CN101733085B - Zirconium-aluminium double-mesoporous material and preparation method thereof - Google Patents
Zirconium-aluminium double-mesoporous material and preparation method thereof Download PDFInfo
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- CN101733085B CN101733085B CN 200910220192 CN200910220192A CN101733085B CN 101733085 B CN101733085 B CN 101733085B CN 200910220192 CN200910220192 CN 200910220192 CN 200910220192 A CN200910220192 A CN 200910220192A CN 101733085 B CN101733085 B CN 101733085B
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Abstract
The invention discloses a zirconium-aluminium double-mesoporous material and a preparation method thereof. In the material, the molar ratio of zirconium to aluminium is 1.35*10<-3>-30*10<-3>:1-1.2; the primary mesoporous aperture is 3 to 5nm; and the secondary mesoporous aperture is 10 to 20nm. The chemical composition of the zirconium-aluminium double-mesoporous material is a zirconium-aluminium composite with the mesoporous aperture of two sizes, which can meet the requirement of macromolecule shape selection and diffusing effect on the aperture distribution of a catalyst carrier and an adsorbent and is a potential acidic catalyst carrier and a refined adsorbent for oil adsorption. The aperture distribution of the material is relatively narrow and can be adjusted in a certain range so as to ensure that the acidity of the material is easily adjusted and provide new possibility for the development of the novel practical industrial catalyst carrier and the adsorbent. The preparation method has the advantages of simple process, easy operation and mild reaction condition.
Description
One, technical field
The invention belongs to field of material synthesis technology, be specifically related to a kind of Zirconium-aluminium double-mesoporous material and preparation method thereof.
Two, background technology
1992, it is the mesoporous material of representative that the Molbil oil company successfully synthesizes first with MCM-41, caused researcher's very big concern, this material specific area height, mesopore orbit with rule, the duct long-range order of arranging helps macromolecular diffusion and conversion, is the ideal material of big Molecular Adsorption, conversion.Along with the continuous development of technology, people work out the more superior two mesoporous material of performance again, and this kind double-mesoporous material not only has the openings of different aperture structure, but also with the advantage in every kind of aperture, thereby can improve the performance of catalyst greatly.As adsorbent, two meso-hole structures can also satisfy the separation requirement to the big Molecular Adsorption matter of different size better simultaneously, and new vitality has been injected in its research that appears as mesoporous material.At present few to the research of double-mesoporous material, and be mainly silica-based or silica-alumina material, chemical composition is comparatively single, and particularly the research about Zirconium-aluminium double-mesoporous material does not appear in the newspapers.
Three, summary of the invention
The purpose of this invention is to provide a kind of Zirconium-aluminium double-mesoporous material and preparation method thereof, to replenish the blank of this type of material.
For achieving the above object, the technical solution used in the present invention is:
The zirconium of Zirconium-aluminium double-mesoporous material of the present invention and the mol ratio of aluminium are 1.35 * 10
-3-30 * 10
-3: 1-1.2; Elementary mesoporous aperture is 3-5nm; Secondary mesoporous aperture is 10-20nm.
The preparation method of Zirconium-aluminium double-mesoporous material of the present invention comprises the steps:
1. under the room temperature, according to the template agent: the mol ratio of NaOH: sec-butyl alcohol=0.2-0.4: 0.04-0.08: 2.5-3.5, above-mentioned raw materials mixed obtaining solution A; According to the mol ratio of aluminium source: sec-butyl alcohol=1.0-1.2: 2.5-3.5, the above-mentioned raw materials mixing is obtained solution B;
2. solution A is mixed with solution B, stir down, the zirconium source aqueous solution that with mass concentration is 6%-10% is by the mixture that injected solution A and solution B in 1-5ml/ minute, and the mol ratio of each raw material is in this mixture: template agent: NaOH: sec-butyl alcohol: aluminium source: water: zirconium source=0.2-0.4: 0.04-0.08: 5.0-7.0: 1.0-1.2: 4.0-50: 1.35 * 10
-3-30 * 10
-3
3. continue to stir after 24 hours, with step 2. the gained mixture at 80 ℃ down after dry 24 hours, again with the gained solid 550 ℃ of following roastings 4 hours, promptly.
Above-mentioned template agent is an aliphatic acid, comprises laurate or stearic acid.
Above-mentioned aluminium source is sec-butyl alcohol or aluminium isopropoxide.
Above-mentioned zirconium source is zirconium oxychloride or zirconium nitrate.
Zirconium-aluminium double-mesoporous material chemical composition of the present invention is zirconium-aluminium complex, mesoporous aperture with two kinds of sizes, can satisfy big molecule and select the requirement to catalyst carrier and adsorbent pore-size distribution of shape and diffusion effect, be the potential acidic catalyst agent carrier and the adsorbent of oil product adsorption refining.The pore-size distribution of this material is comparatively narrow simultaneously, and can regulate within the specific limits, makes its acidity that has be easy to modulation, for the exploitation of novel practical Industrial Catalysis agent carrier and adsorbent provide new may.Preparation method's technology of the present invention is simple, easy operating, reaction condition gentleness.
Four, description of drawings
Fig. 1 is the N of Zirconium-aluminium double-mesoporous material of the present invention
2-adsorption/desorption curve map;
Fig. 2 is the BJH graph of pore diameter distribution of Zirconium-aluminium double-mesoporous material of the present invention;
Fig. 3 is the two mesoporous high resolution electron microscopy figure of zirconium aluminium of the present invention.
Five, the specific embodiment
This material has the hysteresis loop of typical meso-hole structure as seen from Figure 1; In the mesoporous as seen from Figure 2 scope, tangible diplopore distribution curve, the aperture concentrates on 3.55nm, 13.5nm respectively; The mesopore orbit arranged in order of this material as seen from Figure 3.
Embodiment 1:
1. under the room temperature, according to stearic acid: NaOH: the mol ratio of sec-butyl alcohol=0.2: 0.04: 2.5, above-mentioned raw materials mixed obtaining solution A; According to aluminium secondary butylate: the mol ratio of sec-butyl alcohol=1.0: 2.5, above-mentioned raw materials mixed obtaining solution B;
2. solution A is mixed with solution B, stir down, with mass concentration be 6% zirconium oxychloride aqueous solution by the mixture that injected solution A and solution B in 1ml/ minute, the mol ratio of each raw material is in this mixture: stearic acid: NaOH: sec-butyl alcohol: aluminium secondary butylate: water: zirconium oxychloride=0.2: 0.04: 5.0: 1.0: 4.0: 1.35 * 10
-3
3. continue to stir after 24 hours, with step 2. the gained mixture at 80 ℃ down after dry 24 hours, again with the gained solid 550 ℃ of following roastings 4 hours, promptly.
The mol ratio of zirconium and aluminium is 1.35 * 10 in the gained sample
-3: 1.0; Elementary aperture is: 4.5nm; Secondary aperture is: 18.0nm.
Embodiment 2:
1. under the room temperature, according to laurate: NaOH: the mol ratio of sec-butyl alcohol=0.3: 0.06: 3.0, above-mentioned raw materials mixed obtaining solution A; According to aluminium isopropoxide: the mol ratio of sec-butyl alcohol=1.1: 3.0, above-mentioned raw materials mixed obtaining solution B;
2. solution A is mixed with solution B, stir down, with mass concentration be 8% zirconium oxychloride aqueous solution by the mixture that injected solution A and solution B in 2ml/ minute, the mol ratio of each raw material is in this mixture: laurate: NaOH: sec-butyl alcohol: aluminium isopropoxide: water: zirconium oxychloride=0.3: 0.06: 6.0: 1.1: 26.0: 1.5 * 10
-3
3. continue to stir after 24 hours, with step 2. the gained mixture at 80 ℃ down after dry 24 hours, again with the gained solid 550 ℃ of following roastings 4 hours, promptly.
The mol ratio of zirconium and aluminium is 1.5 * 10 in the gained sample
-3: 1.1; Elementary aperture is: 3.8nm; Secondary aperture is: 16.0nm.
Embodiment 3:
1. under the room temperature, according to stearic acid: NaOH: the mol ratio of sec-butyl alcohol=0.4: 0.08: 3.5, above-mentioned raw materials mixed obtaining solution A; According to aluminium secondary butylate: the mol ratio of sec-butyl alcohol=1.2: 3.5, above-mentioned raw materials mixed obtaining solution B;
2. solution A is mixed with solution B, stir down, with mass concentration be 10% the zirconium nitrate aqueous solution by the mixture that injected solution A and solution B in 5ml/ minute, the mol ratio of each raw material is in this mixture: stearic acid: NaOH: sec-butyl alcohol: aluminium secondary butylate: water: zirconium nitrate=0.4: 0.08: 7.0: 1.2: 50: 30 * 10
-3
3. continue to stir after 24 hours, with step 2. the gained mixture at 80 ℃ down after dry 24 hours, again with the gained solid 550 ℃ of following roastings 4 hours, promptly.
The mol ratio of zirconium and aluminium is 1.5 * 10 in the gained sample
-3: 1.2; Elementary aperture is: 3.5nm; Secondary aperture is: 13.0nm.
Claims (5)
1. Zirconium-aluminium double-mesoporous material, it is characterized in that: the zirconium of this material and the mol ratio of aluminium are 1.35 * 10
-3-30 * 10
-3: 1-1.2; Elementary mesoporous aperture is 3-5nm; Secondary mesoporous aperture is 10-20nm.
2. a method for preparing the described Zirconium-aluminium double-mesoporous material of claim 1 comprises the steps:
1. under the room temperature, according to the template agent: the mol ratio of NaOH: sec-butyl alcohol=0.2-0.4: 0.04-0.08: 2.5-3.5, above-mentioned raw materials mixed obtaining solution A; According to the mol ratio of aluminium source: sec-butyl alcohol=1.0-1.2: 2.5-3.5, the above-mentioned raw materials mixing is obtained solution B;
2. solution A is mixed with solution B, stir down, the zirconium source aqueous solution that with mass concentration is 6%-10% is by the mixture that injected solution A and solution B in 1-5ml/ minute, and the mol ratio of each raw material is in this mixture: template agent: NaOH: sec-butyl alcohol: aluminium source: water: zirconium source=0.2-0.4: 0.04-0.08: 5.0-7.0: 1.0-1.2: 4.0-50: 1.35 * 10
-3-30 * 10
-3
3. continue to stir after 24 hours, with step 2. the gained mixture at 80 ℃ down after dry 24 hours, again with the gained solid 550 ℃ of following roastings 4 hours, promptly.
3. the preparation method of a kind of Zirconium-aluminium double-mesoporous material according to claim 2, it is characterized in that: described template agent is laurate or stearic acid.
4. the preparation method of a kind of Zirconium-aluminium double-mesoporous material according to claim 2, it is characterized in that: described aluminium source is sec-butyl alcohol or aluminium isopropoxide.
5. the preparation method of a kind of Zirconium-aluminium double-mesoporous material according to claim 2, it is characterized in that: described zirconium source is zirconium oxychloride or zirconium nitrate.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1380250A (en) * | 2002-01-30 | 2002-11-20 | 太原理工大学 | Double mesopore molecular sieve and its preparation method |
| CN1417115A (en) * | 2002-12-16 | 2003-05-14 | 中国科学院山西煤炭化学研究所 | Double Si-Al mesopore molecular sieve and its synthesis |
| CN1942401A (en) * | 2004-04-07 | 2007-04-04 | 罗狄亚化学公司 | Zirconium and yttrium oxide-based composition, method for preparing same and use thereof in a catalyst system |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1380250A (en) * | 2002-01-30 | 2002-11-20 | 太原理工大学 | Double mesopore molecular sieve and its preparation method |
| CN1417115A (en) * | 2002-12-16 | 2003-05-14 | 中国科学院山西煤炭化学研究所 | Double Si-Al mesopore molecular sieve and its synthesis |
| CN1942401A (en) * | 2004-04-07 | 2007-04-04 | 罗狄亚化学公司 | Zirconium and yttrium oxide-based composition, method for preparing same and use thereof in a catalyst system |
Non-Patent Citations (2)
| Title |
|---|
| JP平3-293035A 1991.12.24 |
| 谷林茂等.介孔材料的研究进展.《云南大学学报(自然科学版)》.2008,第30卷369-372. * |
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