ATE355904T1 - Zusammensetzung eines molekularsiebkatalysators, seine herstellung und seine verwendung in einem umwandlungsverfahren - Google Patents

Zusammensetzung eines molekularsiebkatalysators, seine herstellung und seine verwendung in einem umwandlungsverfahren

Info

Publication number
ATE355904T1
ATE355904T1 AT02749644T AT02749644T ATE355904T1 AT E355904 T1 ATE355904 T1 AT E355904T1 AT 02749644 T AT02749644 T AT 02749644T AT 02749644 T AT02749644 T AT 02749644T AT E355904 T1 ATE355904 T1 AT E355904T1
Authority
AT
Austria
Prior art keywords
molecular sieve
catalyst composition
conversion process
composition
sieve catalyst
Prior art date
Application number
AT02749644T
Other languages
English (en)
Inventor
Stephen N Vaughn
Luc R M Martens
Kenneth R Clem
Machteld M Mertens
Albert E Schweizer
Yun-Feng Chang
Original Assignee
Exxonmobil Chem Patents Inc
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=27489456&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=ATE355904(T1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Priority claimed from US09/891,674 external-priority patent/US6440894B1/en
Priority claimed from US10/052,058 external-priority patent/US6710008B2/en
Application filed by Exxonmobil Chem Patents Inc filed Critical Exxonmobil Chem Patents Inc
Application granted granted Critical
Publication of ATE355904T1 publication Critical patent/ATE355904T1/de

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Classifications

    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42Catalytic treatment
    • C10G3/44Catalytic treatment characterised by the catalyst used
    • C10G3/48Catalytic treatment characterised by the catalyst used further characterised by the catalyst support
    • C10G3/49Catalytic treatment characterised by the catalyst used further characterised by the catalyst support containing crystalline aluminosilicates, e.g. molecular sieves
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00Catalysts comprising molecular sieves
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00Catalysts comprising molecular sieves
    • B01J29/82Phosphates
    • B01J29/84Aluminophosphates containing other elements, e.g. metals, boron
    • B01J29/85Silicoaluminophosphates [SAPO compounds]
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027Powdering
    • B01J37/0045Drying a slurry, e.g. spray drying
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08Heat treatment
    • B01J37/10Heat treatment in the presence of water, e.g. steam
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00Aliphatic unsaturated hydrocarbons
    • C07C11/02Alkenes
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00Aliphatic unsaturated hydrocarbons
    • C07C11/02Alkenes
    • C07C11/04Ethene
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00Aliphatic unsaturated hydrocarbons
    • C07C11/02Alkenes
    • C07C11/06Propene
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/62Catalyst regeneration
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10After treatment, characterised by the effect to be obtained
    • B01J2229/26After treatment, characterised by the effect to be obtained to stabilize the total catalyst structure
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30After treatment, characterised by the means used
    • B01J2229/36Steaming
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30After treatment, characterised by the means used
    • B01J2229/42Addition of matrix or binder particles
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/60Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00Catalysts comprising molecular sieves
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00Catalysts comprising molecular sieves
    • C07C2529/82Phosphates
    • C07C2529/84Aluminophosphates containing other elements, e.g. metals, boron
    • C07C2529/85Silicoaluminophosphates (SAPO compounds)
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/20C2-C4 olefins
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals
    • Y02P20/52Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00Technologies relating to oil refining and petrochemical industry
    • Y02P30/20Technologies relating to oil refining and petrochemical industry using bio-feedstock
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00Technologies relating to oil refining and petrochemical industry
    • Y02P30/40Ethylene production

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Thermal Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Steroid Compounds (AREA)
AT02749644T 2001-06-25 2002-06-24 Zusammensetzung eines molekularsiebkatalysators, seine herstellung und seine verwendung in einem umwandlungsverfahren ATE355904T1 (de)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US09/891,674 US6440894B1 (en) 2001-06-25 2001-06-25 Methods of removing halogen from non-zeolitic molecular sieve catalysts
US10/052,058 US6710008B2 (en) 2002-01-17 2002-01-17 Method of making molecular sieve catalyst
US36590202P 2002-03-20 2002-03-20
US36598102P 2002-03-20 2002-03-20

Publications (1)

Publication Number Publication Date
ATE355904T1 true ATE355904T1 (de) 2007-03-15

Family

ID=27489456

Family Applications (2)

Application Number Title Priority Date Filing Date
AT02749644T ATE355904T1 (de) 2001-06-25 2002-06-24 Zusammensetzung eines molekularsiebkatalysators, seine herstellung und seine verwendung in einem umwandlungsverfahren
AT02780885T ATE373517T1 (de) 2001-06-25 2002-06-24 Herstellung einer molsiebkatalysatorzusammensetzung und verwendung bei umwandlungsverfahren

Family Applications After (1)

Application Number Title Priority Date Filing Date
AT02780885T ATE373517T1 (de) 2001-06-25 2002-06-24 Herstellung einer molsiebkatalysatorzusammensetzung und verwendung bei umwandlungsverfahren

Country Status (12)

Country Link
EP (2) EP1412084B1 (de)
JP (1) JP4781627B2 (de)
KR (1) KR100886532B1 (de)
CN (1) CN1239262C (de)
AT (2) ATE355904T1 (de)
AU (1) AU2002350150B2 (de)
BR (1) BR0210670A (de)
CA (1) CA2451667C (de)
DE (2) DE60222559D1 (de)
NO (1) NO20035656L (de)
WO (2) WO2003000412A1 (de)
ZA (1) ZA200309671B (de)

Families Citing this family (34)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7071136B2 (en) 2003-05-21 2006-07-04 Exxonmobil Chemical Patents Inc Attrition resistant molecular sieve catalysts
US6951830B2 (en) * 2003-08-05 2005-10-04 Exxonmobil Chemical Patents Inc. Molecular sieve catalyst compositions, their production and use in conversion processes
US7125821B2 (en) 2003-09-05 2006-10-24 Exxonmobil Chemical Patents Inc. Low metal content catalyst compositions and processes for making and using same
US7122500B2 (en) * 2003-09-22 2006-10-17 Exxonmobil Chemical Patents Inc. Molecular sieve catalyst composition, its making and use in conversion processes
US7241713B2 (en) 2003-10-02 2007-07-10 Exxonmobil Chemical Patents Inc. Molecular sieve catalyst composition, its making and use in conversion processes
US7241716B2 (en) * 2003-11-10 2007-07-10 Exxonmobil Chemical Patents Inc. Protecting catalytic sites of metalloaluminophosphate molecular sieves
US7312369B2 (en) 2004-04-28 2007-12-25 Exxonmobil Chemical Patents Inc. Attrition resistant molecular sieve catalyst, method of making and process for using
US7253331B2 (en) * 2004-05-12 2007-08-07 Exxonmobil Chemical Patents Inc. Molecular sieve catalyst composition, its making and use in conversion processes
US7456330B2 (en) 2005-01-31 2008-11-25 Exxonmobil Chemical Patents Inc. Molecular sieve catalyst composition, its making and use in conversion processes
US7453020B2 (en) 2005-01-31 2008-11-18 Exxonmobil Chemical Patents Inc. Molecular sieve catalyst composition, its making and use in conversion processes
EP1846156B1 (de) * 2005-01-31 2018-08-08 ExxonMobil Chemical Patents Inc. Molsiebkatalysatorzusammensetzungen, herstellung davon und verwendung bei umwandlungsverfahren
CN101111313B (zh) * 2005-01-31 2010-05-12 埃克森美孚化学专利公司 分子筛催化剂组合物,其制备和在转化方法中的应用
US7449611B2 (en) 2005-01-31 2008-11-11 Exxonmobil Chemical Patents Inc. Molecular sieve catalyst composition, its making and use in conversion processes
US7737316B2 (en) 2005-06-24 2010-06-15 Exxonmobil Chemical Patents Inc. Method of flocculation and formulation of crystalline materials
US7309679B2 (en) * 2005-08-08 2007-12-18 Uop Llc Attrition resistant MTO catalyst
US7329625B2 (en) 2005-11-02 2008-02-12 Exxonmobil Chemical Patents Inc. Attrition resistant molecular sieve catalyst
US7767871B2 (en) 2005-12-22 2010-08-03 Exxonmobil Chemical Patents Inc. Method of recovering crystalline material and compositions therefrom
BRPI0810133B1 (pt) 2007-04-26 2023-01-17 Johnson Matthey Public Limited Company Método para converter óxidos de nitrogênio de um gás em nitrogênio, sistema de escapamento para um motor de combustão interna de queima pobre veicular, e, aparelho
US7772337B2 (en) 2007-09-21 2010-08-10 Exxonmobil Chemical Patents Inc. Method of formulating a molecular sieve catalyst composition by controlling component addition
US7732537B2 (en) 2008-01-29 2010-06-08 Exxonmobil Chemical Patents Inc. Methods addressing aging in flocculated molecular sieve catalysts for hydrocarbon conversion processes
EP2098287A1 (de) * 2008-03-03 2009-09-09 ExxonMobil Chemical Patents Inc. Verfahren zur Formulierung einer Molekularsiebkatalysatorzusammensetzung mittels Kontrolle der Komponentenhinzufügung
KR100950477B1 (ko) 2008-03-05 2010-03-31 주식회사 하이닉스반도체 전하 트랩층을 갖는 불휘발성 메모리소자의 제조방법
WO2010085708A2 (en) 2009-01-23 2010-07-29 Signa Chemistry, Inc. Catalytic dehydration of alcohols using phase pure, calcined single and multi-site heterogeneous catalysts
PL2440328T3 (pl) 2009-06-12 2017-06-30 Albemarle Europe Sprl. Katalizatory z sitem molekularnym sapo, ich otrzymywanie i zastosowania
KR101193973B1 (ko) 2009-10-22 2012-10-24 현대엔지니어링 주식회사 고강도를 갖는 sapo-34 미소구형체 촉매, 이의 제조방법 및 이를 이용한 경질올레핀의 제조방법
JP6336396B2 (ja) 2011-11-24 2018-06-06 インディアン インスティテュート オブ テクノロジー 水精製のための多層有機−テンプレート−ベーマイト−ナノアーキテクチャ
CN104520706B (zh) 2012-04-17 2017-03-01 印度理工学院 使用量子簇检测水流量
CN103418430A (zh) * 2012-05-16 2013-12-04 中国石油化工股份有限公司 高耐磨流化床催化剂的制备方法
WO2016032636A1 (en) * 2014-08-26 2016-03-03 Exxonmobil Chemical Patents Inc. Treatment of off-gas in the production of para-xylene by the methylation of toluene and/or benzene
DK3356039T3 (da) * 2015-09-30 2021-04-06 Vito Nv Vlaamse Instelling Voor Tech Onderzoek Nv Fremgangsmåde til fremstilling af en katalytisk bulkstruktur og dets anvendelse i methanol til olefiner-reaktioner
CN105709856B (zh) * 2016-04-15 2019-03-15 中国石油大学(华东) 一种调变金属在分子筛上分布的催化剂的制备方法
CN106268929A (zh) * 2016-07-21 2017-01-04 无锡威孚环保催化剂有限公司 Cha分子筛scr整体式催化剂的制备方法
CN109701634B (zh) * 2017-10-26 2021-09-03 中国石油化工股份有限公司 合成气制备低碳烃的催化剂组合物及其用途
CN115023446B (zh) * 2020-01-27 2024-08-30 台塑工业美国公司 制备催化剂的工艺和催化剂组合物

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Publication number Priority date Publication date Assignee Title
US4861938A (en) * 1987-07-07 1989-08-29 Uop Chemical conversion process
CA1315300C (en) * 1987-07-07 1993-03-30 William Howard Henstock Chemical conversion process
US5095163A (en) * 1991-02-28 1992-03-10 Uop Methanol conversion process using SAPO catalysts
TWI234556B (en) * 1997-07-23 2005-06-21 Mitsubishi Gas Chemical Co Catalysts for methanol conversion reactions
WO1999021651A1 (en) * 1997-10-29 1999-05-06 Exxon Chemical Patents Inc. Method for making catalysts containing silicoaluminophosphate molecular sieve and catalyst thus prepared
US6049017A (en) * 1998-04-13 2000-04-11 Uop Llc Enhanced light olefin production
US6710008B2 (en) * 2002-01-17 2004-03-23 Exxonmobil Chemical Patents Inc. Method of making molecular sieve catalyst

Also Published As

Publication number Publication date
CN1535177A (zh) 2004-10-06
AU2002350150B2 (en) 2008-02-07
NO20035656D0 (no) 2003-12-17
EP1401573B1 (de) 2007-03-07
EP1412084B1 (de) 2007-09-19
CA2451667A1 (en) 2003-01-03
JP4781627B2 (ja) 2011-09-28
KR100886532B1 (ko) 2009-03-02
ATE373517T1 (de) 2007-10-15
EP1412084A1 (de) 2004-04-28
WO2003000413B1 (en) 2003-03-06
KR20040012973A (ko) 2004-02-11
EP1401573A1 (de) 2004-03-31
BR0210670A (pt) 2004-10-13
DE60218673D1 (de) 2007-04-19
DE60222559D1 (de) 2007-10-31
JP2004537398A (ja) 2004-12-16
NO20035656L (no) 2004-02-20
CA2451667C (en) 2012-03-27
WO2003000412A1 (en) 2003-01-03
ZA200309671B (en) 2005-02-23
WO2003000413A1 (en) 2003-01-03
CN1239262C (zh) 2006-02-01

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