JP4446130B2 - コバルト及びスカンジウムを基礎とした触媒の調製方法 - Google Patents
コバルト及びスカンジウムを基礎とした触媒の調製方法 Download PDFInfo
- Publication number
- JP4446130B2 JP4446130B2 JP50528099A JP50528099A JP4446130B2 JP 4446130 B2 JP4446130 B2 JP 4446130B2 JP 50528099 A JP50528099 A JP 50528099A JP 50528099 A JP50528099 A JP 50528099A JP 4446130 B2 JP4446130 B2 JP 4446130B2
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- cobalt
- scandium
- synthesis gas
- temperature
- 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
Links
- 239000003054 catalyst Substances 0.000 title claims description 63
- 238000000034 method Methods 0.000 title claims description 33
- 229910052706 scandium Inorganic materials 0.000 title claims description 28
- 229910017052 cobalt Inorganic materials 0.000 title claims description 25
- 239000010941 cobalt Substances 0.000 title claims description 25
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims description 25
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 title claims description 18
- 238000002360 preparation method Methods 0.000 title description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- 230000015572 biosynthetic process Effects 0.000 claims description 15
- 229930195733 hydrocarbon Natural products 0.000 claims description 14
- 150000002430 hydrocarbons Chemical class 0.000 claims description 14
- 238000003786 synthesis reaction Methods 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- 238000000151 deposition Methods 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000012018 catalyst precursor Substances 0.000 claims description 4
- 238000010304 firing Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 239000007809 chemical reaction catalyst Substances 0.000 claims 2
- 230000002194 synthesizing effect Effects 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 16
- 239000007789 gas Substances 0.000 description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 239000004215 Carbon black (E152) Substances 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 238000005470 impregnation Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 238000002161 passivation Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 150000001868 cobalt Chemical class 0.000 description 3
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000005909 Kieselgur Substances 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- DFCYEXJMCFQPPA-UHFFFAOYSA-N scandium(3+);trinitrate Chemical compound [Sc+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O DFCYEXJMCFQPPA-UHFFFAOYSA-N 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000001261 hydroxy acids Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000003893 lactate salts Chemical class 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 229940095064 tartrate Drugs 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- 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
- B01J37/0205—Impregnation in several steps
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
- C07C1/0425—Catalysts; their physical properties
- C07C1/0445—Preparation; Activation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
- C07C2521/04—Alumina
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- C07C2521/08—Silica
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/10—Magnesium; Oxides or hydroxides thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of zinc, cadmium or mercury
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of rare earths
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of germanium, tin or lead
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/74—Iron group metals
- C07C2523/75—Cobalt
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (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 |
|---|---|---|---|
| IT97MI001510A IT1292423B1 (it) | 1997-06-26 | 1997-06-26 | Procedimento per la preparazione di un catalizzatore a base di cobalto e scandio |
| IT97A001510 | 1997-06-26 | ||
| PCT/EP1998/003873 WO1999000190A1 (en) | 1997-06-26 | 1998-06-20 | Process for the preparation of a catalyst based on cobalt and scandium |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| JP2000516856A JP2000516856A (ja) | 2000-12-19 |
| JP2000516856A5 JP2000516856A5 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) | 2005-12-22 |
| JP4446130B2 true JP4446130B2 (ja) | 2010-04-07 |
Family
ID=11377443
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP50528099A Expired - Fee Related JP4446130B2 (ja) | 1997-06-26 | 1998-06-20 | コバルト及びスカンジウムを基礎とした触媒の調製方法 |
Country Status (14)
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BR0016078B1 (pt) * | 1999-12-01 | 2014-04-01 | Sasol Tech Pty Ltd | Processo para preparar um precursor de catalisador de cobalto de fischer-tropsch. |
| JP4139883B2 (ja) * | 2002-02-08 | 2008-08-27 | 独立行政法人産業技術総合研究所 | 多種の固体触媒の迅速調製方法及びそのための装置 |
| JP4857565B2 (ja) * | 2005-01-27 | 2012-01-18 | 株式会社Ｉｈｉ | フィッシャー・トロプシュ合成触媒とその製造方法 |
| EP2055381A4 (en) * | 2006-08-25 | 2011-10-12 | Nippon Steel Eng Co Ltd | CATALYST FOR PRODUCING HYDROGEN CARBON HYDROGEN, METHOD FOR THE PRODUCTION OF CATALYST, METHOD FOR REGENERATING CATALYST AND METHOD FOR PRODUCING HYDROGEN CARBON FUEL FROM SYNTHETIC GAS |
| GB2482171B (en) * | 2010-07-22 | 2018-04-11 | Gtl F1 Ag | Catalyst treatment |
| PE20150841A1 (es) * | 2012-10-24 | 2015-06-05 | Sasol Tech Pty Ltd | Catalizadores |
| WO2016138165A1 (en) * | 2015-02-25 | 2016-09-01 | Sgc Energia S.A. (Formerly-Gi-Gasification International S.A.) | Systems, methods, and apparatuses for fischer-tropsch reactor cascade |
| JPWO2017131231A1 (ja) * | 2016-01-29 | 2018-11-22 | Ｊｘｔｇエネルギー株式会社 | フィッシャー・トロプシュ合成用触媒の製造方法及び炭化水素の製造方法 |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4088671A (en) * | 1976-03-19 | 1978-05-09 | Gulf Research & Development Company | Conversion of synthesis gas using a cobalt-ruthenium catalyst |
| US4585798A (en) * | 1981-10-13 | 1986-04-29 | Gulf Research & Development Company | Synthesis gas conversion using ruthenium-promoted cobalt catalyst |
| US5227407A (en) * | 1985-12-30 | 1993-07-13 | Exxon Research And Engineering Company | Water addition for increased CO/H2 hydrocarbon synthesis activity over catalysts comprising cobalt, ruthenium and mixtures thereof which may include a promoter metal |
| US4801573A (en) * | 1987-10-23 | 1989-01-31 | 501 Den Norske Stats Oljeslenskap A.S. | Catalyst for production of hydrocarbons |
| ATE116171T1 (de) * | 1990-09-25 | 1995-01-15 | Allied Signal Inc | Herstellung von komplexen hohlräumen in gussstücken. |
| NZ244132A (en) * | 1991-08-28 | 1993-12-23 | Broken Hill Pty Co Ltd | Fischer-tropsch catalysts comprising cobalt and scandium. |
| WO1994004476A1 (en) * | 1992-08-25 | 1994-03-03 | The Broken Hill Proprietary Company Limited | Producing blendstock |
| NO313086B1 (no) * | 1995-08-04 | 2002-08-12 | Inst Francais Du Petrole | Fremgangsmåte for fremstilling av en katalysator, katalysator som kan oppnås derved, katalysatorblanding oppnådd derved samtfremgangsmåte for syntese av hydrokarboner |
-
1997
- 1997-06-26 IT IT97MI001510A patent/IT1292423B1/it active IP Right Grant
-
1998
- 1998-06-20 CN CN98800891A patent/CN1128012C/zh not_active Expired - Fee Related
- 1998-06-20 RU RU99105744/04A patent/RU2201801C2/ru not_active IP Right Cessation
- 1998-06-20 ID IDW990108A patent/ID21346A/id unknown
- 1998-06-20 CA CA002264697A patent/CA2264697C/en not_active Expired - Fee Related
- 1998-06-20 WO PCT/EP1998/003873 patent/WO1999000190A1/en active IP Right Grant
- 1998-06-20 DE DE69812577T patent/DE69812577T2/de not_active Expired - Lifetime
- 1998-06-20 ES ES98938643T patent/ES2195369T3/es not_active Expired - Lifetime
- 1998-06-20 JP JP50528099A patent/JP4446130B2/ja not_active Expired - Fee Related
- 1998-06-20 US US09/147,737 patent/US6096790A/en not_active Expired - Fee Related
- 1998-06-20 EP EP98938643A patent/EP0934115B1/en not_active Expired - Lifetime
- 1998-06-25 MY MYPI98002891A patent/MY129167A/en unknown
- 1998-12-28 SA SA98190949A patent/SA98190949B1/ar unknown
-
1999
- 1999-02-24 NO NO19990880A patent/NO317872B1/no not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| RU2201801C2 (ru) | 2003-04-10 |
| JP2000516856A (ja) | 2000-12-19 |
| EP0934115B1 (en) | 2003-03-26 |
| IT1292423B1 (it) | 1999-02-08 |
| US6096790A (en) | 2000-08-01 |
| CN1230901A (zh) | 1999-10-06 |
| ITMI971510A0 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) | 1997-06-26 |
| MY129167A (en) | 2007-03-30 |
| CA2264697C (en) | 2007-05-22 |
| DE69812577D1 (de) | 2003-04-30 |
| EP0934115A1 (en) | 1999-08-11 |
| ES2195369T3 (es) | 2003-12-01 |
| NO990880L (no) | 1999-04-26 |
| NO317872B1 (no) | 2004-12-27 |
| DE69812577T2 (de) | 2004-01-29 |
| ID21346A (id) | 1999-05-27 |
| SA98190949B1 (ar) | 2006-03-15 |
| NO990880D0 (no) | 1999-02-24 |
| WO1999000190A1 (en) | 1999-01-07 |
| ITMI971510A1 (it) | 1998-12-26 |
| CA2264697A1 (en) | 1999-01-07 |
| CN1128012C (zh) | 2003-11-19 |
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