CN109160522A - A kind of method of solvent-free solid-phase synthesis total silicon SOD zeolite - Google Patents
A kind of method of solvent-free solid-phase synthesis total silicon SOD zeolite Download PDFInfo
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- CN109160522A CN109160522A CN201811036549.0A CN201811036549A CN109160522A CN 109160522 A CN109160522 A CN 109160522A CN 201811036549 A CN201811036549 A CN 201811036549A CN 109160522 A CN109160522 A CN 109160522A
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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
- C01B39/04—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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- 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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- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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Abstract
The present invention relates to molecular sieve technologies of preparing, it is desirable to provide a kind of method of solvent-free solid-phase synthesis total silicon SOD zeolite.Include: that silicon source, alkali source, ethylene glycol are placed in mortar, is ground；Then it goes in reaction kettle, in 160~240 DEG C of 4~96h of crystallization；Product is filtered, is dried to get total silicon SOD zeolite is arrived；The molar ratio range of each reaction raw materials additive amount is SiO2∶Na2O: ethylene glycol=1: 0.02~0.1: 0.2~1.0.Solvent-free solid-phase of the invention synthesizes total silicon SOD zeolite method, greatly improves the yield of total silicon SOD zeolite, farthest reduces the use of organic matter, and synthetic operation is simple, easy.Product not only maintains good crystallinity and purity, has good reactivity.Entire production process has remained the state of a solid phase, and which reduces unnecessary waste discharge and losses in process of production.Used inorganic raw material is environmentally friendly, and price is less expensive, is of great significance in practical chemical production field.
Description
Technical field
The invention belongs to molecular sieve preparation methods, more particularly to the method for solvent-free solid-phase synthesis total silicon SOD zeolite.
Background technique
Zeolite can be divided into aperture, mesoporous and large pore zeolite according to the division of duct size.Wherein such as Y, Beta macropore boil
Stone is widely used in the catalysis such as FCC, alkylation reaction, in another example the mesopore zeolites such as ZSM-5, IM-5 are widely used in two
During toluene isomery, alkylation etc..Pore zeolite can be divided into octatomic ring and hexatomic ring zeolite.Wherein, octatomic ring zeolite is answered
In MTO and SCR reaction process.And hexatomic ring zeolite is often used for catalyst carrier, adsorbing separation, semiconductor, pigment
Equal fields.SOD received the extensive concern of researcher as a kind of important hexatomic ring zeolite in recent years.
Usual its sieve and silica-sesquioxide ratio of SOD zeolite is 2, is usually synthesized under hydrothermal conditions.In order to improve hydro-thermal method
Existing defect, researcher have developed solventless method to improve the synthesis (CN201210118788.7) of this rich aluminium SOD zeolite
To eliminate discharge of wastewater problem.Relative to rich aluminium SOD zeolite, total silicon SOD zeolite has wider application.But it is this at present
Zeolite is usually to be synthesized in the presence of the organic solvents such as a large amount of ethylene glycol or glycerine by solvent heat, a large amount of organic
The use of solvent significantly increases synthesis cost, and leads to the low yield of zeolite product.Therefore, it needs to improve total silicon
The synthetic method of SOD zeolite.
Summary of the invention
The technical problem to be solved by the present invention is to overcome deficiency in the prior art, provide a kind of solvent-free solid-phase synthesis
The method of total silicon SOD zeolite.
In order to solve the technical problem, solution of the invention is:
A kind of method of solvent-free solid-phase synthesis total silicon SOD zeolite is provided, comprising the following steps:
Silicon source, alkali source, ethylene glycol are placed in mortar, ground；Then it goes in reaction kettle, in 160~240 DEG C of crystalline substances
Change 4~96h；Product is filtered, is dried to get total silicon SOD zeolite is arrived；
The molar ratio range of each reaction raw materials additive amount is SiO2∶Na2O: ethylene glycol=1: 0.02~0.1: 0.2~1.0.
In the present invention, the silicon source is solid silicone or white carbon black.
In the present invention, the alkali source is sodium hydroxide, sodium metasilicate or potassium hydroxide.
Inventive principle description:
1, compared with the technology of the synthesizing aluminum-enriched SOD zeolite of solventless method described in the CN201210118788.7, the present invention only makes
With a small amount of ethylene glycol.The difference of its technical principle is: rich aluminium SOD zeolite usually requires to be closed in the presence of a large amount of inorganic bases
At framework si-al ratio 1 can not improve, this results in its hydrophobicity poor.In addition, being 1 in uninanned platform silica alumina ratio
In SOD zeolite, compound particle size is small, still has very big challenge for the SOD zeolite of synthesizing micron-grade.And this hair
In bright, a small amount of ethylene glycol is only used only, the SOD zeolite of total silicon can be obtained, due to lacking aluminium atom, hydrophobicity is than original
Have greatly improved, furthermore the granular size of this ethylene glycol guiding total silicon SOD zeolite synthesis is micron order.
2, due to two synthetic system basicity are different, the present invention can be further improved yield.?
Due to the presence of sodium hydroxides a large amount of in system in CN201210118788.7, cause the basicity of system high, so that one
The silica divided, which finally dissolves, leads to the reduction of its yield, and in the presence of ethylene glycol template, lead to it for neutral substance
For the sodium hydroxide of needs in synthetic system with regard to seldom, the basicity of its last system is just very low.Therefore, CN201210118788.7
For the solventless method synthetic technology normal yield 85%, maximum yield of the present invention can reach 98%.
Compared with the background art, advantageous effect of the invention is:
1, solvent-free solid-phase of the invention synthesizes total silicon SOD zeolite method, greatly improves the production of total silicon SOD zeolite
Rate farthest reduces the use of organic matter, and synthetic operation is simple, easy.
2, the product that the present invention obtains not only maintains good crystallinity and purity, has good reactivity.It is whole
A production process has remained the state of a solid phase, which reduces unnecessary waste discharge in process of production with
And loss.
3, inorganic raw material of the present invention is environmentally friendly, and price is less expensive, thus leads in practical Chemical Manufacture
Domain is of great significance.
Detailed description of the invention
Fig. 1 is the XRD spectra that solvent-free solid-phase synthesizes total silicon SOD zeolite；
Fig. 2 is the SEM photograph that solvent-free solid-phase synthesizes total silicon SOD zeolite.
Fig. 3 is the XRD spectra of the rich aluminium SOD zeolite in comparative example.
Fig. 4 is the SEM photograph of the rich aluminium SOD zeolite in comparative example.
Specific embodiment
Embodiment 1: solvent-free solid-phase synthesizes total silicon SOD zeolite
By 0.5g Na2SiO3·9H2O, 1.57g solid silicone, 1g ethylene glycol are placed in mortar and grind, then at 200 DEG C
Lower crystallization for 24 hours can complete crystallization；Product filters, and product can be obtained after drying.
The molar ratio of reaction raw materials are as follows: SiO2∶Na2O: ethylene glycol=1: 0.06: 0.6
Obtaining its structure by XRD analysis is total silicon SOD zeolite (Fig. 1), and finds out that the method obtains by SEM photograph
Total silicon SOD zeolite be bulk cubic (Fig. 2), particle size be 10-20 microns.Wherein, yield 98%.
Comparative example 1: the synthesis of rich aluminium SOD zeolite
By 3.045g Na2SiO3·9H2O、1.18gNaAlO2It is placed in mortar and grinds, then crystallization 4h is at 80 DEG C
It can complete crystallization；Product filters, and product can be obtained after drying.
The molar ratio of reaction raw materials are as follows: SiO2∶Na2O∶Al2O3=1: 1: 0.5
Obtaining its structure by XRD analysis is SOD zeolite (Fig. 3), and finds out the richness that the method obtains by SEM photograph
Aluminium SOD zeolite is nanoparticle (Fig. 4), and particle size is 200 nanometer of -1 microns.Wherein, yield 85%.
Embodiment 2: solvent-free solid-phase rapid synthesis total silicon SOD zeolite
By 0.16g Na2SiO3·9H2O, 1.62g solid silicone, 0.35g ethylene glycol are placed in mortar and grind, and then exist
Crystallization 4h can complete crystallization at 240 DEG C；Product filters, and product can be obtained after drying.
The molar ratio of reaction raw materials are as follows: SiO2∶Na2O: ethylene glycol=1: 0.02: 0.2
Embodiment 3: solvent-free Low Temperature Solid-Phase synthesizes total silicon SOD zeolite
By 0.8g Na2SiO3·9H2O, 1.5g white carbon black, 1.7g ethylene glycol are placed in mortar and grind, then at 160 DEG C
Crystallization 96h can complete crystallization；Product filters, and product can be obtained after drying.
The molar ratio of reaction raw materials are as follows: SiO2∶Na2O: ethylene glycol=1: 0.1: 1.0
Embodiment 4: total silicon SOD zeolite is synthesized by alkali source solvent-free solid-phase of NaOH
0.12g NaOH, 1.67g solid silicone, 1.7g ethylene glycol are placed in mortar and are ground, then the crystallization at 200 DEG C
48h can complete crystallization；Product filters, and product can be obtained after drying.
The molar ratio of reaction raw materials are as follows: SiO2∶Na2O: ethylene glycol=1: 0.05: 1.0
Embodiment 5: total silicon SOD zeolite is synthesized by alkali source solvent-free solid-phase of KOH
0.15g KOH, 1.67g solid silicone, 1.25g ethylene glycol are placed in mortar and are ground, then the crystallization at 200 DEG C
18h can complete crystallization；Product filters, and product can be obtained after drying.
The molar ratio of reaction raw materials are as follows: SiO2∶K2O: ethylene glycol=1: 0.04: 0.75
The above is only several case study on implementation of the invention, not does limitation in any form to the present invention,
Although the present invention is disclosed as above with preferable case study on implementation, however, it is not intended to limit the invention, any skill for being familiar with this profession
Art personnel, without departing from the scope of the present invention, when the structure and technology contents using the disclosure above make it is a little
Change or be modified to the equivalence enforcement case of equivalent variations.But anything that does not depart from the technical scheme of the invention, foundation
Technical spirit of the invention still belongs to the present invention to any simple modification, equivalent change and modification made by the above case study on implementation
In technical proposal scope.
Claims (3)
1. a kind of method of solvent-free solid-phase synthesis total silicon SOD zeolite, which comprises the following steps:
Silicon source, alkali source, ethylene glycol are placed in mortar, ground；Then it goes in reaction kettle, in 160~240 DEG C of crystallization 4
~96h；Product is filtered, is dried to get total silicon SOD zeolite is arrived；
The molar ratio range of each reaction raw materials additive amount is SiO2∶Na2O: ethylene glycol=1: 0.02~0.1: 0.2~1.0.
2. the method according to claim 1, wherein the silicon source is solid silicone or white carbon black.
3. the method according to claim 1, wherein the alkali source is sodium hydroxide, sodium metasilicate or potassium hydroxide.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811036549.0A CN109160522B (en) | 2018-09-06 | 2018-09-06 | Method for synthesizing all-silicon SOD zeolite by solvent-free solid phase |
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| CN201811036549.0A CN109160522B (en) | 2018-09-06 | 2018-09-06 | Method for synthesizing all-silicon SOD zeolite by solvent-free solid phase |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110040740A (en) * | 2019-05-09 | 2019-07-23 | 嘉兴学院 | The method that crystal seed is oriented to method synthesis total silicon SOD zeolite |
| CN110078095A (en) * | 2019-05-09 | 2019-08-02 | 嘉兴学院 | The method that crystal seed is oriented to method synthesis total silicon ZSM-39 zeolite |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0333283B1 (en) * | 1988-03-15 | 1993-01-07 | Shell Internationale Researchmaatschappij B.V. | Crystalline silicon-rich (metallo) silicates of the sodalite type and process for preparing such (metallo)silicates |
| CN102627287A (en) * | 2012-04-20 | 2012-08-08 | 浙江大学 | Method for synthesizing molecular sieve under solvent-free condition through grinding solid phase raw materials |
| CN108264056A (en) * | 2018-03-02 | 2018-07-10 | 浙江大学 | A kind of method of no sodium solvent-free route synthesis total silicon Beta zeolite molecular sieve |
-
2018
- 2018-09-06 CN CN201811036549.0A patent/CN109160522B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0333283B1 (en) * | 1988-03-15 | 1993-01-07 | Shell Internationale Researchmaatschappij B.V. | Crystalline silicon-rich (metallo) silicates of the sodalite type and process for preparing such (metallo)silicates |
| CN102627287A (en) * | 2012-04-20 | 2012-08-08 | 浙江大学 | Method for synthesizing molecular sieve under solvent-free condition through grinding solid phase raw materials |
| CN108264056A (en) * | 2018-03-02 | 2018-07-10 | 浙江大学 | A kind of method of no sodium solvent-free route synthesis total silicon Beta zeolite molecular sieve |
Non-Patent Citations (3)
| Title |
|---|
| LIMIN REN ET AL.: "Solvent-Free Synthesis of Zeolites from Solid Raw Materials", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》 * |
| SUK BONG HONG ET AL.: "Host-Guest Interactions in Pure-Silica and Aluminosilicate Sodalites Containing Ethylene Glycol as a Guest Molecule", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》 * |
| XIANGJU MENG ET AL.: "Solvent-free synthesis of zeolite catalysts", 《SCIENCE CHINA CHEMISTRY》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110040740A (en) * | 2019-05-09 | 2019-07-23 | 嘉兴学院 | The method that crystal seed is oriented to method synthesis total silicon SOD zeolite |
| CN110078095A (en) * | 2019-05-09 | 2019-08-02 | 嘉兴学院 | The method that crystal seed is oriented to method synthesis total silicon ZSM-39 zeolite |
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| CN109160522B (en) | 2022-04-22 |
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