CA2547318C - Layered support material for catalysts - Google Patents
Layered support material for catalysts Download PDFInfo
- Publication number
- CA2547318C CA2547318C CA2547318A CA2547318A CA2547318C CA 2547318 C CA2547318 C CA 2547318C CA 2547318 A CA2547318 A CA 2547318A CA 2547318 A CA2547318 A CA 2547318A CA 2547318 C CA2547318 C CA 2547318C
- Authority
- CA
- Canada
- Prior art keywords
- support material
- catalyst
- palladium
- gold
- bonding agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- 239000000463 material Substances 0.000 title claims abstract description 237
- 239000003054 catalyst Substances 0.000 title claims abstract description 179
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 269
- 239000010931 gold Substances 0.000 claims abstract description 130
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 102
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 96
- 230000003197 catalytic effect Effects 0.000 claims abstract description 90
- 238000000034 method Methods 0.000 claims abstract description 89
- 229910052737 gold Inorganic materials 0.000 claims abstract description 68
- 239000010948 rhodium Substances 0.000 claims abstract description 43
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 35
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910052751 metal Inorganic materials 0.000 claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 claims abstract description 27
- 239000002184 metal Substances 0.000 claims abstract description 27
- 239000012041 precatalyst Substances 0.000 claims abstract description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 20
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 85
- 239000002243 precursor Substances 0.000 claims description 64
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 63
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- -1 niobia Chemical compound 0.000 claims description 19
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- 230000008569 process Effects 0.000 description 11
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- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- PZKNFJIOIKQCPA-UHFFFAOYSA-N oxalic acid palladium Chemical compound [Pd].OC(=O)C(O)=O PZKNFJIOIKQCPA-UHFFFAOYSA-N 0.000 description 1
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- HVAMZGADVCBITI-UHFFFAOYSA-M pent-4-enoate Chemical compound [O-]C(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-M 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000003134 recirculating effect Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 150000003283 rhodium Chemical class 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- SDKPSXWGRWWLKR-UHFFFAOYSA-M sodium;9,10-dioxoanthracene-1-sulfonate Chemical compound [Na+].O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2S(=O)(=O)[O-] SDKPSXWGRWWLKR-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 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
- B01J23/48—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
- 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
- B01J23/54—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
- B01J23/66—Silver or 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- 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
-
- 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
- B01J37/0072—Preparation of particles, e.g. dispersion of droplets in an oil bath
-
- 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
- B01J37/0201—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
- 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
- B01J37/0248—Coatings comprising impregnated particles
-
- 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
- B01J37/16—Reducing
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US53093603P | 2003-12-19 | 2003-12-19 | |
| US60/530,936 | 2003-12-19 | ||
| PCT/US2004/038814 WO2005065821A1 (en) | 2003-12-19 | 2004-11-19 | Layered support material for catalysts |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2547318A1 CA2547318A1 (en) | 2005-07-21 |
| CA2547318C true CA2547318C (en) | 2010-11-02 |
Family
ID=34748748
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA2547318A Expired - Fee Related CA2547318C (en) | 2003-12-19 | 2004-11-19 | Layered support material for catalysts |
Country Status (15)
| Country | Link |
|---|---|
| EP (1) | EP1694437A1 (ko) |
| JP (1) | JP4772694B2 (ko) |
| KR (1) | KR100890655B1 (ko) |
| CN (1) | CN100569364C (ko) |
| AR (1) | AR056250A1 (ko) |
| AU (1) | AU2004311900B2 (ko) |
| BR (1) | BRPI0416406A (ko) |
| CA (1) | CA2547318C (ko) |
| NO (1) | NO20062528L (ko) |
| NZ (1) | NZ547073A (ko) |
| PL (1) | PL380018A1 (ko) |
| RU (1) | RU2380154C2 (ko) |
| UA (1) | UA94208C2 (ko) |
| WO (1) | WO2005065821A1 (ko) |
| ZA (1) | ZA200604363B (ko) |
Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| PL382741A1 (pl) * | 2004-12-20 | 2007-12-10 | Celanese International Corporation | Zmodyfikowane materiały podłoża dla katalizatorów |
| DE102007025443A1 (de) * | 2007-05-31 | 2008-12-04 | Süd-Chemie AG | Pd/Au-Schalenkatalysator enthaltend HfO2, Verfahren zu dessen Herstellung sowie dessen Verwendung |
| DE102007025223A1 (de) | 2007-05-31 | 2008-12-04 | Süd-Chemie AG | Zirkoniumoxid-dotierter VAM-Schalenkatalysator, Verfahren zu dessen Herstellung sowie dessen Verwendung |
| DE102007025362A1 (de) | 2007-05-31 | 2008-12-11 | Süd-Chemie AG | Dotierter Pd/Au-Schalenkatalysator, Verfahren zu dessen Herstellung sowie dessen Verwendung |
| DE102007025442B4 (de) | 2007-05-31 | 2023-03-02 | Clariant International Ltd. | Verwendung einer Vorrichtung zur Herstellung eines Schalenkatalysators und Schalenkatalysator |
| DE102007025444A1 (de) * | 2007-05-31 | 2008-12-11 | Süd-Chemie AG | VAM-Schalenkatalysator, Verfahren zu dessen Herstellung sowie dessen Verwendung |
| CN101428238B (zh) * | 2007-11-07 | 2011-02-09 | 中国石油化工股份有限公司上海石油化工研究院 | 热稳定性的层状复合载体 |
| DE102008059341A1 (de) * | 2008-11-30 | 2010-06-10 | Süd-Chemie AG | Katalysatorträger, Verfahren zu seiner Herstellung sowie Verwendung |
| JP2011121048A (ja) * | 2009-12-09 | 2011-06-23 | Rohm & Haas Co | 固体触媒物質をブレンドし、管状構造物に装填する方法 |
| DE102011101459A1 (de) * | 2011-05-13 | 2012-11-15 | Süd-Chemie AG | Verfahren zur Herstellung eines metallhaltigen Schalenkatalysators ohne Zwischenkalzinierung |
| DE102012008714A1 (de) * | 2012-05-03 | 2013-11-07 | Clariant Produkte (Deutschland) Gmbh | Vorimprägnierung von Schalenkatalysatoren mit einem Acetat |
| DE102013015436A1 (de) * | 2012-09-19 | 2014-03-20 | Clariant International Ltd. | Kupfer-promotierter Schalenkatalysator zur Herstellung von Alkenylcarbonsäureestern |
| RU2722157C1 (ru) * | 2015-07-22 | 2020-05-27 | Басф Корпорейшн | Катализаторы с высокой геометрической площадью поверхности для получения винилацетатного мономера |
| CN105478154B (zh) * | 2015-12-14 | 2019-09-03 | 中石化南京催化剂有限公司 | 一种用于高活性流体床催化剂 |
| KR102309341B1 (ko) * | 2017-11-30 | 2021-10-05 | 롯데케미칼 주식회사 | 열적 안정성이 향상된 코어-쉘 구조의 촉매담체 및 이의 제조방법 |
| EP4201519A1 (de) | 2021-12-21 | 2023-06-28 | Clariant International Ltd | Schalenkatalysator zur herstellung von alkenylcarbonsäureestern mit verbesserter pd- und au-verteilung |
| EP4201523A1 (de) | 2021-12-21 | 2023-06-28 | Clariant International Ltd | Schalenkatalysator zur herstellung von alkenylcarbonsäureestern mit verbesserter pd-verteilung |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2469204A1 (fr) * | 1979-11-12 | 1981-05-22 | Inst Francais Du Petrole | Nouveaux catalyseurs de dealkylation, a la vapeur d'eau, d'hydrocarbures aromatiques |
| DE19501891C1 (de) * | 1995-01-23 | 1996-09-26 | Degussa | Verfahren zur Herstellung eines Trägerkatalysators und seine Verwendung für die Produktion von Vinylacetat |
| IN188013B (ko) * | 1995-05-23 | 2002-08-10 | Hoechst Celanese Corp | |
| US5705679A (en) * | 1996-04-02 | 1998-01-06 | Nicolau; Ioan | Honeycomb catalyst for vinyl acetate synthesis |
| DE19613791C2 (de) * | 1996-04-04 | 2002-01-31 | Celanese Chem Europe Gmbh | Katalysator, Verfahren zu seiner Herstellung und Verfahren zur Herstellung von Vinylacetat |
| SA97180048B1 (ar) * | 1996-05-24 | 2005-12-21 | هوكست سيلانس كوربوريشن | محفز بلاديوم - ذهب palladium gold ثنائي المعدن متغاير الخواص heterogeneous bimetallic vinyl acetate لإنتاج أسيتات فينيل |
| EP1060016A4 (en) * | 1998-02-05 | 2002-11-27 | Engelhard Corp | PREVENTING AGE OF PD-AU VINYL ACETATE CATALYSTS |
| ID26891A (id) * | 1998-06-02 | 2001-02-15 | Celanese Internasional Corp | Katalis vinil asetat yang terdiri dari palladium logam dan emas yang dibuat dengan potasium aurat |
| DE19827844A1 (de) * | 1998-06-23 | 1999-12-30 | Aventis Res & Tech Gmbh & Co | Verfahren zur Herstellung von Schalenkatalysatoren durch CVD-Beschichtung |
| JP2000024518A (ja) * | 1998-07-10 | 2000-01-25 | Tokyo Roki Co Ltd | 触媒装置の製造方法 |
| US6358882B1 (en) * | 1998-12-08 | 2002-03-19 | The Standard Oil Company | Fluid bed vinyl acetate catalyst |
| DE19914066A1 (de) * | 1999-03-27 | 2000-10-05 | Celanese Chem Europe Gmbh | Katalysatoren für die Gasphasenoxidation von Ethylen und Essigsäure zu Vinylacetat, Verfahren zu ihrer Herstellung und ihre Verwendung |
| US6303537B1 (en) * | 1999-11-17 | 2001-10-16 | Celanese International Corporation | Vinyl acetate catalyst comprising metallic palladium and gold and prepared utilizing sonication |
-
2004
- 2004-11-19 WO PCT/US2004/038814 patent/WO2005065821A1/en not_active Application Discontinuation
- 2004-11-19 AU AU2004311900A patent/AU2004311900B2/en not_active Ceased
- 2004-11-19 CA CA2547318A patent/CA2547318C/en not_active Expired - Fee Related
- 2004-11-19 JP JP2006545663A patent/JP4772694B2/ja not_active Expired - Fee Related
- 2004-11-19 KR KR1020067010646A patent/KR100890655B1/ko not_active IP Right Cessation
- 2004-11-19 UA UAA200606851A patent/UA94208C2/ru unknown
- 2004-11-19 EP EP04811517A patent/EP1694437A1/en not_active Withdrawn
- 2004-11-19 CN CNB2004800372009A patent/CN100569364C/zh not_active Expired - Fee Related
- 2004-11-19 RU RU2006119178/04A patent/RU2380154C2/ru not_active IP Right Cessation
- 2004-11-19 AR ARP040104282A patent/AR056250A1/es active IP Right Grant
- 2004-11-19 PL PL380018A patent/PL380018A1/pl not_active IP Right Cessation
- 2004-11-19 ZA ZA200604363A patent/ZA200604363B/en unknown
- 2004-11-19 BR BRPI0416406-7A patent/BRPI0416406A/pt not_active Application Discontinuation
- 2004-11-19 NZ NZ547073A patent/NZ547073A/en not_active IP Right Cessation
-
2006
- 2006-06-01 NO NO20062528A patent/NO20062528L/no not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| UA94208C2 (ru) | 2011-04-26 |
| JP2007514540A (ja) | 2007-06-07 |
| AR056250A1 (es) | 2007-10-03 |
| RU2006119178A (ru) | 2007-12-20 |
| CN1929916A (zh) | 2007-03-14 |
| EP1694437A1 (en) | 2006-08-30 |
| KR20060100454A (ko) | 2006-09-20 |
| WO2005065821A1 (en) | 2005-07-21 |
| CA2547318A1 (en) | 2005-07-21 |
| AU2004311900B2 (en) | 2008-10-02 |
| PL380018A1 (pl) | 2006-12-11 |
| NO20062528L (no) | 2006-07-03 |
| NZ547073A (en) | 2010-05-28 |
| BRPI0416406A (pt) | 2007-01-09 |
| KR100890655B1 (ko) | 2009-03-26 |
| JP4772694B2 (ja) | 2011-09-14 |
| CN100569364C (zh) | 2009-12-16 |
| AU2004311900A1 (en) | 2005-07-21 |
| ZA200604363B (en) | 2007-10-31 |
| RU2380154C2 (ru) | 2010-01-27 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKLA | Lapsed |
Effective date: 20141119 |