CN103979570B - The synthetic method of a kind of novel ordered big hole-mesoporous-micropore multi-stage porous Si-Al molecular sieve - Google Patents
The synthetic method of a kind of novel ordered big hole-mesoporous-micropore multi-stage porous Si-Al molecular sieve Download PDFInfo
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Abstract
The invention provides the synthetic method of a kind of novel ordered big hole-mesoporous-micropore multi-stage porous Si-Al molecular sieve.The method has organically combined template and molecular sieve turns brilliant process, by the controlled selection to macropore template and mesoporous template, prepares mutually through three-dimensional ordered macroporous-mesoporous multi-stage artery structure with different pore size size; Utilize micro porous molecular sieve structure directing agent to prepare Si-Al molecular sieve ordered micro-cellular structure, realize the regulation and control of macropore, mesoporous and micropore canals size.The inventive method simple possible, operational condition is easy to control and synthesis cycle is short, is expected to the application extension of molecular sieve to sieve the organic macromolecule catalytic field that cannot relate to conventional molecular.
Description
Technical field
The present invention relates to Zeolite synthesis technical field, particularly relate to the synthetic method of a kind of ordered big hole-mesoporous-micropore multi-stage porous Si-Al molecular sieve.
Background technology
90% is about had to produce by means of catalytic process in the chemical products that modern petrochemical and synthesis chemical engineering industry provide.Catalyzer is the core of catalysis technique, has very important effect to Catalytic processes development.In recent years, zeolite molecular sieve is as environmentally friendly solid acid catalyst, be widely used in the key areas such as petrochemical complex, petroleum cracking and organic macromolecule synthesis, just progressively replace the liquid acid catalyst that current industrial conventional sulfuric acid, hydrofluoric acid and aluminum chloride etc. have severe corrosive.But the micropore canals size of zeolite molecular sieve greatly limit guest molecule mass transfer performance in the catalyst, thus causing duct inner product C catalyst deactivation prob, the circulation diffusion therefore improving zeolite molecular sieve becomes one of important channel of improving its catalytic performance.
By preparing multi-stage pore zeolite molecular sieve in conjunction with mesoporous and that macropore duct is excellent mass transfer performance, for the application bottleneck solving zeolite molecular sieve provides brand-new approach.Due to the existence of its multi-stage artery structure, multi-stage pore zeolite molecular sieve has open pore passage structure and the pore volume of super large, substantially increases the circulation diffusion of catalystic material, thus effectively enhances the interaction between guest molecule and avtive spot.On the other hand, due to order and the homogeneity of the mesopore orbit in multistage pore canal, improve the selective catalysis performance of catalystic material largely, reduce the generation of the by product in catalytic process, simplify the separating-purifying process of final product.Therefore design and synthesis multifunctional multistage hole zeolite molecular sieve becomes the study hotspot of the zeolite molecular sieve of novel texture and function.
The research of current multi-stage porous molecular sieve mainly concentrates on synthesis and the catalytic applications of mesopore molecular sieve and large pore molecular sieve.Usually adopt the post treatment method of desiliconization or dealuminzation to realize the introducing of mesopore orbit in molecular sieve crystal in industry, utilizing template in molecular screen material, construct mesoporous or macroporous structure is prepare hierarchical pore molecular sieve catalyst approach the most effectively at present.There is the synthesis that the solid particulate of meso-scale, tensio-active agent and cationic polymers are widely used in mesoporous molecular sieve catalyst material.As Xiao Fengshou study group utilizes relatively cheap cationic polymers to go out a series of holocrystalline mesopore molecular sieve Beta catalyzer [Angew.Chem.Int.Ed.2006,118,3162-3165.] as mesoporous Template preparation; Perhaps originally waiting [CN102295297B] quietly utilizes carbohydrate to go out mesoporous Si-Al molecular sieve for Template preparation.In addition, king's Yao etc. [CN102633279B] utilize the template with macropore size successfully to prepare the SAPO sieve particle with through-type macropore.The research work of Most current only achieves the introducing in single additional duct in molecular sieve catalyst.
Up to the present, only there is minority examples of many successful about the preparation with foramen magnum-mesoporous multi-stage porous molecular sieve, as Javier study group [Nat.Chem., 2012,4,825-831.] successful design synthesizes foramen magnum-mesoporous hierarchical pore MFI type zeolite molecular sieve, Su Baolian study group [Angew.Chem.Int.Ed.2011,50,11156-11161.] propose semi-solid phase rotating crystal method first and prepare a series of foramen magnum-mesoporous multi-stage pore zeolite molecular sieve as theoretical foundation.Above-mentioned existing example only achieves introduces macropore and mesopore orbit in system simultaneously, but the still unrealized controllable adjustment to macropore, mesoporous duct attribute (comprising pore size, pore passage structure and specific surface area attribute etc.).。
In addition, the research of existing multi-stage pore zeolite molecular sieve mainly concentrates on constructing of hierarchical porous structure, and the regulation and control for multistage pore canal order rarely have report.But, in molecular screen material, the circulation diffusion for research multi-stage porous molecular sieve is provided theoretical model by constructing of orderly pore passage structure, thus provide possibility for the research of Mutual Influence Law built between multi-stage artery structure, molecule circulation diffusion and catalytic performance, and then provide the theoretical direction of science for the design and synthesis of new and effective hierarchical pore molecular sieve catalyst.Therefore, develop the molecular formula catalyzer with orderly multi-stage artery structure and there is important scientific meaning, cause the concern of researchers in recent years.As Ryoo study group [Nat.Mater.2006,5,718-723.] utilizes organosilane macromole to go out three-dimensional order as mesoporous Template preparation and the controlled mesoporous zeolite molecular sieve in aperture.AndreasStein study group [J.Am.Chem.Soci.1999,121,4308-4309.] utilizes monodispersed polystyrene microsphere to prepare three-dimensional ordered macroporous molecular sieve first as macropore template.At present existing the orderly of mesoporous or macropore is only confined to the controlledly synthesis of multi-stage pore zeolite molecular sieve multistage pore canal order, possesses ordered big hole and order mesoporous multi-stage pore zeolite molecular sieve not yet has report simultaneously.
Summary of the invention
The object of the present invention is to provide the synthetic method of a kind of ordered big hole-mesoporous-micropore multi-stage porous Si-Al molecular sieve.
The present invention for solving the problems of the technologies described above adopted scheme is:
A synthetic method for novel ordered big hole-mesoporous-micropore multi-stage porous Si-Al molecular sieve, it is characterized in that, it comprises the following steps:
1) formation of three-dimensional order matrix: macropore template and silica nanosphere are dispersed in the aqueous solution, obtain suspension solution, described silica nanosphere is as mesoporous template and silicon source; Be dissolved in described suspension solution by organic carbon source and carry out supersound process, the preferred 0.5-2h of ultrasonic time, then carries out evaporation self-assembly, obtains mixing solutions;
2) in step 1) add acid with strong oxidizing property in the mixing solutions that obtains and carry out carbonization solidification treatment, obtain the persursor material of macropore template/silica nanosphere/carbon mixing;
3) aluminium source and micro porous molecular sieve ZSM-5 structure directing agent being dissolved in the water, then by step 2) persursor material that obtains is transferred to described containing in the mixed aqueous solution of aluminium source and micro porous molecular sieve ZSM-5 structure directing agent, stirs, then except anhydrating; Except the method for anhydrating utilizes rotary evaporation in vacuo method, its temperature used is 40 ~ 100 DEG C, and rotating speed used is 300 ~ 600r/min, and the time used is 0.5 ~ 4h;
4) by step 3) mixing solutions that obtains is transferred in autoclave, it is that micro porous molecular sieve is nanocrystalline that the silica nanosphere in presoma is turned a crystalline substance under the effect of structure directing agent, obtain macropore template/molecular sieve nanocrystalline/carbon mixing material;
5) removal step 4) macropore template/molecular sieve of obtaining is nanocrystalline/carbon mixing material in macropore template and carbon material, obtain ordered big hole-mesoporous-micropore multi-stage porous Si-Al molecular sieve.
In such scheme, described macropore template is monodispersed polymer microballoon or monodispersed inorganic microspheres, described polymer microballoon is the one in polystyrene microsphere, poly (methyl methacrylate) micro-sphere or polystyrene-poly methyl methacrylate-polymethyl acrylic acid propyl sulfonic acid sodium copolymer microsphere, the uniform particle diameter of the microballoon of described macropore template and size dimension controllable adjustment within the scope of 100-1000nm, the uniform particle diameter of the nanometer ball of described mesoporous template and size dimension controllable adjustment within the scope of 5-50nm.
In such scheme, described step 1) in the mass ratio of macropore template, organic carbon source and mesoporous template be (6-8): (0.8-1.2): 1, described step 1) in the aqueous solution and the mass ratio of mesoporous template be (80-200): 1.
In such scheme, described step 2) in acid with strong oxidizing property and step 1) in the mass ratio of mesoporous template be (0.08-0.12): 1.
In such scheme, described step 3) in aluminium source, micro porous molecular sieve ZSM-5 structure directing agent and step 1) in the mol ratio in silicon source be 0-0.02:0.6-0.8:1; Described step 3) in the quality of water and step 1) in the mass ratio in silicon source be (10-30): 1.
In such scheme, described step 2) in carbonization solidification treatment process comprise preliminary carbonization process and secondary carbonization process, the temperature that wherein preliminary carbonization is used is 80 ~ 120 DEG C, and the time used is 4 ~ 8h, secondary carbonization temperature used is 150-180 DEG C, and the time used is 4 ~ 8h.
In such scheme, described step 4) in micro porous molecular sieve ZSM-5 to turn a brilliant temperature be 100 ~ 150 DEG C, turning the brilliant time is 0.5 ~ 5 day.
In such scheme, described step 3) in churning time be 15 ~ 40 DEG C, churning time is 1 ~ 4h.
In such scheme, described step 1) in evaporation self assembling process temperature used be 30 ~ 60 DEG C, the time used is 12 ~ 48h.
In such scheme, described step 5) in remove macropore template and carbon material method be specially: by step 4) turn a brilliant mixture completely and wash with water and remove macropore template by the method for high-temperature roasting or solution corrosion after drying, utilize the method for high-temperature roasting to remove carbon material further simultaneously; Drying conditions is vacuum-drying, and its drying temperature is 60 ~ 120 DEG C, and time of drying is 2 ~ 36h.
Wherein, the method removing polymer microballoon macropore template is high-temperature roasting method and solution corrosion method, and the maturing temperature that wherein high-temperature roasting method is used is 500 ~ 600 DEG C, and roasting time is 4 ~ 8h; Solution corrosion method corrosion temperature used is 10 ~ 40 DEG C, and etching time is 2 ~ 6h.Described solution corrosion method solvent used is the one in trichloromethane, tetrahydrofuran (THF) or dimethyl formamide.The mass ratio of solution and polymer microballoon is (10 ~ 30): 1.
The method removing inorganic microspheres macropore template is high-temperature roasting method, and maturing temperature used is 500 ~ 600 DEG C, and roasting time is 4 ~ 8h.
Organic carbon source is the one in glucose, sucrose, fructose, lactose, maltose, Glycerose, starch or Mierocrystalline cellulose; Acid with strong oxidizing property is preferably the vitriol oil; Aluminium source is the one in sodium metaaluminate, Tai-Ace S 150, aluminum nitrate or aluminum isopropylate; Micro porous molecular sieve ZSM-5 structure directing agent is TPAOH or 4-propyl bromide.
Principle of the present invention is: first by macropore template polymer (inorganic) microballoon and silica nanosphere single dispersing at the aqueous solution, after pervaporation self assembling process, polymer microballoon forms three-dimensional order arranged, monodispersed silica nanosphere will be dispersed in the space of three-dimensional order matrix simultaneously, thus forms three-dimensional ordered mesoporous structure.By changing the size of polymer microballoon and silica nanosphere, carrying out organic assembling, finally can prepare the ordered big hole-mesoporous multilevel hierarchy of different pore size size.Then organic carbon source is added, in make it be dispersed in three-dimensional ordered mesoporous duct that silicon oxide pellets is piled into, utilize acid with strong oxidizing property at high temperature to carry out carbonization process process, above-mentioned three-dimensional order matrix is cured by the carbon formed, and obtains persursor material.Then the persursor material prepared is impregnated in the mixing solutions containing aluminium source and micro porous molecular sieve structure directing agent, stirring makes it fully mix, aluminum source compound molecule and micro porous molecular sieve structure directing agent molecule uniformly penetrating are entered in presoma system, then carries out turning brilliant.Finally remove macropore template polymer microballoon and mesoporous support carbon material, prepare ordered big hole-mesoporous-micropore multi-stage pore canal molecular sieve catalyzer.
The invention has the beneficial effects as follows: realize ordered big hole, mesoporous and micropore constructing in same molecular sieve system, while improving molecular sieve catalyst guest molecule circulation diffusion, also improve selectivity of catalyst catalytic performance widely.Simultaneously foramen magnum-mesoporous-micropore multi-stage artery structure is ordered 3 D structure, aperture is homogeneous adjustable, and in multi-stage porous molecular sieve system, mutually through between macropore, mesoporous and micropore canals.In addition, the multi-stage porous molecular sieve that the present invention develops combines multi-stage artery structure and molecular sieve both advantage nanocrystalline, impart the three-dimensional open-framework that molecular sieve catalyst is more open, the nano molecular sieve crystal simultaneously forming catalyzer substantially reduces mass transfer path, effectively improves its catalytic activity.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of gained sieve sample in the embodiment of the present invention 1.
Fig. 2 is the scanning electron microscope (SEM) photograph of gained sieve sample in the embodiment of the present invention 2.
Fig. 3 is the scanning electron microscope (SEM) photograph of gained sieve sample in the embodiment of the present invention 3.
Fig. 4 is the scanning electron microscope (SEM) photograph of gained sieve sample in the embodiment of the present invention 4.
Fig. 5 is the scanning electron microscope (SEM) photograph of gained sieve sample in the embodiment of the present invention 5.
Fig. 6 is the XRD figure of gained sieve sample in the embodiment of the present invention 6.
Fig. 7 is the XRD figure of gained sieve sample in the embodiment of the present invention 7.
Fig. 8 is gained sieve sample in the embodiment of the present invention 8
29siNMR and
27alNMR schemes.
Fig. 9 is the nitrogen adsorption figure of gained sieve sample in the embodiment of the present invention 9.
Embodiment
Below in conjunction with drawings and Examples, the present invention will be described further, but content of the present invention is not only confined to the following examples.
Embodiment 1
By the silica nanosphere of the polystyrene microsphere of the 20g500nm of uniform particle diameter, 3g20nm, 3g sucrose adds to ultrasonic 1h in 400g ultrapure water makes it dispersed, evaporate self-assembly 12h at 60 DEG C of temperature after, to add after the 0.3g vitriol oil at 100 DEG C secondary carbonization 6h at preliminary carbonization 6h and 160 DEG C, obtain the persursor material of polystyrene microsphere/silica nanosphere/carbon mixing.Above-mentioned persursor material is joined the aqueous solution (the TPAOH aqueous solution+30mlDIH of 0.082g sodium metaaluminate+30ml1M of sodium metaaluminate and TPAOH
2o), after fully stirring 2h at 20 DEG C, at the temperature of 60 DEG C, remove the water molecules in mixed system with the rotating speed rotary evaporation in vacuo 2h of 1r/s, aluminum ion and structure directing agent molecule are evenly infiltrated in presoma system.Said mixture is transferred in 50mL autoclave, at 120 DEG C of temperature, turn brilliant 24h.After the mixture of nanocrystalline for the polystyrene microsphere/ZSM-5 molecular sieve of gained/carbon being transferred to 60 DEG C of vacuum drying oven inner drying 24h, roasting 6h at 570 DEG C, removing macropore template polystyrene microballoon and carbon propping material, thus obtain ordered big hole-mesoporous-micropore multi-stage porous ZSM-5 molecular sieve.Scintigram is shown in accompanying drawing 1.Product maintains complete three-dimensional ordered macroporous-mesoporous pore passage structure as seen from the figure, (a) and Fig. 1 (b) of composition graphs 1 can find out that macropore diameter is 500nm, and its macropore hole wall is formed by the accumulation of the silicon oxide particle after crystalline substance that turns of about 20nm.
Embodiment 2
By the silica nanosphere of the poly (methyl methacrylate) micro-sphere of the 28g100nm of uniform particle diameter, 4g5nm, 3.2g glucose adds to ultrasonic 2h in 550g ultrapure water makes it dispersed, evaporate self-assembly 48h at 40 DEG C of temperature after, to add after the 0.32g vitriol oil at 110 DEG C secondary carbonization 8h at preliminary carbonization 5h and 150 DEG C, obtain the persursor material of poly (methyl methacrylate) micro-sphere/silica nanosphere/carbon mixing.Above-mentioned persursor material is joined the aqueous solution (the TPAOH aqueous solution+80mlDIH of 0.08g aluminum isopropylate+40ml1M of aluminum isopropylate and TPAOH
2o), after fully stirring 1h at 30 DEG C, at the temperature of 70 DEG C, remove the water molecules in mixed system with the rotating speed rotary evaporation in vacuo 1.5h of 2r/s, aluminum ion and structure directing agent molecule are evenly infiltrated in presoma system.Said mixture is transferred in 150mL autoclave, at 150 DEG C of temperature, turn brilliant 16h.After the mixture of nanocrystalline for the poly (methyl methacrylate) micro-sphere/ZSM-5 molecular sieve of gained/carbon being transferred to 80 DEG C of vacuum drying oven inner drying 16h, said mixture is immersed in 500mL trichloromethane and at 20 DEG C, stir 4h removing macropore template poly (methyl methacrylate) micro-sphere, after the mixture of nanocrystalline for the ZSM-5 molecular sieve of gained/carbon being transferred to 100 DEG C of vacuum drying oven inner drying 8h, at 400 DEG C, continue roasting 4h except carbon elimination propping material, thus obtain ordered big hole-mesoporous-micropore multi-stage porous ZSM-5 molecular sieve.Scintigram is shown in accompanying drawing 2.Product maintains complete three-dimensional ordered macroporous-mesoporous pore passage structure as seen from the figure, composition graphs 2 (a) and Fig. 2 (b) can find out that macropore diameter is 100nm, and its macropore hole wall is formed by the accumulation of the silicon oxide particle after crystalline substance that turns of about 5nm.
Embodiment 3
By the silica nanosphere of the carbosphere of the 8g300nm of uniform particle diameter, 1g20nm, 1.2g fructose adds to ultrasonic 0.5h in 80g ultrapure water makes it dispersed, evaporate self-assembly 12h at 50 DEG C of temperature after, to add after the 0.12g vitriol oil at 80 DEG C secondary carbonization 4h at preliminary carbonization 8h and 180 DEG C, obtain the persursor material of carbosphere/silica nanosphere/carbon mixing.Above-mentioned persursor material is joined the aqueous solution (0.06g aluminum isopropylate+2.66g 4-propyl bromide+15mlDIH of Tai-Ace S 150 and 4-propyl bromide
2o), after fully stirring 2h at 15 DEG C, at the temperature of 50 DEG C, remove the water molecules in mixed system with the rotating speed rotary evaporation in vacuo 1h of 2r/s, aluminum ion and structure directing agent molecule are evenly infiltrated in presoma system.Said mixture is transferred in 15mL autoclave, at 100 DEG C of temperature, turn brilliant 48h.After the mixture of nanocrystalline for the carbosphere/ZSM-5 molecular sieve of gained/carbon being transferred to 100 DEG C of vacuum drying oven inner drying 4h, said mixture roasting 7h at 400 DEG C is removed macropore template carbosphere and carbon propping material carbon propping material, thus obtains ordered big hole-mesoporous-micropore multi-stage porous ZSM-5 molecular sieve.Scintigram is shown in accompanying drawing 3.Product maintains complete three-dimensional ordered macroporous-mesoporous pore passage structure as seen from the figure, composition graphs 3 (a) and Fig. 3 (b) can find out that macropore diameter is 300nm, and its macropore hole wall is formed by the accumulation of the silicon oxide particle after crystalline substance that turns of about 20nm.
Embodiment 4
By the silica nanosphere of the polystyrene microsphere of the 12g600nm of uniform particle diameter, 2g50nm, 2g lactose adds to ultrasonic 2h in 200g ultrapure water makes it dispersed, evaporate self-assembly 36h at 30 DEG C of temperature after, to add after the 0.2g vitriol oil at 90 DEG C secondary carbonization 5h at preliminary carbonization 7h and 170 DEG C, obtain the persursor material of polystyrene microsphere/silica nanosphere/carbon mixing.Above-mentioned persursor material is joined the aqueous solution (the TPAOH aqueous solution+36mlDIH of 0.022g aluminum nitrate+20ml1M of aluminum nitrate and TPAOH
2o), after fully stirring 1h at 40 DEG C, at the temperature of 80 DEG C, remove the water molecules in mixed system with the rotating speed rotary evaporation in vacuo 0.5h of 1r/s, aluminum ion and structure directing agent molecule are evenly infiltrated in presoma system.Said mixture is transferred in 25mL autoclave, at 110 DEG C of temperature, turn brilliant 36h.After the mixture of nanocrystalline for the polystyrene microsphere/ZSM-5 molecular sieve of gained/carbon being transferred to 70 DEG C of vacuum drying oven inner drying 12h, said mixture is immersed in 300mL dimethyl formamide and at 40 DEG C, stir 2h removing macropore template polystyrene microballoon, after the mixture of nanocrystalline for the ZSM-5 molecular sieve of gained/carbon being transferred to 120 DEG C of vacuum drying oven inner drying 2h, at 500 DEG C, continue roasting 3h except carbon elimination propping material, thus obtain ordered big hole-mesoporous-micropore multi-stage porous ZSM-5 molecular sieve.Scintigram is shown in accompanying drawing 4.Product maintains complete three-dimensional ordered macroporous-mesoporous pore passage structure as seen from the figure, composition graphs 4 (a) and Fig. 4 (b) can find out that macropore diameter is 600nm, and its macropore hole wall is formed by the accumulation of the silicon oxide particle after crystalline substance that turns of about 50nm.
Embodiment 5
By the polystyrene-poly of the 21g300nm of uniform particle diameter methyl methacrylate-polymethyl acrylic acid propyl sulfonic acid sodium microballoon, the silica nanosphere of 3g30nm, 3.6g maltose adds to ultrasonic 1h in 600g ultrapure water makes it dispersed, evaporate self-assembly 36h at 60 DEG C of temperature after, to add after the 0.36g vitriol oil at 120 DEG C secondary carbonization 6h at preliminary carbonization 6h and 160 DEG C, obtain the persursor material of polystyrene-poly methyl methacrylate-polymethyl acrylic acid propyl sulfonic acid sodium microballoon/silica nanosphere/carbon mixing.Above-mentioned persursor material is joined the aqueous solution (0.164g sodium metaaluminate+8g tetrapropyl hydroxide bromine+90mlDIH of sodium metaaluminate and tetrapropyl hydroxide bromine
2o), after fully stirring 2h at 40 DEG C, at the temperature of 90 DEG C, remove the water molecules in mixed system with the rotating speed rotary evaporation in vacuo 0.5h of 1r/s, aluminum ion and structure directing agent molecule are evenly infiltrated in presoma system.Said mixture is transferred in 150mL autoclave, at 130 DEG C of temperature, turn brilliant 16h.After the mixture of nanocrystalline for the polystyrene-poly of gained methyl methacrylate-polymethyl acrylic acid propyl sulfonic acid sodium microballoon/ZSM-5 molecular sieve/carbon is transferred to 90 DEG C of vacuum drying oven inner drying 10h, roasting 8h at 550 DEG C, removing macropore template polystyrene-polymethylmethacrylate-polymethyl acrylic acid propyl sulfonic acid sodium microballoon and carbon propping material, thus obtain ordered big hole-mesoporous-micropore multi-stage porous ZSM-5 molecular sieve.Transmission plot is shown in accompanying drawing 5.Product maintains complete three-dimensional ordered macroporous-mesoporous pore passage structure as seen from the figure, composition graphs 5 (a) and Fig. 5 (b) can find out that macropore diameter is 300nm, and its macropore hole wall is formed by the accumulation of the silicon oxide particle after crystalline substance that turns of about 30nm, turn the corner angle of the nanocrystalline appearance profile of the molecular sieve after crystalline substance clearly, instead of transparent spherical (amorphous silica bead).
Embodiment 6
By the silica nanosphere of the poly (methyl methacrylate) micro-sphere of the 16g700nm of uniform particle diameter, 2g40nm, 1.6g Glycerose adds to ultrasonic 1h in 240g ultrapure water makes it dispersed, evaporate self-assembly 24h at 40 DEG C of temperature after, to add after the 0.16g vitriol oil at 80 DEG C secondary carbonization 6h at preliminary carbonization 8h and 160 DEG C, obtain the persursor material of poly (methyl methacrylate) micro-sphere/silica nanosphere/carbon mixing.Above-mentioned persursor material is joined the aqueous solution (0.11g Tai-Ace S 150+6g tetrapropyl hydroxide bromine+40mlDIH of Tai-Ace S 150 and tetrapropyl hydroxide bromine
2o), after fully stirring 2h at 20 DEG C, at the temperature of 60 DEG C, remove the water molecules in mixed system with the rotating speed rotary evaporation in vacuo 2h of 2r/s, aluminum ion and structure directing agent molecule are evenly infiltrated in presoma system.Said mixture is transferred in 50mL autoclave, at 100 DEG C of temperature, turn brilliant 60h.After the mixture of nanocrystalline for the poly (methyl methacrylate) micro-sphere/ZSM-5 molecular sieve of gained/carbon being transferred to 80 DEG C of vacuum drying oven inner drying 16h, said mixture is immersed in 300mL tetrahydrofuran (THF) and at 30 DEG C, stir 3h removing macropore template poly (methyl methacrylate) micro-sphere, after the mixture of nanocrystalline for the ZSM-5 molecular sieve of gained/carbon being transferred to 120 DEG C of vacuum drying oven inner drying 2h, at 400 DEG C, continue roasting 4h except carbon elimination propping material, thus obtain ordered big hole-mesoporous-micropore multi-stage porous ZSM-5 molecular sieve.Wide-angle diffraction XRD spectra is shown in accompanying drawing 6.As seen from the figure, in 2 θ=8 ° and 23 ° of places there is the characteristic diffraction peak of ZSM-5 zeolite, and peak is high by force, illustrates in product to exist to turn the good ZSM-5 zeolite molecular sieve of brilliant degree in a large number.There is the characteristic peak of extremely weak amorphous silica in product simultaneously at about 25 °, illustrate that the unformed monox nanometer ball in raw material has turned brilliant success substantially.
Embodiment 7
By the polystyrene-poly of the 24g400nm of uniform particle diameter methyl methacrylate-polymethyl acrylic acid propyl sulfonic acid sodium microballoon, the silica nanosphere of 4g10nm, 4g starch adds to ultrasonic 2h in 350g ultrapure water makes it dispersed, evaporate self-assembly 24h at 60 DEG C of temperature after, to add after the 0.4g vitriol oil at 100 DEG C secondary carbonization 6h at preliminary carbonization 6h and 170 DEG C, obtain the persursor material of polystyrene-poly methyl methacrylate-polymethyl acrylic acid propyl sulfonic acid sodium microballoon microballoon/silica nanosphere/carbon mixing.Above-mentioned persursor material is joined the aqueous solution (0.042g aluminum nitrate+12g tetrapropyl hydroxide bromine+80mlDIH of aluminum nitrate and tetrapropyl hydroxide bromine
2o), after fully stirring 2h at 40 DEG C, at the temperature of 100 DEG C, remove the water molecules in mixed system with the rotating speed rotary evaporation in vacuo 0.5h of 2r/s, aluminum ion and structure directing agent molecule are evenly infiltrated in presoma system.Said mixture is transferred in 150mL autoclave, at 120 DEG C of temperature, turn brilliant 48h.After the mixture of nanocrystalline for the polystyrene-poly of gained methyl methacrylate-polymethyl acrylic acid propyl sulfonic acid sodium/ZSM-5 molecular sieve/carbon being transferred to 70 DEG C of vacuum drying oven inner drying 16h, roasting 6h at 600 DEG C, removing macropore template polystyrene-polymethylmethacrylate-polymethyl acrylic acid propyl sulfonic acid sodium microballoon and carbon propping material, thus obtain ordered big hole-mesoporous-micropore multi-stage porous ZSM-5 molecular sieve.Small-angle diffraction XRD spectra is shown in accompanying drawing 7.There is an obvious diffraction peak at about 1 degree as can be seen from Figure, illustrate that product has orderly meso-hole structure.
Embodiment 8
By the silica nanosphere of the polystyrene microsphere of the 18g900nm of uniform particle diameter, 3g30nm, 2.4g Mierocrystalline cellulose adds to ultrasonic 2h in 300g ultrapure water makes it dispersed, evaporate self-assembly 24h at 60 DEG C of temperature after, to add after the 0.24g vitriol oil at 90 DEG C secondary carbonization 7h at preliminary carbonization 8h and 150 DEG C, obtain the persursor material of polystyrene microsphere/silica nanosphere/carbon mixing.Above-mentioned persursor material is joined the aqueous solution (the TPAOH aqueous solution+45mlDIH of 0.082g sodium metaaluminate+40ml1M of sodium metaaluminate and TPAOH
2o), after fully stirring 1h at 40 DEG C, at the temperature of 70 DEG C, remove the water molecules in mixed system with the rotating speed rotary evaporation in vacuo 1.5h of 1r/s, aluminum ion and structure directing agent molecule are evenly infiltrated in presoma system.Said mixture is transferred in 100mL autoclave, at 130 DEG C of temperature, turn brilliant 24h.After the mixture of nanocrystalline for the polystyrene microsphere/ZSM-5 molecular sieve of gained/carbon being transferred to 80 DEG C of vacuum drying oven inner drying 8h, said mixture is immersed in 400mL trichloromethane and at 40 DEG C, stir 1.5h removing macropore template polystyrene microballoon, after the mixture of nanocrystalline for the ZSM-5 molecular sieve of gained/carbon being transferred to 100 DEG C of vacuum drying oven inner drying 6h, at 550 DEG C, continue roasting 2h except carbon elimination propping material, thus obtain ordered big hole-mesoporous-micropore multi-stage porous ZSM-5 molecular sieve.The ZSM-5 zeolite molecular sieve that Fig. 8 (a) is gained
29si nuclear magnetic resonance map, the ZSM-5 zeolite molecular sieve that Fig. 8 (b) is gained
27al nuclear magnetic resonance map.(silicon species of two terminal hydroxy group is connected by all there are not Q2 species in the product after Fig. 8 (a) known turn of crystalline substance, chemical shift is at-92ppm), form primarily of Q4 species (silicon species of the not coupling end hydroxyl of complete condensation), there are a small amount of Q3 species (connecting the silicon species of a terminal hydroxy group).Illustrate that product degree of crystallinity is very high.This illustrates that the condensation degree of dissolved of the product silicon species of gained is higher.Substantially existed with the aluminium species of four-coordination (chemical shift 54ppm) by the known product of Fig. 8 (b) and there is not hexa-coordinate aluminium (chemical shift 0ppm), aluminium due to four-coordination is in the frame position of molecular sieve, and the aluminium of hexa-coordinate is in the non-frame position of molecular sieve.This illustrates that the aluminium in the product after turning crystalline substance exists in the mode of four-coordination in the skeleton of ZSM-5 zeolite molecular sieve substantially.
Embodiment 9
By the silica nanosphere of the polystyrene microsphere of the 10g1000nm of uniform particle diameter, 1.25g50nm, 1.25g sucrose adds to ultrasonic 0.5h in 60g ultrapure water makes it dispersed, evaporate self-assembly 12h at 50 DEG C of temperature after, to add after the 0.125g vitriol oil at 90 DEG C secondary carbonization 4h at preliminary carbonization 5h and 160 DEG C, obtain the persursor material of polystyrene microsphere/silica nanosphere/carbon mixing.Above-mentioned persursor material is joined the aqueous solution (the TPAOH aqueous solution+36mlDIH of 0.05g aluminum isopropylate+16ml1M of aluminum isopropylate and TPAOH
2o), after fully stirring 2h at 20 DEG C, at the temperature of 60 DEG C, remove the water molecules in mixed system with the rotating speed rotary evaporation in vacuo 2h of 1r/s, aluminum ion and structure directing agent molecule are evenly infiltrated in presoma system.Said mixture is transferred in 50mL autoclave, at 150 DEG C of temperature, turn brilliant 24h.After the mixture of nanocrystalline for the polystyrene microsphere/ZSM-5 molecular sieve of gained/carbon being transferred to 90 DEG C of vacuum drying oven inner drying 6h, roasting 6h at 570 DEG C, removing macropore template polystyrene microballoon and carbon propping material, thus obtain ordered big hole-mesoporous-micropore multi-stage porous ZSM-5 molecular sieve.The nitrogen adsorption curve of the ZSM-5 zeolite molecular sieve that Fig. 9 (a) is gained, the micropore size distribution plan of the ZSM-5 zeolite molecular sieve that Fig. 9 (b) is gained, Fig. 9 (c) mesoporous pore size distribution plan.By the compound result that the adsorption isothermal curve of the product after Fig. 9 (a) known turn of crystalline substance is I and IV adsorption isothermal curve, there is hysteresis loop, illustrate in product and comprise micropore and mesopore orbit structure.The micropore size of composition graphs 9 (b) and the known product of Fig. 9 (c) mainly concentrates on about 0.44nm, there is the meso-hole structure of aperture at about 3.8nm in material simultaneously, illustrates that the ordered mesoporous pore canals turned in brilliant rear product is not destroyed.These results suggest that in product to there is orderly foramen magnum-mesoporous structure, the relative narrower of pore distribution simultaneously.
Claims (8)
1. a synthetic method for novel ordered big hole-mesoporous-micropore multi-stage porous Si-Al molecular sieve, it is characterized in that, it comprises the following steps:
1) formation of three-dimensional order matrix: macropore template and silica nanosphere are dispersed in the aqueous solution, obtain suspension solution, described silica nanosphere is as mesoporous template and silicon source; Organic carbon source is dissolved in described suspension solution and carries out supersound process, then carry out evaporation self-assembly, obtain mixing solutions;
2) add acid with strong oxidizing property in the mixing solutions obtained in step 1) and carry out carbonization solidification treatment, obtain the persursor material of macropore template/silica nanosphere/carbon mixing;
3) aluminium source and micro porous molecular sieve ZSM-5 structure directing agent being dissolved in the water, then by step 2) persursor material that obtains is transferred to described containing in the mixed aqueous solution of aluminium source and micro porous molecular sieve ZSM-5 structure directing agent, stirs, then except anhydrating;
4) mixing solutions that step 3) obtains is transferred in autoclave, by the silica nanosphere in presoma under the effect of structure directing agent turn a crystalline substance be that micro porous molecular sieve is nanocrystalline, obtain macropore template/molecular sieve nanocrystalline/carbon mixing material;
5) removal step 4) macropore template/molecular sieve of obtaining is nanocrystalline/carbon mixing material in macropore template and carbon material, obtain ordered big hole-mesoporous-micropore multi-stage porous Si-Al molecular sieve, the mass ratio of the macropore template in described step 1), organic carbon source and mesoporous template is (6-8): (0.8-1.2): 1, and the mass ratio of the aqueous solution in described step 1) and mesoporous template is (80-200): 1; Described step 2) in acid with strong oxidizing property and the mass ratio of mesoporous template in step 1) be (0.08-0.12): 1.
2. synthetic method as claimed in claim 1, it is characterized in that, described macropore template is monodispersed polymer microballoon or monodispersed inorganic microspheres, described polymer microballoon is the one in polystyrene microsphere, poly (methyl methacrylate) micro-sphere or polystyrene-poly methyl methacrylate-polymethyl acrylic acid propyl sulfonic acid sodium copolymer microsphere, the uniform particle diameter of the microballoon of described macropore template and size dimension controllable adjustment within the scope of 100-1000nm, the uniform particle diameter of the nanometer ball of described mesoporous template and size dimension controllable adjustment within the scope of 5-50nm.
3. synthetic method as claimed in claim 1, it is characterized in that, the mol ratio in the silicon source in the aluminium source in described step 3), micro porous molecular sieve ZSM-5 structure directing agent and step 1) is (0-0.02): (0.6-0.8): 1; The mass ratio in the silicon source in described step 3) in the quality of water and step 1) is (10-30): 1.
4. synthetic method as claimed in claim 1, it is characterized in that, described step 2) in carbonization solidification treatment process comprise preliminary carbonization process and secondary carbonization process, the temperature that wherein preliminary carbonization is used is 80 ~ 120 DEG C, time used is 4 ~ 8h, secondary carbonization temperature used is 150-180 DEG C, and the time used is 4 ~ 8h.
5. synthetic method as claimed in claim 1, is characterized in that, a turn brilliant temperature of the micro porous molecular sieve ZSM-5 in described step 4) is 100 ~ 150 DEG C, and turning the brilliant time is 0.5 ~ 5 day.
6. synthetic method as claimed in claim 1, it is characterized in that, the churning time in described step 3) is 15 ~ 40 DEG C, and churning time is 1 ~ 4h.
7. synthetic method as claimed in claim 1, is characterized in that, the temperature used of the evaporation self assembling process in described step 1) is 30 ~ 60 DEG C, and the time used is 12 ~ 48h.
8. synthetic method as claimed in claim 1, it is characterized in that, the method removing macropore template and carbon material in described step 5) is specially: step 4) is turned brilliant mixture completely and wash with water and remove macropore template by the method for high-temperature roasting or solution corrosion after drying, utilize the method for high-temperature roasting to remove carbon material further simultaneously.
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