CN112047357A - Method for synthesizing Omgea zeolite molecular sieve - Google Patents
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- CN112047357A CN112047357A CN202010992459.XA CN202010992459A CN112047357A CN 112047357 A CN112047357 A CN 112047357A CN 202010992459 A CN202010992459 A CN 202010992459A CN 112047357 A CN112047357 A CN 112047357A
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- C—CHEMISTRY; METALLURGY
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- 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
- C01B39/34—Type ZSM-4
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- 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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Abstract
The invention discloses a method for quickly synthesizing an Omega 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 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 0.25-2 days, and performing suction filtration, washing and drying on a product to obtain the Omega zeolite molecular sieve raw powder. The method takes choline as a template agent, quickly synthesizes the Omega zeolite molecular sieve under the hydrothermal synthesis condition, has the advantages of short synthesis period, environmental friendliness and low cost, and meets the aim of green sustainable development.
Description
Technical Field
The invention belongs to a preparation method of a molecular sieve, and particularly relates to a method for synthesizing an Omega zeolite molecular sieve by using a green cheap template.
Background
Zeolite molecular sieves are widely used in petrochemical and fine chemical processes due to their characteristics of high specific surface area, large pore volume, adjustable acid density, and the like. The Omega zeolite molecular sieve has a one-dimensional 12-membered ring channel structure and belongs to P63A/mmc space group. The pore channels of the Omega zeolite catalyst have excellent shape selectivity and are applied to the hydroisomerization reaction which is important in industrial catalysis.
In the current reports on the preparation of Omega zeolite molecular sieves, organic templates commonly used are tetramethylammonium hydroxide, dioxane, piperazine and the like. It is worth noting that tetramethylammonium hydroxide has toxicity and strong corrosivity, and can accelerate the consumption of production equipment and pollute the environment in the process of synthesizing the Omgea zeolite molecular sieve; dioxane has toxicity and chemical carcinogenicity, and the synthetic route of the Omega zeolite molecular sieve does not meet the requirement of green environmental protection; piperazine is combustible in case of high heat, and decomposes to release toxic gas, thereby greatly influencing the ecological environment in the process of synthesizing the Omega zeolite molecular sieve. The organic template has the defects of high cost, serious environmental pollution, long synthesis period and the like, and is not beneficial to the industrial production of the Omega zeolite catalyst. Recently, researchers have found that the template-free seed crystal method can also synthesize Omega zeolite, but the crystallization time required is longer and the obtained product is more aluminum-rich, which affects the industrial application thereof to some extent. Therefore, the development of a green low-cost template agent for quickly synthesizing the Omega zeolite molecular sieve has important research significance.
Disclosure of Invention
The invention mainly aims to overcome the defects in the prior art and provides a method for quickly synthesizing an Omega zeolite molecular sieve by using choline as a template for the first time.
The invention provides a preparation method of an Omega 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 8-18: 1: 2.35-3.05: 2.84-3.60: 133-208Uniformly 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 template agent R into the silicon-aluminum gel, and stirring, wherein the template agent R is choline; and then placing the mixture into a reaction kettle, wherein the crystallization temperature is 100-180 ℃, the crystallization time is 0.25-2 days, and performing suction filtration, washing and drying on a product to obtain the Omega zeolite molecular sieve raw powder.
In particular, the aluminum source is pseudoboehmite.
In particular, the alkali source is sodium hydroxide.
In particular, the silicon source is fine silica gel.
The invention has the beneficial effects that: the invention firstly provides choline as a template agent, and the Omega zeolite molecular sieve is quickly synthesized under the hydrothermal synthesis condition. At present, in the reports about the synthesis of Omega zeolite molecular sieves, the used template agents mainly comprise tetramethylammonium hydroxide, dioxane and piperazine, and the template agents have potential production hazards such as toxicity, carcinogenicity, flammability and the like, and do not meet the requirements of green sustainable development. According to the method, the Omega zeolite molecular sieve is successfully prepared by using choline for the first time by adjusting the proportion of the starting raw materials and the crystallization conditions.
Compared with the prior art, the invention has the following advantages:
1. the method for preparing the Omega zeolite molecular sieve by using the choline 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 method for preparing the Omega zeolite molecular sieve by using the choline as the template agent greatly shortens the synthesis period, reduces the energy consumption, improves the efficiency and meets the requirement of rapid production.
3. The product prepared by the invention not only maintains good crystallinity and purity, but also has good adsorption and catalysis capability. 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 Omega zeolite molecular sieve product.
FIG. 2: SEM image of Omega zeolite molecular sieve product.
Detailed Description
Example 1 preparation of Omega Zeolite samples
Firstly, 0.76g of sodium hydroxide is dissolved in 8.9g of deionized water, 0.486g of pseudo-boehmite is added into the deionized water, 2.4g of fine silica gel is added after the solution is clarified, the stirring is continued, and then 3.3g of choline is slowly added and the stirring is carried out until the gel is uniform; adding the reaction raw materials into a polytetrafluoroethylene stainless steel reaction kettle, crystallizing at 180 ℃ for 0.25 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 have a structure of Omega zeolite molecular sieve. FIG. 2 is a Scanning Electron Micrograph (SEM) of the synthesized sample, and it can be seen from the SEM that the synthesized product shows the shape of the nanorod clusters.
Example 2 preparation of Omega Zeolite samples
Firstly, 0.76g of sodium hydroxide is dissolved in 8.9g of deionized water, 0.486g of pseudo-boehmite is added into the deionized water, after the solution is clarified, 3.6g of fine silica gel is added into the solution, the solution is continuously stirred, and then 3.3g of choline is slowly added into the solution and stirred until the solution is uniformly gelled; 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 Omega Zeolite samples
Firstly, 0.76g of sodium hydroxide is dissolved in 8.9g of deionized water, 0.486g of pseudo-boehmite is added into the deionized water, 1.6g of fine silica gel is added after the solution is clarified, the stirring is continued, and then 3.3g of choline is slowly added and the stirring is carried out until the gel is uniform; 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 Omega Zeolite samples under Low base conditions
Firstly, 0.63g of sodium hydroxide is dissolved in 8.9g of deionized water, 0.486g of pseudo-boehmite is added into the deionized water, after the solution is clarified, 2.4g of fine silica gel is added into the solution, the solution is continuously stirred, and then 3.3g of choline is slowly added into the solution and stirred until the solution is uniformly gelled; 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 Omega Zeolite samples under high base conditions
Firstly, 0.81g of sodium hydroxide is dissolved in 8.9g of deionized water, 0.486g of pseudo-boehmite is added into the deionized water, after the solution is clarified, 2.4g of fine silica gel is added into the solution, the solution is continuously stirred, and then 3.3g of choline is slowly added into the solution and stirred until the solution is uniformly gelled; 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 Omega Zeolite samples
Firstly, 0.76g of sodium hydroxide is dissolved in 8.9g of deionized water, 0.486g of pseudo-boehmite is added into the deionized water, 2.4g of fine silica gel is added after the solution is clarified, the stirring is continued, and then 2.6g of choline is slowly added and the stirring is carried out until the gel is uniform; 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 Omega Zeolite samples
Firstly, 0.76g of sodium hydroxide is dissolved in 8.9g of deionized water, 0.486g of pseudo-boehmite is added into the deionized water, 2.4g of fine silica gel is added after the solution is clarified, the stirring is continued, 4.0g of choline is slowly added, and the stirring is carried out until the gel is uniform; 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 Omega Zeolite samples
Firstly, 0.76g of sodium hydroxide is dissolved in 6.1g of deionized water, 0.486g of pseudo-boehmite is added into the deionized water, 2.4g of fine silica gel is added after the solution is clarified, the stirring is continued, and then 3.3g of choline is slowly added and the stirring is carried out until the gel is uniform; 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 9 preparation of Omega Zeolite samples
Firstly, 0.76g of sodium hydroxide is dissolved in 10.6g of deionized water, 0.486g of pseudo-boehmite is added into the deionized water, 2.4g of fine silica gel is added after the solution is clarified, the stirring is continued, and then 3.3g of choline is slowly added and the stirring is carried out until the gel is uniform; 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 10 preparation of Omega Zeolite samples
Firstly, 0.76g of sodium hydroxide is dissolved in 8.9g of deionized water, 0.486g of pseudo-boehmite is added into the deionized water, 2.4g of fine silica gel is added after the solution is clarified, the stirring is continued, and then 3.3g of choline is slowly added and the stirring is carried out until the gel is uniform; adding the reaction raw materials into a polytetrafluoroethylene stainless steel reaction kettle, crystallizing at 100 ℃ for 2 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 11 preparation of Omega Zeolite samples
Firstly, 0.76g of sodium hydroxide is dissolved in 8.9g of deionized water, 0.486g of pseudo-boehmite is added into the deionized water, 2.4g of fine silica gel is added after the solution is clarified, the stirring is continued, and then 3.3g of choline is slowly added and the stirring is carried out until the gel is uniform; 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.
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 (4)
1. A method for synthesizing an Omega zeolite molecular sieve is characterized in that the addition amount of each reaction raw material is controlled to ensure that SiO is added2:Al2O3:Na2O:R:H2The molar ratio of O is 8-18: 1: 2.35-3.05: 2.84-3.60: 133-208, 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; and then placing the mixture into a reaction kettle, wherein the crystallization temperature is 100-180 ℃, the crystallization time is 0.25-2 days, and performing suction filtration, washing and drying on a product to obtain the Omega zeolite molecular sieve raw powder.
2. The method of claim 1, wherein said aluminum source is pseudoboehmite.
3. The process of claim 1, wherein said source of alkalinity is sodium hydroxide.
4. The method of claim 1, wherein the silicon source is a fine silica gel.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2798923A1 (en) * | 1999-09-29 | 2001-03-30 | Inst Francais Du Petrole | PROCESS FOR THE PREPARATION OF A MTT STRUCTURAL TYPE ZEOLITE USING STRUCTURING SPECIFIC PRECURSORS |
| CN104428248A (en) * | 2012-07-20 | 2015-03-18 | UniZeo株式会社 | Method for producing maz-type zeolite |
| CN109437230A (en) * | 2018-11-30 | 2019-03-08 | 中国石油大学(华东) | A method of preparing composite molecular screen |
| CN110562994A (en) * | 2019-09-27 | 2019-12-13 | 浙江天地环保科技有限公司 | method for synthesizing SSZ-13 molecular sieve by converting mixed template agent dry glue and application thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2798923A1 (en) * | 1999-09-29 | 2001-03-30 | Inst Francais Du Petrole | PROCESS FOR THE PREPARATION OF A MTT STRUCTURAL TYPE ZEOLITE USING STRUCTURING SPECIFIC PRECURSORS |
| CN104428248A (en) * | 2012-07-20 | 2015-03-18 | UniZeo株式会社 | Method for producing maz-type zeolite |
| CN109437230A (en) * | 2018-11-30 | 2019-03-08 | 中国石油大学(华东) | A method of preparing composite molecular screen |
| CN110562994A (en) * | 2019-09-27 | 2019-12-13 | 浙江天地环保科技有限公司 | method for synthesizing SSZ-13 molecular sieve by converting mixed template agent dry glue and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| ZHANG FEN 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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Application publication date: 20201208 |