CN102963896A - Preparation method of mullite precursor and nano mullite - Google Patents
Preparation method of mullite precursor and nano mullite Download PDFInfo
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- CN102963896A CN102963896A CN2012104938356A CN201210493835A CN102963896A CN 102963896 A CN102963896 A CN 102963896A CN 2012104938356 A CN2012104938356 A CN 2012104938356A CN 201210493835 A CN201210493835 A CN 201210493835A CN 102963896 A CN102963896 A CN 102963896A
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Abstract
The invention relates to a preparation method of a mullite precursor and nano mullite. According to the method, aluminum powder, silica sol and hydrochloric acid are used as initial raw materials of mullite, copper-zinc mixed ions are used as catalysts, and then a nano mullite precursor is prepared by a chemical method; and the nano mullite can be obtained by high-temperature calcination. According to the method provided by the invention, the raw materials are easily available, the preparation technology is relatively simple, large special equipment is not needed, investment is small, the production cost is relatively low, the production cycle of the product is short, the efficiency and purity are high, the shape is controllable, the repeatability is good, and the production can be performed as required; the particle size of the prepared nano mullite is mainly distributed between 60nm and 120nm; and the method has better prospects in industrial application.
Description
Technical field
The present invention relates to the preparation method of mullite material, be specifically related to the preparation method of a kind of mullite precursor, nano mullite.
Background technology
Mullite is a series of mineral general designations that are comprised of aluminosilicate, the mineral that aluminosilicate at high temperature generates, have that good thermal shock stability, loading softening are high, thermal expansivity is low, thermal conductivity is low, dielectric coefficient is low, good chemical stability is good and the characteristics such as optical property, use in fields such as chemical industry, metallurgy, environmental protection, aerospace, Electronic Packaging and optical materials.But natural mullite seldom, the overwhelming majority is to adopt the artificial synthesis preparation, and the above-mentioned performance of mullite and its grain size and distribution is in close relations, the performance that presents of synthesis of nano mullite is more outstanding, and the synthetic mullite has significantly extended the range of application of mullite.
The preparation method that nano mullite is commonly used is divided into Physical and chemical method.Physical has high-energy ball milling method, solvent evaporated method, inert gases agglomeration method etc., these method complex process equipment, and production cost is high, and energy utilization rate is low, yields poorly, and its application is restricted.Chemical method has solid reaction process, wet chemistry method (comprising the precipitator method, hydrothermal method Heshui solution etc.), sol-gel method, microemulsion method, chemical gas-phase method etc.Chemical method prepares that nano mullite is many to carry out in solution, do not need special equipment, has simple to operately, and purity is high, the advantages such as easy control of reaction.The preparation nano mullite adopts chemical method more at present.As, disclosing a kind of mullite powder that adopts among the patent documentation CN101182001 is the method that raw material prepares nano mullite, at first with mullite powder: sodium hydroxide and/or yellow soda ash: urea: water is hybrid reaction (2～12h) according to a certain percentage, then adding a certain proportion of Glacial acetic acid and anion surfactant reacts (after 2～12h) again, then filter, washing, get powder after the drying, again with powder, dimethyl sulfoxide (DMSO), yellow soda ash, amphotericses etc. mix afterreaction (2～12h) according to a certain percentage, at last again through filtering, washing, after the drying obtain stay-in-grade nano mullite after the powder calcination, but involved formula material is numerous in this technical scheme, and complicated process of preparation; A kind of preparation method of nano mullite powder is disclosed among the patent documentation CN101456561, it at first is with the inorganic salt solution of aluminium and silicon sol according to a certain percentage behind the mix and blend, prepare again the mixing liquid of citric acid and ethylene glycol, and then with two kinds of liquid mixing, again through preparing nano mullite powder after three sections intensifications, the insulation, although the starting material wide material sources that this technical scheme adopts are easy to get, with low cost, low for equipment requirements, its preparation process is still very complicated; Several methods that prepare nano mullite powder are also disclosed respectively among patent documentation CN101700979A, CN101700980A, the CN101717262A for another example, although gained nano mullite size distribution is even, pattern is controlled, reaction time is short, good reproducibility, but it need to adopt the valuable raw materials such as aluminum nitrate and tetraethoxy, causes its production cost higher, is difficult to popularize.
Summary of the invention
The technical problem to be solved in the present invention is a kind of method for preparing nano mullite take aluminium powder and silicon sol as presoma, and this processing method is simple to operation, and equipment is few, invests littlely, and production cost is low, and efficient is high, and products obtained therefrom purity is high.
For solving the problems of the technologies described above, the technical solution used in the present invention is:
A kind of preparation method of mullite precursor may further comprise the steps:
(1) in situation about stirring, aluminium powder is added 0.2～0.6 molL
-1In the dilute hydrochloric acid solution, until till reaction soln became clear colorless solution by muddiness, wherein the mol ratio of dilute hydrochloric acid and aluminium powder was 3.01～3.05:1, makes liquor alumini chloridi;
(2) in situation about stirring, get a certain amount of distilled water and add 20～40
WtIn the silicon sol solution of %, be stirred to mixing, preparing concentration is 0.05～0.20 molL
-1Silicon sol;
(3) in situation about stirring, described liquor alumini chloridi is slowly added in the upper step gained silicon sol, and making aluminium, silicon mol ratio in the reaction soln is 3.0～3.2:1, be 0.5～2.0:100 adding copper zinc catalyst solution according to cupric ion and zine ion mole number sum and silicon mole ratio simultaneously, and under 30～40 ℃ temperature, stir 3.0～6.0h, then at 50～80 ℃ of lower 12～24h that place, utilize at last the Infrared Heating oven dry, collect dry thing, namely get mullite precursor; Described copper zinc catalyst solution can copper and the vitriol of zinc prepare, wherein the mol ratio of cupric ion and zine ion is 3～6:1, and the total concn of cupric ion and zine ion is 0.1～0.5 molL
-1
A kind of preparation method of nano mullite may further comprise the steps:
(1) prepares mullite precursor by above-mentioned preparation method;
(2) get step gained mullite precursor fine grinding after, place again the heating by electric cooker device with 5～20 ℃ of min
-1Temperature rise rate be heated to 1000 ℃～1200 ℃ the insulation 0.5～6.0h after, namely get nano mullite.
The present invention has actively useful effect:
The raw material sources that adopt are extensive, and price is low; Simple to operation, the safety of processing method, equipment is few, invest little, the production of founding the factory easily; Life cycle of the product is short, and efficient is high, and cost is low, and purity is high, and pattern is controlled, and good reproducibility can be produced as required.The particle diameter of the nano mullite of preparation mainly is distributed between 60～120nm.
Description of drawings
Fig. 1 is the process flow diagram that the inventive method prepares nano mullite;
Fig. 2, Fig. 4, Fig. 6 are respectively the XRD figure spectrum of the nano mullite of the different batches of preparing with the inventive method;
Fig. 3, Fig. 5, Fig. 7 are respectively the SEM collection of illustrative plates of the nano mullite of the different batches of preparing with the inventive method.
Embodiment
Further set forth the present invention below in conjunction with specific embodiment.Test method among the following embodiment if no special instructions, is ordinary method.Used test materials and reagent among the following embodiment, if no special instructions, all available from conventional chemical reagent shop.
The preparation method of 1 one kinds of nano mullites of embodiment may further comprise the steps:
Weighing 5.76 gram aluminium powders, and then slowly to put into 1290 ml concentration under the condition that stirs be 0.5 molL
-1In the hydrochloric acid soln, until after the complete reaction, slowly adding 1000ml concentration is 0.6 molL
-1In the silicon sol, adding simultaneously copper zinc catalyst solution 4ml(cupric ion and zine ion mol ratio is 6:1, and copper zinc total mol concentration is 0.3 molL
-1), and under 35 ℃ temperature, stir 4h, then at 80 ℃ of lower 16h that place, then with the Infrared Heating oven dry, will dry at last rear fine powder and put into electric furnace after levigate and be heated to 1150 ℃ (temperature rise rate is～5 ℃ of min
-1), and insulation 6h, can prepare nano mullite.XRD and the SEM of the nano mullite of preparation see respectively Fig. 2 and Fig. 3, and the particle diameter of nano mullite mainly is distributed between 60～120nm.
The preparation method of 2 one kinds of nano mullites of embodiment may further comprise the steps:
Weighing 2.70 gram aluminium powders, and then slowly to put into 1050ml concentration under the condition that stirs be 0.3 molL
-1In the hydrochloric acid soln, until after the complete reaction, slowly adding 667ml concentration is 0.05 molL again
-1In the silicon sol, (cupric ion and zine ion mol ratio are 3:1, and volumetric molar concentration is 0.5 molL to add simultaneously copper zinc catalyst solution
-1) 16ml, and under 40 ℃ temperature, stir 5h, then at 60 ℃ of lower 24h that place, then with the Infrared Heating oven dry, will dry at last rear gained powder and put into electric furnace after levigate and be heated to 1000 ℃ (temperature rise rate is～20 ℃ of min
-1), and be incubated 0.5 h, namely get nano mullite.XRD and the SEM of the nano mullite of preparation see respectively Fig. 4 and Fig. 5, and the particle diameter of nano mullite mainly is distributed between 60～100nm.
The preparation method of 3 one kinds of nano mullites of embodiment may further comprise the steps:
Weighing 5.58 gram aluminium powders, and then slowly to put into 1040 ml concentration under the condition that stirs be 0.6 molL
-1In the hydrochloric acid soln, until after the complete reaction, slowly adding 1000ml concentration is 0.6 molL
-1In the silicon sol, (cupric ion and zine ion mol ratio are 5:1, and volumetric molar concentration is 0.1 molL to add simultaneously copper zinc catalyst solution
-1) 4ml, and under 30 ℃ temperature, stir 3h, then at 75 ℃ of lower 12h that place, then with the Infrared Heating oven dry, will dry at last rear fine powder and put into electric furnace after levigate and be heated to 1200 ℃ (temperature rise rate is～10 ℃ of min
-1), and insulation 5h, can prepare nano mullite.XRD and the SEM of the nano mullite of preparation see respectively Fig. 6 and Fig. 7, and the particle diameter of nano mullite mainly is distributed between 80～120nm.
Although above the present invention is described in detail with a general description of the specific embodiments, on basis of the present invention, can make some modifications or improvements it, this will be apparent to those skilled in the art.Therefore, these modifications or improvements all belong to the scope of protection of present invention without departing from theon the basis of the spirit of the present invention.
Claims (3)
1. the preparation method of a mullite precursor may further comprise the steps:
(1) in situation about stirring, gets aluminium powder and add 0.2～0.6 molL
-1In the dilute hydrochloric acid solution, until till reaction soln becomes clear colorless solution by muddiness, keep dilute hydrochloric acid excessive in the reaction process, make liquor alumini chloridi;
(2) in situation about stirring, get a certain amount of distilled water and add 20～40
WtIn the silicon sol solution of %, be stirred to mixing, preparing concentration is 0.05～0.20 molL
-1Silicon sol;
(3) in situation about stirring, described liquor alumini chloridi is slowly added in the upper step gained silicon sol, and making aluminium, silicon mol ratio in the reaction soln is 3.0～3.2:1, simultaneously according to cupric ion and zine ion mole number sum: silicon mole number=0.5～2.0:100 adds copper zinc catalyst solution, and under 30～40 ℃ temperature, stir 3.0～6.0h, then at 50～80 ℃ of lower 12～24h that place, utilize at last the Infrared Heating oven dry, collect dry thing, namely get mullite precursor; The mol ratio of cupric ion and zine ion is 3～6:1 in the described copper zinc catalyst solution, and the total concn of cupric ion and zine ion is 0.1～0.5 molL
-1
2. the preparation method of mullite precursor according to claim 1 is characterized in that, in described step (1), and the excessive 0.01～0.05mol of dilute hydrochloric acid.
3. the preparation method of a nano mullite may further comprise the steps:
(1) prepares mullite precursor by claim 1 or 2 described preparation methods;
(2) get step gained mullite precursor fine grinding after, place again the heating by electric cooker device with 5～20 ℃ of min
-1Temperature rise rate be heated to 1000 ℃～1200 ℃ the insulation 0.5～6.0h after, namely get nano mullite.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05105419A (en) * | 1991-05-24 | 1993-04-27 | Chichibu Cement Co Ltd | Production of spherical ceramic powder |
| CN101456561A (en) * | 2008-12-25 | 2009-06-17 | 浙江科技学院 | Method for preparing nano mullite powder |
| CN102503387A (en) * | 2011-09-27 | 2012-06-20 | 中国地质大学（武汉） | Method for preparing high-purity super-fine mullite powder |
-
2012
- 2012-11-28 CN CN201210493835.6A patent/CN102963896B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05105419A (en) * | 1991-05-24 | 1993-04-27 | Chichibu Cement Co Ltd | Production of spherical ceramic powder |
| CN101456561A (en) * | 2008-12-25 | 2009-06-17 | 浙江科技学院 | Method for preparing nano mullite powder |
| CN102503387A (en) * | 2011-09-27 | 2012-06-20 | 中国地质大学（武汉） | Method for preparing high-purity super-fine mullite powder |
Non-Patent Citations (4)
| Title |
|---|
| A.K.CHAKRAVORTY: "Effect of pH on 980℃ spine phase-mullite formation of Al2O3-SiO2 gels", 《JOURNAL OF MATERIALS SCIENCE》 * |
| BISWAJOY BAGCHI ET AL.: "Nanocrystalline Mullite Synthesis at a Low Temperature: Effect of Copper Ions", 《JOURNAL OF THE AMERICAN CERAMIC SOCIETY》 * |
| BISWAJOY BAGCHI ETAL.: "Effect of nickel and cobalt ions on low temperature synthesis of mullite by sol-gel technique", 《JOURNAL OF SOL-GEL SCIENCE AND TECHNOLOGY》 * |
| ERNO E.KISS ETAL.: "INFLUENCE OF TRANSITION METAL IONS ON THE TEXTURAL PROPERTIES OF ALUMINA AND ALUMINASILICATES", 《REACTION KINETICS AND CATALYSIS LETTERS》 * |
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