CN1250455C - Method for preparing light temperature-resistance high surface area alumina and aluminiferous composite oxide - Google Patents
Method for preparing light temperature-resistance high surface area alumina and aluminiferous composite oxide Download PDFInfo
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- CN1250455C CN1250455C CN 200310101244 CN200310101244A CN1250455C CN 1250455 C CN1250455 C CN 1250455C CN 200310101244 CN200310101244 CN 200310101244 CN 200310101244 A CN200310101244 A CN 200310101244A CN 1250455 C CN1250455 C CN 1250455C
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Abstract
The present invention discloses a method of preparing high surface area aluminum oxide of high-temperature resistance and composite oxide containing aluminum. The method comprises the following steps: preparing inverse microemulsions by a surface active agent, a cosurfactant, a non-water soluble organic solvent, water, an inorganic salt and an alkaline substance as raw materials; mixing the two inverse microemulsions for reaction to prepare collosol; filtering, drying, baking, etc. to obtain high-heat stable aluminum oxide and composite oxide material containing aluminum. The aluminum oxide and the composite oxide containing aluminum prepared by the method of the present invention are baked at 1100 DEG C for 10 hours, and all of the specific surface areas can maintain more than 50m<2>/g. If the aluminum oxide modified by Si is baked at 1100 DEG C for 10 hours, the specific surface area is 185.2m<2>/g. The oxide material prepared by the method has the advantages that the distribution of the particle diameter is uniform, the size of the particle diameter is controllable, the operation condition is mild, the process is simple and easy to realize, the cost of raw material is low, and raw material is easily acquired.
Description
Technical field
The present invention relates to a kind of method of synthesizing resistant to elevated temperatures high surface area alumina and containing the aluminium composite oxide material, relate in particular to a kind of method that adopts the prepared by reverse microemulsion method aluminum oxide and contain aluminium composite oxide.
Background technology
Oxide compound that uses under hot environment and operational condition and composite oxide material (as aluminum oxide and contain aluminium composite oxide) are the high-performance solid support materials of catalyzer such as motor vehicle vent gas purification catalysis agent and methane catalytic combustion, and purposes is very extensive.As high performance solid support material, aluminum oxide and contain the particle diameter, granularity, resistance to elevated temperatures of aluminium composite oxide material and after high-temperature roasting parameter such as retainable specific surface area all can produce bigger influence to the performance of catalyzer such as cleaning catalyst for tail gases of automobiles and methane catalytic combustion.
Along with the continuous development of modernization industry, the demand of the energy is increased day by day, though the Energy Mix of countries in the world is not quite similar, have a bit undoubtedly, that is exactly that coal, oil, Sweet natural gas etc. act as a fuel still occupy very big ratio in Energy Mix.Because these resources all are Nonrenewable resources, how these resources are carried out abundant reasonable use, have caused the concern that people are increasing.And catalyticcombustion is considered to make fuel to be able to fully burning to obtain the most effectual way of multipotency as far as possible.Compare with flame, catalyticcombustion also has air-fuel ratio height, NO
xWith advantage such as discharge of poisonous waste amounts such as CO are little, has far reaching significance so it is furtherd investigate.Consider high service temperature, the good catalytic material of exploitation high high-temp stability just becomes the key of catalytic combustion technology development.
In addition, with the purification of environment protection vehicle exhaust of close concern to each other also be the countries in the world question of common concern, the raising of the three-way catalyst performance that purifying vehicle exhaust is used also depends on the performance of the solid support material of novel high thermal stability.The many reactions in chemical industry such as the steam reforming reaction of methane etc. also all need be operated under comparatively high temps.This shows that the research and development of High-temperature Materials for Catalytic Combustion has very important science and realistic meanings.Wherein preparation method's innovation plays a part very important in the building-up process of novel material.
The method of synthesis oxide and composite oxide material is a lot, even use identical raw material and composition, because preparation method's difference, the performance of gained material still has very big difference.The method for preparing aluminum oxide and contain the aluminium composite oxide material has varied, mainly contains coprecipitation method, sol-gel method, mechanical mixing, pickling process, Mierocrystalline cellulose template agent method, heat of solution synthesis method, reverse microemulsion process etc.
Coprecipitation method and sol-gel method are to utilize chemical reaction to prepare the common method of oxide compound and composite oxide material, the composite oxide material component of preparation distributes more even, and can be by selecting the suitable precursor raw material, temperature, strength of solution, acid-basicity and order of addition(of ingredients) by the conditioned reaction process wait the performance of controlling product, so coprecipitation method and sol-gel method are synthesizing high temperature high surface area alumina and the common method that contains the aluminium composite oxide material.Document ((1) Tatsuro Hriuchi, Toshihiko Osaki, Toyohiko Sujiyama et al, High surface area alumina aerogel atelevate temeperatures.J.Chem.Soc.Faraday Trans., 1994,90 (17): 2573-2578; (2) Tatsuro Hriuchi, Laiyuan Chen, Toshihiko Osaki et al, A novelcatalyst support with high thermal stability derived from silica-modifiedalumina aerogel.Catal.Lett., 1999,58:89-92; (3) Tatsuro Hriuchi, ToshihikoOsaki, Toyohiko Sujiyama et al, 1300 ℃ of by preparing of Maintenance of large surface area of aluminaheated at elevated temperatures above silica-containingpseudobohmite.Journal of non-crystalline solids, 2001,291:187-198) reported the aerogel that is equipped with high temperature high surface area silicon modified aluminas with the sol-gel legal system, this aerogel specific surface area behind 1100 ℃ of following roasting 5h remains on 70-300m
2/ g.One of problem that this method exists is that the salt that it adopts is an alkoxide, compares with inorganic salt to cost an arm and a leg, and is unfavorable for scale operation.Also need in the method in addition to use ethanol to carry out supercritical drying, make process comparatively complicated, and need to consume ethanol in the drying process, thereby production cost is increased as solvent.
It is the thought of template that the Mierocrystalline cellulose template agent method comes from the porous polymer mold, and the filamentary material that is used as template should have nanoporous and capillary canal.Make in this way the pore structure of the metal oxide of preparation and complex metal oxides depend on the performance of template, just as the process of making cast iron with mould.Cellulose materials as template mainly contains cellulose crystallite powder, chromatographic paper, regenerated cellulose, the paper of weighing, electro-photographic paper, cellulose nitrate and cellulose acetate etc.Its operating process is: with the precursor dissolving of salt, carry out processing such as drying, roasting after template absorbs earlier, promptly get product.Document (A.N.Shigapov, G.W.Graham, R.W.McCabe et al., The preparation ofhigh-surface area, thermal-stable, metal-oxide catalysts and supports by acellulose templating approach.Applied catalysis A:General, 2001,210:287-300) reported that with Whatman filter paper be the La modified aluminas that template makes, its surface-area is 141m after 1050 ℃ of roastings
2/ g.Up to the present, it is still rare to utilize Mierocrystalline cellulose template agent method borolon and contain the report of aluminium composite oxide, and this may be still waiting to improve with the thermostability of the composite oxide material of preparation, and problems such as the selection that relates to template and consumption are relevant.
The thermolysis synthesis method is a kind of method of utilizing the organic medium synthetic inorganic material, and this method is to utilize alkoxide to decompose in organic medium to come synthesis oxide and composite oxides.The document that relates to has: (1) Masashi Inoue, Hiroshi Kominami and Tomoyuki Inui, Thermaltransformation of γ-alumina formed by thermal decomposition of aluminumalkoxide in organic media.J.Am.Ceram.Soc., 1992,75 (9): 2597-2598; (2) Masashi Inoue, Hirokazu Tanino, Yasuhiko Kondo et al., Formation ofmicrocrystalline α-alumina by glycothermal treatment of gibbsite.Communication of the American Ceramic Society, 1989,72 (2): 352-353; (3) Piyasan Praserthdam, Masashi Inoue, Okorn Mekasuvandumrong et al., Effectof organic solvents on the thermal stability of porous silica-modified aluminapowders prepared via one pot solvothermal synthesis.Inorganic chemistrycommunications, 2000,3:671-676.As being the aluminum oxide of the silicon modification of medium preparation with the propyl carbinol, this aluminum oxide has wrinkle shape laminate structure, compares with spheroidal particle, and this structure has better thermostability, and its surface-area can remain on 169m after 1150 ℃ high-temperature roasting
2/ g.But this synthetic method need be carried out under certain temperature and pressure, and investment that this certainly will will increase manufacturing facilities and bigger energy expenditure are unfavorable for suitability for industrialized production.
Microemulsion method is a kind of effective ways of synthesis of nano particulate, the principal feature of this method is that the size distribution of products obtained therefrom is controlled easily, good stability, and operational condition gentleness, process is also fairly simple, and can carry out functional modification to the material for preparing by surface modification.Document (Andrey J.Zarur, Henry H.Hwu and Jackie Y.Ying, Reverse microemulsion-mediate synthesisand structural evolution ofbarium hexaaluminate nanoparticles.Langmuir, 2000,16:3042-3049) reported and utilize reverse micro emulsion to do hydrolysis and polycondensation that medium carries out barium and aluminium-alcohol salt, successfully synthesized nano level six barium aluminates, behind 1300 ℃ of high temperature, specific surface area still can remain on 100m
2More than/the g, its weak point is that the starting raw material that is adopted is an alkoxide, and especially a large amount of uses of barium isopropylate make that the cost of raw material is very high.
Summary of the invention
The technical issues that need to address of the present invention are to disclose a kind of method that adopts the aluminum oxide of the resistant to elevated temperatures high surface area of prepared by reverse microemulsion method and contain aluminium composite oxide; to overcome the many deficiencies that exist in the prior art, satisfy fields such as industrial production, environment protection and catalyticcombustion to high temperature resistant high surface area alumina and contain the demand of aluminium composite oxide.
The technological line that the present invention adopts is such: with tensio-active agent, cosurfactant, water-insoluble solvent, water, inorganic salt and ammoniacal liquor is raw material, make behind the reverse micro emulsion and will two kinds of microemulsions to mix the back and generate colloidal sols, after filtration, after processing such as drying, roasting acquisition have high-temperature stable high surface area aluminum oxide and contain the aluminium composite oxide material.Aluminum oxide of the present invention and contain aluminium composite oxide and have following chemical general formula:
aAl-bM
n-cO
Wherein: M is a metallic element, comprises in alkali earth metal, the 4th main group element, rare earth element and the transition metal one or more, and O is an oxygen element;
n＝1，2，3，4，5，6
0＜a≤1，b＝0～1，c＝0.5～3
Wherein the add-on of M is 0～95% (wt) of Al content.
Its preparation method comprises the steps: that the aqueous solution that will contain alkaline matter joins in the reverse micro emulsion that contains inorganic salt, the reverse micro emulsion that perhaps will contain alkaline matter joins in the aqueous solution that contains inorganic salt, the reverse micro emulsion that perhaps will contain alkaline matter joins in the reverse micro emulsion that contains inorganic salt, be stirred to the pH value while dripping and be 8.0-10.0, after filtering, filter cake is at 50～100 ℃ of down dry 2～24h, 800～1300 ℃ of roastings 0.5～30 hour can obtain aluminum oxide of the present invention and contain aluminium composite oxide.
The said reverse micro emulsion that contains alkaline matter is the mixture of low-carbon alcohol cosurfactant, water-insoluble organic solvent and the water of alkaline matter and tensio-active agent, C3～C6, and said alkaline matter comprises ammoniacal liquor, ammonium salt or ammonia.The reverse micro emulsion that contains alkaline matter is preparation like this: the aqueous solution of alkaline matter is joined in the mixture of tensio-active agent, cosurfactant and water-insoluble organic solvent, and stirring and emulsifying gets final product.Wherein:
Tensio-active agent: cosurfactant: water-insoluble organic solvent=1: 1～3: 7～10, volume ratio;
Water: water-insoluble organic solvent=1: 1～8, volume ratio;
The degree of alkaline matter counts 1～10% with reverse micro emulsion weight.
The said reverse micro emulsion that contains inorganic salt is the mixture of low-carbon alcohol cosurfactant, water-insoluble organic solvent and the water of inorganic salt and tensio-active agent, C3～C6.Said inorganic salt are nitrate, vitriol or the muriate of Al, and comprise one or more nitrate, vitriol or the muriate in alkali earth metal, the 4th main group element, rare earth element or the transition metal, preferably nitrate; When the element except that Al used as properties-correcting agent, the metal acid esters that also can use C2～C8 was as raw material.The reverse micro emulsion that contains inorganic salt is preparation like this: the aqueous solution that will contain inorganic salt adds tensio-active agent, the low-carbon alcohol cosurfactant of C3～C6 and the mixture of water-insoluble organic solvent, and stirring and emulsifying gets final product.Wherein:
Tensio-active agent: cosurfactant: water-insoluble organic solvent=1: 1～3: 7～10, volume ratio;
Water: water-insoluble organic solvent=1: 1～8, volume ratio;
The degree of inorganic salt counts 1～10% with reverse micro emulsion weight.
Said tensio-active agent comprises a kind of in polyalkylene glycol alkyl phenyl ether, alkylbenzene phenolic group Soxylat A 25-7, phenol Soxylat A 25-7, fatty alcohol-polyoxyethylene ether, lipid acid-polyoxyethylene or other polyoxyethylene glycol;
Said low-carbon alcohol is preferably n-hexyl alcohol;
Said water-insoluble organic solvent is a kind of in hexanaphthene, octane-iso or the hexahydroaniline.
Adopt the aluminum oxide of method preparation of the present invention and contain aluminium composite oxide behind 1100 ℃ of roasting 10h, the specific surface area of measuring with the BET method still remains on 50m
2More than/the g, be much higher than the prepared sample of ordinary method, and the size distribution of sample is even, size is controlled, and the aluminum oxide of preparation and the particle that contains aluminium composite oxide are nanometer particle.Nanoparticle is by number less atom or molecular composition, its atom or molecule are in metastable state on thermodynamics, make nanoparticle in the chemical property that keeps material, show peculiar performance at aspects such as magnetic, photoabsorption, thermal resistance, chemically reactive, catalysis and fusing points, therefore method of the present invention also can be used for the synthetic of other specific function materials.This method operational condition gentleness, process is simple, is convenient to realize; Simultaneously the raw material (being generally inorganic salt such as nitrate) that adopts of this method cheap, be easy to get, use alkoxide to compare with needs as the preparation method of raw material, can reduce raw material and production cost greatly with present method.
In a word, method of the present invention be applicable to that the preparation grain size is evenly distributed, controlled, granularity is little, specific surface area is big, high high-temp stability is good aluminum oxide and contain the aluminum composite metal oxide material.Present method also can be applicable to the preparation of other metal oxides and composite oxides.
Description of drawings
Fig. 1 is the specific surface area of aluminum oxide after the different condition roasting of different preparation method's preparations.
Fig. 2 is the specific surface area of barium modified aluminas after the different condition roasting of different preparation method's preparations.
Fig. 3 is the specific surface area of silicon modified aluminas after the different condition roasting of different preparation method's preparations.
Among the figure, curve (1) is the surface area values of the sample of method preparation of the present invention; Curve (2) is the surface area values of the sample of literature method preparation.
Embodiment
With the synthetic Al of reverse microemulsion process
2O
3
With the Triton X-100 is tensio-active agent, and n-hexyl alcohol is a cosurfactant, and hexanaphthene is an oil phase, wherein surfactants/cosurfactants/hexanaphthene=5/6/37 (volume ratio).
In preparation process earlier with tensio-active agent, cosurfactant, hexanaphthene with above-mentioned mixed, be divided into two parts after stirring, every part of 430ml, dripping concentration in a copy of it is the aluminum nitrate aqueous solution of 27.3wt%, add-on is 50ml, stir while dripping, till clear, the gained mixture is the reverse micro emulsion of aluminum nitrate;
Drip concentration and be 25～28% ammoniacal liquor in another part, add-on is 50ml, stirs while dripping, must light blue clear liquid the reverse micro emulsion that is ammoniacal liquor.
At room temperature the reverse micro emulsion with ammoniacal liquor is added drop-wise in the reverse micro emulsion of aluminum nitrate, is to filter after 8.0 to the pH value, and filter cake is being carried out roasting behind the dry 12h down at 100 ℃.Sample after the roasting adopts the BET method to measure its specific surface area, and the result is shown in (1) among Fig. 1.As seen from Figure 1, the Al for preparing with this method
2O
3Its specific surface area can remain on 51.5m behind 1100 ℃ of roasting 10h
2/ g.
Al with the synthetic Ba modification of reverse microemulsion process
2O
3
Adopt embodiment 1 used tensio-active agent, cosurfactant and oil phase, with the identical ratio preparation aluminum nitrate and the reverse micro emulsion of ammoniacal liquor, different is to have added the 0.14g nitrate of baryta in aqueous solution of aluminum nitrate.Other building-up process is identical with embodiment 1.(1) is gained sample BET specific surface area after the roasting under different condition among Fig. 2.The result shows that its specific surface area is 89.7m behind 1100 ℃ of roasting 10h
2/ g is higher than the pure Al of preparation in the same way
2O
3Specific surface area.Document (Acta PhySico-Chimica Sinica, 2001,17 (11): 1036-1039) reported the barium Modification on Al of using immersion process for preparing
2O
3Its surface-area is 41m behind 1100 ℃ of roasting 10h
2/ g; With sol-gel method (SCI, 2001,23 (5): 947-949) Zhi Bei barium Modification on Al
2O
3Behind 1100 ℃ of roasting 32h, its maximum surface area is 27.3m
2/ g.The barium Modification on Al of Comparative Examples 2 usefulness sol-gel methods preparation
2O
3After identical condition was handled, its surface-area only was 24.0m
2/ g is as (2) among Fig. 2.
Embodiment 3
With the synthetic silicon Modification on Al of reverse microemulsion process
2O
3
Adopt embodiment 1 used tensio-active agent, cosurfactant and oil phase, with the identical ratio preparation aluminum nitrate and the reverse micro emulsion of ammoniacal liquor, different is to have added the 1.3g tetraethoxy in aqueous solution of aluminum nitrate.Other building-up process is identical with embodiment 1.(1) is gained sample specific surface area value after the roasting under different condition among Fig. 3, and its specific surface area can remain on 174.9m behind 1100 ℃ of roasting 10h
2/ g is higher than the pure Al with the same procedure preparation far away
2O
3Specific surface area.Silicon Modification on Al with the preparation of sol-gel method
2O
3Its surface-area is 116.7m after identical condition is handled
2/ g (Comparative Examples 3).
Embodiment 4
With the synthetic silicon Modification on Al of reverse microemulsion process
2O
3
In embodiment 3, the add-on of tetraethoxy is increased to 2.6g, other building-up process is identical with embodiment 3.Prepared sample its specific surface area behind 1100 ℃ of roasting 10h is 185.2m
2/ g.
Embodiment 5
With the synthetic silicon Modification on Al of reverse microemulsion process
2O
3
In embodiment 3, substitute tetraethoxy as properties-correcting agent with butyl silicate, and keep the add-on of Si constant, other building-up process is identical with embodiment 3.Prepared sample its specific surface area behind 1100 ℃ of roasting 10h is 176.3m
2/ g.
Comparative Examples 1
The employing document (Gong Maochu, Zhang Jie, the grace of woods etc.: the preparation of high temperature resistant high surface alumina oxide and character. SCI, 2001,23 (5): 947-949) Bao Dao sol-gel legal system is equipped with Al
2O
3
As the contrast of embodiment 1, adopt the sol-gel method to prepare Al
2O
3, under agitation condition in aqueous solution of aluminum nitrate dropping ammonia to pH be 8.8-9, after filtration, washing, drying, roasting etc. handle the back and measure its surface-area, among its result such as Fig. 1 (2).
Comparative Examples 2
Be equipped with the barium Modification on Al with the sol-gel legal system
2O
3
As the contrast of embodiment 2, adopt the sol-gel method to prepare the barium Modification on Al
2O
3, under agitation condition in aqueous solution of aluminum nitrate dropping ammonia to pH be 8.8-9, wherein be dissolved with an amount of nitrate of baryta in the aqueous solution of aluminum nitrate, after filtration, washing, drying, roasting etc. handle the back and measure its surface-area, among its result such as Fig. 2 (2).The result shows, under identical roasting condition, and the barium Modification on Al that adopts reverse microemulsion process of the present invention to make
2O
3Specific surface area will be far above sample with the preparation of sol-gel method.
Comparative Examples 3
The Al that is equipped with the silicon modification with the sol-gel legal system
2O
3
As the contrast of embodiment 3, adopt the sol-gel method to prepare the Al of silicon modification
2O
3, under agitation condition in aqueous solution of aluminum nitrate dropping ammonia to pH be 8.8-9, wherein be dissolved with an amount of tetraethoxy in the aqueous solution of aluminum nitrate.After filtration, washing, drying, roasting etc. handle the back and measure its surface-area, among its result such as Fig. 3 (2).The result shows, under identical roasting condition, and the silicon Modification on Al that adopts reverse microemulsion process of the present invention to make
2O
3Specific surface area will be far above the sample of sol-gel method preparation.
Claims (8)
1. method for preparing high temperature resistant high surface area alumina or contain aluminium composite oxide, it is characterized in that, preparation process comprises the steps: that the reverse micro emulsion that will contain alkaline matter joins in the reverse micro emulsion that contains inorganic salt, control pH value is 8.0-10.0, after filtration, after filtration cakes torrefaction and the roasting, promptly obtain the aluminum oxide of high thermal stability or contain the aluminium composite oxide material; Said alkaline matter is selected from ammoniacal liquor, ammonium salt or ammonia, said inorganic salt are nitrate, vitriol or the muriate of Al, and one or more nitrate, vitriol or the muriate in 0～95% alkali earth metal, the 4th main group element, rare earth element or the transition metal of Al content.
2. method according to claim 1 is characterized in that, the said reverse micro emulsion that contains alkaline matter is the mixture of low-carbon alcohol cosurfactant, water-insoluble organic solvent and the water of alkaline matter and tensio-active agent, C3～C6.
3. method according to claim 2 is characterized in that tensio-active agent: cosurfactant: water-insoluble organic solvent=1: 1～3: 7～10, volume ratio;
Water: water-insoluble organic solvent=1: 1～8, volume ratio;
The degree of alkaline matter counts 1～10% with reverse micro emulsion weight.
4. method according to claim 1 is characterized in that, the said reverse micro emulsion that contains inorganic salt is the mixture of low-carbon alcohol cosurfactant, water-insoluble organic solvent and the water of inorganic salt and tensio-active agent, C3～C6.
5. method according to claim 4 is characterized in that tensio-active agent: cosurfactant: water-insoluble organic solvent=1: 1～3: 7～10, volume ratio;
Water: water-insoluble organic solvent=1: 1～8, volume ratio;
The degree of inorganic salt counts 1～10% with reverse micro emulsion weight.
6. method according to claim 2 is characterized in that, said water-insoluble organic solvent comprises a kind of in hexanaphthene, octane-iso or the hexahydroaniline.
7. method according to claim 4 is characterized in that, said water-insoluble organic solvent comprises a kind of in hexanaphthene, octane-iso or the hexahydroaniline.
8. according to each described method of claim 2～7, it is characterized in that said tensio-active agent is selected from polyalkylene glycol alkyl phenyl ether, alkylbenzene phenolic group Soxylat A 25-7, phenol Soxylat A 25-7, fatty alcohol-polyoxyethylene ether or lipid acid-polyoxyethylene.
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| CN100484621C (en) * | 2006-10-25 | 2009-05-06 | 中国科学院大连化学物理研究所 | Method for preparing large surface improved aluminium oxide with high temperature resistant performance |
| CN100427395C (en) * | 2006-11-02 | 2008-10-22 | 兰州大学 | Preparation method of mono dispersion nano-alpha aluminium oxide particle powder |
| CN101559963B (en) * | 2008-04-18 | 2012-12-12 | 兰州大学 | Method using microemulsion to prepare three-dimensional netty activated aluminium oxide |
| KR20100073704A (en) * | 2008-12-23 | 2010-07-01 | 삼성전기주식회사 | Methods of manufacturing complex oxide nano particles and complex oxide nano particles manufactured thereby |
| CN106032286B (en) * | 2015-03-13 | 2017-09-29 | 中国石油化工股份有限公司 | A kind of production method of aluminum oxide |
| CN104860341B (en) * | 2015-05-26 | 2018-10-19 | 华东理工大学 | A kind of preparation method of high temperature resistant and high specific surface aluminium |
| CN109200955B (en) * | 2018-11-14 | 2021-06-08 | 中国科学院兰州化学物理研究所 | Organic-inorganic dual-network structure phenolic aldehyde/alumina aerogel composite material and preparation method thereof |
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Assignee: Wuxi Weifu Lida catalytic converter Co. Ltd. Assignor: East China University of Science and Technology Contract fulfillment period: 2007.7.1 to 2012.6.30 contract change Contract record no.: 2008310000218 Denomination of invention: Method for preparing light temperature-resistance high surface area alumina and aluminiferous composite oxide Granted publication date: 20060412 License type: Exclusive license Record date: 20081114 |
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