CA1182098A - Boro-aluminosilicates having zeolite structure, process for their manufacture, and their use - Google Patents
Boro-aluminosilicates having zeolite structure, process for their manufacture, and their useInfo
- Publication number
- CA1182098A CA1182098A CA000410405A CA410405A CA1182098A CA 1182098 A CA1182098 A CA 1182098A CA 000410405 A CA000410405 A CA 000410405A CA 410405 A CA410405 A CA 410405A CA 1182098 A CA1182098 A CA 1182098A
- Authority
- CA
- Canada
- Prior art keywords
- boro
- oxides
- tetramethylammonium
- expressed
- boron
- 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
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B35/00—Boron; Compounds thereof
- C01B35/08—Compounds containing boron and nitrogen, phosphorus, oxygen, sulfur, selenium or tellurium
- C01B35/10—Compounds containing boron and oxygen
- C01B35/1009—Compounds containing boron and oxygen having molecular-sieve properties
-
- 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
- B01J29/86—Borosilicates; Aluminoborosilicates
-
- 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
- C07C2529/86—Borosilicates; Aluminoborosilicates
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Abstract of the disclosure:
The invention provides boro-aluminosilicates having a zeo-lite structure, a process for their manufacture, and their use. For their manufacture, a mixture of silicon, aluminum, boron, sodium, potassium and tetramethylammonium compounds and water is prepared in a specific quantitative ratio, and heated in a closed vessel. The boro-aluminosilicates are used as catalysts in the manufacture of hydrocarbons, especially C2-C4-olefins, from methanol.
The invention provides boro-aluminosilicates having a zeo-lite structure, a process for their manufacture, and their use. For their manufacture, a mixture of silicon, aluminum, boron, sodium, potassium and tetramethylammonium compounds and water is prepared in a specific quantitative ratio, and heated in a closed vessel. The boro-aluminosilicates are used as catalysts in the manufacture of hydrocarbons, especially C2-C4-olefins, from methanol.
Description
~ ~ ~2~
- 2 ~ ~OE 81/F 221 Zeolites are crystalline aluminosilicates, in which due to a three-dimensional linkage of SiO4 and Al04 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 exchangers, adsorbents and catalysts (D.~l. 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.
Zeol:itcs of the pentasil type tfor example Zeolite ZSM-5) become increasingly important as catalysts for the conver-sion of methanol to hydrocarbons.
Because of the numerous application possibilities as cataly3ts, there is great interest in novel zeolites having 3p~cific catalytical properties.
Vcry lntcr~sting zeolites are for exarnple obtained by incorporatlng other elements .instead of aluminum and/or silicon into the æeolite frame. Thus, zeolites of the pentasil series are known which contain boron (German Offenlegungsschrift No. 2,830,787), iron (German Offenle-gun~sschrift 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) or chromium (German Offenlegungsschrift No.
2,831,630) in tetrahedral position.
Subject of the present invention are boro-aluminosili-cates having a zeolite structure 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.
Zeol:itcs of the pentasil type tfor example Zeolite ZSM-5) become increasingly important as catalysts for the conver-sion of methanol to hydrocarbons.
Because of the numerous application possibilities as cataly3ts, there is great interest in novel zeolites having 3p~cific catalytical properties.
Vcry lntcr~sting zeolites are for exarnple obtained by incorporatlng other elements .instead of aluminum and/or silicon into the æeolite frame. Thus, zeolites of the pentasil series are known which contain boron (German Offenlegungsschrift No. 2,830,787), iron (German Offenle-gun~sschrift 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) or chromium (German Offenlegungsschrift No.
2,831,630) in tetrahedral position.
Subject of the present invention are boro-aluminosili-cates having a zeolite structure which
- 3 - HOE 81/F 221 a) have the following composition:
SiO2 (0.20 ~ 0.103 ~Al203 + B20~ : -(0.15 0.1) ~Na2O + K2Q7 : (0.15 - 0.1) R2O
expressed as molar ratio of oxides; R being tetramethyl-ammonium, and b) have the characteristic X-ray diffraction pattern set forth below in Table 1:
Table 1 Interplanar Spacing Relative Intensity d ~ ~ ~ I/Io ¦11.50 ~ 0.2 very strong 7.56 ~ 0.1 medium 6.62 ~ 0.1 strong 6.32 ~ 0.1 weak 5.7~ ~ 0.1 ll
SiO2 (0.20 ~ 0.103 ~Al203 + B20~ : -(0.15 0.1) ~Na2O + K2Q7 : (0.15 - 0.1) R2O
expressed as molar ratio of oxides; R being tetramethyl-ammonium, and b) have the characteristic X-ray diffraction pattern set forth below in Table 1:
Table 1 Interplanar Spacing Relative Intensity d ~ ~ ~ I/Io ¦11.50 ~ 0.2 very strong 7.56 ~ 0.1 medium 6.62 ~ 0.1 strong 6.32 ~ 0.1 weak 5.7~ ~ 0.1 ll
4.56 ~ 0.1 medium 1l.33 ~ 0.1 strong 3.76 0.1 very strong 3.58 ~ 0.1 ~trong 3.31 ~ 0.1 weak 3.15 ~ 0.1 medium 2.84 ~ 0.1 very strong 2.68 ~ 0.1 weak 2.48 ~ 0.1 Io = intensity of the strongest line or peak.
3o The intensities of Table 1 are defined as follows:
relative intensity 100 I/Io _ .
very strong 80 100 strong 50 80 medium 20 - 50 weak 0 - 20 ~ ~209~
~ 4 - HOR 81/F 221 The aluminum/boron ratio of the zeolites of the invention is generally Al203 = o 4 _ oOg~
preferably A123 = 0.75 - 0.99 A1203 ~ B203 expressed a.s molar ratio of the oxides.
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 zeolites of the invention are prepared by mixing water wlth silicon, aluminum, boron, sodium, potassium and tetramethylammonium compounds, and heating the mixture in a olosed vesselO
The starting coMpounds are generally used in the fol.lowing ratio, expressed as molar ratio of the oxides:
2~
2 : ( ll ~ 0.025) Al203 : (0.04 ~ 0.025) B203 :
(0.2 o.o8) Na20 : (0.2 ~ 0.15) K20 : (0.1 ~ o.o8) R20:
(25 - 10) H20 preferably in a ratio of SiO2 : (0.035 - 0.01) Al203 : (0.05 0.015) B203:
(0.2 ~ o.o8) Na20 :(0.2 ~ 0.15) K20 : (0.01 ~ o.o8) R20:
(25 - 10) H20;
R being tetramethylammonium.
~ ~ 82~
3o The intensities of Table 1 are defined as follows:
relative intensity 100 I/Io _ .
very strong 80 100 strong 50 80 medium 20 - 50 weak 0 - 20 ~ ~209~
~ 4 - HOR 81/F 221 The aluminum/boron ratio of the zeolites of the invention is generally Al203 = o 4 _ oOg~
preferably A123 = 0.75 - 0.99 A1203 ~ B203 expressed a.s molar ratio of the oxides.
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 zeolites of the invention are prepared by mixing water wlth silicon, aluminum, boron, sodium, potassium and tetramethylammonium compounds, and heating the mixture in a olosed vesselO
The starting coMpounds are generally used in the fol.lowing ratio, expressed as molar ratio of the oxides:
2~
2 : ( ll ~ 0.025) Al203 : (0.04 ~ 0.025) B203 :
(0.2 o.o8) Na20 : (0.2 ~ 0.15) K20 : (0.1 ~ o.o8) R20:
(25 - 10) H20 preferably in a ratio of SiO2 : (0.035 - 0.01) Al203 : (0.05 0.015) B203:
(0.2 ~ o.o8) Na20 :(0.2 ~ 0.15) K20 : (0.01 ~ o.o8) R20:
(25 - 10) H20;
R being tetramethylammonium.
~ ~ 82~
- 5 - HOE 81~F 221 As compounds, there are used for example silica gel, potas-sium silicate, sodium silicate, aluminurn hydroxide, aluminum sulfate 7 boron trioxide, boric acid, borax, sodium hydroxide, sodium sulfate, potassium hydroxide, potassium sulfate, tetramethylammonium hydroxide, tetramethylammonium chloride.
Other silicon, aluminum, boron, potassium, sodium and tetramethylammonium compounds are also suitable for the manufacture of the zeolites according to the invention.
The mixture of the compounds chosen and water is ge-nerally heated for 12 to 300, preferably 24 to 200, hoursat a temperature of from 60 to 150C, peferably 80 to 140C, in a closed vessel.
The crystalline zeolites which are formed are isola-ted in usual manner, for example by filtration, washed and dried. They can be converted according to known methods to catalytically active forms, for example by calcination and/or ion exchange tD.W. Breck, Zeolite Molecular Sieves, 1974).
hfter conversion to the catalytically active form, the zeolites of the invention display a considerably re-duced deposition of coke and a pronouncedly increased aotivity e~p~cially in the oonversion of methanol to hy-drooarbon~, above all C2 C4-olefins, as compared to the boron free offretites according to German Offenle-~ungssohrift No. 1,806 ,154. It is surprising that zeoliteshaving the characteristics according to the invention can be obtained b~ means of the indicated method.
The following Examples illustrate the invention with-out limiting it in its scope. All X-ray diffraction data as indicated were obtained by means of a computer-controlled powder diffractometer D-500 of the Siemens company. The radiation was the K- doublet of copper.
I ~2~9~
- ~ - ^ HOE 81/F 221 Example 1 98 g of 40 weight ~ colloidal silica gel are introduced into a solution of 1.6 g of boron trioxide, 7.2 g of sodium hydroxide, 17.8 g of potassium hydroxide, 4.5 g of sodium aluminate (54 weight % of Al2O3, 41 weight % of Na20) and 4.2 g of tetramethylammonium chloride in 125 g of water.
The suspension so obtained is homogenized by thorough stirring, and heated for 95 hours at 95C in a closed vessel. The product obtained is filtered off 9 washed with water and dried at 120C. According to chemical analysis, the product is composed as folllows, expressed as molar ratio of oxides:
SiO2 : 00112 Al203 : 0.012 B203 : 0.050 Na20 : 0.120 K2O : 0-041 R20 R - tetramethylammonium.
The result of X-ray diffraction is listed in Table 2.
~0 Table _ ____ ~nt,erplanar Spacing Relative Intensity d C ~ J ~/Io ~ ____,_ _ 11.50 88 7.5l~ 20
Other silicon, aluminum, boron, potassium, sodium and tetramethylammonium compounds are also suitable for the manufacture of the zeolites according to the invention.
The mixture of the compounds chosen and water is ge-nerally heated for 12 to 300, preferably 24 to 200, hoursat a temperature of from 60 to 150C, peferably 80 to 140C, in a closed vessel.
The crystalline zeolites which are formed are isola-ted in usual manner, for example by filtration, washed and dried. They can be converted according to known methods to catalytically active forms, for example by calcination and/or ion exchange tD.W. Breck, Zeolite Molecular Sieves, 1974).
hfter conversion to the catalytically active form, the zeolites of the invention display a considerably re-duced deposition of coke and a pronouncedly increased aotivity e~p~cially in the oonversion of methanol to hy-drooarbon~, above all C2 C4-olefins, as compared to the boron free offretites according to German Offenle-~ungssohrift No. 1,806 ,154. It is surprising that zeoliteshaving the characteristics according to the invention can be obtained b~ means of the indicated method.
The following Examples illustrate the invention with-out limiting it in its scope. All X-ray diffraction data as indicated were obtained by means of a computer-controlled powder diffractometer D-500 of the Siemens company. The radiation was the K- doublet of copper.
I ~2~9~
- ~ - ^ HOE 81/F 221 Example 1 98 g of 40 weight ~ colloidal silica gel are introduced into a solution of 1.6 g of boron trioxide, 7.2 g of sodium hydroxide, 17.8 g of potassium hydroxide, 4.5 g of sodium aluminate (54 weight % of Al2O3, 41 weight % of Na20) and 4.2 g of tetramethylammonium chloride in 125 g of water.
The suspension so obtained is homogenized by thorough stirring, and heated for 95 hours at 95C in a closed vessel. The product obtained is filtered off 9 washed with water and dried at 120C. According to chemical analysis, the product is composed as folllows, expressed as molar ratio of oxides:
SiO2 : 00112 Al203 : 0.012 B203 : 0.050 Na20 : 0.120 K2O : 0-041 R20 R - tetramethylammonium.
The result of X-ray diffraction is listed in Table 2.
~0 Table _ ____ ~nt,erplanar Spacing Relative Intensity d C ~ J ~/Io ~ ____,_ _ 11.50 88 7.5l~ 20
6.60 74 6.32 14 5.73 l~.56 29 l~.32 53 3.75 100 3.58 68 3.30 17 3.15 3 2.8l~ 87 2.67 18 L2.48 11 _. _ _ ___ _ 1 ~2~9~
~ 7 - HOE 81/F 221 Example 2 2.3 g of borax, 8.5 g of sodium hydroxide, ~7.8 g of`
potassium hydroxide and 2.3 g of sQdium aluminate (composed as in Example 1) are dissolved in 125 ml of water. 98 g of 40 weight % colloidal silica gel are added with stirring to this solution, and then 14.0 g of 25 weight % aqueous tetramethylammonium hydroxide solution are added to the suspension obtained. After homogenization, the mixture so formed is heated for 72 hours at 105C in a closed vessel.
After work-up as in Example 1 a crystalline product is ob-tained which is composed as follows, expressed as molar ratio of oxides:
SiO2 : 0.107 Al203 : 0.016 B203 : o.o48 Na20 : 0.123 K2O : 0.046 R20 R = tetramethylammonium.
The X r~y diffrackion data correspond to those indicated in Table 1.
Example 3 A s~spension of 3.2 g of boron trioxide, 21.4 g of so-dlum hydroxid~, 35.6 g of potassium hydroxide, 1.4 g of alu-mlnu~n hydrox:lde, 8~4 g of tetramethylammonium chloride, 250 g ~5 of water and 195 g of 40 weight ~ colloidal silica gel is prepared, and heated for 190 hours at 95C in a closed vessel. After work-up as in Example 1, a crystalline product having the ~ollowing composition, expressed as molar ratio of oxides, is obtained:
3o SiO2 : 0-100 Al2O3 : 0.034 B203 : 0.053 Na20 : 0.118 K20 : 0.045 R20 R - tetramethylammonium.
The X ray diffraction data correspond to those indicated in Table 1.
1 ~2~g~
- 8 ~ HOE 81~F 221 Example 4 A suspension of 4.8 g of boron trioxide, 21.-4 g of sodium hydroxide, 35.6 g of potassium hydroxide, 0.7 g of aluminum hydroxide, 8.4 g of tetramethylammonium chloride, 250 g of water and 195 g of 40 weight % colloidal silica gel is prepared and heated for 570 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:
10 SiO2 : 0.058 Al203 : 0.060 B203 : 0.051 Na20 : 0.118 K20 : 0.047 R20 R _ tetramethylammonium.
The product has an offretite structure (X-ray diffraction pattern as in Table 1).
~ 7 - HOE 81/F 221 Example 2 2.3 g of borax, 8.5 g of sodium hydroxide, ~7.8 g of`
potassium hydroxide and 2.3 g of sQdium aluminate (composed as in Example 1) are dissolved in 125 ml of water. 98 g of 40 weight % colloidal silica gel are added with stirring to this solution, and then 14.0 g of 25 weight % aqueous tetramethylammonium hydroxide solution are added to the suspension obtained. After homogenization, the mixture so formed is heated for 72 hours at 105C in a closed vessel.
After work-up as in Example 1 a crystalline product is ob-tained which is composed as follows, expressed as molar ratio of oxides:
SiO2 : 0.107 Al203 : 0.016 B203 : o.o48 Na20 : 0.123 K2O : 0.046 R20 R = tetramethylammonium.
The X r~y diffrackion data correspond to those indicated in Table 1.
Example 3 A s~spension of 3.2 g of boron trioxide, 21.4 g of so-dlum hydroxid~, 35.6 g of potassium hydroxide, 1.4 g of alu-mlnu~n hydrox:lde, 8~4 g of tetramethylammonium chloride, 250 g ~5 of water and 195 g of 40 weight ~ colloidal silica gel is prepared, and heated for 190 hours at 95C in a closed vessel. After work-up as in Example 1, a crystalline product having the ~ollowing composition, expressed as molar ratio of oxides, is obtained:
3o SiO2 : 0-100 Al2O3 : 0.034 B203 : 0.053 Na20 : 0.118 K20 : 0.045 R20 R - tetramethylammonium.
The X ray diffraction data correspond to those indicated in Table 1.
1 ~2~g~
- 8 ~ HOE 81~F 221 Example 4 A suspension of 4.8 g of boron trioxide, 21.-4 g of sodium hydroxide, 35.6 g of potassium hydroxide, 0.7 g of aluminum hydroxide, 8.4 g of tetramethylammonium chloride, 250 g of water and 195 g of 40 weight % colloidal silica gel is prepared and heated for 570 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:
10 SiO2 : 0.058 Al203 : 0.060 B203 : 0.051 Na20 : 0.118 K20 : 0.047 R20 R _ tetramethylammonium.
The product has an offretite structure (X-ray diffraction pattern as in Table 1).
Claims (6)
OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A boro-aluminosilicate having a zeolite structure which (a) has the following composition:
SiO2 : (0.20 ? 0.10) [Al2O3 + B2O3] :
(0.15 ? 0.1) [Na2O + K2O] : (0.15 ? 0.1) R2O
expressed as molar ratios of oxides; R being tetramethyl ammonium, and (b) has the characteristic X-ray diffraction pattern set forth below
SiO2 : (0.20 ? 0.10) [Al2O3 + B2O3] :
(0.15 ? 0.1) [Na2O + K2O] : (0.15 ? 0.1) R2O
expressed as molar ratios of oxides; R being tetramethyl ammonium, and (b) has the characteristic X-ray diffraction pattern set forth below
2. A boro-aluminosilicate as claimed in claim 1 whierein the aluminum/boron ratio is = 0.4 - 0.99, expressed as molar ratio of oxides.
3. A boro-aluminosilicate as claimed in claim 1 wherein the aluminum/boron ratio is = 0.75 - 0.99.
4. A process for the preparation of a boro-aluminosilicate as claimed in claim 1 in which a mixture of silicon, aluminum, boron, sodium, potassium and tetramethylammonium compound and water is prepared, which is composed as follows, expressed as molar ratio of oxides SiO2 : (0.04 ? 0.025) Al2O3 : (0.04 ? 0.025) B2O3 :
(0.2 ? 0.08) Na2O : (0.2 ? 0.15) K2O : (0.1 ? 0.08) R2O (25 ? 10) H2O, R being tetramethylammonium, and the mixture is heated in a closed vessel.
(0.2 ? 0.08) Na2O : (0.2 ? 0.15) K2O : (0.1 ? 0.08) R2O (25 ? 10) H2O, R being tetramethylammonium, and the mixture is heated in a closed vessel.
5. A process as claimed in claim 4 in which the mixture to be heated is composed as follows, expressed as molar ratio of oxides:
SiO2 : (0.035 ? 0.01) Al2O3 : (0.05 ? 0.015) B2O3:
(0.2 ? 0.08) Na2O : (0.2 ? 0.15) K2O : (0.01 ? 0.08) R2O : (25 ? 10) H2O;
R being tetramethylammonium.
SiO2 : (0.035 ? 0.01) Al2O3 : (0.05 ? 0.015) B2O3:
(0.2 ? 0.08) Na2O : (0.2 ? 0.15) K2O : (0.01 ? 0.08) R2O : (25 ? 10) H2O;
R being tetramethylammonium.
6. A process for the preparation of a C2-C4-olefin in which methanol is reacted in the presence of a boro-alumino-silicate as claimed in claim 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3134316.3 | 1981-08-31 | ||
| DE19813134316 DE3134316A1 (en) | 1981-08-31 | 1981-08-31 | BORO ALUMOSILICATES WITH ZEOLITE STRUCTURE AND METHOD FOR THE PRODUCTION THEREOF |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1182098A true CA1182098A (en) | 1985-02-05 |
Family
ID=6140480
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000410405A Expired CA1182098A (en) | 1981-08-31 | 1982-08-30 | Boro-aluminosilicates having zeolite structure, process for their manufacture, and their use |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0073483A3 (en) |
| JP (1) | JPS5841714A (en) |
| AU (1) | AU8782182A (en) |
| CA (1) | CA1182098A (en) |
| DE (1) | DE3134316A1 (en) |
| NZ (1) | NZ201753A (en) |
| ZA (1) | ZA826312B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FI76005C (en) * | 1983-10-17 | 1988-09-09 | Neste Oy | ALUMINUM-BOR-SILICATE CATALYST, FREQUENCY FOR FRAMSTAELLNING AV DENNA OCH ALKYLERINGSPROCESS. |
| AU584127B2 (en) * | 1984-10-25 | 1989-05-18 | Mobil Oil Corporation | Hydrocracking catalyst composition and hydrocracking process using same |
| JPS63174542A (en) * | 1987-01-13 | 1988-07-19 | Canon Inc | Brushless motor |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL238953A (en) * | 1958-05-08 | |||
| DE2830787B2 (en) * | 1978-07-13 | 1981-02-19 | Basf Ag, 6700 Ludwigshafen | Process for the production of nitrogen-containing crystalline metal silicates with a zeolite structure |
-
1981
- 1981-08-31 DE DE19813134316 patent/DE3134316A1/en not_active Withdrawn
-
1982
- 1982-08-26 EP EP82107848A patent/EP0073483A3/en not_active Withdrawn
- 1982-08-30 ZA ZA826312A patent/ZA826312B/en unknown
- 1982-08-30 NZ NZ201753A patent/NZ201753A/en unknown
- 1982-08-30 CA CA000410405A patent/CA1182098A/en not_active Expired
- 1982-08-30 JP JP57149372A patent/JPS5841714A/en active Pending
- 1982-08-30 AU AU87821/82A patent/AU8782182A/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| ZA826312B (en) | 1983-07-27 |
| JPS5841714A (en) | 1983-03-11 |
| AU8782182A (en) | 1983-03-10 |
| NZ201753A (en) | 1985-07-12 |
| EP0073483A3 (en) | 1983-10-26 |
| EP0073483A2 (en) | 1983-03-09 |
| DE3134316A1 (en) | 1983-03-10 |
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