ES2092428A1 - Material de estructura tipo zeolita de poros ultragrandes con un red constituida por oxidos de silicio y titanio; su sintesis y utilizacion para la oxidacion selectiva de productos organicos. - Google Patents
Material de estructura tipo zeolita de poros ultragrandes con un red constituida por oxidos de silicio y titanio; su sintesis y utilizacion para la oxidacion selectiva de productos organicos.Info
- Publication number
- ES2092428A1 ES2092428A1 ES09301327A ES9301327A ES2092428A1 ES 2092428 A1 ES2092428 A1 ES 2092428A1 ES 09301327 A ES09301327 A ES 09301327A ES 9301327 A ES9301327 A ES 9301327A ES 2092428 A1 ES2092428 A1 ES 2092428A1
- Authority
- ES
- Spain
- Prior art keywords
- utilization
- silicone
- synthesis
- selective oxidation
- structure material
- 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
Links
- 239000000463 material Substances 0.000 title abstract 3
- 230000003647 oxidation Effects 0.000 title abstract 3
- 238000007254 oxidation reaction Methods 0.000 title abstract 3
- 239000010457 zeolite Substances 0.000 title abstract 2
- 229910021536 Zeolite Inorganic materials 0.000 title 1
- 230000015572 biosynthetic process Effects 0.000 title 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 title 1
- 229920001296 polysiloxane Polymers 0.000 title 1
- 239000011148 porous material Substances 0.000 title 1
- 238000003786 synthesis reaction Methods 0.000 title 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 6
- 239000010936 titanium Substances 0.000 abstract 3
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 abstract 2
- 239000007864 aqueous solution Substances 0.000 abstract 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 abstract 2
- 239000000377 silicon dioxide Substances 0.000 abstract 2
- 229910002012 Aerosil® Inorganic materials 0.000 abstract 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract 1
- 239000002253 acid Substances 0.000 abstract 1
- 150000001298 alcohols Chemical class 0.000 abstract 1
- 150000001336 alkenes Chemical class 0.000 abstract 1
- 230000001588 bifunctional effect Effects 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 abstract 1
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 150000002118 epoxides Chemical class 0.000 abstract 1
- 150000002334 glycols Chemical class 0.000 abstract 1
- 238000000265 homogenisation Methods 0.000 abstract 1
- 150000002500 ions Chemical class 0.000 abstract 1
- 150000003457 sulfones Chemical class 0.000 abstract 1
- 150000003462 sulfoxides Chemical class 0.000 abstract 1
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 abstract 1
- 150000003568 thioethers Chemical class 0.000 abstract 1
- 229910052719 titanium Inorganic materials 0.000 abstract 1
Classifications
-
- 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
-
- 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
- B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Catalysts (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
MATERIAL DE ESTRUCTURA TIPO ZEOLITA DE POROS ULTRAGRANDES CON UNA RED CONSTITUIDA POR OXIDOS DE SILICIO Y TITANIO: SU SINTESIS Y UTILIZACION PARA LA OXIDACION SELECTIVA DE PRODUCTOS ORGANICOS. SE TRATA DE UN MATERIAL CONSTITUIDO POR SILICOTITANATOS DE ESTRUCTURA CRISTALINA SEMEJANTE A LAS ZEOLITAS TIPO MCM-41 CARACTERIZADO POR CONTENER EN SU RED ATOMOS DE TITANIO Y CANALES EN SU ESTRUCTURA POROSA CUYOS DIMENSIONES MEDIAS SUPERAN LOS 10 A LO QUE LE PERMITE CATALIZAR REACCIONES EN LAS QUE INTERVIENEN MOLECULAS ORGANICAS VOLUMINOSAS TALES COMO OXIDAR OLEFINAS A EPOXIDOS Y GLICOLES, ALCOHOLES A CETONAS, TIOETERES A SULFOXIDOS Y SULFONAS, Y FENOL A CATECOL E HIDROQUINONA Y SI SE INTRODUCE A1 EN LA ESTRUCTURA, ES POSIBLE PREPARAR CATALIZADORES BIFUNCIONALES OXIDANTE-ACIDO/BASE. PARA CONSEGUIR ESTE PRODUCTO SE PARTE DE UNA DISOLUCION ACUOSA QUE CONTIENE EL ION NR1R2R3R4+ Y OTRA QUE CONTIENE HIDROXIDO DE TETRAMETIL AMONIO Y UNA FUENTE DE SILICE (P.E. AEROSILCO). TRAS LA HOMOGENEIZACION SE AÑADE MASSILICE, Y LA FUENTE DE TI [P.E. TI(C2OH5)4]. EL GEL RESULTANTE SE CALIENTA EN UN AUTOCLAVE A UNA TEMPERATURA ENTRE 80 Y 200 C. EL GEL OBTENIDO SE ACTIVA POR CALCINACION ENTRE 350 Y 800 C. SE EMPLEA PARA LA OXIDACION CATALITICA.
Priority Applications (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ES09301327A ES2092428B1 (es) | 1993-06-15 | 1993-06-15 | Material de estructura tipo zeolita de poros ultragrandes con un red constituida por oxidos de silicio y titanio; su sintesis y utilizacion para la oxidacion selectiva de productos organicos. |
| DK94917687T DK0655278T3 (da) | 1993-06-15 | 1994-06-10 | Strukturmateriale af zeolithtypen med ultrastore porer og et gitter sammensat af silicium- og titanoxider, dets syntese og |
| EP94917687A EP0655278B1 (en) | 1993-06-15 | 1994-06-10 | Structure material of the zeolite type with ultralarge pores and a lattice comprised of silicone and titanium oxides; its synthesis and utilization for the selective oxidation of organic products |
| DE69417518T DE69417518T2 (de) | 1993-06-15 | 1994-06-10 | Strukturmaterial vom zeolithtypus mit ultragrossen poren und einem gitter aus silizium-und titaniumoxyden; dessen synthese und verwendung zur selektiven oxydation von organischen produkten |
| AT94917687T ATE178224T1 (de) | 1993-06-15 | 1994-06-10 | Strukturmaterial vom zeolithtypus mit ultragrossen poren und einem gitter aus silizium- und titaniumoxyden; dessen synthese und verwendung zur selektiven oxydation von organischen produkten |
| CA002142336A CA2142336C (en) | 1993-06-15 | 1994-06-10 | Structure material of the zeolite type with ultralarge pores and a lattice comprised of silicone and titanium oxides, its synthesis and utilization for the selective oxidation of organic products |
| PCT/ES1994/000059 WO1994029022A1 (es) | 1993-06-15 | 1994-06-10 | Material de estructura tipo zeolita de poros ultragrandes con una red constituida por oxidos de silicio y titanio; su sintesis y utilizacion para la oxidacion selectiva de productos organicos |
| US08/413,867 US5783167A (en) | 1993-06-15 | 1995-02-15 | Structure material of the zeolite type with ultralarge pores and a lattice comprised of silicone and titanium oxides: its synthesis and utilization for the selective oxidation of organic products |
| GR990401670T GR3030587T3 (en) | 1993-06-15 | 1999-06-23 | Structure material of the zeolite type with ultralarge pores and a lattice comprised of silicone and titanium oxides; its synthesis and utilization for the selective oxidation of organic products. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ES09301327A ES2092428B1 (es) | 1993-06-15 | 1993-06-15 | Material de estructura tipo zeolita de poros ultragrandes con un red constituida por oxidos de silicio y titanio; su sintesis y utilizacion para la oxidacion selectiva de productos organicos. |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| ES2092428A1 true ES2092428A1 (es) | 1996-11-16 |
| ES2092428B1 ES2092428B1 (es) | 1997-08-01 |
Family
ID=8282204
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| ES09301327A Expired - Fee Related ES2092428B1 (es) | 1993-06-15 | 1993-06-15 | Material de estructura tipo zeolita de poros ultragrandes con un red constituida por oxidos de silicio y titanio; su sintesis y utilizacion para la oxidacion selectiva de productos organicos. |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US5783167A (es) |
| EP (1) | EP0655278B1 (es) |
| AT (1) | ATE178224T1 (es) |
| CA (1) | CA2142336C (es) |
| DE (1) | DE69417518T2 (es) |
| DK (1) | DK0655278T3 (es) |
| ES (1) | ES2092428B1 (es) |
| GR (1) | GR3030587T3 (es) |
| WO (1) | WO1994029022A1 (es) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2165773A1 (es) * | 1998-08-04 | 2002-03-16 | Sumitomo Chemical Co | Proceso para producir oxido de propileno. |
| ES2165771A1 (es) * | 1999-07-20 | 2002-03-16 | Sumitomo Chemical Co | Catalizador de oxido de silicio que contiene titanio. |
| ES2166271A1 (es) * | 1998-08-04 | 2002-04-01 | Sumitomo Chemical Co | Catalizador de oxido de silicio con contenido en titanio. |
Families Citing this family (33)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2092428B1 (es) * | 1993-06-15 | 1997-08-01 | Univ Valencia Politecnica | Material de estructura tipo zeolita de poros ultragrandes con un red constituida por oxidos de silicio y titanio; su sintesis y utilizacion para la oxidacion selectiva de productos organicos. |
| US5663384A (en) * | 1996-03-06 | 1997-09-02 | Arco Chemical Technology, L.P. | Asymetric epoxidation using a titanium-containing zeolite and a chiral hydroperoxide |
| US5718878A (en) * | 1996-07-12 | 1998-02-17 | Akzo Nobel N.V. | Mesoporous titania and process for its preparation |
| US5688484A (en) * | 1996-07-29 | 1997-11-18 | Arco Chemical Technology, L.P. | Non-hydrothermal method of making a titanium-containing zeolite |
| CA2215490A1 (fr) * | 1996-10-11 | 1998-04-11 | Elf Atochem S.A. | Catalyseur a base de titano-silicalites et procede d'obtention d'hydroxylamine n,n-disubstituee |
| JPH10139419A (ja) * | 1996-11-11 | 1998-05-26 | Yukong Ltd | 非結晶性中間細孔モレキュラーシーブの製造方法及びそのモレキュラーシーブ |
| US6042807A (en) * | 1997-04-02 | 2000-03-28 | Arco Chemical Technology, L.P. | Tellurium-containing molecular sieves |
| JP3174829B2 (ja) * | 1997-05-30 | 2001-06-11 | 経済産業省産業技術総合研究所長 | 多孔性チタノシリケート及びその製造方法 |
| IT1296573B1 (it) * | 1997-11-27 | 1999-07-14 | Enichem Spa | Procedimento per l'ossidazione di composti aromatici a idrossiaromatici |
| KR100639048B1 (ko) * | 1998-08-04 | 2006-10-27 | 스미또모 가가꾸 가부시키가이샤 | 티탄-함유 산화규소 촉매, 이의 제조 방법 및 당해 촉매를 사용하는 프로필렌 옥사이드의 제조방법 |
| ES2156506B1 (es) * | 1998-10-14 | 2002-03-01 | Sumitomo Chemical Co | Metodo para la produccion de oxido de propileno. |
| ES2160044B1 (es) * | 1999-03-16 | 2002-06-16 | Univ Valencia Politecnica | Oxidacion de *-pineno. |
| DE60121914D1 (de) | 2000-02-02 | 2006-09-14 | Sumitomo Chemical Co | Geformter katalysator, verfahren zu dessen herstellung sowie verfahren zur herstellung einer oxirankomponente |
| DE10047435A1 (de) | 2000-09-26 | 2002-04-11 | Degussa | Verfahren zur Herstellung von Oximen |
| US6488741B2 (en) | 2001-01-23 | 2002-12-03 | The Trustess Of The University Of Pennsylvania | Light hydrocarbon separation using 8-member ring zeolites |
| JP2002239381A (ja) | 2001-02-22 | 2002-08-27 | Sumitomo Chem Co Ltd | チタン含有珪素酸化物触媒の製造方法及び触媒 |
| RU2196764C2 (ru) * | 2001-03-26 | 2003-01-20 | Институт катализа им. Г.К.Борескова СО РАН | Способ получения замещенных хинонов, катализатор для его осуществления и способ получения катализатора |
| ES2183710B1 (es) * | 2001-04-12 | 2004-01-16 | Univ Valencia Politecnica | Proceso y catalizadores para la eliminacion de compuestos de azufre de la fraccion diesel. |
| US6417378B1 (en) * | 2001-10-09 | 2002-07-09 | Arco Chemical Technology, L.P. | Direct epoxidation process using pre-treated titanium zeolite |
| AU2002356941A1 (en) * | 2001-11-15 | 2003-06-10 | Pq Holding, Inc. | Method for controlling synthesis conditions during molecular sieve synthesis using combinations of quaternary ammonium hydroxides and halides |
| ES2192967B1 (es) * | 2001-11-20 | 2004-09-16 | Universidad Politecnica De Valencia. | Proceso y catalizadores para la oxidacion de compuestos de azufre de las fracciones gasolina, queroseno y diesel. |
| JP4265212B2 (ja) * | 2002-12-19 | 2009-05-20 | 住友化学株式会社 | チタン含有珪素酸化物触媒の製造方法 |
| CN100384733C (zh) * | 2005-08-15 | 2008-04-30 | 中国石油化工股份有限公司 | 含钛mcm-41分子筛的制备方法 |
| KR100727288B1 (ko) * | 2005-10-14 | 2007-06-13 | 한국과학기술원 | 메조다공성 골격을 갖는 미세다공성 결정성 분자체의제조방법 |
| ES2685497T3 (es) * | 2006-09-25 | 2018-10-09 | Chevron U.S.A. Inc. | Preparación de tamices moleculares utilizando un agente director de estructura y un catión de amonio cuaternario de N,N,N-trialquil bencilo |
| US20080159950A1 (en) * | 2006-12-27 | 2008-07-03 | Miller Stephen J | Preparation of molecular sieve ssz-13 |
| US8057782B2 (en) * | 2006-12-27 | 2011-11-15 | Chevron U.S.A. Inc. | Preparation of small pore molecular sieves |
| RU2422361C1 (ru) * | 2009-10-27 | 2011-06-27 | Учреждение Российской Академии Наук Институт Нефтехимии И Катализа Ран | Способ получения мезопористых элементосиликатов |
| RU2420455C1 (ru) * | 2009-10-27 | 2011-06-10 | Учреждение Российской Академии Наук Институт Нефтехимии И Катализа Ран | Способ получения мезопористых аморфных смешанных элементосиликатов |
| MY189509A (en) | 2016-07-29 | 2022-02-16 | Sumitomo Chemical Co | Method for producing propylene oxide |
| CN107930610B (zh) | 2017-11-29 | 2019-09-20 | 万华化学集团股份有限公司 | 一种烯烃环氧化催化剂的制备方法及由此制备的催化剂 |
| ES3063934T3 (en) | 2019-09-25 | 2026-04-21 | Sumitomo Chemical Company Ltd | Method for producing propylene oxide |
| WO2021192592A1 (ja) | 2020-03-27 | 2021-09-30 | 住友化学株式会社 | プロピレンオキサイドの製造装置、及び、プロピレンオキサイドの製造方法 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1991018833A1 (en) * | 1990-05-28 | 1991-12-12 | Engelhard Corporation | Large-pored molecular sieves containing at least one octahedral site and tetrahedral sites of at least one type |
| US5160717A (en) * | 1984-04-26 | 1992-11-03 | Uop | Titanium-aluminum-silicon-oxide molecular sieve compositions |
| WO1993002013A1 (en) * | 1991-07-24 | 1993-02-04 | Mobil Oil Corporation | Synthetic porous crystalline material, its synthesis and use |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1127311B (it) * | 1979-12-21 | 1986-05-21 | Anic Spa | Materiale sintetico,cristallino,poroso costituito da ossidi di silicio e titanio,metodo per la sua preparazione e suoi usi |
| JP2573511B2 (ja) * | 1988-04-06 | 1997-01-22 | 久俊 浅岡 | チタニウム、アルミニウム、ケイ素及びホウ素の各四面体酸化物の組合せによる組成物及びその製造方法 |
| US5174888A (en) * | 1990-01-25 | 1992-12-29 | Mobil Oil Corp. | Catalytic conversion |
| US5102643A (en) * | 1990-01-25 | 1992-04-07 | Mobil Oil Corp. | Composition of synthetic porous crystalline material, its synthesis |
| US5196633A (en) * | 1990-01-25 | 1993-03-23 | Mobil Oil Corp. | Catalytic conversion |
| US5246689A (en) * | 1990-01-25 | 1993-09-21 | Mobil Oil Corporation | Synthetic porous crystalline material its synthesis and use |
| ES2092428B1 (es) * | 1993-06-15 | 1997-08-01 | Univ Valencia Politecnica | Material de estructura tipo zeolita de poros ultragrandes con un red constituida por oxidos de silicio y titanio; su sintesis y utilizacion para la oxidacion selectiva de productos organicos. |
-
1993
- 1993-06-15 ES ES09301327A patent/ES2092428B1/es not_active Expired - Fee Related
-
1994
- 1994-06-10 CA CA002142336A patent/CA2142336C/en not_active Expired - Lifetime
- 1994-06-10 DK DK94917687T patent/DK0655278T3/da active
- 1994-06-10 DE DE69417518T patent/DE69417518T2/de not_active Expired - Lifetime
- 1994-06-10 AT AT94917687T patent/ATE178224T1/de active
- 1994-06-10 EP EP94917687A patent/EP0655278B1/en not_active Expired - Lifetime
- 1994-06-10 WO PCT/ES1994/000059 patent/WO1994029022A1/es not_active Ceased
-
1995
- 1995-02-15 US US08/413,867 patent/US5783167A/en not_active Expired - Lifetime
-
1999
- 1999-06-23 GR GR990401670T patent/GR3030587T3/el unknown
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5160717A (en) * | 1984-04-26 | 1992-11-03 | Uop | Titanium-aluminum-silicon-oxide molecular sieve compositions |
| WO1991018833A1 (en) * | 1990-05-28 | 1991-12-12 | Engelhard Corporation | Large-pored molecular sieves containing at least one octahedral site and tetrahedral sites of at least one type |
| WO1993002013A1 (en) * | 1991-07-24 | 1993-02-04 | Mobil Oil Corporation | Synthetic porous crystalline material, its synthesis and use |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2165773A1 (es) * | 1998-08-04 | 2002-03-16 | Sumitomo Chemical Co | Proceso para producir oxido de propileno. |
| ES2166271A1 (es) * | 1998-08-04 | 2002-04-01 | Sumitomo Chemical Co | Catalizador de oxido de silicio con contenido en titanio. |
| ES2165771A1 (es) * | 1999-07-20 | 2002-03-16 | Sumitomo Chemical Co | Catalizador de oxido de silicio que contiene titanio. |
Also Published As
| Publication number | Publication date |
|---|---|
| DK0655278T3 (da) | 1999-10-11 |
| DE69417518T2 (de) | 1999-10-21 |
| ATE178224T1 (de) | 1999-04-15 |
| CA2142336A1 (en) | 1994-12-16 |
| EP0655278B1 (en) | 1999-03-31 |
| DE69417518D1 (de) | 1999-05-06 |
| ES2092428B1 (es) | 1997-08-01 |
| GR3030587T3 (en) | 1999-10-29 |
| EP0655278A1 (en) | 1995-05-31 |
| CA2142336C (en) | 2004-12-07 |
| WO1994029022A1 (es) | 1994-12-22 |
| US5783167A (en) | 1998-07-21 |
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