JPS5691841A - Catalyst supporter and cracking catalyst into which said supporter is mixed - Google Patents

Catalyst supporter and cracking catalyst into which said supporter is mixed

Info

Publication number
JPS5691841A
JPS5691841A JP17731880A JP17731880A JPS5691841A JP S5691841 A JPS5691841 A JP S5691841A JP 17731880 A JP17731880 A JP 17731880A JP 17731880 A JP17731880 A JP 17731880A JP S5691841 A JPS5691841 A JP S5691841A
Authority
JP
Japan
Prior art keywords
supporter
catalyst
mixed
cracking
cracking catalyst
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
JP17731880A
Other languages
English (en)
Other versions
JPS642417B2 (ja
Inventor
Uoren Chiesutaa Aasaa
Arubaato Sutoubaa Uiriamu
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.)
ExxonMobil Oil Corp
Original Assignee
Mobil Oil Corp
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
Application filed by Mobil Oil Corp filed Critical Mobil Oil Corp
Publication of JPS5691841A publication Critical patent/JPS5691841A/ja
Publication of JPS642417B2 publication Critical patent/JPS642417B2/ja
Granted 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
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J29/166—Y-type faujasite
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/08—Silica
    • 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
    • B01J29/061—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing metallic elements added to the zeolite
    • 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
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • 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
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
    • B01J29/12—Noble metals
    • B01J29/126—Y-type faujasite
    • 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
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
    • B01J29/14—Iron group metals or copper
    • B01J29/146—Y-type faujasite
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • 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
    • 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
    • B01J2229/26—After treatment, characterised by the effect to be obtained to stabilize the total catalyst structure
    • 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
    • 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
    • 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
    • B01J29/65—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, 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
    • 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
    • B01J29/04—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
    • B01J29/7011—MAZ-type, e.g. Mazzite, Omega, ZSM-4 or LZ-202
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/633—Pore volume less than 0.5 ml/g
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/66—Pore distribution
    • B01J35/69—Pore distribution bimodal

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
JP17731880A 1979-12-17 1980-12-17 Catalyst supporter and cracking catalyst into which said supporter is mixed Granted JPS5691841A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US06/104,522 US4326993A (en) 1979-12-17 1979-12-17 Novel cracking catalysts and catalyst supports

Publications (2)

Publication Number Publication Date
JPS5691841A true JPS5691841A (en) 1981-07-25
JPS642417B2 JPS642417B2 (ja) 1989-01-17

Family

ID=22300940

Family Applications (1)

Application Number Title Priority Date Filing Date
JP17731880A Granted JPS5691841A (en) 1979-12-17 1980-12-17 Catalyst supporter and cracking catalyst into which said supporter is mixed

Country Status (6)

Country Link
US (1) US4326993A (ja)
EP (1) EP0032298B1 (ja)
JP (1) JPS5691841A (ja)
AU (1) AU540103B2 (ja)
CA (1) CA1155104A (ja)
DE (1) DE3070659D1 (ja)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60143834A (ja) * 1983-08-16 1985-07-30 アシユランド・オイル・インコ−ポレ−テツド 炭化水素供給油転化方法
JPH02501454A (ja) * 1987-08-12 1990-05-24 インターキャット，インコーポレイティド 耐摩耗性マトリックス中へ微細結晶触媒成分を配分する方法
JP2010531219A (ja) * 2007-06-27 2010-09-24 中国石油化工股▲ふん▼有限公司 接触分解触媒、ならびに、その製造および使用

Families Citing this family (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4442223A (en) * 1979-12-17 1984-04-10 Mobil Oil Corporation Catalyst and catalyst support compositions
US4440868A (en) * 1981-12-07 1984-04-03 Ashland Oil, Inc. Carbo-metallic oil conversion catalysts
US4877514A (en) * 1981-12-07 1989-10-31 Ashland Oil, Inc. Carbo-metallic oil conversion process and catalysts
US4612298A (en) * 1981-12-07 1986-09-16 Ashland Oil, Inc. Carbo-metallic oil conversion catalysts
US4784747A (en) * 1982-03-22 1988-11-15 Mobil Oil Corporation Catalysts over steam activated zeolite catalyst
CA1211428A (en) * 1982-09-30 1986-09-16 Joseph F. Porinchak Alumina-silica cogel
US4519897A (en) * 1982-12-27 1985-05-28 Akzo Nv Fluid cracking process using sepiolite-containing catalyst composition
US4493902A (en) * 1983-02-25 1985-01-15 Engelhard Corporation Fluid catalytic cracking catalyst comprising microspheres containing more than about 40 percent by weight Y-faujasite and methods for making
EP0185812A1 (en) * 1984-12-20 1986-07-02 Exxon Research And Engineering Company Thermally stable mixed oxide gels
US4908344A (en) * 1986-05-02 1990-03-13 W. R. Grace & Co.-Conn. Hydroprocessing catalyst and support having bidisperse pore structure
CA1284982C (en) * 1986-05-02 1991-06-18 Carmo Joseph Pereira Hydroprocessing catalyst and support having bidisperse pore structure
JPH0729049B2 (ja) * 1987-04-30 1995-04-05 三菱重工業株式会社 燃焼排ガス中の砒素化合物除去方法
US4846960A (en) * 1987-07-02 1989-07-11 Phillips Petroleum Company Catalytic cracking
US4794095A (en) * 1987-07-02 1988-12-27 Phillips Petroleum Company Catalytic cracking catalyst
US4968405A (en) * 1988-07-05 1990-11-06 Exxon Research And Engineering Company Fluid catalytic cracking using catalysts containing monodispersed mesoporous matrices
JPH045610U (ja) * 1990-04-27 1992-01-20
US6395676B2 (en) 1994-02-22 2002-05-28 The Standard Oil Company Process for the preparation of fluid bed vinyl acetate catalyst
US5466652A (en) * 1994-02-22 1995-11-14 The Standard Oil Co. Process for the preparation of vinyl acetate catalyst
DE69535514T2 (de) * 1994-02-22 2008-02-14 The Standard Oil Co., Cleveland Verfahren zur Herstellung eines Trägers eines Katalysators für die Vorbereitung von Vinylacetat in einem Wirbelbett
WO1996021707A1 (en) * 1995-01-13 1996-07-18 Ashland Inc. Hydrocarbon conversion catalyst additives and processes
JPH11300208A (ja) 1998-04-21 1999-11-02 Idemitsu Kosan Co Ltd 接触分解触媒
JP2003144925A (ja) * 2001-11-07 2003-05-20 Sud-Chemie Catalysts Inc 一酸化炭素シフト反応用触媒の製造方法
US6858556B2 (en) * 2002-02-25 2005-02-22 Indian Oil Corporation Limited Stabilized dual zeolite single particle catalyst composition and a process thereof
EP2990463B1 (en) 2014-08-27 2018-07-11 Indian Oil Corporation Limited A catalyst additive composition for catalytic cracking, a process of preparation thereof and cracking processes of using thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS53100985A (en) * 1977-02-16 1978-09-02 Mobil Oil Cracking catalyst having improved resistance against metal poisoning action

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1542451C3 (de) * 1965-03-30 1974-01-31 Mobil Oil Corp., New York, N.Y. (V.St.A.) Verfahren zur Herstellung eines Kohlenwasserstoffumwandlungskatalysators
US3417030A (en) * 1966-02-23 1968-12-17 Universal Oil Prod Co High surface area alumina and catalyst composite
GB1231826A (ja) * 1967-07-31 1971-05-12
FR96049E (fr) * 1967-10-27 1972-05-19 Texaco Development Corp Procédé pour la conversion catalytique d'hydrocarbures.
US3617485A (en) * 1969-02-20 1971-11-02 Chevron Res Hydrocracking catalyst comprising an amorphous aluminosilicate component, a group viii component and rhenium, and process using said catalyst
BE757725A (fr) * 1969-10-21 1971-04-20 Exxon Research Engineering Co Procede de preparation de catalyseurs sio2 - al2o3 - nio
CA983463A (en) 1971-03-17 1976-02-10 Harry S. Grand Catalyst and method of preparing same
US3933621A (en) * 1972-10-24 1976-01-20 Chevron Research Company Catalytic cracking process using steamed cogelled silica alumina catalyst
US3867308A (en) * 1973-12-10 1975-02-18 Grace W R & Co Process for preparing a petroleum cracking catalyst
US3943064A (en) * 1974-07-11 1976-03-09 Aluminum Company Of America High strength alumina-silica catalyst substrates having high surface area
US4034053A (en) * 1975-12-08 1977-07-05 Mobil Oil Corporation Selective production of para-xylene
US4217240A (en) * 1976-09-02 1980-08-12 E. I. Du Pont De Nemours And Company Stable aluminosilicate aquasols having uniform size particles and their preparation
CA1097308A (en) * 1976-10-15 1981-03-10 Charles J. Plank Method of making fluid catalysts
US4111846A (en) * 1977-05-06 1978-09-05 W. R. Grace & Co. Hydrosol and catalyst preparation
EP0002899B1 (en) * 1977-12-23 1983-03-16 The British Petroleum Company p.l.c. Method for preparing aluminosilicates and their use as catalyst supports and catalysts

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS53100985A (en) * 1977-02-16 1978-09-02 Mobil Oil Cracking catalyst having improved resistance against metal poisoning action

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60143834A (ja) * 1983-08-16 1985-07-30 アシユランド・オイル・インコ−ポレ−テツド 炭化水素供給油転化方法
JPH0216955B2 (ja) * 1983-08-16 1990-04-18 Ashland Oil Inc
JPH02501454A (ja) * 1987-08-12 1990-05-24 インターキャット，インコーポレイティド 耐摩耗性マトリックス中へ微細結晶触媒成分を配分する方法
JP2010531219A (ja) * 2007-06-27 2010-09-24 中国石油化工股▲ふん▼有限公司 接触分解触媒、ならびに、その製造および使用
US9486795B2 (en) 2007-06-27 2016-11-08 China Petroleum & Chemical Corporation Catalytic cracking catalyst, its preparation and use

Also Published As

Publication number Publication date
DE3070659D1 (en) 1985-06-20
CA1155104A (en) 1983-10-11
AU540103B2 (en) 1984-11-01
AU6507280A (en) 1981-06-25
EP0032298A2 (en) 1981-07-22
JPS642417B2 (ja) 1989-01-17
EP0032298A3 (en) 1981-10-14
US4326993A (en) 1982-04-27
EP0032298B1 (en) 1985-05-15

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