CN111592007A - Method for growing mesoporous molecular sieve by attaching crystals on surface of microporous molecular sieve - Google Patents
Method for growing mesoporous molecular sieve by attaching crystals on surface of microporous molecular sieve Download PDFInfo
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- CN111592007A CN111592007A CN202010442406.0A CN202010442406A CN111592007A CN 111592007 A CN111592007 A CN 111592007A CN 202010442406 A CN202010442406 A CN 202010442406A CN 111592007 A CN111592007 A CN 111592007A
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- 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
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- C—CHEMISTRY; METALLURGY
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- 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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- 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
- C01B39/20—Faujasite type, e.g. type X or Y
- C01B39/24—Type Y
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- 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
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
- C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
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Abstract
The invention relates to the technical field of inorganic materials and catalysis, and discloses a method for growing a mesoporous molecular sieve by epimorphic growth on the surface of a microporous molecular sieve, wherein the microporous molecular sieve is one of ZSM-5, ZSM-35, HZSM-5 and Y molecular sieves. The active solution is a combined compound prepared from a template agent, silicon dioxide, aluminum oxide, sodium oxide and water, and the molar ratio of various raw materials in the active solution is 1-2: 0.05-0.1: 0.15-0.25: 0.15: 60 to 100. The method is characterized in that ions are introduced into the microporous molecular sieve by KBr, the electric field performance on the surface of the microporous molecular sieve is changed, so that ion exchange is facilitated, and further, the charge distribution is changed, so that the microporous molecular sieve is subjected to ion exchange with a composite compound prepared from a template agent, silicon dioxide, aluminum oxide and sodium oxide, and after pore wall crystallization, the mesoporous molecular sieve is prepared by epicrystal growth.
Description
Technical Field
The invention relates to the technical field of inorganic materials and catalysis, in particular to a method for growing a mesoporous molecular sieve by attaching crystals on the surface of a microporous molecular sieve.
Background
The microporous molecular sieve has the properties of large surface area, high hydrothermal stability, rich and uniform micropores, adjustable surface properties and the like, is widely used as a catalyst and has been widely applied to petrochemical industry, molecular sieves are often applied to synthesis of petrochemical industry and organic intermediates and separation of substances as the catalyst, the mesoporous molecular sieve with crystal attachment growth on the surface of the microporous molecular sieve is crystal attachment growth on the surface of zeolite by methods such as an ion exchange method and the like to obtain an expected pore diameter, and the mesoporous molecular sieve and the microporous molecular sieve are compounded to obtain a composite molecular sieve with better performance, so that the material is expected to have wide application prospects in the aspects of adsorption and catalysis of macromolecules.
The prior method for producing the mesoporous molecular sieve by the epicrystals has low catalytic capability and selectivity, and the product obtained by combining the microporous molecular sieve and the mesoporous molecular sieve has the advantages that under the same reaction condition, mesopores are not easy to form, the crystallization degree of the products is poor, and the catalytic activity and the selectivity can not meet the requirements, so the method for growing the mesoporous molecular sieve by the epicrystals on the surface of the microporous molecular sieve is provided.
Disclosure of Invention
In order to solve the above technical problems, the present invention provides an inorganic material and a catalyst x, which are achieved by the following specific technical means:
a method for growing a mesoporous molecular sieve by attaching crystals on the surface of a microporous molecular sieve comprises the following steps:
s1, grinding KBr and microporous molecular sieve raw powder into a standard sieve with the aperture of 0.05mm, and then violently stirring the standard sieve with a hexadecyl trimethyl ammonium chloride solution at the temperature of 30-50 ℃ for 25-30 hours to form a prepared suspension;
s2, sequentially dissolving an aluminum source, an alkali source and a silicon source in deionized water, and uniformly stirring until the mixture is white, thereby forming precursor sol of the mesoporous molecular sieve;
s3, dripping the sol of S2 into the prepared suspension of S1, adding an active solution, continuously stirring for 15 minutes, and adding 50% acetic acid to adjust the pH value to be 8-10;
s4, putting the material S3 into a crystallization kettle containing polytetrafluoroethylene, adjusting the temperature to 110-120 ℃ for crystallization for 1-3 hours, crystallizing under the hydrothermal condition of autogenous pressure and crystallization temperature, filtering, washing and drying the obtained crystallization liquid, drying at 100 ℃ for 24-48 hours, and calcining at the rate of 2-3 ℃ in air atmosphere for 8 hours to obtain the product.
Preferably, the microporous molecular sieve is one of ZSM-5, ZSM-35, HZSM-5 and Y molecular sieves.
Preferably, the aluminum source is one of aluminum sulfate, aluminum nitrate or aluminum hydroxide, the silicon source is one of silica gel, white carbon black and monodisperse silica, and the alkali source is lithium hydroxide.
Preferably, the active solution is a combined compound prepared from a template agent, silicon dioxide, aluminum oxide, sodium oxide and water, and the molar ratio of various raw materials in the active solution is 1-2: 0.05-0.1: 0.15-0.25: 0.15: 60 to 100.
Preferably, the template agent is C6H13 (CH)3)3NBR、C8-18N+(CH3)3、C16N+(CH3)3And C10-16N + CH3(CH2CH3)2One or more of (a).
Advantageous effects
Compared with the prior art, the invention provides a method for growing a mesoporous molecular sieve by attaching crystals on the surface of a microporous molecular sieve, which has the following beneficial effects:
according to the method for growing the mesoporous molecular sieve by epimorphic growth on the surface of the microporous molecular sieve, ions are introduced into the microporous molecular sieve by KBr, the electric field performance on the surface of the microporous molecular sieve is changed, so that ion exchange is facilitated, the charge distribution is changed, the microporous molecular sieve is subjected to ion exchange with a combined compound prepared from a template agent, silicon dioxide, aluminum oxide and sodium oxide, and after pore wall crystallization, the mesoporous molecular sieve is prepared by epimorphic growth.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention is further described below by way of examples:
the first embodiment is as follows:
a method for growing a mesoporous molecular sieve by attaching crystals on the surface of a microporous molecular sieve comprises the following steps:
wherein the microporous molecular sieve is one of ZSM-5, ZSM-35, HZSM-5 and Y molecular sieves.
The aluminum source is one of aluminum sulfate, aluminum nitrate or aluminum hydroxide, the silicon source is one of silica gel, white carbon black and monodisperse silicon dioxide, and the alkali source is lithium hydroxide.
The active solution is a combined compound prepared from a template agent, silicon dioxide, aluminum oxide, sodium oxide and water, and the molar ratio of various raw materials in the active solution is 1-2: 0.05-0.1: 0.15-0.25: 0.15: 60 to 100.
Wherein the template agent is C6H13 (CH)3)3NBR、C8-18N+(CH3)3、C16N+(CH3)3And C10-16N + CH3(CH2CH3)2One or more of (a).
S1, grinding 0.5g of KBr and microporous molecular sieve raw powder into a standard sieve with the aperture of 0.05mm, and then violently stirring 4.3g of hexadecyltrimethylammonium chloride solution at the temperature of 30-50 ℃ for 25-30 hours to form a prepared suspension;
s2, sequentially dissolving an aluminum source, an alkali source and a silicon source in deionized water, and uniformly stirring until the mixture is white, thereby forming precursor sol of the mesoporous molecular sieve;
s3, dropping the sol of S2 into the preliminary suspension of S1, adding a solvent of 1: 0.05:0.15: 0.15: stirring the template agent, silicon dioxide, aluminum oxide, sodium oxide and water in a molar ratio of 60 for 15 minutes, and adding 50% acetic acid to adjust the pH value to be between 8 and 10;
s4, putting the material S3 into a crystallization kettle containing polytetrafluoroethylene, adjusting the temperature to 110-120 ℃ for crystallization for 1-3 hours, crystallizing under the hydrothermal condition of autogenous pressure and crystallization temperature, filtering, washing and drying the obtained crystallization liquid, drying at 100 ℃ for 24-48 hours, and calcining at the rate of 2-3 ℃ in air atmosphere for 8 hours to obtain the product.
Example two:
a method for growing a mesoporous molecular sieve by attaching crystals on the surface of a microporous molecular sieve comprises the following steps:
s1, grinding 0.75g of KBr and microporous molecular sieve raw powder into a standard sieve with the aperture of 0.05mm, and then violently stirring 6.7g of hexadecyltrimethylammonium chloride solution at the temperature of 30-50 ℃ for 25-30 hours to form a prepared suspension;
s2, sequentially dissolving an aluminum source, an alkali source and a silicon source in deionized water, and uniformly stirring until the mixture is white, thereby forming precursor sol of the mesoporous molecular sieve;
s3, dropping the sol of S2 into the preliminary suspension of S1, adding a suspension of 1.5: 0.07:0.2: 0.15: after stirring the template agent, silicon dioxide, aluminum oxide, sodium oxide and water in a molar ratio of 80 for 15 minutes, adding 50% acetic acid to adjust the pH value to be between 8 and 10;
s4, putting the material S3 into a crystallization kettle containing polytetrafluoroethylene, adjusting the temperature to 110-120 ℃ for crystallization for 1-3 hours, crystallizing under the hydrothermal condition of autogenous pressure and crystallization temperature, filtering, washing and drying the obtained crystallization liquid, drying at 100 ℃ for 24-48 hours, and calcining at the rate of 2-3 ℃ in air atmosphere for 8 hours to obtain the product.
Example three:
a method for growing a mesoporous molecular sieve by attaching crystals on the surface of a microporous molecular sieve comprises the following steps:
s1, grinding 1.1g of KBr and microporous molecular sieve raw powder into a standard sieve with the aperture of 0.05mm, and then violently stirring 8.1g of hexadecyltrimethylammonium chloride solution at the temperature of 30-50 ℃ for 25-30 hours to form a prepared suspension;
s2, sequentially dissolving an aluminum source, an alkali source and a silicon source in deionized water, and uniformly stirring until the mixture is white, thereby forming precursor sol of the mesoporous molecular sieve;
s3, dropping the sol of S2 into the preliminary suspension of S1, adding a suspension of 2: 0.1:0.25: 0.15: stirring 100 mol of template agent, silicon dioxide, aluminum oxide, sodium oxide and water for 15 minutes, and adding 50% acetic acid to adjust the pH value to be 8-10;
s4, putting the material S3 into a crystallization kettle containing polytetrafluoroethylene, adjusting the temperature to 110-120 ℃ for crystallization for 1-3 hours, crystallizing under the hydrothermal condition of autogenous pressure and crystallization temperature, filtering, washing and drying the obtained crystallization liquid, drying at 100 ℃ for 24-48 hours, and calcining at the rate of 2-3 ℃ in air atmosphere for 8 hours to obtain the product.
Comparative example:
a method for growing a mesoporous molecular sieve by attaching crystals on the surface of a microporous molecular sieve comprises the following steps:
s1, grinding 1g of KBr and microporous molecular sieve raw powder into a standard sieve with the aperture of 0.05mm, and then violently stirring 7.5g of hexadecyltrimethylammonium chloride solution at the temperature of 30-50 ℃ for 25-30 hours to form a prepared suspension;
s2, sequentially dissolving an aluminum source, an alkali source and a silicon source in deionized water, and uniformly stirring until the mixture is white, thereby forming precursor sol of the mesoporous molecular sieve;
s3, dropping the sol of S2 into the preliminary suspension of S1, adding a suspension of 2: 0.08:0.2: 0.15: after stirring the template agent, silicon dioxide, aluminum oxide, sodium oxide and water in a molar ratio of 80 for 15 minutes, adding 50% acetic acid to adjust the pH value to be between 8 and 10;
s4, putting the material S3 into a crystallization kettle containing polytetrafluoroethylene, adjusting the temperature to 110-120 ℃ for crystallization for 1-3 hours, crystallizing under the hydrothermal condition of autogenous pressure and crystallization temperature, filtering, washing and drying the obtained crystallization liquid, drying at 100 ℃ for 24-48 hours, and calcining at the rate of 2-3 ℃ in air atmosphere for 8 hours to obtain the product.
Examples reaction performance results
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (5)
1. A method for growing a mesoporous molecular sieve by attaching crystals on the surface of a microporous molecular sieve comprises the following steps:
s1, grinding KBr and microporous molecular sieve raw powder into a standard sieve with the aperture of 0.05mm, and then violently stirring the standard sieve with a hexadecyl trimethyl ammonium chloride solution at the temperature of 30-50 ℃ for 25-30 hours to form a prepared suspension;
s2, sequentially dissolving an aluminum source, an alkali source and a silicon source in deionized water, and uniformly stirring until the mixture is white, thereby forming precursor sol of the mesoporous molecular sieve;
s3, dripping the sol of S2 into the prepared suspension of S1, adding an active solution, continuously stirring for 15 minutes, and adding 50% acetic acid to adjust the pH value to be 8-10;
s4, putting the material S3 into a crystallization kettle containing polytetrafluoroethylene, adjusting the temperature to 110-120 ℃ for crystallization for 1-3 hours, crystallizing under the hydrothermal condition of autogenous pressure and crystallization temperature, filtering, washing and drying the obtained crystallization liquid, drying at 100 ℃ for 24-48 hours, and calcining at the rate of 2-3 ℃ in air atmosphere for 8 hours to obtain the product.
2. The method of claim 1, wherein the mesoporous molecular sieve is grown on the surface of the microporous molecular sieve by epicrystal growth, and the method comprises the following steps: the microporous molecular sieve is one of ZSM-5, ZSM-35, HZSM-5 and Y molecular sieves.
3. The method of claim 1, wherein the mesoporous molecular sieve is grown on the surface of the microporous molecular sieve by epicrystal growth, and the method comprises the following steps: the aluminum source is one of aluminum sulfate, aluminum nitrate or aluminum hydroxide, the silicon source is one of silica gel, white carbon black and monodisperse silicon dioxide, and the alkali source is lithium hydroxide.
4. The method of claim 1, wherein the mesoporous molecular sieve is grown on the surface of the microporous molecular sieve by epicrystal growth, and the method comprises the following steps: the active solution is a combined compound prepared from a template agent, silicon dioxide, aluminum oxide, sodium oxide and water, and the molar ratio of various raw materials in the active solution is 1-2: 0.05-0.1: 0.15-0.25: 0.15: 60 to 100.
5. The method of claim 1, wherein the mesoporous molecular sieve is grown on the surface of the microporous molecular sieve by epicrystal growth, and the method comprises the following steps: the template agent is C6H13 (CH)3)3NBR、C8-18N+(CH3)3、C16N+(CH3)3And C10-16N + CH3(CH2CH3)2One or more of (a).
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1762806A (en) * | 2004-10-21 | 2006-04-26 | 中国石油天然气股份有限公司 | Method for mesoporous molecular sieve overgrowth on microporous molecular sieve surface |
| CN104043477A (en) * | 2013-03-14 | 2014-09-17 | 中国科学院青岛生物能源与过程研究所 | ZSM-5/MCM-48 composite molecular sieve, preparation method and application thereof |
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- 2020-05-22 CN CN202010442406.0A patent/CN111592007A/en not_active Withdrawn
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1762806A (en) * | 2004-10-21 | 2006-04-26 | 中国石油天然气股份有限公司 | Method for mesoporous molecular sieve overgrowth on microporous molecular sieve surface |
| CN104043477A (en) * | 2013-03-14 | 2014-09-17 | 中国科学院青岛生物能源与过程研究所 | ZSM-5/MCM-48 composite molecular sieve, preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 张海娟: ""MCM-41在微孔分子筛Y上的附晶生长"", 《化工学报》 * |
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