CN107973319B - A kind of method of uninanned platform ZSM-23 zeolite - Google Patents
A kind of method of uninanned platform ZSM-23 zeolite Download PDFInfo
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- CN107973319B CN107973319B CN201711252763.5A CN201711252763A CN107973319B CN 107973319 B CN107973319 B CN 107973319B CN 201711252763 A CN201711252763 A CN 201711252763A CN 107973319 B CN107973319 B CN 107973319B
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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
- 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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Abstract
The present invention relates to molecular sieve preparation methods, it is desirable to provide a kind of method of uninanned platform ZSM-23 zeolite.It is to be placed in silicon source, silicon source, Fluorine source in mortar with as 1, the 3- diisopropyl iodonium imidazolide salts of organic formwork agent, silicon source used, silicon source, the molar ratio range of Fluorine source and organic formwork agent are 1: 0~0.01: 0.5~2: 0.05~0.3；Transposition is in reaction kettle after the ground processing of raw material, 0.5~15d of crystallization under the conditions of 100~200 DEG C；Reaction product is filtered, drying, obtains ZSM-23 zeolite.The method increase synthetic yields, reduce the use of organic formwork agent, and using nonvolatile ammonium fluoride completely instead of HF, and synthetic operation is simple and easy.Organic formwork agent toxicity used is low, at low cost, has application prospect.Inorganic raw material used by producing is environmentally friendly, and price is less expensive, thus the present invention 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 uninanned platform ZSM-23 zeolite.
Background technique
ZSM-23 zeolite be it is a kind of comprising five-membered ring, hexatomic ring, ten-ring duct the medium hole with MTT topological structure
The silica-rich zeolite of diameter.The scientists such as Plank are reported for the first time using pyrrolidines as organic formwork synthesis ZSM-23 molecular screen
Method (USP4076,842).Later, researcher has found that it shows in isomerization of butene, xylene isomerization and MTG reaction
Very excellent performance out causes the enthusiasm that people study ZSM-23 zeolite.
At this stage, in the synthesis of ZSM-23 zeolite, main the problem of there are two aspects: its synthesize all under hydrothermal conditions into
Row, synthesis cost is higher and inefficiency；Used organic formwork agent is mostly organic amine (such as isopropylamine, dimethylamine etc.),
Its toxicity is big, high volatility.For the problem of hydrothermal synthesis poor efficiency, also there is the method for proposing uninanned platform zeolite, still
By up to the present, synthesis to ZSM-23 zeolite is simultaneously failed.For the big problem of organic formwork agent toxicity, Zones religion
Seminar is awarded using hydroxide 1, the ionic liquid of this green of 3- diisopropyl imidazoles is synthesized as template.But hydrogen
Oxidation 1,3- diisopropyl imidazoles synthesis cost is higher, and the HF of extremely volatile severe toxicity has been used in synthesis, this is unfavorable
In the production of zeolite.
A kind of method for having synthesized ZSM-23 zeolite with having developed solvent-free inexpensive hypotoxicity in this patent, this method
The yield of ZSM-23 zeolite is greatly improved, the cost using organic formwork agent is reduced, it is complete using nonvolatile ammonium fluoride
Entirely instead of HF, and synthetic operation is simple and easy.
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 uninanned platform ZSM-
The method of 23 zeolites.
In order to solve the technical problem, solution of the invention is:
A kind of method of uninanned platform ZSM-23 zeolite is provided, comprising the following steps:
Silicon source, silicon source, Fluorine source and 1, the 3- diisopropyl iodonium imidazolide salts as organic formwork agent are placed in mortar, it is used
Silicon source, silicon source, the molar ratio range of Fluorine source and organic formwork agent are 1: 0~0.01: 0.5~2: 0.05~0.3；Raw material is ground
Transposition is in reaction kettle after processing, 0.5~15d of crystallization under the conditions of 100~200 DEG C；Reaction product is filtered, drying,
Obtain ZSM-23 zeolite.
In the present invention, the silicon source is solid silicone or white carbon black.
In the present invention, source of aluminium is boehmite or aluminium hydroxide.
In the present invention, the Fluorine source is ammonium fluoride or ammonium acid fluoride.
In the present invention, the organic formwork agent is 1,3- diisopropyl iodonium imidazolide salts.
In the present invention, to reduce the crystallization time, crystal seed is added into reaction system before starting the reaction to accelerate crystalline substance
Change speed, the mass ratio for controlling zeolite seed crystal and silicon source is 5~10%.
Inventive principle description:
In the prior art, volatile highly toxic organic amine or hydrogen at high cost are used usually under hydrothermal system
The hydrogen fluoride of 1,3- diisopropyl imidazoles and high volatility is aoxidized as template and mineralizer, this considerably increases zeolite molecules
It sieves the cost of synthesis and causes the generation of a large amount of waste water.
The present invention provides use the organic formwork agent of inexpensive hypotoxicity, nonvolatile ammonium fluoride as mineralizer in nothing
ZSM-23 zeolite molecular sieve synthetic method is realized under solvent solid phase conditions.
Compared with prior art, the beneficial effects of the present invention are:
1, the method for solvent-free solid-phase synthesis ZSM-23 zeolite improves its synthetic yield, reduces making for organic formwork agent
With using nonvolatile ammonium fluoride completely instead of HF, and synthetic operation is simple and easy.
2, compared with the background art, this product not only maintains good crystallinity and purity, has good catalysis anti-
Answer activity.Entire production process does not use solvent, used which reduces unnecessary loss in process of production
Organic formwork agent toxicity is low, at low cost, has application prospect.Produce used by inorganic raw material it is environmentally friendly, price compared with
It is cheap, thus the present invention is of great significance in practical chemical production field.
Detailed description of the invention
Fig. 1 is the XRD spectra of uninanned platform ZSM-23 zeolite；
Fig. 2 is the SEM photograph of uninanned platform ZSM-23 zeolite.
Specific embodiment
Embodiment 1: uninanned platform ZSM-23 zeolite
By 1.6g solid silicone, 1g ammonium fluoride, 0.37g 1,3- diisopropyl iodonium imidazolide salts (T) are placed in grinding and grind,
Then at 160 DEG C crystallization 3d can complete crystallization, product filter, product can be obtained after drying.Reaction raw materials proportion is as follows
(molar ratio):
1SiO2:1NH4F:0.05T
Obtaining its structure by XRD analysis is ZSM-23 zeolite (Fig. 1), and be can be seen that typically by SEM photograph
Belong to the Rod-like shape (Fig. 2) of ZSM-23 zeolite.
Embodiment 2: solvent-free high―temperature nuclei ZSM-23 zeolite
By 1.6g solid silicone, 2g ammonium fluoride and 0.74g 1,3- diisopropyl iodonium imidazolide salts are placed in grinding and grind,
Then at 200 DEG C crystallization 1d can complete crystallization, product filter, product can be obtained after drying.Reaction raw materials proportion is as follows
(molar ratio):
1SiO2:2NH4F:0.1T
Embodiment 3: solvent-free low temperature synthesizes ZSM-23 zeolite
By 1.6g solid silicone, 0.5g ammonium fluoride, 2.22g 1,3- diisopropyl iodonium imidazolide salts and 0.16g ZSM-23
Zeolite seed crystal be placed in grinding in grind, then at 100 DEG C crystallization 15d can complete crystallization, product filter, after drying can be obtained
Product.Reaction raw materials match following (molar ratio):
1SiO2:0.5NH4F:0.3T
Embodiment 4: the uninanned platform zeolite of ZSM-23 containing aluminium
By 1.6g white carbon black, 0.04g boehmite, 1g ammonium acid fluoride, 0.37g 1,3- diisopropyl iodonium imidazolide salts are placed in
Ground in grinding, then at 160 DEG C crystallization 4d can complete crystallization, product filter, product can be obtained after drying.Reaction is former
Material matches following (molar ratio):
1SiO2:0.01Al2O3:1NH4F:0.05T
Embodiment 5: solvent-free high―temperature nuclei ZSM-23 containing aluminium zeolite
By 1.6g solid silicone, 0.01g aluminium hydroxide, 1g ammonium fluoride, 0.74g 1,3- diisopropyl iodonium imidazolide salts are placed in
Ground in grinding, then at 200 DEG C crystallization 1d can complete crystallization, product filter, product can be obtained after drying.Reaction is former
Material matches following (molar ratio):
1SiO2:0.005Al2O3:1NH4F:0.1T
Embodiment 6: the quick uninanned platform ZSM-23 zeolite of high temperature
By 1.6g solid silicone, 1g ammonium fluoride, 0.74g 1,3- diisopropyl iodonium imidazolide salts and 0.08g ZSM-23 boiling
Stone crystal seed be placed in grinding in grind, then at 200 DEG C crystallization 0.5d can complete crystallization, product filter, after drying can be obtained
Product.Reaction raw materials match following (molar ratio):
1SiO2:1NH4F:0.1T
Embodiment 7: solvent-free high―temperature nuclei ZSM-23 containing aluminium zeolite
By 1.6g solid silicone, 0.01g aluminium hydroxide, 1g ammonium fluoride, 0.74g 1,3- diisopropyl iodonium imidazolide salts and
0.12g ZSM-23 zeolite seed crystal be placed in grinding in grind, then at 160 DEG C crystallization 1d can complete crystallization, product filter,
Product can be obtained after drying.Reaction raw materials match following (molar ratio):
1SiO2:0.005Al2O3:1NH4F:0.1T
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 (5)
1. a kind of method of uninanned platform ZSM-23 zeolite, which comprises the following steps:
Silicon source, silicon source, Fluorine source and 1, the 3- diisopropyl iodonium imidazolide salts as organic formwork agent are placed in mortar, silicon used
Source, silicon source, the molar ratio range of Fluorine source and organic formwork agent are 1: 0~0.01: 0.5~2: 0.05~0.3；The ground place of raw material
Transposition is in reaction kettle after reason, 0.5~15 d of crystallization under the conditions of 100~200 DEG C；Reaction product is filtered, drying,
Obtain ZSM-23 zeolite.
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 source of aluminium is boehmite or aluminium hydroxide.
4. the method according to claim 1, wherein the Fluorine source is ammonium fluoride or ammonium acid fluoride.
5. the method according to claim 1, wherein to reduce the crystallization time, before starting the reaction to anti-
It answers and crystal seed is added in system to accelerate crystallization rate, the mass ratio for controlling zeolite seed crystal and silicon source is 5~10%.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108914244B (en) * | 2018-06-19 | 2021-05-11 | 江苏迪胺新材料科技有限公司 | Preparation method for synthesizing conductive polymer polyaniline nano-fiber by taking molecular sieve as seed crystal in guiding manner |
| CN109279621B (en) * | 2018-09-13 | 2020-05-12 | 浙江大学 | Method for synthesizing silicon-based zeolite molecular sieve by adopting general ionothermal method |
| CN109721067B (en) * | 2019-02-03 | 2022-04-22 | 嘉兴学院 | Method for synthesizing aluminum-rich ZSM-23 zeolite by sustainable route |
| CN113979444B (en) * | 2020-07-27 | 2023-11-24 | 中国石油化工股份有限公司 | Preparation method of molecular sieve with FER structure and molecular sieve with FER structure |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4490342A (en) * | 1983-04-29 | 1984-12-25 | Mobil Oil Corporation | Synthesis of ZSM-23 zeolite |
| US5405596A (en) * | 1993-06-29 | 1995-04-11 | Mobil Oil Corp. | Synthesis of crystalline ZSM-23 |
| CN102897785B (en) * | 2011-07-29 | 2014-10-01 | 中国石油化工股份有限公司 | Synthesis method for ZSM-23 molecular sieve |
| CN105753012A (en) * | 2016-01-22 | 2016-07-13 | 嘉兴学院 | Solvent-free solid-phase synthesis method for PERFER zeolite layered precursor |
| CN107151023A (en) * | 2017-06-01 | 2017-09-12 | 嘉兴学院 | The method of the solvent-free solid-phase synthesis synthesis zeolites of ZSM 48 |
-
2017
- 2017-12-01 CN CN201711252763.5A patent/CN107973319B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4490342A (en) * | 1983-04-29 | 1984-12-25 | Mobil Oil Corporation | Synthesis of ZSM-23 zeolite |
| US5405596A (en) * | 1993-06-29 | 1995-04-11 | Mobil Oil Corp. | Synthesis of crystalline ZSM-23 |
| CN102897785B (en) * | 2011-07-29 | 2014-10-01 | 中国石油化工股份有限公司 | Synthesis method for ZSM-23 molecular sieve |
| CN105753012A (en) * | 2016-01-22 | 2016-07-13 | 嘉兴学院 | Solvent-free solid-phase synthesis method for PERFER zeolite layered precursor |
| CN107151023A (en) * | 2017-06-01 | 2017-09-12 | 嘉兴学院 | The method of the solvent-free solid-phase synthesis synthesis zeolites of ZSM 48 |
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