CN112062137A - Preparation method of MAZ zeolite molecular sieve - Google Patents
Preparation method of MAZ zeolite molecular sieve Download PDFInfo
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- CN112062137A CN112062137A CN202010992614.8A CN202010992614A CN112062137A CN 112062137 A CN112062137 A CN 112062137A CN 202010992614 A CN202010992614 A CN 202010992614A CN 112062137 A CN112062137 A CN 112062137A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
- C01B39/48—Other types characterised by their X-ray diffraction pattern and their defined composition using at least one organic template directing agent
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/04—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 using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
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- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
- C01P2004/16—Nanowires or nanorods, i.e. solid nanofibres with two nearly equal dimensions between 1-100 nanometer
Abstract
The invention discloses a preparation method of an MAZ zeolite molecular sieve, which comprises the steps of uniformly mixing an aluminum source, an alkali source and deionized water, and adding a silicon source under stirring; continuing stirring until the solution is uniform to form silicon-aluminum gel, adding a certain amount of choline chloride into the silicon-aluminum gel, and stirring; and then placing the mixture into a reaction kettle, wherein the crystallization temperature is 100-180 ℃, the crystallization time is 0.5-2.5 days, and performing suction filtration, washing and drying on a product to obtain the MAZ zeolite molecular sieve raw powder. The invention takes choline chloride as a template agent to synthesize the rodlike MAZ zeolite molecular sieve under the condition of hydrothermal synthesis, and has the advantages of environmental friendliness and low cost.
Description
Technical Field
The invention belongs to a preparation method of a molecular sieve, and particularly relates to a green template agent for preparing an MAZ zeolite molecular sieve.
Background
The zeolite molecular sieve is a kind of special pore canal with skeleton structureA microporous crystalline material of structure. In addition, zeolite molecular sieves are widely used in important fields such as adsorption and catalysis due to their characteristics of high specific surface area, large pore volume, adjustable acid density and the like. The MAZ zeolite molecular sieve has a one-dimensional 12-membered ring channel structure, and belongs to P63A/mmc space group. MAZ zeolites are widely used in aromatic alkylation, hydroisomerization, petroleum cracking, and isomerization of paraffins and aromatics.
In the existing process of synthesizing the MAZ zeolite molecular sieve, common organic templates comprise tetramethylammonium hydroxide, dioxane, piperazine and the like. Among them, tetramethylammonium hydroxide is most widely used. However, tetramethylammonium hydroxide has toxicity and strong corrosivity, dioxane has toxicity and chemical carcinogenicity, and piperazine is combustible when meeting high heat and decomposes to release toxic gas. The use of the template agent not only has higher cost, but also pollutes the environment. The development of an environment-friendly green template agent for preparing the MAZ zeolite molecular sieve has very important research significance. In recent years, researchers have found that choline chloride has the ability to direct synthesis of zeolite molecular sieves, and although choline chloride has been described in the prior art for use in the preparation of CHA zeolites, SSZ zeolites, and the like, there is no report on the preparation of MAZ zeolites.
Disclosure of Invention
The invention mainly aims to overcome the defects in the prior art and provides a method for synthesizing a rodlike MAZ zeolite molecular sieve by using choline chloride as a template for the first time.
The invention provides a preparation method of an MAZ zeolite molecular sieve, which comprises the following steps:
the amount of each reaction material added was controlled so that SiO was present2:Al2O3:Na2O:R:H2The molar ratio of O is 8-20: 1: 2.65-3.44: 4.46-9.82: 93-250, an aluminum source, an alkali source and deionized water are uniformly mixed, and a silicon source is added under stirring; continuing stirring until the solution is uniform to form silicon-aluminum gel, adding a certain amount of template agent R into the silicon-aluminum gel, and stirring, wherein the template agent R is choline chloride; and then placing the mixture into a reaction kettle, wherein the crystallization temperature is 100-180 ℃, the crystallization time is 0.5-2.5 days, and performing suction filtration, washing and drying on a product to obtain the MAZ zeolite molecular sieve raw powder.
In particular, the aluminium source is sodium aluminate.
In particular, the alkali source is sodium hydroxide.
In particular, the silicon source is silica sol.
The invention has the beneficial effects that: the invention firstly provides choline chloride as a template agent to synthesize the rodlike MAZ zeolite molecular sieve under the condition of hydrothermal synthesis. At present, the reports about the synthesis of the MAZ zeolite molecular sieve are that the used template agents mainly comprise tetramethylammonium hydroxide, dioxane and piperazine, and the template agents have potential production hazards such as toxicity, carcinogenicity and flammability and do not meet the requirements of green sustainable development. According to the method, the rodlike MAZ zeolite molecular sieve is successfully prepared by using choline chloride for the first time by adjusting the proportion of starting raw materials and crystallization conditions.
Compared with the prior art, the invention has the following advantages:
1. the method for preparing the MAZ zeolite molecular sieve by using the choline chloride as the template agent not only greatly reduces the emission of pollutants, but also reduces the synthesis cost, and meets the requirements of green and sustainable development.
2. The product prepared by the invention not only maintains good crystallinity and purity, but also has good adsorption capacity. In addition, the adopted inorganic raw materials are environment-friendly and low in cost, so that the discovery has important significance in the field of actual chemical production.
Drawings
FIG. 1: XRD pattern of MAZ zeolite molecular sieve product.
FIG. 2: SEM image of MAZ zeolite molecular sieve product.
Detailed Description
EXAMPLE 1 preparation of MAZ Zeolite samples
Firstly, adding 0.94g of sodium aluminate into 6.8g of water, uniformly mixing, adding 0.53g of sodium hydroxide, after the solution is clarified, dropwise adding 8.4g of silica sol, continuously stirring, adding 3.5g of choline chloride, and stirring until uniform gel is formed; adding the reaction raw materials into a polytetrafluoroethylene stainless steel reaction kettle, crystallizing at 150 ℃ for 1 day to finish crystallization, cooling at room temperature, washing with deionized water to be neutral, filtering the product, and drying in the air at 100 ℃ to obtain the product.
FIG. 1 is an X-ray diffraction pattern (XRD) of the synthesized product, which was analyzed by X-ray diffraction to be a MAZ zeolite molecular sieve. FIG. 2 is a Scanning Electron Micrograph (SEM) of the synthesized sample, from which it can be seen that the synthesized product exhibits a nanorod morphology.
EXAMPLE 2 preparation of MAZ Zeolite samples
Firstly, adding 0.94g of sodium aluminate into 10.8g of water, uniformly mixing, adding 0.53g of sodium hydroxide, after the solution is clarified, dropwise adding 12.0g of silica sol, continuously stirring, adding 3.5g of choline chloride, and stirring until uniform gel is formed; adding the reaction raw materials into a polytetrafluoroethylene stainless steel reaction kettle, crystallizing at 150 ℃ for 1 day to finish crystallization, cooling at room temperature, washing with deionized water to be neutral, filtering the product, and drying in the air at 100 ℃ to obtain the product.
EXAMPLE 3 preparation of MAZ Zeolite samples
Firstly, adding 0.94g of sodium aluminate into 3.8g of water, uniformly mixing, adding 0.53g of sodium hydroxide, after the solution is clarified, dropwise adding 4.8g of silica sol, continuously stirring, adding 3.5g of choline chloride, and stirring until uniform gel is formed; adding the reaction raw materials into a polytetrafluoroethylene stainless steel reaction kettle, crystallizing at 150 ℃ for 1 day to finish crystallization, cooling at room temperature, washing with deionized water to be neutral, filtering the product, and drying in the air at 100 ℃ to obtain the product.
Example 4 preparation of MAZ Zeolite samples under Low base conditions
Firstly, adding 0.94g of sodium aluminate into 6.8g of water, uniformly mixing, adding 0.40g of sodium hydroxide, after the solution is clarified, dropwise adding 8.4g of silica sol, continuously stirring, adding 3.5g of choline chloride, and stirring until uniform gel is formed; adding the reaction raw materials into a polytetrafluoroethylene stainless steel reaction kettle, crystallizing at 150 ℃ for 1 day to finish crystallization, cooling at room temperature, washing with deionized water to be neutral, filtering the product, and drying in the air at 100 ℃ to obtain the product.
EXAMPLE 5 preparation of MAZ Zeolite samples under high base conditions
Firstly, adding 0.94g of sodium aluminate into 6.8g of water, uniformly mixing, adding 0.65g of sodium hydroxide, after the solution is clarified, dropwise adding 8.4g of silica sol, continuously stirring, adding 3.5g of choline chloride, and stirring until uniform gel is formed; adding the reaction raw materials into a polytetrafluoroethylene stainless steel reaction kettle, crystallizing at 150 ℃ for 1 day to finish crystallization, cooling at room temperature, washing with deionized water to be neutral, filtering the product, and drying in the air at 100 ℃ to obtain the product.
EXAMPLE 6 preparation of MAZ Zeolite samples
Firstly, adding 0.94g of sodium aluminate into 6.8g of water, uniformly mixing, adding 0.53g of sodium hydroxide, after the solution is clarified, dropwise adding 8.4g of silica sol, continuously stirring, adding 2.5g of choline chloride, and stirring until uniform gel is formed; adding the reaction raw materials into a polytetrafluoroethylene stainless steel reaction kettle, crystallizing at 150 ℃ for 1 day to finish crystallization, cooling at room temperature, washing with deionized water to be neutral, filtering the product, and drying in the air at 100 ℃ to obtain the product.
Example 7 preparation of MAZ Zeolite sample
Firstly, adding 0.94g of sodium aluminate into 6.8g of water, uniformly mixing, adding 0.53g of sodium hydroxide, after the solution is clarified, dropwise adding 8.4g of silica sol, continuously stirring, adding 5.5g of choline chloride, and stirring until uniform gel is formed; adding the reaction raw materials into a polytetrafluoroethylene stainless steel reaction kettle, crystallizing at 150 ℃ for 1 day to finish crystallization, cooling at room temperature, washing with deionized water to be neutral, filtering the product, and drying in the air at 100 ℃ to obtain the product.
Example 8 preparation of MAZ Zeolite samples under Low temperature conditions
Firstly, adding 0.94g of sodium aluminate into 6.8g of water, uniformly mixing, adding 0.53g of sodium hydroxide, after the solution is clarified, dropwise adding 8.4g of silica sol, continuously stirring, adding 3.5g of choline chloride, and stirring until uniform gel is formed; adding the reaction raw materials into a polytetrafluoroethylene stainless steel reaction kettle, crystallizing at 100 ℃ for 2.5 days to finish crystallization, cooling at room temperature, washing with deionized water to be neutral, filtering the product, and drying in the air at 100 ℃ to obtain the product.
Example 9 preparation of MAZ Zeolite samples under high temperature conditions
Firstly, adding 0.94g of sodium aluminate into 6.8g of water, uniformly mixing, adding 0.53g of sodium hydroxide, after the solution is clarified, dropwise adding 8.4g of silica sol, continuously stirring, adding 3.5g of choline chloride, and stirring until uniform gel is formed; adding the reaction raw materials into a polytetrafluoroethylene stainless steel reaction kettle, crystallizing at 180 ℃ for 0.5 day to finish crystallization, cooling at room temperature, washing with deionized water to be neutral, filtering the product, and drying in the air at 100 ℃ to obtain the product.
Note:amolar ratio in the initial gel.
Although the invention has been described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention. However, any simple modification, equivalent change and modification made to the above embodiments according to the technical essence of the present invention are still within the technical scope of the present invention, unless the contents of the technical solution of the present invention are departed.
Claims (10)
1. A process for preparing MAZ zeolite molecular sieve features that the addition of raw materials is controlled to make SiO be in the form of particles2:Al2O3:Na2O:R:H2The molar ratio of O is 8-20: 1: 2.65-3.44: 4.46-9.82: 93-250, an aluminum source, an alkali source and deionized water are uniformly mixed, and a silicon source is added under stirring; continuing stirring until the solution is uniform to form silicon-aluminum gel, adding a certain amount of template agent R into the silicon-aluminum gel, and stirring, wherein the template agent R is choline chloride; then placing the mixture into a reaction kettle, wherein the crystallization temperature is 100-180 ℃, and the crystallization is carried outAnd (5) performing suction filtration, washing and drying on the product for 0.5-2.5 days to obtain the MAZ zeolite molecular sieve raw powder.
2. The method of claim 1, wherein the aluminum source is sodium aluminate.
3. The method of claim 1, wherein the alkali source is sodium hydroxide.
4. The method of claim 1, wherein the silicon source is silica sol.
5. The method of claim 1, wherein 0.94g of sodium aluminate is added to 6.8g of water and mixed uniformly, 0.53g of sodium hydroxide is added thereto, after the solution is clarified, 8.4g of silica sol is added dropwise, stirring is continued, 3.5g of choline chloride is added, and then stirring is carried out until a uniform gel is formed; adding the reaction raw materials into a polytetrafluoroethylene stainless steel reaction kettle, crystallizing at 150 ℃ for 1 day to finish crystallization, cooling at room temperature, washing with deionized water to be neutral, filtering the product, and drying in the air at 100 ℃ to obtain the product.
6. The method of claim 1, wherein 0.94g of sodium aluminate is added to 10.8g of water and mixed uniformly, 0.53g of sodium hydroxide is added thereto, after the solution is clarified, 12.0g of silica sol is added dropwise, stirring is continued, 3.5g of choline chloride is added, and then stirring is carried out until a uniform gel is formed; adding the reaction raw materials into a polytetrafluoroethylene stainless steel reaction kettle, crystallizing at 150 ℃ for 1 day to finish crystallization, cooling at room temperature, washing with deionized water to be neutral, filtering the product, and drying in the air at 100 ℃ to obtain the product.
7. The method of claim 1, wherein 0.94g of sodium aluminate is added to 3.8g of water and mixed uniformly, 0.53g of sodium hydroxide is added thereto, after the solution is clarified, 4.8g of silica sol is added dropwise, stirring is continued, 3.5g of choline chloride is added, and then stirring is carried out until a uniform gel is formed; adding the reaction raw materials into a polytetrafluoroethylene stainless steel reaction kettle, crystallizing at 150 ℃ for 1 day to finish crystallization, cooling at room temperature, washing with deionized water to be neutral, filtering the product, and drying in the air at 100 ℃ to obtain the product.
8. The method of claim 1, wherein 0.94g of sodium aluminate is added to 6.8g of water and mixed uniformly, 0.40g of sodium hydroxide is added thereto, after the solution is clarified, 8.4g of silica sol is added dropwise, stirring is continued, 3.5g of choline chloride is added, and then stirring is carried out until a uniform gel is formed; adding the reaction raw materials into a polytetrafluoroethylene stainless steel reaction kettle, crystallizing at 150 ℃ for 1 day to finish crystallization, cooling at room temperature, washing with deionized water to be neutral, filtering the product, and drying in the air at 100 ℃ to obtain the product.
9. The method of claim 1, wherein 0.94g of sodium aluminate is added to 6.8g of water and mixed uniformly, 0.65g of sodium hydroxide is added thereto, after the solution is clarified, 8.4g of silica sol is added dropwise, stirring is continued, 3.5g of choline chloride is added, and then stirring is carried out until a uniform gel is formed; adding the reaction raw materials into a polytetrafluoroethylene stainless steel reaction kettle, crystallizing at 150 ℃ for 1 day to finish crystallization, cooling at room temperature, washing with deionized water to be neutral, filtering the product, and drying in the air at 100 ℃ to obtain the product.
10. The method of claim 1, wherein 0.94g of sodium aluminate is added to 6.8g of water and mixed uniformly, 0.53g of sodium hydroxide is added thereto, after the solution is clarified, 8.4g of silica sol is added dropwise, stirring is continued, 2.5g of choline chloride is added, and then stirring is carried out until a uniform gel is formed; adding the reaction raw materials into a polytetrafluoroethylene stainless steel reaction kettle, crystallizing at 150 ℃ for 1 day to finish crystallization, cooling at room temperature, washing with deionized water to be neutral, filtering the product, and drying in the air at 100 ℃ to obtain the product.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4021447A (en) * | 1975-04-30 | 1977-05-03 | Mobil Oil Corporation | Synthesis of zeolite ZSM-4 |
| CN104428248A (en) * | 2012-07-20 | 2015-03-18 | UniZeo株式会社 | Method for producing maz-type zeolite |
| CN107250497A (en) * | 2015-02-26 | 2017-10-13 | 庄信万丰股份有限公司 | Passive NOx adsorbent |
-
2020
- 2020-09-21 CN CN202010992614.8A patent/CN112062137A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4021447A (en) * | 1975-04-30 | 1977-05-03 | Mobil Oil Corporation | Synthesis of zeolite ZSM-4 |
| CN104428248A (en) * | 2012-07-20 | 2015-03-18 | UniZeo株式会社 | Method for producing maz-type zeolite |
| CN107250497A (en) * | 2015-02-26 | 2017-10-13 | 庄信万丰股份有限公司 | Passive NOx adsorbent |
Non-Patent Citations (3)
| Title |
|---|
| HE DAWEI ET AL.: "Eco‐friendly synthesis of high silica zeolite Y with choline as green and innocent structure-directing agent", 《CHINESE JOURNAL OF CATALYSIS》 * |
| ZHANG FENG ET AL.: "Design of fast crystallization of nanosized zeolite omega crystals at higher temperatures", 《CHINESE JOURNAL OF CATALYSIS》 * |
| 龚朝兵等: "Mazzite型沸石分子筛", 《化学通报》 * |
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