NZ206145A - Titanium,zirconium and/or hafnium containing zeolites - Google Patents

Titanium,zirconium and/or hafnium containing zeolites

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Publication number
NZ206145A
NZ206145A NZ206145A NZ20614583A NZ206145A NZ 206145 A NZ206145 A NZ 206145A NZ 206145 A NZ206145 A NZ 206145A NZ 20614583 A NZ20614583 A NZ 20614583A NZ 206145 A NZ206145 A NZ 206145A
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NZ
New Zealand
Prior art keywords
zirconium
titanium
hafnium
strong
expressed
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Application number
NZ206145A
Inventor
H Battes
H Litterer
E I Leupold
F Wunder
W Ebertz
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Hoechst Ag
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Application filed by Hoechst Ag filed Critical Hoechst Ag
Publication of NZ206145A publication Critical patent/NZ206145A/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
    • C01B39/065—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
    • B01J29/50—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the erionite or offretite type, e.g. zeolite T, as exemplified by patent document US2950952
    • 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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Description

New Zealand Paient Spedficaiion for Paient Number £06145 2061 4 'leuinop Od iS1BQ uoijBoiiqry • • S861030 *2 "B* •••••• "••••• !>%[ f£ Zgy VWjggQ , W Vd&l'&vtr&Q'f yoft \z y-i eg • ;sseio C'4-U-£-' -'poiU uoiiBoyjoadg ej9|dtuoo t?S - '("(' — :(s)9iBQ AllJOUJ N. Z.No.
NEW ZEALAND Patents Act, 1953 COMPLETE SPECIFICATION "TITANIUM-, ZIRCONIUM- AND/OR HAFNIUM-CONTAINING ZEOLITES, A PROCESS FOR THEIR PREPARATION, AND THEIR USE." We, HOECHST AKTIENGESELLSCHAFT, a corporation organized under the laws of the Federal Republic of Germany, of D-62 30 Frankfurt/ Main 80. Federal Republic of Germany, do heareby 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: - 206145 Zeolites is the nam.e given to, in particular, crystalline aluminosi licates in which regular structures with cavities and pores are formed by a threedimensiona I linking of SiO^ and AIO4 tetrahedra. In the hydrated 5 state these pores and cavities are full of water. The water can be removed, or be replaced by other molecules, without affecting the crystal structure. The negative charges of the AlO^ tetrahedra are compensated by cations. These cations can be replaced, if desired, by other cations. 10 The properties described permit the use of zeolites as ion exchange materials, adsorbents and catalysts (D.W. Breck: Zeolite Molecular Sieves, 1974).
For example, zeolites of the X, Y, mordenite, erionite and offretite types are of considerable technical 15 interest for catalyzing conversion reactions of hydrocarbons, such as cracking, hydrocracking or isomerizations . Zeolites of the pentasil type (for example zeolite ZSM-5) are becoming increasing important as catalysts for converting methanol to hydrocarbons.
Because of the numerous possibilities of using them as catalysts, there is great interest in new zeolites having specific catalytical properties. For example, very interesting zeolites are obtained by incorporating elements other than aluminum and/or silicon into the zeolite skele-25 ton. For instance, zeolites of the pentasil seriesr^ . tfv alia, have been disclosed as containing boron 206145 iron, arsenic, antimony , vanadium, chromium or gallium on tetrahedral sites. Moreover, titanosilicates (U.S. Patent 3,329,481) and zirconosilicates (U.S. Patent 3,329,4 80) with a seolite structure have been disclosed.
Furthermore, the following have already been described: boron-containing zeolites, gallium- and/or indium-containing zeolites, titanium-containing zeolites as well as zirconium-and/or hafnium-containing zeolites.
The invention relates to titanium-, zirconium- and/ or hafnium-containing zeolites which a) contain, in addition to sodium and potassium, the 20 elements silicon and aluminum and at least one element from the group consisting of titanium, zirconium and hafnium in the following ratio, expressed in molar ratios of oxides: (Si02 + M02):(0.02 - 0.30)Al203 25 where M is equal to titanium, zirconium and/or hafnium, and b) have, in the X-ray diffraction diagram, the characteristic signals listed in Table 1: s 206145 Table 1 Lattice plane distances d (£) Relative intensity l/In 11.4 + 0.3 5 9.2 + 0.2 7.6 + 0.2 6.6 + 0.1 .7 + 0.1 5.35 + 0.1 4.56+0.1 4.32 + 0.1 4.16 + 0.1 3.81 + 0.1 3.75 + 0.1 3.59 + 0.1 3.30 + 0.1 3.15 + 0.1 2.86 + 0.1 2.80 + 0.1 strong to very strong weak weak to medium medi urn to st rong weak to medium weak medium to strong strong weak medium to strong strong to very strong strong to very strong medium medium strong to very strong weak to medium In the Table, IQ is the intensity of the strongest signal The intensities in Table 1 have been classified as follows: Relative intensity 100 i/i0 very strong 80 - 100 strong 50-80 medium - 50 weak 0 CM 1 o In general, the ratio of silicon to titanium, conium and/or hafnium in the zeolites according to the 206145 invention should be: Si02 - = 0.4 - 0.99 Si02 + M02 preferably Si 02 =0.7-0.99 S i 02 + M02 expressed in molar ratios of the oxides, where M is equal to titanium, zirconium and/or hafnium.
The lattice structure of the zeolites according to the invention is similar to those of the following synthetic zeolites: Zeolite T (U.S. Patent 2,950,952), Zeolite ZSM-34, and the a luminosi I icate zeolite described in German Patent Application P 32 17 322.9.
The zeolites according to the invention differ from these three abovementioned synthetic zeolites in their composition, in particular by the fact that they contain at least one element from the group consisting of titanium, zirconium and hafnium. The zeolites according to the by the fact that organic constituents (templates), such as choline compounds or other hydroxyalkylammonium compounds, are absent.
The titanium- and zirconium- and/or hafnium- -containing zeolites —— , 206145 / respectively likewise have a structure which is similar to that of the zeolites according to the invention, but they differ from the latter by the fact that they contain choline compounds. 5 In the course of the synthesis these choline compounds generally act as templates and affect the structure. After the synthesis they are generally removed from the crystal lattice by decomposing them using calcination. The titanium-, zirconium- and/or hafnium-containing zeolites 10 according to the invention are thus distinguished from the known zeolites : r ; by two significant advan tages: - there is no need to add expensive choline compounds 15 during the synthesis - the calcination of the synthesized product can be dispensed with.
The titanium-, zirconium- and/or hafnium-containing zeolites according to the invention differ in structure, 20 and by the fact that an organic ammonium compound is absent, from the titanosi licates described in U.S. Patent 3/329,481, the zirconosilicates described in U.S. Patent 3,329,480, the titanium-containing zeolites and the zirconium and/or hafnium-containing zeolites.
The zeolites according to the invention can be prepared by mixing titanium, zirconium and/or hafnium-,--- .
./-V \ v # jj 206145 compounds with aluminum, silicon, sodium and potassium compounds and water, and heating this mixture in a sealed vessel. Before this mixture is heated it preferably has seed crystals of a zeolite of a similar structural 5 type added to it.
The starting compounds are generally used in the following ratio as expressed in molar ratios of the oxides (Si02 + m02) : (0.02 - 0.30)Al203 : (0.05 - 0.70)Na20: (0.02 - 0.30)K20 : (5 - 90)h20, preferably in the ratio 10 (Si02 + mo2) : (0.02 - 0.18)Al203 : (0.10 - 0.60)Na20 : (0.04 - 0.20)K20 : (5 - 40)H20, where M is equal to titanium, zirconium and/or hafnium.
The ratio of silicon to titanium, zirconium and/or hafnium in the mixture of the starting compounds is in 15 general Si02 = 0.4 - 0.99 Si02 + M02 preferab ly 20 Si02 : = 0.6 - 0.99 Si02+M02 expressed in molar ratios of the oxides, where M is equal to titanium, zirconium and/or hafnium.
Examples of titanium, zirconium and hafnium com pounds which can be used are titanium halides, titanium sulfate, titanium oxide sulfate, titanium alcoholates, sodium titanate, potassium titanate, titanium dioxide, zir conium halides, zirconium sulfate, zirconium alcoholates, 206145 zirconium nitrate, zirconium dioxide, zirconyl halides, zirconyl sulfate, sodium zirconate, potassium zirconate, hafnium halides, hafnium dioxide and hafnium oxychloride. However, other titanium, zirconium and hafnium compounds 5 are also suitable for preparing the zeolites according to the invention.
Examples of silicon, aluminum, sodium and potassium compounds which can be used are silica gel, potassium silicate, sodium silicate, sodium aluminate, potassium 10 aluminate, aluminum halides, aluminum metahydroxide, potassium hydroxide, potassium sulfate, potassium halides, sodium hydroxide, sodium sulfate and sodium halides. However, other silicon, aluminum, potassium and sodium compounds are also suitable for preparing the zeolites 15 according to the invention.
If seed crystals are used, they are generally added in an amount of 0.1 to 20% by weight, preferably in an amount of 0.5 to 10% by weight, relative to the total amount of all other components of the reaction mixture. 20 Suitable seed crystals can come from any zeolite with an identical or similar lattice structure, for example syn- / ''' thetic zeolites or natural erionite. v The mixture of whichever compounds have been chosen is heated together with water in a sealed vessel for 48 to 2,000 hours in general, preferably 48 to 1,000 hours, at a temperature between 80 and 160°C, preferably between 90 and 150oC. 2 0 6145 The zeolites formed are isolated in a customary manner, for example by filtration, washed and dried. They can be converted into the catalytically active forms by known methods, for example by ion exchange (D.W. Breck, 5 Zeolite Molecular Sieves, 1974).
After their conversion into the catalytically active forms, the zeolites according to the invention are distinguished in particular by a high degree of selectivity and by low coking in the course of converting 10 methanol into lower olefins. This reaction is carried out, for example, at temperatures of 350 - 430°C and with a water content in the methanol of 0 to 80% by weight or with crude methanol.
The following examples are intended to illustrate 15 the invention without limiting it in any way. All the X-ray diffraction data given were recorded using a Siemens computei—controlled D-500 powder diffractometer. Copper-K-alpha radiation was used.
E xamp le 1 18.4 g of sodium aluminate (54% by weight of AI2O3, 41% by weight of Na20), 23.5 g of sodium hydroxide and 8.6 g of potassium hydroxide are dissolved in 130 g of water. 203 g of 40% by weight colloidal silica gel, 16.4 g of titanium ethanolate, THOC^j)^, and 4 g of seed 25 crystals (natural erionite) are introduced in succession, with thorough stirring, into this solution. The resulting mixture is. homogenized and heated in a sealed vessel at 155°C for 192 hours. ' The product formed is filtered off, washed with water and dried at 120oC. 206145 The product contains silicon, aluminum and titanium in the following proportions, expressed in molar ratios of oxides: Si02 : 0.068 Al203 : 0.084 Ti02.
The result of the X-ray diffraction analysis is given in Table 2 .
Table 2 Lattice plane distances Relative intensity d (A) 200 I/I0 11.48 100 9.20 3 7.58 16 6.64 44 6.35 14 5.75 21 .35 3 4.58 43 4.34 51 4.16 6 3.82 47 3.78 92 3.60 80 3.33 37 3.18 31 2.91 8 2.87 81 . 2.80 5 2.69 9 2.48 7

Claims (11)

  1. 206145 - 11 - Examp le 2 18.4 g of sodium aluminate (54% by weight of Al203, 41% by weight of Na20)/ 23.5 g of sodium hydroxide and 8.6 g of potassium hydroxide are dissolved in 130 g of 5 water. 203 g of 40% by weight colloidal silica gel, 20.4 g of zirconium sulfate, Zr(S04>2, and 4 g of seed crystals (natural erionite) are introduced in succession, with thorough stirring, into this solution. The resulting mixture is homogenized and heated in a sealed 10 vessel at 150°C for 192 hours. The product formed is filtered off, washed with water and dried at 120°C. The product contains silicon, aluminum and zirconium in the following proportions, expressed in molar ratios of oxi des: 15 Si02 : 0.071 Al203 : 0.062 Zr02. The X-ray diffraction data correspond to those given i n Table 1. 206145 - 12 - WHAT <CTWE CLAIM J&: I. A titanium-, zirconium- and/or hafnium-containing zeolite which a) contains, in addition to sodium and potassium, the elements silicon and aluminum and at least one element from the group consisting of titanium, zirconium and hafnium in the following ratio, expressed in molar ratios of oxides: (Si02 + M02>:(0.02 - 0.30)Al203 where M is equal to titanium, zirconium and/or hafnium, and b) has, in the X-ray diffraction diagram, the characteristic signals listed below: Lattice plane distances Relative intensity d (I?) I/ID II.4 +_ 0.3 strong to very strong 9.2 + 0.2 weak 7.6 +_ 0.2 weak to medium 6.6 +_ 0.1 medium to strong 5.7 +_ 0.1 weak to medium 5.35 +0.1 weak 4.56 +_ 0.1 medium to strong 4.32 + 0.1 st rong 4.16 +_ 0.1 weak 3.81 +_ 0.1 medium to strong 3.75 + 0.1 strong to very strong 3.59 + 0.1 strong to very strong 3.30 + 0.1 3.15 + 0.1 medium $h medium *-'£ir i.-iijS 4- ■ Mte g v * *06145 Lattice plant distances Relative intensity d (%) I/I0 2.86 +_ 0.1 strong to very strong 2.80 +_ 0.1 weak to medium In the Table, 10 is the intensity of the strongest signal.
  2. 2. A titanium-, zirconium- and/or hafnium-containing zeolite as claimed in.claim 1, wherein the ratio of silicon to titanium, zirconium and/or hafnium is: Si 02 = 0.4 - 0.99 Si02 + M02 expressed in molar ratios of the oxides, where M is equal to titanium, zirconium and/or hafnium.
  3. 3. A titanium-, zirconium- and/or hafnium-containing zeolite as claimed in claim 1, wherein the ratio of silicon to titanium, zirconium and/or hafnium is: Si02 = o.7 - 0.99 Si02 + M(>2 expressed in molar ratios of the oxides, where M is equal to titanium, zirconium and/or hafnium. A.
  4. A process for preparing a titanium-, zirconium- and/or hafnium-containing zeolite as claimed in any one of claims 1 to 3, which comprises preparing a mixture of silicon, aluminum, sodium and potassium compounds, water and at least one compound from the group consisting of titanium, zirconium and hafnium compounds, which has the following composition as expressed in molar ratios of the oxides: m - 14 - (Si02 + M02> : (0.02 - 0.30)Al203 : (0.05 - 0.70)Na20 : (0.02 - 0.30)K20 : (5 - 90)H20 where M is equal to titanium, zirconium and/or hafnium, and heating this mixture in a sealed vessel.
  5. 5. The process as claimed in claim 4, wherein the mixture to be heated has the following composition as expressed in molar ratios of the oxides: (Si02 + M02> : (0.02 - 0.18)Al203 : (0.10 - 0.60)Na20 : (0.04 - 0.20)K20 : (5 - 40)h20, where M is equal to titanium, zirconium and/or hafnium.
  6. 6. The process as claimed in claim 4 or 5, wherein the ratio of silicon to titanium, zirconium and/or hafnium in the mixture of the starting compounds is: Si°2 = 0.4 - 0.99 Si02 + M02 expressed in molar ratios of the oxides, where M is equal to titanium, zirconium and/or hafnium.
  7. 7. The process as claimed in either of claims 4 or 5, wherein the ratio of silicon to titanium, zirconium and/or hafnium in the mixture of the starting compounds is: Si02 = 0.6 - 0.99 Si02 + M02 expressed in molar ratios of the oxides, where M is equal to titanium, zirconium and/or hafnium.
  8. 8. The process as claimed in any one of claims 4 to 7, wherein the mixture to be heated has seed crystals of a zeolite of a similar structural type added to it. 206145 - 15 -
  9. 9. Use of a titanium-, zirconium- and/or hafnium- containing zeolite as claimed in any one of claims 1 to 3, as a catalyst in the preparation of C2~ to C^-olefins from methanol.
  10. 10. A zeolite according to claim 1 substantially as herein described or exemplified.
  11. 11. A process according to claim 4 substantially as herein described or exemplified. HOECHST AKTIENGESELLSCHAFT By Their Attorneys HENRY HUGHES LIMITED By:
NZ206145A 1982-11-05 1983-11-03 Titanium,zirconium and/or hafnium containing zeolites NZ206145A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19823240870 DE3240870A1 (en) 1982-11-05 1982-11-05 ZEOLITES CONTAINING TITANIUM, ZIRCONIUM AND / OR HAFNIUM AND METHOD FOR THE PRODUCTION THEREOF AND THEIR USE

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NZ206145A true NZ206145A (en) 1985-12-13

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EP (1) EP0111147B1 (en)
JP (1) JPS5997521A (en)
AU (1) AU2100283A (en)
CA (1) CA1206459A (en)
DE (2) DE3240870A1 (en)
NZ (1) NZ206145A (en)
ZA (1) ZA838200B (en)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4892720A (en) * 1984-04-26 1990-01-09 Uop Substituted aluminosilicate compositions and process for preparing same
LU85515A1 (en) * 1984-08-28 1986-03-11 Belge Etat CATALYSTS FOR THE CONVERSION OF ETHANOL TO ETHYLENE AND THEIR USE
US4686029A (en) * 1985-12-06 1987-08-11 Union Carbide Corporation Dewaxing catalysts and processes employing titanoaluminosilicate molecular sieves
JP2573511B2 (en) * 1988-04-06 1997-01-22 久俊 浅岡 Composition by combination of titanium, aluminum, silicon and boron tetrahedral oxides and method for producing the same
DD288364A5 (en) * 1989-10-16 1991-03-28 ������@�����`������@ ���@������� k�� METHOD FOR THE PRODUCTION OF FINE CRYSTALLINE ALUMOSILICATES WITH PENTASIL STRUCTURE
US9416017B2 (en) * 2014-07-03 2016-08-16 Chevron U.S.A. Inc. Method for making molecular sieve SSZ-98

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL238953A (en) * 1958-05-08
NZ185397A (en) * 1976-11-04 1979-12-11 Mobil Oil Corp Crystalline aluminosilicate zeolites and use as catalysts
DE3136686A1 (en) * 1981-09-16 1983-04-21 Hoechst Ag, 6230 Frankfurt "GALLIUM- AND / OR INDIUM-CONTAINING ZEOLITHES AND METHOD FOR THE PRODUCTION THEREOF AND THEIR USE"
DE3136684A1 (en) * 1981-09-16 1983-04-21 Hoechst Ag, 6230 Frankfurt "GALLIUM- AND / OR INDIUM-CONTAINING ZEOLITES AND METHOD FOR THE PRODUCTION THEREOF AND THEIR USE"
DE3141285A1 (en) * 1981-10-17 1983-04-28 Hoechst Ag, 6230 Frankfurt Zirconium- and/or hafnium-containing zeolites and a process for their preparation, and their use
DE3217322A1 (en) * 1982-05-08 1983-11-10 Hoechst Ag, 6230 Frankfurt CRYSTALLINE ALUMINOSILICATE ZEOLITE, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE
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

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EP0111147A1 (en) 1984-06-20
CA1206459A (en) 1986-06-24
EP0111147B1 (en) 1986-05-14
DE3240870A1 (en) 1984-05-10
JPS5997521A (en) 1984-06-05
AU2100283A (en) 1984-05-10
DE3363538D1 (en) 1986-06-19
ZA838200B (en) 1984-06-27

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