CN102583411B - Method for producing mullite by using fly ash - Google Patents
Method for producing mullite by using fly ash Download PDFInfo
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- CN102583411B CN102583411B CN201210005536.3A CN201210005536A CN102583411B CN 102583411 B CN102583411 B CN 102583411B CN 201210005536 A CN201210005536 A CN 201210005536A CN 102583411 B CN102583411 B CN 102583411B
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Abstract
The invention relates to a method for producing mullite by using fly ash, relating to the technical field of comprehensive utilization of solid wastes and synthesis of refractory materials. According to the method, the solid waste fly ash is used as a raw material, and the mullite is prepared by pretreating, desiliconizing, pickling, desiliconizing for the second time and calcinating. Compared with the prior art, the method has the characteristics of wide raw material sources, no addition of aluminum source raw materials, high adaptability of the raw materials, high mullite yield, high quality, low production cost, low energy consumption, no secondary solid pollutants, obvious economic benefit and environmental benefit and the like.
Description
Technical field
The synthesis technical field that the present invention relates to refractory materials, concrete, the present invention relates to the production method of mullite.
Background technology
Mullite (3Al
2o
32SiO
2) be the alumina hydrochlorate mineral of aluminium, be Al
2o
3-SiO
2the crystalline compound of system unique stable existence under normal pressure, there is the advantages such as refractoriness is high, heat-shock resistance, chemical resistance of concrete, creep-resistant property is good, refractoriness under load is high, volume stability is good, electrical insulating property is strong, be desirable high grade refractory, be widely used in the industry such as metallurgy, glass, pottery, chemistry, electric power, national defence, combustion gas and cement.
Seldom, industrial mullite is mainly synthetic and obtains the natural mullite mineral of occurring in nature.In prior art, the method for mullite synthesizing mainly contains electric smelting method and sintering process.
Electric smelting method is that the melting in electric arc of mixed raw material is formed, for example CN 1974475A discloses the manufacture method of the electrofused mullite of a kind of pottery and fire resisting material field, concrete steps are: (1) the first step is the preprocessing process of aluminium ash, at 1100 ℃, carry out calcination and process aluminium scrap ash, make metal A l wherein partly be transformed into Al
2o
3, the aluminium ash after calcination is put into tank, add hydrochloric acid to clean, the aluminium ash of pickling is dried; (2) second step is electric smelting process, take aluminium ash, alumina and silica is raw material, aluminium ash, alumina and silica are respectively 30～80%: 0～50% by weight percentage: proportioning in 10～20% scope, mix, add in electric arc furnace, melting, pour out cooling, broken pulverizing, sorting, obtain mullite, it is main raw material(s) that this invention adopts wasted aluminium ash, is equipped with bauxitic clay and silica and produces electrofused mullite material, has both reduced the cost of mullite, consumed again the wasted aluminium ash that easily causes environmental pollution, shortcoming is that current consumption is large, synthesis condition is harsh.
Sintering process can be divided into silica-alumina gel method and mineral facies political reform according to raw materials used different in kind.Wherein silica-alumina gel method is to adopt respectively inorganic and organic raw material to make sial colloid according to certain chemical constitution, and then at high temperature roasting forms.Shortcoming is that energy consumption is higher, and organic raw material is expensive.Mineral facies political reform is to form with natural mineral high-temperature calcinations in kiln such as alumine, kaolin, agalmatolite, flint claies, for example CN1312237 A discloses a kind of method of synthetic mullite, and it is that one or more materials of take in alumine, kaolin, clay, silica, aluminum oxide are raw material, through selecting materials, coupling, pulverize, moulding, dry, burn till, cooling, the method synthetic mullite burning till with kiln, the production cost of this invention is 10%～40% of electric furnace electric smelting method, the indices of product approaches and reaches the index of the mullite of electric furnace electric smelting method production, widespread use for mullite, the body of heater quality that particularly comprehensively improves high temperature smelting furnace provides condition, there is material choice wide ranges, the feature that production cost is low, the shortcoming of the method is except energy consumption height, also owing to having larger difference between its mineral composition and mullite composition, cause mullite transformation efficiency not high, waste resource.
Also there is technology to adopt flyash to mix a certain amount of bauxitic clay or technical grade aluminum oxide obtains mullite through high-temperature calcination.Flyash, is in the flue gas from coal combustion, to receive the thin ash of catching, and flyash is the main solid waste that coal-burning power plant discharges.The main oxides of power plants flyash consists of: SiO
2, Al
2o
3, FeO, Fe
2o
3, CaO, TiO
2deng.Flyash is one of industrial residue that the current discharge capacity of China is larger, and along with the development of power industry, the flyash quantity discharged of coal-burning power plant increases year by year.A large amount of flyash does not add processing, will produce airborne dust, atmosphere pollution; If enter water system, can cause river to silt up, and toxic chemical substance wherein also can work the mischief to human body and biology.CN 101643359A discloses a kind of coal ash for manufacturing that utilizes for the method for porzite powder, and flyash and bauxitic clay raw material are put into respectively to deironing after ball mill for dry grinding; Flyash and bauxitic clay after the deironing of learning from else's experience is processed are put into respectively alumina crucible, and alumina crucible is placed in globars resistance furnace and is heated, and after naturally cooling, take out; Flyash after naturally cooling and bauxitic clay are stirred, and take out after being placed in the rear naturally cooling of the interior heating of globars resistance furnace, obtain the porzite powder of different grain size and alumina content.This invention is that the solid waste coal ash of coal-burning power plant's discharge is carried out mullite synthesizing, not only contributes to save natural resource, reduces production costs, and is conducive to environment protection; Preparation temperature is low, has avoided high-temperature calcination, has saved mineral wealth and the energy; By controlling the add-on of bauxitic clay, regulate proportioning raw materials, can synthesize the mullite aggregate of different alumina contents.The shortcoming of the method is that in the raw material mixing, technical grade price of aluminium oxide is higher, and bauxitic clay, fireclay resource are deficient gradually simultaneously, are subject to market and policy implication larger.
Summary of the invention
For the deficiencies in the prior art, one of object of the present invention is to provide a kind of method of utilizing flyash to produce mullite, have raw material sources wide, without adding aluminium source raw material, the feature such as adaptability to raw material is strong, mullite productive rate is high, quality better, production cost is low, energy consumption is little, do not produce secondary solid pollutent, economy and obvious environment benefit.
The described method of utilizing flyash to produce mullite, comprises the following steps:
(1) flyash is ground to screening, magnetic separation;
(2) flyash after magnetic separation is mixed to reaction desiliconization with strong base solution;
(3) desiliconization flyash step (2) being obtained mixes with strong acid solution, pickling impurity removal;
(4) flyash step (3) being obtained mixes with strong base solution, the desiliconization of reaction secondary;
(5) flyash roasting step (4) being obtained, obtains mullite.
Preferably, described in step (1), grind preferably dry grinding, particularly preferably adopt ball mill dry grinding; Preferred spheres grinding media is a kind or the combination of at least 2 kinds in zirconium oxide balls, wolfram varbide abrading-ball, aluminum oxide abrading-ball, is particularly preferably aluminum oxide abrading-ball; Preferably abrading-ball is 1: 1～5: 1 with flyash quality ratio, more preferably 2: 1～4: 1, is particularly preferably 2: 1～3: 1; The preferred described dry grinding time is more than 0.5h, such as 0.6h, 0.8h, 0.9h, 1h, 1.05h, 1.1h, 4.1h, 5h, 6h, 8h, 9h, 9.95h, 10h etc., and 0.7～10h more preferably, more preferably 0.8～6h, is particularly preferably 1～4h.
Preferably, described in step (1), screening was 40～500 mesh sieves, more preferably crossed 50～400 mesh sieves, more preferably crossed 60～350 mesh sieves, particularly preferably crossed 60～320 mesh sieves.
Preferably, in step (1), after being mixed with water, flyash after screening carries out magnetic separation, further preferred powder coal ash and water are 0.5: 1～10: 1 by liquid-solid mass ratio, such as 0.6: 1,0.8: 1,1: 1,1.1: 1,1.2: 1,1.5: 1,2: 1,4: 1,4.5: 1,9: 1,9.5: 1,9.9: 1 etc., more preferably 1: 1～8: 1, be particularly preferably 1: 1～5: 1; Preferably magneticstrength is 100～5000mT, for example, 100mT, 101mT, 102mT, 110mT, 199mT, 201mT, 1999mT, 2000mT, 2001mT, 4959mT, 4999mT, 5000mT etc., more preferably 150～3000mT, is particularly preferably 200～2000mT; Preferred described magnetic separation is carried out in magnetic separator; Preferably magnetic separator drum speed is 10～100rmin
-1, 15～80rmin more preferably
-1, be particularly preferably 20～60rmin
-1.
Preferably, highly basic described in step (2) is for carrying out any alkali of desilication reaction, its typical but non-limiting example has: sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, calcium hydroxide, strontium hydroxide, hydrated barta, mercuric hydroxide, thallous hydroxide, thallic hydroxide, silver diamminohydroxide, 1 kind or the combination of at least 2 kinds in choline, be preferably sodium hydroxide, potassium hydroxide, 1 kind or the combination of at least 2 kinds in calcium hydroxide, described combination typical case but the example of non-limit have: sodium hydroxide, the combination of potassium hydroxide, potassium hydroxide, the combination of calcium hydroxide, sodium hydroxide, potassium hydroxide, the combination of calcium hydroxide etc., sodium hydroxide more preferably, a kind of or its combination in potassium hydroxide, be particularly preferably sodium hydroxide.
Preferably, described in step (2), the solvent of strong base solution is preferably water.
Preferably, described in step (2), strong base solution mass concentration is 2%～50%, such as 2.1%, 2.2%, 4.9%, 29%, 29.9%, 30.1%, 48%, 49%, 49.9% etc., more preferably 3%～40%, be particularly preferably 5%～30%.
Preferably, described in step (2), flyash and strong base solution are 0.2: 1～18: 1 by liquid-solid mass ratio, such as 0.21: 1,0.22: 1,0.25: 1,0.49: 1,0.51: 1,8.9: 1,8.99: 1,9.1: 1,14: 1,14.9: 1,14.99: 1 etc., more preferably 0.3: 1～15: 1, more preferably 0.4: 1～11: 1, be particularly preferably 0.5: 1～9: 1.
Preferably, react desiliconization and carry out under whipped state described in step (2), further preferred described stir speed (S.S.) is 50～1000rmin
-1, 51rmin for example
-1, 52rmin
-1, 55rmin
-1, 149rmin
-1, 151rmin
-1, 745rmin
-1, 749rmin
-1, 990rmin
-1, 995rmin
-1, 999rmin
-1deng, 100～850rmin more preferably
-1, be particularly preferably 150～750rmin
-1.
Preferably, described in step (2), reacting desiliconization temperature is room temperature～250 ℃, such as 25 ℃, 30 ℃, 90.1 ℃, 91 ℃, 149 ℃, 220 ℃, 240 ℃, 245 ℃, 249 ℃, 249.5 ℃ etc., more preferably 40～200 ℃, more preferably 70～170 ℃, be particularly preferably 90～150 ℃.
Preferably, it is more than 0.2h described in step (2), reacting desiliconization time, such as 0.21h, 0.22h, 0.25h, 0.51h, 11.9h, 23h, 23.5h, 23.9h etc., more preferably 0.3～24h, more preferably 0.4～18h, is particularly preferably 0.5～12h.
Preferably, flyash after desiliconization described in step (2) is filtered, and enter again step (3) after washing, further preferably water is washed till pH=7～9, such as pH=7.05, pH=7.1, pH=7.2, pH=7.5, pH=7.9, pH=7.95, pH=8.9, pH=8.95, pH=8.99 etc., more preferably be washed to pH=7～8.5, be particularly preferably washed to pH=7～8; The solid mass ratio of preferred described water lotion is 0.5: 1～10: 1, such as 0.6: 1,0.8: 1,1: 1,1.1: 1,1.2: 1,1.5: 1,2: 1,4: 1,4.5: 1,9: 1,9.5: 1,9.9: 1 etc., more preferably 1: 1～8: 1, be particularly preferably 1: 1～5: 1.
Preferably, in step (3), described strong acid is for carrying out any acid of removal of impurities reaction, be preferably inorganic acid, its typical but non-limiting example has: sulfuric acid, nitric acid, perchloric acid, hydrochloric acid, Hydrogen bromide, hydroiodic acid HI, the acid of hydrogen astatine, hydrogen telluric acid, hyperbromic acid, hydrogen is folded acid iodide, chloric acid, bromic acid, silicofluoric acid, chlorine plumbic acid, metaphosphoric acid, osmic acid, permanganic acid, selenic acid, ferric acid, hydrogen borate, fluosulfonic acid, cyanic acid, 1 kind or the combination of at least 2 kinds in thiocyanic acid, described combination typical case but the example of non-limit have: sulfuric acid, the combination of nitric acid, perchloric acid, hydrochloric acid, hydrobromic combination, sulfuric acid, nitric acid, perchloric acid, the combination of hydrochloric acid etc., hydrochloric acid more preferably, sulfuric acid, permanganic acid, nitric acid, perchloric acid, 1 kind or its combination in chloric acid, sulfuric acid more preferably, nitric acid, 1 kind or its combination in hydrochloric acid, be particularly preferably hydrochloric acid.
Preferably, described in step (3), strong acid solution mass concentration is 2%～50%, such as 2.1%, 2.2%, 4.9%, 29%, 29.9%, 30.1%, 48%, 49%, 49.9% etc., more preferably 3%～40%, be particularly preferably 5%～30%.
Preferably, described in step (3), strong acid solution is strong aqueous acid.
Preferably, described in step (3), flyash and strong acid solution are 0.5: 1～10: 1 by liquid-solid mass ratio, such as 0.6: 1,0.8: 1,1: 1,1.1: 1,1.2: 1,1.5: 1,2: 1,4: 1,4.5: 1,9: 1,9.5: 1,9.9: 1 etc., more preferably 1: 1～8: 1, be particularly preferably 1: 1～5: 1.
Preferably, in step (3), pickling impurity removal reaction is carried out under whipped state, and further preferred described stir speed (S.S.) is 50～1000rmin
-1, 51rmin for example
-1, 52rmin
-1, 55rmin
-1, 149rmin
-1, 151rmin
-1, 745rmin
-1, 749rmin
-1, 990rmin
-1, 995rmin
-1, 999rmin
-1deng, 100～850rmin more preferably
-1, be particularly preferably 150～750rmin
-1.
Preferably, in step (3), pickling impurity removal reaction is carried out at 10～150 ℃, such as 10.5 ℃, 11 ℃, 12 ℃, 19 ℃, 50 ℃, 90 ℃, 110 ℃, 140 ℃, 145 ℃, 149 ℃, 149.5 ℃ etc., more preferably 15～120 ℃, more preferably 18～110 ℃, be particularly preferably 20～95 ℃.
Preferably, in step (3), the pickling impurity removal reaction times is more than 0.2h, such as 0.21h, 0.22h, 0.25h, 0.31h, 1h, 2h, 5h, 10h, 13h, 23h, 23.5h, 23.9h, 24h etc., 0.3～24h more preferably, more preferably 0.4～18h, is particularly preferably 0.5～12h.
Preferably, flyash after step (3) removal of impurities is filtered, and enter again step (4) after washing, further preferably water is washed till pH=5～7, such as pH=5.01, pH=5.05, pH=5.1, pH=5.2, pH=5.9, pH=6.9, pH=6.99 etc., more preferably be washed to pH=5.5～7, be particularly preferably washed to pH=6～7; The solid mass ratio of preferred described water lotion is 0.5: 1～10: 1, such as 0.6: 1,0.8: 1,1: 1,1.1: 1,1.2: 1,1.5: 1,2: 1,4: 1,4.5: 1,9: 1,9.5: 1,9.9: 1 etc., more preferably 1: 1～8: 1, be particularly preferably 1: 1～5: 1.
Preferably, highly basic described in step (4) is for carrying out any alkali of desilication reaction, its typical but non-limiting example has: sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, calcium hydroxide, strontium hydroxide, hydrated barta, mercuric hydroxide, thallous hydroxide, thallic hydroxide, silver diamminohydroxide, 1 kind or the combination of at least 2 kinds in choline, be preferably sodium hydroxide, potassium hydroxide, 1 kind or the combination of at least 2 kinds in calcium hydroxide, described combination typical case but the example of non-limit have: sodium hydroxide, the combination of potassium hydroxide, potassium hydroxide, the combination of calcium hydroxide, sodium hydroxide, potassium hydroxide, the combination of calcium hydroxide etc., sodium hydroxide more preferably, a kind of or its combination in potassium hydroxide, be particularly preferably sodium hydroxide.
Preferably, described in step (4), the solvent of strong base solution is preferably water.
Preferably, described in step (4), strong base solution mass concentration is 2%～50%, such as 2.1%, 2.2%, 4.9%, 29%, 29.9%, 30.1%, 48%, 49%, 49.9% etc., more preferably 3%～40%, be particularly preferably 5%～30%.
Preferably, described in step (4), flyash and strong base solution are 0.2: 1～17: 1 by liquid-solid mass ratio, such as: 0.21: 1,0.22: 1,0.25: 1,0.29: 1,1: 1,2: 1,8: 1,15: 1,16: 1,16.5: 1,16.8: 1,16.9: 1 etc., more preferably 0.3: 1～15: 1, more preferably 0.4: 1～12: 1, be particularly preferably 0.5: 1～9: 1.
Preferably, react secondary desiliconization and carry out under whipped state described in step (4), further preferred described stir speed (S.S.) is 50～1000rmin
-1, 51rmin for example
-1, 52rmin
-1, 55rmin
-1, 149rmin
-1, 151rmin
-1, 745rmin
-1, 749rmin
-1, 990rmin
-1, 995rmin
-1, 999rmin
-1deng, 100～850rmin more preferably
-1, be particularly preferably 150～750rmin
-1.
Preferably, described in step (4), reacting secondary desiliconization temperature is 10～200 ℃, such as 10.1 ℃, 10.2 ℃, 10.5 ℃, 11 ℃, 19 ℃, 50 ℃, 100 ℃, 150 ℃, 190 ℃, 195 ℃, 199 ℃, 199.5 ℃ etc., more preferably 15～180 ℃, more preferably 18～160 ℃, be particularly preferably 20～150 ℃.
Preferably, it is more than 0.2h described in step (4), reacting secondary desiliconization time, such as 0.21h, 0.22h, 0.25h, 0.31h, 1h, 2h, 5h, 5.9h, 10h, 13h, 23h, 23.5h, 23.9h, 24h etc., 0.3～24h more preferably, more preferably 0.4～12h, is particularly preferably 0.5～6h.
Preferably, flyash after step (4) secondary desiliconization is filtered, and enter again step (5) after washing, further preferably water is washed till pH=7～7.5, such as pH=7.01, pH=7.02, pH=7.04, pH=7.05, pH=7.4, pH=7.45, pH=7.49, pH=7.5 etc., more preferably be washed to pH=7～7.1, be particularly preferably washed to pH=7; The solid mass ratio of preferred described water lotion is 0.5: 1～10: 1, such as 0.6: 1,0.8: 1,1: 1,1.1: 1,1.2: 1,1.5: 1,2: 1,4: 1,4.5: 1,9: 1,9.5: 1,9.9: 1 etc., more preferably 1: 1～8: 1, be particularly preferably 1: 1～5: 1.
Preferably, in step (5), before roasting, flyash is dried, is particularly preferably dried to constant weight; Preferably drying temperature is 40～200 ℃, such as 40.1 ℃, 40.2 ℃, 40.5 ℃, 41 ℃, 80.1 ℃, 119 ℃, 180 ℃, 190 ℃, 195 ℃, 199 ℃, 199.5 ℃, 199.9 ℃ etc., more preferably 50～180 ℃, more preferably 70～150 ℃, be particularly preferably 80～120 ℃; Preferred described dry employing loft drier.
Described constant weight, confession under directions test product double dry or blazing after weight differential weight of (sample 1g) below 0.3mg.Be dried to constant weight for the second time and each time later weigh and all should under prescribed condition, continue dry after 1 hour, to carry out.Weighing for the second time of ignition to constant weight should be carried out after continuing blazing 30 minutes.Should take out immediately after each dry and put into moisture eliminator, to be cooledly to room temperature, weigh.
Preferably, described in step (5), maturing temperature is 800～2000 ℃, such as 801 ℃, 802 ℃, 805 ℃, 949 ℃, 951 ℃, 1599 ℃, 1601 ℃, 1900 ℃, 1990 ℃, 1999 ℃ etc., more preferably 850 ℃～1800 ℃, more preferably 900～1700 ℃, be particularly preferably 950 ℃～1600 ℃.
Preferably, described in step (5), roasting time is more than 0.2h, such as 0.21h, 0.22h, 0.25h, 0.31h, 0.51h, 1h, 2h, 3.9h, 5h, 5.9h, 10h, 13h, 14.9h, 15h, 24h etc., 0.3～15h more preferably, more preferably 0.4～8h, is particularly preferably 0.5～4h.
Preferably, described in step (5), roasting is carried out in stoving oven.
Preferably, desiliconization filtrate can be recycled to desilication reaction, further preferably uses 3～5 circulations.
Preferably, desiliconization filtrate causticization, spent liquor evaporation concentrate are realized to the recycle of strong base solution.
Preferably, pickling impurity removal filtrate can be recycled to pickling impurity removal reaction, further preferably uses 3～5 circulations.
Preferably, the acidifying of pickling impurity removal filtrate, evaporation and concentrating are realized to the recycle of strong acid solution.
Preferably, the recovery by evaporation condensed water is or/and the gradient circulation of washing water realizes the recycle of water, and the water that is further preferably used as gradient circulation is processed after 3～5 circulations, realizes recycling of water.
The gradient circulation of described water refers to and adopts the water that contains low concentration eluted material to remove to wash the slip to be washed that contains higher concentration eluted material.
Compared with prior art, the invention has the advantages that:
1) flyash belongs to solid pollutant, and quantity discharged is huge, utilizes flyash to produce mullite and can realize utilization of waste as resource, and social benefit is remarkable; Technological process does not produce secondary solid pollutent, obvious environment benefit; Without adding the aluminium source raw materials such as bauxitic clay or commercial alumina, production cost is low, remarkable in economical benefits.
2) technological process is less demanding to alumina content in flyash, and adaptability to raw material is strong; Meanwhile, mullite productive rate is high, quality better, remarkable in economical benefits.
Accompanying drawing explanation
Fig. 1 is the process flow sheet of one embodiment of the present of invention.
Embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art should understand, described embodiment helps to understand the present invention, should not be considered as concrete restriction of the present invention.
Embodiment 1
Flyash being put into ball mill dry grinding, take alumina balls masonry as ball-milling medium, is 3: 1 by the mass ratio of abrading-ball and flyash, grinds 2h, selects 120～320 object flyash; Flyash being mixed by liquid-solid ratio with water at 3: 1, put into magnetic separator, is 500mT by magneticstrength, drum speed 40rmin
-1carry out magnetic separation, and collect concentrate, mine tailing; Flyash after magnetic separation is mixed by liquid-solid ratio with 15% sodium hydroxide solution at 3: 1, move into reactor, at stir speed (S.S.) 300rmin
-1, react 2.0h at 130 ℃; Reaction slurry is moved into filter and carry out separation, and be to wash at 2: 1 by liquid-solid ratio, wash to pH=8.0; By the flyash after washing, by liquid-solid ratio, be to mix at 3: 1 with 20% hydrochloric acid, move into reactive tank, at stir speed (S.S.) 300rmin
-1, react 0.5h at 80 ℃; Reaction slurry is moved into filter and carry out separation, and be to wash at 2: 1 by liquid-solid ratio, wash to pH=6.0; Flyash after washing is mixed by liquid-solid ratio with 15% sodium hydroxide solution at 3: 1, move into reactor, at stir speed (S.S.) 300rmin
-1, react 1.0h at 95 ℃; Reaction slurry is moved into filter and carry out separation, and be to wash at 2: 1 by liquid-solid ratio, wash to pH=7.0; Dried flyash is moved to stoving oven, and roasting 1.0h at 1400 ℃, obtains mullite product, and its technical indicator reaches GB and requires (M70, wherein alumina content is 72.598%).
Embodiment 2
Flyash being put into ball mill dry grinding, take alumina balls masonry as ball-milling medium, is 3: 1 by the mass ratio of abrading-ball and flyash, grinds 2h, selects 60～120 object flyash; Flyash being mixed by liquid-solid ratio with water at 3: 1, put into magnetic separator, is 500mT by magneticstrength, drum speed 40rmin
-1carry out magnetic separation, and collect concentrate, mine tailing; Flyash after magnetic separation is mixed by liquid-solid ratio with 20% sodium hydroxide solution at 2: 1, move into reactor, at stir speed (S.S.) 200rmin
-1, react 2h at 104 ℃; Reaction slurry is moved into filter and carry out separation, and be to wash at 2: 1 by liquid-solid ratio, wash to pH=8.0; By the flyash after washing, by liquid-solid ratio, be to mix at 2: 1 with 10% hydrochloric acid, move into reactive tank, at stir speed (S.S.) 200rmin
-1, react 1h at 95 ℃; Reaction slurry is moved into filter and carry out separation, and be to wash at 2: 1 by liquid-solid ratio, wash to pH=6.0; Flyash after washing is mixed by liquid-solid ratio with 20% sodium hydroxide solution at 2: 1, move into reactor, at stir speed (S.S.) 300rmin
-1, react 1.5h at 125 ℃; Reaction slurry is moved into filter and carry out separation, and be to wash at 2: 1 by liquid-solid ratio, wash to pH=7.0; Dried flyash is moved to stoving oven, and roasting 0.5h at 1400 ℃, obtains mullite product, and its technical indicator reaches GB and requires (M70, wherein alumina content is 68.193%).
Embodiment 3
Flyash being put into ball mill dry grinding, take alumina balls masonry as ball-milling medium, is 3: 1 by the mass ratio of abrading-ball and flyash, grinds 2h, selects 120～320 object flyash; Flyash being mixed by liquid-solid ratio with water at 3: 1, put into magnetic separator, is 500mT by magneticstrength, drum speed 40rmin
-1carry out magnetic separation, and collect concentrate, mine tailing; Flyash after magnetic separation is mixed by liquid-solid ratio with 10% sodium hydroxide solution at 2: 1, move into reactor, at stir speed (S.S.) 200rmin
-1, react 1.5h at 104 ℃; Reaction slurry is moved into filter and carry out separation, and be to wash at 2: 1 by liquid-solid ratio, wash to pH=8.0; By the flyash after washing, by liquid-solid ratio, be to mix at 3: 1 with 15% hydrochloric acid, move into reactive tank, at stir speed (S.S.) 100rmin
-1, react 0.5h at 80 ℃; Reaction slurry is moved into filter and carry out separation, and be to wash at 2: 1 by liquid-solid ratio, wash to pH=6.0; Flyash after washing is mixed by liquid-solid ratio with 15% sodium hydroxide solution at 1: 1, move into reactor, at stir speed (S.S.) 200rmin
-1, react 2.0h at 95 ℃; Reaction slurry is moved into filter and carry out separation, and be to wash at 2: 1 by liquid-solid ratio, wash to pH=7.0; Dried flyash is moved to stoving oven, and roasting 1.0h at 1200 ℃, obtains mullite product, and its technical indicator reaches GB and requires (M70, wherein alumina content is 69.625%).
Embodiment 4
Flyash being put into ball mill dry grinding, take alumina balls masonry as ball-milling medium, is 3: 1 by the mass ratio of abrading-ball and flyash, grinds 2h, selects 60～120 object flyash; Flyash being mixed by liquid-solid ratio with water at 3: 1, put into magnetic separator, is 500mT by magneticstrength, drum speed 40rmin
-1carry out magnetic separation, and collect concentrate, mine tailing; Flyash after magnetic separation is mixed by liquid-solid ratio with 10% sodium hydroxide solution at 3: 1, move into reactor, at stir speed (S.S.) 300rmin
-1, react 1.5h at 130 ℃; Reaction slurry is moved into filter and carry out separation, and be to wash at 2: 1 by liquid-solid ratio, wash to pH=8.0; By the flyash after washing, by liquid-solid ratio, be to mix at 1: 1 with 20% hydrochloric acid, move into reactive tank, at stir speed (S.S.) 200rmin
-1, react 1.5h at 60 ℃; Reaction slurry is moved into filter and carry out separation, and be to wash at 2: 1 by liquid-solid ratio, wash to pH=6.0; Flyash after washing is mixed by liquid-solid ratio with 10% sodium hydroxide solution at 3: 1, move into reactor, at stir speed (S.S.) 200rmin
-1, react 0.5h at 105 ℃; Reaction slurry is moved into filter and carry out separation, and be to wash at 2: 1 by liquid-solid ratio, wash to pH=7.0; Dried flyash is moved to stoving oven, and roasting 1.5h at 1000 ℃, obtains mullite product, and its technical indicator reaches GB and requires (M70, wherein alumina content is 68.426%).
Embodiment 5
Flyash being put into ball mill dry grinding, take alumina balls masonry as ball-milling medium, is 3: 1 by the mass ratio of abrading-ball and flyash, grinds 2h, selects 120～320 object flyash; Flyash being mixed by liquid-solid ratio with water at 3: 1, put into magnetic separator, is 500mT by magneticstrength, drum speed 40rmin
-1carry out magnetic separation, and collect concentrate, mine tailing; Flyash after magnetic separation is mixed by liquid-solid ratio with 15% sodium hydroxide solution at 4: 1, move into reactor, at stir speed (S.S.) 400rmin
-1, react 1.0h at 95 ℃; Reaction slurry is moved into filter and carry out separation, and be to wash at 2: 1 by liquid-solid ratio, wash to pH=8.0; By the flyash after washing, by liquid-solid ratio, be to mix at 2: 1 with 25% hydrochloric acid, move into reactive tank, at stir speed (S.S.) 300rmin
-1, react 2.0h at 20 ℃; Reaction slurry is moved into filter and carry out separation, and be to wash at 2: 1 by liquid-solid ratio, wash to pH=6.0; Flyash after washing is mixed by liquid-solid ratio with 15% sodium hydroxide solution at 2: 1, move into reactor, at stir speed (S.S.) 100rmin
-1, react 1.0h at 115 ℃; Reaction slurry is moved into filter and carry out separation, and be to wash at 2: 1 by liquid-solid ratio, wash to pH=7.0; Dried flyash is moved to stoving oven, and roasting 2.0h at 1200 ℃, obtains mullite product, and its technical indicator reaches GB and requires (M70, wherein alumina content is 69.625%).
Embodiment 6
Flyash being put into ball mill dry grinding, take tungsten-carbide ball masonry as ball-milling medium, is 1: 1 by the mass ratio of abrading-ball and flyash, grinds 10h, selects 40～120 object flyash; Flyash being mixed by liquid-solid ratio with water at 0.5: 1, put into magnetic separator, is 100mT by magneticstrength, drum speed 100rmin
-1carry out magnetic separation, and collect concentrate, mine tailing; Flyash after magnetic separation is mixed by liquid-solid ratio with 2% potassium hydroxide solution at 18: 1, move into reactor, at stir speed (S.S.) 50rmin
-1, react 24h under room temperature; Reaction slurry being moved into filter and carry out separation, is 10: 1 to mix with 50% nitric acid by liquid-solid ratio by flyash, moves into reactive tank, at stir speed (S.S.) 50rmin
-1, react 24h at 10 ℃; Reaction slurry is moved into filter and carry out separation, and be to wash at 10: 1 by liquid-solid ratio, wash to pH=5.0; Flyash after washing is mixed by liquid-solid ratio with 50% potassium hydroxide solution at 0.2: 1, move into reactor, at stir speed (S.S.) 50rmin
-1, react 24h at 10 ℃; Reaction slurry is moved into filter and carry out separation, and be to wash at 10: 1 by liquid-solid ratio, wash to pH=7.5; At 40 ℃, be dried, dried flyash is moved to stoving oven, roasting 15h at 800 ℃, obtains mullite product, and its technical indicator reaches GB and requires (M70, wherein alumina content is 69.572%).
Embodiment 7
Flyash being put into ball mill dry grinding, take zirconia ball masonry as ball-milling medium, is 5: 1 by the mass ratio of abrading-ball and flyash, grinds 0.5h, selects 350～500 object flyash; Flyash being mixed by liquid-solid ratio with water at 10: 1, put into magnetic separator, is 5000mT by magneticstrength, drum speed 10rmin
-1carry out magnetic separation, and collect concentrate, mine tailing; Flyash after magnetic separation is mixed by liquid-solid ratio with 50% potassium hydroxide solution at 0.2: 1, move into reactor, at stir speed (S.S.) 1000rmin
-1, react 0.2h at 250 ℃; Reaction slurry is moved into filter and carry out separation, and be to wash at 10: 1 by liquid-solid ratio, wash to pH=9.0; By the flyash after washing, by liquid-solid ratio, be to mix at 0.5: 1 with 2% sulfuric acid, move into reactive tank, at stir speed (S.S.) 1000rmin
-1, react 0.2h at 150 ℃; Reaction slurry is moved into filter and carry out separation, and be to wash at 0.5: 1 by liquid-solid ratio, wash to pH=7.0; Flyash after washing is mixed by liquid-solid ratio with 2% potassium hydroxide solution at 17: 1, move into reactor, at stir speed (S.S.) 1000rmin
-1, react 0.2h at 200 ℃; Reaction slurry is moved into filter and carry out separation, and be to wash at 0.5: 1 by liquid-solid ratio, wash to pH=7; At 200 ℃, be dried, dried flyash is moved to stoving oven, roasting 0.2h at 2000 ℃, obtains mullite product, and its technical indicator reaches GB and requires (M70, wherein alumina content is 70.145%).
Embodiment 8
Flyash being put into ball mill dry grinding, take alumina balls masonry as ball-milling medium, is 2: 1 by the mass ratio of abrading-ball and flyash, grinds 0.7h, selects 50～150 object flyash; Flyash being mixed by liquid-solid ratio with water at 9: 1, put into magnetic separator, is 3000mT by magneticstrength, drum speed 15rmin
-1carry out magnetic separation, and collect concentrate, mine tailing; Flyash after magnetic separation is mixed by liquid-solid ratio with 3% potassium hydroxide solution at 15: 1, move into reactor, at stir speed (S.S.) 100rmin
-1, react 18h at 40 ℃; Reaction slurry is moved into filter and carry out separation, and be to wash at 0.5: 1 by liquid-solid ratio, wash to pH=7.0; By the flyash after washing, by liquid-solid ratio, be to mix at 8: 1 with 3% perchloric acid, move into reactive tank, at stir speed (S.S.) 100rmin
-1, react 18h at 15 ℃; Reaction slurry is moved into filter and carry out separation, and flyash is mixed by liquid-solid ratio with 3% potassium hydroxide solution at 15: 1, move into reactor, at stir speed (S.S.) 100rmin
-1, react 12h at 15 ℃; Reaction slurry is moved into filter and carry out separation, and be to wash at 8: 1 by liquid-solid ratio, wash to pH=7.1; At 120 ℃, be dried to constant weight, dried flyash is moved to stoving oven, roasting 0.3h at 2000 ℃, obtains mullite product, and its technical indicator reaches GB and requires (M70, wherein alumina content is 69.972%).
Applicant's statement, the present invention illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, do not mean that the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to the selection of the interpolation of the equivalence replacement of each raw material of product of the present invention and ancillary component, concrete mode etc., within all dropping on protection scope of the present invention and open scope.
Claims (139)
1. utilize flyash to produce a method for mullite, it is characterized in that, said method comprising the steps of:
(1) flyash is ground to screening, magnetic separation;
(2) flyash after magnetic separation is mixed to reaction desiliconization with strong base solution;
(3) desiliconization flyash step (2) being obtained mixes with strong acid solution, pickling impurity removal;
(4) flyash step (3) being obtained mixes with strong base solution, the desiliconization of reaction secondary;
(5) flyash roasting step (4) being obtained, obtains mullite;
Described in step (3), strong acid solution mass concentration is 2%～50%, described in step (3), flyash and strong acid solution are 0.5:1～10:1 by liquid-solid mass ratio, in step (3), pickling impurity removal reaction is carried out at 10～150 ℃, and in step (3), the pickling impurity removal reaction times is more than 0.2h.
2. the method for claim 1, is characterized in that, grinds preferably dry grinding described in step (1).
3. method as claimed in claim 2, is characterized in that, the described grinding of step (1) adopts ball mill dry grinding.
4. method as claimed in claim 3, is characterized in that, ball-milling medium is a kind or the combination of at least 2 kinds in zirconium oxide balls, wolfram varbide abrading-ball, aluminum oxide abrading-ball.
5. method as claimed in claim 4, is characterized in that, described ball-milling medium is aluminum oxide abrading-ball.
6. method as claimed in claim 4, is characterized in that, described abrading-ball is 1:1～5:1 with flyash quality ratio.
7. method as claimed in claim 6, is characterized in that, described abrading-ball is 2:1～4:1 with flyash quality ratio.
8. method as claimed in claim 7, is characterized in that, described abrading-ball is 2:1～3:1 with flyash quality ratio.
9. method as claimed in claim 2, is characterized in that, the described dry grinding time is more than 0.5h.
10. method as claimed in claim 9, is characterized in that, the described dry grinding time is 0.7～10h.
11. methods as claimed in claim 10, is characterized in that, the described dry grinding time is 0.8～6h.
12. methods as claimed in claim 11, is characterized in that, the described dry grinding time is 1～4h.
13. the method for claim 1, is characterized in that, described in step (1), screening was 40～500 mesh sieves.
14. methods as claimed in claim 13, is characterized in that, described in step (1), screening was 50～400 mesh sieves.
15. methods as claimed in claim 14, is characterized in that, described in step (1), screening was 60～350 mesh sieves.
16. methods as claimed in claim 15, is characterized in that, described in step (1), screening was 60～320 mesh sieves.
17. the method for claim 1, is characterized in that, in step (1), after the flyash after screening is mixed with water, carry out magnetic separation.
18. methods as claimed in claim 17, is characterized in that, in step (1), magnetic separation coal ash and water are 0.5:1～10:1 by liquid-solid mass ratio.
19. methods as claimed in claim 18, is characterized in that, in step (1), magnetic separation coal ash and water are 1:1～5:1 by liquid-solid mass ratio.
20. the method for claim 1, is characterized in that, magnetic separation magneticstrength is 100～5000mT.
21. methods as claimed in claim 20, is characterized in that, magnetic separation magneticstrength is 150～3000mT.
22. methods as claimed in claim 21, is characterized in that, magnetic separation magneticstrength is 200～2000mT.
23. the method for claim 1, is characterized in that, described magnetic separation is carried out in magnetic separator.
24. methods as claimed in claim 23, is characterized in that, magnetic separator drum speed is 10～100rmin
-1.
25. methods as claimed in claim 24, is characterized in that, magnetic separator drum speed is 15～80rmin
-1.
26. methods as claimed in claim 25, is characterized in that, magnetic separator drum speed is 20～60rmin
-1.
27. methods as claimed in claim 1 or 2, it is characterized in that, highly basic described in step (2), for carrying out any alkali of desilication reaction, is selected from a kind or the combination of at least 2 kinds in sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, calcium hydroxide, strontium hydroxide, hydrated barta, mercuric hydroxide, thallous hydroxide, thallic hydroxide, silver diamminohydroxide, choline.
28. methods as claimed in claim 27, is characterized in that, the described highly basic of step (2) is a kind or the combination of at least 2 kinds in sodium hydroxide, potassium hydroxide, calcium hydroxide.
29. methods as claimed in claim 28, is characterized in that, the described highly basic of step (2) is a kind or its combination in sodium hydroxide, potassium hydroxide.
30. methods as claimed in claim 29, is characterized in that, the described highly basic of step (2) is sodium hydroxide.
31. methods as claimed in claim 1 or 2, is characterized in that, described in step (2), the solvent of strong base solution is water.
32. methods as claimed in claim 1 or 2, is characterized in that, described in step (2), strong base solution mass concentration is 2%～50%.
33. methods as claimed in claim 32, is characterized in that, described in step (2), strong base solution mass concentration is 3%～40%.
34. methods as claimed in claim 33, is characterized in that, described in step (2), strong base solution mass concentration is 5%～30%.
35. methods as claimed in claim 1 or 2, is characterized in that, described in step (2), flyash and strong base solution are 0.2:1～18:1 by liquid-solid mass ratio.
36. methods as claimed in claim 35, is characterized in that, described in step (2), flyash and strong base solution are 0.3:1～15:1 by liquid-solid mass ratio.
37. methods as claimed in claim 36, is characterized in that, described in step (2), flyash and strong base solution are 0.4:1～11:1 by liquid-solid mass ratio.
38. methods as claimed in claim 37, is characterized in that, described in step (2), flyash and strong base solution are 0.5:1～9:1 by liquid-solid mass ratio.
39. the method for claim 1, is characterized in that, react desiliconization and carry out under whipped state described in step (2).
40. methods as claimed in claim 39, is characterized in that, described stir speed (S.S.) is 50～1000rmin
-1.
41. methods as claimed in claim 40, is characterized in that, described stir speed (S.S.) is 100～850rmin
-1.
42. methods as claimed in claim 41, is characterized in that, described stir speed (S.S.) is 150～750rmin
-1.
43. the method for claim 1, is characterized in that, described in step (2), reacting desiliconization temperature is room temperature～250 ℃.
44. methods as claimed in claim 43, is characterized in that, described in step (2), reacting desiliconization temperature is 40～200 ℃.
45. methods as claimed in claim 44, is characterized in that, described in step (2), reacting desiliconization temperature is 70～170 ℃.
46. methods as claimed in claim 45, is characterized in that, described in step (2), reacting desiliconization temperature is 90～150 ℃.
47. the method for claim 1, is characterized in that, it is more than 0.2h described in step (2), reacting desiliconization time.
48. methods as claimed in claim 47, is characterized in that, described in step (2), reacting desiliconization time is 0.3～24h.
49. methods as claimed in claim 48, is characterized in that, described in step (2), reacting desiliconization time is 0.4～18h.
50. methods as claimed in claim 49, is characterized in that, described in step (2), reacting desiliconization time is 0.5～12h.
51. the method for claim 1, is characterized in that, the flyash after desiliconization described in step (2) is filtered, and enter step (3) after washing again.
52. methods as claimed in claim 51, is characterized in that, are washed to pH=7～9.
53. methods as claimed in claim 52, is characterized in that, are washed to pH=7～8.5.
54. methods as claimed in claim 53, is characterized in that, are washed to pH=7～8.
55. methods as claimed in claim 51, is characterized in that, the solid mass ratio of described water lotion is 0.5:1～10:1.
56. methods as claimed in claim 55, is characterized in that, the solid mass ratio of described water lotion is 1:1～8:1.
57. methods as claimed in claim 56, is characterized in that, the solid mass ratio of described water lotion is 1:1～5:1.
58. the method for claim 1, is characterized in that, in step (3), described strong acid is for carrying out any acid of removal of impurities reaction.
59. methods as claimed in claim 58, it is characterized in that, described strong acid is inorganic acid, is selected from a kind or the combination of at least 2 kinds in sulfuric acid, nitric acid, perchloric acid, hydrochloric acid, Hydrogen bromide, hydroiodic acid HI, the acid of hydrogen astatine, hydrogen telluric acid, hyperbromic acid, the folded acid iodide of hydrogen, chloric acid, bromic acid, silicofluoric acid, chlorine plumbic acid, metaphosphoric acid, osmic acid, permanganic acid, selenic acid, ferric acid, hydrogen borate, fluosulfonic acid, cyanic acid, thiocyanic acid.
60. methods as claimed in claim 59, is characterized in that, described strong acid is a kind or its combination in hydrochloric acid, sulfuric acid, permanganic acid, nitric acid, perchloric acid, chloric acid.
61. methods as claimed in claim 60, is characterized in that, described strong acid is a kind or its combination in sulfuric acid, nitric acid, hydrochloric acid.
62. methods as claimed in claim 61, is characterized in that, described strong acid is hydrochloric acid.
63. the method for claim 1, is characterized in that, described in step (3), strong acid solution mass concentration is 3%～40%.
64. methods as described in claim 63, is characterized in that, described in step (3), strong acid solution mass concentration is 5%～30%.
65. the method for claim 1, is characterized in that, described in step (3), strong acid solution is strong aqueous acid.
66. the method for claim 1, is characterized in that, described in step (3), flyash and strong acid solution are 1:1～8:1 by liquid-solid mass ratio.
67. methods as described in claim 66, is characterized in that, described in step (3), flyash and strong acid solution are 1:1～5:1 by liquid-solid mass ratio.
68. the method for claim 1, is characterized in that, in step (3), pickling impurity removal reaction is carried out under whipped state.
69. methods as described in claim 68, is characterized in that, described stir speed (S.S.) is 50～1000rmin
-1.
70. methods as described in claim 69, is characterized in that, described stir speed (S.S.) is 100～850rmin
-1.
71. methods as described in claim 70, is characterized in that, described stir speed (S.S.) is 150～750rmin
-1.
72. the method for claim 1, is characterized in that, in step (3), pickling impurity removal reaction is carried out at 15～120 ℃.
73. methods as described in claim 72, is characterized in that, in step (3), pickling impurity removal reaction is carried out at 18～110 ℃.
74. methods as described in claim 73, is characterized in that, in step (3), pickling impurity removal reaction is carried out at 20～95 ℃.
75. the method for claim 1, is characterized in that, in step (3), the pickling impurity removal reaction times is 0.3～24h.
76. methods as described in claim 75, is characterized in that, in step (3), the pickling impurity removal reaction times is 0.4～18h.
77. methods as described in claim 76, is characterized in that, in step (3), the pickling impurity removal reaction times is 0.5～12h.
78. the method for claim 1, is characterized in that, the flyash after step (3) removal of impurities is filtered, and enter step (4) after washing again.
79. methods as described in claim 78, is characterized in that, are washed to pH=5～7.
80. methods as described in claim 79, is characterized in that, are washed to pH=5.5～7.
81. methods as described in claim 80, is characterized in that, are washed to pH=6～7.
82. methods as described in claim 78, is characterized in that, the solid mass ratio of described water lotion is 0.5:1～10:1.
83. methods as described in claim 82, is characterized in that, the solid mass ratio of described water lotion is 1:1～8:1.
84. methods as described in claim 83, is characterized in that, the solid mass ratio of described water lotion is 1:1～5:1.
85. the method for claim 1, it is characterized in that, highly basic described in step (4), for carrying out any alkali of desilication reaction, is selected from a kind or the combination of at least 2 kinds in sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, calcium hydroxide, strontium hydroxide, hydrated barta, mercuric hydroxide, thallous hydroxide, thallic hydroxide, silver diamminohydroxide, choline.
86. methods as described in claim 85, is characterized in that, highly basic described in step (4) is a kind or the combination of at least 2 kinds in sodium hydroxide, potassium hydroxide, calcium hydroxide.
87. methods as described in claim 86, is characterized in that, highly basic described in step (4) is a kind of or its combination in sodium hydroxide, potassium hydroxide.
88. methods as described in claim 87, is characterized in that, described in step (4), highly basic is sodium hydroxide.
89. the method for claim 1, is characterized in that, described in step (4), the solvent of strong base solution is water.
90. the method for claim 1, is characterized in that, described in step (4), strong base solution mass concentration is 2%～50%.
91. methods as described in claim 90, is characterized in that, described in step (4), strong base solution mass concentration is 3%～40%.
92. methods as described in claim 91, is characterized in that, described in step (4), strong base solution mass concentration is 5%～30%.
93. the method for claim 1, is characterized in that, described in step (4), flyash and strong base solution are 0.2:1～17:1 by liquid-solid mass ratio.
94. methods as described in claim 93, is characterized in that, described in step (4), flyash and strong base solution are 0.3:1～15:1 by liquid-solid mass ratio.
95. methods as described in claim 94, is characterized in that, described in step (4), flyash and strong base solution are 0.4:1～12:1 by liquid-solid mass ratio.
96. methods as described in claim 95, is characterized in that, described in step (4), flyash and strong base solution are 0.5:1～9:1 by liquid-solid mass ratio.
97. the method for claim 1, is characterized in that, react secondary desiliconization and carry out under whipped state described in step (4).
98. methods as described in claim 97, is characterized in that, described stir speed (S.S.) is 50～1000rmin
-1.
99. methods as described in claim 98, is characterized in that, described stir speed (S.S.) is 100～850rmin
-1.
100. methods as described in claim 99, is characterized in that, described stir speed (S.S.) is 150～750rmin
-1.
101. the method for claim 1, is characterized in that, described in step (4), reacting secondary desiliconization temperature is 10～200 ℃.
102. methods as described in claim 101, is characterized in that, described in step (4), reacting secondary desiliconization temperature is 15～180 ℃.
103. methods as described in claim 102, is characterized in that, described in step (4), reacting secondary desiliconization temperature is 18～160 ℃.
104. methods as described in claim 103, is characterized in that, described in step (4), reacting secondary desiliconization temperature is 20～150 ℃.
105. the method for claim 1, is characterized in that, it is more than 0.2h described in step (4), reacting secondary desiliconization time.
106. methods as described in claim 105, is characterized in that, described in step (4), reacting secondary desiliconization time is 0.3～24h.
107. methods as described in claim 106, is characterized in that, described in step (4), reacting secondary desiliconization time is 0.4～12h.
108. methods as described in claim 107, is characterized in that, described in step (4), reacting secondary desiliconization time is 0.5～6h.
109. the method for claim 1, is characterized in that, the flyash after step (4) secondary desiliconization is filtered, and enter step (5) after washing again.
110. methods as described in claim 109, is characterized in that, are washed to pH=7～7.5.
111. methods as described in claim 110, is characterized in that, are washed to pH=7～7.1.
112. methods as described in claim 111, is characterized in that, are washed to pH=7.
113. methods as described in claim 109, is characterized in that, the solid mass ratio of described water lotion is 0.5:1～10:1.
114. methods as described in claim 113, is characterized in that, the solid mass ratio of described water lotion is 1:1～8:1.
115. methods as described in claim 114, is characterized in that, the solid mass ratio of described water lotion is 1:1～5:1.
116. the method for claim 1, is characterized in that, in step (5), before roasting, flyash are dried.
117. methods as described in claim 116, is characterized in that, are dried to constant weight.
118. methods as described in claim 117, is characterized in that, drying temperature is 40～200 ℃.
119. methods as described in claim 118, is characterized in that, drying temperature is 50～180 ℃.
120. methods as described in claim 119, is characterized in that, drying temperature is 70～150 ℃.
121. methods as described in claim 120, is characterized in that, drying temperature is 80～120 ℃.
122. methods as described in claim 116, is characterized in that described dry employing loft drier.
123. the method for claim 1, is characterized in that, described in step (5), maturing temperature is 800～2000 ℃.
124. methods as described in claim 123, is characterized in that, maturing temperature described in step (5) is 850 ℃～1800 ℃.
125. methods as described in claim 124, is characterized in that, described in step (5), maturing temperature is 900～1700 ℃.
126. methods as described in claim 125, is characterized in that, maturing temperature described in step (5) is 950 ℃～1600 ℃.
127. the method for claim 1, is characterized in that, described in step (5), roasting time is more than 0.2h.
128. methods as described in claim 127, is characterized in that, described in step (5), roasting time is 0.3～15h.
129. methods as described in claim 128, is characterized in that, described in step (5), roasting time is 0.4～8h.
130. methods as described in claim 129, is characterized in that, described in step (5), roasting time is 0.5～4h.
131. the method for claim 1, is characterized in that, described in step (5), roasting is carried out in stoving oven.
132. the method for claim 1, is characterized in that, desiliconization filtrate can be recycled to desilication reaction.
133. methods as described in claim 132, is characterized in that, desiliconization filtrate can be recycled 3～5 and is circulated to desilication reaction.
134. methods as described in claim 132, is characterized in that, desiliconization filtrate causticization, spent liquor evaporation concentrate are realized to the recycle of strong base solution.
135. the method for claim 1, is characterized in that, pickling impurity removal filtrate can be recycled to pickling impurity removal and reacts.
136. methods as described in claim 135, is characterized in that, pickling impurity removal filtrate can be recycled 3～5 and is circulated to pickling impurity removal reaction.
137. methods as described in claim 135, is characterized in that, the acidifying of pickling impurity removal filtrate, evaporation and concentrating are realized to the recycle of strong acid solution.
138. the method for claim 1, is characterized in that, the recovery by evaporation condensed water is or/and the gradient circulation of washing water realizes the recycle of water.
139. methods as described in claim 138, is characterized in that, as the water of gradient circulation, after 3～5 circulations, process, and realize recycling of water.
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| CN103274419A (en) * | 2013-06-04 | 2013-09-04 | 天津大学 | Removal method of amorphous silicon dioxide in high-aluminum fly ash |
| CN103708480A (en) * | 2013-11-28 | 2014-04-09 | 内蒙古工业大学 | Method for preparing microcrystalline mullite from fly ash |
| CN104371703B (en) * | 2014-11-03 | 2017-07-21 | 中国科学院过程工程研究所 | A kind of method that petroleum fracturing propping agent is prepared by raw material of aluminous fly-ash |
| CN104671811B (en) * | 2015-02-13 | 2016-10-05 | 中国科学院过程工程研究所 | A kind of method utilizing two sections of acid treatments of aluminous fly-ash to prepare mullite |
| CN106220190A (en) * | 2015-11-12 | 2016-12-14 | 中国科学院过程工程研究所 | A kind of method utilizing aluminous fly-ash to prepare mullite |
| CN107285774B (en) * | 2016-04-05 | 2020-04-24 | 神华集团有限责任公司 | Method for preparing mullite from white mud or fly ash and prepared mullite |
| CN112707716A (en) * | 2019-10-24 | 2021-04-27 | 中国科学院过程工程研究所 | Mullite-corundum composite ceramic, and preparation method and application thereof |
| CN110734083B (en) * | 2019-11-20 | 2020-09-29 | 内蒙古日盛可再生资源有限公司 | Desiliconization method of high-alumina fly ash |
| CN111606339B (en) * | 2020-05-22 | 2023-01-10 | 内蒙古蒙泰集团有限公司 | Method for preparing aluminum-silicon oxide by using fly ash |
| CN114276815B (en) * | 2020-09-27 | 2022-11-29 | 中国科学院过程工程研究所 | Preparation method of modified fly ash, modified fly ash prepared by preparation method and application of modified fly ash |
| CN115340391B (en) * | 2021-05-14 | 2023-10-20 | 中国科学院过程工程研究所 | Desilication fly ash and preparation method and application thereof |
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| CN1325432C (en) * | 2004-05-12 | 2007-07-11 | 清华大学 | Agglomeration method for synthesizing mullite by using high aluminous fly ash |
| CN102167338B (en) * | 2010-02-26 | 2013-03-13 | 昊青薪材（北京）技术有限公司 | Technology for preparing hydrated sodium aluminosilicate by utilizing high-alumina coal gangue and fly ash alkali soluble desiliconization |
| CN102092734A (en) * | 2010-11-29 | 2011-06-15 | 中煤平朔煤业有限责任公司 | Method for preparing sodium silicate solution and mullite refractory material with fly ash |
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