CN102826565B - Preparation method of multi-stage pore channel beta molecular screen - Google Patents
Preparation method of multi-stage pore channel beta molecular screen Download PDFInfo
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Abstract
A preparation method of a multi-stage pore channel beta molecular screen belongs to the technical field of preparation of a multi-stage pore channel molecular screen. The preparation method is as follows: synthesizing the multi-stage pore channel beta molecular screen in one step by pseudo solid phase aluminosilicate; the molecular screen comprises a honeycomb-shaped structure or a plurality of particles in the size of 5micron to 60micron, the honeycomb-shaped structure or particles are polymerized by small crystal particles of a nano-level molecular screen, and the size of the small crystal particles of the nano-level molecular screen is 10nm to 100nm; and the aperture of one of meso pores formed by the polymerization of the small crystal particles of the nano-level molecular screen is 3nm to 45nm, and the aperture of a micro-pore is 0.6nm to 0.8nm. A second template agent is not in need during the synthesis process, so that the synthesis cost is reduced and the synthesis step is simplified; and in addition, the filtering is not in need after the crystallization is finished, therefore, the yield of the molecular screen is greatly enhanced.
Description
Technical field
The invention belongs to technical field prepared by multi-stage pore canal molecular sieve.Be specifically related to the method for a kind of nothing the second template one-step synthesis multistage pore canal Beta molecular sieve in " plan solid phase ".
Background technology
Tradition micro porous molecular sieve is widely used in fine chemistry industry and petrochemical industry as catalyzer.But when the molecule of reactant and micro porous molecular sieve aperture (being generally less than 1.5nm) approach or are larger, the speed of reaction depends on the diffusion of reaction molecular in micro porous molecular sieve to a great extent, and the diffusional limitation of reactant in micro porous molecular sieve is easy to cause " carbon distribution " and makes molecular sieve catalyst inactivation, greatly reduce the work-ing life of molecular sieve catalyst, therefore just need to improve the diffusion-condition of reactant molecule in molecular sieve.
Multi-stage pore canal molecular sieve integrates micropore and mesoporous even macropore, the good diffusibility of shape selectivity, high reaction activity and mesoporous material with micro porous molecular sieve, can further improve the particularly diffusibility of larger reactant molecule in molecular sieve of reactant molecule, strengthen its anti-" carbon deposit " performance.
The synthetic method of multi-stage pore canal molecular sieve can be divided into the second template and nothing the second template agent method.The second template mainly comprises hard template method and soft template method, without the second template, mainly comprises dealuminzation and desiliconization method.Patent CN101538049 discloses a kind of method that adopts soft or hard template to prepare multistage pore canal Beta molecular sieve, in hydrothermal system, adopt carbon granule generating under ordered mesoporous pore canals constraint as hard template, adding small molecules organic ammonium soft template is micropore Beta molecular sieve by the mesoporous Si-Al converted in-situ of parcel carbon granule again, and the Beta molecular sieve that can obtain multistage pore canal after soft or hard template is removed in roasting.
The method of the employing desiliconizations such as Groen obtains multistage pore canal Beta molecular sieve (Microporous and Mesoporous Materials. 2008,114:93-102), this method is the micropore Beta molecular sieve that adopts NaOH solution-treated routine, thereby produces mesoporous by optionally removing framework silicon.This treatment process is simple, but after processing, causes Beta microporous molecular sieve pore volume to decline, and formed intracrystalline pore is likely discontinuous.
deng adopt vapor phase process successfully synthesize multistage pore canal Beta molecular sieve (Journal of the American Chemical Society. 2011,133:5284-5295), the method is different from traditional hydrothermal method, multistage pore canal Beta molecular sieve is synthetic in water vapor atmosphere, and the method is not introduced the second extra template.
Summary of the invention
The object of the present invention is to provide a kind of multistage pore canal Beta molecular sieve, it is characterized in that described multi-stage pore canal molecular sieve is comprised of micropore and mesoporous two class ducts, it comprises " cellular " structure or size is 5-60 micron macrobead, " cellular " structure or macrobead are polymerized by nano-class molecular sieve small-particle, the size of the little crystal grain of nano-class molecular sieve is 10-100 nanometer, the mesoporous aperture being polymerized by the little crystal grain of nano-class molecular sieve is 3-45 nanometer, and micropore size is 0.6-0.8 nanometer.
Another object of the present invention is to provide a kind of preparation method of multi-stage pore canal molecular sieve, it is characterized in that in " plan solid phase " system synthetic, synthetic in the silico-aluminate solid that contains certain moisture, this is different from hydrothermal method (water solution system) and the vapor phase process (water vapour system) of traditional synthesis of molecular sieve, and the method does not need the second extra template.
The preparation method of multi-stage pore canal molecular sieve provided by the invention comprises the following steps:
(1) according to certain material proportion, first silicon source, aluminium source and organic formwork agent are mixed, after mixing, add alkali source, obtain silico-aluminate original solution;
(2) under room temperature, stir 0.5-12 hour, then evaporate to dryness moisture wherein at certain evaporate to dryness temperature, obtains " plan solid phase " silico-aluminate;
(3) " plan solid phase " silico-aluminate of step (1) gained is transferred in airtight static reaction still to crystallization 2h-120h under 110-200 ℃ of crystallization temperature;
(4) after crystallization completes, because the present invention is synthetic in " plan solid phase ", product do not need through filtration even dry just can dinectly bruning, at 550 ℃, calcine after within 4 hours, removing organic formwork agent and just can obtain having the molecular sieve of multistage pore canal.
In the present invention (1), silicon source, aluminium source are respectively with SiO
2, Al
2o
3meter, SiO feeds intake
2with Al
2o
3molar ratio range between 16-500,30-120 preferably; Template and SiO
2molar ratio range between 0.1-0.9,0.3-0.6 preferably; OH
-with SiO
2molar ratio range is at 0.3-0.8, preferably 0.4-0.6.
Aluminium source in step of the present invention (1) can be selected from one or more of Ludox AS-30, Ludox AS-40, Ludox HS-30, Ludox HS-40, aerosil, silica gel, tetraethoxy etc.; Optional one or more from Tai-Ace S 150, aluminum nitrate, sodium metaaluminate, aluminum isopropylate, aluminium secondary butylate etc. in aluminium source; Alkali source can be selected from a kind of of sodium hydroxide, potassium hydroxide etc., preferably sodium hydroxide.Described organic formwork agent can be selected from tetraethyl ammonium hydroxide (TEAOH);
The preferred 1-6 hour of churning time described in step in the present invention (2), the water content H of " plan solid phase " silico-aluminate
2o and SiO
2mol ratio between 0.5-5.7,2.0-4.2 preferably.
Evaporate to dryness temperature described in step in the present invention (2) is 40 ℃-95 ℃, preferably 60 ℃-80 ℃, in order to obtain more " plan solid phase " silico-aluminate of low water content, can vacuumize under environment 30 ℃-80 ℃ dry.
Preferably 140 ℃-180 ℃ of crystallization temperatures described in step in the present invention (3); Crystallization time is 12-72 hour preferably.
What by the present invention (1) (2) (3), obtain is the Beta molecular sieve with multi-stage artery structure, it comprises " cellular " structure or size is 5-60 micron macrobead, these macrobeads are polymerized by the little crystal grain of nano-class molecular sieve of 10-100 nanometer, the mesoporous aperture being polymerized by the little crystal grain of nano-class molecular sieve is 3-45 nanometer, 3.5-15 nanometer preferably, the aperture of the microvoid structure that multi-stage pore canal molecular sieve comprises is 0.6-0.8 nanometer.
Compared with prior art, multi-stage pore canal molecular sieve of the present invention is synthetic in " plan solid phase ", be different from traditional hydrothermal method and vapor phase process, and in building-up process without adding " extra " second template, reduced synthetic cost, simplified synthesis step, and the Beta Crystallization of Zeolite in the present invention does not need after completing to filter, avoided the loss of the molecular sieve quality brought thus, mesoporous aperture of the present invention also can regulate and control by changing synthesis condition simultaneously.
In present method synthesized Beta molecular sieve, there is micropore and mesoporous multi-stage artery structure, and there is a certain size the little crystal grain of nano level.The invention has the advantages that, the polymerization of nano-class molecular sieve small-particle forms the mesopore orbit with certain size size, overcome the problem of the difficult filtering separation that nano molecular sieve exists in application, improved reactant molecule, the diffusibility of larger reactant molecule in Beta molecular sieve particularly, the effective rate of utilization that improves molecular sieve Adsorption, has strengthened its anti-Coking Behavior, has extended the work-ing life of molecular sieve in catalyzed reaction.
Accompanying drawing explanation
Fig. 1 is the X-ray diffraction spectrogram of the synthetic multistage pore canal Beta molecular sieve of the embodiment of the present invention 1.
Fig. 2 is " cellular " structure of the synthetic multistage pore canal Beta molecular sieve of the embodiment of the present invention 1.
Fig. 3 is the scanning electron microscope (SEM) photograph of the synthetic multistage pore canal Beta molecular sieve of the embodiment of the present invention 1.
Fig. 4 is the high-resolution-ration transmission electric-lens figure of the synthetic multistage pore canal Beta molecular sieve of the embodiment of the present invention 1.
Fig. 5 is the micropore size distribution plan of the synthetic multistage pore canal Beta molecular sieve of the embodiment of the present invention 1.
Fig. 6 is the mesoporous graph of pore diameter distribution of the synthetic multistage pore canal Beta molecular sieve of the embodiment of the present invention 1.
Embodiment
Below in conjunction with drawings and Examples, embodiment of the present invention are further illustrated, but the present invention is not limited to listed embodiment.Also should be included in interior other any known change of scope that the present invention protects.
Embodiment 1
By 4g aerosil, 1.48g Tai-Ace S 150 and 11.21g massfraction, be first the aqueous solution of 35% tetraethyl ammonium hydroxide, add 0.132g sodium hydroxide after mixing, obtain silico-aluminate original solution, the mol ratio of raw material is SiO
2: Al
2o
3: TEA
+: OH
-=1:0.033:0.4:0.45, stirs under room temperature 1 hour, and then evaporate to dryness moisture wherein at 70 ℃, obtains " plan solid phase " silico-aluminate, records wherein water content H
2o and SiO
2mol ratio is 2.1.Get " plan solid phase " silico-aluminate of 5g gained, and transfer in airtight static reaction still, crystallization 60h at 140 ℃ of crystallization temperatures, after crystallization completes, the sample of synthesized speed with 2 ℃/min in retort furnace is warming up to 550 ℃ of calcining at constant temperature 4h from room temperature, obtain final sample, yield is 98%.
X-ray diffraction shows that this sample is Beta molecular sieve (accompanying drawing 1), and there is " cellular " structure (accompanying drawing 2), scanning electron microscope (accompanying drawing 3) and high-resolution-ration transmission electric-lens (accompanying drawing 4) show that the diameter of the little crystal grain of each nano level is 15-30 nanometer, and can see regular lattice fringe from high-resolution-ration transmission electric-lens.The specific surface area of sample is 691m
2/ g, total pore volume is 0.889ml/g, mesoporous pore volume is 0.680 ml/g.By HK method, calculated the pore size distribution (accompanying drawing 5) of the micropore of Beta molecular sieve.The mesoporous pore size distribution 10-30 nanometer of being calculated Beta molecular sieve by BJH method, most probable is distributed as 12 nanometers (accompanying drawing 6).
Embodiment 2
By 4g aerosil, 0.74g Tai-Ace S 150 and 11.21g massfraction, be first the aqueous solution of 35% tetraethyl ammonium hydroxide, add 0.132g sodium hydroxide after mixing, obtain silico-aluminate original solution, the mol ratio of raw material is SiO
2: Al
2o
3: TEA
+: OH
-=1:0.0167:0.4:0.45, stirs under room temperature 6 hours, and then evaporate to dryness moisture wherein at 70 ℃, obtains " plan solid phase " silico-aluminate, records wherein water content H
2o and SiO
2mol ratio 2.1.Get " plan solid phase " silico-aluminate of 5g gained, and transfer in airtight static reaction still, crystallization 60h at 140 ℃ of crystallization temperatures, after crystallization completes, the sample of synthesized speed with 2 ℃/min in retort furnace is warming up to 550 ℃ of calcining at constant temperature 4h from room temperature, obtain final sample, yield is 98%.
X-ray diffraction shows that the sample obtaining is Beta molecular sieve, and the specific surface area of sample is 648m
2/ g, total pore volume is 0.786ml/g, and mesoporous pore volume is 0.577 ml/g, and mesoporous most probable is distributed as 13 nanometers.
Embodiment 3
By 33.33g massfraction, be first that 30% silicon-dioxide, 3.70g Tai-Ace S 150 and 28.02g massfraction are the aqueous solution of 35% tetraethyl ammonium hydroxide, add 0.33g sodium hydroxide after mixing, obtain silico-aluminate original solution, the mol ratio of raw material is SiO
2: Al
2o
3: TEA
+: OH
-=1:0.033:0.4:0.45, stirs under room temperature 1 hour, and then evaporate to dryness moisture wherein at 70 ℃, obtains " plan solid phase " silico-aluminate, records wherein water content H
2o and SiO
2mol ratio is 3.0.Get " plan solid phase " silico-aluminate of 5g gained, and transferred in airtight static reaction still, brilliant 60h at 140 ℃ of crystallization temperatures, after crystallization completes, the sample of synthesized speed with 2 ℃/min in retort furnace is warming up to 550 ℃ of calcining at constant temperature 4h from room temperature, and yield is 99%.
X-ray diffraction shows that the sample obtaining is Beta molecular sieve, and the specific surface area of sample is 661m
2/ g, total pore volume is 0.823ml/g, and mesoporous pore volume is 0.635 ml/g, and mesoporous most probable is distributed as 9 nanometers.
Embodiment 4
Get " plan solid phase " silico-aluminate of 5g embodiment 3 gained, and transferred in airtight static reaction still, crystallization 8h at 180 ℃ of crystallization temperatures, after crystallization completes, the molecular sieve of synthesized speed with 2 ℃/min in retort furnace is warming up to 550 ℃ of calcining at constant temperature 4h from room temperature, and yield is 98%.X-ray diffraction shows that the sample obtaining is Beta molecular sieve, and the specific surface area of sample is 649m
2/ g, total pore volume is 0.948ml/g, and mesoporous pore volume is 0.776 ml/g, and mesoporous most probable is distributed as 12 nanometers.
Embodiment 5
Get " plan solid phase " silico-aluminate of 5g embodiment 3 gained, and transferred in airtight static reaction still, crystallization 6h at 140 ℃ of crystallization temperatures, after crystallization completes, the molecular sieve of synthesized speed with 2 ℃/min in retort furnace is warming up to 550 ℃ of calcining at constant temperature 4h from room temperature, and yield is 96%.X-ray diffraction shows that the sample obtaining is Beta molecular sieve, and the specific surface area of sample is 607m
2/ g, total pore volume is 0.478ml/g, and mesoporous pore volume is 0.312 ml/g, and mesoporous most probable is distributed as 4 nanometers.
Claims (3)
1. the preparation method of a multistage pore canal Beta molecular sieve, described multi-stage pore canal molecular sieve is comprised of micropore and mesoporous two class ducts, it comprises " cellular " structure or size is 5-60 micron macrobead, " cellular " structure or macrobead are polymerized by the little crystal grain of nano-class molecular sieve, the size of the little crystal grain of nano-class molecular sieve is 10-100 nanometer, the mesoporous aperture being polymerized by the little crystal grain of nano-class molecular sieve is 3-45 nanometer, and micropore size is 0.6-0.8 nanometer;
It is characterized in that following steps:
(1) silicon source, aluminium source and organic formwork agent are mixed, after mixing, add alkali source, obtain silico-aluminate original solution, silicon source, aluminium source are respectively with SiO
2, Al
2o
3meter, SiO feeds intake
2with Al
2o
3mol ratio is 30; Template and SiO
2mol ratio is 0.4; OH-and SiO in alkali source
2mol ratio is 0.45;
(2) under room temperature, stir 0.5-12 hour, then evaporate to dryness moisture wherein at 40 ℃ of-95 ℃ of evaporate to dryness temperature, obtains water content H
2o/SiO
2mol ratio is 0.5-5.7's " plan solid phase " silico-aluminate;
(3) " plan solid phase " silico-aluminate of step (2) gained is transferred in airtight static reaction still to crystallization 2-120 hour under 110-200 ℃ of crystallization temperature;
(4), after crystallization completes, at 550 ℃, calcine after within 4 hours, removing organic formwork agent and just can obtain having the molecular sieve of multistage pore canal.
2. the preparation method of multistage pore canal Beta molecular sieve according to claim 1, is characterized in that, churning time is 1-6 hour, and evaporate to dryness temperature is 60 ℃-80 ℃.
3. the preparation method of multistage pore canal Beta molecular sieve according to claim 1, is characterized in that the water content H of " plan solid phase " silico-aluminate
2o and SiO
2mol ratio is 2.0-4.2.
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| CN103964458B (en) * | 2013-01-29 | 2015-09-16 | 中国石油大学(北京) | Beta zeolite of a kind of high silica alumina ratio multistage pore canal and preparation method thereof |
| CN103318911B (en) * | 2013-04-07 | 2015-06-03 | 华东理工大学 | Preparation method of beta zeolite with multilevel pore canals |
| JP6228677B2 (en) * | 2013-08-20 | 2017-11-08 | 中国科学院大▲連▼化学物理研究所Ｄａｌｉａｎ Ｉｎｓｔｉｔｕｔｅ Ｏｆ Ｃｈｅｍｉｃａｌ Ｐｈｙｓｉｃｓ，Ｃｈｉｎｅｓｅ Ａｃａｄｅｍｙ Ｏｆ Ｓｃｉｅｎｃｅｓ | Beta-type molecular sieve having a hierarchical structure and manufacturing method thereof |
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| CN104402020A (en) * | 2014-08-07 | 2015-03-11 | 华南理工大学 | Micro-mesoporous beta molecular sieve and preparation method and application thereof |
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| CN109133087A (en) * | 2017-06-27 | 2019-01-04 | 中国科学院大连化学物理研究所 | A kind of synthetic method of Beta molecular sieve |
| CN109894145A (en) * | 2017-12-07 | 2019-06-18 | 中国科学院大连化学物理研究所 | A kind of fischer-tropsch synthetic catalyst and its preparation and application containing zeolite molecular sieve |
| CN111099609B (en) * | 2018-10-25 | 2022-05-24 | 中国石油化工股份有限公司 | Synthesis method of beta molecular sieve |
| CN112624142B (en) * | 2021-01-19 | 2022-06-28 | 吉林大学 | Preparation method of nano hierarchical pore Beta molecular sieve |
| CN112591765B (en) * | 2021-02-05 | 2021-07-09 | 福州大学 | Neutral polymer guiding step hole Beta molecular sieve and green preparation method thereof |
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