CN102380362A - Ordered zirconia-alumina mesoporous material and its preparation method - Google Patents
Ordered zirconia-alumina mesoporous material and its preparation method Download PDFInfo
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- CN102380362A CN102380362A CN2011102516548A CN201110251654A CN102380362A CN 102380362 A CN102380362 A CN 102380362A CN 2011102516548 A CN2011102516548 A CN 2011102516548A CN 201110251654 A CN201110251654 A CN 201110251654A CN 102380362 A CN102380362 A CN 102380362A
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Abstract
The invention relates to an ordered zirconia-alumina mesoporous material and its preparation method, which belongs to the inorganic porous material and catalyst preparation field. The invention is characterized in that the material has a high and ordered mesoporous structure, its mesoporous diameter is 5.0-8.0nm, the specific surface area is 200-300m<2>/g, and the atomic ratio of Zr to Al of the material is 0.1-1.6. The synthetic method comprises the following steps: dissolving a surfactant, organic carboxylic acid and inorganic acid in an ethanol solution containing a little of deionized water according to the ratio of the synthetic material, adding zirconium source and aluminum source while stirring, continuously stirring for certain time, performing solvent volatilization on the reactant, heat treating and high temperature roasting to obtain the ordered zirconia-alumina mesoporous material. The invention has the advantages of simple process, high repetition rate and environmental protection.
Description
Technical field
A kind of orderly Zirconia-alumina mesoporous material of the present invention and preparation method thereof belongs to inorganic hole material and Preparation of Catalyst field.Have high-specific surface area and pore volume in particular to a kind of, and the Zr/Al atomic ratio is adjustable, and the ZrO of meso-hole structure high-sequential
2-Al
2O
3Mesoporous material and preparation method thereof.
Background technology
The use of solid acid catalyst can be avoided traditional liquid acid, like HF, and H
2SO
4And H
3PO
4High toxicity and highly corrosive, have easily separated with reclaim reusable characteristics.Yet, be the catalytic efficiency that the acidic catalyst of representative also far can not reach liquid acid at present with the sulfidation-oxidation zirconium.Zirconia is a kind of multifunction catalyst carrier with acidity with alkalescence of moderate, can change into through sulphation, phosphorylation or wolframic acid to be a kind of strong solid acid.The sulfidation-oxidation zirconium has stronger acidity, but because of the zirconia specific area less, its SO
4 2-Load capacity be very limited.Use cation or anion surfactant to be the synthesising mesoporous zirconia of template (J.Chem.Soc.Chem.Commun.1995,2083.; Mater.Chem.1996,6,89.; J.Mater.Chem.1996,6,89.), though can improve the specific area and the SO of zirconia material
4 2-Load capacity, but gained material heat endurance is relatively poor, is higher than 600 ℃ of mesoporous subsiding of roasting, zirconic crystalline form transfers the monocline phase to by the four directions easily mutually, thereby has reduced and SO
4 2-Binding degree and the acidity of catalyst.
Bibliographical information is introduced Al in zirconia
2O
3Can reduce cubic phase ZrO
2Phase transfer, increase ZrO
2Stability, and improve ZrO
2Decentralization and specific area, thereby increase acid catalysis performance (J.Catal.2001,204,498. of material greatly; Catal.Commun.2006,7,209.).At present, preparation ZrO
2-Al
2O
3The method of material mainly comprises: coprecipitation (Catal.Today, 2004,93,595.), sol-gel process (Appl.Catal.B, 1999,21,79.; Micropor.Mesopor.Mater.1998,20,293.) and the method (Appl.Catal.A., 1998,170,225.) of grafting etc.Yet, through the prepared ZrO that obtains of these methods
2-Al
2O
3Material is disordered structure, and specific area and pore volume are lower.
Summary of the invention
A kind of orderly Zirconia-alumina mesoporous material of the present invention and preparation method thereof, its purpose are to improve the stability and the specific area of existing mesoporous zirconia material, thereby improve SO
4 2-Load capacity; And the intensity of corresponding acid site number and acid; Preparation has bigger specific area and pore volume, and the pore passage structure high-sequential, and has the mesoporous material than peracidity simultaneously; Thereby effectively improve oxide mesoporous material activity, selectivity and stability in catalytic reactions such as catalytic pyrolysis, esterification, acylated, widen its range of application simultaneously.
A kind of orderly Zirconia-alumina mesoporous material of the present invention is characterized in that described ZrO
2-Al
2O
3Mesoporous material has orderly two-dimentional hexagonal mesoporous structure and high heat endurance, and its mesoporous aperture is 5.0～8.0nm, and specific area is 200～300m
2/ g, the Zr/Al atomic ratio of material is 0.1～1.6.
The preparation method of above-mentioned a kind of orderly Zirconia-alumina mesoporous material; It is characterized in that in self assembling process; Add zirconium source and aluminium source simultaneously, induce the temperature and time of self assembly through introducing organic carboxyl acid and adjusting solvent evaporates, thus the hydrolysis-rate of polymerization in control zirconium source and aluminium source; Make material on the organic and inorganic boundary layer, have aluminium hydroxyl (Al-OH) and the zirconium hydroxyl (Zr-OH) that complete polymerization does not relatively more take place; And and triblock copolymer non-ionic surface active agent micella between through interaction of hydrogen bond, form the high mesoporous material of order, its concrete technology is:
According to (10-80) zirconium source: (10-100) aluminium source: (0-30) organic carboxyl acid: (20-120) inorganic acid: (1000-2500) ethanol: (100-350) deionized water: the mole charge ratio of 1.0 surfactants; With surfactant, organic carboxyl acid and inorganic acid solution in containing the ethanolic solution of small amount of deionized water; And under agitation add zirconium source and aluminium source simultaneously; Keeping system temperature is 20-60 ℃, continuous stirring 6-24 hour, pours reactant mixture into the second alcohol and water that under 30-60 ℃ of temperature, volatilizees in the culture dish subsequently; Time is 48-72 hour; At last with resulting sample under 80-150 ℃ of temperature heat treatment 24-48 hour, and, make ZrO in 500-800 ℃ of following roasting 5-10 hour
2-Al
2O
3Mesoporous material.
The preparation method of above-mentioned a kind of orderly Zirconia-alumina mesoporous material; It is characterized in that described surfactant be gather oxireme as hydrophilic block, to gather epoxy third rare or gather the rare nonionic block copolymer as hydrophobic block of epoxy fourth; Its molecular formula is EOnPOmEOn, or molecular formula is EOnBOmEOn; Here PO is a propylene oxide, and EO is an oxireme, and BO is the epoxy butylene, wherein: n=10-180, m=5-100.
The preparation method of above-mentioned a kind of orderly Zirconia-alumina mesoporous material is characterized in that described aluminium source is aluminium isopropoxide, aluminum nitrate, aluminium chloride or aluminum sulfate.
The preparation method of above-mentioned a kind of orderly Zirconia-alumina mesoporous material is characterized in that described zirconium source is zirconium oxychloride, zirconium sulfate, propyl alcohol zirconium or zirconium nitrate.
The preparation method of above-mentioned a kind of orderly Zirconia-alumina mesoporous material is characterized in that described inorganic acid is hydrochloric acid, sulfuric acid, nitric acid or phosphoric acid.
The preparation method of above-mentioned a kind of orderly Zirconia-alumina mesoporous material is characterized in that described organic carboxyl acid is citric acid, glacial acetic acid or oxalic acid.
The present invention has following advantage:
(1) prepared ZrO
2-Al
2O
3Mesoporous material Zr/Al atomic ratio is adjustable;
(2) prepared ZrO
2-Al
2O
3Mesoporous material pore structure high-sequential, and specific surface and pore volume are bigger, and the aperture is adjustable at 5.0～8.0nm;
(3) prepared ZrO
2-Al
2O
3Mesoporous material roasting under 650 ℃ of conditions, structural behaviour does not change;
(4) preparation process is simple and easy to do, and fidelity factor is high;
(5) additive is organic carboxyl acid, and is cheap and easy to get, avirulence, environmentally safe.
Description of drawings
Fig. 1 is ZrO
2-Al
2O
3The XRD spectra of mesoporous material.
Fig. 2 is ZrO
2-Al
2O
3The nitrogen adsorption-desorption thermoisopleth of mesoporous material and corresponding graph of pore diameter distribution.
The specific embodiment
Below through embodiment the present invention is described further.
With 3.2g EO
106PO
70EO
106Joining 20mL with the 0.4g citric acid contains in the ethanolic solution of 2.0g 12M hydrochloric acid; At room temperature stirring dissolves surfactant fully; In system, add 0.016mol aluminium isopropoxide and 0.004mol zirconium oxychloride simultaneously;, after 24 hours reactant mixture is poured in the culture dish in 45 ℃ of processing 48 hours in 30 ℃ of stirrings.At last with sample in 100 ℃ of following heat treatments 24 hours, and 550 ℃ of roastings 5 hours.Obtain ZrO
2-Al
2O
3Mesoporous material.The nitrogen absorption result shows that its mesoporous aperture is 5.5nm, and specific area is 265m
2/ g, pore volume are 0.39cm
3/ g.Roasting is 5 hours under 650 ℃ of conditions, and structural behaviour does not change.
With 3.2g EO
106PO
70EO
106Joining 20mL with the 0.4g citric acid contains in the ethanolic solution of 2.0g 12M hydrochloric acid; At room temperature stirring dissolves surfactant fully; In system, add 0.012mol aluminium isopropoxide and 0.009mol zirconium oxychloride simultaneously;, after 24 hours reactant mixture is poured in the culture dish in 45 ℃ of processing 48 hours in 30 ℃ of stirrings.At last with sample in 100 ℃ of following heat treatments 24 hours, and 550 ℃ of roastings 5 hours.Obtain ZrO
2-Al
2O
3Mesoporous material.The nitrogen absorption result shows that its mesoporous aperture is 6.2nm, and specific area is 238m
2/ g, pore volume are 0.32cm
3/ g.Roasting is 5 hours under 650 ℃ of conditions, and structural behaviour does not change.
With 3.2g EO
106PO
70EO
106Joining 20mL with the 0.4g citric acid contains in the ethanolic solution of 2.0g 12M hydrochloric acid; At room temperature stirring dissolves surfactant fully; In system, add 0.008mol aluminium isopropoxide and 0.012mol zirconium oxychloride simultaneously;, after 24 hours reactant mixture is poured in the culture dish in 45 ℃ of processing 48 hours in 30 ℃ of stirrings.At last with sample in 100 ℃ of following heat treatments 24 hours, and 550 ℃ of roastings 5 hours.Obtain ZrO
2-Al
2O
3Mesoporous material.The nitrogen absorption result shows that its mesoporous aperture is 6.5nm, and specific area is 214m
2/ g, pore volume are 0.31cm
3/ g.Roasting is 5 hours under 650 ℃ of conditions, and structural behaviour does not change.
With 1.6g EO
20PO
70EO
20Joining 20mL with the 0.8g citric acid contains in the ethanolic solution of 2.0g 12M hydrochloric acid; At room temperature stirring dissolves surfactant fully; In system, add 0.016mol aluminium isopropoxide and 0.004mol zirconium oxychloride simultaneously;, after 24 hours reactant mixture is poured in the culture dish in 45 ℃ of processing 48 hours in 30 ℃ of stirrings.At last with sample in 100 ℃ of following heat treatments 24 hours, and 550 ℃ of roastings 5 hours.Obtain ZrO
2-Al
2O
3Mesoporous material.The nitrogen absorption result shows that its mesoporous aperture is 7.0nm, and specific area is 253m
2/ g, pore volume are 0.46cm
3/ g.Roasting is 5 hours under 650 ℃ of conditions, and structural behaviour does not change.
With 1.6g EO
20PO
70EO
20Joining 20mL with the 0.8g citric acid contains in the ethanolic solution of 2.0g 12M hydrochloric acid; At room temperature stirring dissolves surfactant fully; In system, add 0.012mol aluminium isopropoxide and 0.009mol zirconium oxychloride simultaneously;, after 24 hours reactant mixture is poured in the culture dish in 45 ℃ of processing 48 hours in 30 ℃ of stirrings.At last with sample in 100 ℃ of following heat treatments 24 hours, and 550 ℃ of roastings 5 hours.Obtain ZrO
2-Al
2O
3Mesoporous material.The nitrogen absorption result shows that its mesoporous aperture is 7.3nm, and specific area is 221m
2/ g, pore volume are 0.42cm
3/ g.Roasting is 5 hours under 650 ℃ of conditions, and structural behaviour does not change.
With 1.6g EO
20PO
70EO
20Joining 20mL with the 0.8g citric acid contains in the ethanolic solution of 2.0g 12M hydrochloric acid; At room temperature stirring dissolves surfactant fully; In system, add 0.008mol aluminium isopropoxide and 0.012mol zirconium oxychloride simultaneously;, after 24 hours reactant mixture is poured in the culture dish in 45 ℃ of processing 48 hours in 30 ℃ of stirrings.At last with sample in 100 ℃ of following heat treatments 24 hours, and 550 ℃ of roastings 5 hours.Obtain ZrO
2-Al
2O
3Mesoporous material.The nitrogen absorption result shows that its mesoporous aperture is 7.4nm, and specific area is 218m
2/ g, pore volume are 0.41cm
3/ g.Roasting is 5 hours under 650 ℃ of conditions, and structural behaviour does not change.
Claims (7)
1. an orderly Zirconia-alumina mesoporous material is characterized in that described ZrO
2-Al
2O
3Mesoporous material has orderly two-dimentional hexagonal mesoporous structure and high heat endurance, and its mesoporous aperture is 5.0～8.0nm, and specific area is 200～300m
2/ g, the Zr/Al atomic ratio of material is 0.1～1.6.
2. the preparation method of the described a kind of orderly Zirconia-alumina mesoporous material of claim 1 is characterized in that this material prepares as follows:
According to (10-80) zirconium source: (10-100) aluminium source: (0-30) organic carboxyl acid: (20-120) inorganic acid: (1000-2500) ethanol: (100-350) deionized water: the mole charge ratio of 1.0 surfactants; With surfactant, organic carboxyl acid and inorganic acid solution in containing the ethanolic solution of small amount of deionized water; And under agitation add zirconium source and aluminium source simultaneously; Keeping system temperature is 20-60 ℃, continuous stirring 6-24 hour, pours reactant mixture into the second alcohol and water that under 30-60 ℃ of temperature, volatilizees in the culture dish subsequently; Time is 48-72 hour; At last with resulting sample under 80-150 ℃ of temperature heat treatment 24-48 hour, and, make ZrO in 500-800 ℃ of following roasting 5-10 hour
2-Al
2O
3Mesoporous material.
3. according to the preparation method of the described a kind of orderly Zirconia-alumina mesoporous material of claim 2; It is characterized in that described surfactant be gather oxireme as hydrophilic block, to gather epoxy third rare or gather the rare nonionic block copolymer as hydrophobic block of epoxy fourth; Its molecular formula is EOnPOmEOn, or molecular formula is EOnBOmEOn; Here PO is a propylene oxide, and EO is an oxireme, and BO is the epoxy butylene, wherein: n=10-180, m=5-100.
4. according to the preparation method of the described a kind of orderly Zirconia-alumina mesoporous material of claim 2, it is characterized in that described aluminium source is aluminium isopropoxide, aluminum nitrate, aluminium chloride or aluminum sulfate.
5. according to the preparation method of the described a kind of orderly Zirconia-alumina mesoporous material of claim 2, it is characterized in that described zirconium source is zirconium oxychloride, zirconium sulfate, propyl alcohol zirconium or zirconium nitrate.
6. according to the preparation method of the described a kind of orderly Zirconia-alumina mesoporous material of claim 2, it is characterized in that described inorganic acid is hydrochloric acid, sulfuric acid, nitric acid or phosphoric acid.
7. according to the preparation method of the described a kind of orderly Zirconia-alumina mesoporous material of claim 2, it is characterized in that described organic carboxyl acid is citric acid, glacial acetic acid or oxalic acid.
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| CN101781817A (en) * | 2009-12-30 | 2010-07-21 | 山东大学 | Zirconia mesoporous fiber and preparation method thereof |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101781817A (en) * | 2009-12-30 | 2010-07-21 | 山东大学 | Zirconia mesoporous fiber and preparation method thereof |
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