CN102049276A - Mesoporous zeolite material with superparamagnetism and preparation method thereof - Google Patents
Mesoporous zeolite material with superparamagnetism and preparation method thereof Download PDFInfo
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- CN102049276A CN102049276A CN200910198405XA CN200910198405A CN102049276A CN 102049276 A CN102049276 A CN 102049276A CN 200910198405X A CN200910198405X A CN 200910198405XA CN 200910198405 A CN200910198405 A CN 200910198405A CN 102049276 A CN102049276 A CN 102049276A
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- mesoporous zeolite
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Abstract
The invention relates to a mesoporous zeolite material which is used for petroleum macromolecular catalytic pyrolysis and has superparamagnetism and a preparation method thereof, and belongs to the field of catalysis of inorganic materials. In the mesoporous zeolite material, magnetic mesoporous zeolite granules are filled in pore paths, the sizes of microporous and mesoporous paths are controlled within the range of between 0.4 and 50 nanometers, and the mesoporous paths are three-dimensionally communicated. The concentration of organic solution containing metal magnetic ions is regulated, and the zeolite mesoporous paths are immersed in the organic solution under the condition of vacuum or heating, so that the solution is volatilized until the zeolite mesoporous paths are dried, and the zeolite mesoporous paths are calcined in air atmosphere and reducing atmosphere. Synthetic cost of the material is reduced, the process is simple, and the mesoporous zeolite material with the superparamagnetism is prepared.
Description
Technical field
The present invention relates to a kind of mesoporous zeolite material and preparation method who is used for the cracking of oil bulky molecular catalysis with superparamagnetism.Belong to inorganic material catalysis field.
Background technology
The micro-pore zeolite molecular sieve is a shape-selective catalyst important in the modern petroleum industry, has characteristics such as the microcellular structure of even prosperity, acid strong and good hydrothermal stability, is used widely in a lot of fields.But because its aperture is less, the major diameter molecule enters the duct difficulty, and diffusional resistance is bigger simultaneously, and the big molecule that forms in its vestibule can not be overflowed fast, thereby has limited it greatly in the bulky molecular catalysis Application for Field.And the multistage pore canal zeolite molecular sieve has the advantage of micro-pore zeolite molecular sieve and mesoporous material simultaneously, can remedy the deficiency of micro porous molecular sieve, for macromolecular reaction provides favourable steric configuration, has very high acidity, hydrothermal stability and meso-hole structure, can when keeping the shape selectivity energy, have good mass transfer ability, at petroleum catalytic cracking, the bulky molecular catalysis reaction and the worker that refines etc. involve the interests of the state and the people and the key area of lifelines of the national economy plays an important role, but because after the zeolitic material use, be difficult to reclaim fully, contaminated environment, the while complicated process of preparation, how to make the recycling efficient of zeolitic material, do not influence simultaneously the environment-friendly materials of the catalytic pyrolysis effect of use, become problem anxious to be solved in the current industrial production.
Summary of the invention
The object of the invention provides and a kind ofly supports magnetisable material in the mesopore orbit of mesoporous zeolite, and preparation has the method for the mesoporous zeolite material of superparamagnetism.Still there is not this type of associated materials report at present.
Technical solution of the present invention: employing ferric nitrate etc. is a magnetic source, enters in the mesopore orbit mesoporous zeolite material that preparation has superparamagnetism.Comprise following preparation process:
1) with dry 2-24 hour of mesoporous zeolite material, preparation magnetic ion and alcoholic solution, molar ratio is 1: 10～1: 1000;
2) vacuum state or heated condition 30-100 ℃, dipping mesoporous zeolite material 2 hours～10 days;
3) zeolitic material that will contain source of iron 200～400 ℃ of roastings 2～18 hours in horse expense stove.
4) back is at Ar/H
2300～500 ℃ of roastings are 2～18 hours in the gaseous mixture;
The mesoporous zeolite molecular sieve preparation method is a lot: aluminium isopropoxide, water, ethanol, ethyl orthosilicate and TPAOH, after mixing stirring according to a certain percentage with mesoporous pore creating material, obtain zeolite mother liquor (Y.S.Tao, Chem.Rev., 2006,106,896-910).
The mesoporous zeolite material with superparamagnetism that the present invention relates to has following composition and architectural feature:
(1) magnetic mesoporous zeolite granular is full of the duct, the controlled mesopore orbit three-dimensional communication of micropore and mesopore orbit size 0.4～50nm.
(2), have a lot of magnetic granules, particle diameter 0.4～100nm in mesopore orbit inside.
(3) magnetic mesoporous zeolite has the inorganic crystal skeleton of micropore and meso-hole structure.
(4) specific area is 100～1800m
2/ g, total pore volume is 0.05～1.5cm
3/ g.
This method has the mesoporous MFI zeolitic material of superparamagnetism except that synthetic, also is applicable to the synthetic multistage hole MTW of three-dimensional communication, BEA, LTA, the Si-Al zeolite molecular sieve of FAU structure.
This method has reduced the synthetic cost of material, and technology is simple, and the mesoporous zeolite material that boils and have superparamagnetism of preparation is significant to cracking of oil bulky molecular catalysis and environmental protection.
Description of drawings
Fig. 1 technological process with mesoporous zeolite material of superparamagnetism provided by the invention.
Fig. 2 mesoporous zeolite scanning of materials electromicroscopic photograph with superparamagnetism provided by the invention.Figure (A) is that 2.4 mesoporous nano ducts figure (B) are 5.6 mesoporous nano ducts, and figure (C) is 13 mesoporous nano ducts, and figure (B) is for supporting magnetic-particle in the figure C mesoporous material.
Fig. 3 mesoporous zeolite material wide-angle XRD scattering with superparamagnetism provided by the invention.Illustrate that this series material is that ZSM-5 is zeolite structured in the typical MFI structure, also occurs the tri-iron tetroxide composition of magnetic simultaneously.
Fig. 4 is provided by the invention, and to have under the room temperature of mesoporous zeolite material of superparamagnetism magnetization curve explanation magnetic-particle size less, and coercivity approaches zero, superparamagnetism occurs.
The nitrogen adsorption curve and the pore size distribution curve of the mesoporous zeolite material of Fig. 5 superparamagnetism provided by the invention.Explanation still keeps mesopore orbit preferably at magnetic material.
The specific embodiment
Embodiment 1:
Synthesizing of the mesoporous MFI zeolitic material of superparamagnetism: the mesoporous zeolite material that will prepare is after dry 2 days, vacuumize or heat 60 ℃, be added dropwise to ferric nitrate and ethanolic solution, the dipping volatilization, horse is taken 350 ℃ of roasting 4h in the stove, restores 400 ℃ of roasting 6h in the atmosphere furnace.The mol ratio of reactant is 1Fe (NO
3)/406Etoh/28MFI.Obtain the mesoporous zeolite material of superparamagnetism.Typical X RD spectrum, TEM, magnetization curve, nitrogen adsorption curve and pore size distribution curve prove that product is the mesoporous zeolite material of superparamagnetism, and its micropore size is 0.57nm, and mesoporous aperture is 13nm, and specific area is 321m
2/ g, total pore volume is 0.70cm
3/ g has magnetic, still keeps mesopore orbit.
Press the non magnetic zeolite of embodiment 1 preparation, add different surfactants and prepare small-size meso-porous aperture.With aluminium isopropoxide, water, ethyl orthosilicate, TPAOH, mixing and stirring obtains the zeolite mother liquor, and dropping sodium solution in mother liquor stirs after 2 hours again, ageing 20 hours is added to above-mentioned drips of solution in the softex kw solution and stirred ageing 4 hours 2 hours.The mol ratio of reactant is 100SiO
2/ 1Al
2O
3/ 18TPAOH/16600H
2O/44NaOH/5.6CTAB.150 ℃ of the hydro-thermals of packing in the stainless steel cauldron, crystallization 14h,, washing, filtering and drying, 600 ℃ of roastings 10 hours, typical TEM (Fig. 2 A) is full of mesopore orbit in the testimonial material, and mesoporous aperture is 2.4 nanometers.
Embodiment 3
Press the non magnetic zeolite of embodiment 1 preparation, add different surfactants and prepare small-size meso-porous aperture.With aluminium isopropoxide, water, ethyl orthosilicate, TPAOH, mixing and stirring obtains the zeolite mother liquor, and dropping sodium solution in mother liquor stirs after 2 hours ageing 13 hours again; Then at ambient temperature, above-mentioned drips of solution is added in the F127 solution stirred ageing 4 hours 2 hours.The mol ratio of reactant is 100SiO
2/ 1Al
2O
3/ 18TPAOH/16600H
2O/44NaOH/5.6CTAB.With pack in the stainless steel cauldron 100 ℃ of hydro-thermals of above-mentioned solution, crystallization 5d, washing, filtering and drying, 600 ℃ of roastings 10 hours, typical TEM (Fig. 2 B) is full of mesopore orbit in the testimonial material,, mesoporous aperture is 5.6 nanometers.
Comparative Examples 1
Press the non magnetic zeolitic material of embodiment 1 preparation.With aluminium isopropoxide, water, ethanol, TPAOH after the PMMA powder mixing and stirring, is added dropwise to ethyl orthosilicate, stirs to obtain the zeolite mother liquor in 1 hour, and dropping sodium solution in mother liquor stirred 2 hours again.The mol ratio of reactant is 600SiO
2/ 10Al
2O
3/ 360TPAOH/16200H
2O/1620EtOH/10NaOH/5PMMA.With pack in the stainless steel cauldron 180 ℃ of hydro-thermals of above-mentioned solution, crystallization 2 days, washing, filtering and drying, 600 ℃ of roastings 10 hours, typical TEM (Fig. 2 C) is full of mesopore orbit in the testimonial material, and mesoporous aperture is 13 nanometers.
Claims (7)
1. have the mesoporous zeolite material preparation method of superparamagnetism, it is characterized in that, will contain the organic solution of metal magnetic ion, regulate concentration, in vacuum or heating dipping zeolite mesopore orbit, with solution evaporation till the drying, roasting under air atmosphere and reducing atmosphere respectively.
2. by the described a kind of mesoporous zeolite material preparation method of claim 1 with superparamagnetism, it is characterized in that, described magnetic ion organic solution is iron nitrate solution, iron chloride, cobalt chloride, cobalt nitrate, nickel chloride, magnetic source and ethanol such as nickel nitrate, organic solutions such as isopropyl alcohol, preparation magnetic ion and alcoholic solution, molar ratio is 1: 10～1: 1000.
3. by the described a kind of mesoporous zeolite material preparation method of claim 1, it is characterized in that with superparamagnetism, vacuum state or heated condition 30-100 ℃, dipping mesoporous zeolite material 2 hours～10 days.
4. by the described a kind of mesoporous zeolite material preparation method of claim 1 with superparamagnetism, it is characterized in that, the mesoporous zeolite material that will contain magnetic source 200～400 ℃ of roastings 2～18 hours in horse expense stove, back 300～500 ℃ of roastings 2～18 hours in the reproducibility gaseous mixture.
5. have the mesoporous zeolite material of superparamagnetism, it is characterized in that, magnetic mesoporous zeolite granular is full of the duct, the controlled mesopore orbit three-dimensional communication of micropore and mesopore orbit size 0.4～50nm.
6. by the described mesoporous zeolite material of claim 5, it is characterized in that, having a lot of magnetic granules in mesopore orbit inside with superparamagnetism, particle diameter 0.4～100nm, specific area is 100～1800m
2/ g, total pore volume is 0.05～1.5cm
3/ g.
7. by the described mesoporous zeolite material of claim 5, it is characterized in that described zeolite molecular sieve is MFI, MTW, BEA, LTA, a kind of in the Si-Al zeolite molecular sieve of FAU structure with superparamagnetism.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106391095A (en) * | 2016-10-18 | 2017-02-15 | 合肥学院 | Porous magnetic zeolite-supported metal catalyst and its preparation method and use |
| CN110075780A (en) * | 2019-06-06 | 2019-08-02 | 复旦大学 | Ultralight magnetic mesoporous nanometer frame |
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| CN101106002A (en) * | 2007-06-15 | 2008-01-16 | 华南师范大学 | Superparamagnetism material carrying CuO and preparation method thereof |
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| CN100406382C (en) * | 2003-10-15 | 2008-07-30 | 中国科学院上海硅酸盐研究所 | Water thermostable cube phase medium aperture aluminosilicate hollow ball and preparation method thereof |
| WO2009021286A1 (en) * | 2007-08-13 | 2009-02-19 | The University Of Queensland | Organosilica encapsulated nanoparticles |
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Non-Patent Citations (2)
| Title |
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| AIMIN ZHANG ET AL: "A novel method of varying the diameter of carbon nanotubes formed on an Fe-supported Y zeolite catalyst", 《MICROPOROUS AND MESOPOROUS MATERIALS》 * |
| 段洪敏等: "乙醇浸渍对Co/SBA-15费托合成催化剂性能的影响", 《催化学报》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106391095A (en) * | 2016-10-18 | 2017-02-15 | 合肥学院 | Porous magnetic zeolite-supported metal catalyst and its preparation method and use |
| CN110075780A (en) * | 2019-06-06 | 2019-08-02 | 复旦大学 | Ultralight magnetic mesoporous nanometer frame |
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