ES2185657T3 - Procedimiento para modificar la selectividad por la forma de un catalizador de zeolita y uso del catalizador modificado. - Google Patents
Procedimiento para modificar la selectividad por la forma de un catalizador de zeolita y uso del catalizador modificado.Info
- Publication number
- ES2185657T3 ES2185657T3 ES94920006T ES94920006T ES2185657T3 ES 2185657 T3 ES2185657 T3 ES 2185657T3 ES 94920006 T ES94920006 T ES 94920006T ES 94920006 T ES94920006 T ES 94920006T ES 2185657 T3 ES2185657 T3 ES 2185657T3
- Authority
- ES
- Spain
- Prior art keywords
- catalyst
- procedure
- selectivity
- modify
- modified
- 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 - Lifetime
Links
- 239000003054 catalyst Substances 0.000 title abstract 5
- 238000000034 method Methods 0.000 title abstract 2
- 201000010001 Silicosis Diseases 0.000 abstract 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract 1
- 229910052782 aluminium Inorganic materials 0.000 abstract 1
- 229910000323 aluminium silicate Inorganic materials 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 abstract 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 abstract 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C6/00—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions
- C07C6/08—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond
- C07C6/12—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond of exclusively hydrocarbons containing a six-membered aromatic ring
- C07C6/123—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond of exclusively hydrocarbons containing a six-membered aromatic ring of only one hydrocarbon
-
- 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
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
-
- 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
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
- C07C2/64—Addition to a carbon atom of a six-membered aromatic ring
- C07C2/66—Catalytic processes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
- C07C2/862—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms
- C07C2/864—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms the non-hydrocarbon is an alcohol
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/12—After treatment, characterised by the effect to be obtained to alter the outside of the crystallites, e.g. selectivation
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/32—Reaction with silicon compounds, e.g. TEOS, siliconfluoride
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/36—Steaming
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/42—Addition of matrix or binder particles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/65—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
-
- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Inorganic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
EN UN PROCESO PARA MODIFICAR LA SELECTIVIDAD DE FORMA DE UN CATALIZADOR ZEOLITO DE ALUMINOSILICATO QUE TIENE UN INDICE MOLAR DE SILICOS ALUMINIOS MENOR A 500, EL CATALIZADOR ES EXPUESTO A AL MENOS DOS SECUENCIAS DE SELECTIVACION EX SITU, DONDE CADA UNA DE ELLAS INCLUYE LOS PASOS DE CONTACTAR EL CATALIZADOR CON UN AGENTE SELECTIVANTE, NORMALMENTE UN COMPUESTO DE ORGANOSILICONA, EN UN PORTADOR Y SUBSECUENTEMENTE CALCINAR EL CATALIZADOR.
Applications Claiming Priority (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/069,254 US5367099A (en) | 1993-05-28 | 1993-05-28 | Selective toluene disproportionation process (STDP) with ex situ selectivated zeolite catalyst |
| US08/069,255 US5403800A (en) | 1993-05-28 | 1993-05-28 | Multiple impregnation technique for the preparation of ex situ selectivated zeolite catalysts |
| US08/069,259 US5365004A (en) | 1993-05-28 | 1993-05-28 | Selective toluene disproportionation process (STDP) with ex situ selectivated zeolite catalysts |
| US08/069,260 US5406015A (en) | 1993-05-28 | 1993-05-28 | Selective ethylbenzene disproportionation processes (SEBDP) with ex situ selectivated zeolite catalyst |
| US08/069,251 US5476823A (en) | 1993-05-28 | 1993-05-28 | Method of preparation of ex situ selectivated zeolite catalysts for enhanced shape selective applications and method to increase the activity thereof |
| US08/069,257 US5382737A (en) | 1993-05-28 | 1993-05-28 | Selective ethylbenzene disproportionation process (SEBDP) with ex situ selectivated zeolite catalysts |
| US14175893A | 1993-10-27 | 1993-10-27 | |
| PCT/US1994/005390 WO1994027934A1 (en) | 1993-05-28 | 1994-05-13 | Process for modifying the shape selectivity of a zeolite catalyst and use of the mofified catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| ES2185657T3 true ES2185657T3 (es) | 2003-05-01 |
Family
ID=27568289
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| ES94920006T Expired - Lifetime ES2185657T3 (es) | 1993-05-28 | 1994-05-13 | Procedimiento para modificar la selectividad por la forma de un catalizador de zeolita y uso del catalizador modificado. |
Country Status (13)
| Country | Link |
|---|---|
| EP (1) | EP0703886B1 (es) |
| JP (1) | JP3717926B2 (es) |
| KR (1) | KR100343665B1 (es) |
| CN (1) | CN1083291C (es) |
| AU (1) | AU677402B2 (es) |
| BR (1) | BR9406693A (es) |
| CA (1) | CA2161875C (es) |
| DE (1) | DE69431625T2 (es) |
| DK (1) | DK0703886T3 (es) |
| ES (1) | ES2185657T3 (es) |
| RU (1) | RU2124944C1 (es) |
| SG (1) | SG67289A1 (es) |
| WO (1) | WO1994027934A1 (es) |
Families Citing this family (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19743165A1 (de) * | 1997-09-30 | 1999-04-01 | Studiengesellschaft Kohle Mbh | Selektive Alkylierung von Aromaten mit oberflächenmodifizierten mikroporösen Mischoxiden |
| US6459006B1 (en) | 1999-05-14 | 2002-10-01 | Exxonmobil Chemical Patents Inc. | Selective methylation to para-xylene using fuel syngas |
| US6388156B1 (en) | 1999-05-14 | 2002-05-14 | Exxonmobil Chemical Patents Inc. | Direct selective synthesis of para-xylene by reacting an aromatic compound with a methylating agent formed from CO, Co2 and H2 |
| US7060864B2 (en) * | 2003-09-30 | 2006-06-13 | Saudi Basic Industries Corporation | Toluene methylation process |
| US7304194B2 (en) | 2005-05-05 | 2007-12-04 | Saudi Basic Industries Corporation | Hydrothermal treatment of phosphorus-modified zeolite catalysts |
| KR101098495B1 (ko) | 2005-08-15 | 2011-12-26 | 상하이 리서치 인스티튜트 오브 페트로케미칼 테크놀로지 시노펙 | 톨루엔 형태 선택성 알킬화반응에 의한 파라-자일렌 제조용촉매의 제조방법 |
| WO2009119725A1 (ja) * | 2008-03-27 | 2009-10-01 | 株式会社ジャパンエナジー | パラ置換芳香族炭化水素の製造方法 |
| US8846559B2 (en) * | 2008-11-03 | 2014-09-30 | Saudi Basic Industries Corporation | Stable shape-selective catalyst for aromatic alkylation and methods of using and preparing |
| US8575055B2 (en) | 2010-03-30 | 2013-11-05 | Uop Llc | Surface-modified zeolites and methods for preparing the same |
| WO2012152406A1 (en) * | 2011-05-09 | 2012-11-15 | Saudi Basic Industries Corporation | Catalyst for the alkylation of aromatic hydrocarbons |
| BR112015030289A2 (pt) * | 2013-06-13 | 2017-07-25 | Exxonmobil Chemical Patents Inc | seletivação de coque de compensação in-situ de catalisador de desproporcionamento de tolueno |
| CN105062204B (zh) * | 2015-07-20 | 2017-06-16 | 苏州宇希新材料科技有限公司 | 一种纳米二氧化钛印刷油墨及其制备方法 |
| CN105153754B (zh) * | 2015-07-20 | 2017-12-19 | 苏州宇希新材料科技有限公司 | 一种纳米氧化锌无机粉体材料的改性方法 |
| CN105062149B (zh) * | 2015-07-20 | 2017-08-08 | 苏州宇希新材料科技有限公司 | 一种纳米二氧化钛的改性方法 |
| WO2017087174A1 (en) * | 2015-11-18 | 2017-05-26 | Exxonmobil Research And Engineering Company | System and process for producing gasoline from oxygenates |
| CN106189368A (zh) * | 2016-06-30 | 2016-12-07 | 无锡市华东电力设备有限公司 | 改性钛白粉、超细晶形陶瓷粉体脱硝催化剂的制备方法 |
| KR102252012B1 (ko) * | 2016-10-04 | 2021-05-17 | 엑손모빌 케미칼 패턴츠 인코포레이티드 | 중질 방향족 탄화수소의 불균화 및 알킬교환 |
| JP6894530B2 (ja) * | 2017-04-27 | 2021-06-30 | 中国科学院大▲連▼化学物理研究所Dalian Institute Of Chemical Physics,Chinese Academy Of Sciences | トルエン、p−キシレン及び軽質オレフィンのうちの少なくとも1種を製造するための触媒のインサイチュ製造方法及び反応プロセス |
| CN108794287B (zh) * | 2017-04-27 | 2020-08-11 | 中国科学院大连化学物理研究所 | 一种制低碳烯烃联产对二甲苯的方法 |
| GB201819416D0 (en) * | 2018-11-29 | 2019-01-16 | Johnson Matthey Plc | Method |
| US11779909B2 (en) | 2018-12-13 | 2023-10-10 | China Petroleum & Chemical Corporation | Hydrocracking catalyst, preparation method therefor and application thereof |
| US10843930B1 (en) | 2019-11-13 | 2020-11-24 | Saudi Arabian Oil Company | Systems and methods for synthesis of ZSM-22 zeolite |
| US10927057B1 (en) * | 2020-01-06 | 2021-02-23 | Uop Llc | Two bed liquid phase isomerization process |
| US11084766B1 (en) * | 2020-02-18 | 2021-08-10 | Uop Llc | Toluene disproportionation using an enhanced UZM-39 aluminosilicate zeolite |
| RU2734985C1 (ru) * | 2020-05-21 | 2020-10-27 | Федеральное государственное бюджетное учреждение науки "Федеральный исследовательский центр "Институт катализа им. Г.К. Борескова Сибирского отделения Российской академии наук" (ИК СО РАН, Институт катализа СО РАН) | Способ приготовления катализатора и способ получения изопропилбензола (варианты) |
| KR102577286B1 (ko) * | 2023-01-16 | 2023-09-11 | 주식회사 파이프랜드 | 강성과 탄성이 향상된 폴리에틸렌 합성수지관 |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4283306A (en) * | 1979-04-20 | 1981-08-11 | E. I. Du Pont De Nemours And Company | Crystalline silica and use in alkylation of aromatics |
| US4402867A (en) * | 1981-12-22 | 1983-09-06 | Mobil Oil Corporation | Silica-modified zeolite catalysts |
| US4559314A (en) * | 1982-03-22 | 1985-12-17 | Mobil Oil Corporation | Zeolite activation |
| US4477583A (en) * | 1983-06-09 | 1984-10-16 | Mobil Oil Corporation | Silica-modified catalyst and use for selective production of para-dialkyl substituted benzenes |
| SU1409321A1 (ru) * | 1985-07-09 | 1988-07-15 | Институт химии нефти СО АН СССР | Способ активации катализатора |
| US5173461A (en) * | 1990-03-21 | 1992-12-22 | Mobil Oil Corporation | Toluene disproportionation catalyst |
| US5321183A (en) * | 1992-03-12 | 1994-06-14 | Mobil Oil Corp. | Process for the regioselective conversion of aromatics to para-disubstituted benzenes |
| US5349114A (en) * | 1993-04-05 | 1994-09-20 | Mobil Oil Corp. | Shape selective hydrocarbon conversions over modified catalyst |
-
1994
- 1994-05-13 EP EP94920006A patent/EP0703886B1/en not_active Expired - Lifetime
- 1994-05-13 WO PCT/US1994/005390 patent/WO1994027934A1/en not_active Ceased
- 1994-05-13 ES ES94920006T patent/ES2185657T3/es not_active Expired - Lifetime
- 1994-05-13 JP JP52040694A patent/JP3717926B2/ja not_active Expired - Lifetime
- 1994-05-13 AU AU70939/94A patent/AU677402B2/en not_active Expired
- 1994-05-13 DE DE69431625T patent/DE69431625T2/de not_active Expired - Lifetime
- 1994-05-13 KR KR1019950705261A patent/KR100343665B1/ko not_active Expired - Lifetime
- 1994-05-13 CN CN94192280A patent/CN1083291C/zh not_active Expired - Lifetime
- 1994-05-13 DK DK94920006T patent/DK0703886T3/da active
- 1994-05-13 BR BR9406693A patent/BR9406693A/pt not_active IP Right Cessation
- 1994-05-13 RU RU95122723A patent/RU2124944C1/ru active
- 1994-05-13 SG SG1996001260A patent/SG67289A1/en unknown
- 1994-05-13 CA CA002161875A patent/CA2161875C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CN1124950A (zh) | 1996-06-19 |
| EP0703886A4 (en) | 1998-04-29 |
| DE69431625D1 (de) | 2002-12-05 |
| WO1994027934A1 (en) | 1994-12-08 |
| EP0703886A1 (en) | 1996-04-03 |
| DE69431625T2 (de) | 2003-02-27 |
| CN1083291C (zh) | 2002-04-24 |
| JP3717926B2 (ja) | 2005-11-16 |
| SG67289A1 (en) | 1999-09-21 |
| CA2161875C (en) | 2006-02-14 |
| CA2161875A1 (en) | 1994-12-08 |
| JPH08509907A (ja) | 1996-10-22 |
| EP0703886B1 (en) | 2002-10-30 |
| BR9406693A (pt) | 1996-01-16 |
| RU2124944C1 (ru) | 1999-01-20 |
| KR960702422A (ko) | 1996-04-27 |
| AU7093994A (en) | 1994-12-20 |
| DK0703886T3 (da) | 2003-03-03 |
| KR100343665B1 (ko) | 2003-03-15 |
| AU677402B2 (en) | 1997-04-24 |
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