CN107973319A - A kind of method of uninanned platform ZSM-23 zeolites - Google Patents
A kind of method of uninanned platform ZSM-23 zeolites Download PDFInfo
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- CN107973319A CN107973319A CN201711252763.5A CN201711252763A CN107973319A CN 107973319 A CN107973319 A CN 107973319A CN 201711252763 A CN201711252763 A CN 201711252763A CN 107973319 A CN107973319 A CN 107973319A
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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 method, it is desirable to provide a kind of method of 23 zeolites of uninanned platform ZSM.It is using silicon source, silicon source, Fluorine source and is placed in mortar as 1,3 diisopropyl iodonium imidazolide salts of organic formwork agent, silicon source used, silicon source, the molar ratio range of Fluorine source and organic formwork agent is 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, is dried, obtains 23 zeolites of ZSM.Synthetic yield is the method increase, reduces the use of organic formwork agent, instead of HF completely using nonvolatile ammonium fluoride, and synthetic operation is simple and practicable.Organic formwork agent toxicity used is low, cost is low, has application prospect.Inorganic raw material is environmentally friendly used by production, and price is less expensive, thus the present invention is of great significance in actual chemical production field.
Description
Technical field
The invention belongs to molecular sieve preparation method, more particularly to the method for uninanned platform ZSM-23 zeolites.
Background technology
ZSM-23 zeolites are a kind of comprising five-membered ring, hexatomic ring, the medium hole with MTT topological structures in ten-ring duct
The silica-rich zeolite in footpath.The scientists such as Plank report using pyrrolidines as organic formwork synthesis ZSM-23 molecular screen first
Method (USP4076,842).Afterwards, researcher has found that it shows in isomerization of butene, xylene isomerization and MTG reactions
Go out very excellent performance, cause the enthusiasm that people study ZSM-23 zeolites.
At this stage, in the synthesis of ZSM-23 zeolites, mainly there is the problem of two aspects：Its synthesize all under hydrothermal conditions into
OK, synthesize that 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 Hydrothermal Synthesiss it is inefficient the problem of, also have propose uninanned platform zeolite method, still
By up to the present, synthesis to ZSM-23 zeolites is simultaneously failed.For organic formwork agent toxicity it is big the problem of, Zones religion
Award seminar and use hydroxide 1, this green ionic liquid of 3- diisopropyl imidazoles is synthesized as template.But hydrogen
It is higher to aoxidize 1,3- diisopropyls imidazoles synthesis cost, and extremely volatile hypertoxic HF has been used in synthesis, this is unfavorable
In the production of zeolite.
A kind of method for having synthesized ZSM-23 zeolites with having developed solvent-free inexpensive hypotoxicity in this patent, this method
The yield of ZSM-23 zeolites is drastically increased, reduces the cost using organic formwork agent, it is complete using nonvolatile ammonium fluoride
HF is instead of entirely, and synthetic operation is simple and practicable.
The content of the invention
The technical problem to be solved in the present invention is overcome deficiency of the prior art, there is provided a kind of uninanned platform ZSM-
The method of 23 zeolites.
To solve technical problem, solution of the invention is：
A kind of method of uninanned platform ZSM-23 zeolites is provided, is comprised the following steps：
It is used using silicon source, silicon source, Fluorine source with being placed in as 1, the 3- diisopropyl iodonium imidazolide salts of organic formwork agent in mortar
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, is dried,
Obtain ZSM-23 zeolites.
In the present invention, the silicon source is solid silicone or white carbon.
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, it is 5~10% to control zeolite seed crystal and the mass ratio of silicon source.
Inventive principle describes：
In the prior art, volatile highly toxic organic amine, or hydrogen of high cost are used usually under hydrothermal system
The hydrogen fluoride of 1,3- diisopropyls imidazoles and high volatility is aoxidized as template and mineralizer, this considerably increases zeolite molecules
Sieve the cost of synthesis and cause 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 methods are realized under solvent solid phase conditions.
Compared with prior art, the beneficial effects of the present invention are：
1st, the method for solvent-free solid-phase synthesis ZSM-23 zeolites improves its synthetic yield, reduces making for organic formwork agent
With instead of HF completely using nonvolatile ammonium fluoride, and synthetic operation is simple and practicable.
2nd, compared with background technology, this product not only maintains good crystallinity and purity, anti-with good catalysis
Should activity.Whole production process does not use solvent, used which reduces unnecessary loss in process of production
Organic formwork agent toxicity is low, cost is low, has application prospect.Inorganic raw material is environmentally friendly used by production, price compared with
It is cheap, thus the present invention is of great significance in actual chemical production field.
Brief description of the drawings
Fig. 1 is the XRD spectra of uninanned platform ZSM-23 zeolites；
Fig. 2 is the SEM photograph of uninanned platform ZSM-23 zeolites.
Embodiment
Embodiment 1：Uninanned platform ZSM-23 zeolites
1.6g solid silicones, 1g ammonium fluorides, 0.37g 1,3- diisopropyls iodonium imidazolide salts (T) are placed in grinding and ground,
Then at 160 DEG C crystallization 3d can complete crystallization, product filter, can obtain product after drying.Reaction raw materials proportioning is as follows
(molar ratio)：
1SiO2:1NH4F:0.05T
It is ZSM-23 zeolites (Fig. 1) to obtain its structure by XRD analysis, and be can be seen that typically by SEM photograph
Belong to the Rod-like shape (Fig. 2) of ZSM-23 zeolites.
Embodiment 2：Solvent-free high―temperature nuclei ZSM-23 zeolites
By 1.6g solid silicones, 2g ammonium fluorides 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, can obtain product after drying.Reaction raw materials proportioning is as follows
(molar ratio)：
1SiO2:2NH4F:0.1T
Embodiment 3：Solvent-free low temperature synthesizes ZSM-23 zeolites
By 1.6g solid silicones, 0.5g ammonium fluorides, 2.22g 1,3- diisopropyls 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 obtain
Product.Reaction raw materials proportioning is following (molar ratio)：
1SiO2:0.5NH4F:0.3T
Embodiment 4：Uninanned platform ZSM-23 containing aluminium zeolites
1.6g white carbons, 0.04g boehmites, 1g ammonium acid fluorides, 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, after drying i.e. can obtain product.Reaction is former
Material proportioning is following (molar ratio)：
1SiO2:0.01Al2O3:1NH4F:0.05T
Embodiment 5：Solvent-free high―temperature nuclei ZSM-23 containing aluminium zeolites
1.6g solid silicones, 0.01g aluminium hydroxides, 1g ammonium fluorides, 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, can obtain product after drying.Reaction is former
Material proportioning is following (molar ratio)：
1SiO2:0.005Al2O3:1NH4F:0.1T
Embodiment 6：The quick uninanned platform ZSM-23 zeolites of high temperature
By 1.6g solid silicones, 1g ammonium fluorides, 0.74g 1,3- diisopropyls iodonium imidazolide salts and 0.08g ZSM-23 boilings
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 obtain
Product.Reaction raw materials proportioning is following (molar ratio)：
1SiO2:1NH4F:0.1T
Embodiment 7：Solvent-free high―temperature nuclei ZSM-23 containing aluminium zeolites
By 1.6g solid silicones, 0.01g aluminium hydroxides, 1g ammonium fluorides, 0.74g 1,3- diisopropyls iodonium imidazolide salts and
0.12g ZSM-23 zeolite seed crystals be placed in grinding in grind, then at 160 DEG C crystallization 1d can complete crystallization, product filter,
Product is can obtain after drying.Reaction raw materials proportioning is following (molar ratio)：
1SiO2:0.005Al2O3:1NH4F:0.1T
The above, is only several case study on implementation of the present invention, and limitation in any form is not done to the present invention,
Although the present invention is disclosed as above with preferable case study on implementation, but is not limited to the present invention, any to be familiar with this professional skill
Art personnel, without departing from the scope of the present invention, when structure and technology contents using the disclosure above make it is a little
Change or be modified to the equivalence enforcement cases of equivalent variations.But every content without departing from technical solution of the present invention, foundation
Any simple modification, equivalent change and modification that the technical spirit of the present invention makees above case study on implementation, still belongs to the present invention
In the range of technical solution.
Claims (6)
- A kind of 1. method of uninanned platform ZSM-23 zeolites, it is characterised in that comprise the following steps：Using silicon source, silicon source, Fluorine source with being placed in as 1, the 3- diisopropyl iodonium imidazolide salts of organic formwork agent 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, 0.5~15d of crystallization under the conditions of 100~200 DEG C；Reaction product is filtered, is dried, is obtained To ZSM-23 zeolites.
- 2. according to the method described in claim 1, it is characterized in that, the silicon source is solid silicone or white carbon.
- 3. according to the method described in claim 1, it is characterized in that, source of aluminium is boehmite or aluminium hydroxide.
- 4. according to the method described in claim 1, it is characterized in that, the Fluorine source is ammonium fluoride or ammonium acid fluoride.
- 5. according to the method described in claim 1, it is characterized in that, the organic formwork agent is 1,3- diisopropyl imidazoles iodine Salt.
- 6. according to the method described in claim 1, it is characterized in that, to reduce the crystallization time, before starting the reaction to anti- Answer and crystal seed is added in system to accelerate crystallization rate, it is 5~10% to control zeolite seed crystal and the mass ratio of silicon source.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108914244A (en) * | 2018-06-19 | 2018-11-30 | 江苏迪胺新材料科技有限公司 | A kind of preparation method being oriented to synthesis conductive polymer polyanilinc nano fiber using molecular sieve as crystal seed |
| CN109279621A (en) * | 2018-09-13 | 2019-01-29 | 浙江大学 | A method of using general ion thermal method synthesis of silica-base zeolite molecular sieve |
| CN109721067A (en) * | 2019-02-03 | 2019-05-07 | 嘉兴学院 | A kind of method of the synthesizing aluminum-enriched ZSM-23 zeolite of sustainable route |
| CN113979444A (en) * | 2020-07-27 | 2022-01-28 | 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 |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108914244A (en) * | 2018-06-19 | 2018-11-30 | 江苏迪胺新材料科技有限公司 | A kind of preparation method being oriented to synthesis conductive polymer polyanilinc nano fiber using molecular sieve as crystal seed |
| CN109279621A (en) * | 2018-09-13 | 2019-01-29 | 浙江大学 | A method of using general ion thermal method synthesis of silica-base zeolite molecular sieve |
| CN109721067A (en) * | 2019-02-03 | 2019-05-07 | 嘉兴学院 | A kind of method of the synthesizing aluminum-enriched ZSM-23 zeolite of sustainable route |
| CN109721067B (en) * | 2019-02-03 | 2022-04-22 | 嘉兴学院 | Method for synthesizing aluminum-rich ZSM-23 zeolite by sustainable route |
| CN113979444A (en) * | 2020-07-27 | 2022-01-28 | 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 |
| 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 |
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