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DE3141283A1 - Titanium-containing zeolites and a process for their preparation, and their use - Google Patents

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

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Publication number
DE3141283A1
DE3141283A1 DE19813141283 DE3141283A DE3141283A1 DE 3141283 A1 DE3141283 A1 DE 3141283A1 DE 19813141283 DE19813141283 DE 19813141283 DE 3141283 A DE3141283 A DE 3141283A DE 3141283 A1 DE3141283 A1 DE 3141283A1
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Prior art keywords
titanium
tio2
sio2
zeolites
mixture
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DE19813141283
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German (de)
Inventor
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 DE19813141283 priority Critical patent/DE3141283A1/en
Priority to AU83401/82A priority patent/AU544046B2/en
Priority to EP82109451A priority patent/EP0077522B1/en
Priority to DE8282109451T priority patent/DE3266412D1/en
Priority to JP57179191A priority patent/JPS5874521A/en
Priority to AU89401/82A priority patent/AU8940182A/en
Priority to ZA827554A priority patent/ZA827554B/en
Priority to NZ202184A priority patent/NZ202184A/en
Priority to CA000413523A priority patent/CA1185224A/en
Publication of DE3141283A1 publication Critical patent/DE3141283A1/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Withdrawn legal-status Critical Current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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The zeolites according to the invention are prepared by producing a mixture of titanium compounds, silicon compounds, aluminium compounds, sodium compounds, tetrapropylammonium compounds and water in specified weight ratios and heating the mixture in a sealed vessel. The zeolites are utilised 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 A10,-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 ersetze. 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, Adsorbentien und Katalysatoren (D.W. Breck: Zeolithe Molecular Sieves, 1974) Zeolithe des X-, Y-, Mordenit-, Lrionit- und Offretit-Typs beispielsweise besitzen als Kata1ysatoren für Umwandlungsreaktionen von Kohlenwasserstoffen wie Cracken, Hydrocracken oder Isomerisierungen beträchtliches technisches Interesse.as well as their use zeolites are crystalline aluminosilicates, at which are regular through a three-dimensional linkage of SiO4 and A10 tetrahedra Structures with cavities and pores arise. These are in the hydrated state Pores and cavities filled with water. This can be done without influencing the Remove crystal structure or replace it with other molecules. The negative charges the AlO4 tetrahedra are compensated by cations. These can be positive towards others charged ions are exchanged. The properties described enable the use of zeolites as ion exchangers, adsorbents and catalysts (D.W. Breck: Zeolithe Molecular Sieves, 1974) Zeolites of the X-, Y-, mordenite, lrionite and Offretite type, for example, have as catalysts for conversion reactions of hydrocarbons such as cracking, hydrocracking or isomerizations technical interest.

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

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 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 among other things, zeolites of the Pentasil series were known, the boron (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) on tetrahedral sites contain.

Auch wurden Titanosilicate (US-PS 3 329 481) und Zirkonosilicate (US-PS 3 329 480) mit Zeolithstruktur bekannt.Titanosilicates (US Pat. No. 3,329,481) and zirconosilicates (US Pat 3 329 480) known with a zeolite structure.

Gegenstand der Erfindung sind Titanoaluminosilikate mit Pentasil-Struktur.The invention relates to titanium aluminosilicates with a pentasil structure.

Für den Begriff Pentasile gilt dabei die Definition von Kokotailo und Meier ("Pentasil family of high silica crystalline materials" in Special Publication No. 33 of the Chemical 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 Kokotailo applies to the term pentasile and Meier ("Pentasil family of high silica crystalline materials" in Special Publication No. 33 of the Chemical 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 Titanoaluminosili cat-c mit ZSM-5-Struktur, vorzugsweise solche mit folgender Zusammensetzung, ausgedrückt in Molverhältnissen der Oxide: SiO2 : (0,001 - 0,15) Al203 : (0,002 - 1,0) TiO2, insbesondere: Sio2 : (0,005 - 0,1) Al203 : (0,01 - 0,4) TiO2.The invention mainly relates to titanoaluminosilicate cat-c ZSM-5 structure, preferably those with the following composition, expressed in Molar ratios of the oxides: SiO2: (0.001 - 0.15) Al203: (0.002 - 1.0) TiO2, in particular: Sio2: (0.005-0.1) Al203: (0.01-0.4) TiO2.

Die erfindungsgemäßen Titanoaluminosilicate lassen sich nach Methoden herstellen, wie sie auch für die Synthese des titanfreien 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 und/oder Anmloniumhydroxid (US-PS 4 199 556).The titanoaluminosilicates according to the invention can be prepared by methods produce as described for the synthesis of the titanium-free zeolite ZSM-5 were, for example using alkylammonium salts (US Pat. No. 3,702,886), 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 ammonium 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.This differs from the titanosilicate according to US Pat. No. 3,329,480 inventive titanoaluminosilicate both by the structure and by the Aluminum content.

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.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 Ausgangsverbindunyen werden im allgemeinen in folgendem Verhältnis eingesetzt, ausgedrückt in Molverhältnissen der Oxide: SiO2 : (001 - 0,2) Al203 : (0e01 - 1,0) TiO2 (0,01 - 0,5) Na2O : (0,02 - 1,0) R2O : (5 - 100) H2O, vorzugsweise im Verhältnis: Sio2 : (0,01 - 0,1) i2O3 : (0,01 - 0,4) TiO2 (0,02 - 0,3) Na2O : (0,03 - 0,6) R2O : (10 - 40) H2O wobei R gleich Tetrapropylammonium ist.The output connections are generally in the following ratio used, expressed in molar ratios of the oxides: SiO2: (001 - 0.2) Al203 : (0e01-1.0) TiO2 (0.01-0.5) Na2O: (0.02-1.0) R2O: (5-100) H2O, preferably in the ratio: Sio2: (0.01 - 0.1) i2O3: (0.01 - 0.4) TiO2 (0.02 - 0.3) Na2O: (0.03-0.6) R2O: (10-40) H2O where R is tetrapropylammonium.

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-, 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, titanium halides, titanium sulfate, sodium hydroxide, sodium sulfate, Sodium halides, tetrapropylammonium hydroxide, tetrapropylammonium halides. but also other silicon, aluminum, titanium, sodium and alkylammonium compounds are 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 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. Sie können nach bekannten Methoden in die katalytisch aktiven Formen überführt werden, z.B. durch Kalzinierung und/oder Ionenaustausch (D.W. Breck, Zeolite Molecular Sieves, 1974) Die erfindungsyemäßen Zeolithe zeichnen sich nach ihrer Uberführung in die katalytisch aktive Form insbesondere aus dadurch 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.by filtration, isolated, washed and dried. You can after known methods can be converted into the catalytically active forms, e.g. by Calcination and / or ion exchange (D.W. Breck, Zeolite Molecular Sieves, 1974) The zeolites according to the invention are notable for their conversion into catalytic ones active form in particular due to a high selectivity and a low one Coke deposition in the conversion of methanol to lower olefins. It is surprising that one with the help of the method indicated at all zeolites with the invention Characteristics.

Die Erfindung soll durch das folgende Bespiel 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 to be explained 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 : 1,66 g Natriumaluminat (54 Gew.% A1203, 41 Gew.% Na2O) und 2,74 g Natriumhydroxid werden in 20 g 20 Gew.tiger w3riger 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.miger wäßriger Tetrapropylammoniumhydroxid-Lösung löst und diese Lösung am Rotationsverdampfer 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 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 29,7 g des erfindungsgemäßen Titanoaluminosilicats.Example: 1.66 g sodium aluminate (54% by weight A1203, 41% by weight Na2O) and 2.74 g of sodium hydroxide are dissolved in 20 g of 20% by weight aqueous tetrapropylammonium hydroxide solution dissolved (solution A), Another solution (solution B) is prepared by adding 62 g of 40% by weight colloidal silica gel in 230 g of 20% 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 become under intense Stirring 2.2 g of titanium tetrachloride added. The resulting suspension is homogenized 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 A1203 : 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, expressed in molar ratios of the oxides: SiO2 : 0.047 TiO2: 0.023 A1203: 0.051 Na2O.

Claims (7)

Patentansprüche: 1. Titanoaluminosilicate mit Pentasilstruktur.Claims: 1. Titanium aluminosilicates with a pentasil structure. 2. Titanoaluminosiiicate mit ZSM-5-Struktur.2. Titanoaluminosilicates with ZSM-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 der Ansprüche 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 Molverhältnissen der Oxide.4. titanoaluminosilicates according to any one of claims 1 to 3, characterized characterized in that they contain silicon, aluminum and titanium in the following proportions: SiO2: (0.005-0.1) Al2O3: (0.01-0.4) TiO2, expressed in molar ratios the oxides. 5. Verfahren zur Herstellung von Titanoaluminosiiicaten nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß man eine Mischung aus Titan-, Silizium-, Natrium-, Tetrapropy lammoni um-, 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 Titanoaluminosiiicaten after a of claims 1 to 4, characterized in that a mixture of titanium, Manufactures silicon, sodium, tetrapropy lammonium, aluminum compounds and water, 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 one 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) Al203 : (0,01 - 0,4) Tio2 : (0,02 - 0,3) Na2O : (0,03 - 0,6) R2O (10 - 40) H20, wobei 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: (0.01-0.1) Al203: (0.01-0.4) Tio2: (0.02-0.3) Na2O: (0.03-0.6) R2O (10 - 40) H20, 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.
DE19813141283 1981-10-17 1981-10-17 Titanium-containing zeolites and a process for their preparation, and their use Withdrawn DE3141283A1 (en)

Priority Applications (9)

Application Number Priority Date Filing Date Title
DE19813141283 DE3141283A1 (en) 1981-10-17 1981-10-17 Titanium-containing zeolites and a process for their preparation, and their use
AU83401/82A AU544046B2 (en) 1981-10-17 1982-05-05 Unloading chute for vessels
EP82109451A EP0077522B1 (en) 1981-10-17 1982-10-13 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
JP57179191A JPS5874521A (en) 1981-10-17 1982-10-14 Titanium-containing zeolites, manufacture and use
AU89401/82A AU8940182A (en) 1981-10-17 1982-10-15 Titanium-containing zeolites
ZA827554A ZA827554B (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
CA000413523A CA1185224A (en) 1981-10-17 1982-10-15 Titanium-containing zeolites, process for their manufacture, and their use

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DE19813141283 DE3141283A1 (en) 1981-10-17 1981-10-17 Titanium-containing zeolites and a process for their preparation, and their use

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ZA (1) ZA827554B (en)

Cited By (7)

* Cited by examiner, † Cited by third party
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EP0111700A1 (en) * 1982-11-05 1984-06-27 Hoechst Aktiengesellschaft Zeolites containing titanium, zirconium and/or hafnium, process for producing them and their use
EP0150740A3 (en) * 1984-01-21 1985-11-21 Hoechst Aktiengesellschaft Process for the preparation of olefines from methanol
US4623526A (en) * 1982-08-26 1986-11-18 Centre De Recherche Industrielle Du Quebec Process for the preparation of a crystalline titanoborosilicate
US4684617A (en) * 1984-04-13 1987-08-04 Union Carbide Corporation Titanium-aluminum-phosphorus-silicon-oxide molecular sieves
US4707345A (en) * 1984-04-26 1987-11-17 Union Carbide Corporation Titanium-aluminum-silicon-oxide molecular sieve compositions and process for preparing the same
US4892720A (en) * 1984-04-26 1990-01-09 Uop Substituted aluminosilicate compositions and process for preparing same
EP2347997A2 (en) 1999-08-20 2011-07-27 Basf Se Method for producing a crystalline, zeolithic solid

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JPH062572B2 (en) * 1982-02-19 1994-01-12 出光興産株式会社 Method for producing crystalline silicate
JPH06644B2 (en) * 1983-09-19 1994-01-05 工業技術院長 Method for producing iron-titanium-metal-containing crystalline silicate
AU580781B2 (en) * 1984-04-26 1989-02-02 Union Carbide Corporation Titanium-aluminum-silicon-oxide molecular sieve compositions
CN111992245A (en) * 2020-05-31 2020-11-27 南京克米斯璀新能源科技有限公司 Catalyst for removing hydroxyl from Fischer-Tropsch oil

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4623526A (en) * 1982-08-26 1986-11-18 Centre De Recherche Industrielle Du Quebec Process for the preparation of a crystalline titanoborosilicate
EP0111700A1 (en) * 1982-11-05 1984-06-27 Hoechst Aktiengesellschaft Zeolites containing titanium, zirconium and/or hafnium, process for producing them and their use
EP0150740A3 (en) * 1984-01-21 1985-11-21 Hoechst Aktiengesellschaft Process for the preparation of olefines from methanol
US4684617A (en) * 1984-04-13 1987-08-04 Union Carbide Corporation Titanium-aluminum-phosphorus-silicon-oxide molecular sieves
US4707345A (en) * 1984-04-26 1987-11-17 Union Carbide Corporation Titanium-aluminum-silicon-oxide molecular sieve compositions and process for preparing the same
US4788380A (en) * 1984-04-26 1988-11-29 Union Carbide Corporation Titanium-aluminum-silicon-oxide molecular sieve compositions
US4892720A (en) * 1984-04-26 1990-01-09 Uop Substituted aluminosilicate compositions and process for preparing same
EP2347997A2 (en) 1999-08-20 2011-07-27 Basf Se Method for producing a crystalline, zeolithic solid

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ZA827554B (en) 1983-08-31
JPS5874521A (en) 1983-05-06

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