CN101538049B - Method for preparing multi-level porous channel beta zeolite - Google Patents
Method for preparing multi-level porous channel beta zeolite Download PDFInfo
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Abstract
The invention provides a method for preparing multi-level porous channel beta zeolite, and belongs to the technical field of preparation and application of the zeolite. The method is characterized in that: carbon grains which are generated under restriction of the sequent meso-porous channels are taken as a hard mold board, and added with a small molecular organic ammonium soft mold board to convert the meso-porous silicon-aluminum coating the carbon grain into the meso-porous beta zeolite in situ, and the meso-porous beta zeolite is calcined to remove the soft and hard mold boards so as to obtain the multi-level porous channel containing beta zeolite. Compared with the zeolite obtained by directly taking the meso-porous carbon as the mold board, the multi-level porous channel beta zeolite synthesized by the method does not need to remove the meso-porous silicon-aluminum first and then introduce the silicon-aluminum species synthesizing the zeolite, thereby reducing complicated working procedures as well as saving raw materials. The method has the advantages of greatly lowering diffusional resistance, reducing secondary reaction, and having better catalytic property and huge potential application values in fields such as petrochemical industry, fine chemical industry, and the like.
Description
Technical field
The preparation method of a kind of beta zeolite with multilevel pore canals of the present invention belongs to fields such as catalytic cracking, catalytic pyrolysis, hydrocracking and fine chemistry industry, specifically, is a kind of β prepare zeolite method with multistage pore canal.
Background technology
Fluid catalytic cracking (FCC) is one of most important technology of petroleum refining industry.The simple catalyst formulation that uses in this technology is difficult to satisfy commercial and the increasing requirement in environmental protection aspect at present, a key factor that improves heavy oil fluid catalytic cracking depth of conversion and yield of light oil is that catalyzer will have suitable pore distribution and acid the distribution, needs catalytic material that the pore passage structure of descending " relay-type " catalytic cracking can be provided to heavy oil molecules.Therefore the synthetic molecular screen material with certain acidity and pore size distribution of research is to try hard to pursue the target of asking due to the scientific worker of this field.
The β zeolite is that the sixties are by Mobil company development product, has unique topological framework, it has three cross one another 12 membered ring channels, the duct is interconnected, its acidity is moderate, and pore volume is suitable, can produce isomerization, and promote charcoal positive ion C-C chain transfer and produce chain or Cheng Huan that this is boosting of octane rating greatly.For the cracking of short chain alkanes, the reformation that can enter the naphthenic hydrocarbon in duct, all be better than y-type zeolite.But since its aperture less (＜0.8nm), diameter is difficult to diffuse in the duct of molecular sieve greater than the oily macromole of weight (slag) of 1nm in the reaction raw materials, and its narrow and small pore passage structure, the rapid diffusion that also influences reacted product molecule is overflowed, thereby cause secondary cracking and green coke amount to increase, a spot of coke can stop up the narrow and small duct that oil gas is rely and passed through, inner a certain part or all of molecular sieve of isolated fully crystal grain and extraneous passage, thereby that part of molecular sieve can not be played a role again, also make the green coke amount increase, this is disadvantageous to heavy oil catalytic cracking reaction.In heavy (slag) oil distillate, molecular diameter occupies suitable ratio greater than the molecule of 1nm, want pressure fuel just the active surface that macromole can be touched must be arranged, it is the accessibility in active centre, will realize macromolecular controlled cracking simultaneously, exploitation has molecular sieve homogeneous, larger aperture and seems very necessary.In sum, a new generation's heavy oil conversion catalyst design and exploitation will be based on the composition and the conversion characteristics of heavy oil, the large, medium and small acidity of constructing gradient pore distribution system and appropriateness that foundation has suitable proportion distributes, to be fit to heavy oil macromole cracked design concept step by step, reach the purpose of strengthening the macromolecular crackability of heavy oil, suppressing its condensation green coke.For this reason, the synthetic porous material that is built into by zeolitic material is the research focus in molecular sieve field in recent years.
Method in common is with the al composition in the leaching zeolites such as mineral acid, EDTA at present, thereby forms the secondary pore of 5-20nm, as the technology of UOP, Mobil and Union Carbon company.The appearance of secondary pore has promoted molecular diffusion, but the problem of bringing is the destruction of crystalline structure and supercage and the partial destruction of chain active sites, and the distribution of secondary pore also be at random with unordered.Meanwhile, research and development such as famous Mobil oil company with M41S (Nature, 1992,359,710-712; J.Am.Chem.Soc., 1992,114,10834-10843, USP5108725), SBA, MSU etc. make people see hope for the meso-porous molecular sieve material and the up-to-date synthetic ICQ-21 of the Spain scientist molecular sieve of representative, for example, and in the ICQ-21 molecular sieve that all has 12 yuan of rings on the three-dimensional (aperture that all has 0.74nm on the three-dimensional, the vestibule that contains 1.18nm), be used for the petroleum refinement process, have good catalytic performance (Nature, 2002,418,514-517).
But the hydrothermal stability of mesopore molecular sieve extreme difference makes it can not industrialization, and ICQ-21 equimolecular sieve also makes it be difficult to move towards application because of the template price of costliness.Mesoporous as if in zeolite, importing with controllable mode, may improve its diffusion greatly, will alleviate this contradiction, the terms of settlement preferably of can yet be regarded as.
In recent years, the raw material of wood-charcoal material extensively is used as material synthetic hard template.Schmidt etc. once used mesoporous carbon black to prepare Ti-Si zeolite (TS-1), improved the catalytic performance (Chem.Commun of Ti-Si zeolite in epoxidation of ethylene, 2000,2157-2158), but the mesoporous pore size distribution broad of the Ti-Si zeolite that obtains, and be difficult to control, crystallographic dimension is also very inhomogeneous.Zhao Tianbo discloses a kind of preparation method of beta zeolite with multilevel pore canals, be to flood monolithic silica column with sucrose solution, drying, polymerization, charing, obtain the charcoal silicon compound, after using the mixing solutions of being made up of aluminium source, mineral alkali, organic amine, water wetting the charcoal silicon compound, crystallization also reclaims product (the open CN 101003378A of Chinese patent).
The charcoal in the different apertures of usefulness synthetic such as Pinnavaia synthesizes as template and has mesoporous nano zeolite ZSM-5, and the pore distribution of synthetic nano-ZSM-5 is very narrow, the crystal grain size is than do template synthetic zeolite evenly (Chem Mater, 2003,15 (8): 1664-1668) with carbon black.It is mesoporous nano-ZSM-5 zeolite (J Am Chem Soc, 2003,125 (20): 6044～6045) about 11nm that Kaneko etc. synthesize the aperture with charcoal-aero gel as template.The mesoporous charcoal CMK-3 of usefulness such as Robert Mokaya do template and have synthesized ultramicropore ZSM-5 (Adv.Mater., 2004,16 (8): 727-732), the aperture of used mesoporous charcoal must be greater than the structure cell of ZSM-5 zeolite, used zeolite sol must be a clear liquid, otherwise ZSM-5 just can not enter growth in the duct of mesoporous charcoal.These methods synthetic have all obtained some progress aspect the multistage pore canal zeolite molecular sieve, but these charcoal templates are to be that template is introduced charcoal source presoma charing with the mesoporous Si-Al molecular sieve mostly, then mesoporous Si-Al are removed and are made with hydrofluoric acid or sodium hydroxide solution.Introduce the sial species clear liquid of synthetic zeolite subsequently within it once more, carry out crystallization.
Summary of the invention
The invention provides a kind of preparation method of beta zeolite with multilevel pore canals, purpose is with after the synthetic charcoal template under the constraint of ordered mesoporous molecular sieve duct, the mesoporous amorphous aluminum silicide converted in-situ that adding small molecules organic ammonium template directly will be wrapped up carbon granule is a zeolite crystal, can form beta zeolite with multilevel pore canals after removing carbon granule with mesopore orbit structure, thereby disclosing the mesoporous charcoal of a kind of and direct application compares as template, need not to remove earlier mesoporous Si-Al, and then the sial species of introducing synthetic zeolite, both reduced complicated step, the preparation method of a kind of beta zeolite with multilevel pore canals that economizes in raw materials again.Institute's synthetic β zeolite has two kinds of independently ducts, and a kind of is the micropore canals of β zeolite itself, also have a kind of by the zeolite nanometer crystalline particle pile up form can be between 10-90nm the mesopore orbit of modulation.The invention has the beneficial effects as follows and to improve and to eliminate the mass transfer limit of macromole greatly, thereby have better catalytic performance in zeolite inside.
The preparation method of a kind of beta zeolite with multilevel pore canals of the present invention, it is characterized in that adopting carbon granule that generates under the ordered mesoporous pore canals constraint as hard template, adding the organic ammonium soft template again, will to wrap up the mesoporous Si-Al material converted in-situ of carbon granule be micropore β zeolite, the method of the β zeolite that obtains containing multistage pore canal after the soft or hard template is removed in roasting, and concrete steps are:
I, in the mesopore molecular sieve duct, prepare the raw material of wood-charcoal material: at first the method for organic polymer precursor body by incipient impregnation is incorporated in the duct of ordered mesoporous molecular sieve and polymerization, then under protection of inert gas, make the polymkeric substance charing in 700～950 ℃ of following pyrolysis, obtain the mixture of mesopore molecular sieve and raw material of wood-charcoal material;
II, will synthesize in the mixture that the used small molecules organic ammonium template of β zeolite joins the mesopore molecular sieve that made by I and raw material of wood-charcoal material;
III, II gained mixture is placed a crucible, again crucible is placed the stainless steel cauldron of band teflon lined, under 140～170 ℃ of temperature, carry out the water vapour auxiliary crystallization and handle 48～168h;
IV, with the mixture of III gained through deionized water wash, 80～120 ℃ of dry backs in retort furnace in 500～600 ℃ of roasting 5～10h, remove the β zeolite that raw material of wood-charcoal material and organic ammonium template obtain having multistage pore canal.
Above-mentioned a kind of beta zeolite with multilevel pore canals preparation method that has is characterized in that described organic polymer precursor body is sucrose, resol or furfuralcohol.
Above-mentioned a kind of beta zeolite with multilevel pore canals preparation method that has, it is characterized in that, described ordered mesoporous molecular sieve is MCM-41, MCM-48, SBA-15 or SBA-16, and the contained silicon-dioxide of its described ordered mesoporous molecular sieve and the molar ratio range of aluminium sesquioxide are: SiO
2/ Al
2O
3=25-∞.
Above-mentioned a kind of beta zeolite with multilevel pore canals preparation method, it is characterized in that described small molecules organic ammonium template is the mixture of tetraethyl ammonium hydroxide or tetraethyl ammonium hydroxide and tetraethylammonium bromide, the mol ratio of tetraethylammonium bromide and tetraethyl ammonium hydroxide is less than 0.5 in its mixture.
Above-mentioned a kind of preparation method with beta zeolite with multilevel pore canals molecular sieve, it is characterized in that, organic polymer precursor body polymerizing condition is: 90-150 ℃ of polyase 13-12 hour, wherein, when used organic polymer precursor body is sucrose, need wiring solution-forming to add, the mass ratio of each component is: 0.8～1.5 sucrose: 0.1～0.2 vitriol oil: 3～7H
2When O or used organic polymer precursor body are furfuralcohol, add oxalic acid, the mol ratio of each component is: 0.8～1.5 furfuralcohol: 0.0～0.1 oxalic acid.
Above-mentioned a kind of preparation method with beta zeolite with multilevel pore canals molecular sieve is characterized in that, carbonization process is at 700-950 ℃ down and during inert nitrogen gas or helium protect, and carries out charing to obtain the charcoal silicon compound in 2～8 hours;
Above-mentioned a kind of beta zeolite with multilevel pore canals preparation method is characterized in that the mol ratio of contained silicon-dioxide is 0.1～0.5 in described small molecules organic ammonium template and the ordered mesoporous molecular sieve.
Above-mentioned a kind of preparation method with beta zeolite with multilevel pore canals molecular sieve is characterized in that described step I can repeat 1～3 time.
The preparation method's of a kind of beta zeolite with multilevel pore canals of the present invention advantage is:
1) only by adding small molecules organic formwork agent tetraethyl ammonium hydroxide, can be the β zeolite with the sial converted in-situ of wrapping up the mesopore molecular sieve of carbon granule, the raw material in the system be fully used.
2) by changing the kind of mesopore molecular sieve, the mesoporous rate that comprises in the adjustable sell of one's property thing β zeolite and the size in mesoporous aperture.
3) by changing the silica alumina ratio of mesopore molecular sieve, but the sial in the modulation β zeolite is when acid.
4) use mesoporous charcoal with existing method and compare, need not to remove earlier mesoporous Si-Al, and then introduce the sial species of synthetic zeolite, both reduced complicated step, saved raw material again as template.
5) the beta zeolite with multilevel pore canals material that obtains by the preparation method who adopts a kind of beta zeolite with multilevel pore canals of the present invention has high zeolite content and evenly flourishing meso-hole structure, therefore can be used widely in fields such as catalysis, fractionation by adsorption.
Description of drawings
Fig. 1 is the transmission electron microscope picture of embodiment of the present invention 1 gained beta zeolite with multilevel pore canals.
Fig. 2 is the sem photograph of embodiment of the present invention 1 gained beta zeolite with multilevel pore canals.
Fig. 3 is the N of embodiment of the present invention 1 gained beta zeolite with multilevel pore canals
2Adsorption figure and graph of pore diameter distribution (interior).
Fig. 4 be embodiment of the present invention 3 gained beta zeolite with multilevel pore canals sem photograph.
Fig. 5 be embodiment of the present invention 5 gained beta zeolite with multilevel pore canals sem photograph.
Table 1 is the pore structure parameter that embodiment of the present invention 1,3 and 5 products therefroms have the beta zeolite with multilevel pore canals molecular sieve.
Further specify the present invention below by embodiment, but the present invention is not subjected to the restriction of these embodiments.
Embodiment:
Embodiment 1:
Get 7.5g MCM-41 (SiO
2/ Al
2O
3=25); add phenol and formaldehyde (phenol and formaldehyde mole ratio are 8) by equi-volume impregnating; 125 ℃ of polymerization 8h in baking oven; the charing under nitrogen protection of gained resol polymkeric substance; the charing program is that 2 ℃/min of temperature rise rate rises to 700 ℃ from room temperature; constant temperature 5h naturally cools to room temperature, and gains are mesoporous and the mixture raw material of wood-charcoal material.Get this mixture 2g and place crucible, the tetraethyl ammonium hydroxide solution that adds 3.0g (wt.48%), after room temperature is placed 10h, crucible packed into fill in the reactor of 5ml water, in 170 ℃ of crystallization 3d, the washing of gained solid, filtration, 100 ℃ of dryings, 550 ℃ of roasting 8h, obtain the beta zeolite with multilevel pore canals powder of white, product is designated as M41B-1.
Embodiment 2:
Get 7.5g MCM-41 (SiO
2/ Al
2O
3=50); press equi-volume impregnating and add sucrose solution (2.5g sucrose: the 0.28g vitriol oil: 6.0g water); 125 ℃ of polymerization 8h in baking oven; resulting polymers charing under nitrogen protection; the charing program is that 2 ℃/min of temperature rise rate rises to 700 ℃ from room temperature; constant temperature 5h naturally cools to room temperature, and gains are mesoporous and the mixture raw material of wood-charcoal material.Get this mixture 2g and place crucible, the tetraethyl ammonium hydroxide solution that adds 0.096g sodium metaaluminate (wt.41%), 0.68g tetraethylammonium bromide and 2.0g (wt.48%), after room temperature was placed 10h, crucible packed into to be filled in the reactor of 3ml water, in 170 ℃ of crystallization 3d, the washing of gained solid, filtration, 100 ℃ of dryings, 550 ℃ of roasting 8h obtain white beta zeolite with multilevel pore canals powder, and product is designated as M41B-2.
Embodiment 3:
Get 6.5g MCM-48 (SiO
2/ Al
2O
3=30); add phenol and formaldehyde (phenol and formaldehyde mole ratio are 8) by equi-volume impregnating; 125 ℃ of polymerization 8h in baking oven; the charing under nitrogen protection of gained resol polymkeric substance; the charing program is that 2 ℃/min of temperature rise rate rises to 700 ℃ from room temperature; constant temperature 5h naturally cools to room temperature, and gains are mesoporous and the mixture raw material of wood-charcoal material.Get this mixture 2g and place crucible, the tetraethyl ammonium hydroxide solution that adds 2.5g (wt.48%), after room temperature is placed 10h, then crucible is packed into and fill in the reactor of 5ml water, in 170 ℃ of crystallization 4d, the gained solid is through washing, filtration, 100 ℃ of dryings, 550 ℃ of roasting 8h, obtain the beta zeolite with multilevel pore canals powder of white, product is designated as M48B-1.
Embodiment 4:
Get 7.5g MCM-48 (SiO
2/ Al
2O
3=25); press equi-volume impregnating and add sucrose solution (2.5g sucrose: the 0.28g vitriol oil: 6.0g water); 125 ℃ of polymerization 8h in baking oven; resulting polymers charing under nitrogen protection; the charing program is that 2 ℃/min of temperature rise rate rises to 800 ℃ from room temperature; constant temperature 5h naturally cools to room temperature, and gains are mesoporous and the mixture raw material of wood-charcoal material.Re-treatment is once again by above-mentioned dipping, polymerization and carbonization process with this mixture.Get gained mixture 2g and place crucible, the tetraethyl ammonium hydroxide solution that adds 3.0g (wt.48%), after room temperature is placed 12h, then crucible is packed into and fill in the reactor of 5ml water, in 170 ℃ of crystallization 5d, the washing of gained solid, filtration, 100 ℃ of dryings, 550 ℃ of roasting 8h, obtain the beta zeolite with multilevel pore canals powder of white, product is designated as M48B-2.
Embodiment 5:
Get 10g AlSBA-15 (SiO
2/ Al
2O
3=25); add phenol and formaldehyde (phenol and formaldehyde mole ratio are 8) by equi-volume impregnating; 125 ℃ of polymerization 8h in baking oven; the charing under nitrogen protection of gained resol polymkeric substance; the charing program is that 2 ℃/min of temperature rise rate rises to 700 ℃ from room temperature; constant temperature 5h naturally cools to room temperature, and gains are mesoporous and the mixture raw material of wood-charcoal material.Get this mixture 2g and place crucible, the tetraethyl ammonium hydroxide solution that adds 3.2g (wt.48%), after room temperature is placed 10h, then crucible is packed into and fill in the reactor of 5ml water, in 170 ℃ of crystallization 4d, the washing of gained solid, filtration, 100 ℃ of dryings, 550 ℃ of roasting 8h, obtain the beta zeolite with multilevel pore canals powder of white, product is designated as S15B-1.
Embodiment 6:
Get 7.5g SiSBA-15; press equi-volume impregnating and add sucrose solution (2.5g sucrose: the 0.28g vitriol oil: 6.0g water); 120 ℃ of polymerization 8h in baking oven; resulting polymers charing under nitrogen protection; the charing program is that 2 ℃/min of temperature rise rate rises to 700 ℃ from room temperature; constant temperature 5h naturally cools to room temperature, and gains are mesoporous and the mixture raw material of wood-charcoal material.Get this mixture 2g and place crucible, the tetraethyl ammonium hydroxide solution that adds 0.16g sodium metaaluminate (wt.41%) and 2.25g (wt.48%), stir, after room temperature was placed 12h, crucible is packed into filled in the reactor of 8ml water then, in 170 ℃ of crystallization 3d, the washing of gained solid, filtration, 100 ℃ of dryings, 550 ℃ of roasting 8h obtain white beta zeolite with multilevel pore canals powder, and product is designated as S15B-2.
Embodiment 7:
Get 7.5g AlSBA-15 (SiO
2/ Al
2O
3=60), press equi-volume impregnating and add furfuralcohol solution, 95 ℃ of polymerization 10h in baking oven; resulting polymers charing under nitrogen protection; the charing program is that 2 ℃/min of temperature rise rate rises to 700 ℃ from room temperature, and constant temperature 5h naturally cools to room temperature, and gains are mesoporous and the mixture raw material of wood-charcoal material.Get this mixture 2g and place crucible, the tetraethyl ammonium hydroxide solution that adds 0.11g sodium metaaluminate (wt.41%) and 2.5g (wt.48%), after room temperature is placed 10h, then crucible is packed into and fill in the reactor of 5ml water, in 170 ℃ of crystallization 4d, the washing of gained solid, filtration, 100 ℃ of dryings, 550 ℃ of roasting 8h, obtain the beta zeolite with multilevel pore canals powder of white, product is designated as S15B-3.
Embodiment 8:
Get 8.0g SiMCM-48; add phenol and formaldehyde (phenol and formaldehyde mole ratio are 8) by equi-volume impregnating; 125 ℃ of polymerization 8h in baking oven; the charing under nitrogen protection of gained resol polymkeric substance; the charing program is that 2 ℃/min of temperature rise rate rises to 700 ℃ from room temperature; constant temperature 5h naturally cools to room temperature, and gains are mesoporous and the mixture raw material of wood-charcoal material.Get this mixture 2g and place crucible, the tetraethyl ammonium hydroxide solution that adds 0.16g sodium metaaluminate (wt.41%) and 3g (wt.48%), stir, after room temperature was placed 10h, crucible is packed into filled in the reactor of 5ml water then, in 170 ℃ of crystallization 3d, the washing of gained solid, filtration, 100 ℃ of dryings, 550 ℃ of roasting 8h obtain white beta zeolite with multilevel pore canals powder, and product is designated as M48B-3.
Embodiment 9:
Get 8.0g SiMCM-48; add phenol and formaldehyde (phenol and formaldehyde mole ratio are 8) by equi-volume impregnating; 125 ℃ of polymerization 8h in baking oven; the charing under nitrogen protection of gained resol polymkeric substance; the charing program is that 2 ℃/min of temperature rise rate rises to 700 ℃ from room temperature; constant temperature 5h naturally cools to room temperature, and gains are mesoporous and the mixture raw material of wood-charcoal material.Get this mixture 2g and place crucible, the tetraethyl ammonium hydroxide solution and the 0.46g tetraethylammonium bromide that add 0.16g sodium metaaluminate (wt.41%), 2.0g (wt.48%) successively, stir, after room temperature was placed 10h, crucible is packed into filled in the reactor of 5ml water then, in 170 ℃ of crystallization 4d, the washing of gained solid, filtration, 100 ℃ of dryings, 550 ℃ of roasting 8h obtain white beta zeolite with multilevel pore canals powder, and product is designated as M48B-4.
Embodiment 10:
Get 8.0g SiSBA-16; add furfuralcohol solution (mol ratio of furfuralcohol and oxalic acid is 250) by equi-volume impregnating; 95 ℃ of polymerization 10h in baking oven; resulting polymers charing under nitrogen protection; the charing program is that 2 ℃/min of temperature rise rate rises to 750 ℃ from room temperature; constant temperature 5h naturally cools to room temperature, and gains are mesoporous and the mixture raw material of wood-charcoal material.Re-treatment is once again by above-mentioned dipping, polymerization and carbonization process with this mixture.Get gained mixture 2g and place crucible, the tetraethyl ammonium hydroxide solution that adds 0.1g sodium metaaluminate (wt.41%), 2.25g (wt.48%), after room temperature is placed 12h, then crucible is packed into and fill in the reactor of 8ml water, in 170 ℃ of crystallization 4d, the washing of gained solid, filtration, 100 ℃ of dryings, 550 ℃ of roasting 8h, obtain the beta zeolite with multilevel pore canals powder of white, product is designated as S16B-1.
Table 1
Claims (5)
1. the preparation method of a beta zeolite with multilevel pore canals, it is characterized in that adopting carbon granule that generates under the ordered mesoporous pore canals constraint as hard template, adding the organic ammonium soft template again, will to wrap up the mesoporous Si-Al material converted in-situ of carbon granule be micropore β zeolite, the method of the β zeolite that obtains containing multistage pore canal after the soft or hard template is removed in roasting, and concrete steps are:
I, in the mesopore molecular sieve duct, prepare the raw material of wood-charcoal material: at first the method for organic polymer precursor body by incipient impregnation is incorporated in the duct of ordered mesoporous molecular sieve and polymerization, then under protection of inert gas, make the polymkeric substance charing in 700～950 ℃ of following pyrolysis, obtain the mixture of mesopore molecular sieve and raw material of wood-charcoal material;
II, will synthesize in the mixture that the used small molecules organic ammonium template of β zeolite joins the mesopore molecular sieve that made by I and raw material of wood-charcoal material;
III, II gained mixture is placed a crucible, again crucible is placed the stainless steel cauldron of band teflon lined, under 140～170 ℃ of temperature, carry out the water vapour auxiliary crystallization and handle 48～168h;
IV, with the mixture of III gained through deionized water wash, 80～120 ℃ of dry backs in retort furnace in 500～600 ℃ of roasting 5～10h, remove the β zeolite that raw material of wood-charcoal material and organic ammonium template obtain having multistage pore canal;
Used organic polymer precursor body is sucrose, resol or furfuralcohol;
Used ordered mesoporous molecular sieve is MCM-41, MCM-48, SBA-15 or SBA-16, and the contained silicon-dioxide of ordered mesoporous molecular sieve and the molar ratio range of aluminium sesquioxide are: SiO
2/ Al
2O
3=25-∞;
Organic polymer precursor body polymerizing condition is: 90-150 ℃ of polyase 13-12 hour, and wherein, when used organic polymer precursor body is sucrose, need wiring solution-forming to add, the mass ratio of each component is: 0.8～1.5 sucrose: 0.1～0.2 vitriol oil: 3～7H
2When O or used organic polymer precursor body are furfuralcohol, add oxalic acid, the mol ratio of each component is: 0.8～1.5 furfuralcohol: greater than 0.0～0.1 oxalic acid.
2. the preparation method of a kind of beta zeolite with multilevel pore canals according to claim 1, it is characterized in that described small molecules organic ammonium template is the mixture of tetraethyl ammonium hydroxide or tetraethyl ammonium hydroxide and tetraethylammonium bromide, the mol ratio of tetraethylammonium bromide and tetraethyl ammonium hydroxide is less than 0.5 in its mixture.
3. the preparation method of a kind of beta zeolite with multilevel pore canals according to claim 1 is characterized in that, carbonization process is at 700-950 ℃ down and during inert nitrogen gas or helium protect, and carries out charing and obtains the charcoal silicon compound in 2～8 hours.
4. the preparation method of a kind of beta zeolite with multilevel pore canals according to claim 1 is characterized in that, the mol ratio of contained silicon-dioxide is 0.1～0.5 in described small molecules organic ammonium template and the ordered mesoporous molecular sieve.
5. the preparation method of a kind of beta zeolite with multilevel pore canals according to claim 1 is characterized in that, described step I repeats 1～3 time.
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| CN112727420B (en) * | 2021-01-21 | 2022-03-22 | 太原理工大学 | Method for exploiting oil and gas products by underground pyrolysis of thick and extra-thick oil shale deposits |
| CN112727419B (en) * | 2021-01-21 | 2022-03-22 | 太原理工大学 | Method for exploiting oil and gas products by underground pyrolysis of thin and medium-thickness oil shale deposits |
| CN115246745B (en) * | 2022-07-14 | 2023-04-11 | 航天特种材料及工艺技术研究所 | High-temperature-resistant composite component aerogel material and preparation method thereof |
| CN115321555B (en) * | 2022-07-25 | 2024-03-15 | 上海科技大学 | Method for synthesizing high-silicon AFX zeolite molecular sieve by using small molecular organic template agent |
| CN115385353A (en) * | 2022-09-14 | 2022-11-25 | 青岛惠城环保科技集团股份有限公司 | Method for preparing Beta molecular sieve by using green low-template agent |
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