ES2192935A1 - Sintesis de zeolita itq-21 - Google Patents

Sintesis de zeolita itq-21

Info

Publication number
ES2192935A1
ES2192935A1 ES200101145A ES200101145A ES2192935A1 ES 2192935 A1 ES2192935 A1 ES 2192935A1 ES 200101145 A ES200101145 A ES 200101145A ES 200101145 A ES200101145 A ES 200101145A ES 2192935 A1 ES2192935 A1 ES 2192935A1
Authority
ES
Spain
Prior art keywords
crystalline material
porous crystalline
preparation
same
organic compounds
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.)
Granted
Application number
ES200101145A
Other languages
English (en)
Other versions
ES2192935B1 (es
Inventor
Canos Avelino Corma
Garcia Fernando Rey
Cabanas Maria Jose Diaz
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Consejo Superior de Investigaciones Cientificas CSIC
Universidad Politecnica de Valencia
Original Assignee
Consejo Superior de Investigaciones Cientificas CSIC
Universidad Politecnica de Valencia
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
Priority to ES200101145A priority Critical patent/ES2192935B1/es
Application filed by Consejo Superior de Investigaciones Cientificas CSIC, Universidad Politecnica de Valencia filed Critical Consejo Superior de Investigaciones Cientificas CSIC
Priority to EP02730314A priority patent/EP1405825B1/en
Priority to ES02730314T priority patent/ES2327395T3/es
Priority to RU2003135790/15A priority patent/RU2296104C2/ru
Priority to DE60232724T priority patent/DE60232724D1/de
Priority to AU2002302660A priority patent/AU2002302660B2/en
Priority to PCT/ES2002/000223 priority patent/WO2002092511A1/es
Priority to CA002447448A priority patent/CA2447448C/en
Priority to AT02730314T priority patent/ATE434589T1/de
Priority to JP2002589403A priority patent/JP4386643B2/ja
Publication of ES2192935A1 publication Critical patent/ES2192935A1/es
Priority to US10/714,571 priority patent/US6849248B2/en
Priority to ZA2003/09511A priority patent/ZA200309511B/en
Application granted granted Critical
Publication of ES2192935B1 publication Critical patent/ES2192935B1/es
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
    • B01J29/035—Microporous crystalline materials not having base exchange properties, such as silica polymorphs, e.g. silicalites
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
    • C01B37/005—Silicates, i.e. so-called metallosilicalites or metallozeosilites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
    • C01B37/02—Crystalline silica-polymorphs, e.g. silicalites dealuminated aluminosilicate zeolites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
    • C01B39/48—Other types characterised by their X-ray diffraction pattern and their defined composition using at least one organic template directing agent
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING 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
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING 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
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/04—Oxides
    • C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING 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
    • C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
    • C10G29/20—Organic compounds not containing metal atoms
    • C10G29/205—Organic compounds not containing metal atoms by reaction with hydrocarbons added to the hydrocarbon oil
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING 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
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
    • C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
    • C10G47/12—Inorganic carriers
    • C10G47/16—Crystalline alumino-silicate carriers
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING 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
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
    • C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
    • C10G47/12—Inorganic carriers
    • C10G47/16—Crystalline alumino-silicate carriers
    • C10G47/20—Crystalline alumino-silicate carriers the catalyst containing other metals or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING 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
    • C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation

Abstract

Síntesis de la Zeolita ITQ-21. Se ha sintetizado un nuevo material poroso cristalino, denominado ITQ-21 que en su forma calcinada presenta los valores de difracción de rayos X que se dan en la Tabla 1. Se describe también la síntesis del material ITQ-21 en presencia de iones fluoruro y utilizando N(16)- metilesparteinio como agente director de estructura. El material es útil en su forma ácida y en forma de catalizador bifuncional en procesos de craqueo catalítico, hidrocraqueo, y alquilación de aromáticos.
ES200101145A 2001-05-14 2001-05-14 Sintesis de zeolita itq-21. Expired - Fee Related ES2192935B1 (es)

Priority Applications (12)

Application Number Priority Date Filing Date Title
ES200101145A ES2192935B1 (es) 2001-05-14 2001-05-14 Sintesis de zeolita itq-21.
AT02730314T ATE434589T1 (de) 2001-05-14 2002-05-10 Poröses kristallines material (zeolith itq-21), herstellungsverfahren dafür und verwendung davon bei der katalytischen umwandlung organischer verbindungen
RU2003135790/15A RU2296104C2 (ru) 2001-05-14 2002-05-10 Пористый кристаллический материал (цеолит itq-21), способ его получения и его применение в процессах каталитической конверсии органических соединений
DE60232724T DE60232724D1 (de) 2001-05-14 2002-05-10 Poröses kristallines material (zeolith itq-21), herstellungsverfahren dafür und verwendung davon beingen
AU2002302660A AU2002302660B2 (en) 2001-05-14 2002-05-10 Porous crystalline material (zeolite itq-21), the preparation method thereof and use of the same in the catalytic conversion of organic compounds
PCT/ES2002/000223 WO2002092511A1 (es) 2001-05-14 2002-05-10 Un material cristalino poroso (zeolita itq-21), su procedimiento de preparación y su uso en la conversión catalítica de compuestos orgánicos
EP02730314A EP1405825B1 (en) 2001-05-14 2002-05-10 Porous crystalline material (zeolite itq-21), the preparation method thereof and the use of same in the catalytic conversion of organic compounds
ES02730314T ES2327395T3 (es) 2001-05-14 2002-05-10 Material cristalino poroso (zeolita itq-21), el metodo de preparacion del mismo y el uso del mismo en la conservacion catalitica de compuestos organicos.
JP2002589403A JP4386643B2 (ja) 2001-05-14 2002-05-10 多孔質結晶性物質（ゼオライトｉｔｑ−２１）、その製造方法および有機化合物の触媒変換におけるその使用
CA002447448A CA2447448C (en) 2001-05-14 2002-05-10 Porous crystalline material (zeolite itq-21), the preparation method thereof and use of same in the catalytic conversion of organic compounds
US10/714,571 US6849248B2 (en) 2001-05-14 2003-11-14 Porous crystalline material (zeolite ITQ-21), the preparation method thereof and use of same in the catalytic conversion of organic compounds
ZA2003/09511A ZA200309511B (en) 2001-05-14 2003-12-08 Porous crystalline material (zeolite itq-21) the preparation method thereof and the use of same in the catalytic conversion of organic compounds

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
ES200101145A ES2192935B1 (es) 2001-05-14 2001-05-14 Sintesis de zeolita itq-21.

Publications (2)

Publication Number Publication Date
ES2192935A1 true ES2192935A1 (es) 2003-10-16
ES2192935B1 ES2192935B1 (es) 2004-08-16

Family

ID=8497771

Family Applications (2)

Application Number Title Priority Date Filing Date
ES200101145A Expired - Fee Related ES2192935B1 (es) 2001-05-14 2001-05-14 Sintesis de zeolita itq-21.
ES02730314T Expired - Lifetime ES2327395T3 (es) 2001-05-14 2002-05-10 Material cristalino poroso (zeolita itq-21), el metodo de preparacion del mismo y el uso del mismo en la conservacion catalitica de compuestos organicos.

Family Applications After (1)

Application Number Title Priority Date Filing Date
ES02730314T Expired - Lifetime ES2327395T3 (es) 2001-05-14 2002-05-10 Material cristalino poroso (zeolita itq-21), el metodo de preparacion del mismo y el uso del mismo en la conservacion catalitica de compuestos organicos.

Country Status (11)

Country Link
US (1) US6849248B2 (es)
EP (1) EP1405825B1 (es)
JP (1) JP4386643B2 (es)
AT (1) ATE434589T1 (es)
AU (1) AU2002302660B2 (es)
CA (1) CA2447448C (es)
DE (1) DE60232724D1 (es)
ES (2) ES2192935B1 (es)
RU (1) RU2296104C2 (es)
WO (1) WO2002092511A1 (es)
ZA (1) ZA200309511B (es)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005118476A1 (es) * 2004-05-28 2005-12-15 Consejo Superior De Investigaciones Científicas Zeolita itq-30
US6998037B2 (en) 2001-10-04 2006-02-14 Consejo Superior De Investigaciones Cientificas Use of zeolite ITQ-21 in the catalytic cracking of organic compounds
US7439411B2 (en) 2002-07-11 2008-10-21 Consejo Superior De Investigaciones Clentificas Zeolite catalyst for the alkylation of aromatic compounds with olefins, alcohols or polyalkylated aromatic compounds
EP2017005A2 (en) 2002-07-11 2009-01-21 Consejo Superior de Investigaciones Cientificas Zeolite catalyst for the alkylation of aromatic compounds with polyalkylated aromatic compounds
US7709408B2 (en) 2002-07-16 2010-05-04 Consejo Superior De Investigaciones Cientificas Catalyst based on a solid microporous crystalline material and method of improving diesel fraction quality using said catalyst

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2204257B1 (es) 2001-11-30 2005-05-01 Universidad Politecnica De Valencia Sintesis de itq-21 en ausencia de iones fluoruro.
ES2200701B1 (es) * 2002-07-16 2005-05-01 Universidad Politecnica De Valencia Catalizador de hidrocraqueo conteniendo un material solido cristalino microporoso y uso de dicho catalizador para el hidrocraqueo de alimentacion de hidrocarburos.
US7410924B2 (en) 2002-07-16 2008-08-12 Consejo Superior De Investigaciones Cientificas Hydrocracking catalyst comprising a microporous crystalline solid material
FR2858334B1 (fr) 2003-07-30 2005-09-02 Inst Francais Du Petrole Solide cristallise im-11 de type structural lta et son procede de preparation
FR2923477B1 (fr) 2007-11-12 2011-03-18 Inst Francais Du Petrole Solide cristallise im-18 et son procede de preparation
FR2923476B1 (fr) 2007-11-12 2010-12-31 Inst Francais Du Petrole Solide cristalise im-17 et son procede de preparation
FR2940266B1 (fr) 2008-12-18 2010-12-31 Inst Francais Du Petrole Solide cristallise im-20 et son procede de preparation
ES2430404B1 (es) * 2012-04-18 2014-09-29 Consejo Superior De Investigaciones Científicas (Csic) Material ITQ-49, su procedimiento de obtención y su uso
KR102321624B1 (ko) * 2014-05-23 2021-11-04 에스케이이노베이션 주식회사 디젤 수율을 극대화할 수 있는 rfcc 공정용 접촉분해촉매 및 이의 제조방법
ES2554648B1 (es) * 2014-06-20 2016-09-08 Consejo Superior De Investigaciones Científicas (Csic) Material ITQ-55, procedimiento de preparación y uso

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5271922A (en) * 1992-10-09 1993-12-21 Chevron Research And Technology Company Process for preparing molecular sieves using a sparteine template
US6043179A (en) * 1997-08-13 2000-03-28 California Institute Of Technology Zeolite CIT-5 and method of making

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3411874A (en) * 1964-11-09 1968-11-19 Mobil Oil Corp Zsm-2 zeolite and preparation thereof
DE3812592A1 (de) 1988-04-15 1989-10-26 Deggendorfer Werft Eisenbau Verfahren zur herstellung von zeolithen
US5393511A (en) * 1988-10-10 1995-02-28 Societe Nationale Elf Aquitaine Synthesis of zeolites of faujasite structure
US6080382A (en) * 1996-12-31 2000-06-27 Chevron U. S. A. Inc. Zeolite SSZ-48

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5271922A (en) * 1992-10-09 1993-12-21 Chevron Research And Technology Company Process for preparing molecular sieves using a sparteine template
US6043179A (en) * 1997-08-13 2000-03-28 California Institute Of Technology Zeolite CIT-5 and method of making

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
BARRETT, P.A. Synthesis in fluoride and hidroxide media and structure of the extra-large pore pure silica zeolite CIT-5. Journal of the Chemical Society, Faraday Transactions, 1998, Vol. 94, n·mero 16, pßginas 2475-2481, ISSN 0956-5000. *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6998037B2 (en) 2001-10-04 2006-02-14 Consejo Superior De Investigaciones Cientificas Use of zeolite ITQ-21 in the catalytic cracking of organic compounds
US7439411B2 (en) 2002-07-11 2008-10-21 Consejo Superior De Investigaciones Clentificas Zeolite catalyst for the alkylation of aromatic compounds with olefins, alcohols or polyalkylated aromatic compounds
EP2017005A2 (en) 2002-07-11 2009-01-21 Consejo Superior de Investigaciones Cientificas Zeolite catalyst for the alkylation of aromatic compounds with polyalkylated aromatic compounds
US7709408B2 (en) 2002-07-16 2010-05-04 Consejo Superior De Investigaciones Cientificas Catalyst based on a solid microporous crystalline material and method of improving diesel fraction quality using said catalyst
US7854834B2 (en) 2002-07-16 2010-12-21 Consejo Superior de Invetigaciones Cientificas Catalyst based on solid microporous crystalline material and method of improving diesel fraction quality using said catalyst
WO2005118476A1 (es) * 2004-05-28 2005-12-15 Consejo Superior De Investigaciones Científicas Zeolita itq-30
ES2246704A1 (es) * 2004-05-28 2006-02-16 Universidad Politecnica De Valencia Zeolita itq-30.
US8115001B2 (en) 2004-05-28 2012-02-14 Consejo Superior De Investigaciones Cientificas Zeolite ITQ-30

Also Published As

Publication number Publication date
DE60232724D1 (de) 2009-08-06
ES2327395T3 (es) 2009-10-29
EP1405825B1 (en) 2009-06-24
EP1405825A1 (en) 2004-04-07
JP2004525065A (ja) 2004-08-19
US20040149964A1 (en) 2004-08-05
RU2296104C2 (ru) 2007-03-27
CA2447448C (en) 2009-11-17
JP4386643B2 (ja) 2009-12-16
RU2003135790A (ru) 2005-05-20
ES2192935B1 (es) 2004-08-16
ZA200309511B (en) 2005-07-27
CA2447448A1 (en) 2002-11-21
WO2002092511A1 (es) 2002-11-21
US6849248B2 (en) 2005-02-01
AU2002302660B2 (en) 2007-03-29
ATE434589T1 (de) 2009-07-15

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