DK173496B1 - Fremgangsmåde til fremstilling af syntesegas ved vanddampreformering under anvendelse af en katalyseret metaloverflade - Google Patents
Fremgangsmåde til fremstilling af syntesegas ved vanddampreformering under anvendelse af en katalyseret metaloverflade Download PDFInfo
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- DK173496B1 DK173496B1 DK199800948A DKPA199800948A DK173496B1 DK 173496 B1 DK173496 B1 DK 173496B1 DK 199800948 A DK199800948 A DK 199800948A DK PA199800948 A DKPA199800948 A DK PA199800948A DK 173496 B1 DK173496 B1 DK 173496B1
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- 238000002407 reforming Methods 0.000 title claims description 24
- 238000000034 method Methods 0.000 title claims description 13
- 229910052751 metal Inorganic materials 0.000 title claims description 12
- 239000002184 metal Substances 0.000 title claims description 12
- 230000015572 biosynthetic process Effects 0.000 title claims description 6
- 238000003786 synthesis reaction Methods 0.000 title claims description 5
- 239000003054 catalyst Substances 0.000 claims description 36
- 239000007789 gas Substances 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 230000003197 catalytic effect Effects 0.000 claims description 7
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims description 6
- 239000008188 pellet Substances 0.000 claims description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 3
- 239000003546 flue gas Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000002485 combustion reaction Methods 0.000 claims description 2
- 239000000446 fuel Substances 0.000 claims description 2
- 238000000629 steam reforming Methods 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims 1
- 239000010970 precious metal Substances 0.000 claims 1
- 239000000463 material Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000011149 active material Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000012700 ceramic precursor Substances 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000006057 reforming reaction Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000007723 transport mechanism Effects 0.000 description 1
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Description
i DK 173496 B1
Denne opfindelse er rettet på fremgangsmåde til fremstilling af syntesegas ved vanddampreformering af et carbon-hydridfødemateriale i kontakt med katalyseret metaloverflade.
5 Betegnelsen benyttes om et katalysatorsystem, hvor et katalysatorlag er fæstnet på overfladen af et andet materiale, f.eks. metalliske overflader. Det andet materiale tjener som en understøttende struktur, der bebringer systemet styrke. Dette tillader udformning af katalysatorformer, 10 der ikke selv ville have en tilstrækkelig mekanisk styrke.
Syntesegas produceres ud fra carbonhydrider ved vanddampreformering ifølge reaktionerne (1)-(3):
CnHm + n H20 6 n CO + (n + y) H2 (-ΔΗ°298 < 0) (1) 15 CO + HzO W C02 + H2 (-ΔΗ°298 = 41 kJ/mol) (2) CH4 + HzO W CO + 3 H2 (-ΔΗ°298 = -206 kJ/mol) (3)
Kendt vanddampreformeringsteknik benytter reformeringskatalysatorer på form af pellets med diverse størrelser og 20 former. Disse katalysatorpellets anbringes i fast leje reaktorer (reformerrør). Reformeringsreaktionen er endotermisk.
I konventionelle reformere tilføres den nødvendige varme til reaktionen fra området uden for rørene normalt som en kombination af stråling og konvektion til den ydre side af et 25 reformerrør. Varmen overføres ved varmeledning gennem rørvæggen til den indre side af røret og overføres ved konvektion til gasfasen. Endelig overføres varme ved konvektion fra gasfasen til katalysatorpellets. Katalysatortemperaturen kan være mere end 100EC lavere end temperaturen af den indre 30 rørvæg ved samme aksiale position på reformerrøret.
En vanddampreformeringskatalysator, hvor det katalytisk aktive materiale er afsat på en metallisk nikkelbærer i form DK 173496 B1 2 af en snoet strimmel er omtalt i U.S. patent nr. 4.400.309.
Det anføres at en således udformet katalyseret overflade reducerer tryktabet over et reformerrør forsynet med denne form for katalysator og at kompressionsenergien reduceres i 5 forhold til de kendte partikkelformede vanddampreforming katalysatorer.
Det er blevet fundet, at trykfaldsreduktioner yderligere forbedres og varmetransporten bliver mere effektiv, når der benyttes katalyseret metaloverflade i vanddampreformerings-10 processen når den katalyserede overflade er i det væsentlige i samme for som væggen. Varmetransporten til katalysatoren forgår ved ledning fra den indre rørvæg. Dette ér en meget mere effektiv transportmekanisme end en transport ved konvektion gennem gasfasen. Resultatet er, at temperaturerne af 15 den indre rørvæg og af katalysatoren er næsten identiske (med en forskel under 5EC). Yderligere kan rørtykkelsen reduceres, se nedenfor, hvilket gør temperaturforskellen mindre mellem den ydre og indre side af reformerrøret. Det er således muligt både at have en højere katalysatortempera-20 tur og en lavere rørtemperatur under fastholdelse af alle andre betingelser, når konventionelle reformerrør erstattes med rør med katalyseret metaloverflade. En lav temperatur for den ydre rørvæg er efterstræbelsesværdig, da dette forlænger levetiden for røret. En høj kataltysatortemperatur er 25 fordelagtig, da reaktionshastigheden vokser med temperaturen, og da ligevægten i reaktion (3) forskydes mod højre, hviket medfører en bedre udnyttelse af fødematerialet.
Tryktabet over et katalysatorforsynet reformerrør er for samme rørdiameter meget lavere end i det konventienelle til-30 fælde. Dette tillader anvendelse af reaktorrør med en mindre diameter under stadig opretholdelse af et acceptabelt tryktab. En mindre rørdiameter medfører en forøget levetid for 3 DK 173496 B1 et rør, fører til tolerance for højere temperaturer og reducerer forbruget af rørmateriale.
Endelig reduceres katalysatormængden ved anvendelse af reformerrør med katalyseret metaloverflade i forhold til 5 konverntionelle reformere med et fast leje af reformeringskatalysatoren.
Fig. 1 viser den forreste del af et anlæg, der producerer syntesegas. Fødematerial 2 forudopvarmes, afsvovles i enhed 4, blandes med procesdamp 6 og opvarmes yderligere før 10 indgang til en adiabatisk præreformer 8. Effluentstrømmen fra præreformer 8 opvarmes yderligere i en i røggaskanalen 12 anbragt varmevekslerspiral og sendes til rørreformeren 14, hvor konversion af methan til hydrogen, carbonmonoxid og carbondioxid finder sted. Viderebearbejdningen af effluent-15 gassen fra rørreformeren afhænger af anvendelsen af produktet .
Katalyseret metaloverflade kan benyttes i to af de på Fig. 1 viste enheder: 1. I forudopvarmerspiral 10 til opvarmning af præreformer-20 effluentgassren før dennes indgang i rørreformer 14.
2. I rørreformer 14.
Katalytisk overtrækning af en metaloverflade (wash-coating) er en velkendt proces (en beskrivelse gives f. eks. i Cybulski, A. og Moulijn, J.A., Structured Catalysts and 25 Reactors, Marcel Dekker, Inc., New York, 1998, kapitel 3 og referencer heri). Et tyndt lag af en opslæmning indeholdende den keramiske precursor anbringes på overfladen, f.eks. ved hjælp af påsprøjtning, påmaling eller neddypning. Efter - påføringen af overtrækket tørres opslæmningen og kalcineres 30 ved en temperatur, der sædvanligvis er i området 350-1000EC. Endelig imprægneres det keramiske lag med det katalytisk 4 DK 173496 B1 aktive materiale. Alternativt påføres det katalytisk aktive materiale samtidigt med den keramiske precursor.
Der findes desværre en række ulemper ved reaktorer med katalyseret metaloverflade i forhold til fast leje 5 reaktorer:
Katalysatorlaget kan ikke erstattes, hvis det mister sin aktivitet, enten ved ældning eller ved forgiftning.
Katalysatorlaget kan kun anbringes på visse materialer. Reaktorrørene skal være fremstillet af en sådan type mate-10 riale, der kan være mere kostbar end et konventionelt rørmateriale. Vanddampreformeringsreaktionerne foregår under betingelser med tryk, og rørtykkelsen er stor, hvorfor materialeprisen i signifikant grad påvirker omkostningerne.
Ydermere kan produktionen af lange rør af katalysator-15 forsynet hardware være vanskelig. Reaktorrøret kan have en længde på 10 m eller mere. Det vil være svært at opnå en jævn tykkelse for reformeringskatalysatoren gennem hele sådan en længde, og midler til opnåelse af et jævnt lag, der kan benyttes i mindre skala, såsom centrifugering af røret 20 er vanskeligere at benytte for denne størrelse rør. Yderligere kan en passende varmebehandling af et rør af denne størrelse være vanskelig.
Disse ulemper kan overvindes ved som nævnt nedenfor at producere det katalysatorforsynede hardware adskilt fra 25 reaktoren.
En metalbærer skæres i passende størrelser. Arket wash-coates som beskrevet ovenfor. Efter denne washcoating formes arket til det relevante udseende. Alternativt formes arket til sit endelige udseende før en washcoating. Den 30 metalliske bærer formes, så den i det væsentlige har samme form som reaktorvæggen og er blevet anbragt i en direkte varmeledende forbindelse med reaktorvæggen.
5 DK 173496 B1
Det vil være muligt at udskifte katalysatorlaget, hvis det ikke mere har en stor nok katalytisk aktivitet. Det dyre stål, der benyttes til opnåelse af adhæsion af katalysatoren til metaloverfladen, vil kun omfatte en ringe del af total-5 metalforbruget. Det katalysatorforsynede hardware kan produceres i mindre sektioner, der vil være lettere at fremstille og håndtere.
I overenstemmelse hermed tilvejebringer denne opfindelse en fremgangsmåde til fremstilling af en hydrogen- og carbon-10 monoxidrig gas ved katalytisk vanddampreformering af et car-bonhydridfødemateriale, omfattende trinnene: (a) at føre en procesgas af carbonhydridfødemateriale gennem en første reaktor med en vanddampreformeringskatalysator op- 15 varmet af en varm gasstrøm; (b) at føre effluenten fra den første reaktor til en følgende rørreaktor indeholdende en vanddampreformeringskatalysator og opvarmet ved afbrænding af brændstof til opnåelse herved af en varm gasstrøm af vanddampreformeret produktgas 20 og en varm strøm af røggas, og som er ejendommelig ved, at en reformeringskatalysator er anbragt på en metallisk bærer med i det væsentlige samme form som væggen i reaktoren og anbragt i varmeledende forbindelse med reaktorvæggen.
I en specifik udførelsesform for opfindelsen tilveje-25 bringes reformeringskatalysatoren i reaktoren i trin b både med en metallisk bærer med i det væsentlige samme form som væggen i reaktoren og anbragt i varmeledende forbindelse med reaktorvæggen og som pellets af reformeringskatalysator.
Claims (4)
1. Fremgangsmåde til fremstilling af en hydrogen- og carbonmonoxidrig gas ved katalytisk vanddampreformering af 5 et carbonhydridfødemateriale, omfattende trinnene: (a) at føre en procesgas af carbonhydridfødemateriale gennem en første reaktor med en vanddampreformeringskatalysator opvarmet af en varm gasstrøm; 10 (b) at føre effluenten fra den første reaktor til en følgende rørreaktor indeholdende en vanddampreformeringskatalysator og opvarmet ved afbrænding af brændstof til opnåelse herved af en varm gasstrøm af vanddampreformeret produktgas og en varm strøm af røggas, og kendetegnet ved, 15 at en reformeringskatalysator er anbragt på en metallisk bærer med i det væsentlige samme form som reaktorvæggen i varmeledende forbindelse med reaktorvæggen i det mindste i reaktoren i trin a.
2. Fremgangsmåde ifølge krav 1, kendetegnet ved, at 20 reformeringskatalysatoren i reaktoren i trin b både er forsynet med en metallisk bærer med i det væsentlige samme form som væggen i reaktoren og anbragt i varmeledende forbindelse med reaktorvæggen og foreligger som pellets af reformeringskatalysator.
3. Fremgangsmåde ifølge krav 1, kendetegnet ved, at reformeringskatalysatoren i trin b foreligger som pellets af reformeringskatalysator.
4. Fremgangsmåde ifølge krav 1, kendetegnet véd, at vanddampreformeringskatalysatoren omfatter nikkel og/eller 30 ædelmetaller. Produktion af syntesegas ved vanddampreformering under anvendelse af katalyseret metaloverflade.
Priority Applications (11)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DK199800948A DK173496B1 (da) | 1998-07-16 | 1998-07-16 | Fremgangsmåde til fremstilling af syntesegas ved vanddampreformering under anvendelse af en katalyseret metaloverflade |
AU49045/99A AU752810B2 (en) | 1998-07-16 | 1999-07-01 | Synthesis gas production by steam reforming using catalyzed hardware |
CNB998094307A CN1187259C (zh) | 1998-07-16 | 1999-07-01 | 使用催化结构件的蒸汽转化法生产合成气 |
US09/743,530 US6746624B1 (en) | 1998-07-16 | 1999-07-01 | Synthesis gas production by steam reforming using catalyzed hardware |
PCT/EP1999/004562 WO2000003579A2 (en) | 1998-07-16 | 1999-07-01 | Synthesis gas production by steam reforming using reactors the walls of which are catalytic |
CA002340698A CA2340698C (en) | 1998-07-16 | 1999-07-01 | Synthesis gas production by steam reforming using catalyzed hardware |
BR9912123-9A BR9912123A (pt) | 1998-07-16 | 1999-07-01 | Produção de gás de sìntese através de regeneração de vapor usando hardware catalisado |
RU2001101486/15A RU2220901C2 (ru) | 1998-07-16 | 1999-07-01 | Получение синтез-газа паровым реформингом с использованием катализированного оборудования |
EP99932779A EP1181240A2 (en) | 1998-07-16 | 1999-07-01 | Synthesis gas production by steam reforming using reactors the walls of which are catalytic |
JP2000559723A JP3790426B2 (ja) | 1998-07-16 | 1999-07-01 | 触媒化ハードウェアを使用した水蒸気改質による合成ガスの生成方法 |
ZA2001/00293A ZA200100293B (en) | 1998-07-16 | 2001-01-10 | Synthesis gas production by steam reforming using catalyzed hardware |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DK94898 | 1998-07-16 | ||
DK199800948A DK173496B1 (da) | 1998-07-16 | 1998-07-16 | Fremgangsmåde til fremstilling af syntesegas ved vanddampreformering under anvendelse af en katalyseret metaloverflade |
Publications (2)
Publication Number | Publication Date |
---|---|
DK199800948A DK199800948A (da) | 2000-03-28 |
DK173496B1 true DK173496B1 (da) | 2001-01-02 |
Family
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DK199800948A DK173496B1 (da) | 1998-07-16 | 1998-07-16 | Fremgangsmåde til fremstilling af syntesegas ved vanddampreformering under anvendelse af en katalyseret metaloverflade |
Country Status (11)
Country | Link |
---|---|
US (1) | US6746624B1 (da) |
EP (1) | EP1181240A2 (da) |
JP (1) | JP3790426B2 (da) |
CN (1) | CN1187259C (da) |
AU (1) | AU752810B2 (da) |
BR (1) | BR9912123A (da) |
CA (1) | CA2340698C (da) |
DK (1) | DK173496B1 (da) |
RU (1) | RU2220901C2 (da) |
WO (1) | WO2000003579A2 (da) |
ZA (1) | ZA200100293B (da) |
Families Citing this family (21)
Publication number | Priority date | Publication date | Assignee | Title |
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CN1117693C (zh) * | 1998-07-21 | 2003-08-13 | 霍尔多托普索埃公司 | 蒸汽重整生产合成煤气 |
US6749829B2 (en) * | 2002-07-23 | 2004-06-15 | Bp Corporation North America Inc. | Hydrogen to steam reforming of natural gas to synthesis gas |
EP1403217A1 (en) | 2002-09-26 | 2004-03-31 | Haldor Topsoe A/S | Process and apparatus for the preparation of synthesis gas |
EP1403215B1 (en) * | 2002-09-26 | 2013-03-13 | Haldor Topsoe A/S | Process and apparatus for the preparation of synthesis gas |
EP1413547A1 (en) * | 2002-09-26 | 2004-04-28 | Haldor Topsoe A/S | Process for the production of synthesis gas |
ES2381105T3 (es) * | 2003-02-05 | 2012-05-23 | Haldor Topsoe A/S | Procedimiento para el tratamiento de gas de síntesis |
US7320778B2 (en) * | 2004-07-21 | 2008-01-22 | Catacel Corp. | High-performance catalyst support |
WO2006045746A1 (en) * | 2004-10-20 | 2006-05-04 | Shell Internationale Research Maatschappij B.V. | Process to prepare a mixture of carbon monoxide and hydrogen |
KR20060081728A (ko) * | 2005-01-10 | 2006-07-13 | 삼성에스디아이 주식회사 | 연료 전지 시스템, 개질기 및 버너 |
US7565743B2 (en) * | 2005-04-14 | 2009-07-28 | Catacel Corp. | Method for insertion and removal of a catalytic reactor cartridge |
US20060230613A1 (en) * | 2005-04-14 | 2006-10-19 | Catacel Corporation | Catalytic reactor cartridge |
US7472936B2 (en) * | 2005-04-14 | 2009-01-06 | Catacel Corp. | Tool for insertion and removal of a catalytic reactor cartridge |
DE102005021500A1 (de) * | 2005-05-10 | 2006-11-16 | Uhde Gmbh | Verfahren zur Aufheizung eines Dampf-/Erdgasgemisches im Bereich eines Gassammelrohres nach einem Primärreformer |
US7682580B2 (en) * | 2005-05-19 | 2010-03-23 | Catacel Corp. | Catalytic reactor having radial leaves |
US7504048B2 (en) * | 2005-06-14 | 2009-03-17 | Air Products And Chemicals, Inc. | Axial convective reformer |
US7501102B2 (en) * | 2005-07-28 | 2009-03-10 | Catacel Corp. | Reactor having improved heat transfer |
US7829035B2 (en) | 2006-01-19 | 2010-11-09 | Massachusetts Institute Of Technology | Oxidation catalyst |
US7501078B2 (en) * | 2007-01-10 | 2009-03-10 | Air Products And Chemicals, Inc. | Process for generating synthesis gas using catalyzed structured packing |
CN101012925B (zh) * | 2007-01-31 | 2012-08-22 | 徐建明 | 烃燃料与水或水蒸汽燃烧产生的废气回收后再循环燃烧利用的方法 |
DE102012222560A1 (de) * | 2012-12-07 | 2014-06-12 | Bayerische Motoren Werke Aktiengesellschaft | Reaktor zur Freisetzung von Wasserstoff |
CN114570400B (zh) * | 2022-03-20 | 2024-03-26 | 胡进 | 降低有机固废热裂解过程中油蜡比例的催化剂、催化剂结构件及应用 |
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CA1008667A (en) * | 1972-06-30 | 1977-04-19 | Foster Wheeler Corporation | Catalytic steam reforming |
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DE2848086C2 (de) | 1978-11-06 | 1986-11-06 | Kernforschungsanlage Jülich GmbH, 5170 Jülich | Röhrenreaktor für katalytische Prozesse |
DE3480192D1 (en) * | 1983-03-25 | 1989-11-23 | Ici Plc | Steam reforming |
US5039510A (en) * | 1983-03-25 | 1991-08-13 | Imperial Chemical Industries Plc | Steam reforming |
DE3424208A1 (de) * | 1984-06-30 | 1986-01-16 | Kernforschungsanlage Jülich GmbH, 5170 Jülich | Verfahren und vorrichtung zur umsatzsteigerung von mit wasserstoffbildung ablaufenden gasreaktionen |
GB9000389D0 (en) * | 1990-01-08 | 1990-03-07 | Ici Plc | Steam reforming |
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US6274113B1 (en) * | 1994-01-04 | 2001-08-14 | Chevron Phillips Chemical Company Lp | Increasing production in hydrocarbon conversion processes |
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EP0834465B1 (en) * | 1996-10-04 | 2000-07-19 | Haldor Topsoe A/S | Steam reforming process |
DK0855366T3 (da) * | 1997-01-22 | 2001-08-13 | Haldor Topsoe As | Syntesegasproduktion ved dampreforming under anvendelse af katalyseret hardware |
DK173052B1 (da) * | 1997-05-05 | 1999-12-06 | Topsoe Haldor As | Fremgangsmåde til fremstilling af ammoniak syntesegas |
DE69933351T2 (de) * | 1998-11-18 | 2007-01-11 | Haldor Topsoe A/S | Verfahren zur Herstellung eines Gegenstandes mit katalytischer Oberflächenschicht |
-
1998
- 1998-07-16 DK DK199800948A patent/DK173496B1/da not_active IP Right Cessation
-
1999
- 1999-07-01 RU RU2001101486/15A patent/RU2220901C2/ru active
- 1999-07-01 US US09/743,530 patent/US6746624B1/en not_active Expired - Lifetime
- 1999-07-01 BR BR9912123-9A patent/BR9912123A/pt not_active IP Right Cessation
- 1999-07-01 CA CA002340698A patent/CA2340698C/en not_active Expired - Lifetime
- 1999-07-01 WO PCT/EP1999/004562 patent/WO2000003579A2/en active IP Right Grant
- 1999-07-01 AU AU49045/99A patent/AU752810B2/en not_active Ceased
- 1999-07-01 CN CNB998094307A patent/CN1187259C/zh not_active Expired - Fee Related
- 1999-07-01 EP EP99932779A patent/EP1181240A2/en not_active Ceased
- 1999-07-01 JP JP2000559723A patent/JP3790426B2/ja not_active Expired - Fee Related
-
2001
- 2001-01-10 ZA ZA2001/00293A patent/ZA200100293B/en unknown
Also Published As
Publication number | Publication date |
---|---|
BR9912123A (pt) | 2001-04-10 |
ZA200100293B (en) | 2002-06-26 |
JP2002520247A (ja) | 2002-07-09 |
CN1187259C (zh) | 2005-02-02 |
WO2000003579A3 (en) | 2001-10-11 |
DK199800948A (da) | 2000-03-28 |
JP3790426B2 (ja) | 2006-06-28 |
AU4904599A (en) | 2000-02-07 |
US6746624B1 (en) | 2004-06-08 |
CA2340698C (en) | 2004-11-30 |
AU752810B2 (en) | 2002-10-03 |
RU2220901C2 (ru) | 2004-01-10 |
EP1181240A2 (en) | 2002-02-27 |
CN1342131A (zh) | 2002-03-27 |
WO2000003579A2 (en) | 2000-01-27 |
CA2340698A1 (en) | 2000-01-27 |
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