CN100484877C - Preparation method for aluminium oxide with high thermal stability and large specific surface area - Google Patents
Preparation method for aluminium oxide with high thermal stability and large specific surface area Download PDFInfo
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- CN100484877C CN100484877C CNB2006100461376A CN200610046137A CN100484877C CN 100484877 C CN100484877 C CN 100484877C CN B2006100461376 A CNB2006100461376 A CN B2006100461376A CN 200610046137 A CN200610046137 A CN 200610046137A CN 100484877 C CN100484877 C CN 100484877C
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Abstract
The invention discloses a preparing method of aluminum oxide with high-heat stability and big specific surface area, which comprises the following steps: 1) dipping excess ammonial solution into aluminum nitrate solution; making the final solution PH>=8.7; washing deposition of generation repetitively; separating; adding to azotic acid at 80-100 deg.c; stirring >=2 h; getting forerunner body collosol; 2) adding into surface activator, alcoholic acid or high molecular polymer as structure guided agent under room temperature; drying at 100-120 deg.c; baking at 3-6 h in the air at 450-600 deg.c; counting as Al in the forerunner body collosol; setting mole ratio of Al ionic and structure guided agent at 1:0.02-1.0.
Description
Technical field
The present invention relates to the preparation of aluminum oxide, is a kind of preparation method with high thermal stability and bigger serface aluminum oxide specifically.
Background technology
Aluminum oxide has bigger specific surface area, suitable pore passage structure and special surface properties, therefore becomes one of support of the catalyst of industrial the most normal use.But the high high-temp stability of aluminum oxide is but perplexing people for a long time.When being higher than 1000 ℃, surperficial sintering can take place aluminum oxide changes mutually with α, causes that pore passage structure is destroyed, specific surface area sharply reduces, and then causes the reunion of the active ingredient of load, and catalytic performance is descended greatly.Therefore, preparation has the novel aluminum oxide of high thermal stability and bigger serface simultaneously, can improve the stability of catalyzer effectively, and this is especially significant in the reaction of high temperature such as purifying vehicle exhaust, catalyticcombustion industrial.
In aluminum oxide, introduce some chemical assistant,,, can alleviate phase transformation, the inhibition high temperature sintering of aluminum oxide by generating complex metal oxides or Solid solution as rare earth metal, alkaline-earth metal or transition metal etc.Can be as La, Si by effectively stoping Al
3+Surface diffusion or the growth that comes the inhibited oxidation aluminium grain of the hydroxyl of eliminating alumina surface (A.F.Ahatrom-Silver sand, C.U.I.Odenbrand, Appl.Catal.A, 1997,153:157); Ba energy and Al generate hexa-aluminate, stop Al
3+Body spread mutually and stablize aluminum oxide structure (J.S.Church, N.W.Cant, D.L.Trimm, Appl.Catal.A, 1993,101:105).At present, mainly concentrate on (Lu Guanzhong, Wang Xingyi etc., CN 1454707A on the different auxiliary agent of selection to improving the aluminum oxide Research on Thermal Stability; Liu Dongyan, Zhang Yuanli etc., CN 1365854A; Lu Guanzhong, WANG Xiaohong, CN1528667A), and less to the report that improves the alumina high temperature thermostability by the structure and the form of controlled oxidation aluminium primary particle.And the alumina material of above-mentioned modification will be as the carrier of high performance cleaning catalyst for tail gases of automobiles or catalyst for catalytic combustion, because catalyzer is under the high temperature more than 1000 ℃ for a long time, its heat-resistant stability still is difficult to meet the demands.
Summary of the invention
The object of the present invention is to provide a kind of preparation method with high thermal stability and bigger serface aluminum oxide.Its product that obtains has nanometer fibrous pattern, and the contact area is little between primary particle, so product has high thermal stability and bigger serface.After 6 hours, specific surface area is up to 462m 500 ℃ of roastings
2/ g, 1000 ℃ of roastings after 6 hours specific surface area up to 174m
2/ g, after 6 hours, specific surface area still can reach 80m 1200 ℃ of roastings
2/ g.
For achieving the above object, the technical solution used in the present invention is:
A kind of preparation method with high thermal stability and bigger serface aluminum oxide, main preparation process is as follows:
1) the excess of ammonia aqueous solution progressively is added drop-wise in aluminum nitrate (concentration of aluminum nitrate does not have too big influence to product, and the concentration that experiment is adopted usually the is 0.5-10mol/L) solution, makes pH 〉=8.7 of final solution; With the precipitation repetitive scrubbing that generates, separate after, add nitric acid and stirred 〉=2 hours in 80-100 ℃, obtain precursor sol;
2) in precursor sol, add tensio-active agent, alcohol acid or high molecular polymer under the room temperature and do structure directing agent, after the 100-120 ℃ of drying, in the air 450-600 ℃ roasting 3-6 hour;
Wherein: in the Al in the precursor sol, the mol ratio of Al ion and structure directing agent is 1:0.02-1.0.
In the step 1) excess of ammonia aqueous solution progressively is added drop-wise in the aluminum nitrate solution, the pH of its final solution is generally 8.7-11.
Step 2) tensio-active agent described in is polyethylene oxide-poly(propylene oxide)-polyethylene oxide, Brij30 (Brij30), hexadecyl trimethyl ammonium bromide, two (2-ethylhexyl) sulfosuccinate sodium or sodium lauryl sulphate; Described alcohol acid is tartrate, oxysuccinic acid or lactic acid; Described high molecular polymer is a polyoxyethylene glycol.
Preparation provided by the invention has high thermal stability and bigger serface method of alumina, and its advantage is:
1. product has bigger serface.The aluminum oxide that the inventive method obtains has nanometer fibrous pattern, and the contact area is little between primary particle, so product has high thermal stability and bigger serface.
2. the product heat-resistant stability is good.After 6 hours, specific surface area is up to 462m 500 ℃ of roastings for product of the present invention
2/ g, 1000 ℃ of roastings after 6 hours specific surface area up to 174m
2/ g, after 6 hours, specific surface area still can reach 80m 1200 ℃ of roastings
2More than/the g.
3. technology is simple, with low cost.The present invention is a raw material with aluminum nitrate, the ammoniacal liquor of cheapness, adopts sol-gel method to prepare precursor sol, and production cost is low; Regulate and control the form of presoma primary particle by adding tensio-active agent, alcohol acid, high molecular polymer, technology is simple, control is convenient; Product has high specific surface area and thermostability, and after 6 hours, specific surface area still can reach 80m 1200 ℃ of roastings
2/ g.Therefore, the aluminum oxide that adopts the present invention to obtain has very big application potential in fields such as purifying vehicle exhaust, catalyst for catalytic combustion, has a wide range of applications in fields such as material, catalysis.
Description of drawings
Fig. 1 is to be transmission electron microscope (TEM) photo of the aluminum oxide that obtains of structure directing agent with polyethylene oxide-poly(propylene oxide)-polyethylene oxide.
Embodiment
Embodiment 1 preparation precursor sol
The 75g aluminum nitrate is dissolved in the 100g deionized water, stirs and dropwise drip weight concentration 2.5% ammoniacal liquor adjusting pH down 3.7.The ammoniacal liquor of disposable adding 350ml 2.5% makes the precipitation pH that obtains〉8.7.Be dispersed in the deionized water with the precipitation repetitive scrubbing that obtains, after filtering, making mixed volume is 200ml, and 80 ℃ of stirrings drip 1M nitric acid 16ml down, continue to stir more than 2 hours, obtain the precursor sol of 1mol/L.
Embodiment 2 is the additive preparation aluminum oxide with the nonionic surface active agent
Get the precursor sol of 40ml by embodiment 1 preparation, add under the room temperature 4.64g polyethylene oxide-poly(propylene oxide)-polyethylene oxide (P123) or 2.88g Brij30 dissolve fully after directly in 110 ℃ dry down, 500 ℃ of roastings are 6 hours in the air.By the TEM photo as can be known, product has nanometer fibrous pattern (seeing Figure of description).Be to measure thermostability, respectively 1000 ℃, 1200 ℃ roastings 6 hours, the product specific surface area sees Table 1 with the aluminum oxide that obtains.
Embodiment 3 is the additive preparation aluminum oxide with the cationic surfactant
The preparation method is with embodiment 2.Difference is: add 3.64g hexadecyl trimethyl ammonium bromide (CTAB).The specific surface area of product sees Table 1.
Embodiment 4 is the additive preparation aluminum oxide with the aniorfic surfactant
The preparation method is with embodiment 2.Difference is: add 2.84g sodium lauryl sulphate (SDS) or 1.67g two (2-ethylhexyl) sulfosuccinate sodium (AOT).The specific surface area of product sees Table 1.
Embodiment 5 is the additive preparation aluminum oxide with tartrate
The preparation method is with embodiment 2.Difference is: add 3g tartrate.The specific surface area of product sees Table 1.
Embodiment 6 is the additive preparation aluminum oxide with the oxysuccinic acid
The preparation method is with embodiment 2.Difference is: add the 2.68g oxysuccinic acid.The specific surface area of product sees Table 1.
Embodiment 7 is the additive preparation aluminum oxide with lactic acid
The preparation method is with embodiment 2.Difference is: add 4.48g lactic acid.The specific surface area of product sees Table 1.
Embodiment 8 is the additive preparation aluminum oxide with the polyoxyethylene glycol
The preparation method is with embodiment 2.Difference is: add 1.6g polyoxyethylene glycol (M=2000).The specific surface area of product sees Table 1.
The specific surface area of table 1 product
Embodiment 9
The 150g aluminum nitrate is dissolved in the 100g deionized water, stirs and dropwise drip weight concentration 2.5% ammoniacal liquor adjusting pH down 3.8; The ammoniacal liquor of disposable adding 600ml 2.5% makes the precipitation pH=10 that obtains; Be dispersed in the deionized water with the precipitation repetitive scrubbing that obtains, after filtering, making mixed volume is 200ml, and 90 ℃ of stirrings drip 1.5M nitric acid 24ml down, continue to stir more than 2 hours, obtain the precursor sol of 2mol/L.
Get the precursor sol of 40ml, directly in 120 ℃ of dryings down, 600 ℃ of roastings are 3 hours in the air after adding 4.64g under the room temperature polyethylene oxide-poly(propylene oxide)-polyethylene oxide (P123) dissolve fully.
Embodiment 10
The 120g aluminum nitrate is dissolved in the 100g deionized water, stirs and dropwise drip weight concentration 2.0% ammoniacal liquor adjusting pH down 3.5; The ammoniacal liquor of disposable adding 400ml 2.0% makes the precipitation pH=9 that obtains; Be dispersed in the deionized water with the precipitation repetitive scrubbing that obtains, after filtering, making mixed volume is 200ml, and 100 ℃ of stirrings drip 1.5M nitric acid 20ml down, continue to stir more than 2 hours, obtain the precursor sol of 1.6mol/L.
Get the precursor sol of 40ml, add under the room temperature 2.88g Brij30 dissolve fully after directly in 100 ℃ dry down, 450 ℃ of roastings are 5 hours in the air.
Claims (2)
1, a kind of preparation method with high thermal stability and bigger serface aluminum oxide is characterized in that: concrete preparation process is as follows:
1) the excess of ammonia aqueous solution progressively is added drop-wise in the aluminum nitrate solution, makes pH 〉=8.7 of final solution; With the precipitation repetitive scrubbing that generates, separate after, add nitric acid and stirred 〉=2 hours in 80-100 ℃, obtain precursor sol;
2) in precursor sol, add tensio-active agent, alcohol acid or high molecular polymer under the room temperature and do structure directing agent, after the 100-120 ℃ of drying, in the air 450-600 ℃ roasting 3-6 hour;
Wherein: in the Al in the precursor sol, the mol ratio of Al ion and structure directing agent is 1:0.02-1.0;
Step 2) tensio-active agent described in is polyethylene oxide-poly(propylene oxide)-polyethylene oxide, Brij30, hexadecyl trimethyl ammonium bromide, two (2-ethylhexyl) sulfosuccinate sodium or sodium lauryl sulphate;
Described alcohol acid is tartrate, oxysuccinic acid or lactic acid; Described high molecular polymer is a polyoxyethylene glycol.
2. according to the described preparation method of claim 1, it is characterized in that: in the step 1) excess of ammonia aqueous solution progressively is added drop-wise in the aluminum nitrate solution, makes the pH=8.7-11 of final solution with high thermal stability and bigger serface aluminum oxide.
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101618886B (en) * | 2008-07-04 | 2011-05-18 | 中国石油化工股份有限公司 | Aluminum hydroxide and preparation method thereof |
| CN101817545B (en) * | 2010-03-03 | 2012-04-25 | 上海交通大学 | Preparation method of mesoporous alumina powder based on saccharides |
| CN102311133B (en) * | 2010-07-07 | 2014-12-10 | 中国石油化工股份有限公司 | Integral macroporous alumina and preparation method thereof |
| CN102923744A (en) * | 2012-11-20 | 2013-02-13 | 中国海洋石油总公司 | Preparation method for aluminum oxide by direct forming method |
| CN103964481A (en) * | 2014-04-11 | 2014-08-06 | 天津市职业大学 | Preparation method for sheet aluminium oxide |
| CN105731504A (en) * | 2014-11-25 | 2016-07-06 | 重庆文理学院 | Method for preparing good-adsorbability nanometer particles |
| CN105561913B (en) * | 2015-12-04 | 2019-03-08 | 盐城市兰丰环境工程科技有限公司 | A kind of preparation method based on cupric component sulfur transfer additive |
| CN108047903A (en) * | 2017-12-19 | 2018-05-18 | 衢州职业技术学院 | Water-fast corrosion-resistant radiator paint and preparation method thereof |
| CN109012666B (en) * | 2018-09-15 | 2021-05-11 | 四川鑫元瑞科技有限公司 | Preparation method of automobile exhaust purification catalyst |
| CN113087000A (en) * | 2021-03-31 | 2021-07-09 | 中国核动力研究设计院 | Preparation method of high-performance spherical alumina for chromatography |
Citations (1)
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| WO2001074713A1 (en) * | 2000-04-03 | 2001-10-11 | The University Of Queensland | Improved mesoporous catalysts |
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| WO2001074713A1 (en) * | 2000-04-03 | 2001-10-11 | The University Of Queensland | Improved mesoporous catalysts |
Non-Patent Citations (3)
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| 溶胶－发泡法制备超细氧化铝. 孙家跃，肖昂，杜海燕等.精细化工，第21卷第4期. 2004 * |
| 高比表面积窄孔分布氧化铝的制备 I. 沉淀条件的影响. 杜明仙，翟效珍，李源等.催化学报，第23卷第5期. 2002 * |
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