CA1142905A - Preparation of a boro-alumino-silicate zeolite of the zsm-5 structural type - Google Patents
Preparation of a boro-alumino-silicate zeolite of the zsm-5 structural typeInfo
- Publication number
- CA1142905A CA1142905A CA000346041A CA346041A CA1142905A CA 1142905 A CA1142905 A CA 1142905A CA 000346041 A CA000346041 A CA 000346041A CA 346041 A CA346041 A CA 346041A CA 1142905 A CA1142905 A CA 1142905A
- Authority
- CA
- Canada
- Prior art keywords
- zsm
- alumino
- boro
- structural type
- preparation
- 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
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
-
- 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
- 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
-
- 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
- C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C01B39/38—Type ZSM-5
- C01B39/40—Type ZSM-5 using at least one organic template directing agent
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/42—Addition of matrix or binder particles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE:
The present invention is directed to a process for the preparation of a boro-alumino-silicate zeolite of the ZSM-5 structural type from SiO2, an alkali and an oxide of a trivalent metal, by hydrothermal crystallization in the presence of an amine, wherein finely ground low-alkali borosilicate glasses are used as the starting material. The crystallization is preferably carried out in the presence of hexamethylenediamine.
The present invention is directed to a process for the preparation of a boro-alumino-silicate zeolite of the ZSM-5 structural type from SiO2, an alkali and an oxide of a trivalent metal, by hydrothermal crystallization in the presence of an amine, wherein finely ground low-alkali borosilicate glasses are used as the starting material. The crystallization is preferably carried out in the presence of hexamethylenediamine.
Description
~z~s The preparation of zeolites of the ZSM-5 type from reaction mixtures which contain SiO2, ~12O3 and an alkali, under hydrothermal conditions in the presence of an amine, has been disclosed. SiO2-containing starting materials are in particular water-glass, various silicas and silicic acid sols.
Because of the low space-time yield, these processes are expensive, since the solids content o~
the reaction mixtures is only about 10% by weight.
The crystallizatio~ requires about 5 days.
We have ~ound that in the preparation of a boro-alumino-silicate zeolite of the ZSM-5 structural type from SiO2, an alkali and an oxide of a trivalent metal, by hydrothermal crystallization in the presence of an amine, a substantial simplification of the process and improvement of the space-time yield is achieved if finely ground low-alkali borosilicate glasses are used as the starting material~
~dvantageously, the process according to the inv~nkion ia carried out in the presence of a diamine, especially hexamethylenediamine.
It is surprising~tha-t reaction mixtures with solids contents of more than 25% by weight can be crystallized if the reackion is carried out in the presence of a diamine and a finely ground glass powder is used as the starting material. Compared to pyrogenic silica, silicic acid sols or waterglass, glass is regarded as a relatively inert material. It was surprising thak glass could be con-ll~Z~1~5 .
Because of the low space-time yield, these processes are expensive, since the solids content o~
the reaction mixtures is only about 10% by weight.
The crystallizatio~ requires about 5 days.
We have ~ound that in the preparation of a boro-alumino-silicate zeolite of the ZSM-5 structural type from SiO2, an alkali and an oxide of a trivalent metal, by hydrothermal crystallization in the presence of an amine, a substantial simplification of the process and improvement of the space-time yield is achieved if finely ground low-alkali borosilicate glasses are used as the starting material~
~dvantageously, the process according to the inv~nkion ia carried out in the presence of a diamine, especially hexamethylenediamine.
It is surprising~tha-t reaction mixtures with solids contents of more than 25% by weight can be crystallized if the reackion is carried out in the presence of a diamine and a finely ground glass powder is used as the starting material. Compared to pyrogenic silica, silicic acid sols or waterglass, glass is regarded as a relatively inert material. It was surprising thak glass could be con-ll~Z~1~5 .
-2- o.z. 0050/033722 verted at all using diamines, which are only weakly basic, and that using this method the space-time yield ~uldevenbe increased substantially The process according to the invention can be : carried out by mixing ~inely ground glass powder with an aqueous solution o~ an organic diamine, the solids con-. . tent ad~antageously being more than 25% ~y weight, and then heating the mixture for from 1 to 10 days at from 100 to 200C under its autogenous pressure, whilst stirring or shakin~, until crystallization occurs.
The.crystals are separated from the mother liquor, washed ~nd dried Preferably, the process is carried out at from 140 to 160C 9 with a reaction time of from 2 to 6 days.
The starting materials used are amines, advan-tageously diamines, for example hexamethylenediamine, in aqueous solution. Various t~pes oX glass may be used. Finely ground low-alkali borosilicate glasses are particularly suitable. In that case, zeolites which are o~ the boro-alumino-3ilicate type and which exhibit the crystal structure of the convention~l ZSM-5 aluminosilicate zeolite are obtained.
The zeolites prepared according to the inventicn contain SiO2 and A1203~ and where appropriate B203, in various ratios depending on the composition of the glass used; for example, they may contain SiO2 and A1203 in a molar ratio or f rom 30:1 to 200:1, ~nd S102 and 323 in a molar ratio of from 3:1 to 2~115 - ~ - o.Z~ C050/033722 200:1, Dependin~ on the type of glass used7 other com-ponents may also be present in the zeolite. Sub-stantial amounts of the amine used may also be accommo-dated in the inter-crystalline pores, This amine can be removed from the pores by, ~or example, combustion, whereby catalytically active materials are produced, The zeolite may also have an alkali content which varies depending on the composition of the glass used. The alkali metal ions can be replaced by protons or other cations with the aid of conventional ion exchange techniques, The zeolites prepared according to the invention can be used as catalysts for the con~ersion of methanol and/or dimethyl ether or ethanol or diethyl ether into aromatic hydrocarbons and/or olefins, The zeolites can furthermore be used in alkylation re-actions and isomerization reactions, The Example which follows illustrates the process according to the invention, EXAMPLE
20 . 45 g of a finely ground commercial borosilicate glass which contains about 80~ by weight of SiO2, 12.9%
by weight of B203 , 2.27% by weight of A1203 and 3,25% by weight of Na20 are introduced into 118 g of a 50 per cent strength aqueous hexamethylene-diamine solution and the mixture is heated for 5 days at 150C under autogenous pressure, whilst being stirred, The crystalline product is filtered off, washed and dried at 100C~ According to X-ray diffraction 96~5 _ 4 _ O.Z. C050/oi3722 analysis, it consists o~ well-crystallized material of the structural type of the co~ventional ZSM-5 alumino-silicate zeolite.
Chemical analysis gives the following results:
5,05/0 of B203; 2.420,6 of A1203; 78.70,6 of SiO; 1,69% of Na~0; remainder hexamethylenediamine/H20, If, under the same reaction conditions, 60 g of the same finely ground glass powder are employed in 118 g of hexamethylenediamine solution9 a 100% crystallized end product is again obtained.
The.crystals are separated from the mother liquor, washed ~nd dried Preferably, the process is carried out at from 140 to 160C 9 with a reaction time of from 2 to 6 days.
The starting materials used are amines, advan-tageously diamines, for example hexamethylenediamine, in aqueous solution. Various t~pes oX glass may be used. Finely ground low-alkali borosilicate glasses are particularly suitable. In that case, zeolites which are o~ the boro-alumino-3ilicate type and which exhibit the crystal structure of the convention~l ZSM-5 aluminosilicate zeolite are obtained.
The zeolites prepared according to the inventicn contain SiO2 and A1203~ and where appropriate B203, in various ratios depending on the composition of the glass used; for example, they may contain SiO2 and A1203 in a molar ratio or f rom 30:1 to 200:1, ~nd S102 and 323 in a molar ratio of from 3:1 to 2~115 - ~ - o.Z~ C050/033722 200:1, Dependin~ on the type of glass used7 other com-ponents may also be present in the zeolite. Sub-stantial amounts of the amine used may also be accommo-dated in the inter-crystalline pores, This amine can be removed from the pores by, ~or example, combustion, whereby catalytically active materials are produced, The zeolite may also have an alkali content which varies depending on the composition of the glass used. The alkali metal ions can be replaced by protons or other cations with the aid of conventional ion exchange techniques, The zeolites prepared according to the invention can be used as catalysts for the con~ersion of methanol and/or dimethyl ether or ethanol or diethyl ether into aromatic hydrocarbons and/or olefins, The zeolites can furthermore be used in alkylation re-actions and isomerization reactions, The Example which follows illustrates the process according to the invention, EXAMPLE
20 . 45 g of a finely ground commercial borosilicate glass which contains about 80~ by weight of SiO2, 12.9%
by weight of B203 , 2.27% by weight of A1203 and 3,25% by weight of Na20 are introduced into 118 g of a 50 per cent strength aqueous hexamethylene-diamine solution and the mixture is heated for 5 days at 150C under autogenous pressure, whilst being stirred, The crystalline product is filtered off, washed and dried at 100C~ According to X-ray diffraction 96~5 _ 4 _ O.Z. C050/oi3722 analysis, it consists o~ well-crystallized material of the structural type of the co~ventional ZSM-5 alumino-silicate zeolite.
Chemical analysis gives the following results:
5,05/0 of B203; 2.420,6 of A1203; 78.70,6 of SiO; 1,69% of Na~0; remainder hexamethylenediamine/H20, If, under the same reaction conditions, 60 g of the same finely ground glass powder are employed in 118 g of hexamethylenediamine solution9 a 100% crystallized end product is again obtained.
Claims (6)
1. Boro-alumino-silicate zeolite of the ZSM-5 structural type.
2. A process for the preparation of a boro-alumino-silicate zeolite of the ZSM-5 structural type from SiO2, an alkali and an oxide of a trivalent metal, by hydro-thermal crystallization in the presence of an amine, wherein finely ground low-alkali borosilicate glasses are used as the starting material.
3. A process as claimed in claim 2, wherein the crystallization is carried out in the presence of a diamine.
4. A process as claimed in claim 3, wherein hexamethylenediamine is used.
5. A process as claimed in claim 2, 3 or 4, wherein the solids content in the reaction mixture is greater than 25% by weight.
6. Method for conversion of lower alcohols and/or dialkyl ethers to hydrocarbons which contain aromatics and/or to olefins, wherein use is made of the zeolites as prepared by a process as claimed in claim 2.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19792909929 DE2909929A1 (en) | 1979-03-14 | 1979-03-14 | METHOD FOR PRODUCING A ZSM-5 STRUCTURAL TYPE |
| DEP2909929.4 | 1979-03-14 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1142905A true CA1142905A (en) | 1983-03-15 |
Family
ID=6065312
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000346041A Expired CA1142905A (en) | 1979-03-14 | 1980-02-20 | Preparation of a boro-alumino-silicate zeolite of the zsm-5 structural type |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0017027B1 (en) |
| AT (1) | ATE3021T1 (en) |
| BR (1) | BR8001493A (en) |
| CA (1) | CA1142905A (en) |
| DE (2) | DE2909929A1 (en) |
| ES (1) | ES489504A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4471148A (en) * | 1982-01-28 | 1984-09-11 | Hoechst Aktiengesellschaft | Process for making catalytically active aluminosilicates and their uses |
| US4708857A (en) * | 1983-07-26 | 1987-11-24 | Centre De Recherche Industrielle Du Quebec | Process for preparing a crystalline iron-borosilicate |
| US5409682A (en) * | 1991-09-21 | 1995-04-25 | Basf Aktiengesellschaft | Preparation of essentially alkali-free borosilicate crystals having a zeolite structure |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IN155637B (en) * | 1980-04-11 | 1985-02-16 | Imp Chemical Ind Plc Formerly | |
| DE3134317A1 (en) * | 1981-08-31 | 1983-03-10 | Hoechst Ag, 6000 Frankfurt | BORO ALUMOSILICATES WITH ZEOLITE STRUCTURE AND METHOD FOR THE PRODUCTION THEREOF |
| DE3136984A1 (en) * | 1981-09-17 | 1983-03-31 | Basf Ag, 6700 Ludwigshafen | METHOD FOR PRODUCING OLEFINES FROM METHANOL / DIMETHYLETHER |
| DE3145712A1 (en) * | 1981-11-19 | 1983-05-26 | Basf Ag, 6700 Ludwigshafen | METHOD FOR PRODUCING OLEFINS BY REALIZING METHANOL AND / OR DIMETHYL ETHER |
| IL68265A (en) * | 1983-03-30 | 1987-03-31 | Yeda Res & Dev | Crystallized glass preparation and use in catalytic alkylation |
| AU572518B2 (en) * | 1983-06-30 | 1988-05-12 | Mobil Oil Corp. | Low sodium porous crystalline zeolite |
| FI76005C (en) * | 1983-10-17 | 1988-09-09 | Neste Oy | ALUMINUM-BOR-SILICATE CATALYST, FREQUENCY FOR FRAMSTAELLNING AV DENNA OCH ALKYLERINGSPROCESS. |
| IT1177164B (en) * | 1984-11-13 | 1987-08-26 | Anic Spa | PROCEDURE FOR THE TRANSFORMATION OF METHANOL AND / OR LOWER ALCOHOLS INTO LIGHT OLEFINS |
| AU586244B2 (en) * | 1985-05-08 | 1989-07-06 | Mobil Oil Corporation | A method for producing zeolite-containing particles |
| US5820876A (en) | 1986-08-28 | 1998-10-13 | Lts Lohmann Therapie-Systeme Gmbh & Co. Kg | Transdermal therapeutic system |
| USRE37934E1 (en) | 1986-08-28 | 2002-12-10 | Lts Lohmann Therapie-Systeme Ag | Transdermal therapeutic system |
| US6126963A (en) | 1986-08-28 | 2000-10-03 | Lts Lohmann Therapie-Systeme Gmbh & Co. Kg | Transdermal therapeutic system, its use and production process |
| DE3812592A1 (en) * | 1988-04-15 | 1989-10-26 | Deggendorfer Werft Eisenbau | METHOD FOR PRODUCING ZEOLITES |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE462147C (en) * | 1926-02-17 | 1928-07-05 | Arthur Rosenheim Dr | Manufacture of base-exchanging substances |
| DE463719C (en) * | 1926-09-02 | 1928-08-02 | Arthur Rosenheim Dr | Process for the production of base-exchanging substances |
| DE2450708A1 (en) * | 1973-10-29 | 1975-04-30 | Grace W R & Co | Zeolite A or sodalite prodn. by crystallisation from soln. - contg. added boron oxide source, increasing crystallisation rate |
| US4049573A (en) * | 1976-02-05 | 1977-09-20 | Mobil Oil Corporation | Zeolite catalyst containing oxide of boron or magnesium |
| IN146957B (en) * | 1976-10-18 | 1979-10-20 | Standard Oil Co | |
| US4139600A (en) * | 1977-04-22 | 1979-02-13 | Mobil Oil Corporation | Synthesis of zeolite ZSM-5 |
| US4108881A (en) * | 1977-08-01 | 1978-08-22 | Mobil Oil Corporation | Synthesis of zeolite ZSM-11 |
| 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 |
| DE2831334A1 (en) * | 1978-07-17 | 1980-02-07 | Basf Ag | METHOD FOR PRODUCING CRYSTALLINE ALUMINOSILICATE ZOLITHES |
-
1979
- 1979-03-14 DE DE19792909929 patent/DE2909929A1/en not_active Withdrawn
-
1980
- 1980-02-20 CA CA000346041A patent/CA1142905A/en not_active Expired
- 1980-03-12 DE DE8080101255T patent/DE3062679D1/en not_active Expired
- 1980-03-12 EP EP80101255A patent/EP0017027B1/en not_active Expired
- 1980-03-12 AT AT80101255T patent/ATE3021T1/en not_active IP Right Cessation
- 1980-03-13 BR BR8001493A patent/BR8001493A/en unknown
- 1980-03-13 ES ES489504A patent/ES489504A1/en not_active Expired
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4471148A (en) * | 1982-01-28 | 1984-09-11 | Hoechst Aktiengesellschaft | Process for making catalytically active aluminosilicates and their uses |
| US4708857A (en) * | 1983-07-26 | 1987-11-24 | Centre De Recherche Industrielle Du Quebec | Process for preparing a crystalline iron-borosilicate |
| US5409682A (en) * | 1991-09-21 | 1995-04-25 | Basf Aktiengesellschaft | Preparation of essentially alkali-free borosilicate crystals having a zeolite structure |
Also Published As
| Publication number | Publication date |
|---|---|
| ATE3021T1 (en) | 1983-04-15 |
| BR8001493A (en) | 1980-11-11 |
| EP0017027B1 (en) | 1983-04-13 |
| EP0017027A1 (en) | 1980-10-15 |
| ES489504A1 (en) | 1980-09-16 |
| DE2909929A1 (en) | 1980-09-25 |
| DE3062679D1 (en) | 1983-05-19 |
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Legal Events
| Date | Code | Title | Description |
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| MKEX | Expiry |