CN105152181A - Preparation method of all-silicon MTN topology structure molecular sieve - Google Patents
Preparation method of all-silicon MTN topology structure molecular sieve Download PDFInfo
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- CN105152181A CN105152181A CN201510533463.9A CN201510533463A CN105152181A CN 105152181 A CN105152181 A CN 105152181A CN 201510533463 A CN201510533463 A CN 201510533463A CN 105152181 A CN105152181 A CN 105152181A
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- molecular sieve
- mtn
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Abstract
The invention discloses a synthesis method of an all-silicon MTN topology structure molecular sieve. The synthesis method includes firstly, dissolving inorganic lamellar precursor in alkali liquor of a certain concentration, and uniformly dispersing a silicon source uniformly under stirring action of strong magnetic force at room temperature to obtain a mixture; secondly, adding template and mineralizer sequentially into the mixture and then stirring to obtain a gel product; thirdly, transferring the gel product to a closed container to crystallize at a temperature of 120-200 DEG C for 3-10 days so as to obtain the all-silicon MTN topology structure molecular sieve. The synthesis method has the advantages that the all-silicon MTN molecular sieve is prepared by directly crystallizing the lamellar silicon source which has wide source and is low in cost and easy to obtain, utilization rate of the silicon source is high, the product has good crystallinity and repeatability, and particle size and shape of the product are controllable; as the template is an environment-friendly solvent, environmental pollution is low; the synthesis method is applicable to large scale industrial production.
Description
Technical field
The present invention relates to the synthesis of molecular sieve, especially a kind of synthetic method of total silicon type MTN molecular sieve, namely using eco-friendly imidazole type ion liquid as template, inorganic laminated presoma as silicon source, Hydrothermal Synthesis total silicon type MTN topological framework molecular sieve.
Background technology
The molecular sieve of MTN type topological framework, it is a kind of caged thing be formed by connecting alternately by five-ring and six-ring basic structural unit, and in each MTN structure cell, cage consists of 8 [5
12] and 8 [5
126
4], larger cage [5
126
4] primarily of five-ring and six-ring composition, its freeboard is of a size of 0.62nm, the 0.25nm but the free aperture of its permission molecular diffusion is but only had an appointment.Although the cage structure feature of MTN type molecular sieve limit its in absorption, be separated and application in catalysis etc., it still has potential using value on nonlinear optical material.
The representative molecular sieve of MTN topological framework is ZSM-39, 1981, Mobil company of the U.S. makes public for the first time the synthetic method (US Patent No. 4 of ZSM-39 molecular sieve, 287, 166 and US Patent No. 4, 259, 306), single template that the method uses is tetraethyl ammonium hydroxide, Tri N-Propyl Amine or tetramethyleneimine, wherein first two list template within 70 hours, obtains ZSM-39 Si-Al molecular sieve 160 DEG C of crystallization, then a kind of single template is in the presence of four urea cobalt complexs, first 160 DEG C of dynamic crystallizations 9 days, then 210 DEG C of dynamic crystallizations obtain ultimate aim ZSM-39 molecular sieve in 5 days.
Nineteen eighty-two, Mobil company of the U.S. have studied the catalytic performance (US4,357,233) of ZSM-39 molecular sieve.
Chinese patent CN102627287B discloses a kind of method can being synthesized ZSM-39 Si-Al molecular sieve by Solid raw materials grinding under condition of no solvent.
Chinese patent CN103145142A disclose a kind of be template with piperidines, Hydrothermal Synthesis contains the heteroatomic ZSM-39 molecular sieve of Ti, V, Cr, Fe, Co or Ni.
In sum, the molecular sieve in the past synthesizing MTN type topological framework mostly is sial or contains heteroatomic molecular sieve, and also environmental pollution is serious for organic amine template used.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of MTN topological framework molecular sieve of total silicon type, the method is using one eco-friendly green solvent imidazole type ion liquid as template, inorganic laminated presoma as silicon source, synthesizes a kind of highly stable, total silicon type MTN topological framework molecular sieve that resistance to acid is strong under hydrothermal conditions.
The object of the present invention is achieved like this:
A preparation method for the MTN topological framework molecular sieve of total silicon type, comprises following concrete steps:
Steps A: inorganic laminated presoma, sodium hydroxide and deionized water are mixed, under room temperature, strong magnetic agitation 0.5 ~ 3 hour, obtains mixture, and wherein, described inorganic laminated presoma is layered silicate; The mol ratio of material is H
2o ︰ SiO
2=10 ~ 80, Na
2o ︰ SiO
2=0.01 ~ 0.1;
Step B: add template, mineralizer successively in the mixture of steps A, at room temperature strong magnetic agitation 1 ~ 3 hour, obtains jel product; Wherein, the mol ratio R ︰ SiO in template (R) and silicon source
2=0.1 ~ 1, mineralizer (M) is M ︰ SiO with the mol ratio in silicon source
2=0.1 ~ 1, described template is at least one in 1-butyl-3-methyl-imidazolium chloride, 1-propyl group-3-methylimidazolium chloride, 1-ethyl-3-methyl-limidazolium, 1-ethyl-3-methyl-imidazolium chloride, 1-butyl-3-methy limidazolium, 1-(2-hydroxyethyl)-3-methylimidazolium chloride, and described mineralizer is at least one in Neutral ammonium fluoride, hydrofluoric acid, Sodium Fluoride, Potassium monofluoride;
Step C: the jel product obtained by step B is transferred in encloses container, 120 ~ 200 DEG C of crystallization 3 ~ 10 days, obtains described total silicon type MTN topological framework molecular sieve.
In the present invention, the layered silicate of steps A is Magaditte (Na
2si
14o
2910H
2o), Kenyaite (Na
2si
22o
4311H
2and Kanemite (NaHSi O)
2o
53H
2o) at least one in.
In the present invention, the preferred 1-of template described in step B (2-hydroxyethyl)-3-methylimidazolium chloride or 1-ethyl-3-methyl-imidazolium chloride, the mol ratio preferred R ︰ SiO in template (R) and silicon source
2=0.1 ~ 0.3, mineralizer preferred fluorinated ammonium, mineralizer (M) is M ︰ SiO with the mol ratio in silicon source
2=0.3 ~ 0.6.
In the present invention, step C crystallization temperature is 150 ~ 180 DEG C, crystallization time preferably 5 ~ 7 days.
By the method disclosed in the present, by regulating the consumption of the basicity of the consumption of inorganic laminated silicate and template, reaction system, crystallization temperature, time and water, the total silicon type MTN molecular sieve of different surface morphology can be obtained.
The present invention utilizes its phase structure of X-ray diffraction technical Analysis and degree of crystallinity, by its pattern of SEM scanning electron microscope observation and grain size.
The present invention adopts inorganic laminated presoma as silicon source, and its advantage is not only wide material sources, cheap, and the inner five-ring of itself, six-ring structure molecular sieve nucleus can be made to be formed fast, greatly can shorten crystallization time; In addition, of the present invention be a kind of eco-friendly green solvent imidazole type ion liquid is template, greatly reduce environmental pollution, synthesize the total silicon type MTN molecular sieve obtained and there is high stability and resistance to acid, it has wide using value on nonlinear optical material, synthetic method is simple to operate, is suitable for large-scale commercial production.
Accompanying drawing explanation
Fig. 1 is X-ray diffractogram (XRD) figure of the MTN type molecular sieve that the embodiment of the present invention 1 is synthesized;
Fig. 2 is scanning electron microscope (SEM) figure of the MTN type molecular sieve that the embodiment of the present invention 1 is synthesized;
Fig. 3 is X-ray diffractogram (XRD) figure of the MTN type molecular sieve of the 2-in-1 one-tenth of the embodiment of the present invention;
Fig. 4 is scanning electron microscope (SEM) figure of the MTN type molecular sieve of the 2-in-1 one-tenth of the embodiment of the present invention;
Fig. 5 is X-ray diffractogram (XRD) figure of the MTN type molecular sieve that the embodiment of the present invention 3 is synthesized;
Fig. 6 is scanning electron microscope (SEM) figure of the MTN type molecular sieve that the embodiment of the present invention 3 is synthesized.
Embodiment
Here is that the present invention is further described by some embodiments; its objective is and better understand content of the present invention; but not any pro forma restriction is done to the present invention; as long as any pro forma simple modification do the embodiment of the present invention and modification, all belong in technical solution of the present invention protection domain.
Embodiment 1
0.32g sodium hydroxide is put in 24.7g deionized water, is stirred to solution clarification, then by 12.26gMagaditte (Na
2si
14o
2910H
2o) join in described solution, stirring at room temperature half an hour.Add 14.1g1-(2-hydroxyethyl)-3-methyl hydrogen oxidation imidazoles (20% aqueous solution) as template and 2.2g Neutral ammonium fluoride, stirring at room temperature 1 hour, obtains jel product, and this product has following mole of composition: SiO
2: H
2o:OH
-: R:F
-=1:10:0.04:0.1:0.3.The jel product obtained is transferred to in teflon-lined stainless steel autoclave, after airtight in 150 DEG C of baking ovens crystallization 7 days, through ordinary method suction filtration, washing and drying, finally obtain solid product.
Diffraction peak has all been there is at 7.8,12.9,15.1,15.8,18.2,19.9,23.8 degree of places in embodiment 1 gained solid product through X ray diffracting spectrum, there is good degree of crystallinity, can analyze as MTN type structure molecular screen, stereoscan photograph display plane of crystal is smooth, and size and shape is all very homogeneous.XRD and SEM characterization result is as Fig. 1 and Fig. 2.
Embodiment 2
0.32g sodium hydroxide is put in 13.5g deionized water, is stirred to solution clarification, then by 12.16gKenyaite (Na
2si
22o
4311H
2o) join in described solution, stirring at room temperature 3 hours.Add 28.2g1-(2-hydroxyethyl)-3-methyl hydrogen oxidation imidazoles (20% aqueous solution) as template and 3.7g Neutral ammonium fluoride, stirring at room temperature 3 hours, obtains jel product, and this product has following mole of composition: SiO
2: H
2o:OH
-: R:F
-=1:10:0.04:0.2:0.5.The jel product obtained is transferred to in teflon-lined stainless steel autoclave, after airtight in 180 DEG C of baking ovens crystallization 5 days, through ordinary method suction filtration, washing and drying, finally obtain solid product.
Diffraction peak has all been there is at 7.8,12.9,15.1,15.8,18.2,19.9,23.8 degree of places in embodiment 2 gained solid product through X ray diffracting spectrum, there is good degree of crystallinity, can analyze as MTN type structure molecular screen, stereoscan photograph display plane of crystal is smooth, and size and shape is all very homogeneous.XRD and SEM characterization result is as Fig. 3 and Fig. 4.
Embodiment 3
0.32g sodium hydroxide is put in 2.3g deionized water, is stirred to solution clarification, then by 13.8gKanemite (NaHSi
2o
53H
2o) join in above-mentioned solution, stirring at room temperature 2 hours.Add 42.3g1-(2-hydroxyethyl)-3-methyl hydrogen oxidation imidazoles (20% aqueous solution) as template and 4.4g Neutral ammonium fluoride, stirring at room temperature 2 hours, obtains jel product, and this product has following mole of composition: SiO
2: H
2o:OH
-: R:F
-=1:10:0.04:0.3:0.6.The jel product obtained is transferred to in teflon-lined stainless steel autoclave, after airtight in 170 DEG C of baking ovens crystallization 6 days, through ordinary method suction filtration, washing and drying, finally obtain solid product.
Diffraction peak has all been there is at 7.8,12.9,15.1,15.8,18.2,19.9,23.8 degree of places in embodiment 3 gained solid product through X ray diffracting spectrum, can analyze as MTN type structure molecular screen, stereoscan photograph display plane of crystal is more coarse, size and shape is relatively homogeneous, XRD and SEM characterization result is as Fig. 5 and Fig. 6.
Claims (4)
1. a preparation method for total silicon type MTN topological framework molecular sieve, is characterized in that the method comprises following concrete steps:
Steps A: inorganic laminated presoma, sodium hydroxide and deionized water are mixed, under room temperature, strong magnetic agitation 0.5 ~ 3 hour, obtains mixture, and wherein, described inorganic laminated presoma is layered silicate; The mol ratio of material is H
2o ︰ SiO
2=10 ~ 80, Na
2o ︰ SiO
2=0.01 ~ 0.1;
Step B: add template, mineralizer successively in the mixture of steps A, at room temperature strong magnetic agitation 1 ~ 3 hour, obtains jel product; Wherein, the mol ratio R ︰ SiO in template (R) and silicon source
2=0.1 ~ 1, mineralizer (M) is M ︰ SiO with the mol ratio in silicon source
2=0.1 ~ 1, described template is at least one in 1-butyl-3-methyl-imidazolium chloride, 1-propyl group-3-methylimidazolium chloride, 1-ethyl-3-methyl-limidazolium, 1-ethyl-3-methyl-imidazolium chloride, 1-butyl-3-methy limidazolium, 1-(2-hydroxyethyl)-3-methylimidazolium chloride, and described mineralizer is at least one in Neutral ammonium fluoride, hydrofluoric acid, Sodium Fluoride, Potassium monofluoride;
Step C: the jel product obtained by step B is transferred in encloses container, 120 ~ 200 DEG C of crystallization 3 ~ 10 days, obtains described total silicon type MTN topological framework molecular sieve.
2. preparation method as claimed in claim 1, is characterized in that layered silicate is Na
2si
14o
2910H
2o, Na
2si
22o
4311H
2o and NaHSi
2o
53H
2at least one in O.
3. preparation method as claimed in claim 1, is characterized in that template described in step B is 1-(2-hydroxyethyl)-3-methylimidazolium chloride or 1-ethyl-3-methyl-imidazolium chloride, and template (R) is R ︰ SiO with the mol ratio in silicon source
2=0.1 ~ 0.3, mineralizer preferred fluorinated ammonium, mineralizer (M) is M ︰ SiO with the mol ratio in silicon source
2=0.3 ~ 0.6.
4. preparation method as claimed in claim 1, it is characterized in that in step C, crystallization temperature is 150 ~ 180 DEG C, crystallization time is 5 ~ 7 days.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN113247915A (en) * | 2021-06-08 | 2021-08-13 | 哈尔滨工程大学 | Method for preparing two-dimensional magadiite/graphene oxide nanosheet compound by using long-carbon-chain imidazole induction |
| CN114873602A (en) * | 2022-03-30 | 2022-08-09 | 南京大学 | Novel phosphorus-silicon molecular sieve material named NPS-2 and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0064577A1 (en) * | 1981-05-07 | 1982-11-17 | Mobil Oil Corporation | Crystalline zeolitic material, synthesis and use thereof |
| 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 |
| CN103145142A (en) * | 2013-02-06 | 2013-06-12 | 太原理工大学 | Synthesis method of heteroatom-containing ZSM-39 molecular sieve |
-
2015
- 2015-08-27 CN CN201510533463.9A patent/CN105152181B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0064577A1 (en) * | 1981-05-07 | 1982-11-17 | Mobil Oil Corporation | Crystalline zeolitic material, synthesis and use thereof |
| 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 |
| CN103145142A (en) * | 2013-02-06 | 2013-06-12 | 太原理工大学 | Synthesis method of heteroatom-containing ZSM-39 molecular sieve |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN113247915A (en) * | 2021-06-08 | 2021-08-13 | 哈尔滨工程大学 | Method for preparing two-dimensional magadiite/graphene oxide nanosheet compound by using long-carbon-chain imidazole induction |
| CN113247915B (en) * | 2021-06-08 | 2022-07-29 | 哈尔滨工程大学 | Method for preparing two-dimensional magadiite/graphene oxide nanosheet compound by using long-carbon-chain imidazole induction |
| CN114873602A (en) * | 2022-03-30 | 2022-08-09 | 南京大学 | Novel phosphorus-silicon molecular sieve material named NPS-2 and preparation method thereof |
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