NZ202185A - Zircono-and/or hafno-aluminosilicates having a pentasil structure,their preparation and use as olefin producing catalysts - Google Patents

Zircono-and/or hafno-aluminosilicates having a pentasil structure,their preparation and use as olefin producing catalysts

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Publication number
NZ202185A
NZ202185A NZ202185A NZ20218582A NZ202185A NZ 202185 A NZ202185 A NZ 202185A NZ 202185 A NZ202185 A NZ 202185A NZ 20218582 A NZ20218582 A NZ 20218582A NZ 202185 A NZ202185 A NZ 202185A
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NZ
New Zealand
Prior art keywords
compounds
zircono
aluminosilicates
hafno
hafnium
Prior art date
Application number
NZ202185A
Inventor
H Baltes
H Litterer
E I Leupold
F Wunder
Original Assignee
Hoechst Ag
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Priority claimed from DE19813141285 external-priority patent/DE3141285A1/en
Priority claimed from DE19823219494 external-priority patent/DE3219494A1/en
Priority claimed from DE19823231467 external-priority patent/DE3231467A1/en
Application filed by Hoechst Ag filed Critical Hoechst Ag
Publication of NZ202185A publication Critical patent/NZ202185A/en

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Classifications

    • 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
    • B01J29/89—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

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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)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)

Description

New Zealand Paient Spedficaiion for Paient Number £02185 202185 HO DRAWINGS Pr iority Date(s): 2. s"-& -&a Complete Specification Filed: Class: •Sf? .'.TT-A'./M,. P.f.i.f.?. .
Publication Date: . P.O. Journal, No: N.Z. No.
NEW ZEALAND Patents Act 1953 COMPLETE SPECIFICATION "Zirconium-and/or hafnium-containing zeolites, process for their manufacture, and their use." We, HOECHST AKTIENGESELLSCHAFT, a corporation organized under the laws of the Federal Republic of Germany,of D-6230 Frankfurt/Main 80, Federal Republic of Germany, do hereby declare the invention, for which we pray that a Patent may be granted to us, and the ;method by which it is to be performed,to be particularly described in and by the following statement:- I r 202185 mq*! m/r K # 15 # Zeolites are crystalline aluminosilicates, in which due tc a three-dimensional linkage of SiO^ and AIO^ tetrahedra regular structures with cavities and pores are formed. In hydrated state, these pores and cavities are filled with water, which, on the other hand, can be easily removed without influencing the crystalline structure, or replaced by other molecules. The negative charges of the AlC^ tetrahedra are balanced by cations, which can be replaced by other ions of positive charge. These properties allow the use of the zeolites as ion exchangers, adsorbents and catalysts (D.W. Breck: Zeolite Molecular Sieves, 197*0 .
Zeolites of the X, Y, mordenite, erionite or offre-tite type, for example, are of considerable interest in the industrial practice as catalysts for hydrocarbon conversion reactions such as cracking, hydrocracking or isomerization. Zeolites of the pentasil type (for example Zeolite ZSM-5) become increasingly important as catalysts for the conversion of methanol to hydrocarbons.
Because of the numerous application possibilities as catalysts, there is great interest in novel zeolites having specific catalytical properties.
Very interesting zeolites are for example obtained by incorporating other elements instead of aluminum and/or silicon into the zeolite frame. Thus, zeolites of the pentasil series are known which contain boron, iron, arsenic, antimony, vanadium, chromium, or gallium in tetrahedral position.
Furthermore, titanosilicates (U.S. Patent No. 3,329,481) and zirconosilicates (U.S. Patent No. 3,329,480) have been described; where, hwoever, a pentasil structure can be safely excluded according to the X-ray diffraction diagram and the chemical composition.
Subject of the invention are zircono- and/or hafno-iminosilicates having a pentasil structure. 1 1 JUL 1985^ 202185 jaaftAwr n?n.i i: By pentasils, there are to be understood those defined by Ko-kotailo and Meier ("Pentasil family of high silica crystalline materials" in: Special Publication No. 33 of the Chemical Society, London 1980). The pentasil family comprises for 5 example the synthetic zeolites ZSM-5 (US Patent No. 3,702,886), ZSM-8 (British Patent No. 1,334,243), ZSM-11 (US Patent No. 3,709,979) and ZSM-23 (US Patent No. 4,076,842).
Subject of the invention are especially zircono- and/or hafno -aluminosilicates having a ZSM-5 structure, 10 preferably those having the following composition, expressed as molar ratio of oxides: Si02 :(Up to 0.15) a12°3 : (°-002 - 1-°) M02> especially Si02 : (Up to 0.1) M?°3 : (0*01 ~ °-^ M°2 > M being zirconium and/or hafnium.
The zirconium and/or hafnium-containing zeolites can be prepared according to the same methods and with the use of 20 the same organic compounds as described for the synthesis of the zirconium- or hafnium-free zeolite ZSM-5, for example with the use of alkylammonium compounds (U.S. Patent No. 3,702,886) alkylamines (U.S. Patent No. 4,151,189) alkyldiamines alkylamines in the presence of alkylation agents (Published European Patent Application No.11362), aminoalcohols (British Patent No.2,023,562) alcohols (U.S. Patents Nos. 4, 199,556, 4,175,114, Published European Patent Application No.42225) ethers (European Patent Application No.51741). *5 Preferably, alkylammonium compounds, alkyl diamines or alkylamines are used in the presence of alkylation agents. Especially preferred alkylammonium compounds are tetrapro- * # 202185 - 4 - Hfi? "Vr iiTil pylammonium compounds, for example the hydroxide or one of the halides. A particularly suitable alkyldiamine is hexa-methylene diamine.
For the synthesis of the zeolites of the invention, 5 one or more compounds from the cited classes are mixed with zirconium and/or hafnium compounds, silicon and sodium compounds , water, and aluminum compounds and the mixture is heated in a closed vessel.
^Before heating the mixture, preferably, seed crystals of a pentasil are furthermore added. In the case where tetrapropylammonium compounds are used, the starting compounds are generally used in the following ratio, expressed as molar ratio of oxides: Si02 : (Up to 0.2) A1,,03 : (0.01 - 1.0) M02 : (0.01 - 0.5) Na20 : (0.02 - 1.0) R20 : (5 - 100) H20, preferably in a ratio of Si02 : (Up to 0.1) A1203 : (0.01 - 0.4) MC>2 : (0.02 - 0.3) Na20 : (0.03 - 0.6) R20 : (10 - 40) H20, M being zirconium and/or hafnium, and R being tetrapropyl-ammonium.
As silicon, aluminum, zirconium, hafnium or sodium compounds, there are used for example silica gel, sodium silicate, alu-25 ininum hydroxide, aluminum sulfate, sodium aluminate, aluminum halides, aluminum metahydroxide, zirconium halides, zirconium sulfate, zirconyl chloride, hafnium halides hafnium sulfate, sodium hydroxide, sodium sulfate, sodium halides. Other compounds of the four cited elements are also 30 suitable for the manufacture of the zeolites according to the invention.
The mixture of the compounds chosen and water is generally heated for 18 to 360, preferably 24 to 240, hours at a temperature of from 100 to 200°C, peferably 130 to 35 170°C, in a closed vessel.
The zeolites which are formed are isolated in usual manner, for example by filtration, washed and dried. They can be converted according to known methods to catalytically "5" 20218 5* : active forms, for example by calcination-and/or ion exchange (D.W. Breck, Zeolite Molecular Sieves, 1374).
After conversion to the catalytical'ly active form, the zeolites of the invention display high selectivity and a 5 considerably reduced deposition of coke in the conversion of methanol to lower olefins. This reaction is carried out, for example, at temperatures between 350 and 430°C using methanol with a water content of 0 to 80 % by weight or* raw methanol.
The following Examples illustrate the invention with out limiting it in its scope. All X-ray diffraction data as indicated were obtained by means of a computer-controlled powder diffractometer D-500 of the Siemens company. The radiation was the K-^K doublet of copper.
Example 1 1.66 g of sodium aluminate (54 weight % Al^O^, 41 weight % Na^O) and 1.48 g of sodium hydroxide are dissolved in 20 g of 20 weight % aqueous tetrapropylammonium 20 hydroxide solution (solution A). A further solution (solution B) is obtained by dissolving 62 g of 40 weight % colloidal silica gel in 230 g of 20 weight % aqueous tetrapropylammonium hydroxide solution and concentrating this solution to a total 220 g in a rotation evaporator. The solu-25 tions A and B are mixed, and 3-78 g of zirconyl chloride ZrOCl^ 8H20 are added to this mixture with thorough stirring. The suspension obtaiend is homogenized and heated for 120 hours at 160°C in a closed vessel. The product formed is filtered off, washed with water and dried at 30 120°C. 27-3 g of zircono-aluminosilicate according to the invention is obtained.
An X-ray diffraction analysis shows a well crystallized product having a ZSM-5 structure. According to a chemical analysis of the product calcined for 16 hours at 35 540°C, it has the following composition, expressed as molar ratio of oxides: ol02 : 0.035 Zr02 . 0.026 A1203 : 0.023 Na20. - 6 n o j Koe-e^=g=-g-rfr-K Example 2 0.77 g of sodium hydroxide are dissolved in 5 g of 20 weight % aqueous tetrapropylaramonium hydroxide solution (solution A). A second solution (solution B) is prepared by 5 dissolving 12.4 g of 40 weight % colloidal silica gel in 45 g of 20 weight % tetrapropylammonium hydroxide solution, and concentrating this solution to a total 45 g in a rotation evaporator. Solutions A and B are mixed. 1.88 g of zirconyl chloride ZrOCl2 * 8 H^O in 5 ml of H20, and 0.1 g of 10 seed crystals (product 1) are added with thorough stirring to this mixture. The suspension formed is homogenized and heated for 160 hours at 150°C in a closed vessel. The product obtained is filtered off, washed with water and dried at 120°C. 4.2 g of zirconosilicate of the invention 15 are obtained. According to X-ray diffraction analysis, the product has a ZSM-5 structure. The chemical analysis of the ■ product calcined for 16 hours at 540°C yields the following composition: Si02 : 0.210 ZrOg : 0.121 Na20 Example 3 The zircono-aluminosilicate having a ZSM-5 structure prepared according to Example 1 (calcined form) is exchan-25 ged with ammonium nitrate solution, and together with a binder (Boehmit) extruded (zeolit^e content 65 weight %), and calcined again as indicated in Example 1. 520 ml/h of 33 weight % aqueous methanol are dosed at a temperature of 350°C under normal pressure to a verti-30 cally positioned, electrically heated tube reactor having a lenght of 1 m and packed with 250 ml of this catalyst. The reaction mixture which forms is cooled, and after separation of the condensable portions the gaseous phase is analyzed. The C2~C^ olefin selectivity is 65 %, and the se-35 lectivity to hydrocarbons having more than 4 carbon atoms is 14 ?. 2,02 nos-a I/fsth-"-g- Comparative Example Operations are as in Example 3; however, instead of the zircono-aluminosilicate a commercial aluminosilicate catalyst having a ZSM-5 structure is used.
The C2~^4 olefin selectivity is 56 %r and the selectivity to hydrocarbons having more than 4 carbon atoms is 23 %. 202185

Claims (14)

WHAT WE CLAIM IS: : '
1. Zircono- and/or haf no-aluminosilicates having a pentasil structure.
2. Zircono- and/or hafno--aluminosilicates 5 having a ZSM-5 structure.
3. Zircono- and/or hafno-aluminosilicates as claimed in Claim 1 or 2, having the following composition, expressed as molar ratio of oxides: 10 Si02 :(Up to 0.15) A1203 : (0.002 - 1.0) M02,. M being zirconium and/or hafnium. 15
4. Zircono- and/or hafno-aluminosilicates as claimed in one of Claims 1 to 3, having the following composition, expressed as molar ratio of oxides: 20 Si02 : (Up to 0.1) A1203 : (0.01 - 0.4) M02, M being zirconium and/or hafnium.
5. A process for the manufacture of zircono- and/or hafno -aluminosilicates as claimed in one of 25 Claims 1 to 4, which comprises mixing zirconium and/or hafnium, silicon and sodium compounds, water, as well as aluminum compounds with one or more organic compounds selected from the group consisting of alkylam-monium compounds, alkylamines, alkyldiamines, aminoal-30 cohols, alcohols and ethers, and heating this mixture in a closed vessel.
6. The process as claimed in Claim 5, which comprises using alkylammoniura compounds as organic compounds. Vs" ~3.TtjU985 10 " ;■ 2021 ss - 9 - ,;i»r cvr r;T^»K
7. The process as claimed in Claim 5, which, comprises using tetrapropylammonium compounds as organic compounds.
8. The process as claimed in Claim 5, which comprises using alkylamines in the presence of alkylating agents as organic compounds.
9. The process as claimed in Claim 5, which comprises using alkyldiamines as organic compounds.
10. The process as claimed in one of Claims 5 to 9, which comprises adding seed crystals of a pentasil to the mixture before heating. 15
11. A process for the manufacture of zircono- and/or hafno- aluminosilicates as claimed in one of Claims 1 to 4, which comprises preparing a mixture of zirconium and/or hafnium compounds, silicon, sodium and tetrapropylammonium compounds , water, as well as- alu-20 minum compounds, vihich has the following composition, expressed as molar ratio of oxides: Si02 : (Up to 0.2) A1203 : (0.01 - 1.0) M02 : (0.01 - 0.5) Na20 : (0.02 - 1.0) R20 : (5 - 100) H20, 25 M being zirconium and/or hafnium, and R being tetrapropylammonium, and heating this mixture in a closed vessel.
12. The process as claimed in Claim 11, wherein the mixture 30 to be heated has. the following composition, expressed as molar ratio of oxides: Si02 : (Up to 0.1) A1203 : (0.01 - 0.4) M02 : 35 (0.02 - 0.3) Na20 : (0.03 - 0.6) R20 : (10 - 40) H20, M being zirconium and/or hafnium, and R being tetrapropylammonium .
13. Use of zircono- and/or hafno-aluminosilicates s/X- 40 as claimed in one of Claims 1 to 4 as catalysts>■^or % the manufacture of C -C., olefins from methanol. j! -n] ^ •}■ A xox |* 5" - 10 -
14. Zircono- and/or hafno aluminosilicates according to claim 1 or claim 2 substantially as herein described. HOECHST AKTIENGESELLSCHAFT By Their Attorneys HENRY HUGHES LIMITED
NZ202185A 1981-10-17 1982-10-15 Zircono-and/or hafno-aluminosilicates having a pentasil structure,their preparation and use as olefin producing catalysts NZ202185A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19813141285 DE3141285A1 (en) 1981-10-17 1981-10-17 Zirconium- and/or hafnium-containing zeolites and a process for their preparation, and their use
DE19823219494 DE3219494A1 (en) 1982-05-25 1982-05-25 Zirconium- and/or hafnium-containing zeolites, process for their preparation and their use
DE19823231467 DE3231467A1 (en) 1982-08-25 1982-08-25 Zirconium- and/or hafnium-containing zeolites, process for their preparation, and their use

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NZ202185A true NZ202185A (en) 1985-10-11

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EP (1) EP0077523B1 (en)
AU (1) AU550136B2 (en)
CA (1) CA1196903A (en)
DE (1) DE3263914D1 (en)
NZ (1) NZ202185A (en)

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU542052B2 (en) * 1980-06-12 1985-02-07 Imperial Chemical Industries Ltd. Zeoliteeuz and its use as a catalyst
DE3217323A1 (en) * 1982-05-08 1983-11-10 Hoechst Ag, 6230 Frankfurt ZIRCON AND / OR HAFNIUM-CONTAINING ZEOLITES AND METHOD FOR THE PRODUCTION THEREOF AND THEIR USE
DE3402020A1 (en) * 1984-01-21 1985-07-25 Hoechst Ag, 6230 Frankfurt METHOD FOR PRODUCING OLEFINS FROM METHANOL
DE3569235D1 (en) * 1984-06-02 1989-05-11 Hoechst Ag Process for the isomerisation of mono- or dichlorotoluene
DE3420707A1 (en) * 1984-06-02 1985-12-05 Hoechst Ag, 6230 Frankfurt METHOD FOR ISOMERIZING O-, M-, AND / OR P-TOLUIDINE
EP0292363B1 (en) * 1987-05-22 1993-04-21 Rhone-Poulenc Chimie Zeolites having an mfi-structure, based on silica and titanium oxide, and method for their synthesis
FR2663919B1 (en) * 1990-06-29 1993-07-02 Rhone Poulenc Chimie SILICA AND ZIRCONIUM OXIDE ZEOLITHS AND THEIR SYNTHESIS PROCESS.
EP0466545A1 (en) * 1990-06-29 1992-01-15 Rhone-Poulenc Chimie Zeolites based on silica and oxides of tetravalent elements, method for their synthesis and their use
FR2666321B1 (en) * 1990-08-29 1992-12-11 Rhone Poulenc Chimie PROCESS FOR THE PREPARATION OF SILICA-BASED ZEOLITHS AND TETRAVALENT ELEMENT OXIDES.
FR2674517B1 (en) * 1991-03-27 1993-07-02 Rhone Poulenc Chimie PROCESS FOR THE PREPARATION OF SILICA-BASED ZEOLITHS AND OXIDES OF TETRAVALENT ELEMENTS.
JPH06340416A (en) * 1990-08-29 1994-12-13 Rhone Poulenc Chim Preparation of zeolite wherein silica and if necessary, oxide of quadrivalent element is used as base material
GB2322364A (en) * 1997-02-14 1998-08-26 Exxon Chemical Patents Inc Zirconium molecular sieve catalysts
US6759360B2 (en) 2002-03-29 2004-07-06 Exxonmobil Chemical Patent Inc. Interior surface modifications of molecular sieves with organometallic reagents and the use thereof for the conversion of oxygenates to olefins

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DD40952A (en) *
US3013987A (en) * 1958-09-24 1961-12-19 Union Carbide Corp Metal loading of molecular sieves
US3329480A (en) * 1963-10-18 1967-07-04 Union Oil Co Crystalline zircono-silicate zeolites
US3329482A (en) * 1963-10-18 1967-07-04 Union Oil Co Methods for the manufacture of group iv-b metallo-silicate zeolites
DE2017807A1 (en) * 1969-05-01 1970-11-12 W.R. Grace & Co., New York, N.Y. (V.St.A.) Synthetic aluminosilicate zeolite and process for its production
US3702886A (en) * 1969-10-10 1972-11-14 Mobil Oil Corp Crystalline zeolite zsm-5 and method of preparing the same
DE2831631A1 (en) * 1978-07-19 1980-02-07 Basf Ag Synthetic crystalline vanadium silicate - with zeolite structure, useful as catalyst in (hydro)cracking processes

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EP0077523A2 (en) 1983-04-27
EP0077523A3 (en) 1983-09-14
DE3263914D1 (en) 1985-07-04
AU550136B2 (en) 1986-03-06
AU8940082A (en) 1983-04-28
EP0077523B1 (en) 1985-05-29
CA1196903A (en) 1985-11-19

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