fixing agent; and reducing at least a palladium-containing precursor by contacting a reducing medium with a zirconia-containing support material. The method of claim 1, wherein the zirconia-containing support material has a specific surface area in the range of about 10 m2 / g to about 60 m2 / g as measured by the BET method. The method of claim 2, wherein the zirconia-containing support material has a BET specific surface area in the range of about 37 m / g to about 60 m / g. The method of claims 1 to 3, wherein the zirconia-containing support material has a BET specific surface area of about 42 m2 / g. The method of claims 1 to 3, wherein the zirconia-containing support material has a BET specific surface area of about 55 m / g. The method of claim 1, wherein the zirconia-containing support material has a pore volume in the range of about 0.1 ml / g to about 0.6 ml / g. The method according to claim 1, wherein the contacting step comprises impregnating the palladium and gold-containing precursors of the support material containing

Claims (40)

1. Способ получения катализатора или прокатализатора, подходящих для содействия получению алкенилалканоатов, включающий:1. A method of producing a catalyst or procatalyst suitable for promoting the production of alkenyl alkanoates, including: введение палладий- и золотосодержащих предшественников в контакт с материалом носителя, содержащим диоксид циркония причем материал носителя, содержащий диоксид циркония, обладает площадью удельной поверхности по БЭТ между примерно 10 м2/г до примерно 135 м2/г;introducing palladium and gold-containing precursors into contact with a carrier material containing zirconia, the carrier material containing zirconia having a BET specific surface area of between about 10 m 2 / g to about 135 m 2 / g; необязательно стадию фиксации с использованием фиксирующего вещества; иoptionally a fixing step using a fixing agent; and восстановление, по меньшей мере, палладийсодержащего предшественника в результате введения восстанавливающей среды в контакт с материалом носителя, содержащим диоксид циркония.reduction of at least a palladium-containing precursor by contacting a reducing medium with a carrier material containing zirconia. 2. Способ по п.1, где материал носителя, содержащий диоксид циркония, характеризуется площадью удельной поверхности в диапазоне от приблизительно 10 м2/г до приблизительно 60 м2/г согласно измерениям по методу БЭТ.2. The method according to claim 1, where the carrier material containing zirconium dioxide, characterized by a specific surface area in the range from about 10 m 2 / g to about 60 m 2 / g according to measurements by the BET method. 3. Способ по п.2, где материал носителя, содержащий диоксид циркония, характеризуется площадью удельной поверхности по методу БЭТ в диапазоне от приблизительно 37 м2/г до приблизительно 60 м2/г.3. The method according to claim 2, where the carrier material containing zirconia is characterized by a specific surface area according to the BET method in the range from about 37 m 2 / g to about 60 m 2 / g. 4. Способ по пп.1-3, где материал носителя, содержащий диоксид циркония, характеризуется площадью удельной поверхности по методу БЭТ приблизительно 42 м2/г.4. The method according to claims 1 to 3, where the carrier material containing zirconia is characterized by a specific surface area according to the BET method of approximately 42 m 2 / g. 5. Способ по пп.1-3, где материал носителя, содержащий диоксид циркония, характеризуется площадью удельной поверхности по методу БЭТ приблизительно 55 м2/г.5. The method according to claims 1 to 3, where the carrier material containing zirconia is characterized by a specific surface area according to the BET method of approximately 55 m 2 / g. 6. Способ по п.1, где материал носителя, содержащий диоксид циркония, характеризуется объемом пор в диапазоне от приблизительно 0,1 мл/г до приблизительно 0,6 мл/г.6. The method according to claim 1, where the carrier material containing zirconia is characterized by a pore volume in the range from about 0.1 ml / g to about 0.6 ml / g 7. Способ по п.1, где стадия введения в контакт включает импрегнирование палладий- и золотосодержащим предшественниками материала носителя, содержащего диоксид циркония.7. The method according to claim 1, where the stage of introduction into contact includes impregnation of palladium and gold-containing precursors of the carrier material containing zirconium dioxide. 8. Способ по п.7, где стадия импрегнирования включает последовательное импрегнирование палладий- и золотосодержащими предшественниками материала носителя, содержащего диоксид циркония.8. The method according to claim 7, where the stage of impregnation includes sequential impregnation of palladium and gold-containing precursors of the carrier material containing zirconium dioxide. 9. Способ по п.1, дополнительно включающий, по меньшей мере, одну стадию фиксации при помощи фиксирующего вещества.9. The method according to claim 1, further comprising at least one stage of fixation using a fixing substance. 10. Способ по п.1, где стадию восстановления проводят до импрегнирования золотосодержащим предшественником.10. The method according to claim 1, where the stage of recovery is carried out before impregnation with a gold-containing precursor. 11. Способ по п.7, где стадия импрегнирования включает совместное импрегнирование палладий- и золотосодержащими предшественниками.11. The method according to claim 7, where the stage of impregnation involves the joint impregnation of palladium and gold-containing precursors. 12. Способ по п.7, где стадия импрегнирования включает импрегнирование материала носителя, содержащего диоксид циркония, растворимыми в воде по существу не содержащими хлоридов растворами предшественников.12. The method according to claim 7, where the impregnation step comprises impregnating a carrier material containing zirconia with water-soluble substantially chloride-free precursor solutions. 13. Способ по п.1, где по существу не содержащие хлоридов палладийсодержащие предшественники включают Pd(NH3)2(NO2)2, Pd(NH3)4(OH)2, Pd(NH3)4(NO3)2, Pd(NO3)2, Pd(NH3)4(OAc)2, Pd(NH3)2(OAc)2, Pd(OAc)2 в КОН или NMe4OH или NaOH, Pd(NH3)4(HCO3)2, оксалат палладия или их комбинации.13. The method according to claim 1, where the essentially chloride-free palladium-containing precursors include Pd (NH 3 ) 2 (NO 2 ) 2 , Pd (NH 3 ) 4 (OH) 2 , Pd (NH 3 ) 4 (NO 3 ) 2 , Pd (NO 3 ) 2 , Pd (NH 3 ) 4 (OAc) 2 , Pd (NH 3 ) 2 (OAc) 2 , Pd (OAc) 2 in KOH or NMe 4 OH or NaOH, Pd (NH 3 ) 4 (HCO 3 ) 2 , palladium oxalate or combinations thereof. 14. Способ по п.1, где по существу не содержащие хлоридов золотосодержащие предшественники включают KAuO2, NaAuO2, NMe4AuO2, Au(OAc)3 в КОН или NMe4OH, HAu(NO3)4 в азотной кислоте или их комбинации.14. The method according to claim 1, where essentially chloride-free gold-containing precursors include KAuO 2 , NaAuO 2 , NMe 4 AuO 2 , Au (OAc) 3 in KOH or NMe 4 OH, HAu (NO 3 ) 4 in nitric acid or their combinations. 15. Способ по п.1, где стадия введения в контакт дополнительно включает введение в контакт с предшественником третьего компонента, содержащим родий.15. The method according to claim 1, where the stage of introduction into contact further includes the introduction into contact with the precursor of the third component containing rhodium. 16. Способ по п.1, дополнительно включающий введение ацетата калия в контакт с материалом носителя, содержащим диоксид циркония.16. The method according to claim 1, further comprising introducing potassium acetate into contact with a carrier material containing zirconia. 17. Способ по п.16, где ацетат калия присутствует в количестве в диапазоне приблизительно от 10 до 70 г/л катализатора.17. The method according to clause 16, where the potassium acetate is present in an amount in the range from about 10 to 70 g / l of the catalyst. 18. Способ по п.1, где стадия введения в контакт включает введение в контакт от приблизительно 1 до приблизительно 10 г палладия и от приблизительно 0,5 до приблизительно 10 г золота на литр катализатора, при этом количество золота находится в диапазоне от приблизительно 10 до приблизительно 125 мас.% при расчете на массу палладия.18. The method according to claim 1, where the stage of contacting includes contacting from about 1 to about 10 g of palladium and from about 0.5 to about 10 g of gold per liter of catalyst, wherein the amount of gold is in the range from about 10 up to about 125 wt.% based on the weight of palladium. 19. Способ по п.18, где атомное отношение между золотом и палладием находится в диапазоне от приблизительно 0,50 до приблизительно 1,00.19. The method according to p, where the atomic ratio between gold and palladium is in the range from about 0.50 to about 1.00. 20. Каталитическая композиция для получения алкенилалканоатов, содержащая:20. A catalytic composition for producing alkenylalkanoates, containing: материал носителя, содержащий диоксид циркония, характеризующийся площадью удельной поверхности по БЭТ в диапазоне от приблизительно 10 м2/г до примерно 135 м2/г, с введенными с ним в контакт, по меньшей мере, палладием и золотом с образованием катализатора или прокатализатора.carrier material containing zirconia characterized by a BET specific surface area in the range of from about 10 m 2 / g to about 135 m 2 / g, with at least palladium and gold contacted with it to form a catalyst or procatalyst. 21. Композиция по п.20, где материал носителя, содержащий диоксид циркония, характеризуется площадью удельной поверхности в диапазоне от приблизительно 10 м2/г до приблизительно 60 м2/г согласно измерениям по методу БЭТ.21. The composition according to claim 20, where the carrier material containing zirconium dioxide, has a specific surface area in the range from about 10 m 2 / g to about 60 m 2 / g according to measurements by the BET method. 22. Композиция по п.21, где материал носителя, содержащий диоксид циркония, характеризуется площадью удельной поверхности по методу БЭТ в диапазоне от приблизительно 37 м2/г до приблизительно 60 м2/г.22. The composition according to item 21, where the carrier material containing zirconia is characterized by a specific surface area according to the BET method in the range from about 37 m 2 / g to about 60 m 2 / g 23. Композиция по пп.20-22, где материал носителя, содержащий диоксид циркония, характеризуется площадью удельной поверхности по методу БЭТ приблизительно 42 м2/г.23. The composition according to claims 20-22, wherein the carrier material containing zirconia is characterized by a specific surface area according to the BET method of approximately 42 m 2 / g. 24. Композиция по пп.20-22, где материал носителя, содержащий диоксид циркония, характеризуется площадью удельной поверхности по методу БЭТ приблизительно 55 м2/г.24. The composition according to claims 20-22, wherein the carrier material containing zirconia is characterized by a specific surface area of about 55 m 2 / g according to the BET method. 25. Композиция по п.20, где материал носителя, содержащий диоксид циркония, характеризуется объемом пор в диапазоне от приблизительно 0,1 мл/г до приблизительно 0,6 мл/г.25. The composition of claim 20, wherein the carrier material comprising zirconia has a pore volume in the range of about 0.1 ml / g to about 0.6 ml / g. 26. Композиция п.20, где палладий и золото подвергают восстановлению.26. The composition of claim 20, where palladium and gold are subjected to reduction. 27. Композиция по п.20, где катализатор или прокатализатор содержат третий компонент, содержащий родий.27. The composition according to claim 20, where the catalyst or procatalyst contains a third component containing rhodium. 28. Композиция по п.20, где катализатор или прокатализатор содержат от приблизительно 1 до приблизительно 10 г палладия и от приблизительно 0,5 до приблизительно 10 г золота на литр катализатора, при этом количество золота находится в диапазоне от приблизительно 10 до приблизительно 125 мас.% при расчете на массу палладия.28. The composition according to claim 20, where the catalyst or procatalyst contains from about 1 to about 10 g of palladium and from about 0.5 to about 10 g of gold per liter of catalyst, while the amount of gold is in the range from about 10 to about 125 wt. .% when calculating the mass of palladium. 29. Композиция по п.20, где катализатор или прокатализатор содержат ацетат калия.29. The composition according to claim 20, where the catalyst or procatalyst contains potassium acetate. 30. Композиция по п.29, где ацетат калия присутствует в количестве в диапазоне приблизительно от 10 до 70 г/л катализатора.30. The composition according to clause 29, where the potassium acetate is present in an amount in the range from about 10 to 70 g / l of the catalyst. 31. Композиция по п.20, где материал носителя, содержащий диоксид циркония, включает частицы материала носителя или измельченный материал носителя.31. The composition of claim 20, wherein the carrier material comprising zirconia comprises particles of a carrier material or ground carrier material. 32. Способ получения алкенилалканоатов, включающий:32. A method for producing alkenyl alkanoates, including: введение исходного сырья, содержащего алкен, алкановую кислоту и окислитель, в контакт с катализатором или прокатализатором, содержащими палладий и золото на материале носителя, содержащем диоксид циркония, характеризующийся площадью удельной поверхности по БЭТ в диапазоне от приблизительно 10 м2/г до примерно 135 м2/г.introducing a feedstock containing alkene, alkanoic acid and an oxidizing agent into contact with a catalyst or procatalyst containing palladium and gold on a carrier material containing zirconia characterized by a BET specific surface area in the range of from about 10 m 2 / g to about 135 m 2 / g 33. Способ по п.32, где материал носителя, содержащий диоксид циркония, характеризуется площадью удельной поверхности в диапазоне от приблизительно 10 м2/г до приблизительно 60 м2/г согласно измерениям по методу БЭТ.33. The method according to p, where the carrier material containing zirconium dioxide, characterized by a specific surface area in the range from about 10 m 2 / g to about 60 m 2 / g according to measurements by the BET method. 34. Способ по п.33, где материал носителя, содержащий диоксид циркония, характеризуется площадью удельной поверхности по методу БЭТ в диапазоне от приблизительно 37 м2/г до приблизительно 60 м2/г.34. The method according to claim 33, wherein the carrier material containing zirconia is characterized by a specific surface area according to the BET method in the range of from about 37 m 2 / g to about 60 m 2 / g. 35. Способ по пп.32-34, где материал носителя, содержащий диоксид циркония, характеризуется площадью удельной поверхности по методу БЭТ приблизительно 42 м2/г.35. The method according to PP.32-34, where the carrier material containing zirconia is characterized by a specific surface area by the BET method of approximately 42 m 2 / g 36. Способ по пп.32-34, где материал носителя, содержащий диоксид циркония, характеризуется площадью удельной поверхности по методу БЭТ приблизительно 55 м2/г.36. The method according to PP.32-34, where the carrier material containing zirconia is characterized by a specific surface area by the BET method of approximately 55 m 2 / g 37. Способ по п.32, где материал носителя, содержащий диоксид циркония, характеризуется объемом пор в диапазоне от приблизительно 0,1 мл/г до приблизительно 0,6 мл/г.37. The method according to p, where the carrier material containing zirconium dioxide, characterized by a pore volume in the range from about 0.1 ml / g to about 0.6 ml / g 38. Способ по п.32, где алкеном является этилен, алкановой кислотой является уксусная кислота, а окислителем является кислородсодержащий газ.38. The method of claim 32, wherein the alkene is ethylene, the alkanoic acid is acetic acid, and the oxidizing agent is an oxygen-containing gas. 39. Способ по п.32, где катализатор или прокатализатор содержат третий компонент, содержащий родий.39. The method according to p, where the catalyst or procatalyst contains a third component containing rhodium. 40. Способ по п.32, где катализатор или прокатализатор содержат от приблизительно 1 до приблизительно 10 г палладия и от приблизительно 0,5 до приблизительно 10 г золота на литр катализатора, при этом количество золота находится в диапазоне от приблизительно 10 до приблизительно 125 мас.% при расчете на массу палладия. 40. The method according to p, where the catalyst or procatalyst contains from about 1 to about 10 g of palladium and from about 0.5 to about 10 g of gold per liter of catalyst, while the amount of gold is in the range from about 10 to about 125 wt. .% when calculating the mass of palladium.
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