DE104800T1 - Verfahren zur herstellung von kristallinen aluminosilikaten. - Google Patents
Verfahren zur herstellung von kristallinen aluminosilikaten.Info
- Publication number
- DE104800T1 DE104800T1 DE198383305073T DE83305073T DE104800T1 DE 104800 T1 DE104800 T1 DE 104800T1 DE 198383305073 T DE198383305073 T DE 198383305073T DE 83305073 T DE83305073 T DE 83305073T DE 104800 T1 DE104800 T1 DE 104800T1
- Authority
- DE
- Germany
- Prior art keywords
- molar ratio
- cations
- silica
- silicon oxide
- ammonia
- 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.)
- Pending
Links
Classifications
-
- 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
- C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
- C10G49/02—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used
- C10G49/08—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/26—Aluminium-containing silicates, i.e. silico-aluminates
- C01B33/28—Base exchange silicates, e.g. zeolites
- C01B33/2807—Zeolitic silicoaluminates with a tridimensional crystalline structure possessing molecular sieve properties; Isomorphous compounds wherein a part of the aluminium ore of the silicon present may be replaced by other elements such as gallium, germanium, phosphorus; Preparation of zeolitic molecular sieves from molecular sieves of another type or from preformed reacting mixtures
- C01B33/2869—Zeolitic silicoaluminates with a tridimensional crystalline structure possessing molecular sieve properties; Isomorphous compounds wherein a part of the aluminium ore of the silicon present may be replaced by other elements such as gallium, germanium, phosphorus; Preparation of zeolitic molecular sieves from molecular sieves of another type or from preformed reacting mixtures of other types characterised by an X-ray spectrum and a definite composition
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
- C07C1/24—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by elimination of water
-
- 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
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
- C07C2/12—Catalytic processes with crystalline alumino-silicates or with catalysts comprising molecular sieves
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
- C07C4/08—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by splitting-off an aliphatic or cycloaliphatic part from the molecule
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
- C07C5/2206—Catalytic processes not covered by C07C5/23 - C07C5/31
- C07C5/222—Catalytic processes not covered by C07C5/23 - C07C5/31 with crystalline alumino-silicates, e.g. molecular sieves
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/321—Catalytic processes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/373—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen with simultaneous isomerisation
- C07C5/393—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen with simultaneous isomerisation with cyclisation to an aromatic six-membered ring, e.g. dehydrogenation of n-hexane to benzene
- C07C5/41—Catalytic processes
-
- 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
- C10G35/00—Reforming naphtha
- C10G35/04—Catalytic reforming
- C10G35/06—Catalytic reforming characterised by the catalyst used
- C10G35/095—Catalytic reforming characterised by the catalyst used containing crystalline alumino-silicates, e.g. 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
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S423/00—Chemistry of inorganic compounds
- Y10S423/35—TON, e.g. Theta-1, ISI-1, KZ-2, ZSM-22, NU-10
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Claims (10)
1. Verfahren zur Herstellung kristalliner Aluminosilicate, die in der Wasserstoff-Form ein Röntgen-Beugungsbild
im wesentlichen wie in Tabelle 1 dieser Anmeldung und, ausgedrückt in den Mol-Verhältnissen
der Oxide, die folgende Zusammensetzung haben:
0,9 + 0,2 M2/nO:Al2O3: XSiO3:yH2O:ZNH3
in welcher M mindestens ein Kation mit einer Wertigkeit von η ist, χ mindestens 10 ist, y/x von 0 bis 5
ist und z/x 0-5 ist, dadurch gekennzeichnet, daß das Verfahren umfaßt, daß man eine Siliciumoxidquelle, eine Aluminiumoxidquelle,
eine Quelle von Alkalimetall(en), Wasser und Ammoniak bis zur Bildung eines homogenen Gels
mischt und das Gel bei einer Temperatur oberhalb 700C
für eine Dauer von mindestens 2 h kristallisiert.
2. Verfahren nach Anspruch 1, in welchem das Kation M
im Zeoliten ausgewählt ist von:H , Ammonium, Alkalimetal
lkationen, Erdalkalimetallkationen, Aluminiumkationen, Galliumkation und Mischungen derselben.
3. Verfahren nach Anspruch 1 oder 2, in welchem die im
Aluminosilicat anwesenden Kationen ganz oder teilweise durch andere Kationen ersetzt sind.
4. Verfahren nach einem der vorhergehenden Ansprüche, in welchem das Mol-Verhältnis von Siliciumoxid zu
Aluminiumoxid, in der Anfangsmischung mindestens 10:1 ist, das Mol-Verhältnis von freiem Alkalimetallhydroxid
(en) zu Wasser größer als 2x10 :1 ist, das Mol-Verhältnis von freiem Alkalimetallhydroxid(en!
_ 2 _ O10480Q
zu Siliciumoxid unter 5:1 liegt, das Mol-Verhältnis von Wasser zu Siliciumoxid im Bereich von 0 bis 100:1
liegt und das Mol-Verhältnis von Ammoniak zu Siliciumoxid von 0,01:1 bis 25:1 beträgt.
5. Verfahren nach Anspruch 4, in welchem in der Anfangsmischung das Mol-Verhältnis von Ammoniak zu Silicium-
oxid von 0,2:1 bis 10:1 ist.
6. Verfahren nach einem der vorhergehenden Ansprüche, in welchem in der Anfangsmischung das Mol-Verhältnis von
Siliciumoxid zu Aluminiumoxid von 45 bis 150:1, das Mol-Verhältnis von Ammoniak zu Siliciumoxid von
0,5:1 bis 4:1 ist.
7. Verfahren nach einem der vorhergehenden Ansprüche, in
welchem das Produkt oder dessen Wasserstoff-Form einem Ionenaustausch oder einer Imprägnierung mit einem der
Metalle oder Gruppen von Metallen oder deren Verbindungen, ausgewählt von Gruppen IB, HB, IHA, IVA, VA,
VIB, VIIB und VIII des Periodischen Systems nach Mendeleef, unterworfen wird.
8. Verfahren nach einem der vorhergehenden Ansprüche, in welchem das Aluminosilicat in einem Bindemittel gebunden
wird vor oder nach der Imprägnierung oder vor oder nach dem Ionenaustausch mit einer der Metallverbindungen,
um einen abriebfesten Katalysator zu bilden.
9. KohlenwasserstoffUmwandlungsreaktion, ausgewählt von;
Alkylierung, Dealkylierung, Dehydrocyclodimerisierung, Aromatisierung, Transalkylierung, Isomerisation, Dehydrierung,
Hydrierung, Krackung, Cyclisation, Oligomerisation und Polymerisation, dadurch gekennzeichnet,
daß eine umzuwandelnde Kohlenwasserstoffbeschickung mit einem kristallinen Aluminosilicat gemäß
einem der vorhergehenden Ansprüche in Berührung gebracht
wird.
10. Verfahren zur Dehydratisierung von Alkoholen zu Olefinen, dadurch gekennzeichnet, daß die Alkoholbeschickung
mit einem kristallinen Aluminosilicat gemäß einem der vorhergehenden Ansprüche 1 bis 8 in
Berührung gebracht wird.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB8225524 | 1982-09-07 |
Publications (1)
Publication Number | Publication Date |
---|---|
DE104800T1 true DE104800T1 (de) | 1984-12-20 |
Family
ID=10532752
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DE8383305073T Expired DE3364195D1 (en) | 1982-09-07 | 1983-09-01 | Improved method of preparing crystalline aluminosilicates |
DE198383305073T Pending DE104800T1 (de) | 1982-09-07 | 1983-09-01 | Verfahren zur herstellung von kristallinen aluminosilikaten. |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DE8383305073T Expired DE3364195D1 (en) | 1982-09-07 | 1983-09-01 | Improved method of preparing crystalline aluminosilicates |
Country Status (7)
Country | Link |
---|---|
US (1) | US4533649A (de) |
EP (1) | EP0104800B1 (de) |
JP (1) | JPS5973426A (de) |
AU (1) | AU559322B2 (de) |
CA (1) | CA1197223A (de) |
DE (2) | DE3364195D1 (de) |
NZ (1) | NZ205457A (de) |
Families Citing this family (24)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
LU85515A1 (fr) * | 1984-08-28 | 1986-03-11 | Belge Etat | Catalyseurs pour la transformation d'ethanol en ethylene et leur utilisation |
US4717560A (en) * | 1985-02-04 | 1988-01-05 | Exxon Research And Engineering Company | Crystalline zeolite composition (ECR-5) having a cancrinite-like structure and process for its preparation |
DE3577432D1 (de) * | 1985-02-05 | 1990-06-07 | Dow Chemical Co | Magnesiumsilicatzusammensetzungen, verfahren zu ihrer herstellung und alkylierungsverfahren unter verwendung dieser zusammensetzungen. |
GB2193222A (en) * | 1986-07-30 | 1988-02-03 | Shell Int Research | Process for the catalytic dewaxing of hydrocarbon oil |
GB8803112D0 (en) * | 1988-02-11 | 1988-03-09 | British Petroleum Co Plc | Zeolite catalysts suitable for hydrocarbon conversion |
JP2727618B2 (ja) * | 1989-01-26 | 1998-03-11 | 三菱瓦斯化学株式会社 | 不飽和カルボン酸エステルの製造方法 |
US5866096A (en) * | 1994-12-09 | 1999-02-02 | Exxon Chemical Patents, Inc. | ZSM-22 zeolite |
US5318766A (en) * | 1992-09-25 | 1994-06-07 | Exxon Research And Engineering Company | Process for preparing LTL nano-crystalline zeolite compositions |
US5599520A (en) * | 1994-11-03 | 1997-02-04 | Garces; Juan M. | Synthesis of crystalline porous solids in ammonia |
DE69729797T2 (de) * | 1996-05-29 | 2004-12-02 | Exxonmobil Chemical Patents Inc., Baytown | Zeolitischer katalysator und seine verwendung bei der kohlenwasserstoffumsetzung |
US6143940A (en) * | 1998-12-30 | 2000-11-07 | Chevron U.S.A. Inc. | Method for making a heavy wax composition |
US6150577A (en) * | 1998-12-30 | 2000-11-21 | Chevron U.S.A., Inc. | Method for conversion of waste plastics to lube oil |
FR2792928B1 (fr) * | 1999-04-29 | 2001-06-29 | Centre Nat Rech Scient | Procede de preparation de zeolite de structure ton |
US6717985B1 (en) | 2000-03-08 | 2004-04-06 | Telefonaktiebolaget Lm Ericsson (Publ) | Technique for efficiently equalizing a transmission channel in a data transmission system |
US6613302B1 (en) * | 2000-11-03 | 2003-09-02 | Uop Llc | UZM-5, UZM-5P and UZM-6: crystalline aluminosilicate zeolites and processes using the same |
DE102006029849A1 (de) * | 2006-06-27 | 2008-01-03 | Nanoscape Ag | Beschichtetes Molekularsieb |
GB0704797D0 (en) | 2007-03-13 | 2007-04-18 | Phoenix Ipr Ltd | Membrane structures and their production and use |
US8529870B2 (en) * | 2007-08-10 | 2013-09-10 | Exxonmobil Research And Engineering Company | Crystalline molecular sieve EMM-7, its synthesis and use |
US8088961B2 (en) * | 2007-12-27 | 2012-01-03 | Chevron U.S.A. Inc. | Process for preparing a pour point depressing lubricant base oil component from waste plastic and use thereof |
US8212097B2 (en) | 2010-07-01 | 2012-07-03 | Uop Llc | Aromatic alkylation process using UZM-5, UZM-5P and UZM-6 zeolites |
US8747807B2 (en) | 2010-07-01 | 2014-06-10 | Uop Llc | UZM-5, UZM-5P, and UZM-6 crystalline aluminosilicate zeolites and methods for preparing the same |
US9266744B2 (en) | 2013-10-10 | 2016-02-23 | Chevron U.S.A. Inc. | Synthesis of borosilicate ton-framework type molecular sieves |
KR20230105338A (ko) | 2020-11-10 | 2023-07-11 | 셰브런 유.에스.에이.인크. | Ton 프레임워크 유형의 제올라이트의 유기주형-무함유 합성 |
US11565943B2 (en) | 2021-02-11 | 2023-01-31 | Chevron U.S.A. Inc. | Synthesis of ton framework type molecular sieves |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1767074C2 (de) * | 1968-03-28 | 1973-01-04 | Badische Anilin- & Soda-Fabrik Ag, 6700 Ludwigshafen | Verfahren zur Herstellung kristalliner Zeolithe |
US3867512A (en) * | 1969-09-10 | 1975-02-18 | Union Oil Co | Method of preparing crystalline {37 l{38 {0 zeolite |
NL7313370A (nl) * | 1973-09-28 | 1975-04-02 | Shell Int Research | Zeoliet. |
NL7803662A (nl) * | 1978-04-06 | 1979-10-09 | Shell Int Research | Werkwijze voor de bereiding van zeolieten. |
CA1150712A (en) * | 1979-12-07 | 1983-07-26 | William J. Ball | Process for the production of crystalline aluminosilicates and their use as catalysts and catalyst supports |
CA1167071A (en) * | 1980-03-15 | 1984-05-08 | William J. Ball | Process for the production of aromatic hydrocarbons |
IN157506B (de) * | 1981-01-08 | 1986-04-12 | British Petroleum Co |
-
1983
- 1983-09-01 US US06/528,528 patent/US4533649A/en not_active Expired - Lifetime
- 1983-09-01 AU AU18633/83A patent/AU559322B2/en not_active Expired
- 1983-09-01 EP EP83305073A patent/EP0104800B1/de not_active Expired
- 1983-09-01 DE DE8383305073T patent/DE3364195D1/de not_active Expired
- 1983-09-01 NZ NZ205457A patent/NZ205457A/en unknown
- 1983-09-01 DE DE198383305073T patent/DE104800T1/de active Pending
- 1983-09-06 CA CA000436067A patent/CA1197223A/en not_active Expired
- 1983-09-07 JP JP58164894A patent/JPS5973426A/ja active Granted
Also Published As
Publication number | Publication date |
---|---|
EP0104800B1 (de) | 1986-06-18 |
AU559322B2 (en) | 1987-03-05 |
DE3364195D1 (en) | 1986-07-24 |
AU1863383A (en) | 1984-03-15 |
EP0104800A1 (de) | 1984-04-04 |
CA1197223A (en) | 1985-11-26 |
JPS5973426A (ja) | 1984-04-25 |
US4533649A (en) | 1985-08-06 |
NZ205457A (en) | 1986-03-14 |
JPH0453807B2 (de) | 1992-08-27 |
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