RU2007124555A - Слоистый композит и способы приготовления и использования этого композита - Google Patents
Слоистый композит и способы приготовления и использования этого композита Download PDFInfo
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- RU2007124555A RU2007124555A RU2007124555/04A RU2007124555A RU2007124555A RU 2007124555 A RU2007124555 A RU 2007124555A RU 2007124555/04 A RU2007124555/04 A RU 2007124555/04A RU 2007124555 A RU2007124555 A RU 2007124555A RU 2007124555 A RU2007124555 A RU 2007124555A
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- outer layer
- composite
- gold
- palladium
- impregnation
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- 239000002131 composite material Substances 0.000 title claims 23
- 238000000034 method Methods 0.000 title claims 14
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims 24
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 12
- 239000010931 gold Substances 0.000 claims 12
- 229910052737 gold Inorganic materials 0.000 claims 12
- 238000005470 impregnation Methods 0.000 claims 12
- 229910052763 palladium Inorganic materials 0.000 claims 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims 10
- 229910052703 rhodium Inorganic materials 0.000 claims 8
- 239000010948 rhodium Substances 0.000 claims 8
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims 8
- 239000011230 binding agent Substances 0.000 claims 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims 6
- 239000003054 catalyst Substances 0.000 claims 6
- 229910052809 inorganic oxide Inorganic materials 0.000 claims 6
- 238000001354 calcination Methods 0.000 claims 5
- 230000003197 catalytic effect Effects 0.000 claims 5
- 125000003342 alkenyl group Chemical group 0.000 claims 3
- 229910052878 cordierite Inorganic materials 0.000 claims 3
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 claims 3
- 238000004519 manufacturing process Methods 0.000 claims 3
- 239000000203 mixture Substances 0.000 claims 3
- 239000010453 quartz Substances 0.000 claims 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims 3
- 239000004408 titanium dioxide Substances 0.000 claims 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims 2
- 239000000835 fiber Substances 0.000 claims 2
- 239000012784 inorganic fiber Substances 0.000 claims 2
- HFLAMWCKUFHSAZ-UHFFFAOYSA-N niobium dioxide Chemical compound O=[Nb]=O HFLAMWCKUFHSAZ-UHFFFAOYSA-N 0.000 claims 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims 2
- 229910010271 silicon carbide Inorganic materials 0.000 claims 2
- 239000000126 substance Substances 0.000 claims 2
- 239000000725 suspension Substances 0.000 claims 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims 1
- 229910052783 alkali metal Inorganic materials 0.000 claims 1
- 150000001340 alkali metals Chemical class 0.000 claims 1
- -1 alkane carboxylic acid Chemical class 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 claims 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 239000001913 cellulose Substances 0.000 claims 1
- 229920002678 cellulose Polymers 0.000 claims 1
- 239000011248 coating agent Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 claims 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 claims 1
- 239000007789 gas Substances 0.000 claims 1
- 239000011521 glass Substances 0.000 claims 1
- 229910002804 graphite Inorganic materials 0.000 claims 1
- 239000010439 graphite Substances 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- 150000002739 metals Chemical class 0.000 claims 1
- 239000002808 molecular sieve Substances 0.000 claims 1
- 229910052901 montmorillonite Inorganic materials 0.000 claims 1
- 229910052863 mullite Inorganic materials 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 229920000642 polymer Polymers 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- 239000002243 precursor Substances 0.000 claims 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- 239000010457 zeolite Substances 0.000 claims 1
- 229910052726 zirconium Inorganic materials 0.000 claims 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/024—Multiple impregnation or coating
- B01J37/0242—Coating followed by impregnation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/52—Gold
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0219—Coating the coating containing organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0221—Coating of particles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- 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
- C07C67/055—Preparation 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/58—Platinum group metals with alkali- or alkaline earth metals
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polymerization Catalysts (AREA)
- Compositions Of Oxide Ceramics (AREA)
Claims (28)
1. Слоистый композит для каталитического производства алкенил алканоатов, содержащий:
внутреннее ядро; и
внешний слой, содержащий тугоплавкий неорганический оксид, волокнистый компонент, неорганическое связующее; и палладий, золото или их смесь в качестве каталитического компонента, диспергированного на внешнем слое.
2. Композит по п.1, в котором волокнистый компонент содержит неорганические волокна, органические волокна или их комбинации.
3. Композит по п.2, в котором неорганические волокна содержат муллит, диоксид титана, титанат калия, оксид алюминия, диоксид циркония, кварц, карбид кремния, кордиерит, стекло или их комбинации.
4. Композит по п.2, в котором органические волокна содержат графит, углерод, полимеры или их комбинации.
5. Композит по п.1, в котором внутреннее ядро содержит альфа-оксид алюминия, тета-оксид алюминия, карбид кремния, металлы, монтмориллонит, кордиерит, гамма-оксид алюминия или их комбинации.
6. Композит по п.1, в котором внешний тугоплавкий неорганический оксид содержит гамма-оксид алюминия, дельта-оксид алюминия, эта-оксид алюминия, тета-оксид алюминия, кварц/оксид алюминия, цеолиты, нецеолитные молекулярные сита, диоксид титана, диоксид циркония, диоксид ниобия или их комбинации.
7. Композит по п.1, в котором неорганическое связующее содержит оксид алюминия, кварц, диоксид циркония, диоксид титана, фосфат алюминия или их комбинации.
8. Композит по п.1, в котором слоистый композит имеет ударное повреждение менее чем примерно 10 вес.%.
9. Композит по п.8, в котором слоистый композит имеет ударное повреждение менее чем примерно 5 вес.%.
10. Композит по п.9, в котором слоистый композит имеет ударное повреждение менее чем примерно 3 вес.%.
11. Композит по п.1, дополнительно содержащий промоторный компонент, диспергированный на внешнем слое, где промоторный компонент содержит щелочной металл.
12. Композит по п.1, дополнительно содержащий органическое связующее вещество.
13. Композит по п.12, в котором органическое связующее вещество содержит поливиниловый спирт (PVA), гидрооксид пропилцеллюлозу или их комбинации.
14. Композит по п.1, в котором внешний слой имеет размещенные на нем от одного до примерно 5 дополнительных слоев, и где смежные слои содержат различные неорганические оксиды.
15. Композит по п.1, в котором внутреннее ядро имеет меньшую емкость для каталитических компонентов относительно внешнего слоя.
16. Способ производства алкенил алканоатов, включающий:
приведение в контакт подачи, содержащей алкен, алканкарбоновую кислоту и кислородосодержащий газ с катализатором, содержащим слоистый композит, содержащий:
внутреннее ядро; и
внешний слой, содержащий тугоплавкий неорганический оксид, волокнистый компонент, неорганическое связующее, и палладий, золото или и то и другое в качестве каталитического компонента, диспергированного на внешнем слое.
17. Способ по п.16, в котором катализатор содержит от примерно 1 до примерно 10 граммов палладия, и от примерно 0,5 до примерно 10 граммов золота на литр катализатора, причем количество золота составляет от примерно 10 до примерно 125 вес.% по весу палладия.
18. Способ по п. 17, в котором катализатор дополнительно содержит калийсодержащий промоторный компонент, диспергированный на внешнем слое в количестве между примерно 10 и примерно 70 граммами на литр катализатора.
19. Способ по п.18, в котором внутреннее ядро содержит кордиерит.
20. Способ по п.19, в котором внешний слой содержит диоксид циркония.
21. Способ приготовления катализатора для производства алкенил алканоата, включающий:
покрытие внутреннего ядра суспензией, содержащей внешний тугоплавкий неорганический оксид, предшественник неорганического связующего, волокнистый компонент, органическое связующее вещество и растворитель, чтобы получить покрытое ядро с внешним слоем; и
прокаливание покрытого ядра при температуре по меньшей мере 200°C в течение времени, достаточного, чтобы связать внешний слой с внутренним ядром, чтобы получить слоистый композит;
где слоистый композит содержит по меньшей мере один каталитический компонент, содержащий палладий, родий, золото или их комбинации.
22. Способ по п.21, дополнительно включающий:
пропитку внешнего слоя раствором, содержащим палладий, родий, золото или их комбинации, чтобы получить пропитанный внешний слой; и
прокаливание внешнего слоя.
23. Способ по п.22, в котором этап пропитки является сопропиткой двумя или более веществами из палладия, родия или золота.
24. Способ по п.22, в котором этап пропитки является последовательной пропиткой двумя или более веществами из палладия, родия или золота.
25. Способ по п.22, в котором этап пропитки включает сопропитку раствором, содержащим палладий и родий, с последующей пропиткой раствором, содержащим золото.
26. Способ по п.22, дополнительно включающий:
пропитку внешнего слоя раствором, содержащим палладий, родий или их смесь;
прокаливание внешнего слоя; и
пропитку внешнего слоя раствором, содержащим золото.
27. Способ по п.22, дополнительно включающий:
пропитку внешнего слоя раствором, содержащим палладий;
прокаливание внешнего слоя;
пропитку внешнего слоя раствором, содержащим родий;
прокаливание внешнего слоя; и
пропитку внешнего слоя раствором, содержащим золото.
28. Способ по п.21, в котором суспензия содержит тугоплавкий неорганический оксид, содержащий палладий, родий, золото или их смесь.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US11/137,180 US8227369B2 (en) | 2005-05-25 | 2005-05-25 | Layered composition and processes for preparing and using the composition |
| US11/137,180 | 2005-05-25 |
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| Publication Number | Publication Date |
|---|---|
| RU2007124555A true RU2007124555A (ru) | 2009-01-10 |
| RU2371249C2 RU2371249C2 (ru) | 2009-10-27 |
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| Application Number | Title | Priority Date | Filing Date |
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| RU2007124555/04A RU2371249C2 (ru) | 2005-05-25 | 2006-03-30 | Слоистый композит и способы приготовления и использования этого композита |
Country Status (19)
| Country | Link |
|---|---|
| US (3) | US8227369B2 (ru) |
| EP (1) | EP1817104A1 (ru) |
| JP (1) | JP2008542468A (ru) |
| KR (1) | KR100889059B1 (ru) |
| CN (1) | CN101218025B (ru) |
| AR (1) | AR056976A1 (ru) |
| AU (1) | AU2006249626B2 (ru) |
| BR (1) | BRPI0606378A2 (ru) |
| CA (1) | CA2586665C (ru) |
| MX (1) | MX2007008068A (ru) |
| MY (1) | MY145301A (ru) |
| NO (1) | NO20073376L (ru) |
| NZ (1) | NZ555038A (ru) |
| PL (1) | PL383723A1 (ru) |
| RU (1) | RU2371249C2 (ru) |
| TW (1) | TW200642760A (ru) |
| UA (1) | UA87878C2 (ru) |
| WO (1) | WO2006127136A1 (ru) |
| ZA (1) | ZA200704865B (ru) |
Families Citing this family (30)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7638459B2 (en) * | 2005-05-25 | 2009-12-29 | Uop Llc | Layered composition and processes for preparing and using the composition |
| EP2081681B1 (en) * | 2006-10-06 | 2016-02-17 | W. R. Grace & Co.-Conn | Process for preparing a sulfur tolerant alumina catalyst support |
| US20080176737A1 (en) * | 2006-12-15 | 2008-07-24 | Antoine Negiz | Process for preparing a layered catalyst composition for a selective hydrogenation process |
| US7816571B2 (en) * | 2006-12-15 | 2010-10-19 | Uop Llc | Selective hydrogenation process using layered catalyst composition |
| US7417003B2 (en) * | 2006-12-29 | 2008-08-26 | Uop Llc | Solid acid catalyst and process for decomposition of cumene hydroperoxide |
| US20100121100A1 (en) * | 2008-11-12 | 2010-05-13 | Daniel Travis Shay | Supported palladium-gold catalysts and preparation of vinyl acetate therewith |
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2006
- 2006-03-30 PL PL383723A patent/PL383723A1/pl not_active Application Discontinuation
- 2006-03-30 JP JP2008513475A patent/JP2008542468A/ja active Pending
- 2006-03-30 EP EP06740271A patent/EP1817104A1/en not_active Withdrawn
- 2006-03-30 RU RU2007124555/04A patent/RU2371249C2/ru not_active IP Right Cessation
- 2006-03-30 WO PCT/US2006/012064 patent/WO2006127136A1/en not_active Ceased
- 2006-03-30 MX MX2007008068A patent/MX2007008068A/es active IP Right Grant
- 2006-03-30 CN CN2006800015689A patent/CN101218025B/zh not_active Expired - Fee Related
- 2006-03-30 ZA ZA200704865A patent/ZA200704865B/xx unknown
- 2006-03-30 KR KR1020077015034A patent/KR100889059B1/ko not_active Expired - Fee Related
- 2006-03-30 CA CA2586665A patent/CA2586665C/en not_active Expired - Fee Related
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- 2006-03-30 NZ NZ555038A patent/NZ555038A/en not_active IP Right Cessation
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- 2006-03-30 UA UAA200706061A patent/UA87878C2/ru unknown
- 2006-04-19 TW TW095113964A patent/TW200642760A/zh unknown
- 2006-04-20 AR ARP060101558A patent/AR056976A1/es unknown
- 2006-04-24 MY MYPI20061876A patent/MY145301A/en unknown
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- 2007-06-29 NO NO20073376A patent/NO20073376L/no not_active Application Discontinuation
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2008
- 2008-04-07 US US12/098,951 patent/US7897804B2/en not_active Expired - Fee Related
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- 2011-02-28 US US13/036,517 patent/US20110152066A1/en not_active Abandoned
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| MY145301A (en) | 2012-01-13 |
| US20080287703A1 (en) | 2008-11-20 |
| NZ555038A (en) | 2009-11-27 |
| MX2007008068A (es) | 2007-07-13 |
| AR056976A1 (es) | 2007-11-07 |
| CA2586665A1 (en) | 2006-11-30 |
| RU2371249C2 (ru) | 2009-10-27 |
| KR100889059B1 (ko) | 2009-03-16 |
| EP1817104A1 (en) | 2007-08-15 |
| JP2008542468A (ja) | 2008-11-27 |
| UA87878C2 (ru) | 2009-08-25 |
| BRPI0606378A2 (pt) | 2009-06-23 |
| CN101218025B (zh) | 2012-11-07 |
| US20060270865A1 (en) | 2006-11-30 |
| WO2006127136A1 (en) | 2006-11-30 |
| KR20070092250A (ko) | 2007-09-12 |
| NO20073376L (no) | 2007-12-19 |
| US20110152066A1 (en) | 2011-06-23 |
| ZA200704865B (en) | 2008-08-27 |
| PL383723A1 (pl) | 2008-05-12 |
| US8227369B2 (en) | 2012-07-24 |
| CA2586665C (en) | 2012-05-15 |
| AU2006249626A1 (en) | 2006-11-30 |
| CN101218025A (zh) | 2008-07-09 |
| AU2006249626B2 (en) | 2008-12-04 |
| US7897804B2 (en) | 2011-03-01 |
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