CN109694081B - Method for synthesizing GME and CHA intergrowth zeolite molecular sieve - Google Patents
Method for synthesizing GME and CHA intergrowth zeolite molecular sieve Download PDFInfo
- Publication number
- CN109694081B CN109694081B CN201710982547.XA CN201710982547A CN109694081B CN 109694081 B CN109694081 B CN 109694081B CN 201710982547 A CN201710982547 A CN 201710982547A CN 109694081 B CN109694081 B CN 109694081B
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- gme
- alkali metal
- zeolite molecular
- polyethylene glycol
- 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.)
- Active
Links
Images
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
- C01B39/023—Preparation of physical mixtures or intergrowth products of zeolites chosen from group C01B39/04 or two or more of groups C01B39/14 - C01B39/48
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention relates to aA synthetic method of GME and CHA intergrowth zeolite molecular sieve aims to solve the technical problem of providing a synthetic method of GME and CHA intergrowth zeolite molecular sieve with low impurity content. The invention adopts the method of preparing the silicon dioxide with the SiO 102:(2.7～4.0)Al2O33.5 to 5.0 basic substance A, (0 to 10.0) polyethylene glycol, (0 to 5.0) alkali metal salt S, (80 to 400) H2And the initial molar ratio of O, namely uniformly mixing a silicon source, an aluminum source, an alkaline substance A, polyethylene glycol, an alkali metal salt S and water to obtain a mixture, and then carrying out hydrothermal crystallization on the mixture at the temperature of 95-155 ℃ for 20-200 hours. The method has the advantages that the cheap polyethylene glycol is used as a template agent, and the obtained GME and CHA intergrowth zeolite molecular sieve product has low impurity content.
Description
Technical Field
The invention relates to a method for synthesizing a zeolite molecular sieve, in particular to a method for synthesizing a GME and CHA intergrowth zeolite molecular sieve.
Background
Zeolite molecular sieves are crystalline silicate materials that, due to some particularities in their structure and chemical properties, have found wide application in the fields of catalysis, adsorption and ion exchange. One key factor determining the application performance of molecular sieves is the characteristics of the pore channels or cage cavities of the molecular sieves, which are determined by the intrinsic crystal structures of the molecular sieves, so that the molecular sieves with new crystal structures are obtained, which is of great significance for developing the application of the molecular sieves.
Zeolites are often found in nature, however, for most natural zeolites, they tend to co-grow with other zeolites or other minerals, thereby rendering their use difficult. Gmelinite (Gmelinite) has a three-dimensional channel system with twelve-and eight-membered rings communicating, which theoretically should have a pore volume comparable to that of mordenite (also a zeolite with twelve-membered ring channels, but which do not communicate with each other); natural gmelinite is often intergrown with Chabazite (Chabazite), the latter crystals are inserted into the crystal lattice of gmelinite, thus blocking the twelve-membered ring channels of gmelinite, so that the actual pore volume is smaller than the theoretical pore volume [ Zeolite Molecular Sieves, Willy, new york ] [ J Am Chem Soc,1978, 3097-. The method has the defects that other impurities with a certain content exist in the natural gmelinite molecular sieve, and the crystallinity of the molecular sieve is greatly influenced.
The method for synthesizing the pure-phase GME structure molecular sieve by an artificial synthesis method has been reported. Patent USP 4061717 provides a method for synthesizing pure phase GME zeolite using a high molecular compound of a di-tertiary amine as a template. Literature reference
Microporus and mesoporus Materials,2000,38,143-149, also synthesized pure Gmelinite molecular sieves using DABCO polymers as templating agents, which products had cyclohexane adsorption capacities significantly higher than the corresponding natural products. These methods are costly and environmentally unfriendly due to the templating agent.
So far, no report exists for synthesizing impurity-free GME and CHA intergrown zeolite molecular sieves by using cheap and environment-friendly polyethylene glycol as a template agent.
Disclosure of Invention
The invention aims to solve the technical problem of the synthesis method of the symbiotic zeolite molecular sieve of GME and CHA with low impurity content, which is not related in the prior art.
In order to solve the technical problems, the following technical scheme is adopted:
the invention provides a method for synthesizing a GME and CHA intergrowth zeolite molecular sieve, which comprises the following steps:
a) according to 10SiO2:(2.7～4.0)Al2O33.5 to 5.0 basic substance A, (0 to 10.0) polyethylene glycol, (0 to 5.0) alkali metal salt S, (80 to 400) H2The initial molar ratio of O, namely uniformly mixing a silicon source, an aluminum source, an alkaline substance A, polyethylene glycol, alkali metal salt S and water to obtain a mixture;
b) and (3) performing hydrothermal crystallization on the mixture at 95-155 ℃ for 20-200 hours, and washing and drying the obtained product to obtain the GME and CHA intergrowth zeolite molecular sieve.
In the above technical solution, preferably, the silicon source includes at least one selected from silica sol, solid silica gel, fumed silica, amorphous silica, and silicone grease.
In the above technical solution, preferably, the aluminum source includes at least one selected from the group consisting of sodium metaaluminate, aluminum sulfate, aluminum nitrate, aluminum isopropoxide, and pseudoboehmite.
In the above technical solution, preferably, the basic substance a includes at least one selected from the group consisting of lithium oxide, sodium oxide, potassium oxide, cesium oxide, lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, and cesium hydroxide.
In the above-described embodiment, preferably, the alkali metal salt S includes at least one selected from an oxalate, a sulfate, an acetate, a nitrate, a carbonate, a phosphate, and a halide of an alkali metal element.
In the above technical solution, preferably, the alkali metal element of the alkali metal salt S includes at least one selected from Li, Na, K, Rb, and Cs.
In the above technical solution, preferably, the average molecular weight of the polyethylene glycol is between 200 and 1000. More preferably between 300 and 500.
In the above technical solution, preferably, the initial molar ratio of the mixture is 10SiO2:(3.0～3.5)Al2O33.5 to 5.0 basic substance A, (2.0 to 8.0) polyethylene glycol, (0 to 5.0) alkali metal salt S, (80 to 400) H2And O. More preferably, the initial molar ratio of the mixture is 10SiO2:(3.0～3.5)Al2O33.5 to 5.0 basic substance A, (4.0 to 8.0) polyethylene glycol, (2.0 to 5.0) alkali metal salt S, (80 to 400) H2And O. More preferably, the initial molar ratio of the mixture is 10SiO2:(3.0～3.5)Al2O33.5 to 5.0 basic substance A (6.0 to 8.0) polyethylene glycol (2.0 to 5.0) alkali metal salt S (80 to 400) H2O。
In the above technical scheme, preferably, the mixture is hydrothermally crystallized at 100-140 ℃ for 60-160 hours. Preferably, the hydrothermal crystallization is carried out at 100-120 ℃ for 80-140 hours.
Natural GME (GME-type zeolite) is often intergrown with chabazite (CHA-type zeolite), but its framework contains considerable amounts of calcium and sodium cations mixed with other impurities, making it difficult to apply as a catalyst in acid catalytic systems. Compared with pure phase GME molecular sieve, the artificially synthesized GME and CHA intergrowth molecular sieve selectively reduces the number of twelve-membered ring channels, and more fully utilizes the eight-membered ring channels in the GME molecular sieve and the three-dimensional eight-membered ring channels of the CHA structure, so that the artificially synthesized GME and CHA intergrowth molecular sieve has a better application prospect in shape-selective catalysis of small molecular products, for example, the reaction of preparing low carbon olefin by methanol conversion, and the eight-membered ring channels from different sources of the intergrowth molecular sieve can generate unique catalytic effect compared with a single CHA channel.
The method for synthesizing the GME and CHA intergrowth zeolite molecular sieve provided by the invention has the advantages that under the combined action of polyethylene glycol, alkali metal ions and alkaline substances, the feeding ratio of reaction raw materials is simultaneously controlled, and the GME and CHA intergrowth zeolite molecular sieve is directionally obtained. The method can easily obtain the GME and CHA intergrown zeolite molecular sieve with low impurity content or even no impurity, and the Si/Al ratio of the zeolite has a wider adjustable range.
Drawings
FIG. 1 is an X-ray diffraction (XRD) pattern of a sample obtained in example 1.
The invention is further illustrated by the following examples, which do not limit the scope of the invention. In each of the examples and comparative examples, the product purity was 10-15 degrees theta in terms of the respective X-ray diffraction (XRD) angles 2theta for the product and the standardoThe ratio of the peak areas of the diffraction peaks in the range is shown, and the standard sample (purity is defined as 100%) is the sample obtained in example 1.
Detailed Description
[ example 1 ]
0.85 g of NaF,3.31 g of 30% aqueous sodium hydroxide solution, 18.3 g of 50% PEG 300 (polyethylene glycol having an average molecular weight of about 300) solution, 1.5 g of water, 2.49 g of sodium metaaluminate and 5.86ml of 40% silica sol solution are mixed uniformly, the molar ratio of the mixture obtained is:
10SiO2：3.0Al2O3：4.0NaF:3.5Na2O:6.0PEG300:175H2O
and (3) transferring the mixture into a reaction kettle, crystallizing at 110 ℃ for 120 hours, washing and drying after the reaction is finished, and identifying that the main product is GME and CHA intergrowth zeolite molecular sieve and the impurity is Na-P1 molecular sieve with the content of less than 1% by XRD.
[ example 2 ]
0.85 g of NaF,3.31 g of 30% sodium hydroxide aqueous solution, 11.0 g of water, 2.49 g of sodium metaaluminate and 5.86ml of 40% silica sol solution are mixed uniformly, and the molar ratio of the mixture is as follows:
10SiO2：3.0Al2O3：4.0NaF:3.5Na2O:0PEG300:175H2O
and (3) transferring the mixture into a reaction kettle, crystallizing at 110 ℃ for 120 hours, washing and drying after the reaction is finished, and identifying that the main product is GME and CHA intergrowth zeolite molecular sieve by XRD, the purity of the molecular sieve is 80 percent, and the impurity is a small amount of Na-P1 molecular sieve.
[ example 3 ]
0.85 g of NaF,4.73 g of 30% aqueous sodium hydroxide solution, 18.3 g of 50% PEG 300 (polyethylene glycol having an average molecular weight of about 300) solution, 1.5 g of water, 2.49 g of sodium metaaluminate and 5.86ml of 40% silica sol solution are mixed uniformly, the molar ratio of the mixture is
10SiO2：3.0Al2O3：4.0NaF:5.0Na2O:6.0PEG300:175H2O
And (3) transferring the mixture into a reaction kettle, crystallizing at 110 ℃ for 120 hours, washing and drying after the reaction is finished, and identifying that the main product is GME and CHA intergrowth zeolite molecular sieve by XRD, the purity of the molecular sieve is 98 percent, and the impurity is a small amount of Na-P1 molecular sieve.
[ example 4 ]
3.31 g of 30% aqueous sodium hydroxide solution, 18.3 g of 50% PEG 300 (polyethylene glycol having an average molecular weight of about 300) solution, 1.5 g of water, 2.49 g of sodium metaaluminate and 5.86ml of 40% silica sol solution are mixed uniformly, the molar ratio of the mixture obtained is:
10SiO2：3.0Al2O3：0NaF:3.5Na2O:6.0PEG300:175H2O
and (3) transferring the mixture into a reaction kettle, crystallizing at 110 ℃ for 120 hours, washing and drying after the reaction is finished, and identifying that the main product is GME and CHA intergrowth zeolite molecular sieve by XRD, wherein the purity of the molecular sieve is 86 percent, and the impurity is a small amount of Na-P1 molecular sieve.
[ example 5 ]
0.85 g of NaF,3.31 g of a 30% aqueous sodium hydroxide solution, 18.3 g of a 50% PEG 300 (polyethylene glycol having an average molecular weight of about 300) solution, 1.5 g of water, 3.32 g of sodium metaaluminate and 5.86ml of a 40% silica sol solution are mixed uniformly, the molar ratio of the mixture obtained is:
10SiO2：4.0Al2O3：4.0NaF:3.5Na2O:6.0PEG300:175H2O
and (3) transferring the mixture into a reaction kettle, crystallizing at 110 ℃ for 120 hours, washing and drying after the reaction is finished, and identifying that the main product is GME and CHA intergrowth zeolite molecular sieve by XRD, the purity of the molecular sieve is 80 percent, and the impurity is a small amount of Na-P1 molecular sieve.
[ example 6 ]
0.85 g of NaF,3.31 g of 30% aqueous sodium hydroxide solution, 18.3 g of 50% PEG 300 (polyethylene glycol having an average molecular weight of about 300) solution, 1.5 g of water, 2.49 g of sodium metaaluminate and 5.86ml of 40% silica sol solution are mixed uniformly, the molar ratio of the mixture obtained is:
10SiO2：3.0Al2O3：4.0NaF:3.5Na2O:6.0PEG300:175H2O
and transferring the mixture into a reaction kettle, crystallizing at 100 ℃ for 144 hours, washing and drying after the reaction is finished, and identifying that the main product is GME and CHA intergrowth zeolite molecular sieve by XRD, the purity of the molecular sieve is 95 percent, and the impurity is a small amount of Na-P1 molecular sieve.
[ example 7 ]
0.85 g of NaF,3.31 g of 30% aqueous sodium hydroxide solution, 18.3 g of 50% PEG 300 (polyethylene glycol having an average molecular weight of about 300) solution, 1.5 g of water, 2.49 g of sodium metaaluminate and 5.86ml of 40% silica sol solution are mixed uniformly, the molar ratio of the mixture obtained is:
10SiO2：3.0Al2O3：4.0NaF:3.5Na2O:6.0PEG300:175H2O
and (3) transferring the mixture into a reaction kettle, crystallizing for 90 hours at 150 ℃, washing and drying after the reaction is finished, and identifying that the main product is GME and CHA intergrowth zeolite molecular sieve by XRD, wherein the purity of the molecular sieve is 80 percent, and the impurity is a small amount of Na-P1 molecular sieve.
[ example 8 ]
0.85 g of NaF,4.63 g of a 30% aqueous potassium hydroxide solution, 18.3 g of a 50% PEG 300 (polyethylene glycol having an average molecular weight of about 300) solution, 1.5 g of water, 2.49 g of sodium metaaluminate and 5.86ml of a 40% silica sol solution are mixed uniformly, the molar ratio of the mixture obtained is:
10SiO2：3.0Al2O3：4.0NaF:3.5K2O:6.0PEG300:175H2O
and (3) transferring the mixture into a reaction kettle, crystallizing at 110 ℃ for 120 hours, washing and drying after the reaction is finished, and identifying that the main product is GME and CHA intergrowth zeolite molecular sieve by XRD, wherein the purity of the molecular sieve is 90 percent, and the impurity is a small amount of Na-P1 molecular sieve.
[ example 9 ]
1.72 g of NaNO33.31 g of 30% aqueous sodium hydroxide solution, 18.3 g of 50% PEG 300 (polyethylene glycol having an average molecular weight of about 300) solution, 1.5 g of water, 2.49 g of sodium metaaluminate and 5.86ml of 40% silica sol solution are mixed uniformly, the molar ratio of the mixture obtained is:
10SiO2：3.0Al2O3：4.0NaNO3:3.5Na2O:6.0PEG300:175H2O
and (3) transferring the mixture into a reaction kettle, crystallizing at 110 ℃ for 120 hours, washing and drying after the reaction is finished, and identifying that the main product is GME and CHA intergrowth zeolite molecular sieve by XRD, wherein the purity of the molecular sieve is 88 percent, and the impurity is a small amount of Na-P1 molecular sieve. .
[ example 10 ]
0.85 g of NaF,3.31 g of a 30% aqueous sodium hydroxide solution, 18.3 g of a 50% PEG 300 (polyethylene glycol having an average molecular weight of about 300) solution, 1.5 g of water, 6.27 g of aluminum isopropoxide and 5.86ml of a 40% silica sol solution are mixed uniformly, the molar ratio of the mixture obtained is:
10SiO2：3.0Al2O3：4.0NaF:3.5Na2O:6.0PEG300:175H2O
and (3) transferring the mixture into a reaction kettle, crystallizing at 110 ℃ for 120 hours, washing and drying after the reaction is finished, and identifying that the main product is GME and CHA intergrowth zeolite molecular sieve by XRD, the purity of the molecular sieve is 92 percent, and the impurity is a small amount of Na-P1 molecular sieve.
[ example 11 ]
0.85 g of NaF,3.31 g of 30% aqueous sodium hydroxide solution, 18.3 g of 50% PEG 300 (polyethylene glycol with the average molecular weight of about 300) solution, 1.5 g of water, 2.49 g of sodium metaaluminate and 3.39 g of white carbon black with the silicon dioxide content of 90% are uniformly mixed, and the molar ratio of the obtained mixture is as follows:
10SiO2：3.0Al2O3：4.0NaF:3.5Na2O:6.0PEG300:175H2O
and (3) transferring the mixture into a reaction kettle, crystallizing at 110 ℃ for 120 hours, washing and drying after the reaction is finished, and identifying that the main product is GME and CHA intergrowth zeolite molecular sieve by XRD, the purity of the molecular sieve is 85 percent, and the impurity is a small amount of Na-P1 molecular sieve.
[ example 12 ]
0.85 g of NaF,3.31 g of a 30% aqueous sodium hydroxide solution, 20.33 g of a 50% PEG1000 (polyethylene glycol having an average molecular weight of about 1000) solution, 1.5 g of water, 2.49 g of sodium metaaluminate and 5.86ml of a 40% silica sol solution are mixed uniformly, the molar ratio of the mixture obtained is:
10SiO2：3.0Al2O3：4.0NaF:3.5Na2O:2.0PEG1000:175H2O
and (3) transferring the mixture into a reaction kettle, crystallizing at 110 ℃ for 120 hours, washing and drying after the reaction is finished, and identifying that the main product is GME and CHA intergrowth zeolite molecular sieve by XRD, the purity of the molecular sieve is 80 percent, and the impurity is a small amount of Na-P1 molecular sieve.
Comparative example 1
This comparative example is without the addition of alkaline substance with respect to example 1.
0.85 g of NaF, 18.3 g of a 50% PEG 300 (polyethylene glycol having an average molecular weight of about 300) solution, 3.5 g of water, 2.49 g of sodium metaaluminate and 5.86ml of a 40% silica sol solution are mixed uniformly, the molar ratio of the mixture obtained is:
10SiO2：3.0Al2O3：4.0NaF:0Na2O:6.0PEG300:175H2O
and (3) transferring the mixture into a reaction kettle, crystallizing at 110 ℃ for 120 hours, washing and drying after the reaction is finished, and identifying that the GME and CHA intergrowth zeolite molecular sieve is basically not generated by XRD.
Claims (9)
1. A method of synthesizing GME and CHA intergrown zeolite molecular sieves comprising the steps of:
a) according to 10SiO2:（2.7~4.0）Al2O33.5 to 5.0 basic substance A, (0 to 10.0) polyethylene glycol, (0 to 5.0) alkali metal salt S, (80 to 400) H2The initial molar ratio of O, namely uniformly mixing a silicon source, an aluminum source, an alkaline substance A, polyethylene glycol, alkali metal salt S and water to obtain a mixture;
b) performing hydrothermal crystallization on the mixture at 95-155 ℃ for 20-200 hours, and washing and drying the obtained product to obtain a GME and CHA intergrowth zeolite molecular sieve;
wherein in step a), the amount of polyethylene glycol and the alkali metal salt S is different from 0.
2. The method of claim 1, wherein the source of silicon comprises at least one selected from the group consisting of silica sol, solid silica gel, fumed silica, amorphous silica, and organosilicates.
3. The method of claim 1, wherein the source of aluminum comprises at least one member selected from the group consisting of sodium metaaluminate, aluminum sulfate, aluminum nitrate, aluminum isopropoxide, and pseudoboehmite.
4. The method of synthesizing a GME and CHA intergrown zeolite molecular sieve of claim 1, wherein the basic species a comprises at least one selected from the group consisting of lithium oxide, sodium oxide, potassium oxide, cesium oxide, lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, and cesium hydroxide.
5. The method of synthesizing a GME and CHA intergrown zeolite molecular sieve of claim 1, wherein the alkali metal salt S comprises at least one selected from the group consisting of oxalates, sulfates, acetates, nitrates, carbonates, phosphates, and halides of alkali metal elements.
6. The method of claim 1, wherein the alkali metal element of the alkali metal salt S comprises at least one selected from Li, Na, K, Rb, Cs.
7. The method of claim 1, wherein the initial molar ratio of the mixture is 10SiO2:（3.0~3.5）Al2O33.5 to 5.0 basic substance A, (2.0 to 8.0) polyethylene glycol, (0 to 5.0) alkali metal salt S, (80 to 400) H2O，
Wherein the alkali metal salt S is used in an amount other than 0.
8. The method for synthesizing the GME and CHA intergrown zeolite molecular sieve according to claim 1, wherein the mixture is hydrothermally crystallized at 100 to 140 ℃ for 60 to 160 hours.
9. The method of synthesizing a GME and CHA intergrown zeolite molecular sieve of claim 1, wherein the polyethylene glycol has an average molecular weight between 200 and 1000.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710982547.XA CN109694081B (en) | 2017-10-20 | 2017-10-20 | Method for synthesizing GME and CHA intergrowth zeolite molecular sieve |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710982547.XA CN109694081B (en) | 2017-10-20 | 2017-10-20 | Method for synthesizing GME and CHA intergrowth zeolite molecular sieve |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109694081A CN109694081A (en) | 2019-04-30 |
| CN109694081B true CN109694081B (en) | 2020-10-30 |
Family
ID=66226376
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710982547.XA Active CN109694081B (en) | 2017-10-20 | 2017-10-20 | Method for synthesizing GME and CHA intergrowth zeolite molecular sieve |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109694081B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113233474B (en) * | 2021-05-31 | 2022-10-28 | 吉林大学 | Preparation method of GME molecular sieve with high silica-alumina ratio |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101003379A (en) * | 2006-01-18 | 2007-07-25 | 中国科学院大连化学物理研究所 | ZSM-35/MCM-22 composite molecular sieve, and preparation method |
| CN101186311A (en) * | 2007-11-22 | 2008-05-28 | 复旦大学 | Y/MCM-48 composite molecular screen and preparation method thereof |
| CN102039200A (en) * | 2009-10-22 | 2011-05-04 | 中国石油天然气股份有限公司 | Y-beta/MCM-41 double microporous-mesoporous composite molecular sieve and preparation method thereof |
| CN102992339A (en) * | 2011-09-15 | 2013-03-27 | 华东理工大学 | Solvent volatilization self-assembly method used for preparing multistage-channel SAPO-34 and SAPO-18 molecular sieves |
| CN104445264A (en) * | 2013-09-24 | 2015-03-25 | 中国石油化工股份有限公司 | Method for synthesizing GME zeolite molecular sieve |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10850265B2 (en) * | 2014-06-18 | 2020-12-01 | Basf Corporation | Molecular sieve catalyst compositions, catalytic composites, systems, and methods |
-
2017
- 2017-10-20 CN CN201710982547.XA patent/CN109694081B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101003379A (en) * | 2006-01-18 | 2007-07-25 | 中国科学院大连化学物理研究所 | ZSM-35/MCM-22 composite molecular sieve, and preparation method |
| CN101186311A (en) * | 2007-11-22 | 2008-05-28 | 复旦大学 | Y/MCM-48 composite molecular screen and preparation method thereof |
| CN102039200A (en) * | 2009-10-22 | 2011-05-04 | 中国石油天然气股份有限公司 | Y-beta/MCM-41 double microporous-mesoporous composite molecular sieve and preparation method thereof |
| CN102992339A (en) * | 2011-09-15 | 2013-03-27 | 华东理工大学 | Solvent volatilization self-assembly method used for preparing multistage-channel SAPO-34 and SAPO-18 molecular sieves |
| CN104445264A (en) * | 2013-09-24 | 2015-03-25 | 中国石油化工股份有限公司 | Method for synthesizing GME zeolite molecular sieve |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109694081A (en) | 2019-04-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US8840864B2 (en) | Method of preparing ZSM-5 zeolite using nanocrystalline ZSM-5 seeds | |
| EP3165280B1 (en) | Scm-11 molecular sieve, a process for producing same and use thereof | |
| CN102256899A (en) | Chabazite-type zeolite and process for producing the same | |
| CN111099612B (en) | Molecular sieve SCM-23, its synthesis method and use | |
| US20130052126A1 (en) | Monolithic zeolite structures with and without hierarchical pore structures and methods for producing the same | |
| CN107848820B (en) | Process for preparing zeolite SSZ-98 | |
| CN1871328A (en) | Crystalline aluminosilicates:UZM-13, UZM-17, UZM-19 and UZM-25 | |
| CN111484037A (en) | Method for synthesizing SSZ-13 molecular sieves with different silicon-aluminum ratios by crystal transformation of Y molecular sieve | |
| CN101421191B (en) | Perturbed synthesis of materials | |
| CN106830004A (en) | SCM-9 molecular sieves and preparation method thereof | |
| CN109592696B (en) | Preparation method of nano-sheet clinoptilolite molecular sieve | |
| CN109694081B (en) | Method for synthesizing GME and CHA intergrowth zeolite molecular sieve | |
| CN107954447B (en) | Nepheline structure molecular sieve with high silica-alumina ratio and preparation method thereof | |
| CN111330635B (en) | Preparation method of SSZ-13 molecular sieve catalyst | |
| CN104445264A (en) | Method for synthesizing GME zeolite molecular sieve | |
| CN104936898B (en) | EUO NES NON zeolite UZM 43 | |
| CN103043681A (en) | Preparation method of nano layered ZSM (Zeolite Molecular Sieve)-5 zeolite molecular sieve | |
| JP2001058816A (en) | NaY TYPE ZEOLITE | |
| CN104098108B (en) | ZSM-5 molecular sieve with rectangular morphology and preparation method thereof | |
| CN104445270A (en) | Method for synthesizing SAPO-34 molecular sieve with high protonic acid content | |
| CN103145145A (en) | Method for synthesizing SAPO-34 molecular sieve by taking A type zeolite as silicon source | |
| CN109694090B (en) | SCM-13 molecular sieve and preparation method thereof | |
| CN112125318B (en) | Method for preparing MFI zeolite based on imidazolyl ionic liquid | |
| KR102197599B1 (en) | Silicoaluminophosphate molecular sieves, manufacturing method, and selective separation of CO2 using thereof | |
| JP4470003B2 (en) | High silica mordenite and its synthesis method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |