CN111439756A - Preparation method of cascade pore heteroatom M-Beta molecular sieve - Google Patents
Preparation method of cascade pore heteroatom M-Beta molecular sieve Download PDFInfo
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Abstract
The invention provides a preparation method of a cascade pore heteroatom M-Beta molecular sieve. Compared with the existing synthesis method, the method can directly synthesize the M-Beta molecular sieve by a one-step steam auxiliary method, and breaks through the inherent defects of the traditional hydrothermal synthesis. Compared with the existing method for synthesizing M-Beta, the method can synthesize the M-Beta molecular sieve with a step pore structure and a regular morphology without a nuclear promoter aluminum and a high-corrosivity crystallization auxiliary agent hydrofluoric acid; the synthesis time is reduced to 48 hours, the steps are simple, and the energy consumption can be effectively reduced; the crystallization liquid is few, and the pollution problem of a large amount of crystallization waste liquid can be effectively avoided; meanwhile, the problem of large amount of waste acid discharge caused by the necessity of using strong acid for pretreatment in the traditional 'secondary isomorphous substitution method' and the aluminum-containing 'one-step synthesis method' is solved.
Description
Technical Field
The invention relates to a preparation method for synthesizing a framework heteroatom M-Beta molecular sieve, in particular to a preparation method for synthesizing a heteroatom M-Beta nanocrystal of [ Al, F ] -Free in one step by steam-assisted conversion.
Background
The Beta molecular sieve is the only molecular sieve with twelve-membered ring three-dimensional cross channels, and has unique pore structure, acidity and good hydrothermal stability. The traditional Beta molecular sieve is silicon-aluminum zeolite, but the application field of the BEA structure cannot be greatly improved only by depending on the traditional Al-Beta zeolite. The introduction of different transition metals (Ti, Fe, Co, Ga, etc.) into the zeolite framework can give the silicon framework separate from each other, well-dispersed, diverse catalytic active centers. The special pore channel structure of the zeolite provides a proper inhabitation space for the metal atoms, so that the metal atoms have the oxidation-reduction property of transition metals and the acidity and shape selectivity of the molecular sieve at the same time, and the possibility of catalyzing diversified reactions by the heteroatom M-Beta zeolite is provided. Meanwhile, the introduction of some heteroatoms can also effectively improve the hydrophilicity and hydrophobicity and the framework stability of the zeolite, thereby improving the thermal stability and the thermal stability of the zeolite framework, and the advantages bring opportunities for the synthesis of porous materials and the expansion of catalytic application thereof, so that various heteroatom M-Beta zeolites are developed successively and receive great attention.
So far, the preparation methods of heteroatom molecular sieves are mainly divided into a one-step hydrothermal synthesis method and a secondary isomorphous substitution method.
The secondary isomorphous substitution method is a secondary synthesis (modification) method, and the method comprises the steps of firstly, carrying out concentrated nitric acid dealumination treatment on a pre-synthesized silicon-aluminum series H-Beta molecular sieve to expose an open silicon hydroxyl nest defect position on a framework of the molecular sieve, and then carrying out post-treatment on a treated Si-Beta carrier. T. Maschmeyer (Nature,1995,378,159) et al use a "wet impregnation" post-treatment process to incorporate organometallic titanium into the framework, but this process requires large amounts of toxic organic solvents and the effective grafting rate of titanium is low. Severino F.Oliveira et al deposited Cu by a "chemical deposition processIIAnd CoIIThe zeolite framework is successfully introduced, but the experimental process of the method is complex, the requirement on an experimental device is high, and the deposition rate of the metal precursor is easily influenced by a plurality of factors. To compensate for the drawbacks of the "wet impregnation method", y.c. chai et al (micropor.mesopor.mater, 2018,264,230) recently developed a "dry impregnation method" to successfully incorporate Pb with a larger ionic radius into the zeolite framework. However, in the zeolite material prepared by the secondary isomorphous substitution method, the hetero atoms are mainly concentrated on the atomic layer (CN104445255A) on the surface of the pore channel and are easy to be on the zeoliteThe non-framework species directly form corresponding heteroatom metal oxides after being roasted and are deposited on the surface of the zeolite.
Compared with a secondary synthesis method, the heteroatom zeolite synthesized by the one-step hydrothermal synthesis method has unique advantages at present. The direct isomorphous growth method makes the hetero atom grow firmly in the zeolite skeleton and present high dispersed state, and this method is not easy to change the channel structure of original zeolite and can synthesize the required hetero atom zeolite directly (CN 1171792C). However, this method of achieving zeolite growth by mass diffusion of the crystallization liquid in large quantities, results in a significant decrease in the concentration of "nutrients" available for zeolite growth, which makes zeolite nucleation difficult, and therefore the amount of template and crystallization time are greatly increased for the one-step hydrothermal process (TEAOH/SiO)2More than or equal to 0.55 and 7 to 14 days, B.R.Wang, Micropor.Mesopor.Mater.,2019,278 and 30) in order to solve the nucleation problem, an aluminum source, a boron source and the like are indispensable as nucleation promoters in the one-step hydrothermal synthesis process of Beta zeolite, which is also the reason that the traditional Beta zeolite is always in a silicon-aluminum system or a silicon-boron system, however, the existence of aluminum in the synthesis system can not only occupy the growth positions of heteroatoms, but also cause the Beta zeolite to have too strong acidity, thereby reducing the selectivity of certain products (D.P.Serrano, Micropor.Mesopor.Mater.200,146 and 35; J. L. Zhang, Chem.Eng.J.,2016,291 and 82) in order to make up the defects of aluminum, Y.Naraki, H.Kessler (Y.Naraki, Adv.Mater, 2, 2016, 125, St.Kessler, Scirf.85, and the like, and the crystallization rate of the crystallization of the fluorine-containing crystal is obviously reduced when the crystallization is caused by introducing a large amount of the crystallization assistant, and the secondary crystallization of the fluorine-containing crystal.
In summary, both the one-step hydrothermal synthesis method and the second isomorphous substitution method are the category of hydrothermal crystallization, and the inherent disadvantages of hydrothermal synthesis, such as large discharge of crystallization liquid, waste of nutrients, excessively long crystallization time, excessively large consumption of template agent, low yield of single kettle, high kettle pressure, etc., are unavoidable (L. m.ren, j.am.chem.soc.,2012,134,15173), so it is very important to develop a new method of heteroatom zeolite with high efficiency, green color and simple steps.
Disclosure of Invention
The invention aims to provide a preparation method for synthesizing a heteroatom M-Beta molecular sieve with stepped pores in one step by using steam assistance without a fluorine source and an aluminum source, which has the advantages of simple steps, short time consumption and small template dosage.
The method comprises the following steps:
1. basic procedure
1) Silicon source of SiO2Calculated as element M, the heteroatom metal is calculated as OH－Counting according to silicon source: heteroatom metal: alkali source: template agent: fully mixing water in a molar ratio of 1: 0-0.07: 0.01-0.8: 0.05-0.5: 20-80, adding pure silicon seed crystals with the mass of 0.001-10% of that of a silicon source, aging at 20-80 ℃ for 0.5-2 hours, and evaporating the aged hydrogel in an oil bath at 50-100 ℃ for 12-48 hours to obtain a templated and seeded xerogel;
2) grinding the dried gel obtained in the step 1), respectively placing the dried gel in a kettle and a small liner according to the mass ratio of water to dry powder of 0.01-1: 1, crystallizing at 120-170 ℃ for 20-96 hours, ion exchanging the obtained product in 1 mol/L ammonium salt solution for 2 hours, washing to be neutral, drying, and calcining at 550 ℃ for 6 hours to obtain the M-Beta molecular sieve.
2. Wherein the molar ratio of the silicon source, the heteroatom source, the alkali source, the template agent and the water is silicon source: heteroatom metal: alkali source: template agent: the ratio of water to silicon is 1: 0-0.04: 0.2-0.5: 0.1-0.25: 30-60, and the addition amount of the seed crystal is 5-10% of the mass of the silicon source.
3. Wherein the aging temperature is 30-60 ℃, the time is 0.5-1 hour, the drying temperature is 60-90 ℃, and the time is 20-40 hours.
4. Wherein the mass ratio of the crystallized water to the dry powder is 0.1-0.5: 1.
5. wherein the crystallization temperature is 140-160 ℃, and the crystallization time is 36-72 hours.
6. Wherein, the silicon source is one or more of white carbon black, silica gel, water glass and silica sol.
7. Wherein, the heteroatom metal source is one or more of titanium sulfate, titanocene dichloride, ferric ammonium citrate, ferric ammonium ethylene diamine tetraacetate, cobalt acetate, cobalt nitrate, gallium chloride and gallium nitrate.
8. Wherein the organic quaternary ammonium base substance is one or more of tetramethylammonium hydroxide, tetraethylammonium hydroxide and tetrapropylammonium hydroxide.
9. Wherein, the alkali source is one or more of sodium hydroxide and potassium hydroxide.
10. Wherein the ammonium salt is one or more of ammonium nitrate, ammonium chloride, ammonium fluoride and ammonium phosphate.
Compared with the prior art for synthesizing the heteroatom M-Beta molecular sieve, the method has the following remarkable advantages: (1) the steam assists nucleation and crystallization, and the crystallization efficiency is high. Compared with the traditional hydrothermal synthesis method, the method fully utilizes the permeation effect of steam to wrap the dry powder 'nutrient substance' in compact water vapor, so that the concentration of the dry powder nutrient substance is greatly improved, and the nucleation efficiency and the crystallization efficiency are obviously improved; (2) the synthesis steps are simple. The diversified heteroatom M-Beta molecular sieve with high crystallinity can be directly synthesized by a one-step synthesis method, and a heteroatom metal source can be directly added in the synthesis process without additional pretreatment; (3) the synthesis time and the synthesis cost are greatly reduced. The method for synthesizing the M-Beta molecular sieve only needs two days for crystallization, and has absolute advantage in time cost; (4) the synthesis cost is greatly reduced. The template agent used in the method is low in consumption, and the used silicon source and the heteroatom metal source are both inorganic substances, so that the material cost is greatly reduced; (5) the product is a nano crystal grain with rich step pore structure. Generally speaking, M-Beta samples in a hydrothermal system are mostly micron-sized single microporous materials, and the synthesized M-Beta molecular sieve is a nano material with rich step pore structures; (6) no aluminum and no fluorine exist in the whole synthesis process; (7) high product yield. The crystallization process of the traditional hydrothermal synthesis needs a large amount of solvent, and after crystallization is finished, partial 'nutrients' such as silicon species, titanium species, fluoride, template agent and the like still exist in the solvent, so that the product yield is relatively low, but the 'steam-assisted method' provided by the invention can be used for synthesizing all the templated 'nutrients' for the M-Beta molecular sieve, and has the product yield close to 100%; (8) low pollution. In general, the residual substances dissolved in the solvent under hydrothermal conditions are directly discharged as pollutants, while the method has almost no discharge of residual crystallization waste liquid, and the synthesis process does not need to use highly corrosive hydrofluoric acid, fluoride and the like.
In combination with the analysis, the one-step steam auxiliary method provided by the invention is a universal method for synthesizing the heteroatom M-Beta molecular sieve, has the characteristic of realizing large-scale industrialization of the M-Beta molecular sieve, greatly reduces the synthesis cost and the environmental load, and greatly improves the application field of the BEA structure molecular sieve.
Drawings
FIG. 1 is an XRD pattern of M-Beta molecular sieves synthesized in examples 1-4 of the present invention.
FIG. 2 UV-Vis sum of M-Beta molecular sieves synthesized in examples 1-4 of the present invention
FT-IR diagram.
FIG. 3 is a TEM image of the M-Beta molecular sieves synthesized in examples 1 to 4 of the present invention.
Detailed Description
The invention provides a preparation method of a cascade pore heteroatom M-Beta molecular sieve, which is characterized by comprising the following steps of:
1) silicon source of SiO2Calculated as element M, the heteroatom metal is calculated as OH－Counting according to silicon source: heteroatom metal: alkali source: template agent: fully mixing water in a molar ratio of 1: 0-0.07: 0.01-0.8: 0.05-0.5: 20-80, adding pure silicon seed crystals with the mass of 0.001-10% of that of a silicon source, aging at 20-80 ℃ for 0.5-2 hours, and evaporating the aged hydrogel in an oil bath at 50-100 ℃ for 12-48 hours to obtain a templated and seeded xerogel;
2) grinding the dried gel obtained in the step 1), respectively placing the dried gel in a kettle and a small liner according to the mass ratio of water to dry powder of 0.01-1: 1, crystallizing at 120-170 ℃ for 20-96 hours, ion exchanging the obtained product in 1 mol/L ammonium salt solution for 2 hours, washing to be neutral, drying, and calcining at 550 ℃ for 6 hours to obtain the M-Beta molecular sieve.
According to the method of the invention, the mole ratio of the silicon source, the heteroatom source, the alkali source, the template agent and the water in the step 1) is preferably that of the silicon source: heteroatom metal: alkali source: template agent: the ratio of water to silicon is 1: 0-0.04: 0.2-0.5: 0.1-0.25: 30-60, and the addition amount of the seed crystal is 5-10% of the mass of the silicon source.
According to the method of the present invention, the inorganic silicon source compound described in step 1) may be a solid silicon source or a liquid silicon source of various high quality purity known in the art. Specifically, the crystal form can be one or more of white carbon black, silica gel, water glass and silica sol, and all of the crystal form can show good relative crystallinity. Preferably white carbon black and silica sol.
According to the process of the present invention, the inorganic heteroatom metal source described in step 1) may be a solid of various high quality purities as are known in the art. Specifically, the metal salt can be one or more of titanium sulfate, titanocene dichloride, ferric ammonium citrate, ferric ammonium ethylene diamine tetraacetate, cobalt acetate, cobalt nitrate, gallium chloride and gallium nitrate. Preferably titanocene dichloride, ferric ammonium citrate, cobalt acetate and gallium nitrate.
According to the process of the present invention, the source of alkalinity as described in step 1) is preferably sodium hydroxide.
According to the method of the present invention, the templating agent described in step 1) may be an organic quaternary ammonium base known in the art. Specifically, the ammonium hydroxide solution may be one or more of tetramethylammonium hydroxide, tetraethylammonium hydroxide and tetrapropylammonium hydroxide solution. Preferably tetraethylammonium hydroxide solution.
According to the method of the invention, the ammonium salt in the step 2) is one or more of ammonium nitrate, ammonium chloride, ammonium fluoride and ammonium phosphate. Ammonium nitrate is preferred.
According to the method, the aging temperature in the step 1) is preferably 30-60 ℃, and the time is 0.5-1 hour.
According to the method, the evaporation temperature in the step 1) is preferably 60-90 ℃, and the time is preferably 20-40 hours.
The aging process described in step 1) is a process known to the person skilled in the art according to the present invention.
The evaporation to dryness process described in step 1) is a process known to the person skilled in the art according to the process of the present invention.
According to the method of the invention, the ratio of the crystallization water to the dry powder in step 2) is preferably crystallization water: the mass of the dry powder is 0.1-0.5: 1.
according to the method, the crystallization temperature in the step 2) is preferably 140-160 ℃, the crystallization time is preferably 36-72 hours, and the product after ion exchange is washed to be neutral and dried, and then calcined for 6 hours at 550 ℃.
The washing, drying and calcining processes described in step 2) according to the process of the present invention are well known to those skilled in the art. For example, the mixture is washed with deionized water for 3 times and then dried at 110 ℃ for 2 to 10 hours.
According to the method of the present invention, the crystallization process in step 2) is a crystallization process known in the art, and the crystallization process is a static crystallization process.
The present invention will be described in detail below with reference to specific examples, but the present invention is not limited to only the following examples.
The reagents in the following examples were obtained from Shanghai Shang good practice Co., Ltd, the organic template from Xia reagent Co., Ltd, and the remaining reagents from Chemicals group Ltd.
The molar amount of the silicon source in the following examples is SiO2Calculated by the molar weight of a heteroatom source as a metal simple substance, and calculated by the molar weight of a template agent as TEA+And (6) counting.
Example 1
This example illustrates the preparation of a heteroatomic Ti-Beta molecular sieve.
Firstly, mixing a silicon source, a titanium source, an alkali source, a template agent and water according to the proportion of white carbon black: titanocene dichloride: NaOH:TEAOH：H2the method comprises the following steps of fully mixing O-1: 0.015:0.1:0.15:50 in a molar ratio, adding seed crystals with the mass being 10% of that of a silicon source, aging at 30 ℃ for 0.5 hour, evaporating aged hydrogel in an oil bath at 60 ℃ for 48 hours to obtain templated and seeded xerogel, grinding the obtained xerogel to have no granular feeling, putting 10g of the xerogel into a small inner liner, putting the small inner liner into a crystallization kettle containing 1g of water, sealing the kettle, crystallizing at 145 ℃ for 48 hours, performing ion exchange on the obtained product in a 1 mol/L ammonium nitrate solution for 2 hours, washing to be neutral, drying, and calcining at 550 ℃ for 6 hours to obtain a product a.
Example 2
This example illustrates the preparation of a heteroatom Fe-Beta molecular sieve.
Firstly, mixing a silicon source, an iron source, an alkali source, a template agent and water according to the proportion of white carbon black: ferric ammonium citrate: NaOH: TEAOH: h2The method comprises the following steps of fully mixing O-1: 0.028:0.16:0.1:40 in a molar ratio, adding seed crystals with the mass of 1% of that of a silicon source, aging at 30 ℃ for 0.5 hour, evaporating aged hydrogel in an oil bath at 70 ℃ for 24 hours to obtain templated and seeded xerogel, grinding the obtained xerogel to have no granular feeling, putting 10g of the xerogel into a small inner liner, putting the small inner liner into a crystallization kettle containing 5g of water, sealing the kettle, crystallizing at 145 ℃ for 48 hours, carrying out ion exchange on the obtained product in 1 mol/L ammonium nitrate solution for 2 hours, washing to be neutral, drying, and calcining at 550 ℃ for 6 hours to obtain a product b.
Example 3
This example illustrates the preparation of a heteroatom Co-Beta molecular sieve.
Firstly, a silicon source, a cobalt source, an alkali source, a template agent and water are mixed according to the following ratio of silica gel: cobalt acetate: NaOH: TEAOH: h2The mixture was mixed well at a molar ratio of 1:0.01:0.09:0.25:40, and then a seed crystal corresponding to 3% by mass of the silicon source was added thereto, followed by aging at 50 ℃ for 0.5 hour. The aged hydrogel was evaporated in an oil bath at 70 ℃ for 24 hours to give a templated and seeded xerogel. The dry gel obtained was ground to no granular sensation, 10g was placed in a small inner liner, which was then placed in a container 15g of water, sealing the kettle, crystallizing at 145 ℃ for 48 hours, ion exchanging the obtained product in 1 mol/L ammonium nitrate solution for 2 hours, washing to neutrality, drying, and calcining at 550 ℃ for 6 hours to obtain a product c.
Example 4
This example illustrates the preparation of a molecular sieve containing heteroatom Ga-Beta.
Firstly, a silicon source, a gallium source, an alkali source and a template agent: water as silica sol: gallium nitrate: NaOH: TEAOH: h2The method comprises the following steps of fully mixing O-1: 0.005:0.16:0.06:50 in a molar ratio, adding seed crystals with the mass being 10% of that of a silicon source, aging at 30 ℃ for 0.5 hour, evaporating aged hydrogel in an oil bath at 50 ℃ for 40 hours to obtain templated and seeded xerogel, grinding the obtained xerogel to have no granular sensation, putting 10g of the xerogel into a small inner liner, putting the small inner liner into a crystallization kettle containing 4g of water, sealing the kettle, crystallizing at 140 ℃ for 72 hours, performing ion exchange on the obtained product in 1 mol/L ammonium nitrate solution for 2 hours, washing to be neutral, drying, and calcining at 550 ℃ for 6 hours to obtain a product d.
XRD, UV-Vis and TEM images of a product a (Ti-Beta), a product b (Fe-Beta), a product c (Co-Beta) and a product d (Ga-Beta) obtained in examples 1-4 are respectively shown in attached figures 1, 2 and 3, so that the heteroatom M-Beta molecular sieve synthesized by the one-step steam auxiliary method provided by the invention is a high-crystallinity nanocrystal with rich step pore structures. By combining the analysis, the method for synthesizing the heteroatom M-Beta molecular sieve by the one-step steam auxiliary method is a universal synthesis method, has the characteristic of realizing large-scale industrialization of the M-Beta molecular sieve, greatly reduces the synthesis cost and the environmental load, and greatly expands the application field of the Beta molecular sieve.
Claims (10)
1. A preparation method of a gradient pore heteroatom M-Beta molecular sieve is characterized by comprising the following steps:
1) silicon source of SiO2Calculated as element M, the heteroatom metal is calculated as OH－Counting according to silicon source: heteroatom metal: alkaliSource: template agent: fully mixing water in a molar ratio of 1: 0-0.07: 0.01-0.8: 0.05-0.5: 20-80, adding pure silicon seed crystals with the mass of 0.001-10% of that of a silicon source, aging at 20-80 ℃ for 0.5-2 hours, and evaporating the aged hydrogel in an oil bath at 50-100 ℃ for 12-48 hours to obtain a templated and seeded xerogel;
2) grinding the dried gel obtained in the step 1), respectively placing the dried gel in a kettle and a small liner according to the mass ratio of 0.01-1: 1 of water to the dried powder, crystallizing the dried gel for 20-96 hours at 120-170 ℃, ion exchanging the obtained product for 2 hours in 1 mol/L ammonium salt solution, washing the product to be neutral, drying the product, and calcining the product for 6 hours at 550 ℃ to obtain the M-Beta molecular sieve.
2. The method according to claim 1, wherein in step 1), the molar ratio of the silicon source, the heteroatom source, the alkali source, the template agent and the water is silicon source: heteroatom metal: alkali source: template agent: the ratio of water to silicon is 1: 0-0.04: 0.2-0.5: 0.1-0.25: 30-60, and the addition amount of the seed crystal is 5-10% of the mass of the silicon source.
3. The method according to claim 1, wherein in the step 1), the aging temperature is 30-60 ℃ for 0.5-1 hour, and the evaporation temperature is 60-90 ℃ for 20-40 hours.
4. The method as claimed in claim 1, wherein in the step 2), the mass ratio of the crystallized water to the dry powder is 0.1-0.5: 1.
5. the method as claimed in claim 1, wherein the crystallization temperature in step 2) is 140 to 160 ℃ and the crystallization time is 36 to 72 hours.
6. The method according to claim 1 or 2, wherein the silicon source is one or more of white carbon black, silica gel, water glass and silica sol.
7. The method of claim 1 or 2, wherein the heteroatom metal source is one or more of titanium sulfate, titanocene dichloride, ferric ammonium citrate, ferric ammonium ethylene diamine tetraacetate, cobalt acetate, cobalt nitrate, gallium chloride and gallium nitrate.
8. The method according to claim 1 or 2, wherein the organic quaternary ammonium base material is one or more of tetramethylammonium hydroxide, tetraethylammonium hydroxide and tetrapropylammonium hydroxide.
9. The method according to claim 1 or 2, wherein the alkali source is one or more of sodium hydroxide and potassium hydroxide.
10. The method according to claim 2, wherein the ammonium salt is one or more of ammonium nitrate, ammonium chloride, ammonium fluoride and ammonium phosphate.
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