KR100582125B1 - α-올레핀의 기상 중합 방법 및 장치 - Google Patents
α-올레핀의 기상 중합 방법 및 장치 Download PDFInfo
- Publication number
- KR100582125B1 KR100582125B1 KR1020017010513A KR20017010513A KR100582125B1 KR 100582125 B1 KR100582125 B1 KR 100582125B1 KR 1020017010513 A KR1020017010513 A KR 1020017010513A KR 20017010513 A KR20017010513 A KR 20017010513A KR 100582125 B1 KR100582125 B1 KR 100582125B1
- Authority
- KR
- South Korea
- Prior art keywords
- reactor
- gas
- polymer
- process according
- compartment
- 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 - Lifetime
Links
- 238000000034 method Methods 0.000 title claims abstract description 50
- 238000012685 gas phase polymerization Methods 0.000 title claims abstract description 17
- 239000004711 α-olefin Substances 0.000 title claims abstract description 16
- 229920000642 polymer Polymers 0.000 claims abstract description 72
- 239000002245 particle Substances 0.000 claims abstract description 53
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 22
- 239000007787 solid Substances 0.000 claims abstract description 14
- 238000000926 separation method Methods 0.000 claims abstract description 10
- 239000007789 gas Substances 0.000 claims description 48
- 239000012495 reaction gas Substances 0.000 claims description 28
- 239000000178 monomer Substances 0.000 claims description 21
- 239000003054 catalyst Substances 0.000 claims description 19
- 239000000843 powder Substances 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 11
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 10
- 238000011144 upstream manufacturing Methods 0.000 claims description 10
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 6
- -1 ethylene, propylene, 1-butene Chemical class 0.000 claims description 6
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims description 6
- 239000000376 reactant Substances 0.000 claims description 4
- 230000001747 exhibiting effect Effects 0.000 claims description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 3
- 239000000470 constituent Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 17
- 238000009826 distribution Methods 0.000 description 14
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 9
- 239000005977 Ethylene Substances 0.000 description 9
- 239000012071 phase Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- 230000002902 bimodal effect Effects 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 5
- 241000237858 Gastropoda Species 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000005243 fluidization Methods 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000009491 slugging Methods 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 150000001925 cycloalkenes Chemical class 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000007726 management method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- 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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/24—Stationary reactors without moving elements inside
- B01J19/2415—Tubular reactors
- B01J19/243—Tubular reactors spirally, concentrically or zigzag wound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/34—Polymerisation in gaseous state
-
- 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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00002—Chemical plants
- B01J2219/00027—Process aspects
- B01J2219/0004—Processes in series
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
-
- 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
- Y02P20/582—Recycling of unreacted starting or intermediate materials
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19907021A DE19907021A1 (de) | 1999-02-19 | 1999-02-19 | Verfahren und Apparatur zur Gasphasenpolymerisation von alpha-Olefinen |
| DE19907021.0 | 1999-02-19 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20010102251A KR20010102251A (ko) | 2001-11-15 |
| KR100582125B1 true KR100582125B1 (ko) | 2006-05-23 |
Family
ID=7898056
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020017010513A Expired - Lifetime KR100582125B1 (ko) | 1999-02-19 | 2000-02-16 | α-올레핀의 기상 중합 방법 및 장치 |
Country Status (13)
| Country | Link |
|---|---|
| US (1) | US6518372B1 (https=) |
| EP (1) | EP1159304B1 (https=) |
| JP (1) | JP4607335B2 (https=) |
| KR (1) | KR100582125B1 (https=) |
| CN (1) | CN1150212C (https=) |
| AR (1) | AR022533A1 (https=) |
| AU (1) | AU3155300A (https=) |
| BR (1) | BR0008345B1 (https=) |
| CA (1) | CA2362839C (https=) |
| DE (2) | DE19907021A1 (https=) |
| ES (1) | ES2204525T3 (https=) |
| RU (1) | RU2238952C2 (https=) |
| WO (1) | WO2000049055A1 (https=) |
Families Citing this family (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6359083B1 (en) * | 2000-05-02 | 2002-03-19 | Eastman Chemical Company | Olefin polymerization process |
| US6673878B2 (en) | 2001-12-19 | 2004-01-06 | Exxonmobil Chemical Patents Inc. | Tubular polymerization reactors and polymers made therein |
| US7745550B2 (en) * | 2001-12-19 | 2010-06-29 | Exxonmobil Chemical Patents Inc. | Tubular polymerization reactors and polymers made therein |
| KR100630887B1 (ko) * | 2004-11-19 | 2006-10-02 | 삼성토탈 주식회사 | 다양한 물성의 제품을 높은 생산성으로 제조하기 위한에틸렌 중합방법 및 이에 이용되는 관형 반응기 |
| US7053163B1 (en) † | 2005-02-22 | 2006-05-30 | Fina Technology, Inc. | Controlled comonomer distribution along a reactor for copolymer production |
| EP1926755A1 (en) * | 2005-09-19 | 2008-06-04 | Basell Poliolefine Italia S.R.L. | Gas-phase process for the polymerization of olefins |
| JP5308795B2 (ja) | 2007-12-11 | 2013-10-09 | 住友化学株式会社 | ポリオレフィン製造方法、並びに、噴流層装置を備えたポリオレフィン製造システム |
| JP5427396B2 (ja) | 2007-12-11 | 2014-02-26 | 住友化学株式会社 | 粉体移送装置、及び、ポリオレフィンの製造方法 |
| JP5308797B2 (ja) | 2007-12-11 | 2013-10-09 | 住友化学株式会社 | オレフィン重合反応装置、ポリオレフィン製造システム、及び、ポリオレフィン製造方法 |
| JP5308794B2 (ja) | 2007-12-11 | 2013-10-09 | 住友化学株式会社 | 噴流層装置を用いたポリオレフィン製造方法 |
| JP5249730B2 (ja) * | 2007-12-11 | 2013-07-31 | 住友化学株式会社 | オレフィン重合反応装置及びポリオレフィン製造方法 |
| RU2486953C2 (ru) * | 2008-04-22 | 2013-07-10 | Юнивейшн Текнолоджиз, Ллк | Реакторная система и способ ее использования |
| JP5545800B2 (ja) | 2009-06-08 | 2014-07-09 | 住友化学株式会社 | 噴流−流動層型オレフィン重合反応装置、ポリオレフィン製造システム、及び、ポリオレフィン製造方法 |
| JP6902337B2 (ja) | 2016-08-03 | 2021-07-14 | 住友化学株式会社 | ヘテロファジックプロピレン重合材料の製造方法 |
| MY187826A (en) * | 2016-11-10 | 2021-10-26 | Basell Polyolefine Gmbh | Olefin polymerization process in a gas-phase reactor comprising a riser unit and a downcomer |
| CA3152938A1 (en) | 2019-10-23 | 2021-04-29 | Nova Chemicals Corporation | Biaxially oriented mdpe film |
| CN111250027B (zh) * | 2020-03-05 | 2022-03-11 | 内蒙古兰格生物科技有限公司 | 药物中间体反应管及生产线 |
| CN111468065B (zh) * | 2020-04-24 | 2022-02-22 | 烟台大学 | 一种高活性聚异丁烯的生产装置及生产工艺 |
| CA3102574A1 (en) * | 2020-06-29 | 2021-12-29 | Nova Chemicals Corporation | Ethylene copolymer for biaxial orientation |
Family Cites Families (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR550233A (fr) | 1922-04-15 | 1923-03-01 | Appareil à circulations automatiques pour réactions physiques ou chimiques entre gaz et liquides | |
| US3842060A (en) * | 1973-08-14 | 1974-10-15 | Dart Ind Inc | Ethylene polymerization process |
| IT1076203B (it) * | 1977-01-12 | 1985-04-27 | Montedison Spa | Procedimento per la polimerizzazione di etilene in fase gas |
| JPS56166208A (en) * | 1980-05-27 | 1981-12-21 | Mitsui Petrochem Ind Ltd | Gas-phase polymerization of olefin |
| JPS57101A (en) * | 1980-06-04 | 1982-01-05 | Mitsui Petrochem Ind Ltd | Method and apparatus for polymerization |
| JPS5761013A (en) * | 1980-10-01 | 1982-04-13 | Sumitomo Chem Co Ltd | Continuous vapor-phase polymerization of alpha-olefin |
| US4424341A (en) * | 1981-09-21 | 1984-01-03 | Phillips Petroleum Company | Separation of solid polymers and liquid diluent |
| DE3217973A1 (de) | 1982-05-13 | 1983-11-17 | Basf Ag, 6700 Ludwigshafen | Verfahren zur herstellung von copolymerisaten des ethylens mit acrylsaeureestern in einem zweizonenreaktor bei druecken oberhalb 500 bar |
| US5208109A (en) | 1982-06-24 | 1993-05-04 | Bp Chemicals Limited | Process for the polymerization and copolymerization of alpha-olefins in a fluidized bed |
| US4740551A (en) | 1986-06-18 | 1988-04-26 | Shell Oil Company | Multistage copolymerization process |
| US5041473A (en) | 1990-06-21 | 1991-08-20 | Union Carbide Chemicals And Plastics Technology Corporation | Process for producing carbon black filled polyethylene resins |
| US5169913A (en) * | 1991-05-31 | 1992-12-08 | Procedyne Corp. | Fluidized multistaged reaction system for polymerization |
| RU2053014C1 (ru) * | 1991-09-30 | 1996-01-27 | Филлипс Петролеум Компани | Устройство для получения этиленового полимера и способ получения этилового полимера |
| HUT70863A (en) | 1992-05-29 | 1995-11-28 | Amoco Corp | Process for polymerization of alpha-olefines |
| EP0574821B1 (en) | 1992-06-18 | 1998-03-11 | Montell Technology Company bv | Process and apparatus for the gas-phase polymerization of olefins |
| IT1275573B (it) * | 1995-07-20 | 1997-08-07 | Spherilene Spa | Processo ed apparecchiatura per la pomimerizzazione in fase gas delle alfa-olefine |
| DE19634450A1 (de) | 1996-08-26 | 1998-03-05 | Basf Ag | Vorrichtung zur kontinuierlichen Durchführung chemischer Reaktionen |
-
1999
- 1999-02-19 DE DE19907021A patent/DE19907021A1/de not_active Withdrawn
-
2000
- 2000-02-08 AR ARP000100530A patent/AR022533A1/es unknown
- 2000-02-16 ES ES00909183T patent/ES2204525T3/es not_active Expired - Lifetime
- 2000-02-16 BR BRPI0008345-3A patent/BR0008345B1/pt not_active IP Right Cessation
- 2000-02-16 AU AU31553/00A patent/AU3155300A/en not_active Abandoned
- 2000-02-16 JP JP2000599791A patent/JP4607335B2/ja not_active Expired - Lifetime
- 2000-02-16 EP EP00909183A patent/EP1159304B1/de not_active Expired - Lifetime
- 2000-02-16 KR KR1020017010513A patent/KR100582125B1/ko not_active Expired - Lifetime
- 2000-02-16 CN CNB008038465A patent/CN1150212C/zh not_active Expired - Lifetime
- 2000-02-16 RU RU2001125668/04A patent/RU2238952C2/ru active
- 2000-02-16 US US09/913,743 patent/US6518372B1/en not_active Expired - Lifetime
- 2000-02-16 CA CA2362839A patent/CA2362839C/en not_active Expired - Lifetime
- 2000-02-16 WO PCT/EP2000/001253 patent/WO2000049055A1/de not_active Ceased
- 2000-02-16 DE DE50002997T patent/DE50002997D1/de not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| KR20010102251A (ko) | 2001-11-15 |
| DE19907021A1 (de) | 2000-08-24 |
| CN1150212C (zh) | 2004-05-19 |
| CA2362839A1 (en) | 2000-08-24 |
| RU2238952C2 (ru) | 2004-10-27 |
| US6518372B1 (en) | 2003-02-11 |
| CN1340063A (zh) | 2002-03-13 |
| DE50002997D1 (de) | 2003-08-28 |
| AU3155300A (en) | 2000-09-04 |
| BR0008345A (pt) | 2002-02-05 |
| JP4607335B2 (ja) | 2011-01-05 |
| ES2204525T3 (es) | 2004-05-01 |
| AR022533A1 (es) | 2002-09-04 |
| EP1159304A1 (de) | 2001-12-05 |
| WO2000049055A1 (de) | 2000-08-24 |
| JP2002537420A (ja) | 2002-11-05 |
| BR0008345B1 (pt) | 2010-12-28 |
| CA2362839C (en) | 2010-05-25 |
| EP1159304B1 (de) | 2003-07-23 |
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