CA1182096A - Gallium- and/or indium-containing zeolites, process for their manufacture, and their use - Google Patents
Gallium- and/or indium-containing zeolites, process for their manufacture, and their useInfo
- Publication number
- CA1182096A CA1182096A CA000411439A CA411439A CA1182096A CA 1182096 A CA1182096 A CA 1182096A CA 000411439 A CA000411439 A CA 000411439A CA 411439 A CA411439 A CA 411439A CA 1182096 A CA1182096 A CA 1182096A
- Authority
- CA
- Canada
- Prior art keywords
- gallium
- indium
- oxides
- molar ratio
- expressed
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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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
- C01B39/065—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
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
-
- 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
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/87—Gallosilicates; Aluminogallosilicates; Galloborosilicates
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/40—Ethylene production
Abstract
Abstract of the disclosure:
The invention provides gallium- and/or indium-containing zeolites, a process for their manufacture, and their use.
For their manufacture, a mixture of silicon, aluminum, sodium, potassium and tetramethylammonium compounds, water and gallium and/or indium compounds is prepared in a spe-cific quantitative ratio, and heated in a closed vessel.
The zeolites may be used as catalysts in the manufacture of hydrocarbons, especially C2-C4-olefins, from methanol.
The invention provides gallium- and/or indium-containing zeolites, a process for their manufacture, and their use.
For their manufacture, a mixture of silicon, aluminum, sodium, potassium and tetramethylammonium compounds, water and gallium and/or indium compounds is prepared in a spe-cific quantitative ratio, and heated in a closed vessel.
The zeolites may be used as catalysts in the manufacture of hydrocarbons, especially C2-C4-olefins, from methanol.
Description
- 2 - HOE 81/F 252 Zeolites are crystalline aluminosilicates 9 in which due to a three-dimensional linkage of SiO4 and AlOI~ 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 Al04 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 exchan~ers, adsorbents and c~talysts (D.W. Breck: Zeolite Molecular Sieves, 1974).
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 conver-slon of methanol to hy~rocarbons.
Because of the numerous application possibilities as catalysts, there is great interest in novel zeolites having ~p~cific catalytical properties.
Very interesting zeolites are for example obtained by incorporating other elements instead of aluminum and/or ~ilicon into the zeolite frame. Thus, zeolites of the pentasil series are known which contain boron (German Offenlegungsschrift No. 2,830,787), iron (German Offenle-gungsschrift No. 2,831,611), arsenic (German Auslegeschrift No. 2,830,830), antimony (German Offenlegungsschrift No.
2,830,787), vanadium (German Offenlegungsschrift No.
2,831,631), chromium (German Offenlegungsschrift No.
2,831,630), or gallium (Belgian Patent No. 882,484) in tetrahedral position.
Subject of the present invention are gallium- and/or indium containing zeolites which ..;~
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 conver-slon of methanol to hy~rocarbons.
Because of the numerous application possibilities as catalysts, there is great interest in novel zeolites having ~p~cific catalytical properties.
Very interesting zeolites are for example obtained by incorporating other elements instead of aluminum and/or ~ilicon into the zeolite frame. Thus, zeolites of the pentasil series are known which contain boron (German Offenlegungsschrift No. 2,830,787), iron (German Offenle-gungsschrift No. 2,831,611), arsenic (German Auslegeschrift No. 2,830,830), antimony (German Offenlegungsschrift No.
2,830,787), vanadium (German Offenlegungsschrift No.
2,831,631), chromium (German Offenlegungsschrift No.
2,831,630), or gallium (Belgian Patent No. 882,484) in tetrahedral position.
Subject of the present invention are gallium- and/or indium containing zeolites which ..;~
- 3 ~ HOE 81/F 252 a~ have the foilowing composition:
SiO2 : (0020 ~ 0.10) ~Al203 t M20~7 (0.15 - 0.1) ~Na20 + K2Q7 : (0.15 - 0~4) R20 expressed as molar ratio of oxides; M being gallium and/or indium and R being tetramethylammonium, and b) have the characteristic X-ray diffraction pattern set forth below in Table l:
Table 1 1 0 . _ _ _ Interplanar Spacing Relative Intensity d ~ R 7 I/Io _ 11.50 + 0.2 very strong 7.56 + 0.1 weak to medium 6.62 + 0.1 medium to strong 6.32 + 0.1 weak 5.74 + 0.1 ,.
SiO2 : (0020 ~ 0.10) ~Al203 t M20~7 (0.15 - 0.1) ~Na20 + K2Q7 : (0.15 - 0~4) R20 expressed as molar ratio of oxides; M being gallium and/or indium and R being tetramethylammonium, and b) have the characteristic X-ray diffraction pattern set forth below in Table l:
Table 1 1 0 . _ _ _ Interplanar Spacing Relative Intensity d ~ R 7 I/Io _ 11.50 + 0.2 very strong 7.56 + 0.1 weak to medium 6.62 + 0.1 medium to strong 6.32 + 0.1 weak 5.74 + 0.1 ,.
4.56 ~ 0.1 medium 4.33 ~ 0.1 medium to strong 3.76 + 0.1 very strong 3.58 - 0.1 medium to strong 3.31 ~ 0.1 weak 3.15 + 0.1 weak to medium 2.84 + 0.1 strong to very strong 2.68 + 0.1 weak to medium 2.48 + 0.1 I weak I
Io = intensity of the strongest line or peak.
3o The inten~ities of Table 1 are defined as follows:
relative intensity 100 I/Io .
very strong 80 - 100 strong 50 80 medium 20 - 50 weak O - 20 1 ~ 8 ~
The novel zeolites of the invention have a structure similar to offretite (German Offenlegungsschrift No. 1,806,154);
however, they have a different composition.
The follo-~ing is valid for tne zeolite of the inYention:
generally A1203 _ = 0.01 ~ 0.99 preferably Al23 = 0.40 - 0.99 A1203 + M203 especially _ A123 _ _ - 0.60 - 0.99 A1203 ~ M203 expressed as molar ratio of the oxides; M being ~allium and/or indium.
The zeolites of the invention are prepared by mixing gallium and/or indium compounds with aluminum, silicon, ~5 ~odlum, pota~sium, tetramethylammonium compounds and water, and heating the mixture in a closed vessel.
The starting compounds are generally used in the following ratio, expres~ed as molar ratio of the oxides:
SiO2 : (0.03 ~ 0.028) Al203 : (0.03 - 0.028) M203 :
(0.2 + o.o8) Na20 : (0.2 ~ 0.15) K20 : (0.1 + 0.08) R20:
(20 ~ 10) H~O
preferably in a ratio of SiO2 : (O.G3 - 0.01) Al203 : (0.03 ~ 0.028) M203:
(0.2 - 0.08) Na20 : (0.2 - 0.10) K20 : (0.035 + 0.015) R20:
(20 ~ 10) H20
Io = intensity of the strongest line or peak.
3o The inten~ities of Table 1 are defined as follows:
relative intensity 100 I/Io .
very strong 80 - 100 strong 50 80 medium 20 - 50 weak O - 20 1 ~ 8 ~
The novel zeolites of the invention have a structure similar to offretite (German Offenlegungsschrift No. 1,806,154);
however, they have a different composition.
The follo-~ing is valid for tne zeolite of the inYention:
generally A1203 _ = 0.01 ~ 0.99 preferably Al23 = 0.40 - 0.99 A1203 + M203 especially _ A123 _ _ - 0.60 - 0.99 A1203 ~ M203 expressed as molar ratio of the oxides; M being ~allium and/or indium.
The zeolites of the invention are prepared by mixing gallium and/or indium compounds with aluminum, silicon, ~5 ~odlum, pota~sium, tetramethylammonium compounds and water, and heating the mixture in a closed vessel.
The starting compounds are generally used in the following ratio, expres~ed as molar ratio of the oxides:
SiO2 : (0.03 ~ 0.028) Al203 : (0.03 - 0.028) M203 :
(0.2 + o.o8) Na20 : (0.2 ~ 0.15) K20 : (0.1 + 0.08) R20:
(20 ~ 10) H~O
preferably in a ratio of SiO2 : (O.G3 - 0.01) Al203 : (0.03 ~ 0.028) M203:
(0.2 - 0.08) Na20 : (0.2 - 0.10) K20 : (0.035 + 0.015) R20:
(20 ~ 10) H20
5 ~
~ 5 - HOE 81/F 252 M being ~allium and/or indium and R being tetramethylam-moniurn.
As compounds, there are used for example silicic acid, potassium silicate, sodium silicate, aluminum hydroxide, aluminum sulfate, sodium aluminate, potassium aluminate, aluminum halides, aluminum methahydroxyide, gallium(III) oxide, gallium(III) nitrate, gallium(III~ sulfate, gallium(III) halides, gallium(III) hydroxide, indium(III) oxide, indium(III) nitrate, indium(III) ulfate, indium(III) halides, indium(III) hydroxide, sodium hydroxide, sodium sulfate, sodium halides, potassium hydroxide, potassium ~ulfate, potassium halides, tetramethylammonium hydroxide, tetramethylam~onium chloride. Other silicon, aluminum, gallium, indium, potassium, sodium and tetramethylammonium compound~ are also suitable for the manufacture of the ~eolites according to the invention.
The mixture of the compounds chosen and water is ge-nerally heated for 12 to 300, preferably 24 to 200, hours at a temperatur-e of from 60 to 150C, pe~erably 80 to 140C, 20 in a ¢losed ves3el.
The crystalline zeolites which are formed are isola-~ed in usual manner, for example by f ltration, washed and dried. They can be converted according to known methods to catalytically active forms, for example by calcination and/or ion exchange (D.W. Breck, Zeolite Molecular Sieves, 1974~.
After conversion to the catalytically active form, the zeolites of the invention display a considerably re-duced deposition of coke and a pronouncedly increased activity especially in the conversion of methanol to hy-drocarbons, as compared to the gallium- or indium~free o~fretites according to German Offenlegungsschrift No.
19806,154. This reaction is earried out, for example, at temperatures between 350 and 430C using methanol with a water content of O 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 ~ndicated were obtained by means of a cornputer-controlled powder diffractometer D-500 of the Siemens company. The radiation was the K-~ doublet of copper.
1 ~82~6
~ 5 - HOE 81/F 252 M being ~allium and/or indium and R being tetramethylam-moniurn.
As compounds, there are used for example silicic acid, potassium silicate, sodium silicate, aluminum hydroxide, aluminum sulfate, sodium aluminate, potassium aluminate, aluminum halides, aluminum methahydroxyide, gallium(III) oxide, gallium(III) nitrate, gallium(III~ sulfate, gallium(III) halides, gallium(III) hydroxide, indium(III) oxide, indium(III) nitrate, indium(III) ulfate, indium(III) halides, indium(III) hydroxide, sodium hydroxide, sodium sulfate, sodium halides, potassium hydroxide, potassium ~ulfate, potassium halides, tetramethylammonium hydroxide, tetramethylam~onium chloride. Other silicon, aluminum, gallium, indium, potassium, sodium and tetramethylammonium compound~ are also suitable for the manufacture of the ~eolites according to the invention.
The mixture of the compounds chosen and water is ge-nerally heated for 12 to 300, preferably 24 to 200, hours at a temperatur-e of from 60 to 150C, pe~erably 80 to 140C, 20 in a ¢losed ves3el.
The crystalline zeolites which are formed are isola-~ed in usual manner, for example by f ltration, washed and dried. They can be converted according to known methods to catalytically active forms, for example by calcination and/or ion exchange (D.W. Breck, Zeolite Molecular Sieves, 1974~.
After conversion to the catalytically active form, the zeolites of the invention display a considerably re-duced deposition of coke and a pronouncedly increased activity especially in the conversion of methanol to hy-drocarbons, as compared to the gallium- or indium~free o~fretites according to German Offenlegungsschrift No.
19806,154. This reaction is earried out, for example, at temperatures between 350 and 430C using methanol with a water content of O 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 ~ndicated were obtained by means of a cornputer-controlled powder diffractometer D-500 of the Siemens company. The radiation was the K-~ doublet of copper.
1 ~82~6
- 6 - HOE 81/F 221 Example 1 98 g of 40 weight % colloidal ~ilica gel are introduced into a solution of 4.3 g OL gallium(III) oxide, 7.2 g of so~
dium hydroxide, 17.8 g of potassium hydroxide, 4.5 g of sodium aluminate (54 weight ~ of Al203, 41 weight % of Na20) and 4.2 g of tetramethylam~onium chloride in 125 g of water.
The mixture so obtained i,5 homogenized by thorough stirring, and heated for 95 hours at 95C in a closed vessel. The product obtained is filtered off, washed with water and dried at 120C. According to chemical analysis, the product is composed as folllows~ expressed as molar ratio of oxides:
SiO2 : 0.088 Al203 : 0~056 Ga203 : 0.028 Na20 : o.o84 ~2 : 0 034 R20 R = tetrarnethylammonium.
The result o~ X-ray diffraction is listed in Table 2.
~0 Tab ___ . _.
Interplanar Spacing Relative Intensity d C ~ ~ I/Io 11.48 ~3
dium hydroxide, 17.8 g of potassium hydroxide, 4.5 g of sodium aluminate (54 weight ~ of Al203, 41 weight % of Na20) and 4.2 g of tetramethylam~onium chloride in 125 g of water.
The mixture so obtained i,5 homogenized by thorough stirring, and heated for 95 hours at 95C in a closed vessel. The product obtained is filtered off, washed with water and dried at 120C. According to chemical analysis, the product is composed as folllows~ expressed as molar ratio of oxides:
SiO2 : 0.088 Al203 : 0~056 Ga203 : 0.028 Na20 : o.o84 ~2 : 0 034 R20 R = tetrarnethylammonium.
The result o~ X-ray diffraction is listed in Table 2.
~0 Tab ___ . _.
Interplanar Spacing Relative Intensity d C ~ ~ I/Io 11.48 ~3
7.52 24 6.60 48 6.3l~ 12 5.73 13 4.58 39 4.34 55 3.75 100 3.58 74 3.31 18 3~15 33 2.86 90 2.67 17 2.48 13 _ _ ~ ~2~9~
Example 2 A mixture of 1.7 g of gallium(III) oxide, 21.4 g of sodium hydroxide, 35.6 g of potassium hydroxide, 7.0 g of aluminum hydroxide, 8.4 g of tetramethylammonium chlorlde, 250 g of water and 195 g of 40 weight % colloidal silica gel is manufactured, and heated for 72 hours in a closed vessel to 110C. After work-up as indicated in Example 1 a crystalline product having the following composition, expressed as molar ratio of oxides, is obtained:
SiO2 : 0.101 Al203 : 0.011 Ga2O3 : 0.022 Na2O : o.o66 K20 0.042 R2O
R = tetramethylammonium.
The X-ray diffraction data correspond to those indicated in Table 1~
Example 3 A mixture of 12.9 g of gallium(III) oxide, 21.4 g of ~odium hydroxide, 35.6 g of potassi.um hydroxide, 0.7 g of alu-mlnurn hydroxide, 8.4 g of tetramethylammonium chlor-ide, 250 g o~ water and 195 e Of 40 weight ~ oolloidal silica gel is prepared, and heated for 120 hours at 95C in a closed vessel. After work-up as in Example 1, a crystalline product having the following composition, expressed as molar ratio of oxides, is obtained:
SiO2 : 0.018 Al203 : 0.102 Ga203 : 0.031 Na2O : 0.076 K20 : 0-043 R2O
R = tetramethylammonium.
The X-ray diffraction data correspond to those indicated in Ta~le 1.
Example 2 A mixture of 1.7 g of gallium(III) oxide, 21.4 g of sodium hydroxide, 35.6 g of potassium hydroxide, 7.0 g of aluminum hydroxide, 8.4 g of tetramethylammonium chlorlde, 250 g of water and 195 g of 40 weight % colloidal silica gel is manufactured, and heated for 72 hours in a closed vessel to 110C. After work-up as indicated in Example 1 a crystalline product having the following composition, expressed as molar ratio of oxides, is obtained:
SiO2 : 0.101 Al203 : 0.011 Ga2O3 : 0.022 Na2O : o.o66 K20 0.042 R2O
R = tetramethylammonium.
The X-ray diffraction data correspond to those indicated in Table 1~
Example 3 A mixture of 12.9 g of gallium(III) oxide, 21.4 g of ~odium hydroxide, 35.6 g of potassi.um hydroxide, 0.7 g of alu-mlnurn hydroxide, 8.4 g of tetramethylammonium chlor-ide, 250 g o~ water and 195 e Of 40 weight ~ oolloidal silica gel is prepared, and heated for 120 hours at 95C in a closed vessel. After work-up as in Example 1, a crystalline product having the following composition, expressed as molar ratio of oxides, is obtained:
SiO2 : 0.018 Al203 : 0.102 Ga203 : 0.031 Na2O : 0.076 K20 : 0-043 R2O
R = tetramethylammonium.
The X-ray diffraction data correspond to those indicated in Ta~le 1.
- 8 = H0~ 81~F 252 Example 4 98 g of 40 weight % colloidal silica gel are intro-duced into a solution of 10.1 g of indium trichloride, 7.2 g of sodium hydroxide, 17.8 g of potassium hydroxide, 4.5 of sodium aluminate (54 weight g Al203, 41 weight %
Na20) and 4.2 g of tetramethylammonium chloride in 125 g of water. The mixture so obtained is homogenized by thorough stirring and heated for 95 hours at 95C in a closed ~essel.
The product obtained is filtered, washed with water, and dried at 120C.
A chemical analysis results in the following compo-~ition, expressed as molar ratio of oxides:
SiO2: 0.099 A1203: 0.038 In203: 0.032 Na20 o.o84 K20 : 0.032 R20 R = tetramethylammonium.
The X-ray diffraction data correspond to those li~ted in Table 1.
Na20) and 4.2 g of tetramethylammonium chloride in 125 g of water. The mixture so obtained is homogenized by thorough stirring and heated for 95 hours at 95C in a closed ~essel.
The product obtained is filtered, washed with water, and dried at 120C.
A chemical analysis results in the following compo-~ition, expressed as molar ratio of oxides:
SiO2: 0.099 A1203: 0.038 In203: 0.032 Na20 o.o84 K20 : 0.032 R20 R = tetramethylammonium.
The X-ray diffraction data correspond to those li~ted in Table 1.
Claims (7)
OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A zeolite containing gallium, indium or gallium and indium which (a) has the following composition:
SiO2 : (0.20 ? 0.10) [Al2O3 + M2O3] :
(0.15 ? 0.1) [Na2O + K2O] : (0.15 ? 0.14) R2O
expressed as molar ratio of oxides; M being gallium, indium or gallium and indium and R being tetramethylammonium, and (b) has the characteristic X-ray diffraction pattern set forth below:
SiO2 : (0.20 ? 0.10) [Al2O3 + M2O3] :
(0.15 ? 0.1) [Na2O + K2O] : (0.15 ? 0.14) R2O
expressed as molar ratio of oxides; M being gallium, indium or gallium and indium and R being tetramethylammonium, and (b) has the characteristic X-ray diffraction pattern set forth below:
2. A zeolite as claimed in claim 1, for which the following is valid:
- = 0.01 - 0.99, expressed as molar ratio of oxides; M being gallium, indium or gallium and indium.
- = 0.01 - 0.99, expressed as molar ratio of oxides; M being gallium, indium or gallium and indium.
3. A zeolite as claimed in claim 1 for which the following is valid:
= 0.40 - 0.99, expressed as molar ratio of oxides; M being gallium, indium or gallium and indium.
= 0.40 - 0.99, expressed as molar ratio of oxides; M being gallium, indium or gallium and indium.
4. A zeolite as claimed in claim 1, claim 2 or claim 3 for which the following is valid:
= 0.60 - 0.99, expressed as molar ratio of oxides; M being gallium, indium or gallium or indium.
= 0.60 - 0.99, expressed as molar ratio of oxides; M being gallium, indium or gallium or indium.
5. A process for the preparation of a zeolite containing gallium, indium or gallium indium as claimed in claim 1 in which a mixture of silicon, aluminum, sodium, potassium and tetramethylammonium compounds, water, gallium, indium or gallium and indium compounds is prepared, having the following composition, expressed in molar ratio of oxides:
SiO2 : (0.03 ? 0.028) Al2O3 : (0.03 ? 0.028) M2O3 : (0.2 ? 0.08) Na2O : (0.2 ? 0.15) K2O : (0.1 ? 0.08) R2O : (20 ? 10) H2O
M being gallium, indium or gallium and indium and R being tetra-methylammonium, and the mixture is heated in a closed vessel.
SiO2 : (0.03 ? 0.028) Al2O3 : (0.03 ? 0.028) M2O3 : (0.2 ? 0.08) Na2O : (0.2 ? 0.15) K2O : (0.1 ? 0.08) R2O : (20 ? 10) H2O
M being gallium, indium or gallium and indium and R being tetra-methylammonium, and the mixture is heated in a closed vessel.
6. A process as claimed in claim 5 wherein the mixture to be heated has the following composition, expressed as molar ratio of oxides:
SiO2 : (0.03 ? 0.01) Al2O3 : (0.03 ? 0.028) M2O3 : (0.2 ? 0.08) Na2O : (0.2 ? 0.10) K2O : (0.034 ? 0.015) R2O : (20 ? 10) H2O
M being gallium, indium, or gallium and indium and R being tetramethylammonium.
SiO2 : (0.03 ? 0.01) Al2O3 : (0.03 ? 0.028) M2O3 : (0.2 ? 0.08) Na2O : (0.2 ? 0.10) K2O : (0.034 ? 0.015) R2O : (20 ? 10) H2O
M being gallium, indium, or gallium and indium and R being tetramethylammonium.
7. A process for the preparation of C2-C4-olefin in which methanol is reacted in the presence of a catalyst as claimed in claim 1, claim 2 or claim 3.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19813136686 DE3136686A1 (en) | 1981-09-16 | 1981-09-16 | "GALLIUM- AND / OR INDIUM-CONTAINING ZEOLITHES AND METHOD FOR THE PRODUCTION THEREOF AND THEIR USE" |
| DEP3136686.4 | 1981-09-16 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1182096A true CA1182096A (en) | 1985-02-05 |
Family
ID=6141770
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000411439A Expired CA1182096A (en) | 1981-09-16 | 1982-09-15 | Gallium- and/or indium-containing zeolites, process for their manufacture, and their use |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0074652B1 (en) |
| JP (1) | JPS5864213A (en) |
| AU (1) | AU8840482A (en) |
| CA (1) | CA1182096A (en) |
| DE (2) | DE3136686A1 (en) |
| NZ (1) | NZ201909A (en) |
| ZA (1) | ZA826758B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4919907A (en) * | 1986-12-22 | 1990-04-24 | Union Oil Company Of California | Crystalline galliosilicate with the zeolite L type structure |
| US4931266A (en) * | 1986-10-22 | 1990-06-05 | Union Oil Company Of California | Crystalline galliosilicate with the erionite-type structure |
| US4994250A (en) * | 1989-09-29 | 1991-02-19 | Union Oil Company Of California | Process for synthesizing a molecular sieve having the offretite structure and containing aluminum and gallium |
| US4995963A (en) * | 1986-12-22 | 1991-02-26 | Union Oil Company Of California | Crystalline galliosilicate with the zeolite L type structure and its use in chemical catalytic conversions |
| US5035868A (en) * | 1986-12-22 | 1991-07-30 | Union Oil Company Of California | Catalyst composition containing a crystalline galliosilicate having the zeolite L type structure |
| US5064793A (en) * | 1986-10-22 | 1991-11-12 | Union Oil Company Of California | Catalyst composition containing a crystalline galliosilicate having the erionite-type structure |
| US5133951A (en) * | 1986-09-04 | 1992-07-28 | Union Oil Company Of California | Process for making a crystalline galliosilicate with the offretite structure |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3240870A1 (en) * | 1982-11-05 | 1984-05-10 | Hoechst Ag, 6230 Frankfurt | ZEOLITES CONTAINING TITANIUM, ZIRCONIUM AND / OR HAFNIUM AND METHOD FOR THE PRODUCTION THEREOF AND THEIR USE |
| GB8308684D0 (en) * | 1983-03-29 | 1983-05-05 | British Petroleum Co Plc | Production of gallium loaded hydrocarbon conversion catalyst |
| DE3770647D1 (en) * | 1986-01-09 | 1991-07-18 | Light Oil Utilization Res Ass | PRODUCTION OF A MIXED STOCK FOR HIGH OCTANE GASOLINE. |
| DE3773439D1 (en) * | 1986-07-11 | 1991-11-07 | Mobil Oil Corp | METHOD FOR CONVERTING OXYGEN-BASED LOWER ALIPHATES TO OLEFINS AND AROMATES BY MEANS OF A GALLIUM-CONTAINING ZSM-5 CATALYST. |
| US6007790A (en) * | 1998-08-13 | 1999-12-28 | Uop Llc | Family of microporous indium silicate compositions |
| CN1269734C (en) * | 2000-11-03 | 2006-08-16 | 环球油品公司 | UZM-5, UZM-5p and UZM-6: crystalline aluminosilicate zeolites and processes using the same |
| US6419895B1 (en) * | 2000-11-03 | 2002-07-16 | Uop Llc | Crystalline aluminosilicate zeolitic composition: UZM-4 |
| US6776975B2 (en) * | 2002-05-09 | 2004-08-17 | Uop Llc | Crystalline aluminosilicate zeolitic composition: UZM-4M |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL238953A (en) * | 1958-05-08 | |||
| US3431219A (en) * | 1967-03-08 | 1969-03-04 | Mobil Oil Corp | Crystalline galliosilicates |
| US4046826A (en) * | 1974-12-06 | 1977-09-06 | N L Industries, Inc. | Process for alkylating aromatic hydrocarbons with synthetic hectorite-type clay catalyst |
| DE2848849A1 (en) * | 1978-11-10 | 1980-05-22 | Mobil Oil Corp | Metal-contg. ZSM-5 type zeolites - useful as hydrocarbon conversion catalysts |
| CA1142500A (en) * | 1979-03-28 | 1983-03-08 | Grace (W.R.) & Co. | Cyclic process for forming high purity zsm-5 catalyst |
-
1981
- 1981-09-16 DE DE19813136686 patent/DE3136686A1/en not_active Withdrawn
-
1982
- 1982-09-11 EP EP82108413A patent/EP0074652B1/en not_active Expired
- 1982-09-11 DE DE8282108413T patent/DE3261241D1/en not_active Expired
- 1982-09-14 NZ NZ201909A patent/NZ201909A/en unknown
- 1982-09-14 JP JP57159046A patent/JPS5864213A/en active Pending
- 1982-09-15 ZA ZA826758A patent/ZA826758B/en unknown
- 1982-09-15 CA CA000411439A patent/CA1182096A/en not_active Expired
- 1982-09-15 AU AU88404/82A patent/AU8840482A/en not_active Abandoned
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5133951A (en) * | 1986-09-04 | 1992-07-28 | Union Oil Company Of California | Process for making a crystalline galliosilicate with the offretite structure |
| US4931266A (en) * | 1986-10-22 | 1990-06-05 | Union Oil Company Of California | Crystalline galliosilicate with the erionite-type structure |
| US4946579A (en) * | 1986-10-22 | 1990-08-07 | Union Oil Company Of California | Chemical conversion processes utilizing catalyst containing crystalline galliosilicate molecular sieves having the erionite-type structure |
| US5064793A (en) * | 1986-10-22 | 1991-11-12 | Union Oil Company Of California | Catalyst composition containing a crystalline galliosilicate having the erionite-type structure |
| US4919907A (en) * | 1986-12-22 | 1990-04-24 | Union Oil Company Of California | Crystalline galliosilicate with the zeolite L type structure |
| US4995963A (en) * | 1986-12-22 | 1991-02-26 | Union Oil Company Of California | Crystalline galliosilicate with the zeolite L type structure and its use in chemical catalytic conversions |
| US5035868A (en) * | 1986-12-22 | 1991-07-30 | Union Oil Company Of California | Catalyst composition containing a crystalline galliosilicate having the zeolite L type structure |
| US4994250A (en) * | 1989-09-29 | 1991-02-19 | Union Oil Company Of California | Process for synthesizing a molecular sieve having the offretite structure and containing aluminum and gallium |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0074652A1 (en) | 1983-03-23 |
| ZA826758B (en) | 1983-07-27 |
| EP0074652B1 (en) | 1984-11-14 |
| JPS5864213A (en) | 1983-04-16 |
| DE3136686A1 (en) | 1983-04-21 |
| DE3261241D1 (en) | 1984-12-20 |
| NZ201909A (en) | 1985-07-31 |
| AU8840482A (en) | 1983-03-24 |
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