CN103949230A - Ultramicropore high-specific surface area and low-aluminum zirconium oxide material and preparation method thereof - Google Patents
Ultramicropore high-specific surface area and low-aluminum zirconium oxide material and preparation method thereof Download PDFInfo
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- CN103949230A CN103949230A CN201410153432.6A CN201410153432A CN103949230A CN 103949230 A CN103949230 A CN 103949230A CN 201410153432 A CN201410153432 A CN 201410153432A CN 103949230 A CN103949230 A CN 103949230A
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Abstract
The invention relates to an ultramicropore low-aluminum zirconium oxide nanometer material and a preparation method of the nanometer material, belonging to the fields of inorganic porous materials and catalyst preparation. The ultramicropore low-aluminum zirconium oxide nanometer material is characterized in that the low-aluminum zirconium oxide material (the atomic ratio of aluminum to zirconium is less than 10%) with a micropore structure is prepared by utilizing a cheap cationic surfactant as a template agent through a one-step method without adding any acid, and the micropore diameters of the low-aluminum zirconium oxide material are within the range of 1.0-2.0nm. The synthetic method comprises the steps of according to the synthetic material proportion, dissolving the surfactant into ethanol solution containing 4.5-5.5% of deionized water, and feeding a zirconium source and an aluminum source at the same time while mixing; continuously mixing for a period of time, and carrying out solvent evaporation, heat treatment and high-temperature roasting on a reactant to obtain the ultramicropore low-aluminum ZrO2 material. The preparation technology is simple, convenient, low in cost and environmentally friendly, thus having potential industrial application prospect.
Description
Technical field
Low aluminum oxidation zirconia material of ultramicropore high-specific surface area of the present invention and preparation method thereof, belongs to inorganic hole material and catalyst preparation field.Contain the technical scheme of low aluminum oxidation zirconia material and preparation method thereof between the ultramicropore level of 1-2nm in particular to a kind of aperture.
Background technology
ZrO
2chemical stability good, not only there is the general character of representative transitions metal oxide, and be unique transition metal oxide simultaneously with surface acidity position, basic sites and oxidisability, reproducibility.Also there is good ion-exchange performance and the oxygen vacancy of surface enrichment simultaneously, thereby all received special concern aspect the catalysis of catalysis, polymerization and the oxidation reaction of reacting at autocatalysis, catalytic hydrogenation, F-T and super acidic catalyst.But conventional oxidation zirconia material specific area is less, aperture is large and pore size distribution is wider, and the carrier that sets it as catalyst is unfavorable for that active component disperses efficiently, has certain limitation.Therefore, in its structure, can effectively introduce its performance is had to the elements such as obvious improved aluminium, become the focus of many scientific research personnel's research.
Adopt surfactant as template to zirconium aluminium composite material both at home and abroad at present, obtain zirconium aluminium presoma by sol-gal process, then remove through calcining or solvent-extracted method the zirconium aluminium hole material obtaining after template molecule, the most more complicated of its synthetic route, the higher difficult industry of cost is amplified or produces.And zirconium aluminium composite material of its report synthesized is mainly mesoporous or large pore material, and taking high aluminium content as main, it is difficult to meet and molecule high to zirconium content component and selects shape and have the reaction of specific demand.Thereby for micropore and mesoporous between erect bridge aperture size enjoy the concern of numerous researchers containing the research and development of low aluminum oxidation zirconia material at the high-specific surface area of ultramicropore scope (1.0 ~ 2.0nm).
Ultramicropore level not only has the feature in poromerics pore structure containing low aluminum oxidation zirconium, but also have the premium properties of aluminium zirconium aspect catalysis concurrently, so not only selecting shape for molecule, this material have the reaction of specific demand that possibility is provided, and for the reaction of while demand high-specific surface area acid-base catalysis, also show the superiority that it is unique.Ultramicropore level can also be served as carrier loaded more active component containing low aluminum oxidation zirconia material, makes super acidic catalyst etc., so such material will have huge using value at petrochemical industry and field of fine chemical.
Summary of the invention
Low aluminum oxidation zirconia material of ultramicropore high-specific surface area of the present invention and preparation method thereof, its object is to solve above-mentioned problems of the prior art, thereby provide one to there is high-specific surface area and pore volume, and aperture contain the technical scheme of low aluminium (aluminium atomic percent zirconium is lower than 10%) zirconia material and synthetic method thereof between the ultramicropore level of 1-2nm.
Ultramicropore high-specific surface area of the present invention is containing low aluminum oxidation zirconia material, it is characterized in that a kind of aluminium atomic percent zirconium is lower than 10% zirconia material, and this material has microcellular structure and high specific area, and its micropore size is 1.0-2.0nm, and specific area exceedes 200m
2/ g.
Above-mentioned ultramicropore high-specific surface area is containing the preparation method of low aluminum oxidation zirconia material, it is characterized in that utilizing cheap cationic surface active agent, in Hydrothermal Synthesis self assembling process, add He Lv source, zirconium source simultaneously, be derived from the acid condition of body hydrolysis and regulate solvent evaporates to induce the temperature and time of self assembly by zirconium, thereby control the hydrolysis-rate of polymerization in He Lv source, zirconium source, make material on organic and inorganic boundary layer, have zirconium hydroxyl (Zr-OH) and aluminium hydroxyl (Al-OH) that complete polymerization does not relatively more occur, and and cationic surface active agent micella between interact by chemical bond, form the low aluminum oxidation zirconia material that contains of micropore level high-specific surface area, its concrete technology is: according to (0.1-5) aluminium source: (0.4-36) zirconium source: (5-50) ethanol: (1-10) deionized water: (1-5) mole charge ratio of surfactant, by surfactant dissolves in the ethanolic solution that contains 4.5-5.5% deionized water, and under agitation add He Lv source, zirconium source simultaneously, maintenance system temperature is 20-60 DEG C, continuous stirring 6-24 hour, subsequently reactant mixture is poured into the second alcohol and water that volatilizees in culture dish at 30-80 DEG C of temperature, time is 48-72 hour, finally roasting 5-10 hour at 400-800 DEG C, make the low aluminium ZrO that contains of ultramicropore level
2material.
Above-mentioned a kind of ultramicropore level, containing the preparation method of low aluminum oxidation zirconia material, is characterized in that described surfactant is cationic pair of dodecyl dimethyl ammonium chloride, and its molecular formula is C
26h
56nCl.
Above-mentioned a kind of ultramicropore level, containing the preparation method of low aluminum oxidation zirconia material, is characterized in that described aluminium source is aluminum nitrate, aluminium isopropoxide, aluminium secondary butylate, sodium metaaluminate, aluminium chloride or aluminum sulfate.
Above-mentioned a kind of ultramicropore level, containing the preparation method of low aluminum oxidation zirconia material, is characterized in that described zirconium source is zirconium sulfate, zirconium oxychloride, zirconyl nitrate, propyl alcohol zirconium or zirconium nitrate.
A kind of ultramicropore level of the present invention has the following advantages containing low aluminum oxidation zirconia material and preparation method thereof tool:
(1) prepared containing a small amount of aluminium ZrO
2poromerics has microcellular structure, and has higher specific area, and atom specific energy reaches lower than 10%;
(2) preparation technology is simple and easy to do, and easily industry is amplified;
(3) surfactant is cheap and easy to get, and preparation process is not added acid, environmentally safe; The present invention has broken through the restriction of aluminium zirconia material aperture size, effectively reduces the content (aluminium atomic percent zirconium lower than 10%) of aluminium at aluminium zirconia material, to expand its range of application.The present invention prepares simple and easy, with low cost and environmental friendliness, and prepared material is with a wide range of applications.
Brief description of the drawings
Fig. 1 ultramicropore high-ratio surface is containing nitrogen adsorption-desorption thermoisopleth and the corresponding graph of pore diameter distribution of low aluminum oxidation zirconia material.
Detailed description of the invention
The present invention is further described by the following examples.
Embodiment 1
3g quaternary ammonium salt is joined in the ethanolic solution that contains 4.5% deionized water, at room temperature stir surfactant is dissolved completely, in system, add 4.83g zirconium oxychloride and 0.15g aluminium isopropoxide simultaneously,, after 24 hours reactant mixture is poured in culture dish and processed 48 hours in 55 DEG C in 35 DEG C of stirrings.Finally by sample 400 DEG C of roastings 5 hours.Obtain Al
2o
3-ZrO
2poromerics.Nitrogen absorption result shows, its micropore size is 1.80nm, and specific area is 195m
2/ g, pore volume is 0.19cm
3/ g.
Embodiment 2
3g quaternary ammonium salt is joined in the ethanolic solution that contains 5% deionized water, at room temperature stir surfactant is dissolved completely, in system, add 4.83g zirconium oxychloride and 0.18g aluminium isopropoxide simultaneously,, after 15 hours reactant mixture is poured in culture dish and processed 50 hours in 60 DEG C in 25 DEG C of stirrings.Finally by sample 500 DEG C of roastings 6 hours.Obtain Al
2o
3-ZrO
2poromerics.Nitrogen absorption result shows, its micropore size is 1.80nm, and specific area is 170m
2/ g, pore volume is 0.15cm
3/ g.
Embodiment 3
3g quaternary ammonium salt is joined in the ethanolic solution that contains 5.5% deionized water, at room temperature stir surfactant is dissolved completely, in system, add 3.22g zirconium oxychloride and 0.12g aluminium isopropoxide simultaneously,, after 20 hours reactant mixture is poured in culture dish and processed 65 hours in 65 DEG C in 40 DEG C of stirrings.Finally by sample 550 DEG C of roastings 8 hours.Obtain Al
2o
3-ZrO
2poromerics.Nitrogen absorption result shows, its micropore size is 1.50nm, and specific area is 160m
2/ g, pore volume is 0.15cm
3/ g.
Embodiment 4
3g quaternary ammonium salt is joined in the ethanolic solution that contains 4.5% deionized water, at room temperature stir surfactant is dissolved completely, in system, add 1.61g zirconium oxychloride and 0.10g aluminium isopropoxide simultaneously,, after 10 hours reactant mixture is poured in culture dish and processed 60 hours in 75 DEG C in 45 DEG C of stirrings.Finally by sample 600 DEG C of roastings 5 hours.Obtain Al
2o
3-ZrO
2poromerics.Nitrogen absorption result shows, its micropore size is 1.50nm, and specific area is 204m
2/ g, pore volume is 0.15cm
3/ g.
Claims (5)
1. ultramicropore high-specific surface area is containing a low aluminum oxidation zirconia material, it is characterized in that a kind of aluminium atomic percent zirconium is lower than 10% zirconia material, and this material has microcellular structure and high specific area, and its micropore size is 1.0-2.0nm, and specific area exceedes 200m
2/ g.
2. the preparation method of a kind of ultramicropore alumine with high specific surface area material claimed in claim 1, it is characterized in that utilizing cheap non-ionic surface active agent, in Hydrothermal Synthesis self assembling process, add He Lv source, zirconium source simultaneously, by regulating the temperature and time of solvent evaporates induction self assembly, thereby control the hydrolysis-polymerisation run in zirconium aluminium source, make material on organic-inorganic world surface layer, have zirconium hydroxyl (Zr-OH) and aluminium hydroxyl (Al-OH) that complete polymerization does not relatively more occur, and and non-ionic surface active agent micella between pass through interaction of hydrogen bond, form the low aluminum oxidation zirconia material that contains of ultramicropore high-ratio surface, its concrete technology is:
According to (2-50) aluminium source: (0.4-36) zirconium source: (5-50) ethanol: (1-10) deionized water: (1-5) mole charge ratio of surfactant, by surfactant dissolves in the ethanolic solution that contains 4.5-5.5% deionized water, and under agitation add He Lv source, zirconium source simultaneously, maintenance system temperature is 20-60 DEG C, continuous stirring 6-24 hour, subsequently reactant mixture is poured into the second alcohol and water that volatilizees in culture dish at 30-80 DEG C of temperature, time is 48-72 hour, finally roasting 5-10 hour at 400-800 DEG C, make the low aluminium ZrO that contains of ultramicropore level
2material.
3. the preparation method containing low aluminum oxidation zirconia material according to a kind of ultramicropore level claimed in claim 2, is characterized in that described surfactant is cationic pair of dodecyl dimethyl ammonium chloride, and its molecular formula is C
26h
56nCl.
4. the preparation method containing low aluminum oxidation zirconia material according to a kind of ultramicropore high-specific surface area claimed in claim 2, is characterized in that described aluminium source is aluminum nitrate, aluminium isopropoxide, aluminium secondary butylate, sodium metaaluminate, aluminium chloride or aluminum sulfate.
5. the preparation method containing low aluminum oxidation zirconia material according to a kind of ultramicropore level claimed in claim 2, is characterized in that described zirconium source is zirconium sulfate, zirconium oxychloride, zirconyl nitrate, propyl alcohol zirconium or zirconium nitrate.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106115780A (en) * | 2016-06-30 | 2016-11-16 | 太原理工大学 | A kind of preparation method of high-specific surface area multi-stage porous alumina zirconia nanocrystal |
| CN106334567A (en) * | 2016-09-22 | 2017-01-18 | 太原理工大学 | Preparation method of nano-sulfated zirconia solid acid material |
| CN109675574A (en) * | 2018-11-22 | 2019-04-26 | 太原理工大学 | A kind of preparation method of multi-stage porous high-specific surface area environment-friendly type denitrating catalyst |
| CN109675577A (en) * | 2019-03-04 | 2019-04-26 | 福州大学 | A kind of nickel-base catalyst and preparation method thereof for carbon dioxide methanation |
| CN112569918A (en) * | 2019-09-29 | 2021-03-30 | 中国石油化工股份有限公司 | Improved zirconium-aluminum composite sol and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070015928A1 (en) * | 2003-07-24 | 2007-01-18 | Akzo Nobel N. V. | Metal ion exchanged solid materials as catalysts for the arylation and the skeletal isomerization of fatty and alkyl esters thereof |
| CN102380362A (en) * | 2011-08-25 | 2012-03-21 | 太原理工大学 | Ordered zirconia-alumina mesoporous material and its preparation method |
| CN103073036A (en) * | 2012-12-25 | 2013-05-01 | 太原理工大学 | Super-microporous high-specific surface area aluminium oxide material and preparation method thereof |
| CN103274465A (en) * | 2013-05-30 | 2013-09-04 | 太原理工大学 | Nano zirconium dioxide with high specific surface area and synthesis method thereof |
| CN103464155A (en) * | 2013-09-10 | 2013-12-25 | 太原理工大学 | Preparation method of ultramicroporous high-specific-area denitrification catalyst material |
-
2014
- 2014-04-17 CN CN201410153432.6A patent/CN103949230A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070015928A1 (en) * | 2003-07-24 | 2007-01-18 | Akzo Nobel N. V. | Metal ion exchanged solid materials as catalysts for the arylation and the skeletal isomerization of fatty and alkyl esters thereof |
| CN102380362A (en) * | 2011-08-25 | 2012-03-21 | 太原理工大学 | Ordered zirconia-alumina mesoporous material and its preparation method |
| CN103073036A (en) * | 2012-12-25 | 2013-05-01 | 太原理工大学 | Super-microporous high-specific surface area aluminium oxide material and preparation method thereof |
| CN103274465A (en) * | 2013-05-30 | 2013-09-04 | 太原理工大学 | Nano zirconium dioxide with high specific surface area and synthesis method thereof |
| CN103464155A (en) * | 2013-09-10 | 2013-12-25 | 太原理工大学 | Preparation method of ultramicroporous high-specific-area denitrification catalyst material |
Non-Patent Citations (2)
| Title |
|---|
| XIAOYAN WANG ET AL.: "Facile synthesis of highly ordered mesoporous alumina with high thermal and hydrothermal stability using zirconia as promoter", 《MATERIALS LETTERS》 * |
| 苏娇娇: "一种简易制备微孔氧化铝-氧化锆材料的方法", 《第十七届全国分子筛学术大会会议论文集》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106115780A (en) * | 2016-06-30 | 2016-11-16 | 太原理工大学 | A kind of preparation method of high-specific surface area multi-stage porous alumina zirconia nanocrystal |
| CN106334567A (en) * | 2016-09-22 | 2017-01-18 | 太原理工大学 | Preparation method of nano-sulfated zirconia solid acid material |
| CN109675574A (en) * | 2018-11-22 | 2019-04-26 | 太原理工大学 | A kind of preparation method of multi-stage porous high-specific surface area environment-friendly type denitrating catalyst |
| CN109675574B (en) * | 2018-11-22 | 2021-08-03 | 太原理工大学 | Preparation method of environment-friendly denitration catalyst with hierarchical pores and high specific surface area |
| CN109675577A (en) * | 2019-03-04 | 2019-04-26 | 福州大学 | A kind of nickel-base catalyst and preparation method thereof for carbon dioxide methanation |
| CN112569918A (en) * | 2019-09-29 | 2021-03-30 | 中国石油化工股份有限公司 | Improved zirconium-aluminum composite sol and preparation method and application thereof |
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Application publication date: 20140730 |