CN100574874C - 环氧乙烷催化剂 - Google Patents
环氧乙烷催化剂 Download PDFInfo
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- CN100574874C CN100574874C CN200480010807A CN200480010807A CN100574874C CN 100574874 C CN100574874 C CN 100574874C CN 200480010807 A CN200480010807 A CN 200480010807A CN 200480010807 A CN200480010807 A CN 200480010807A CN 100574874 C CN100574874 C CN 100574874C
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- 239000003054 catalyst Substances 0.000 title claims abstract description 63
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 title abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 32
- 229910052709 silver Inorganic materials 0.000 claims abstract description 29
- 239000004332 silver Substances 0.000 claims abstract description 29
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000007864 aqueous solution Substances 0.000 claims abstract description 12
- 238000012545 processing Methods 0.000 claims abstract description 6
- 239000003513 alkali Substances 0.000 claims description 6
- JECYNCQXXKQDJN-UHFFFAOYSA-N 2-(2-methylhexan-2-yloxymethyl)oxirane Chemical compound CCCCC(C)(C)OCC1CO1 JECYNCQXXKQDJN-UHFFFAOYSA-N 0.000 claims description 3
- 230000006872 improvement Effects 0.000 claims description 3
- 150000001447 alkali salts Chemical class 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 57
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 28
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 24
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 21
- 239000011734 sodium Substances 0.000 description 11
- 238000007598 dipping method Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 8
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- 238000006243 chemical reaction Methods 0.000 description 7
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 239000005864 Sulphur Substances 0.000 description 6
- 238000001354 calcination Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 229910052783 alkali metal Inorganic materials 0.000 description 5
- 150000001340 alkali metals Chemical class 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 229910052792 caesium Inorganic materials 0.000 description 4
- 230000004087 circulation Effects 0.000 description 4
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
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- 239000001569 carbon dioxide Substances 0.000 description 3
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
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- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001663 caesium Chemical class 0.000 description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 2
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 description 2
- FLJPGEWQYJVDPF-UHFFFAOYSA-L caesium sulfate Chemical compound [Cs+].[Cs+].[O-]S([O-])(=O)=O FLJPGEWQYJVDPF-UHFFFAOYSA-L 0.000 description 2
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- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
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- 229910001923 silver oxide Inorganic materials 0.000 description 2
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 2
- 238000007669 thermal treatment Methods 0.000 description 2
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 description 1
- WWILHZQYNPQALT-UHFFFAOYSA-N 2-methyl-2-morpholin-4-ylpropanal Chemical compound O=CC(C)(C)N1CCOCC1 WWILHZQYNPQALT-UHFFFAOYSA-N 0.000 description 1
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 241001379910 Ephemera danica Species 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910001515 alkali metal fluoride Inorganic materials 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000011365 complex material Substances 0.000 description 1
- 238000004320 controlled atmosphere Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
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- 238000010168 coupling process Methods 0.000 description 1
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- 238000010790 dilution Methods 0.000 description 1
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- 229910001882 dioxygen Inorganic materials 0.000 description 1
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- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
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- 159000000011 group IA salts Chemical class 0.000 description 1
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- 150000002641 lithium Chemical class 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- XKPJKVVZOOEMPK-UHFFFAOYSA-M lithium;formate Chemical compound [Li+].[O-]C=O XKPJKVVZOOEMPK-UHFFFAOYSA-M 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229940100890 silver compound Drugs 0.000 description 1
- 150000003379 silver compounds Chemical class 0.000 description 1
- XNGYKPINNDWGGF-UHFFFAOYSA-L silver oxalate Chemical compound [Ag+].[Ag+].[O-]C(=O)C([O-])=O XNGYKPINNDWGGF-UHFFFAOYSA-L 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
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- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
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- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
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- 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
- 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
- B01J23/50—Silver
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- 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
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- 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
- B01J37/0203—Impregnation the impregnation liquid containing organic compounds
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- 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
- B01J37/0207—Pretreatment of the support
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- 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
- B01J37/06—Washing
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- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
本发明涉及环氧乙烷催化剂，所述催化剂包含淀积在氧化铝载体上的银，所述氧化铝载体已用碱性盐的水溶液处理，在处理过程中保持所述处理水溶液的pH值高于8。
Description
发明背景
相关申请
本申请涉及2002年4月8日提交的同时待审的申请系列号10/118,192。
发明领域
本发明涉及用于将乙烯氧化为环氧乙烷的银催化剂，特别涉及制备具有改进性能的催化剂载体，使得包含所述载体的催化剂具有增强的效用。
现有技术描述
2002年4月8日提交的申请系列号10/118,192对现有技术进行了全面的描述。2002年4月8日提交的所述系列号10/118,192所公开的内容通过全文引用结合到本文中来。
在所述同时待审的专利中，描述了这样一种方法，其中在预处理过程中至少25％的表面钠从载体移出，并被高达10ppm的锂部分取代。适当地，所述载体用碱性盐溶液(例如碳酸锂)预处理。
发明简述
现已发现在整个预处理过程中所述载体在高pH值下进行预处理可得到优良的催化剂。所述pH值应高于8，并优选高于9。在预处理过程中pH值保持在约10-13.0之间的恒定值时得到最佳结果。本发明的一个特点为在所述载体的预处理过程中向处理溶液中加入碱以保持所需的高pH值。
本发明提供了一种制备用于生产环氧乙烷的催化剂的方法，所述催化剂包含负载在氧化铝载体上的银，所述方法的改进之处包括在低于100℃下将所述氧化铝载体与碱性水溶液接触，并在处理过程中通过加入碱使所述碱性溶液的pH值保持在8以上。
发明详述
如上所述，本发明涉及2002年4月8日提交的同时待审的申请系列号10/118,192所描述的通用方法的改进，该专利所公开的内容通过引用结合到本文中来。根据所述方法，至少25％的载体表面的钠离子移出并被高达10ppm的锂离子取代。现在根据本发明，载体的预处理在pH值高于8，优选高于9，最优选为10-13.0下进行。在一个特别优选的实施方案中，在所述载体的预处理过程中通过向所述溶液中连续或间歇加入碱使所述处理溶液的pH值保持在10-13.0的范围内。
根据本发明，在载体(例如氧化铝)的预处理过程中使用碱性处理水溶液，即包含锂化合物(例如氯化锂、碳酸锂、硝酸锂、甲酸锂、氢氧化锂等)的溶液，调节与所述载体接触的溶液的pH值高于8，优选高于9，最优选为10-13.0的范围内。在预处理过程中载体与溶液接触，通过间歇或连续另外加入碱使所述溶液的pH值保持在所需的范围内。最优选加入碱的速率足以在整个载体预处理过程中使处理溶液保持在恒定的pH值。
本发明优选的被处理载体为那些主要包含α-氧化铝，特别是那些包含高达约15％重量二氧化硅的载体。特别优选的载体的孔隙率为约0.1-1.0cm3/g，优选约0.2-0.7cm3/g。用BET方法测定，优选的载体还具有较低的表面积，即约0.2-2.0m2/g，优选0.4-1.6m2/g，最优选0.5-1.3m2/g。参见J.Am.Chem.Soc.60，3098-16(1938)。采用水银孔度计方法测定孔隙率，参见Drake和Ritter，Ind.Eng.Chem.Anal.Ed.，17，787(1945)。由表面积和表观孔隙率测量仪测定孔和孔径分布。
对于工业环氧乙烷生产应用的用途，希望所述载体能形成规则形状的丸、球、环等。希望所述载体颗粒具有3-12mm、优选4-10mm的等效直径，其通常与催化剂所放置的管子的内径匹配。等效直径为与所使用的载体颗粒具有相同的外表面(即忽略了颗粒内部孔的表面)与体积比率的球体的直径。
使用已处理的载体制备的本发明优选的催化剂包含高达约30％重量的银(用金属表示)，所述银淀积在多孔耐火载体的表面上并遍布各孔隙。银含量高于整个催化剂重量的20％为有效的，但使该催化剂没必要这么昂贵。银含量(用金属表示)优选为催化剂总重量的约5-20％，而特别优选银含量为8-15％。
除了银，本发明制备的催化剂还包含助催化剂，特别是临界量的碱金属助催化剂组分。基于催化剂的重量计算，碱金属助催化剂(用碱金属表示)的用量不多于3000ppm，优选所述催化剂包含催化剂重量的400-1500ppm，更优选500-1200ppm的碱金属。优选的碱金属为铯，不过还可使用锂、钾、铷及其混合物。
任选本发明的实践还提供了硫作为促催化组分。硫组分可以硫酸盐(例如硫酸铯、硫酸铵等)加至催化剂载体的浸渍溶液中。美国专利4,766,105描述了硫助催化剂的用途，例如在第10栏，第53-60行，并且所公开的内容通过引用结合到本文中来。当使用了硫助催化剂时，硫(用元素表示)的用量优选为催化剂重量的5-300ppm。
所述催化剂还可包含氟助催化剂，所述氟催化剂(用元素表示)的用量为催化剂重量的10-300ppm。可使用氟化铵、碱金属氟化物等。
优选通过将载体浸入银/胺浸渍溶液中或通过微湿含浸(incipientwetness)技术将银加至载体中。含银的液体通过吸收、毛细管作用和/或真空渗透至载体的孔中。部分取决于溶液中银盐的浓度，可使用一次浸渍或一系列浸渍，使用或不使用中间干燥。为了得到在优选范围内的银含量的催化剂，合适的浸渍溶液通常包含5-50％重量的银(用金属表示)。所使用的确切浓度将取决于所需的银含量、载体的特性、液体的粘度以及银化合物的溶解性和其他因素。
可通过常规的方法浸渍已预处理的载体。将所述载体置于银溶液中，直到所有的溶液都被载体吸收。最优选将干燥的经预处理的载体置于真空下，并随后引入银溶液。仅当所有的载体颗粒都涂覆了溶液或当液体的量足以覆盖所使用的载体的量时才除去真空。这样保证了载体的所有孔均已被浸渍溶液所充满。
如上所述，所述浸渍溶液的特点为银/胺溶液，优选例如美国专利3,702,259所充分描述的银/胺溶液，其公开的内容通过引用结合到本文中来。
浸渍后，分离任何过量的浸渍溶液，并将用银和助催化剂浸渍的载体煅烧或活化。在本发明大多数优选的实施方案中，如1996年4月2日授权的共同转让的美国专利5,504,052以及1996年1月16日提交的同时待审的申请系列号08/587,281共同描述的方法进行煅烧，其公开的内容通过引用结合到本文中来。通过以下方法完成煅烧：优选以渐变速率将已浸渍的载体加热至200-500℃，保持足够的时间使所含的银转化为银金属并分解有机材料随后作为挥发性物质除去。
任选已浸渍的载体保持在惰性气氛下并且温度高于300℃或更高，在银的内部吸收了大量的氧，这会对催化剂的特性产生副作用。本发明中任选使用的惰性气氛为基本不含氧的气体。
一种较少采用的可选的煅烧方法为在空气流中加热催化剂，温度不超过300℃，优选不超过270℃。
根据本发明制备的催化剂具有改进的特性，特别是稳定性，用于采用分子氧气相氧化乙烯生产环氧乙烷。通常该反应的反应温度为约150-400℃，通常为约200-300℃，并且反应压力为0.5-35巴。反应物料混合物包含0.5-20％的乙烯和3-15％的氧，余量包含比较惰性的物质如氮气、二氧化碳、甲烷、乙烷、氩气等。每次通过催化剂时通常仅有一部分乙烯产生反应，并且在分离所需的环氧乙烷产品，并随后除去适量的吹扫气流和二氧化碳以避免惰性和/或副产物的不可控制的累积之后，未反应的物料返回至氧化反应器中。
以下的实施例说明本发明。
实施例-1
a.制备银/胺络合物原料溶液：
使用以下的组分制备银溶液(份数以重量计)：
氧化银-834份
草酸-442份
去离子水-1000份
乙二胺-500份
室温下，将氧化银与水混合，随后逐步加入草酸。该混合物搅拌15分钟，此时黑色的氧化银悬浮液已变为灰/褐色草酸银。过滤该混合物并用3升去离子水洗涤固体。
将样品放置在冰浴中并搅拌，同时缓慢加入乙二胺和水(以66％/34％的混合物)，使反应温度保持低于33℃。加入所有的乙二胺/水混合物后，室温下过滤该溶液。澄清的滤液用作制备催化剂的银/胺原料溶液。
b.加入助催化剂：
将上述制得的澄清的银原料溶液用66/34的乙二胺/水混合物稀释。另外，向该稀释的银溶液中加入氢氧化铯和硫酸氢铵，使所制备的催化剂包含11％的银、400ppm的硫和800ppm的铯。
c.催化剂浸渍：
将采用本文所述方法预处理的150g载体样品放置于压力容器中，随后暴露于真空中直到压力降至50mmHg。在仍为真空下的烧瓶中引入200ml已调制的银/助催化剂溶液。将容器的压力升至大气压，并将内含物震摇数分钟。从该溶液中分离该催化剂，随后准备煅烧。
d.催化剂煅烧：
通过加热催化剂高达该银盐的分解温度进行银的煅烧和淀积。通过在具有多个加热区的炉子中，在受控大气下加热进行煅烧。将催化剂放置在移动带上，在室温下进入炉子。随着催化剂从一个加热区通向另一个加热区温度逐步升高。催化剂通过七个加热区时，温度可升至高达400℃。经过加热区后，该移动带通过一个冷却区，逐步将催化剂的温度冷却至低于100℃。在炉子中总的停留时间为22分钟。
e.催化剂测试：
在一根用熔盐浴加热的不锈钢管中测试催化剂。包含15％的乙烯、7％的氧和78％的惰性气体(主要为氮和二氧化碳)的气体混合物在300psig的压力下通过催化剂。最初调整反应温度使所得到的环氧乙烷的产量为160千克/(小时.立方米催化剂)。在这种低的生产速率下试验约一周之后，提高反应温度使环氧乙烷的产量为330千克/(小时.立方米催化剂)。
所使用的载体为低钠载体，主要由α-氧化铝制备，并具有以下规格：
表-1
实施例-2
在65℃下，在pH＝11下用0.02N氯化锂的水溶液处理载体A：
步骤1.通过加入所需量的LiOH调节处理溶液(0.02N LiCl的水溶液)的pH为指定值。将500g载体样品放置于压力容器中，随后暴露于真空中直到压力降至50mmHg。在仍为真空下引入1500ml氯化锂处理溶液。当加入所有的溶液时，将容器的压力升至大气压。随后将该载体和该液体转移至带夹套的加料漏斗中，并将该锂溶液循环通过载体床。该溶液以约5升/小时的速率稳定地流至漏斗的顶部。该溶液也以相同的速率从漏斗的底部排出，漏斗中溶液的量保持在比载体的量高出约1英寸。将热的液体循环通过夹套保持温度在65℃。
该处理容器还配备了包含0.1N LiOH溶液的滴定管和pH计。pH计检测器浸没在处理漏斗的顶部。按需加入数滴LiOH溶液，以保持循环溶液的pH值为指定值11.0。为保持该溶液的pH值为指定值所加入的0.1N LiOH溶液的总量为20ml。持续30分钟，最后排出溶液，称重并留样分析。
步骤2.通过加入1500ml新的LiCl溶液并将该处理再继续30分钟来重复步骤1。锂处理步骤共计进行5个循环。在不同的循环中为保持目标pH值所需的LiOH的量列于下表中：
表1
| 周期# | 1 | 2 | 3 | 4 | 5 |
| 加入的0.1NLiOH(ml) | 20 | 10 | 10 | 10 | 10 |
步骤3.在最后一个循环后，在室温下用1500ml水洗涤载体30分钟。不调节水洗步骤的pH值。再次水洗，随后排出液体并在150℃下将载体干燥5小时。
下表总结了对载体的锂处理的结果：
表2
| 实施例 | 所使用的溶液 | pH | 处理温度℃ | 移出的Na，ppm(Na removed) |
| 1C比较实施例 | 载体未经处理 | |||
| 2 | 0.02N LiCl | 11 | 65 | 67 |
如实施例1中所描述，将该载体用于制备催化剂，并在高的生产速率330千克/(小时.立方米催化剂)下测试该催化剂。同样，将未处理的载体用于制备催化剂，并在相同的生产速率下测试。催化剂测试验证了在载体经过处理后制备的催化剂具有改进的稳定性，见表3。
表3
在330千克/(小时.立方米催化剂)生产速率下催化剂的选择性
| 实施例 | 200小时的选择性 | 300小时的选择性 | 400小时的选择性 | 500小时的选择性 |
| 1C | 80.8 | 80.3 | 80 | 79.2 |
| 2 | 80.0 | 80.0 | 80.3 | 80.3 |
比较实施例B
设计本实施例以说明α-氧化铝表面对缓冲处理溶液pH值的固有趋势。
将1000g载体A用pH为11的3000ml氢氧化铵水溶液处理。该方法的细节与实施例2的步骤1相同，不同之处在于在载体的处理过程中未调节溶液的pH值。如表B中所示，该溶液的pH值持续下降。
表B
| 时间(小时) | 起始 | 0.25 | 1 | 2 |
| pH | 11.04 | 10.18 | 9.81 | 9.64 |
实施例3-7
采用上述方法在不同的pH值下进行一系列的载体预处理，步骤如下：
步骤1.通过加入所需量的LiOH调节处理溶液(0.02N LiCl的水溶液)的pH为指定值。使用与实施例2中所描述的类似的方法处理500g载体A样品，不同之处在于在各种情况下使用不同的pH值。
下表总结了对载体A进行锂处理的结果。
表4
| 试样 | 溶液 | pH | 处理温度℃ | 移出的Na，ppm |
| 3 | 0.02N LiCl | 12 | 65 | 139 |
| 4 | 0.02N LiCl | 11 | 65 | 67 |
| 5 | 0.02N LiCl | 10.5 | 65 | 63 |
| 6 | 0.02N LiCl | 10 | 65 | 50 |
| 7 | 0.02N LiCl | 9.5 | 65 | 44 |
显然钠移出的速率与处理溶液的pH值成比例。
实施例8
在65℃下，使用pH值为11的0.02N的CsCl溶液重复实施例2。使用1.0N的CsOH溶液调节该铯溶液的pH值。移出钠的量为80.4ppm。
实施例9
在65℃下，使用pH值为11的0.02N的KCl溶液重复实施例2。使用1.0N的KOH溶液调节该铯溶液的pH值。移出钠的量为78ppm。
实施例10
使用实施例2中相同的方法用pH值为11的LiOH溶液洗涤载体B试样。移出钠的量为180ppm。
实施例11
使用实施例2中相同的方法用pH值为11的LiOH溶液洗涤载体C试样。移出钠的量为188ppm。
实施例12
在65℃下，使用pH值为11的0.3N的NH4OH溶液重复实施例2。在处理过程中使用浓的氢氧化铵溶液调节该溶液的pH值。移出钠的量为53ppm。
实施例13-15
采用实施例1中详细描述的方法，将150g载体样品用于制备银催化剂。煅烧后，在高生产速率(330千克EO/(小时.立方米催化剂)下测试该催化剂以确定它们的相对稳定性。表5总结了测试结果并与未预处理的载体所得到的结果对比：
表5
| 实施例# | 载体 | 200小时的选择性 | 250小时的选择性 | 300小时的选择性 | 350小时的选择性 | 400小时的选择性 | 450小时的选择性 |
| 1C | 未处理 | 80.7 | 80.5 | 80.1 | 79.8 | 79.5 | 79.4 |
| 13 | 6 | 80.5 | 80.3 | 80.2 | 80 | 79.8 | 79.7 |
| 14 | 5 | 79.6 | 79.8 | 79.8 | 79.8 | 79.8 | 79.8 |
| 15 | 3 | 80.2 | 80.3 | 80.4 | 80.4 | 80.4 | 80.4 |
显然在较高的pH值下洗涤载体得到最大的稳定性。
实施例16-17
类似于实施例16，将150g已洗涤的载体B和C试样用于制备银催化剂，并在高生产速率(330千克EO/(m3.小时)下测试该催化剂以确定它们的相对稳定性。表6总结了测试结果。
表6
| 实施例# | 载体 | 200小时的选择性 | 250小时的选择性 | 300小时的选择性 | 350小时的选择性 | 400小时的选择性 | 450小时的选择性 |
| 16 | 9 | 80.2 | 80.3 | 80.2 | 80.3 | 80.3 | 80.4 |
| 17 | 10 | 79.6 | 79.8 | 79.7 | 79.8 | 79.9 | 79.8 |
由上可见，使用本发明的经处理的载体制备的催化剂用于生产环氧乙烷具有高度的稳定性和有效性。
Claims (1)
1.一种制备用于生产环氧乙烷的催化剂的方法，所述催化剂包含负载在氧化铝载体上的银，所述方法的改进之处包括在低于100℃下将所述氧化铝载体与碱性水溶液接触，并在处理过程中通过加入碱使所述碱性水溶液的pH值保持在10.0～13.0的范围内。
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| TWI632138B (zh) * | 2013-05-16 | 2018-08-11 | 科學設計股份有限公司 | 具有降低鈉含量之建基於銀之環氧乙烷觸媒 |
| US20210039074A1 (en) | 2018-02-07 | 2021-02-11 | Basf Se | Method for preparing a silver impregnation solution |
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| EP3659703A1 (en) | 2018-11-28 | 2020-06-03 | Basf Se | Catalyst for producing ethylene oxide by gas-phase oxidation |
| EP3885038A1 (en) | 2020-03-27 | 2021-09-29 | Basf Se | Process for producing an epoxidation catalyst |
| US20230256420A1 (en) | 2020-06-26 | 2023-08-17 | Basf Se | Shaped catalyst body for the production of ethylene oxide |
| WO2021260140A1 (en) | 2020-06-26 | 2021-12-30 | Basf Se | Production of porous alpha-alumina supports from boehmitic derived aluminas |
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| EP4284552A1 (en) | 2021-01-26 | 2023-12-06 | Basf Se | Epoxidation catalyst |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4242235A (en) * | 1977-12-22 | 1980-12-30 | Produits Chimiques Ugine Kuhlmann | Supports for silver catalysts utilized in the production of ethylene oxide |
| EP0315911A1 (en) * | 1987-11-06 | 1989-05-17 | Mitsubishi Petrochemical Co., Ltd. | Silver-deposited catalyst for production of ethylene oxide |
| US5418202A (en) * | 1993-12-30 | 1995-05-23 | Shell Oil Company | Ethylene oxide catalyst and process |
| US5929259A (en) * | 1996-06-05 | 1999-07-27 | Shell Oil Company | Preparation of ethylene oxide and catalyst |
| CN1317991A (zh) * | 1998-09-14 | 2001-10-17 | 国际壳牌研究有限公司 | 制备具有改进催化性能的催化剂的方法 |
| CN1377731A (zh) * | 2001-04-04 | 2002-11-06 | 中国石油化工股份有限公司 | 乙烯环氧化反应的银催化剂 |
| CN1400053A (zh) * | 2001-07-27 | 2003-03-05 | 中国石油化工股份有限公司 | 用于生产环氧乙烷的银催化剂 |
Family Cites Families (30)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1170663A (en) | 1967-03-22 | 1969-11-12 | Shell Int Research | Process for preparing Silver Catalysts |
| US3563913A (en) | 1967-10-30 | 1971-02-16 | Shell Oil Co | Silver catalyst production |
| US3702259A (en) | 1970-12-02 | 1972-11-07 | Shell Oil Co | Chemical production of metallic silver deposits |
| US4010115A (en) | 1972-01-07 | 1977-03-01 | Shell Oil Company | Catalyst for the oxidation of ethylene to ethylene oxide |
| US3962136A (en) | 1972-01-07 | 1976-06-08 | Shell Oil Company | Catalyst for production of ethylene oxide |
| GB1491447A (en) | 1973-12-05 | 1977-11-09 | Ici Ltd | Alkylene oxide production and catalysts therefor |
| GB1489335A (en) * | 1973-10-26 | 1977-10-19 | Shell Int Research | Catalyst for the production of ethylene oxide |
| US4212772A (en) | 1976-05-19 | 1980-07-15 | Basf Aktiengesellschaft | Catalyst for the manufacture of ethylene oxide |
| DE2861030D1 (en) | 1977-11-19 | 1981-11-26 | Basf Ag | Process for preparing an ethylene oxide catalyst |
| DE2844402A1 (de) | 1978-10-12 | 1980-04-30 | Basf Ag | Silber enthaltende traegerkatalysatoren, verfahren zu ihrer herstellung und verfahren zur herstellung von aethylenoxid mittels dieser katalysatoren |
| US4368144A (en) | 1980-12-22 | 1983-01-11 | Nippon Shokubai Kagaku Kogyo Co., Ltd. | Silver catalyst for production of ethylene oxide |
| JPS57180434A (en) | 1981-04-30 | 1982-11-06 | Mitsubishi Petrochem Co Ltd | Silver catalyst for production of ethylene oxide |
| DE3528313A1 (de) | 1985-08-07 | 1987-02-12 | Basf Ag | Silberkatalysator, seine herstellung und verwendung |
| JPH084745B2 (ja) | 1986-05-09 | 1996-01-24 | 三菱化学株式会社 | エチレンオキシド製造用銀触媒 |
| US4766105A (en) | 1986-10-31 | 1988-08-23 | Shell Oil Company | Ethylene oxide catalyst and process for preparing the catalyst |
| IL84232A (en) | 1986-10-31 | 1992-06-21 | Shell Int Research | Catalyst and process for the catalytic production of ethylene oxide |
| US5057481A (en) | 1987-02-20 | 1991-10-15 | Union Carbide Chemicals And Plastics Technology Corporation | Catalyst composition for oxidation of ethylene to ethylene oxide |
| US4908343A (en) | 1987-02-20 | 1990-03-13 | Union Carbide Chemicals And Plastics Company Inc. | Catalyst composition for oxidation of ethylene to ethylene oxide |
| EP0357293B1 (en) | 1988-08-30 | 1996-02-28 | Union Carbide Corporation | Catalysts for the production of ethylene oxide and their preparation processes |
| US5102848A (en) | 1990-09-28 | 1992-04-07 | Union Carbide Chemicals & Plastics Technology Corporation | Catalyst composition for oxidation of ethylene to ethylene oxide |
| US5447897A (en) | 1993-05-17 | 1995-09-05 | Shell Oil Company | Ethylene oxide catalyst and process |
| US5545603A (en) * | 1994-11-01 | 1996-08-13 | Shell Oil Company | Ethylene oxide catalyst and process |
| US5504052A (en) | 1994-12-02 | 1996-04-02 | Scientific Design Company, Inc. | Silver catalyst preparation |
| EP0716884B2 (en) | 1994-12-15 | 2009-09-23 | Shell Internationale Researchmaatschappij B.V. | Process for preparing ethylene oxide catalysts |
| US5705661A (en) | 1995-09-25 | 1998-01-06 | Mitsubishi Chemical Corporation | Catalyst for production of ethylene oxide |
| DE69919425T2 (de) | 1998-02-20 | 2005-09-08 | Nippon Shokubai Co. Ltd. | Silberkatalysator zur Herstellung von Ethylenoxid , Verfahren zu seiner Herstellung und Verfahren zur Herstellung von Ethylenoxid |
| CN1167500C (zh) | 1998-09-14 | 2004-09-22 | 国际壳牌研究有限公司 | 用于由催化剂表面除去可离子化物质以提高催化性能的方法 |
| CA2343836C (en) | 1998-09-14 | 2007-12-04 | Shell Internationale Research Maatschappij B.V. | Epoxidation catalyst carrier, preparation and use thereof |
| US6987080B2 (en) * | 2002-03-01 | 2006-01-17 | Scientific Design Company, Inc. | Ethylene oxide catalyst carrier preparation |
| US6750173B2 (en) * | 2002-04-08 | 2004-06-15 | Scientific Design Company, Inc. | Ethylene oxide catalyst |
-
2003
- 2003-04-23 US US10/421,468 patent/US6846774B2/en not_active Expired - Lifetime
-
2004
- 2004-04-01 BR BRPI0409614-2A patent/BRPI0409614A/pt not_active IP Right Cessation
- 2004-04-01 CN CN200480010807A patent/CN100574874C/zh not_active Expired - Lifetime
- 2004-04-01 JP JP2006509618A patent/JP4866235B2/ja not_active Expired - Lifetime
- 2004-04-01 KR KR1020057020072A patent/KR101013915B1/ko active IP Right Grant
- 2004-04-01 EP EP04749657.5A patent/EP1622709B1/en not_active Expired - Lifetime
- 2004-04-01 WO PCT/US2004/010151 patent/WO2004094055A2/en active Application Filing
- 2004-04-01 RU RU2005136234/04A patent/RU2331477C2/ru active
- 2004-04-01 AU AU2004232807A patent/AU2004232807B2/en not_active Expired
- 2004-04-01 MX MXPA05011385 patent/MX253299B/es active IP Right Grant
- 2004-04-01 CA CA2522821A patent/CA2522821C/en not_active Expired - Lifetime
- 2004-04-22 TW TW093111279A patent/TWI406706B/zh active
- 2004-05-10 SA SA04250113A patent/SA04250113B1/ar unknown
-
2005
- 2005-09-08 IN IN4029DE2005 patent/IN2005DE04029A/en unknown
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4242235A (en) * | 1977-12-22 | 1980-12-30 | Produits Chimiques Ugine Kuhlmann | Supports for silver catalysts utilized in the production of ethylene oxide |
| EP0315911A1 (en) * | 1987-11-06 | 1989-05-17 | Mitsubishi Petrochemical Co., Ltd. | Silver-deposited catalyst for production of ethylene oxide |
| US5418202A (en) * | 1993-12-30 | 1995-05-23 | Shell Oil Company | Ethylene oxide catalyst and process |
| US5929259A (en) * | 1996-06-05 | 1999-07-27 | Shell Oil Company | Preparation of ethylene oxide and catalyst |
| CN1317991A (zh) * | 1998-09-14 | 2001-10-17 | 国际壳牌研究有限公司 | 制备具有改进催化性能的催化剂的方法 |
| CN1377731A (zh) * | 2001-04-04 | 2002-11-06 | 中国石油化工股份有限公司 | 乙烯环氧化反应的银催化剂 |
| CN1400053A (zh) * | 2001-07-27 | 2003-03-05 | 中国石油化工股份有限公司 | 用于生产环氧乙烷的银催化剂 |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI406706B (zh) | 2013-09-01 |
| RU2005136234A (ru) | 2006-03-20 |
| EP1622709A2 (en) | 2006-02-08 |
| BRPI0409614A (pt) | 2006-04-18 |
| MX253299B (es) | 2008-01-11 |
| WO2004094055A3 (en) | 2005-01-06 |
| CA2522821A1 (en) | 2004-11-04 |
| RU2331477C2 (ru) | 2008-08-20 |
| TW200505567A (en) | 2005-02-16 |
| CN1802211A (zh) | 2006-07-12 |
| KR101013915B1 (ko) | 2011-02-14 |
| WO2004094055A2 (en) | 2004-11-04 |
| US20040214719A1 (en) | 2004-10-28 |
| JP2006524130A (ja) | 2006-10-26 |
| EP1622709B1 (en) | 2017-12-13 |
| CA2522821C (en) | 2012-07-10 |
| MXPA05011385A (es) | 2006-05-25 |
| AU2004232807A1 (en) | 2004-11-04 |
| EP1622709A4 (en) | 2007-09-05 |
| SA04250113B1 (ar) | 2007-10-29 |
| KR20060058054A (ko) | 2006-05-29 |
| IN2005DE04029A (zh) | 2007-08-24 |
| AU2004232807B2 (en) | 2009-10-29 |
| JP4866235B2 (ja) | 2012-02-01 |
| US6846774B2 (en) | 2005-01-25 |
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