DE3219495A1 - Titanium-containing zeolites, process for their preparation and their use - Google Patents

Titanium-containing zeolites, process for their preparation and their use

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Publication number
DE3219495A1
DE3219495A1 DE19823219495 DE3219495A DE3219495A1 DE 3219495 A1 DE3219495 A1 DE 3219495A1 DE 19823219495 DE19823219495 DE 19823219495 DE 3219495 A DE3219495 A DE 3219495A DE 3219495 A1 DE3219495 A1 DE 3219495A1
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Prior art keywords
titanium
zeolites
tio2
sio2
al2o3
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German (de)
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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 AU83401/82A priority Critical patent/AU544046B2/en
Application filed by Hoechst AG filed Critical Hoechst AG
Priority to DE19823219495 priority patent/DE3219495A1/en
Priority to DE8282109451T priority patent/DE3266412D1/en
Priority to EP82109451A priority patent/EP0077522B1/en
Priority to AU89401/82A priority patent/AU8940182A/en
Priority to CA000413523A priority patent/CA1185224A/en
Priority to NZ202184A priority patent/NZ202184A/en
Publication of DE3219495A1 publication Critical patent/DE3219495A1/en
Withdrawn legal-status Critical Current

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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
    • C01B39/065—Galloaluminosilicates; Group IVB- metalloaluminosilicates; Ferroaluminosilicates
    • 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
    • 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 titanium-containing zeolites, to a process for their preparation, and to their use. To prepare the zeolites, titanium compounds, silicon compounds, aluminium compounds, sodium compounds and tetrapropylammonium compounds are mixed with water in specified ratios, and the mixture is heated in a sealed container. The zeolites are used as catalysts in the preparation of C2-C4-olefins from methanol.

Description

Titanhaltige Zeolithe und Verfahren zu ihrer HerstellungTitanium-containing zeolites and processes for their preparation

sowie ihre Verwendung Zeolithe sind kristalline Aluminosilicate, bei denen durch eine dreidimensionale Verknüpfung von SiO4- und A104-Tetraedern regelmäßige Strukturen mit Hohlräumen und Poren entstehen. Im hydratisierten Zustand sind diese Poren und Hohlräume mit Wasser gefüllt. Dieses läßt sic ohne Beeinflussung der Kristallstruktur entfernen oder durch andere Moleküle ersetzen. Die negativen Ladungen der AlO4-Tetraeder werden durch Kationen kompensiert. Diese können gegen andere positiv geladene Ionen ausgetauscht werden. Die geschilderten Eigenschaften ermöglichen die Verwendung der Zeolithe als Ionenaustauscher, Adsorbenti.en und Katalysatoren (D.W. Breck: Zeolite Molecular Sicves, 1974).as well as their use zeolites are crystalline aluminosilicates, at which are regular through a three-dimensional linkage of SiO4 and A104 tetrahedra Structures with cavities and pores arise. These are in the hydrated state Pores and cavities filled with water. This leaves sic without influencing the crystal structure remove or replace with other molecules. The negative charges of the AlO4 tetrahedra are compensated by cations. These can counteract other positively charged ions be replaced. The properties described enable its use of zeolites as ion exchangers, adsorbents and catalysts (D.W. Breck: Zeolite Molecular Sicves, 1974).

Zeolithe des X-, Y-, Mordenit-, Erionit- und Offretit-Typs beispielsweise besitzen als Katalysatoren für Umwandlungsreaktionen von Kohlenwasserstoffen wie Cracken, Hydrocracken oder Isomerisierungen beträchtliches technisches Interesse.Zeolites of the X, Y, mordenite, erionite and offretite types, for example have as catalysts for conversion reactions of hydrocarbons such as Cracking, hydrocracking or isomerizations of considerable technical interest.

Zeolithe vom Pentasil-Typ (z.B. Zeolith ZSM-5) gewinnen als Katalysatoren für die Umwandlung von Methanol zu Kohlenwasserstoffen steigende Bedeutung.Zeolites of the pentasil type (e.g. zeolite ZSM-5) are used as catalysts increasing importance for the conversion of methanol to hydrocarbons.

Aufgrund der zahlreichen Einsatzmöglichkeiten als Katalysatoren besteht großes Interesse an neuen Zeolithen mit spezifischen katalytischen Eigenschaften.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 Pertasil-Reihe bekannt, die Bor (DE-OS-2 746 790), Eisen (DE-OS 2 831 611) , Arsen (DE-AS 2 830 830), Antim(n (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 were among other things known zeolites of the Pertasil series, the boron (DE-OS-2 746 790), Eisen (DE-OS 2 831 611), arsenic (DE-AS 2 830 830), Antim (n (DE-OS 2 830 787), vanadin (DE-OS 2 831 631), chromium (DE-OS 2 831 630) or gallium (BE-PS 882 484) on tetrahedral sites contain.

Auch wurden Titanosilicate (US-PS 3 329 481) und Zirkono-.silicate (US-PS 3 329 480) mit Zeolithstruktur bekannt.Titanosilicates (US Pat. No. 3,329,481) and zirconosilicates have also been found (US Pat. No. 3,329,480) with a zeolite structure.

Gegenstand der Erfindung sind Titanoaluminosilikate mit Pentasil-Struktur Für den Begriff Pentasile gilt dabei die Definition von Kokotailo und Meier ("Pentasil family of high silica crystalline materialst in Special Publication No. 33 of the Chemical Socicty, 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), Gegenstand der Erfindung sind vor a) lem Titanoaluminosilicate mit ZSM-5-Struktur, vorzugsweise solche mit folgender Zusammensetzung, ausgedrückt in Molverhältnissen der Oxide: SiO2 : (0,001 - 0,15) Al2O3: : (0,002 - 1,0) TiO2, insbesondere: SiO2 : (0,005 - 0,1) Al2O3 : (0,01 - 0,4) TiO2.The invention relates to titanium aluminosilicates with a pentasil structure The definition of Kokotailo and Meier ("Pentasil family of high silica crystalline materialst in Special Publication No. 33 of the Chemical Society, London 1980). The Pentasil family includes, for example, the synthetic ones Zeolites ZSM-5 (US-PS 3,702,886), ZSM-8 (GB-PS 1,334,243), ZSM-11 (US-PS 3,709,979) and ZSM-23 (US Pat. No. 4,076,842), the invention relates to a) titanoaluminosilicates with ZSM-5 structure, preferably those with the following composition expressed in molar ratios of the oxides: SiO2: (0.001 - 0.15) Al2O3:: (0.002 - 1.0) TiO2, in particular: SiO2: (0.005-0.1) Al2O3: (0.01-0.4) TiO2.

Die erfindungsgemäßen Titanoaluminosilicate lassen sich nach Methoden herstellen, wie sie auch riir die Synthese des titanfreien Zeolithen ZSM-5 beschrieben wurden, beispielsweise unter Verwendung von Alky lamrnaniumsalzen (US-PS 3 702 88G), 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 und/oder Isunoniumhydroxid (US-PS 4 199 556).The titanoaluminosilicates according to the invention can be prepared by methods as described for the synthesis of the titanium-free zeolite ZSM-5 were, for example using alkyl amminium salts (US Pat. No. 3,702,888), of trialkylamines in the simultaneous presence of alkylating agents (DE-AS 2 212 810), of diamines (DE-OS 2 831 334) and / or of seed crystals in Presence or absence of alcohols and / or isunonium hydroxide (U.S. Patent 4,199 556).

Von dem Titanosilicat gemäß US-PS 3 329 480 unterscheidet sich das erfindungsgemäße Titanoaluminosilicat sowohl durch die Struktur wie auch durch den Aluminiumgehalt, Ein bevorzugtes Verfahren zur Synthese der erfindungsgemäßen Titanoaluminosilicate besteht darin, daß man Titan-, Silizium-, Natrium-, Tetrapropylammonium- und Aluminiumverbindungen mit Wasser mischt und dieses Gemisch in einem geschlossenen Gefäß erhitzt. Diesem Gemisch können darüberhinaus vor dem Erhitzen Impfkristalle zugesetzt werden.This differs from the titanosilicate according to US Pat. No. 3,329,480 inventive titanoaluminosilicate both by the structure and by the Aluminum content, a preferred method for synthesizing the titanoaluminosilicates of the invention consists in using titanium, silicon, sodium, tetrapropylammonium and aluminum compounds mixed with water and heated this mixture in a closed vessel. This one In addition, seed crystals can be added to the mixture before heating.

Die Ausgangsverbindungen werden im allgemeinen in folgendem Verhältnis eingesetzt, ausgedrückt in Molverhältnissen der Oxide: SiO2 : (0,01 - 0,2) Al2O3 : (0,01 - 1,0) TiO2: (0,01 - 0,5) Na2O : (0,02 - 1,0) R2O : (5 - 100) H2O, vorzugsweise im Verhältnis: SiO2 : (0,01 - n,l) Al203 : (0,01 - 0,4) TiO2 (0,02 - 0,3) Na2O : (0,03 - 0,6) R2O : (10 - 40) H2O wobei R gleich Tetrapropylmmonium ist.The starting compounds are generally in the following ratio used, expressed in molar ratios of the oxides: SiO2: (0.01 - 0.2) Al2O3 : (0.01-1.0) TiO2: (0.01-0.5) Na2O: (0.02-1.0) R2O: (5-100) H2O, preferably in the ratio: SiO2: (0.01 - n, l) Al203: (0.01 - 0.4) TiO2 (0.02 - 0.3) Na2O: (0.03-0.6) R2O: (10-40) H2O where R is tetrapropylmmonium.

Als Verbindungen können beispielsweise eingesetzt werden: Kieselsäuregel, Natriumsilicat, Aluminiumhydroxid, Aluminiumsulfat, Natriumaluminat, Aluminiumhalogenide, Aluminiummetahydroxid, Titanhalogenide, Titansulfat, Natriumhydroxid, Natriumsulfat, Natriumhalogenide, Tetrapropylammoniumhydroxid, Tetrapropylammoniumhalogenide. Aber auch andere Silizium-,Aluminium- Titan-, Natriula- und Alkylammoni.umverbindungen 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, titanium halides, titanium sulfate, sodium hydroxide, sodium sulfate, Sodium halides, tetrapropylammonium hydroxide, tetrapropylammonium halides. but also other silicon, aluminum, titanium, sodium and alkylammonium compounds suitable. for the production of the zeolites according to the invention.

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 200°C, vorzugsweise zwischen 130 und 1700C, in einem gesclllossenen 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 200 ° C, 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, gewaschel und getrocknet Sie können nach bekannten Methoden in di katalytisch aktiven Formen überführt werden, z.B. durch Kalzinierung und/odex Ionenaustausch (D.W. Breck, Zeolite Molecular Sieves, 1974).by filtration, isolated, washed and dried you can after known methods are converted into di catalytically active forms, e.g. by Calcination and / or ion exchange (D.W. Breck, Zeolite Molecular Sieves, 1974).

Die erfindungsgemäßen Zeolithe zeichnen sich nach ihrer Überführung in diese katalytisch 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 this catalytically 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 help of the method indicated, zeolites at all obtained with the features of the invention.

Die Erfindung soll durch das folgende Beispiel erläutert werden, wobei das Beispiel aber in keiner Weise einschränkend sein soll. Alle angegebenen Röntgenbeugungsdaten wurden mit einem computergesteuerten Pulverdiffraktometer D-500 der Firma Siemens aufgenommen. Es wurde Kupfer-K-α-Stellung verwandt.The invention is illustrated by the following example, wherein however, the example is not intended to be limiting in any way. All given X-ray diffraction data were with a computer-controlled powder diffractometer D-500 from Siemens recorded. The copper K-α position was used.

Beispiel 1 1,66 g Natriumaluminat (54 Gew.% Al203, 41 Gew.% Na2O) und 2,74 g Natriumhydroxid weiden 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 Gew.%iger wäßriger Tetrapropylammoniumhydroxid-Lösung löst und diese Lösung am Rotation3ver'dampfer auf insgesamt 230 g einengt. Lösung A und Lösung B werden miteinander vermischt, Zu dieser Mischung werden unter intensivem Rühren 2,2 g Titantetrachlorid gegeben. Die entstandene Suspension wird homoyenisiert und in einem geschlossenen Gefäß 120 h auf 1600C erhitzt. Das entstandene Produkt wird abfiltriert, mit Wasser gewaschen und bei 1200C getrocknet. Man erhält 29,7 g des erfindungsgemäßen Titanoaluminosilcats.Example 1 1.66 g of sodium aluminate (54% by weight Al203, 41% by weight Na2O) and 2.74 g of sodium hydroxide are found 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 230 g. solution A and solution B are mixed together, to this mixture are under intense Stirring 2.2 g of titanium tetrachloride added. The resulting suspension is homoenized and heated in a closed vessel to 160.degree. C. for 120 h. The resulting product is filtered off, washed with water and dried at 1200C. 29.7 is obtained g of the titanoaluminosilicate according to the invention.

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 : 0,047 TiO2 : 0,023 Al2O3 : 0,051 Na2O.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 in terms of molar ratios of the oxides; SiO2 : 0.047 TiO2: 0.023 Al2O3: 0.051 Na2O.

Beispiel 2 In einen senkrecht angeordneten, elektrisch beheizten Rohrreaktor von 1 m Länge, der mit 250 ml Katalysator auf Basis des in Beispiel 1 hergestellten Titanoaluminosilikats mit ZSM-5-Struktur gefüllt ist, dosiert man stündlich 520 ml 33 gew.-%iges wasserhaltiges Methanol bei einer Temperatur von 350°C und Normaldruck. Das entstehende Reaktionsgemisch wird abgekühlt, und nach Abtrennung der kondensierbaren Anteile wird die gasförmige Phase analysiert.Example 2 In a vertically arranged, electrically heated tubular reactor of 1 m length, the one with 250 ml of catalyst based on that prepared in Example 1 Titanoaluminosilicate with a ZSM-5 structure is filled, 520 is dosed every hour ml of 33% strength by weight aqueous methanol at a temperature of 350 ° C. and normal pressure. The resulting reaction mixture is cooled, and after the condensables have been separated off The gaseous phase is analyzed.

Die C2-C4-Olefin-Selektivität ist 64 % und die Selktivität zu Kohlenwasserstoffen mit mehr als 4 C-Atomen ist 13 %.The C2-C4 olefin selectivity is 64% and the selectivity to hydrocarbons with more than 4 carbon atoms is 13%.

Vergleichsbeispiel: Die Arbeitsweise ist wie in Beispiel 2, nur daß statt des Titanoaluminosilikats ein handelsüblicher Aluminosilikat-Katalysator mit ZSM-5-Struktur eingesetzt wi.rd.Comparative example: The procedure is as in Example 2, only that instead of the titanoaluminosilicate, a commercially available aluminosilicate catalyst ZSM-5 structure used wi.rd.

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. Titanoaluminosilicate mit Pentasilstruktur.Claims: 1. Titanium aluminosilicates with a pentasil structure. 2. Titanoaluminosilicate mit ZSH-5-Struktur.2. Titanoaluminosilicates with ZSH-5 structure. 3. Titanoaluminosilicate nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß sie Silizium, Aluminium und Titan im folgenden Verhältnis enthalten: SiO2 : (0,001 - 0,15) Al2O3 : (0,002 - 1,0) TiO2 , ausgedrückt in Molverhältnissen der Oxide.3. titanoaluminosilicates according to claim 1 or 2, characterized in that that they contain silicon, aluminum and titanium in the following ratio: SiO2: (0.001 - 0.15) Al2O3: (0.002 - 1.0) TiO2, expressed in molar ratios of the Oxides. 4. Titanoaluminosilicate nach einem d Ansprüchc 1 bis 3, dadurch gekennzeichnet, daß sie Silizium, Aluminium und Titan im folgenden Verhältnis enthalten: SiO2 : (0,005 - 0,1) Al2O3 : (0,01 - 0,4) TiO2, ausgedrückt in Molverhä].tnissen der Oxide.4. titanoaluminosilicates according to ad claims 1 to 3, characterized in that that they contain silicon, aluminum and titanium in the following ratio: SiO2: (0.005-0.1) Al2O3: (0.01-0.4) TiO2, expressed in molar ratios of the oxides. 5. Verfahren zur Herstellung von Titanoaluminosilicaten nach einem der Ansprüche 1 bis 4, durch gekennzeichnet, daß man eine Mischung aus Titan-, Silizium-, Natrium-, Tetrapropylammonium-, Aluminiumverbindungen und Wasser herstellt, die folgende Zusammensetzung hat, ausgedrückt in Molverhältnissen der Oxide: SiO2 (0,01 - 0,2) Al2O3:(0,01 - 1,0) TiO2 (0,01 - 0,5) Na2O : (0,02 - 1,0) R2O (5-100) H2O, wobei R gleich Tetrapropylammonium ist, und diese Mischung in einem geschlossenen Gefäß erhitzt.5. Process for the preparation of titanoaluminosilicates according to a of claims 1 to 4, characterized in that a mixture of titanium, silicon, Produces sodium, tetrapropylammonium, aluminum compounds and water that has the following composition, expressed in molar ratios of the oxides: SiO2 (0.01 - 0.2) Al2O3: (0.01 - 1.0) TiO2 (0.01 - 0.5) Na2O: (0.02 - 1.0) R2O (5-100) H2O, where R is tetrapropylammonium, and this mixture in a closed Vessel heated. 6. Verfahren nach Anspruch 5, dadurch gekennzeichnet, daß die zu erhitzende Mischung folgende Zusammensetzung hat, ausgedrückt in Molverhältnissen der Oxide: Sio2 : (0,01 - 0,1) Al2O3 : (0,01 - 0,4) TiO2 (0,02 - 0,3) Na2O : (0,03 - 0,6) R2O: (10 - 40) wobei R gleich Tetrapropylammoniurn 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: (0.01-0.1) Al2O3: (0.01-0.4) TiO2 (0.02-0.3) Na2O: (0.03-0.6) R2O: (10 - 40) where R is tetrapropylammonium. 7. Verwendung von Titanoaluminosilicaten nach einem der Ansprüche 1 bis 4 als Katalysatoren bei der Herstellung von C2- bis C4-Olefinen aus Methanol.7. Use of titanium aluminosilicates according to one of the claims 1 to 4 as catalysts in the production of C2 to C4 olefins from methanol.
DE19823219495 1981-10-17 1982-05-25 Titanium-containing zeolites, process for their preparation and their use Withdrawn DE3219495A1 (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
AU83401/82A AU544046B2 (en) 1981-10-17 1982-05-05 Unloading chute for vessels
DE19823219495 DE3219495A1 (en) 1982-05-25 1982-05-25 Titanium-containing zeolites, process for their preparation and their use
DE8282109451T DE3266412D1 (en) 1981-10-17 1982-10-13 Titanium-containing zeolites, process for their preparation and their use
EP82109451A EP0077522B1 (en) 1981-10-17 1982-10-13 Titanium-containing zeolites, process for their preparation and their use
AU89401/82A AU8940182A (en) 1981-10-17 1982-10-15 Titanium-containing zeolites
CA000413523A CA1185224A (en) 1981-10-17 1982-10-15 Titanium-containing zeolites, process for their manufacture, and their use
NZ202184A NZ202184A (en) 1981-10-17 1982-10-15 Titanium-containing zeolites and use as olefin producing catalysts

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