CA1206460A - Titanium-, zirconium- and/or hafnium-containing zeolites, a process for their preparation, and their use - Google Patents
Titanium-, zirconium- and/or hafnium-containing zeolites, a process for their preparation, and their useInfo
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- CA1206460A CA1206460A CA000440453A CA440453A CA1206460A CA 1206460 A CA1206460 A CA 1206460A CA 000440453 A CA000440453 A CA 000440453A CA 440453 A CA440453 A CA 440453A CA 1206460 A CA1206460 A CA 1206460A
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- zeolite
- hafnium
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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
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- 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
-
- 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
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
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- 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
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- 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
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- 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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- 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)
Abstract
Abstract of the disclosure:
The invention relates to titanium-, zirconium-and/or hafnium-containing zeolites, to a process for their preparation, and to their use. They are prepared by mixing, for example, titanium, zirconium and/or hafnium compounds with aluminum, silicon, sodium and potassium compounds and water as well as an organic ammonium com-pound in specified mixing ratios and heating the mixture in a sealed vessel. The zeolites are used as catalysts in the preparation of C2-C4-olefins from methanol.
The invention relates to titanium-, zirconium-and/or hafnium-containing zeolites, to a process for their preparation, and to their use. They are prepared by mixing, for example, titanium, zirconium and/or hafnium compounds with aluminum, silicon, sodium and potassium compounds and water as well as an organic ammonium com-pound in specified mixing ratios and heating the mixture in a sealed vessel. The zeolites are used as catalysts in the preparation of C2-C4-olefins from methanol.
Description
~6~
- 2 - HOE ~2lF 217 Zeolites is the name given to, ;n particular, crystalline aluminosilicates ;n which regular structures with cavit;es and pores are formed by a threedimensional l;nking of SiO4 and AlO4 te~rahedra. In the hyd-rated sta~e these pores and cavities are full of water~The water can be removed, or be replaced by other mole-cules, ~;thout affecting the crystal structure. The nega-tive charges of AlO4 tetrahedra are compensated by cations. These cat;ons can be replaced, if desired, by 10 other cations. The properties descr;bed permit the use of these zeolites as ion exchange mater;als~ adsorbents and catalysts tD~W. Breck: Zeolite Molecular Sieves, 1974).
For example, zeolites of the X, Y, morden;te, erion;te and offret;te types are of considerable technical 15 in.erest for catalyzing conversion reac~ions of hydrocar-bons, such as crack;ng, hydrocracking or isomerizations.
Zeol;tes of the pentas;l type ~for example, zeol;te ZSM-5) are becoming increasingly important as catalysts for con-verting methanol to hydro~arbons.
Because of the numerous possibil;t;es of using them as catalysts, there is great interest in new zeolites hav;ng spec;f;c catalyt;cal propertiesO For example~ very ;nteresting zeol;tes are obta;ned by incorporating elements other than aluminum and/or s;licon ;nto the zeoli~e skele-2~ ton~ For ;nstance, zeol;tes of the pentas;l ser;es, inter al;a, have been disclosed as conta;n;ng boron tGerman - , ' ~ ' - ` ,, i~ '`
For example, zeolites of the X, Y, morden;te, erion;te and offret;te types are of considerable technical 15 in.erest for catalyzing conversion reac~ions of hydrocar-bons, such as crack;ng, hydrocracking or isomerizations.
Zeol;tes of the pentas;l type ~for example, zeol;te ZSM-5) are becoming increasingly important as catalysts for con-verting methanol to hydro~arbons.
Because of the numerous possibil;t;es of using them as catalysts, there is great interest in new zeolites hav;ng spec;f;c catalyt;cal propertiesO For example~ very ;nteresting zeol;tes are obta;ned by incorporating elements other than aluminum and/or s;licon ;nto the zeoli~e skele-2~ ton~ For ;nstance, zeol;tes of the pentas;l ser;es, inter al;a, have been disclosed as conta;n;ng boron tGerman - , ' ~ ' - ` ,, i~ '`
- 3 -Offenlegungsschrift 2,830,787), ;ron (German Offenlegungs-schr;ft 2,831"6113, arsen;c (~erman Auslegeschr;ft 2,830,830), an~imony ~German Offenlegungsschrift 2,830,787), vanadium SGerman Offenlegungsschrift 2,831,6313, chrom;um tGerman Offenlegungsschrift 2,831,630) or gallium (~elgian Patent 882~484) on tetrahPdron sites. Moreover, titano~
silicates (U.S. Patent 3,329,481 and German Offenlegungs-schrift 3,047,798) and z;rconosil;cates (U.S. Patent 3,329,480) w;th a zeolite structure have been d;sclosed.
~urthermore, the follo~ing have already been des-cribed: boron-containing zeolites, gallium- and/or indium-conta;n;ng zeolites~ titanium-containing zeolites as ~ell as zircon;um- and/or hafnium-contain;ng zeolites (Canadian Patent Applications 410,405, 410,415, 411,439, 411,429, 15 413,523, 413,530~ 427,626 and 427,625).
The invention relates to t;tanium-, zircon;um- and/
or hafnium-containing zeolites ~h;ch a) con~ain silicon, aluminum, sodium, potassium, an 20 organic ammonium compound and a~ least one element from the group consist;ng of titanium, ircon;um and hafnium in the folLo~ing rat;o SSiO2 + M3z) : ~0.02 - 0~30)Al203 : ~0.05 - 0.30) (Na20 + K20) : (0.01 - 0~30)RzO~
25 expressed in molar ratios of the oxides, ~here M is equal to titanium, zirconium and/or hafniumD R denotes a~monium radicaLs of the general formuLae (HOCH2CHz~4N~
~HOCH2CH2)3R1N or (HOCH2CH2)2R~R2N, and the radicals R1 and R2 can be identical or different and denote alkyl, substituted alkyl, cycloalkyl, substituted cycloaLkyl, aryl, substituted aryl or hydrogen, an~
b) have, in the X-ray diffraction diagram, the charac-teristic signals listed in Table 1:
S Table 1 Lattise distances Relative intensity d(R? ItIo __ _ _ _ ___ 11.5 ~ 0.3 strong to very strong 9.2 ~ 0.2 weak -10 7~6 + 0.2 weak to medium 606 ~ 0.1 med;um ~o strong 6.3 ~ 0.1 weak 5.7 ~ 0.1 - weak 5.35 ~ 0.1 weak
silicates (U.S. Patent 3,329,481 and German Offenlegungs-schrift 3,047,798) and z;rconosil;cates (U.S. Patent 3,329,480) w;th a zeolite structure have been d;sclosed.
~urthermore, the follo~ing have already been des-cribed: boron-containing zeolites, gallium- and/or indium-conta;n;ng zeolites~ titanium-containing zeolites as ~ell as zircon;um- and/or hafnium-contain;ng zeolites (Canadian Patent Applications 410,405, 410,415, 411,439, 411,429, 15 413,523, 413,530~ 427,626 and 427,625).
The invention relates to t;tanium-, zircon;um- and/
or hafnium-containing zeolites ~h;ch a) con~ain silicon, aluminum, sodium, potassium, an 20 organic ammonium compound and a~ least one element from the group consist;ng of titanium, ircon;um and hafnium in the folLo~ing rat;o SSiO2 + M3z) : ~0.02 - 0~30)Al203 : ~0.05 - 0.30) (Na20 + K20) : (0.01 - 0~30)RzO~
25 expressed in molar ratios of the oxides, ~here M is equal to titanium, zirconium and/or hafniumD R denotes a~monium radicaLs of the general formuLae (HOCH2CHz~4N~
~HOCH2CH2)3R1N or (HOCH2CH2)2R~R2N, and the radicals R1 and R2 can be identical or different and denote alkyl, substituted alkyl, cycloalkyl, substituted cycloaLkyl, aryl, substituted aryl or hydrogen, an~
b) have, in the X-ray diffraction diagram, the charac-teristic signals listed in Table 1:
S Table 1 Lattise distances Relative intensity d(R? ItIo __ _ _ _ ___ 11.5 ~ 0.3 strong to very strong 9.2 ~ 0.2 weak -10 7~6 + 0.2 weak to medium 606 ~ 0.1 med;um ~o strong 6.3 ~ 0.1 weak 5.7 ~ 0.1 - weak 5.35 ~ 0.1 weak
4.56 ~ 0.1 ~eak to medium 4.32 ~ 0.1 strong 4016 ~ 0.1 weak 3081 ~ 0.1 med;um to strong 3u75 ~ 0.1 strong to very strong 3.59 + 0.1 s~rong to very strong 3030 ~ 0.1 medium 3.15 ~ 0.1 medium 2.86 ~ 0.1 strong to very strong 2.80 + 0.1 weak to medium 2.67 ~ 0.1 - weak to medium 2.49 ~ 0.1 weak to medium In ~he Table, Io denotes the intensity of the strongest signalr The intensit;es given in Table 1 have been classified as follows:
- s -Relative intensity 100 I/Io very strong 80 - 100 strong 50 - 80 medium 20 - 50
- s -Relative intensity 100 I/Io very strong 80 - 100 strong 50 - 80 medium 20 - 50
5 weak 0 - 20 ~ he zeolites according to the invent;on preferably have the follo~ing composition as expressed in molar ra tios of the oxides-~SiO2 ~ M02) : (0.08 - 0.18) Al203 : tO.05 ~ 0~30) 10 (Na20 ~ K20): 0.01 - 0~,30) R20, where M ;s equal to titanium, zirconium and/or hafnium, R
has the abovement;oned mean;ng and is preferabLy (HOSH2 CH~)3R1N~
R~ and R2 have the abovement;oned mean;ngs, 15 and preferably are alkyl radicals of at most 5 carbon atoms each, or hydrogenr in particular methyl, ethyl or h~drogen. R1 and R2 can be different, but preferably R1 = R~, ;n particular R1 = R2 = methyl.
In general, the ra~io of sil;con to titanium, zir-20 con;um and/or hafn;um in the zeolites according to the;nvent;on should be:
S;O~
= 0.~ - D.~9 S;2 ~ M0z 25 preferably sio2 - ~ 0.7 - 0.99 , SiO2 ~- M2 expressed ;n molar rat;os of the oxides, where M is equal .:
, ,,
has the abovement;oned mean;ng and is preferabLy (HOSH2 CH~)3R1N~
R~ and R2 have the abovement;oned mean;ngs, 15 and preferably are alkyl radicals of at most 5 carbon atoms each, or hydrogenr in particular methyl, ethyl or h~drogen. R1 and R2 can be different, but preferably R1 = R~, ;n particular R1 = R2 = methyl.
In general, the ra~io of sil;con to titanium, zir-20 con;um and/or hafn;um in the zeolites according to the;nvent;on should be:
S;O~
= 0.~ - D.~9 S;2 ~ M0z 25 preferably sio2 - ~ 0.7 - 0.99 , SiO2 ~- M2 expressed ;n molar rat;os of the oxides, where M is equal .:
, ,,
6~
to t;tanium, z;rcon;um and/or hafnium.
The novel zeolites according to the invention have a structure simiLar to that of erionite (L.W~ StapLes, J.A.
Gard, Mineralogical Maga~ine, Volume 32 t1959), page Z61 et seq.) or that of the synthetic zeolites T ~U~S~ Patent 2,950 952) and ZSM-34 ~German Offenlegungsschrift 2,749,0Z4) but they differ from these in the composition, in particu-lar by the fact that they contain at least one element from the group consisting of ~itanium, zircon;um and haf-10 nium and by the nature of $he organic ammonium compound.
A further crystalline aLuminosiLicate of thisstructuraL type was recently described in Canadian Patent Application 427,627 ~ The zeolites accord;ng to the invention d;ffer from this aluminosilicate by the fact 15 that they contain titanium, zirconium and/or hafnium and that they have d;fferent catalytical propert;es.
The titan;um-, z;rconium and/or hafnium-contain~
ing zeol;tes accord;ng to the invent;on d;ffer from the ti~anosilicates according to U.S. Patent 3~3290481 and 20 ~erman Offenlegungsschrift 3,047~798, the zirconosiLicates described in U.S. Paten~ 3,329,480, the titanium~contain-;ng zeolites described in Canadian Patent Application 413,523 and the z;rcon;um- and/or hafnium-containing zeolite~ described in Canadian Patent Application 413,530 in terms of the structure and by the nature of the organ;c ammon;um compound.
The titanium-, ~irconium and/or hafnium-containing zeoLites according to the invention differ from the titan-;um-contain;ng and zirconium- andJor hafnium-containing .
.~
~2~
to t;tanium, z;rcon;um and/or hafnium.
The novel zeolites according to the invention have a structure simiLar to that of erionite (L.W~ StapLes, J.A.
Gard, Mineralogical Maga~ine, Volume 32 t1959), page Z61 et seq.) or that of the synthetic zeolites T ~U~S~ Patent 2,950 952) and ZSM-34 ~German Offenlegungsschrift 2,749,0Z4) but they differ from these in the composition, in particu-lar by the fact that they contain at least one element from the group consisting of ~itanium, zircon;um and haf-10 nium and by the nature of $he organic ammonium compound.
A further crystalline aLuminosiLicate of thisstructuraL type was recently described in Canadian Patent Application 427,627 ~ The zeolites accord;ng to the invention d;ffer from this aluminosilicate by the fact 15 that they contain titanium, zirconium and/or hafnium and that they have d;fferent catalytical propert;es.
The titan;um-, z;rconium and/or hafnium-contain~
ing zeol;tes accord;ng to the invent;on d;ffer from the ti~anosilicates according to U.S. Patent 3~3290481 and 20 ~erman Offenlegungsschrift 3,047~798, the zirconosiLicates described in U.S. Paten~ 3,329,480, the titanium~contain-;ng zeolites described in Canadian Patent Application 413,523 and the z;rcon;um- and/or hafnium-containing zeolite~ described in Canadian Patent Application 413,530 in terms of the structure and by the nature of the organ;c ammon;um compound.
The titanium-, ~irconium and/or hafnium-containing zeoLites according to the invention differ from the titan-;um-contain;ng and zirconium- andJor hafnium-containing .
.~
~2~
- 7 -zeolites of sim;Lar structure (Canadian Patent Applications 427,626 and 427,625 respectively~ by the nature of the organic ammonium rompound. The zeolites according to the invention are further distinguished by a different crystal shape and by much bigger crystall;tes.
The zeoLites according to the invention can be prepared by m;xing an RX ammonium compound with aluminum, silicon, sodium and pota~sium compounds and ~ater as well as at least one compound from the group consis~ing of 10 titanium, zirconium andlor hafnium compounds, and heating the m;xture ;n a sealed vesselO The R of RX has the above-ment;oned meanin~. Seed crystals can also be added to the mixture before it is heated.
The starting compo~nds are generally used in the 15 following ratio as expressed in molar ratios of the oxides:
(SiO2 + M02~ : tO.02 - 0.30) Al203 : tO.OZ - 0.70) Na20: O.D2 - 0.30) K20: (0.02 - 0.5) R20: (1D 90?
H20 o preferably ;n the ratio 20 SSi2 + M02) : O.OZ 0~18) Al2a3: (0.10 - 0.60) Na20 : tO.04 - 0.20) K20 : tO.10 - 0.40) R20 :
(10 - 40) H20, ~here M is equal to ~itanium, zirconium and/or hafnium and R has the above~entioned meaning.
In general:
S'02 ___________ = 0.4 o 0.99 S~2 ~ M2 preferably , .~
si~2 - = 0.6 - 0~9 SiO2 '~ M2 expressed in molar ratios of the oxides, where M is equal 5 to t;tanium, zirconium and/or hafnium.
An RX ammonium compound can be any water-soluble salt oF R. X can denote~ for example~ hydroxylr chloride, bromide, iodide, sulfate, phosphate, sulfonate~ carboxy-late, carbonate or sulfite.
The RX ammonium compound can be used as a substance, but ;t is preferably produced ;n s;tu in the reaction mix ture by using a mix~ure of triethanolam;ne and/or dietha-nolamine on the one hand and a compound of the general fornlula R1Y on the other hand, R1 having the àbove-15 ment;oned meaning. Y ;s generally hydroxyl, monoalkyl sulfate, halide or sulfonate, in particular hydroxyl.
R1Y is preferably methanol, ethanol, propanol, butanol, ethylene glycol, 1,Z propylene alycol, dimethyl su~fate, diethyl sulfate, methyl ;odide, ethyl iodide, 20 propyl iodide, methyl p-toluenesulfonate, ethyl p-toluene-sulfonate or propyl p-toluenesulfonate. R1Y is in par-t;cular methanol, ethanol or ethylene glycolO The molar rat;o of R1Y to amine ttriethanolamine and/or `diethanol-amine) ;s in general 075 ~0 20~ preferably 1 to 10, in par~
~ .
25 ticular 4 to lG.
- However, the zeolites according to the invention oan also be prepared ~;th satisfactory crystallinity in the absence of a compound of the general ~ormula R1Y, i~e.
in the presence of only ~riethanolamine and/or diethanol~
~ , ............................ .
~` . . .
- ` ~2~6~
amine.
Examples of titanium, zirconium and hafnium com-pounds ~h1ch can be used are titanium halide, titanium sulfate, titanium ox;de sulfate, titanium alcoholates, sodium titanate, potassium titanate, titanium dioxide, zir-conium halide, zircon;um sulfat~, zirconium alcoholates, zirconium nitrate, zirconium dioxide~ zirconyl halide, zirconyl sul~ate~ sodium zirconate, potassium zirconate, hafnium hal;de, hafnium dioxide and hafnium oxychloride.
10 However, other titanium, zircon;um and hafniu~ compounds are also suitable for preparing the zeolites according to the inventionc Examples of silicon, alum;num, sodium and potas-s;um compounds wh;ch can be used are silica ael~ potass;um 15 s;licate, sodium sil;cate~ sodium aluminate, potassium alum;nate~ aluminum halides, alum;num metahydroxide, potas-s;um hydroxide, potass;um sulfate, potassium halides, sod;um hydroxide, sodium sulfate and sodium halides.
HoweYer, other silicon, aluminum, potass;um and sodium 20 compounds are a~so suitab~e for prep3ring the zeolites accordiny to the ;nventionn The ~ixture of whichever compounds have been cho-sen together w;th water is heated in a sealed vessel for 18 to 1,000 hours in general, preferably 24 to 500 hours, 25 at a temperature bet~een 80 and 200C, preferably bet-ween 110 and 160C.
The zeol;tes forméd are isolated ;n a customary manner, for example by f;ltrat;on, washed and dr;ed. They can be ~onverted into the catalytically act;ve forms by . .
~6~Q
known methods, for example by calcination and/or ion ex~
change (DnW~ 3reck, ZeoLite Molecular Sieves, 1974).
After their conversion into the catalytically active formr the zeolites according to the ;nvention are distinguished in particular by a hi~h degre~ of selecti~
vity and by low coking in the course of converting methanol into low olefins. This reaction is carried out, for example, at temperatures of 350 - ~30C and with a water content in the methanol of 0 to 80% by weight or ~ith 10 crude methanol.
The follo~ing examples are intended to illustrate the invention without limiting it in any way. All the X-ray diffract;on data given were recorded using a Siemens computer-controlled D-500 powder diffractometer.
15 Copper-K-alpha radiation was used.
Example 1_ 17.92 g of sodium aluminate (5~% by weight of Alz03, 41X by weight of Na20), and 9.5 g of sodium hydroxide, 10 9 of potassium hydroxide, 77~6 g of triethan-20 olamine and 56 g of ethylene glycol are dissolved in 240 mlof water ~solut;on A). 14.2 g of t;tan;um ethanolate, T;(OC2Hs)4, are d;ssolved in 40 9 of ethylene glycol (solution B). 178 9 of 40% by weight strength collo;dal s;lica gel are then introduGed ~;th thorough st;rr;ng into 25 solution A, ollowed by soiution av The result;ng mixture is homo~en;zed and ;s then heated ;n a st;rred autoclave at 150C for 120 hours. The product formed is f;ltered off, washed with water and dried at 120S.
The product has the X-ray diff raction pattern ' . , .
~z~
reproduced in Table 2.
Chemical analysis reveals the following composi-tion as expressed ;n ~olar ratios of oxides:
SiO2 : 0.147 Al203 : 0.058 TiO2 : 0.073 Na20 :
S O.û91 K20 : 0.060 R20, where R ;s equal to (I~OCII2CH2)4N, Table 2 Lattice plane d;stances Relative intensity d(~) 100 IIIo _ 10 1'i.3 84 9.2 4 7.55 17 6 . 60 6~
6.29 6 5~,70 4 5.3~ 3 4.51 12 4.2~ 59 ~.1b, 3 . 8[) 24 3 74 1 n~
3 J 56 . ~5 3.31 22 3.15 45 2.91 2 2 . 86 ~ 65 2.84 79 2.80 18 .~- 2.67 - 2~
. '' ~
Example 2 11.2 g o-f sodium aluminate t54% by weight of Al203, ~1% by weight of Na20), 5.9 g of sodium hydroxide, 5.3 g of potassium hydroxide, 48.7 9 of triethanolamine and 31 g of methanol are dissolved in 150 ml of waterO To this solution are added, first, 100 9 of 40~ by weight stren~th colloidal silica gel and ~hen 22.Z g of titanium tetrachloride. The resulting mixture is homogenized and is heated in a sealed vessel at 140C for 226 hours.
10 The product formed is f;ltered off, washed ~I;th water and dried at 120C.
The product has the X-ray data given ;n Table 1 and the following chernical composition as expressed in molar ratios of oxides-15 S;02 : 0.180 T;02 : 0.125 Al20Example 3 .
11.2 9 of sodium aluminate, 5.9 g of sod;um hyd-rox;de, 5.3 g of potassium hydroxide and 3473 g of dieth-anolamine are dissolved in 150 ml of water. To this solu-.20 t;on are added, in succession, 110 g of 40% by weightstrength colloidal sil;ca gel~ a solution of 17.~ g of t;tan;um ethanolate, Ti(OCzH5)4 ;n 85 9 of ethanol~
and 2 g of seed crystals from Example 1~ The result;n~
mixture is homogenized and is heated in a sealed vessel 25 at 150C for 192 hours. The product formed is filtered off, washed w;th water and dr;ed at 120~C Tlle product has the X-ray diffract;on pattern g;ven in Table 1 and the following chemical composition as expressed in molar rat;os of oxides , , .
~2~;46~
S;2 : 0-100 TiO2 0.132 A~203 Example 4 17~92 9 of sod;um alum;nate ~54% by weight of Al203, 41% by wei~ht of NazO), 9.5 9 of sodium hyd-rox;de, 10 9 of potassium hydroxide, 77.6 9 of triethan-olam;ne and 96 9 of ethylene glycol are dissolved in 240 ml of ~ater. To- this solution are added, with thorough stir~
r;ng, first 178 9 of 40% by weight strength colloidal s;lica gel and then 17.7 9 of zirconium sulfate in a l;t-10 tle ~ater. The resulting mixture is homo~enized and thenheated at 150C in a st rred autoclave for 120 hours~
The product formed is filtered off~ washed with water and dr;ed at 120C.
The product has the X-ray diffraction pattern 15 reproduced in Table 1.
Chemical analysis reveals the following composi-tion as expressed in molar ratios of oxides:
SiO2 . 0.143 Al203 : 0.049 ~rO2 : 0~ 052 Na20 :
0.068 K20 : 0.062 R20, 20 ~here~ R ;s equal to ~HOCH2CHz)4N.
.
.
.
. : '' ' . ~ ' .
. . ..
The zeoLites according to the invention can be prepared by m;xing an RX ammonium compound with aluminum, silicon, sodium and pota~sium compounds and ~ater as well as at least one compound from the group consis~ing of 10 titanium, zirconium andlor hafnium compounds, and heating the m;xture ;n a sealed vesselO The R of RX has the above-ment;oned meanin~. Seed crystals can also be added to the mixture before it is heated.
The starting compo~nds are generally used in the 15 following ratio as expressed in molar ratios of the oxides:
(SiO2 + M02~ : tO.02 - 0.30) Al203 : tO.OZ - 0.70) Na20: O.D2 - 0.30) K20: (0.02 - 0.5) R20: (1D 90?
H20 o preferably ;n the ratio 20 SSi2 + M02) : O.OZ 0~18) Al2a3: (0.10 - 0.60) Na20 : tO.04 - 0.20) K20 : tO.10 - 0.40) R20 :
(10 - 40) H20, ~here M is equal to ~itanium, zirconium and/or hafnium and R has the above~entioned meaning.
In general:
S'02 ___________ = 0.4 o 0.99 S~2 ~ M2 preferably , .~
si~2 - = 0.6 - 0~9 SiO2 '~ M2 expressed in molar ratios of the oxides, where M is equal 5 to t;tanium, zirconium and/or hafnium.
An RX ammonium compound can be any water-soluble salt oF R. X can denote~ for example~ hydroxylr chloride, bromide, iodide, sulfate, phosphate, sulfonate~ carboxy-late, carbonate or sulfite.
The RX ammonium compound can be used as a substance, but ;t is preferably produced ;n s;tu in the reaction mix ture by using a mix~ure of triethanolam;ne and/or dietha-nolamine on the one hand and a compound of the general fornlula R1Y on the other hand, R1 having the àbove-15 ment;oned meaning. Y ;s generally hydroxyl, monoalkyl sulfate, halide or sulfonate, in particular hydroxyl.
R1Y is preferably methanol, ethanol, propanol, butanol, ethylene glycol, 1,Z propylene alycol, dimethyl su~fate, diethyl sulfate, methyl ;odide, ethyl iodide, 20 propyl iodide, methyl p-toluenesulfonate, ethyl p-toluene-sulfonate or propyl p-toluenesulfonate. R1Y is in par-t;cular methanol, ethanol or ethylene glycolO The molar rat;o of R1Y to amine ttriethanolamine and/or `diethanol-amine) ;s in general 075 ~0 20~ preferably 1 to 10, in par~
~ .
25 ticular 4 to lG.
- However, the zeolites according to the invention oan also be prepared ~;th satisfactory crystallinity in the absence of a compound of the general ~ormula R1Y, i~e.
in the presence of only ~riethanolamine and/or diethanol~
~ , ............................ .
~` . . .
- ` ~2~6~
amine.
Examples of titanium, zirconium and hafnium com-pounds ~h1ch can be used are titanium halide, titanium sulfate, titanium ox;de sulfate, titanium alcoholates, sodium titanate, potassium titanate, titanium dioxide, zir-conium halide, zircon;um sulfat~, zirconium alcoholates, zirconium nitrate, zirconium dioxide~ zirconyl halide, zirconyl sul~ate~ sodium zirconate, potassium zirconate, hafnium hal;de, hafnium dioxide and hafnium oxychloride.
10 However, other titanium, zircon;um and hafniu~ compounds are also suitable for preparing the zeolites according to the inventionc Examples of silicon, alum;num, sodium and potas-s;um compounds wh;ch can be used are silica ael~ potass;um 15 s;licate, sodium sil;cate~ sodium aluminate, potassium alum;nate~ aluminum halides, alum;num metahydroxide, potas-s;um hydroxide, potass;um sulfate, potassium halides, sod;um hydroxide, sodium sulfate and sodium halides.
HoweYer, other silicon, aluminum, potass;um and sodium 20 compounds are a~so suitab~e for prep3ring the zeolites accordiny to the ;nventionn The ~ixture of whichever compounds have been cho-sen together w;th water is heated in a sealed vessel for 18 to 1,000 hours in general, preferably 24 to 500 hours, 25 at a temperature bet~een 80 and 200C, preferably bet-ween 110 and 160C.
The zeol;tes forméd are isolated ;n a customary manner, for example by f;ltrat;on, washed and dr;ed. They can be ~onverted into the catalytically act;ve forms by . .
~6~Q
known methods, for example by calcination and/or ion ex~
change (DnW~ 3reck, ZeoLite Molecular Sieves, 1974).
After their conversion into the catalytically active formr the zeolites according to the ;nvention are distinguished in particular by a hi~h degre~ of selecti~
vity and by low coking in the course of converting methanol into low olefins. This reaction is carried out, for example, at temperatures of 350 - ~30C and with a water content in the methanol of 0 to 80% by weight or ~ith 10 crude methanol.
The follo~ing examples are intended to illustrate the invention without limiting it in any way. All the X-ray diffract;on data given were recorded using a Siemens computer-controlled D-500 powder diffractometer.
15 Copper-K-alpha radiation was used.
Example 1_ 17.92 g of sodium aluminate (5~% by weight of Alz03, 41X by weight of Na20), and 9.5 g of sodium hydroxide, 10 9 of potassium hydroxide, 77~6 g of triethan-20 olamine and 56 g of ethylene glycol are dissolved in 240 mlof water ~solut;on A). 14.2 g of t;tan;um ethanolate, T;(OC2Hs)4, are d;ssolved in 40 9 of ethylene glycol (solution B). 178 9 of 40% by weight strength collo;dal s;lica gel are then introduGed ~;th thorough st;rr;ng into 25 solution A, ollowed by soiution av The result;ng mixture is homo~en;zed and ;s then heated ;n a st;rred autoclave at 150C for 120 hours. The product formed is f;ltered off, washed with water and dried at 120S.
The product has the X-ray diff raction pattern ' . , .
~z~
reproduced in Table 2.
Chemical analysis reveals the following composi-tion as expressed ;n ~olar ratios of oxides:
SiO2 : 0.147 Al203 : 0.058 TiO2 : 0.073 Na20 :
S O.û91 K20 : 0.060 R20, where R ;s equal to (I~OCII2CH2)4N, Table 2 Lattice plane d;stances Relative intensity d(~) 100 IIIo _ 10 1'i.3 84 9.2 4 7.55 17 6 . 60 6~
6.29 6 5~,70 4 5.3~ 3 4.51 12 4.2~ 59 ~.1b, 3 . 8[) 24 3 74 1 n~
3 J 56 . ~5 3.31 22 3.15 45 2.91 2 2 . 86 ~ 65 2.84 79 2.80 18 .~- 2.67 - 2~
. '' ~
Example 2 11.2 g o-f sodium aluminate t54% by weight of Al203, ~1% by weight of Na20), 5.9 g of sodium hydroxide, 5.3 g of potassium hydroxide, 48.7 9 of triethanolamine and 31 g of methanol are dissolved in 150 ml of waterO To this solution are added, first, 100 9 of 40~ by weight stren~th colloidal silica gel and ~hen 22.Z g of titanium tetrachloride. The resulting mixture is homogenized and is heated in a sealed vessel at 140C for 226 hours.
10 The product formed is f;ltered off, washed ~I;th water and dried at 120C.
The product has the X-ray data given ;n Table 1 and the following chernical composition as expressed in molar ratios of oxides-15 S;02 : 0.180 T;02 : 0.125 Al20Example 3 .
11.2 9 of sodium aluminate, 5.9 g of sod;um hyd-rox;de, 5.3 g of potassium hydroxide and 3473 g of dieth-anolamine are dissolved in 150 ml of water. To this solu-.20 t;on are added, in succession, 110 g of 40% by weightstrength colloidal sil;ca gel~ a solution of 17.~ g of t;tan;um ethanolate, Ti(OCzH5)4 ;n 85 9 of ethanol~
and 2 g of seed crystals from Example 1~ The result;n~
mixture is homogenized and is heated in a sealed vessel 25 at 150C for 192 hours. The product formed is filtered off, washed w;th water and dr;ed at 120~C Tlle product has the X-ray diffract;on pattern g;ven in Table 1 and the following chemical composition as expressed in molar rat;os of oxides , , .
~2~;46~
S;2 : 0-100 TiO2 0.132 A~203 Example 4 17~92 9 of sod;um alum;nate ~54% by weight of Al203, 41% by wei~ht of NazO), 9.5 9 of sodium hyd-rox;de, 10 9 of potassium hydroxide, 77.6 9 of triethan-olam;ne and 96 9 of ethylene glycol are dissolved in 240 ml of ~ater. To- this solution are added, with thorough stir~
r;ng, first 178 9 of 40% by weight strength colloidal s;lica gel and then 17.7 9 of zirconium sulfate in a l;t-10 tle ~ater. The resulting mixture is homo~enized and thenheated at 150C in a st rred autoclave for 120 hours~
The product formed is filtered off~ washed with water and dr;ed at 120C.
The product has the X-ray diffraction pattern 15 reproduced in Table 1.
Chemical analysis reveals the following composi-tion as expressed in molar ratios of oxides:
SiO2 . 0.143 Al203 : 0.049 ~rO2 : 0~ 052 Na20 :
0.068 K20 : 0.062 R20, 20 ~here~ R ;s equal to ~HOCH2CHz)4N.
.
.
.
. : '' ' . ~ ' .
. . ..
Claims (18)
OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A zeolite containing at least one member of the group of titanium, zirconium and hafnium which (a) contains silicon, aluminum, sodium, potassium, at least one element from the group consisting of titanium, zircon-ium and hafnium and an organic ammonium compound in the following ratio:
(SiO2 + MO2) : (0.02 - 0.30) Al2O3 : (0.05 -0.30) (Na2O + K2O) : (0.01 - 0.30) R2O , expressed in molar ratios of the oxides, where M is equal to at least one member of the group of titanium, zirconium and hafnium, R denotes ammonium radicals of the general formulae (HOCH2CH2)4N, (HOCH2CH2)3R1N or (HOCH2CH2)2R1R2N, and the radicals R1 and R2 can be identical or different and denote alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, aryl, substituted aryl or hydrogen, and (b) has, in the X-ray diffraction diagram, the character-istic signals listed in Table 1:
Table 1 (continued) In the Table, Io denotes the intensity of the strongest signal.
(SiO2 + MO2) : (0.02 - 0.30) Al2O3 : (0.05 -0.30) (Na2O + K2O) : (0.01 - 0.30) R2O , expressed in molar ratios of the oxides, where M is equal to at least one member of the group of titanium, zirconium and hafnium, R denotes ammonium radicals of the general formulae (HOCH2CH2)4N, (HOCH2CH2)3R1N or (HOCH2CH2)2R1R2N, and the radicals R1 and R2 can be identical or different and denote alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, aryl, substituted aryl or hydrogen, and (b) has, in the X-ray diffraction diagram, the character-istic signals listed in Table 1:
Table 1 (continued) In the Table, Io denotes the intensity of the strongest signal.
2. A zeolite as claimed in claim 1, which has the fol-lowing composition:
(SiO2 + MO2) : (0.08 - 0.18) Al2O3 : (0.05 - 0.30) (Na2O + K2O) : (0.01 - 0.30) R2O.
(SiO2 + MO2) : (0.08 - 0.18) Al2O3 : (0.05 - 0.30) (Na2O + K2O) : (0.01 - 0.30) R2O.
3. A zeolite as claimed in claim 1 wherein R1 and R2 are alkyl radicals of at most 5 carbon atoms each or hydrogen.
4. A zeolite as claimed in claim 1, claim 2 or claim 3, wherein R1 and R2 are methyl, ethyl or hydrogen.
5. A zeolite as claimed in claim 1, claim 2 or claim 3, wherein R1 is equal to R2.
6. A zeolite as claimed in claim 1, claim 2 or claim 3, wherein R1 and R2 are equal to methyl.
7. A zeolite as claimed in claim 1, claim 2 or claim 3, wherein expressed in molar ratios of the oxides.
8. A zeolite as claimed in claim 1, claim 2 or claim 3 wherein expressed in molar ratios of the oxides.
9. A process for preparing a zeolite as claimed in claim 1, which comprises preparing a mixture of silicon, aluminium, sodium, potassium, and organic ammonium compounds and water as well as at least one compound from the group consisting of titanium, zirconium and hafnium compounds, which has the follow-ing composition as expressed in molar ratios of the oxides:
(SiO2 + MO2) : (0.02 - 0.30) Al2O3 : (0.02 - 0.70) Na2O : (0.02 - 0.30) K2O : (0.02 - 0.50) R2O :
(10 - 90) H2O, and heating this mixture in a sealed vessel.
(SiO2 + MO2) : (0.02 - 0.30) Al2O3 : (0.02 - 0.70) Na2O : (0.02 - 0.30) K2O : (0.02 - 0.50) R2O :
(10 - 90) H2O, and heating this mixture in a sealed vessel.
10. A process as claimed in claim 9, wherein the mixture to be heated has the following composition as expressed in molar ratios of the oxides:
(SiO2 + MO2) : (0.02 - 0.18) Al2O3 : (0.10 - 0.60) Na2O : (0.04 - 0.20) K2O : (0.10 - 0.40) R2O :
(10 - 40) H2O:
(SiO2 + MO2) : (0.02 - 0.18) Al2O3 : (0.10 - 0.60) Na2O : (0.04 - 0.20) K2O : (0.10 - 0.40) R2O :
(10 - 40) H2O:
11. A process as claimed in claim 9 wherein the ammonium compound is replaced by an equivalent amount of triethanolamine and/or diethanolamine together with a compound of the formula R1Y where R1 is equal to alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, aryl, substituted aryl or hydrogen, and Y is equal to hydroxyl, monoalkyl sulfate, halide or sulfonate.
12. A process as claimed in claim 11, wherein R1Y is equal to methanol, ethanol, propoanol, butanol, ethylene glycol, 1,2-propylene glycol, dimethyl sulfate, diethyl sulfate, methyl iodide, ethyl iodide, propyl iodide, methyl p-toluenesulfonate, ethyl p-toluenesulfonate or propyl p-toluene sulfonate.
13. A process as claimed in claim 11, wherein R1Y is equal to methanol, ethanol or ethylene glycol.
14. A process as claimed in claim g or claim 10, wherein the ammonium compound is replaced by an equivalent amount of tri-ethanolamine.
15. A process as claimed in claim 9 or claim 10, wherein the ammonium compound is replaced by an equivalent amount of diethanolamine.
16. A process as claimed in either of claim 9 or claim 10, wherein the mixture of the starting compounds is in accordance with:
expressed in molar ratios of theoxides.
expressed in molar ratios of theoxides.
17. A process as claimed in either of claim 9 or claim 10, wherein the mixture of the starting compounds is in accordance with:
expressed in molar ratios of the oxides.
expressed in molar ratios of the oxides.
18. A process for the preparation of a C2 - C4- olefin from methanol in which the reaction is carried out in the presence of a zeolite as claimed in claim l, claim 2 or claim 3.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19823240869 DE3240869A1 (en) | 1982-11-05 | 1982-11-05 | ZEOLITES CONTAINING TITANIUM, ZIRCONIUM AND / OR HAFNIUM AND METHOD FOR THE PRODUCTION THEREOF AND THEIR USE |
| DEP3240869.2 | 1982-11-05 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1206460A true CA1206460A (en) | 1986-06-24 |
Family
ID=6177360
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000440453A Expired CA1206460A (en) | 1982-11-05 | 1983-11-04 | Titanium-, zirconium- and/or hafnium-containing zeolites, a process for their preparation, and their use |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0111700B1 (en) |
| JP (1) | JPS59107919A (en) |
| AU (1) | AU2100183A (en) |
| CA (1) | CA1206460A (en) |
| DE (2) | DE3240869A1 (en) |
| NZ (1) | NZ206144A (en) |
| ZA (1) | ZA838199B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4707345A (en) * | 1984-04-26 | 1987-11-17 | Union Carbide Corporation | Titanium-aluminum-silicon-oxide molecular sieve compositions and process for preparing the same |
| CA1254188A (en) * | 1984-04-26 | 1989-05-16 | Bonita K. Marcus | Titanium-aluminum-silicon-oxide molecular sieve compositions |
| US4892720A (en) * | 1984-04-26 | 1990-01-09 | Uop | Substituted aluminosilicate compositions and process for preparing same |
| IT1222022B (en) * | 1987-07-14 | 1990-08-31 | Montedipe Spa | METHOD FOR THE PREPARATION OF A CATALYST FOR THE AMMOSSIMATION OF CARBONYL COMPOUNDS |
| 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 |
| DE102022116274A1 (en) | 2022-06-29 | 2024-01-04 | Gehr-Kunststoff-Extrusionsgesellschaft mbH | ANTIBACTERIAL THERMOPLASTIC SUBSTRATE |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DK155176C (en) * | 1978-06-22 | 1989-07-17 | Snam Progetti | PROCEDURE FOR THE PREPARATION OF ALUMINUM OXIDE MODIFIED SILICON Dioxide |
| DE3141283A1 (en) * | 1981-10-17 | 1983-04-28 | Hoechst Ag, 6230 Frankfurt | Titanium-containing zeolites and a process for their preparation, 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 |
-
1982
- 1982-11-05 DE DE19823240869 patent/DE3240869A1/en not_active Withdrawn
-
1983
- 1983-11-02 EP EP83110895A patent/EP0111700B1/en not_active Expired
- 1983-11-02 DE DE8383110895T patent/DE3365167D1/en not_active Expired
- 1983-11-03 NZ NZ206144A patent/NZ206144A/en unknown
- 1983-11-03 ZA ZA838199A patent/ZA838199B/en unknown
- 1983-11-04 CA CA000440453A patent/CA1206460A/en not_active Expired
- 1983-11-04 JP JP58206081A patent/JPS59107919A/en active Pending
- 1983-11-04 AU AU21001/83A patent/AU2100183A/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| NZ206144A (en) | 1985-12-13 |
| ZA838199B (en) | 1984-06-27 |
| JPS59107919A (en) | 1984-06-22 |
| DE3240869A1 (en) | 1984-05-10 |
| EP0111700B1 (en) | 1986-08-06 |
| EP0111700A1 (en) | 1984-06-27 |
| AU2100183A (en) | 1984-05-10 |
| DE3365167D1 (en) | 1986-09-11 |
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