CN100595146C - Core-shell structure zeolite multilevel ordered mesopore and micropore composite material and preparation method thereof - Google Patents
Core-shell structure zeolite multilevel ordered mesopore and micropore composite material and preparation method thereof Download PDFInfo
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- CN100595146C CN100595146C CN200710040767A CN200710040767A CN100595146C CN 100595146 C CN100595146 C CN 100595146C CN 200710040767 A CN200710040767 A CN 200710040767A CN 200710040767 A CN200710040767 A CN 200710040767A CN 100595146 C CN100595146 C CN 100595146C
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Abstract
The invention belongs to the field of media-micro-hole composite materials techniques. In particular, the invention relates to a shell-core structured zeolite multi-layered media-micro-hole compositematerial and method for preparing same. The material is a regular polyhedron in appearance and has shell-core structure. The polyhedron shell is of single-crystal structure and the core is piled up bynano-crystals, and the material also has the inherent micro-holes of the zeolite molecular screen and the media-holes produced by piling up of the nano-crystal. Therefore, the material has the media-micro-hole two hole-channels compound holes structure. The invention uses NaSiO3 as the silica source, the metal Al extracted from Ni/Al alloy by the NaSiO3 as the aluminum source and athylamine and the residue Raney Ni of Ni/Al alloy extraction as the auxiliary. The material is obtained by crystallizing the zeolite synthesizing solution in the regular crystallization condition and the shell thickness of the single-crystal and the core nano-crystal appearance can be controlled by crystallization temperature and time.
Description
Technical field
The invention belongs to mesoporous micropore composite material technical field, be specifically related to a kind of nucleocapsid structure euthalite (ANA) multilevel ordered mesopore and micropore composite material and preparation method thereof.
Background technology
According to the pure definition of understanding with applied chemistry in the world, porous material can be divided into three classes by the aperture: and poromerics (aperture＜2nm), mesoporous material (2nm＜aperture＜50nm) and large pore material (aperture＞50nm).Zeolite is a very representational class poromerics, and it has uniqueness, regular crystalline structure and pore structure, thereby has special " shape selective catalysis " function and strong adsorption separation performance, thereby is widely used in catalysis, absorption and the field such as separates.But be subjected to the restriction of narrow and small pore passage structure, micro-pore zeolite is not fully up to expectations to relating to macromolecular application.1992, Mobil company reported to be M41S series mesopore molecular sieve synthetic of representative with MCM-41.This class material has caused investigator's extensive attention immediately owing to have regular pore passage structure and very narrow pore size distribution behind report.But its hole wall is thinner, thereby thermostability and hydrothermal stability are all relatively poor.After this Bao Dao some mesopore molecular sieves, such as SBA-15, thermostability has had bigger raising.But, owing to form silica, the aluminum-oxygen tetrahedron random arrangement of mesopore molecular sieve hole wall, thereby this molecular sieve analog hydrothermal stability is poor, and only possess slightly acidic, greatly limited its industrial application.Both are had complementary advantages, and the bibliographical information of this respect is few.Kloetstra etc. have reported example (the Kloetstra K.R. at micropore FAU zeolite surface growth one deck MCM-41 mesopore molecular sieve, Zandbergen H.W., Jansen J.C., van Bekkum H.Overgrowth of Mesoprous MCM-41 on Faujasite[J] .Micropor.Mater., 1996,6 (5-6): 287-293.), Karlsson (Karlsson A., Stocker M., Schmidt R.Composites of micro-and mesoporous materials:simultaneous syntheses of MFI/MCM-41like phases by a mixed template approach[J] .Micropor.Mesopor.Mater., 1999,27 (2-3): 181-192.) and (Huang L.M. such as Li Quanzhi, Guo W.P., Deng P., Xue Z.Y., Li Q.Z.Investigationof Synthesizing MCM-41/ZSM-5 Composites[J] .J.Phys.Chem.B, 2000,104 (13): 2817-2823.) adopt mixed templates method and Steppecd crystallization to synthesize MFI/MCM-41 double hole channel molecular sieve respectively.Though above-mentioned materials reacts at some, as demonstrating good catalytic performance in the vacuum grease cracking, structurally approach the mesoporous of mechanically mixing and micro porous molecular sieve material, can not overcome deficiency separately, bring into play synergy mesoporous, micro porous molecular sieve.
Summary of the invention
The object of the present invention is to provide complex type molecular sieve material of a kind of mesoporous pore size distribution homogeneous, applied range, excellent property and preparation method thereof.
Complex type molecular sieve material provided by the invention, it is a kind of zeolite multilevel ordered mesopore and micropore Composite Double duct molecular screen material with nucleocapsid structure, it has following feature: (1) material appearance is regular polyhedron, (2) material has nucleocapsid structure, the polyhedron shell is a single crystal structure, and polyhedron inside is piled up by nanocrystal and formed; The polyhedron outer casing thickness is 100nm ~ 10 μ m, and the pattern of inner nanocrystal is nano particle or nanometer rod; (3) have zeolite molecular sieve inherent micropore and nanocrystal and pile up produce mesoporous, thereby have mesoporous-micropore double hole channel composite pore structural; (4) specific surface 25-120m2g-1, pore volume 0.10-0.55cm3g-1; (5) product structure is stable, and framework of molecular sieve does not destroy after 500-800 ℃ of following roasting.
In the matrix material of the present invention, the silica alumina ratio of silicon aluminate zeolite is 1-3.
The present invention also provides the preparation method of above-mentioned matrix material, comprises with water glass as the silicon source, alumel is progressively added in 70-110 ℃ the sodium silicate aqueous solution, stirs 1-3h with the aluminium in the extracting alumel; As the aluminium source, as auxiliary, stir the adding ethamine and the vitriol oil down with the metallic aluminium in the water glass extracting alumel, regulate the pH value, obtain zeolite synthesis liquid to 9-10 with Raney Ni remaining behind ethamine and the extracting alumel; Pack into after zeolite synthesis liquid stirs in the reactor, seal, crystallization temperature is 150-200 ℃, and crystallization time is 24 hours-22 days.
The mol ratio of synthetic each raw material scope preferably is: Al2O3/SiO2=0.15-0.60, H2O/SiO2=10-50, C2H5NH2/SiO2=1.0-1.5, OH-/SiO2=0.005-0.02.
By temperature, the time that the control zeolite synthesis liquid-crystalizes, can control the thickness of nucleocapsid structure matrix material polyhedron shell and the pattern of the inner nanocrystal of polyhedron.
Description of drawings
Fig. 1 is the X-ray diffraction spectrogram of 8 days ANA zeolite multilevel ordered mesopore and micropore composite material of 180 ℃ of crystallization.
Fig. 2 is the sem photograph of 8 days ANA zeolite multilevel ordered mesopore and micropore composite material of 180 ℃ of crystallization, the regular polyhedron appearance of display material.
Fig. 3 is the sem photograph of the cracked ANA zeolite multilevel ordered mesopore and micropore composite material of the shell of 180 ℃ of crystallization 8d, the nucleocapsid structure of display material (polyhedron inside is piled up by many nanocrystals and formed).
Fig. 4 is the N of the nucleocapsid structure ANA zeolite multilevel ordered mesopore and micropore composite material of 180 ℃ of crystallization 8d
2Adsorption curve.
Fig. 5 is the sem photograph of the different ANA zeolite multilevel ordered mesopore and micropore composite material of polyhedron outer casing thickness.Wherein, (a) 200 ℃ of crystallization 72h, outer casing thickness 120nm, (b) 180 ℃ of crystallization 6d, outer casing thickness 500nm.
Fig. 6 is the sem photograph of the nanocrystal of the inner different-shape of polyhedron.Wherein, (a) 180 ℃ of crystallization 24h, inside is nano particle, and (b) 150 ℃ of crystallization are 14 days, and inside is nanometer rod.
Embodiment
The invention is further illustrated by the following examples.
Specific embodiments of the invention:
Embodiment 1: the Ni-Al alloy is progressively joined in 90 ℃ the sodium silicate aqueous solution, stir 2h, with the aluminium in the extracting Ni-Al alloy.Add the ethamine and the vitriol oil then under the vigorous stirring, and regulate pH=9.6, the mole of entire reaction liquid consists of SiO
2: Na
2O: Ni: Al: C
2H
5NH
2: H
2SO
4: H
2O=1: 1: 0.22: 0.48: 1.26: 0.63: 19.After question response liquid stirs, in the reactor of packing into, sealing, 180 ℃ of crystallization 8 days, suction filtration is washed to neutrality, and is dry under the room temperature, back 550 ℃ of roastings 6 hours.The characterization result of products therefrom corresponding diagram 1-4.
Embodiment 2: the Ni-Al alloy is joined gradually in 100 ℃ the sodium silicate aqueous solution, vigorous stirring 1h is with the aluminium in the extracting Ni-Al alloy.Add the ethamine and the vitriol oil then under the vigorous stirring, and regulate pH=10, the mole of entire reaction liquid consists of SiO
2: Na
2O: Ni: Al: C
2H
5NH
2: H
2SO
4: 4H
2O=1: 1: 0.22: 0.48: 1.34: 0.63: 24.After question response liquid stirs, in the reactor of packing into, sealing, 200 ℃ of crystallization 72h, suction filtration is washed to neutrality, and is dry under the room temperature, back 600 ℃ of roastings 3 hours.Products therefrom corresponding diagram 1, the characterization result of Fig. 5 a.
Embodiment 3: the Ni-Al alloy is joined gradually in 95 ℃ the sodium silicate aqueous solution, vigorous stirring 1.5h is with the aluminium in the extracting Ni-Al alloy.Add the ethamine and the vitriol oil then under the vigorous stirring, and regulate pH=9.8, the mole of entire reaction liquid consists of SiO
2: Na
2O: Ni: Al: C
2H
5NH
2: H
2SO
4: H
2O=1: 1: 0.22: 0.48: 1.30: 0.63: 22.After question response liquid stirs, in the reactor of packing into, sealing, 150 ℃ of crystallization 14d, suction filtration is washed to neutrality, and is dry under the room temperature, back 550 ℃ of roastings 6 hours.Products therefrom corresponding diagram 1, the characterization result of Fig. 6 b.
Claims (2)
1, a kind of core-shell structure zeolite multilevel ordered mesopore and micropore matrix material, it is characterized in that: with water glass as the silicon source, with the metallic aluminium in the water glass extracting alumel as the aluminium source, with Raney Ni remaining behind ethamine and the water glass extracting alumel as auxiliary, prepare by following step: alumel is joined gradually in 70-110 ℃ the sodium silicate aqueous solution, stir 1-3h, with the aluminium in the extracting alumel; Stir the adding ethamine and the vitriol oil down, regulate the pH value, obtain zeolite synthesis liquid to 9-10; Pack into after zeolite synthesis liquid stirs in the crystallization still, seal, crystallization temperature is 150-200 ℃, and crystallization time is 24h-22 days; The mol ratio of synthetic each raw material is: Al
2O
3/ SiO
2=0.15-0.60, H
2O/SiO
2=10-50, C
2H
5NH
2/ SiO
2=1.0-1.5, OH
-/ SiO
2=0.005-0.02; (1) this matrix material appearance is regular polyhedron, and (2) material has nucleocapsid structure, and the polyhedron shell is a single crystal structure, and polyhedron inside is piled up by nanocrystal and formed; The polyhedron outer casing thickness is 100nm～10 μ m, and the pattern of inner nanocrystal is nano particle or nanometer rod; (3) have zeolite molecular sieve inherent micropore and nanocrystal and pile up produce mesoporous, thereby have mesoporous-micropore double hole channel composite pore structural; (4) specific surface 25-120m
2G
-1, pore volume 0.10-0.55cm
3G
-1(5) product structure is stable, and framework of molecular sieve does not destroy after 500-800 ℃ of following roasting.
2, a kind of preparation method of the matrix material described in claim 1, it is characterized in that with water glass as the silicon source, with the metallic aluminium in the water glass extracting alumel as the aluminium source, with remaining Raney Ni behind ethamine and the extracting alumel as auxiliary, concrete steps are: alumel is joined gradually in 70-110 ℃ the sodium silicate aqueous solution, stir 1-3h, with the aluminium in the extracting alumel; Stir the adding ethamine and the vitriol oil down, regulate the pH value, obtain zeolite synthesis liquid to 9-10; Pack into after zeolite synthesis liquid stirs in the crystallization still, seal, crystallization temperature is 150-200 ℃, and crystallization time is 24h-22 days; The mol ratio of synthetic each raw material is: Al
2O
3/ SiO
2=0.15-0.60, H
2O/SiO
2=10-50, C
2H
5NH
2/ SiO
2=1.0-1.5, OH
-/ SiO
2=0.005-0.02.
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