CN1296311C - Method for preparing mullite nano powder using alumine as raw material - Google Patents
Method for preparing mullite nano powder using alumine as raw material Download PDFInfo
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- CN1296311C CN1296311C CN 200410060213 CN200410060213A CN1296311C CN 1296311 C CN1296311 C CN 1296311C CN 200410060213 CN200410060213 CN 200410060213 CN 200410060213 A CN200410060213 A CN 200410060213A CN 1296311 C CN1296311 C CN 1296311C
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Abstract
The present invention provides a method for synthesizing mullite nanometer powder, which takes natural bauxite of which the storage capacity is abundant in China as raw materials which are roasted in the temperature of 800 to 1200 DEG C and are prepared into the mullite nanometer powder by a water heating method. The present invention has the characteristics of cheap raw material, low reacting temperature, simple method and low productive cost. The purity of obtained mullite is high, and the contents of the mullite are above 80%. The agglomeration of powder is small, crystal grains of the powder is less than 40 nm, and secondary particle diameter is less than 200 nm. The mullite nanometer powder prepared by the present invention has good performance and can be widely used for a plurality of fields, such as metallurgy, ceramic, electron, etc. The present invention can greatly improve the added value of bauxite products, and reduce the preparing cost of the mullite nanometer powder.
Description
Affiliated field
The present invention relates to a kind of preparation method of ceramic powder, be specifically related to a kind of preparation method by bauxitic clay hydro-thermal mullite synthesizing nano-powder.
Background technology
Mullite itself has many excellent physical properties, as: low-expansion coefficient, low thermal conductance, low creep, low-k, high heat shock resistance and hot strength etc.These characteristics of mullite make it be used widely in various fields such as refractory materials, high-temperature structural material, microelectronic packaging material, optical material and dielectric and high temperature protection coating, and important industrial value is arranged.And nano-powder is little owing to size, and surface atom accounts for sizable ratio, thereby the surface energy height, has high activity, and the more conventional powder of its fusing point and sintering temperature is much lower; It is incorporated in refractory materials, the high-temperature structural material as additive, is expected to improve its sintering character and microstructure, thereby influence the mechanical property of such material consumingly.
Employed mullite grog in refractory industry is to be raw material with the natural mineral mostly, adopts sintering process and electric smelting method synthetic.Common natural mineral raw has superfine green coke jewel, alumina fine fodder, Suzhou soil, kaolinite, coal gangue, and kyanite, andaluzite, sillmanite etc.In order to regulate the Al of raw material
2O
3/ SiO
2Ratio, the general ways such as adding silica powder, commercial alumina or its middle product aluminium hydroxide that adopts.Technical process with the natural matter mullite synthesizing has bigger variation with raw materials used difference, but generally can be divided into two big classes, promptly wet method and dry method (Zhong Xiangchong: " and DEVELOPMENTS OF REFRACTORY RAW MATERIALS IN CHINA. silicate circular ", 1997,4:45-46; Wang Zetian, Yan Hangjian: " Zhong Xiangchong refractory materials selected theses ", metallurgical industry press, 1991,12:118-119).
Wet process is: batching-mixing fine grinding (wet method)-pickling deironing-filtration-drying-briquetting-burn till (electric smelting)-grog.
The dry method flow process is: batching-mixing fine grinding (dry method)-electromagnetism deironing-briquetting-drying-burn till (electric smelting)-grog.
The preparation method of the mullite nano powder of document record mainly is:
1, sol-gel method (is reined in and is liked sea etc.: " sol-gel method prepares mullite powder ", Journal of Inorganic Materials, 2001,5:555-558): utilize the single-phase precursor of metal alkoxide Prepared by Sol Gel Method mullite, with the mullite collosol and gelization, the calcining of drying and grinding gel obtains the mullite nano powder then; Or employing Al
2O
3Colloidal sol and SiO
2Than being modulated to colloidal sol, ageing is converted into gel to colloidal sol then according to the metering of mullite chemistry, grinds and calcine to obtain the mullite nano powder; Or utilize Al
2O
3Colloidal sol and SiO
2The colloidal sol that colloidal sol mixes is hydro-thermal mullite synthesizing presoma in autoclave, and calcining obtains then.These three kinds of methods are all relevant with sol-gel processing, adopt alkoxide or colloidal sol as raw material, and deficiency is that the production cycle is long, and the cost height is difficult for industrialization.
2, hydrothermal method: mostly adopt with the same raw material of sol-gel method carry out hydrothermal crystallizing prepare the mullite precursor dry then, grind, calcining makes (C.Kaya, J.Y.He: " Nanostructured ceramicpowders by hydrothermal synthesis and their applications ", Microporousand Mesoporous Materials54 (2002): 37-49; T.R.N Kutty, M.Nayak: " Photoluminescence of Eu2+-doped mullite (xAl2O3ySiO2; X/y=3/2and2/1) prepared by a hydrothermal method ", Materials Chemistry and Physics65 (2000): 158-165); Also have and utilize (Wang Yinye etc.: " principal crystalline phase be preparation, structural characterization and the performance test of mullite composite nanocrystalline ", Chinese Journal of Chemical Physics, 2001,4) of kaolin Hydrothermal Preparation principal crystalline phase for the mullite composite nanocrystalline.With this method synthetic mullite powder is micro mist but not nano-powder, and mullite content is lower.
3, high-temperature spray cracking metal-salt method: this method adopts the organic slat solution of aluminium and silicon to spray in inert gas carrier and the synthetic (P.Murugavel etc.: " Preparation and characterizationof sub-micron spherical particles of Al2O3 that make, SiO2and mullite ", MaterialsChemistry and Physics 53 (1998): 247-251); It is reported the mullite particulate (M.Ocana etc.: " Preparation by pyrolysis ofaerosols and structural characterization of Fe-doped mullite powders ", Materials Research Bulletin 35 (2000): 775-788) that can under low temperature (673K), synthesize 0.2 ~ 0.6um; Also there is report to adopt natural topaz hot gas to decompose (X.Miao: " Porous mullite cermics fromnatural topaz ", Materials Letters 38 1999:167-172) of system porous mullite.
4, (S.Bhattacharjee etc.: Preparation of zirconiatoughened mullite by thermal plasma.Materials Letters 43 (2000): 77-80): this method is usually used in synthetic zirconium hardened mullite (ZTM) to the hot solution plasma method.
5, salt scorification: aluminium salt and silicon sol are pressed the mixed mullite miropowder (L.Saadi etc.: " Synthesis of Mullite Precursors in MoltenSalts.Influence of the Molten Alkali Nitrate and Additives ", Journal ofthe European Ceramic Society 19 (1999): 517-520) of getting of stoichiometric ratio in fused sodium and sylvite.
Summary of the invention
The objective of the invention is with the abundant natural alumina of reserves is raw material, add the phase transformation auxiliary agent, utilize the characteristics of hydrothermal solution, through specific technology crystal growth, the development mullite nano powder that synthesis technique is simple, cost is low, added value is high improves the value of bauxitic clay greatly.
Technical scheme of the present invention is:
The preparation method of alumina base mullite nano-powder is a main raw material with the alumine, adopts Hydrothermal Preparation technology, the steps include:
A. the hydrochloric acid soln that with alumine and hydrochloric acid and vitriolic mixed acid solution or concentration is 10-36% mixes, and under agitation is heated to 40-80 ℃, constant temperature 1-10 hour, leaves standstill 1-3 days, then water thorough washing, suction filtration, oven dry;
B. with the alumine 95-100 part after the pickling deironing, mullite seed 1-5 part, ground altogether 1-2 hour, then at 500-600 ℃ of following preroasting 1-3 hour, through 800-1200 ℃ of roasting 2-8 hour, levigate again;
C. with the alumine 3-7 part after the roasting, be equipped with an amount of mineralizer, 100 parts of solvents, add 0.1-0.4 part dispersion agent again, put into autoclave after fully stirring, be warming up to 100-200 ℃, be incubated 2-10 hour and carry out hydro-thermal reaction, take out, the suction filtration washing, remove mineralizer and dissolved metal ion, further alcohol is washed, suction filtration, places 100 ℃ of following temperature dry then, grind, promptly get product.
In above-mentioned preparation method, alumine is raw material, and the mass percent of main component is after its calcination: Al
2O
350-85%, SiO
25-30%, Fe
2O
30.5-2.5%, TiO
22.5-4%; Alumine after the roasting is levigate to D
90≤ 10 μ m; Mixing acid is that the sulfuric acid of the hydrochloric acid of concentration 10-36% and concentration 40-60% mixes according to 1: 1 volume ratio; The add-on of acid solution is counted the 50-150% of alumine weight with HCl.Used mineralizer is NaOH or NaCl, and its concentration is respectively 0.2-2.0mol/L and 0.3～2.6mol/L.Solvent for use is the deionized water that contains ammoniacal liquor 0-50% massfraction.Used dispersion agent is ethanol, polyacrylate, poly-methyl acrylate, polyoxyethylene glycol, the basic sodium sulfonate of dodecane, one or more in the polycarboxylate ether.
Compared with prior art, the invention has the advantages that:
1, raw material of the present invention is cheap, and temperature of reaction is low, and method is simple, and production cost is low.
2, the mullite purity that obtains is higher, and the content of mullite is more than 80%.
3, little with synthetic mullite nano powder reuniting of the present invention, aggregate particle size＜200nm.
Embodiment
Below in conjunction with embodiment the present invention is further described, but is not limited to the following example.
Embodiment 1
Raw material: alumine, its chemical constitution such as table 1.
Table 1
| Form (after the calcination) | Al 2O 3 | SiO 2 | Fe 2O 3 | CaO | MgO | TiO 2 | Na 2O |
| Wt％ | 68.08 | 26.82 | 0.55 | 0.08 | 0.85 | 1.97 | 1.64 |
Alumine pickling deironing: take by weighing an amount of alumine, adding concentration is 15% hydrochloric acid soln, and its add-on is 60% of an alumine weight, is heated to 50 ℃ of insulations 6 hours, stirs simultaneously; It is left standstill 3 days then; Suction filtration and water thorough washing, oven dry.
Roasting: get 97 parts of alumines, 3 parts of mullite seeds after the pickling, the common grinding 1 hour put into the roasting of globars electric furnace in ball mill, 520 ℃ of insulations 3 hours, again through 1000 ℃ of insulations 8 hours; Alumine after the roasting is levigate to D
90≤ 6 μ m.
Hydrothermal Preparation mullite nano powder: with 4 parts of the bauxitic clays after the roasting, be equipped with 100 parts of deionized waters that contain ammoniacal liquor 20% massfraction, add NaOH (concentration is 0.6mol/L), the deionized water that adds 0.2 part of dodecane 20% massfraction again adds NaOH (concentration is 0.6mol/L), adds 0.2 part of Sodium dodecylbenzene sulfonate again and makes dispersion agent, put into autoclave (compactedness is 70%) after fully stirring, sealing is warmed up to 160 ℃, is incubated 8 hours and carries out hydro-thermal reaction; Product is taken out in the cooling back from reactor, carry out the suction filtration washing repeatedly, further with washing with alcohol, suction filtration, to improve the dispersiveness of powder; Place under 100 ℃ of temperature dryly then, the filter cake behind the mill-drying, obtain the alumina base mullite nano-powder.
Through XRD analysis, the product principal crystalline phase is a mullite, and other has a small amount of Al
2O
3Phase.If be approximately the content of each thing phase with the integral area of various thing phase highest peaks, the relative content of mullite can reach more than 80%.The grain fineness number of product is 53.9nm, median size 110nm, aggregate particle size distribution range 9.5～178nm in the present embodiment.
Embodiment 2
Raw material: alumine chemical constitution such as table 2.
Table 2
| Form (after the calcination) | Al 2O 3 | SiO 2 | Fe 2O 3 | TiO 2 | MgO | CaO | Na 2O |
| Wt％ | 81.66 | 10.03 | 0.54 | 3.56 | 1.77 | 0.46 | 1.53 |
Take by weighing an amount of alumine, the hydrochloric acid of the concentration 30% of 1: 1 by volume proportioning of adding and the vitriolic mixed acid solution of concentration 60%, its add-on is 100% (in HCl) of alumine weight, is heated to 80 ℃ of insulations 1 hour, stirs simultaneously; It is left standstill 1 day then; Powder is dried, ground to form to suction filtration and water thorough washing.
Get 5 parts of 95 parts of alumines after the pickling and mullite seeds, ground altogether 2 hours, 550 ℃ of preroastings 1 hour, 1140 ℃ of roastings 6 hours; Alumine after the roasting is levigate to D
90≤ 8 μ m.
With 6 parts of the bauxitic clays after the roasting, be equipped with 100 parts of deionized waters that contain ammoniacal liquor 10% massfraction, add NaOH (concentration is 1.2mol/L), the ammonium polyacrylate that adds 0.2 part is again made dispersion agent, put into autoclave (compactedness is 80%) after fully stirring, sealing is warmed up to 140 ℃, is incubated 6 hours and carries out hydro-thermal reaction; Product is taken out in the cooling back from reactor, carry out the suction filtration washing repeatedly, and further alcohol is washed, suction filtration; Place 100 ℃ of following temperature dry, the filter cake behind the mill-drying, obtain the alumina base mullite nano-powder.
Through XRD analysis, the product principal crystalline phase is a mullite, and other has a small amount of Al
2O
3Phase.If be approximately the content of each thing phase with the integral area of various thing phase highest peaks, the relative content of mullite can reach more than 80%.The grain fineness number 53.9nm of product and mean particle size 110nm in the present embodiment, aggregate particle size distribution range 17～410nm.
Embodiment 3
Raw material: alumine, chemical ingredients such as table 3.
Table 3
| Form (after the calcination) | Al 2O 3 | SiO 2 | Fe 2O 3 | TiO 2 | MgO | CaO | Na 2O |
| Wt％ | 57.72 | 20.69 | 2.16 | 2.68 | 1.39 | 0.51 | 1.73 |
Take by weighing an amount of alumina, it is an amount of to add concentration and be 30% hydrochloric acid, and its add-on is 120% of an alumine weight, is heated to 70 ℃ of insulations 2 hours, stirs simultaneously; It is left standstill 2 days then; Powder is dried, ground to form to suction filtration and water thorough washing.
Get 2 parts of 98 parts of alumines after the pickling and mullite seeds, ground altogether 2 hours, 560 ℃ of preroastings 2 hours, 1200 ℃ of roastings 3 hours; Alumina after the roasting is levigate to D
90≤ 10 μ m.
With 5 parts of the bauxitic clays after the roasting, be equipped with 100 parts of deionized waters that contain ammoniacal liquor 50% massfraction, add NaCl (concentration is 2.0mol/L), the polyoxyethylene glycol that adds 0.4 part is again made dispersion agent, puts into autoclave (compactedness is 85%) after fully stirring, sealing, be warmed up to 180 ℃, be incubated 3 hours and carry out hydro-thermal reaction, product is taken out in the cooling back from reactor, carry out the suction filtration washing repeatedly, further alcohol is washed, suction filtration; Be lower than under 100 ℃ of temperature dryly, the filter cake behind the mill-drying, obtaining the alumina base mullite nano-powder.
Through XRD analysis, the product principal crystalline phase is a mullite, and other has a small amount of Al
2O
3Phase.If be approximately the content of each thing phase with the integral area of various thing phase highest peaks, the relative content of mullite can reach more than 80%.The grain fineness number 58.4nm of product and median size 170nm aggregate particle size distribution range 17.4nm～583nm in the present embodiment.
Claims (4)
1, the preparation method of alumina base mullite nano-powder is a main raw material with alumine, mullite seed, adopts Hydrothermal Preparation technology, it is characterized in that:
A. the hydrochloric acid soln that with alumine and hydrochloric acid and vitriolic mixed acid solution or concentration is 10-36% mixes, under agitation be heated to 40-80 ℃, constant temperature 1-10 hour, left standstill 1-3 days, water thorough washing, suction filtration, oven dry then, wherein, mixing acid is that the sulfuric acid of the hydrochloric acid of concentration 10-36% and concentration 40-60% mixes according to 1: 1 volume ratio, and the add-on of acid solution is counted the 50-150% of alumine weight with HCl;
B. with the alumine 95-100 part after the pickling deironing, mullite seed 1-5 part, ground altogether 1-2 hour, then at 500-600 ℃ of following preroasting 1-3 hour, through 800-1200 ℃ of roasting 2-8 hour, levigate again;
C. with the alumine 3-7 part after the roasting, be equipped with an amount of mineralizer, 100 parts
Solvent adds 0.1-0.4 part dispersion agent again, puts into autoclave after fully stirring, be warming up to 100-200 ℃, be incubated 2-10 hour and carry out hydro-thermal reaction, take out, mineralizer and dissolved metal ion are removed in the suction filtration washing, and further alcohol is washed, suction filtration, place 100 ℃ of following temperature dry then, grind, promptly get product, wherein, mineralizer is NaOH or NaCl, and its concentration is respectively 0.2-2.0mol/L and 0.3～2.6mol/L, and solvent is the deionized water that contains ammoniacal liquor 0-50% massfraction.
2, according to the preparation method of the described alumina base mullite nano-powder of claim 1, it is characterized in that: alumine is raw material, and the mass percent of main component is after its calcination: Al
2O
350-85%, SiO
25-30%, Fe
2O
30.5-2.5%, TiO
22.5-4%.
3, according to the preparation method of the described alumina base mullite nano-powder of claim 1, it is characterized in that: the alumine after the roasting is levigate to D
90≤ 10 μ m.
4, according to the preparation method of the described alumina base mullite nano-powder of claim 1, it is characterized in that: described dispersion agent is one or more in ethanol, polyacrylate, poly-methyl acrylate, polyoxyethylene glycol, Sodium dodecylbenzene sulfonate and the polycarboxylate ether.
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