RU2007120390A - Модифицированные материалы носителей для катализаторов - Google Patents
Модифицированные материалы носителей для катализаторов Download PDFInfo
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- RU2007120390A RU2007120390A RU2007120390/04A RU2007120390A RU2007120390A RU 2007120390 A RU2007120390 A RU 2007120390A RU 2007120390/04 A RU2007120390/04 A RU 2007120390/04A RU 2007120390 A RU2007120390 A RU 2007120390A RU 2007120390 A RU2007120390 A RU 2007120390A
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- 239000003054 catalyst Substances 0.000 title claims abstract 24
- 239000012876 carrier material Substances 0.000 title claims 14
- 238000000034 method Methods 0.000 claims abstract 38
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract 30
- 239000002243 precursor Substances 0.000 claims abstract 13
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract 12
- 239000000463 material Substances 0.000 claims abstract 12
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims abstract 10
- 239000003607 modifier Substances 0.000 claims abstract 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract 6
- 229910052737 gold Inorganic materials 0.000 claims abstract 6
- 239000010931 gold Substances 0.000 claims abstract 6
- 229910052763 palladium Inorganic materials 0.000 claims abstract 6
- 238000006243 chemical reaction Methods 0.000 claims abstract 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract 3
- 239000012190 activator Substances 0.000 claims abstract 3
- 125000003342 alkenyl group Chemical group 0.000 claims abstract 3
- 229910052760 oxygen Inorganic materials 0.000 claims abstract 3
- 229910052700 potassium Inorganic materials 0.000 claims abstract 3
- 239000011591 potassium Substances 0.000 claims abstract 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract 2
- 239000005977 Ethylene Substances 0.000 claims abstract 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract 2
- 239000007789 gas Substances 0.000 claims abstract 2
- 238000004519 manufacturing process Methods 0.000 claims abstract 2
- 239000001301 oxygen Substances 0.000 claims abstract 2
- 230000003197 catalytic effect Effects 0.000 claims 7
- 239000000243 solution Substances 0.000 claims 7
- 238000001354 calcination Methods 0.000 claims 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims 4
- 239000007864 aqueous solution Substances 0.000 claims 4
- 238000005470 impregnation Methods 0.000 claims 4
- 229910052749 magnesium Inorganic materials 0.000 claims 4
- 239000011777 magnesium Substances 0.000 claims 4
- 229910052758 niobium Inorganic materials 0.000 claims 4
- 239000010955 niobium Substances 0.000 claims 4
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims 4
- 229910052719 titanium Inorganic materials 0.000 claims 4
- 239000010936 titanium Substances 0.000 claims 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims 2
- 229910052726 zirconium Inorganic materials 0.000 claims 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims 1
- 229910052684 Cerium Inorganic materials 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 claims 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims 1
- 229910002651 NO3 Inorganic materials 0.000 claims 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims 1
- 229910052777 Praseodymium Inorganic materials 0.000 claims 1
- 229910052783 alkali metal Inorganic materials 0.000 claims 1
- -1 alkali metal acetate Chemical class 0.000 claims 1
- 229910052788 barium Inorganic materials 0.000 claims 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims 1
- 229910052791 calcium Inorganic materials 0.000 claims 1
- 239000011575 calcium Substances 0.000 claims 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- 229910052746 lanthanum Inorganic materials 0.000 claims 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims 1
- 229910052750 molybdenum Inorganic materials 0.000 claims 1
- 239000011733 molybdenum Substances 0.000 claims 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims 1
- 229910052701 rubidium Inorganic materials 0.000 claims 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims 1
- 229910052712 strontium Inorganic materials 0.000 claims 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims 1
- 229910052715 tantalum Inorganic materials 0.000 claims 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims 1
- 229910052720 vanadium Inorganic materials 0.000 claims 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 1
- 229910052727 yttrium Inorganic materials 0.000 claims 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims 1
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- B01J23/66—Silver or gold
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
- C07C67/05—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds with oxidation
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Abstract
1. Способ получения алкенилалканоатов, включающий:введение исходного сырья, содержащего этилен, уксусную кислоту и кислородсодержащий газ, в контакт с катализатором или прокатализатором, полученным на материале носителя, с образованием винилацетата, где перед добавлением палладийсодержащего и золотосодержащего каталитических компонентов материал носителя модифицируют в результате добавления раствора предшественника модификатора к материалу носителя, где материал носителя выбирают из диоксида циркония, титаносиликата или цирконосиликата.2. Способ по п.1, где перед добавлением каталитических компонентов модифицированный материал носителя подвергают прокаливанию.3. Способ по п.1 или 2, где соотношение этилацетата и винилацетата составляет величину, меньшую приблизительно 800 ч./млн.4. Способ по п.1 или 2, где соотношение этилацетата и полученного алкенилалканоата составляет величину, меньшую приблизительно 250 ч./млн.5. Способ по п.1 или 2, где катализатор или прокатализатор содержит калиевый активатор.6. Способ по п.1 или 2, где катализатор или прокатализатор характеризуется селективностью получения СО, меньшей приблизительно 9,0%.7. Способ по п.6, где катализатор или прокатализатор характеризуется селективностью получения СО, меньшей приблизительно 9,0%, при степени превращения О45%.8. Способ по п.7, где соотношение этилацетата и винилацетата составляет величину, меньшую приблизительно 800 ч./млн, и где катализатор или прокатализатор характеризуется селективностью получения СО, меньшей приблизительно 9,0%.9. Способ по п.8, где соотношение этилацетата и винилацетата составляет величину, меньшую приблизительно 800 ч./млн, и �
Claims (30)
1. Способ получения алкенилалканоатов, включающий:
введение исходного сырья, содержащего этилен, уксусную кислоту и кислородсодержащий газ, в контакт с катализатором или прокатализатором, полученным на материале носителя, с образованием винилацетата, где перед добавлением палладийсодержащего и золотосодержащего каталитических компонентов материал носителя модифицируют в результате добавления раствора предшественника модификатора к материалу носителя, где материал носителя выбирают из диоксида циркония, титаносиликата или цирконосиликата.
2. Способ по п.1, где перед добавлением каталитических компонентов модифицированный материал носителя подвергают прокаливанию.
3. Способ по п.1 или 2, где соотношение этилацетата и винилацетата составляет величину, меньшую приблизительно 800 ч./млн.
4. Способ по п.1 или 2, где соотношение этилацетата и полученного алкенилалканоата составляет величину, меньшую приблизительно 250 ч./млн.
5. Способ по п.1 или 2, где катализатор или прокатализатор содержит калиевый активатор.
6. Способ по п.1 или 2, где катализатор или прокатализатор характеризуется селективностью получения СО2, меньшей приблизительно 9,0%.
7. Способ по п.6, где катализатор или прокатализатор характеризуется селективностью получения СО2, меньшей приблизительно 9,0%, при степени превращения О2 45%.
8. Способ по п.7, где соотношение этилацетата и винилацетата составляет величину, меньшую приблизительно 800 ч./млн, и где катализатор или прокатализатор характеризуется селективностью получения СО2, меньшей приблизительно 9,0%.
9. Способ по п.8, где соотношение этилацетата и винилацетата составляет величину, меньшую приблизительно 800 ч./млн, и где катализатор или прокатализатор характеризуется селективностью получения СО2, меньшей приблизительно 9,0%, при степени превращения О2 45%.
10. Способ по п.6, где соотношение этилацетата и винилацетата составляет величину, меньшую приблизительно 250 ч./млн, и где катализатор или прокатализатор характеризуется селективностью получения СО2, меньшей приблизительно 9,0%.
11. Способ по п.10, где соотношение этилацетата и винилацетата составляет величину, меньшую приблизительно 250 ч./млн, и где катализатор или прокатализатор характеризуется селективностью получения СО2, меньшей приблизительно 9,0%, при степени превращения О2 45%.
12. Способ по п.1 или 2, где раствор предшественника модификатора содержит ниобий, титан, магний или их комбинации.
13. Способ по п.1 или 2, где после добавления каталитических компонентов материал носителя подвергают прокаливанию.
14. Способ по п.1 или 2, где материал носителя представляет собой слоистый материал носителя.
15. Способ получения катализатора или прокатализатора, подходящего для получения алкенилалканоатов, включающий:
импрегнирование материала носителя водным раствором предшественника модификатора;
импрегнирование модифицированного материала водным раствором предшественника каталитического компонента и
восстановление предшественника каталитического компонента в результате введения материала носителя в контакт с восстанавливающей средой,
где материал носителя выбирают из диоксида циркония, титаносиликата или цирконосиликата.
16. Способ по п.15, дополнительно включающий прокаливание модифицированного материала носителя в невосстанавливающей атмосфере перед импрегнированием водным раствором предшественника каталитического компонента.
17. Способ по п.15 или 16, где стадия прокаливания модифицированного материала носителя включает прокаливание при температуре от приблизительно 300°С до приблизительно 700°С.
18. Способ по п.15 или 16, где первая стадия импрегнирования включает импрегнирование материала носителя модификатором в количестве от приблизительно 0,1 до приблизительно 4,0% при расчете на массу материала носителя.
19. Способ по п.15 или 16, где водный раствор предшественника каталитического компонента содержит золото, палладий или их комбинацию.
20. Способ по п.15 или 16, где атомное отношение между золотом и палладием находится в диапазоне от приблизительно 0,3 до приблизительно 0,90.
21. Способ по п.15 или 16, где раствор предшественника модификатора содержит барий, магний, церий, калий, кальций, ниобий, тантал, титан, иттрий, стронций, цирконий, лантан, празеодим, ванадий, молибден, рубидий или их бинарные комбинации.
22. Способ по п.21, где раствор предшественника модификатора содержит ниобий, титан, магний, цирконий или их комбинации.
23. Способ по п.22, где раствор предшественника модификатора содержит ниобий, титан, магний или их комбинации.
24. Способ по п.21, где раствор предшественника модификатора содержит хлорид, нитрат, оксалат, лактат или их комбинации.
25. Способ по п.15 или 16, где материал носителя представляет собой слоистый материал носителя.
26. Способ по п.15 или 16, дополнительно включающий прокаливание после импрегнирования модифицированного материала носителя раствором предшественника каталитического компонента.
27. Способ по п.15 или 16, дополнительно включающий введение катализатора или прокатализатора в контакт с активатором.
28. Способ по п.15 или 16, дополнительно включающий введение ацетата щелочного металла в контакт с материалом носителя в количестве приблизительно от 10 до 70 г на один 1 л катализатора.
29. Способ по п.28, где стадия введения в контакт каталитического компонента включает введение в контакт от приблизительно 1 до приблизительно 10 г палладия на 1 л катализатора и от приблизительно 0,5 до приблизительно 10 г золота на 1 л катализатора, при этом количество золота находится от приблизительно 10 до приблизительно 125% при расчете на массу палладия.
30. Катализатор или прокатализатор, полученные в соответствии со способом по пп.15-29.
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- 2005-11-21 JP JP2007546694A patent/JP2008524217A/ja active Pending
- 2005-11-21 EP EP11174393A patent/EP2380661A3/en not_active Withdrawn
- 2005-11-21 EP EP05825484A patent/EP1827682A2/en not_active Withdrawn
- 2005-11-21 MX MX2007006486A patent/MX2007006486A/es active IP Right Grant
- 2005-11-21 KR KR1020077012528A patent/KR100932575B1/ko not_active Expired - Fee Related
- 2005-11-21 UA UAA200706060A patent/UA95442C2/ru unknown
- 2005-11-21 PL PL382741A patent/PL382741A1/pl not_active Application Discontinuation
- 2005-11-21 CN CN2005800426323A patent/CN101124043B/zh not_active Expired - Fee Related
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- 2005-11-21 AU AU2005319574A patent/AU2005319574B2/en not_active Ceased
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- 2005-11-21 WO PCT/US2005/042651 patent/WO2006068764A2/en not_active Ceased
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Also Published As
| Publication number | Publication date |
|---|---|
| EP2380661A3 (en) | 2012-02-01 |
| KR100932575B1 (ko) | 2009-12-17 |
| KR20070093971A (ko) | 2007-09-19 |
| ZA200704864B (en) | 2008-08-27 |
| CN101124043B (zh) | 2012-10-10 |
| TWI391182B (zh) | 2013-04-01 |
| RU2422433C2 (ru) | 2011-06-27 |
| KR100978977B1 (ko) | 2010-08-30 |
| AU2005319574A1 (en) | 2006-06-29 |
| UA95442C2 (ru) | 2011-08-10 |
| MY146433A (en) | 2012-08-15 |
| AR052801A1 (es) | 2007-04-04 |
| AU2005319574B2 (en) | 2009-09-24 |
| NZ555037A (en) | 2011-03-31 |
| EP2380661A2 (en) | 2011-10-26 |
| CN101124043A (zh) | 2008-02-13 |
| KR20090101308A (ko) | 2009-09-24 |
| EP1827682A2 (en) | 2007-09-05 |
| CA2586584C (en) | 2011-01-18 |
| BRPI0518825A2 (pt) | 2008-12-09 |
| US20060135809A1 (en) | 2006-06-22 |
| WO2006068764A2 (en) | 2006-06-29 |
| NO20072769L (no) | 2007-05-31 |
| PL382741A1 (pl) | 2007-12-10 |
| TW200633776A (en) | 2006-10-01 |
| US20080153692A1 (en) | 2008-06-26 |
| CA2586584A1 (en) | 2006-06-29 |
| JP2008524217A (ja) | 2008-07-10 |
| WO2006068764A3 (en) | 2006-11-09 |
| US7518014B2 (en) | 2009-04-14 |
| MX2007006486A (es) | 2007-07-04 |
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