DE3219494A1 - Zirconium- and/or hafnium-containing zeolites, process for their preparation and their use - Google Patents

Zirconium- and/or hafnium-containing zeolites, process for their preparation and their use

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DE3219494A1
DE3219494A1 DE19823219494 DE3219494A DE3219494A1 DE 3219494 A1 DE3219494 A1 DE 3219494A1 DE 19823219494 DE19823219494 DE 19823219494 DE 3219494 A DE3219494 A DE 3219494A DE 3219494 A1 DE3219494 A1 DE 3219494A1
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zirconium
hafnium
compounds
zeolites
aluminosilicates
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Herbert Dr. 6230 Frankfurt Baltes
Ernst-Ingo Dr. 6391 Westerfeld Leupold
Heinz Dr. 6200 Wiesbaden Litterer
Friedrich Dr. 6093 Flörsheim Wunder
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Hoechst AG
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Hoechst AG
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Priority to EP82109452A priority patent/EP0077523B1/en
Priority to DE8282109452T priority patent/DE3263914D1/en
Priority to AU89400/82A priority patent/AU550136B2/en
Priority to CA000413530A priority patent/CA1196903A/en
Priority to NZ202185A priority patent/NZ202185A/en
Publication of DE3219494A1 publication Critical patent/DE3219494A1/en
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    • 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
    • C01B39/08—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 the aluminium atoms being wholly replaced
    • C01B39/085—Group IVB- metallosilicates
    • 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
    • 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
    • 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
    • C01B39/065—Galloaluminosilicates; Group IVB- metalloaluminosilicates; Ferroaluminosilicates
    • 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
    • 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
    • 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
    • C07C2529/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
    • 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
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
    • 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
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/40—Ethylene production

Abstract

The invention relates to zirconium- and/or hafnium-containing zeolites, to a process for their preparation, and to their use. To prepare the zeolites, zirconium compounds and/or hafnium compounds as well as silicon compounds, sodium compounds and tetrapropylammonium compounds and water and, if appropriate, additionally aluminium compounds, are mixed in specified ratios and heated in a sealed container. The zeolites are used as catalysts in the preparation of C2-C4-olefins from methanol.

Description

Zirkon- und/oder hafniumbaltige Zeolithe und VerfahrenZirconia and / or hafnium containing zeolites and processes

zu ihrer Herstellung sowie ihre Verwendung Als Zeolithe bezeichnet man vor allem kristallineAluminosilicate, bei denen durch eine dreidimensionale Verknüpfung von SiO4 - und AlO4- Tetraedern regelmäßige Strukturen mit Hohlräumen und Poren entstehen. Im hydratisierten Zustand sind diese Poren und Hohlräume mit Wasser gefüllt. Dieses läßt sich ohne Beeinflussung der Kristallstruktur entfernen oder durch andere Moleküle ersetzen. Die negativen Ladungen der AlO4-Tetracder werden durch Kationen kompensiert. Diese können gegen andere positiv geladene Ionen ausgetauscht werden Die- geschilderten Eigenschaften exmöglichen die Verwendung der Zeolithe als Ionenaustauscher, Adsorbentien und Katalysatoren (D.W. Breck: Zeolithe Molecular Sieves, 1974) Zeolithe des X-, Y-, Mordenit-, Erionit- und Offretit-Typs beispielsweise besitzen als Katalysatoren für Umwandlungsreaktionen von Kohlenwas serstoffen wie. Cracken, Hydrocracken oder Isomari.sierungen beträchtliches technisches Interesse. Zeolithe vom Pentasil-Typ (z.B. Zeolith ZSM-5) gewinnen als Katalysatoren für die Umwandlung von Methanol zu Kohlenwasserstoffen steigende Bedeutung.for their production as well as their use referred to as zeolites mainly crystalline aluminosilicates, which are three-dimensional Linking SiO4 and AlO4 tetrahedra regular structures with cavities and pores arise. In the hydrated state, these pores and voids are with Filled with water. This can be removed without affecting the crystal structure or replace it with other molecules. The negative charges of the AlO4 tetracder are compensated by cations. These can be exchanged for other positively charged ions The properties described enable the use of the zeolites as ion exchangers, adsorbents and catalysts (D.W. Breck: Zeolithe Molecular Sieves, 1974) X, Y, mordenite, erionite and offretite type zeolites, for example have as catalysts for conversion reactions of hydrocarbons such as. Cracking, hydrocracking or isomariations of considerable technical interest. Zeolites of the pentasil type (e.g. zeolite ZSM-5) win as catalysts for the Conversion of methanol to hydrocarbons increasing in importance.

Aufgrund der zahlreichen Einsatzmöglichkeiten als Katalysatoren besteht großes Interesse an neuen Zeolithen mit spezifischen katalytischen Eigenschalten.Because of the numerous possible uses as catalysts great interest in new zeolites with specific catalytic properties.

Beispielsweise erhält man sehr interessante Zeolithe, wenn man anstelle von Aluminium oder/und Silizium andere Elemente in das Zeolith-Gerüst einbaut. So wurden unter anderem Zeolithe der Pentasil-Reihe bekannt, die -Bor (DE-OS 2 746 790), Eisen (DE-OS 2 831 611), Arsen (DE-AS 2 830.830), Antimon (DE-OS 2 830 787), Vanadin (DE-OS 2 831 631), Chrom (DE-OS 2 831 630) oder Gallium (BE-PS 882 484) auf Tetraederplätzen enthalten.For example, you get very interesting zeolites if you instead of of aluminum and / or silicon incorporates other elements into the zeolite framework. So Zeolites of the Pentasil series became known, the -Bor (DE-OS 2 746 790), iron (DE-OS 2 831 611), arsenic (DE-AS 2 830.830), antimony (DE-OS 2 830 787), Vanadium (DE-OS 2 831 631), chromium (DE-OS 2 831 630) or gallium (BE-PS 882 484) included on tetrahedral sites.

Auch wurden Titanosilicate (US-PS 3 329 481) und Zirkonosilicate (US-PS 3 329 480) mit Zeolithstruktur bekannt, bei denen aber aufgrund des Röntgenbeugungsdiagramms und der chemischen Zusammensetzung eine Pentasil-Struktur mit Sicherheit auszuschließen ist.Titanosilicates (US Pat. No. 3,329,481) and zirconosilicates (US Pat 3 329 480) with a zeolite structure are known, but based on the X-ray diffraction diagram and the chemical composition to exclude a pentasil structure with certainty is.

Gegenstand der Erfindung sind Zirkono- und/oder Hafno-Silicate bzw. - Aluminosilicate mit Pentasil-Struktur.The invention relates to zircono- and / or hafno-silicates or - Aluminosilicates with a pentasil structure.

flir den Begriff Pentasile gilt dabei die Definition von Xokotailo und Meier ("Pentasil family of high silicon crystalline materials in Special Publication No. 33 of the Chernical Society London 1980). Die Pentasil-Familie umfaßt beispielsweise die synthetischen Zeolithe ZSM-5 (US-PS 3 702 886), ZSM-8 (GB- PS 1 334 243), ZSM-11 (US-PS 3 709 979) und ZSM-23 (US-PS 4 076 842).The definition of Xokotailo applies to the term Pentasile and Meier ("Pentasil family of high silicon crystalline materials in Special Publication No. 33 of the Chernical Society London 1980). For example, the Pentasil family includes the synthetic zeolites ZSM-5 (U.S. Patent 3,702,886), ZSM-8 (British Patent 1,334,243), ZSM-11 (U.S. Patent 3,709,979) and ZSM-23 (U.S. Patent 4,076,842).

Gegenstand der Erfindung sind vor allem Zirkono- und/oder Hafno- Silicate bzw. -Aluminosilicate mit ZSM-5 - Struktur, vorzugsweise solche mit folgender Zusammensetzung, ausgedrückt in Molverhältnissen der Oxide: SiO2 : ( 0 - 0,15) Al203 : (0,002 - 1,0) MO2, insbesondere SiO2 : (O - 0,1) Al203 : (0,01 - 0,4) MO2, wobei N gleich Zirkon und/oder Hafnium ist.The invention primarily relates to zirconosilicates and / or hafnosilicates or aluminosilicates with ZSM-5 structure, preferably those with the following composition, expressed in molar ratios of the oxides: SiO2: (0 - 0.15) Al203: (0.002 - 1.0) MO2, especially SiO2: (O - 0.1) Al203: (0.01 - 0.4) MO2, where N is zirconium and / or hafnium.

Die erfindungsgemäßen zirkon- und/oder hafniumhaltigen Zeolithe lassen sich nach Methoden herstellen, wie sie auch für die Synthese des zirkon- bzw. hafniumfreien Zeolithen ZSM-5 beschrieben wurden, beispielsweise unter Verwendung von Alkylammoniumsalzen (US-PS 3 702 886), von Trialkylaminen bei gleichzeitiger Anwesenheit von Alkylierungsmitteln (DE-AS 2 212 810), von Diaminen <DE-OS 2 831 334) und/oder von Impfkristallen in Gegenwart oder Abwesenheit von Alkoholen undyoder Ammoniumhydroxid (US-PS 4 199 556).The zirconium and / or hafnium-containing Zeolites can be produced according to methods that are also used for the synthesis of the zirconium or hafnium-free zeolites ZSM-5 have been described, for example using of alkylammonium salts (US Pat. No. 3,702,886), of trialkylamines with simultaneous Presence of alkylating agents (DE-AS 2 212 810), of diamines <DE-OS 2 831 334) and / or of seed crystals in the presence or absence of alcohols undyor ammonium hydroxide (U.S. Patent 4,199,556).

Ein bevorzugtes Verfahren zur Synthese der erfindungsmäßen Zeolithe besteht darin, daß man Zirkon-und/oder Hafnium- sowie Silizium-, Natrium- und Tetrapropylammoniumverbindungen, sowie im Falle der Aluminosilicate noch zusätzlich Aluminiumverbindungen, mit Wasser mischt und dieses Gemisch in einem geschlossenen Gefäß erhitzt. Diesem Gemisch können darüberhinaus vor dem Erhitzen Impfkristalle zugesetzt werden.A preferred method for synthesizing the zeolites according to the invention consists in that zirconium and / or hafnium as well as silicon, sodium and tetrapropylammonium compounds, as well as in the case of the aluminosilicates additionally aluminum compounds with water mixes and this mixture is heated in a closed vessel. This mixture can moreover, seed crystals are added prior to heating.

Die Ausgangsverbindungen werden im allgemeinen in folgendem Verhältnis eingesetzt, ausgedrückt in Molverhältnissen der Oxide: SiO2 : (0 - 0,2) Al2O3 : (0,01 - 1,0) MO2 (0,01 - 0,5) Na2O: (0,02 - 1,0) R20 : (5 - 100) H2O, vorzugsweise im Verhältnis sio2 : (O - 0,1) Al2O3 : (0,01 - 0,4) MO2 (0,02 - 0,3) Na2O : (0,03 - O,G) R2O : (10 -- 40) 112°, wobei M gleich Zirkon und/oder Hafnium und R gleich Tetrapropylammonium ist.The starting compounds are generally in the following ratio used, expressed in molar ratios of the oxides: SiO2: (0 - 0.2) Al2O3: (0.01-1.0) MO2 (0.01-0.5) Na2O: (0.02-1.0) R20: (5-100) H2O, preferably in the ratio sio2: (O - 0.1) Al2O3: (0.01 - 0.4) MO2 (0.02 - 0.3) Na2O: (0.03 - O, G) R2O: (10 - 40) 112 °, where M is zirconium and / or hafnium and R is tetrapropylammonium.

Als Verbindungen können beispielsweise eingesetzt werden: Kieselsäuregel, Natriumsilicat, Aluminiumhydroxid, Aluminiumsulfat, Natriumaluminat, Aluminiumhalogenide, Aluminiummetahydroxid Zirkonhalogenide, Zirkonsulfat, Zirkonylchlorid, Hafniumhalogenide, Hafniumsulfat, Natriumhydroxid, Natriumsulfat1 Natriumhalogenide, Tetrapropylammoniumhydroxid, Tetrapropylammoniumhalogenide. Aber auch andereSiiizium-, Aluminium, Zirkon-, Hafnium-, Natrium- und Alkylammoniumverbindungen eignen sich für die Herstellung der erfindungsgemäßen Zeolithe.The following compounds can be used, for example: silica gel, Sodium silicate, aluminum hydroxide, aluminum sulfate, sodium aluminate, aluminum halides, Aluminum metahydroxide zirconium halides, zirconium sulfate, zirconyl chloride, hafnium halides, Hafnium sulfate, sodium hydroxide, sodium sulfate1 sodium halides, tetrapropylammonium hydroxide, Tetrapropylammonium halides. But also other silicon, aluminum, zirconium, hafnium, Sodium and alkylammonium compounds are suitable for the preparation of the invention Zeolites.

Das Gemisch der jeweils gewählten Verbindungen mit Wasser wird im allgemeinen 18 bis 360 Stunden, vorzugsweise 24 bis 240 Stunden lang auf eine Temperatur zwischen 100 und 2000C, vorzugsweise zwischen 130 und 1700C, in einem geschlossenen Gefäß erhitzt.The mixture of the compounds selected in each case with water is im generally 18 to 360 hours, preferably 24 to 240 hours at one temperature between 100 and 2000C, preferably between 130 and 1700C, in a closed Vessel heated.

Die gebildeten Zeolithe werden in üblicher Weise, z.B.The zeolites formed are used in a conventional manner, e.g.

durch Filtration, isoliert, gewaschen und getrocknet.by filtration, isolated, washed and dried.

Sie könne nach bekannten Methoden in die katalytisch aktiven Formen überführt werden1 z.B. durch Kalzinierung und/oder Ionenaustausch (D.W. Breck, Zeolite Molecular Sieves, 1974).They can be converted into the catalytically active forms by known methods be transferred1 e.g. by calcination and / or ion exchange (D.W. Breck, Zeolite Molecular Sieves, 1974).

Die erfindungsgemäßen Zeolithe zeichnen sich nach ihrer Überführung in die liatalytisch aktive Form insbesondere aus durch eine hohe Selektivität und durch eine geringe Koksabscheidung bei der Umwandlung von Methanol in niedere Olefine. Es ist überraschend, daß man mit hilfe der angegebenen Methode überhaupt Zeolithe mit den erfindungsgemäßen Merkmalen erhält.The zeolites according to the invention are notable for their conversion in the liatalytically active form in particular due to a high selectivity and due to a low coke deposition in the conversion of methanol to lower olefins. It is surprising that with the aid of the method indicated, zeolites at all obtained with the features of the invention.

Die Erfindung soll durch die folgenden Beispiele erläutert werden, wobei die Beispiele aber in keiner Weise einschränkend sein sollen. Alle angegebenen Röntgenbeugungsdaten wurden mit einem computergesteuerten Pulverdiffraktometer D-500 der Firma Siemens aufgenommen. Es wurde Kupfer-K-α-Strahlung verwandt.The invention is to be illustrated by the following examples, however, the examples are not intended to be limiting in any way. All specified X-ray diffraction data were obtained using a computer-controlled powder diffractometer D-500 the company Siemens added. Copper-K-α radiation was used.

Beispiel 1 1,66 g Natriumaluminat (54 Gew.% Al203, 41 Gew.% Na2O) und 1,48 g Natriumhydroxid werden in 20 g 20 Gew.%iger wäßriger Tetrapropylammoniumhydroxid-Lösung gelöst (Lösung A). Eine weitere Lösung (Lösung B) wird hergestellt, indem man 62 g 40 Gew.%iges kolloidales Kieselgel in 230 g 20 Gç.%iger wäßriger Tetrapropylammoniumhydroxid-Lösung löst und diese Lösung am Rotationsverdampfer auf insgesamt 220 g- einengt. Lösung A und Lösung B werden miteinander vermischt. Zu dieser Mischung werden unter intensivem Rühren 3,78 g Zirkonylchlorid ZrOCl2 - 8 H2O gegeben. Die entstandene Suspension wird homogenisiert und in einem geschlossenen Gefäß 120 h auf 1600C erhitzt. Das entstandene Produkt wird abfiltriert, mit Wasser gewaschen und bei 1200C getrocknet. Man erhält 27,3 g des erfindungsgemäßen Zirkonoaluminosilicats.Example 1 1.66 g of sodium aluminate (54% by weight Al203, 41% by weight Na2O) and 1.48 g of sodium hydroxide are dissolved in 20 g of 20% strength by weight aqueous tetrapropylammonium hydroxide solution dissolved (solution A). Another solution (solution B) is prepared by adding 62 g of 40% strength by weight colloidal silica gel in 230 g of 20% strength by weight aqueous tetrapropylammonium hydroxide solution dissolves and this solution is concentrated on a rotary evaporator to a total of 220 g. solution A and solution B are mixed together. To this mixture become under intense Stir 3.78 g of zirconyl chloride ZrOCl2 - 8 H2O are added. The resulting suspension is homogenized and heated to 1600C in a closed vessel for 120 h. That The resulting product is filtered off, washed with water and dried at 1200C. 27.3 g of the zirconoaluminosilicate according to the invention are obtained.

Die Röntgenbeugungsanalyse zeigt ein gut kristallines Produkt mit ZSM-5 - Struktur. Die chemische Analyse des 16 Stunden bei 5400C kalzinierten Produktes zeigt folgende Zusammensetzung, ausgedrückt in Molverhältnissen der Oxide: SiO2 : 0,035 ZrO2 : 0,026 Al203 : 0,023 Na2O Beispiel 2 0,77 g Natriumhydroxid werden in 5 g 20 Gew.%iger wäßriger Tetrapropylammoniumhydroxid-Lösung gelöst (Lösung A). Eine zweite Lösung (Lösung B) wird hergestellt, indem man 12,4 g 40 Gew.%iges kolloidales Kieselgel in 45 g 20 Gew.%iger Tetrapropylammoniumhydroxid-Lösung löst und diese Lösung am Rotationsverdampfer auf insgesamt 45 g einengt. Lösung A und Lösung B werden miteinander vermischt. Zu dieser Mischung werden unter intensivem Rühren 1,88 g Zirkonylchlorid ZrOCl2 . 8 H2O in 5 ml H20 und 0,1 g Impfkristalle (aus Beispiel 1 gegeben. Die entstandene Suspension wird homogenisiert und in einem geschlossenen Gefäß 160 h auf 150°C erhitzt. Das entstandene Produkt wird abfiltiert, mit Wasser gewaschen und bei 1200C getrocknet. Man erhält 4,2 g des erfindungsgemäßen Zirkonosilicats.The X-ray diffraction analysis shows a well-crystalline product ZSM-5 structure. The chemical analysis of the product calcined for 16 hours at 5400C shows the following composition, expressed in molar ratios of the oxides: SiO2 : 0.035 ZrO2: 0.026 Al203: 0.023 Na2O Example 2 0.77 g sodium hydroxide are dissolved in 5 g of 20% strength by weight aqueous tetrapropylammonium hydroxide solution (solution A). A second solution (solution B) is prepared by adding 12.4 g of 40% by weight dissolves colloidal silica gel in 45 g of 20% strength by weight tetrapropylammonium hydroxide solution and this solution is concentrated on a rotary evaporator to a total of 45 g. Solution A and Solution B are mixed together. To this mixture become under intense Stirring 1.88 g of zirconyl chloride ZrOCl2. 8 H2O in 5 ml H20 and 0.1 g seed crystals (given from Example 1. The resulting suspension is homogenized and in a closed vessel heated to 150 ° C for 160 h. The resulting product is filtered off, washed with water and dried at 1200C. 4.2 g of the invention are obtained Zirconosilicate.

Das Produkt besitzt laut Röntgenbeugunysanalyse eine ZSM-5 -Struktur. Die chemische Analyse des 16 Stunden bei 5400C kalzinierten Produktes zeigt folgende Zusammensetzung: SiO2 : 0,210 ZrO2: 0,121 Na2O Beispiel 3 In einen senkrecht angeordneten, elektrisch beheizten Rohrreaktor von 1 m Länge, der mit 250 ml Katalysator auf Basis des in Beispiel 1 hergestellten Zirkonoaluminosilikats mit ZSM-5-Struktur gefüllt ist, dosiert man stündlich 520 ml 33 gew.-%iges wasserhaltiges Methanol bei einer Temperatur von 3500C und Normaldruck. Das entstehende Reaktionsgemisch wird abgekühlt, und nach Abtrennung der kondensierbaren Anteile wird die gasförmige Phase analysiert.According to X-ray diffraction analysis, the product has a ZSM-5 structure. The chemical analysis of the product calcined for 16 hours at 5400 ° C. shows the following Composition: SiO2: 0.210 ZrO2: 0.121 Na2O Example 3 In a vertically arranged, electrically heated tubular reactor of 1 m length, with 250 ml of catalyst based on the zirconium aluminosilicate prepared in Example 1 is filled with ZSM-5 structure, 520 ml of 33% by weight aqueous solution are dosed every hour Methanol at a temperature of 3500C and normal pressure. The resulting reaction mixture is cooled, and after the condensable components have been separated off, it becomes gaseous Phase analyzed.

Di C2-C4-Olefin-Selektivität ist 65 % und die Selektivität zu Kohlenwasserstoffen mit mehr als 4 C-Atomen ist 14 %.The C2-C4 olefin selectivity is 65% and the selectivity to hydrocarbons with more than 4 carbon atoms is 14%.

Vergleichsbeispiel: Die Arbeitsweise ist wie in Beispiel 3, nur daß statt des Zirkonoaluminosliikats ein handelsüblicher Aluminosilikat-Katalysator mit ZSM-5-Struktur eingesetzt wird.Comparative example: The procedure is as in Example 3, only that instead of the zirconium aluminosilicate, a commercially available aluminosilicate catalyst with ZSM-5 structure is used.

Die C2-C4-Olefin-Selektivität ist 56 % und die Selektivität zu Kohlenwasserstoffen mit mehr als 4 C-Atomen ist 23 %.The C2-C4 olefin selectivity is 56% and the selectivity to hydrocarbons with more than 4 carbon atoms is 23%.

Claims (7)

Patentansprüche: 1. Zirkono- und/oder Hafno-Silicate bzw. - Aluminosilicate mit Pentasilstruktur.Claims: 1. Zircono- and / or Hafno-silicates or - aluminosilicates with pentasil structure. 2. Zirkono- und/oder Hafno-Silicate bzw. -Aluminosilicate mit ZSM-5 - Struktur.2. Zircono- and / or Hafno-silicates or -aluminosilicates with ZSM-5 - structure. 3. Zirkono- und/oder Hafno-Silicate bzw. - Aluminosilicate nach Anspruch 1 oder 2, gekennzeichnet durch folgende . Zusammensetzung ausgedrückt in Molverhältnissen der Oxide: SiO2: (0 - 0,15) Al2O3: (0,002-1,0) MO2 wobei M gleich Zirkon und/oder Hafnium ist.3. Zircono- and / or Hafno-silicates or - aluminosilicates according to claim 1 or 2, characterized by the following. Composition expressed in molar ratios of oxides: SiO2: (0 - 0.15) Al2O3: (0.002-1.0) MO2 where M equals zirconium and / or Is hafnium. 4. Zirkono- und/oder Hafno-Silicate bzw. - Aluminosilicate nach einem der Ansprüche 1 bis 3, gekennzeichnet durch folgende Zusammensetzung1 ausgedrückL in Molverhältnissen der Oxide: SiO2: (0 - 0,1) Al2O3: (0,01 - 0,4) MO2 wobei M gleich Zirkon und/oder Hafnium ist.4. Zircono- and / or Hafno-silicates or - aluminosilicates after a of claims 1 to 3, characterized by the following composition 1 expressed in molar ratios of the oxides: SiO2: (0 - 0.1) Al2O3: (0.01 - 0.4) MO2 where M is the same Is zirconium and / or hafnium. 5. Verfahren zur Herstellung von Zirkono- und/oder Hafno-Silicaten bzw. - Aluminosilicaten nach einem der Ansprüche 1 bis 4, dadurch gekennzeicllnct, daß man eine Mischung aus Zirkon undZoder Hafnium-,sowie Silizium-, Natrium-, Tetrapropylammoniumverbindungen und Wasser, sowie ggf Aluminiumverbindungen herstellt, die folgende Zusammensetzung hat, ausgedrückt in Molver hältnissen der Oxide: SiO2 : (0 - 0,2) Al203 : (0t01 - 1,0) MO2 : (0,01 - 0,5) Nå2O : (0,02 - 1,0) R2O : (5 - 100) H2O, wobei M gleich Zirkon und/oder Hafnium und R gleich Tetrapropylammonium ist, und diese Mischung in einem geschlossenen Gefäß erhitzt.5. Process for the production of zircono- and / or hafno-silicates or - aluminosilicates according to one of claims 1 to 4, characterized thereby, that one is a mixture of zirconium and Z or hafnium, as well as silicon, sodium, tetrapropylammonium compounds and water, and possibly aluminum compounds, has the following composition has, expressed in molar proportions of the oxides: SiO2: (0 - 0.2) Al203: (0t01 - 1.0) MO2: (0.01 - 0.5) Nå2O: (0.02 - 1.0) R2O: (5 - 100) H2O, where M is zirconium and / or hafnium and R is tetrapropylammonium, and this mixture is heated in a closed vessel. 6. Verfahren nach Anspruch 5, dadurch gekennzeichnet, daß die zu erhitzende Mischung folgende Zusammensetzung hat, ausgedrückt in Molverhältnissen der Oxide: SiO2 : (0 - 0,1) A1203 : (0,01 - 0,4) M?2 (0,02 - 0,3) Na2O : (0,03 - 0,6)R2O : (10 - 40) H2O, wobei M gleich Zirkon und/oder Hafnium und R gleich Tetrapropylammonium ist.6. The method according to claim 5, characterized in that the to be heated Mixture has the following composition, expressed in molar ratios of the oxides: SiO2: (0 - 0.1) A1203: (0.01 - 0.4) M? 2 (0.02 - 0.3) Na2O: (0.03 - 0.6) R2O: (10 - 40) H2O, where M is zirconium and / or hafnium and R is tetrapropylammonium is. 7. Verwendung von Zirkono- und/oder Hafno-Silicaten bzw.7. Use of zircono- and / or hafno-silicates or - Aluminosilicaten nach einem der Ansprüche 1 bis 4 als Katalysatoren bei der Herstellung von C2~ bis C4 - Olefinen aus Methanol. - Aluminosilicates according to any one of claims 1 to 4 as catalysts in the production of C2 ~ to C4 - olefins from methanol.
DE19823219494 1981-10-17 1982-05-25 Zirconium- and/or hafnium-containing zeolites, process for their preparation and their use Withdrawn DE3219494A1 (en)

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Application Number Priority Date Filing Date Title
DE19823219494 DE3219494A1 (en) 1982-05-25 1982-05-25 Zirconium- and/or hafnium-containing zeolites, process for their preparation and their use
EP82109452A EP0077523B1 (en) 1981-10-17 1982-10-13 Zeolites containing zirconium and/or hafnium, process for producing them and their use
DE8282109452T DE3263914D1 (en) 1981-10-17 1982-10-13 Zeolites containing zirconium and/or hafnium, process for producing them and their use
AU89400/82A AU550136B2 (en) 1981-10-17 1982-10-15 Zirconium and/or hafnium containing zeolites
CA000413530A CA1196903A (en) 1981-10-17 1982-10-15 Zirconium- and/or hafnium-containing zeolites, process for their manufacture, and their use
NZ202185A NZ202185A (en) 1981-10-17 1982-10-15 Zircono-and/or hafno-aluminosilicates having a pentasil structure,their preparation and use as olefin producing catalysts

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