CN102515221A - Method for extracting alumina and amorphous silica from fly ash or coal gangue - Google Patents
Method for extracting alumina and amorphous silica from fly ash or coal gangue Download PDFInfo
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Abstract
The invention relates to a method for extracting alumina and amorphous silica from fly ash or coal gangue. The fly ash or coal gangue is calcined and then crushed, the amount of the required alkali metal sulfate is calculated based on the content of alumina in the fly ash, and mixing and roasting are carried out according to the molar ratio of sulfur trioxide in the alkali metal sulfate and the alumina in the fly ash or coal gangue; and water is added into reaction products for immersion, and mixing is carried out for solid-liquid separation to obtain sulfate solution and amorphous SiO2. The alkali metal coke sulfate is adopted to decompose the fly ash, volatile gases cannot be produced easily at low temperature, reaction can be carried out in confined conditions, and thus the rate of alumina extraction can be improved. The rate of alumina extraction is higher than 80 percent. The reaction conditions are mild, the corrosion to equipment is reduced, the operation is safe, no waste gas or waste water can be produced, the recycling of all materials can be realized easily, the fly ash can be completely decomposed, and the produced alumina product has high purity and can meet the requirements of YS/T 274-1998 Alumina for the purity of metallurgical alumina products.
Description
Technical field:
The present invention relates to a kind of method of alumina of from fossil oil, extracting, especially from flyash or coal gangue, extract Al with alkali metal sulfates decomposed powder coal ash or coal gangue
2O
3, and obtain non-crystalline state SiO
2Method.
Technical background:
The main chemical composition of flyash is silicon-dioxide, aluminum oxide.Alumina content surpasses 40% in China's some areas flyash, can be as the bauxite resource utilization.At present, the work of from flyash, extracting aluminum oxide has obtained a large amount of achievements, and the application of partly having put into production.At present, from flyash, extract method of alumina and relate generally to alkaline process, soda-lime sintering process, acid system, using acid and alkali combination method and ammonium sulfate method.
The principle of alkaline process is under the highly basic effect, and aluminum oxide in the flyash and alkali effect generate sodium aluminate, and sodium aluminate is produced white lake through the water-soluble sodium aluminate solution that obtains through the method that kind of branch or carbon divide, and calcining at last obtains aluminum oxide.
The soda-lime ratio juris is to have under the quicklime existence condition, with alkali decomposed powder coal ash, makes the reaction of wherein most of silicon and calcium generate insoluble silico-calcium compound, separates under water-soluble condition with the sodium aluminate that generates simultaneously, prepares aluminum oxide by sodium aluminate solution again.
Acid technological process is under strong acidic condition, and with the aluminum oxide stripping, realization separates with siliceous oxide compound, obtains alumina product through further removal of impurities again.Representative is the hydrochloric acid acid pasting of vitriol oil method and fluidized bed ash.
Using acid and alkali combination method is on the basis is dissolved in acid, and the acid aluminium salt that obtains is obtained the alumina mixture of impure (iron etc.) through condensing crystal-thermolysis, dissolves through alkali again, separates deironing, obtains the wrought aluminum acid sodium solution, prepares aluminum oxide on this basis.
CN1868884 discloses a kind of " extracting the aluminum oxide method of co-producing white carbon black simultaneously in the flyash ", with the flyash abrasive dust, adds ammonium sulfate after the activation; In reactant, add entry again; Filter, in filtrating, add ammonia, obtain white lake and ironic hydroxide mixed precipitation; Obtain pure cerium hydroxide aluminium, the Al that fires at last through adding kind of a carbon branch again after with sodium hydroxide solution aluminum hydroxide precipitation being melted at last
2O
3Adopting ammonium sulfate is that circulatory mediator extracts aluminum oxide, has both overcome acid system (sulfuric acid, hydrochloric acid) technology to harm and environmental protection problem that equipment corrosion brings, has improved the extraction yield of aluminum oxide again.
CN101117228 discloses " a kind of method of alumina of from flyash, extracting ", from flyash, extracts method of alumina, relates to a kind of process method that residue behind the aluminum oxide is extracted in aluminum oxide and comprehensive utilization of from flyash, extracting.It is characterized in that its method is to allocate ammonium sulfate into flyash to carry out sintering; The gained solid obtains the solution of sulfur acid aluminium ammonium after stripping; This solution obtains the solid exsiccated ammonium alum through the crystalline method, and solid sulphuric acid aluminium ammonium and ammonia gas react obtain white lake and ammonium sulfate, through washing and filtering; Obtain solid white lake, white lake can obtain alumina product after roasting; The ammonium sulfate that gets into liquid phase continues to recycle after evaporation.
CN101734698A discloses " a kind of prepare method of alumina by aluminiferous material " prepared products such as aluminum oxide by aluminiferous materials such as bauxite, high-iron bauxite, alunite, kaolin, bauxitic clay, flyash, coal gangue, aluminium ash, nepheline, clays method; This method may further comprise the steps: (1) is broken with aluminiferous material, and levigate back is baking mixed with ammonium sulfate; (2) product of roasting (grog) water-soluble, filter and to obtain aluminum ammonium sulfate solution and filter residue; (3) with ammonia aluminum ammonium sulfate solution deironing, heavy aluminium or recrystallization are prepared aluminum oxide, simultaneously the reclaim(ed) sulfuric acid ammonium; (4) filter residue prepares silica product, and the recrement iron content is as iron-smelting raw material.
These three inventions all adopt the ammonium sulfate method to extract aluminum oxide, decompose through ammonium sulfate to produce a large amount of ammonias, and the rapid gas-liquid processes of multisteps such as liquid phase absorption formation exsiccated ammonium alum, sulphate decomposition and sulphur trioxide absorption that experience again realize circulation.
The above-mentioned various aluminum oxide method of from flyash, extracting cuts both ways, and adopts strong acid, the highly basic of very corrosive mostly, and high to equipment requirements, production operation is dangerous big, and technology is numerous and diverse.Existing ammonium sulfate method technology is complicated, and therefore, suitability for industrialized production is main with traditional alkaline process still at present.
Summary of the invention:
The object of the invention just is to be directed against above-mentioned to the deficiency that technology is arranged, and a kind of AlO and non-crystalline state SiO of from flyash or coal gangue, extracting is provided
2Method.
The objective of the invention is to realize through following technical scheme:
From flyash or coal gangue, extract AlO and non-crystalline state SiO
2Method, comprise following order and step:
A, be broken to less than 200 orders with flyash or through the colliery powder of 700-1600 ℃ of calcining after 0.5-3.0 hour;
B, calculate the amount of needed alkali metal sulfates or alkali metal sulphuric acid hydrogen salt according to alumina content in flyash or the coal gangue; According in contained sulphur trioxide and flyash or the coal gangue in pyrosulphate or the hydrosulfate salic mol ratio; The mol ratio that is sulphur trioxide/aluminum oxide is 1.0～6.0 to carry out proportioning; Through mixing, roasting is 1～6 hour under 300～450 ℃ of conditions;
C, in the material that above-mentioned reaction generates, add entry, liquid-solid ratio is 5～20L/kg, soaking and stirring more than 60 ℃ 20～90 minutes, carries out solid-liquid separation while hot, must contain the vitriol mixing solutions and the non-crystalline state SiO of aluminium, iron, sodium, potassium
2
D, the vitriol mixing solutions that contains aluminium, iron, sodium, potassium is carried out deironing, POV aluminium, sodium, potassium salt soln, obtain blended Tai-Ace S 150, sodium, sylvite crystal through evaporation concentration;
E, with blended Tai-Ace S 150, sodium, sylvite crystal 700～800 ℃ of calcinings 1-6 hour, decompose the sulfur trioxide gas that generates and absorb through sodium sulfate or potassium sulfate solution;
F, aluminum oxide+sodium sulfate that calcining is obtained or vitriolate of tartar are with 50～100 ℃ hot water dissolving, and liquid-solid ratio is 10～20L/Kg, obtains aluminum oxide solid and sodium sulfate or potassium sulfate solution through solid-liquid separation, washing;
After g, sodium sulfate or potassium sulfate solution absorb sulfur trioxide gas,, obtain sodium pyrosulfate or sal enixum solid, turn back to the circulation that step b realizes oxysulfide through condensing crystal;
H, to step f, the aluminum oxide that obtains through further drip washing, drying, 1100～1200 ℃ of calcining temperature 1～4 hour, obtain the metallurgical-grade aluminum oxide product.
The described alkali metal sulfates of step b is selected from any of sodium pyrosulfate, POTASSIUM PYROSULPHATE, sodium pyrosulfate, sal enixum.
Gained non-crystalline state SiO among the step c
2, warp and yellow soda ash mixed sintering, water-soluble, filter, be used to prepare white carbon black to liquid acidifying, ageing, solid-liquid separation washing, after dry.
Beneficial effect: what the present invention adopted is basic metal pyrosulphate or alkali metal sulphuric acid hydrogen salt decomposed powder coal ash; Because basic metal pyrosulphate or alkali metal sulphuric acid hydrogen salt are difficult for producing volatile gases at low temperature; Can react in confined conditions; Guaranteed carrying out smoothly of solid state reaction, thereby improved the extraction yield of aluminum oxide, alumina extraction ratio is higher than 80%.Reaction conditions of the present invention is gentle; Little to equipment corrosion, operational safety does not produce waste gas waste water; Various material circulations are easy to realize; The flyash complete decomposition, the alumina product purity that makes is high, and be up to state standards " YS/T 274-1998 aluminum oxide " is to the requirement of metallurgical-grade aluminum oxide product gas purity.
Description of drawings:
Accompanying drawing: the method process flow sheet that from flyash or coal gangue, extracts aluminum oxide and amorphous silicon di-oxide
Embodiment:
Do further detailed description below in conjunction with accompanying drawing and embodiment:
From flyash or coal gangue, extract AlO and non-crystalline state SiO
2Method, comprise following order and step:
A, be broken to less than 200 orders with flyash or through the colliery powder of 700-1600 ℃ of calcining after 0.5-3.0 hour;
B, calculate the amount of needed alkali metal sulfates or alkali metal sulphuric acid hydrogen salt according to alumina content in flyash or the coal gangue; According in contained sulphur trioxide and flyash or the coal gangue in pyrosulphate or the hydrosulfate salic mol ratio; The mol ratio that is sulphur trioxide/aluminum oxide is 1.0～6.0 to carry out proportioning; Through mixing, roasting is 1～6 hour under 300～450 ℃ of conditions;
C, in the material that above-mentioned reaction generates, add entry, liquid-solid ratio is 5～20L/kg, soaking and stirring more than 60 ℃ 20～90 minutes, carries out solid-liquid separation while hot, must contain the vitriol mixing solutions and the non-crystalline state SiO of aluminium, iron, sodium, potassium
2
D, the vitriol mixing solutions that contains aluminium, iron, sodium, potassium is carried out deironing, POV aluminium, sodium, potassium salt soln, obtain blended Tai-Ace S 150, sodium, sylvite crystal through evaporation concentration;
E, with blended Tai-Ace S 150, sodium, sylvite crystal 700～800 ℃ of calcinings 1-6 hour, decompose the sulfur trioxide gas that generates and absorb through sodium sulfate or potassium sulfate solution;
F, aluminum oxide+sodium sulfate that calcining is obtained or vitriolate of tartar are with 50～100 ℃ hot water dissolving, and liquid-solid ratio is 10～20L/Kg, obtains aluminum oxide solid and sodium sulfate or potassium sulfate solution through solid-liquid separation, washing;
After g, sodium sulfate or potassium sulfate solution absorb sulphur trioxide,, obtain sodium pyrosulfate or sal enixum solid, turn back to the circulation that step b realizes oxysulfide through condensing crystal;
H, to step f, the aluminum oxide that obtains through further drip washing, drying, 1100～1200 ℃ of calcining temperature 1～4 hour, obtain the metallurgical-grade aluminum oxide product.
The described alkali metal sulfates of step b is selected from any of sodium pyrosulfate, POTASSIUM PYROSULPHATE, sodium pyrosulfate, sal enixum.
Gained non-crystalline state SiO among the step c
2, warp and yellow soda ash mixed sintering, water-soluble, filter, be used to prepare white carbon black to liquid acidifying, ageing, solid-liquid separation washing, after dry.
Raw material adopts the coal-powder boiler flyash of certain heat power plant's output circulating fluid bed coal ash and certain power plant's output, and its chemical ingredients is as shown in table 1.
Table 1 chemical composition of PCA (wt%): 1-circulating fluidized bed ash, 2-coal-powder boiler flyash
Embodiment 1
A, with coal-powder boiler flyash ball milling, fineness is crossed 200 mesh sieves;
B, get above-mentioned flyash 10 grams and 23 gram sodium pyrosulfate mixed grindings, in the high alumina crucible of packing into, in High Temperature Furnaces Heating Apparatus, be heated to 400 ℃ from room temperature, roasting was taken out after 4 hours, was cooled to below 100 ℃;
C, in above-mentioned product of roasting, add 100 milliliters of hot water, under 85 ℃ of conditions, stir and soaked 30 minutes, carry out solid-liquid separation while hot, till drip washing residue to the sulfate radical-free ion, must contain the vitriol mixing solutions and the non-crystalline state SiO of aluminium, iron, sodium, potassium
2Non-crystalline state SiO
2, warp and yellow soda ash mixed sintering, water-soluble, filter, be used to prepare white carbon black to liquid acidifying, ageing, solid-liquid separation washing, after dry.
D, according to ferrous ion amount in the liquid, add excessive slightly potassium permanganate oxidant, be stirred to purple at 80 ℃ and disappear, add the manganous sulfate solid with the potassium permanganate equimolar amount, it is static to stir the back, carries out solid-liquid separation, obtains the POV salts solution.With this POV salts solution condensing crystal, obtain Tai-Ace S 150, sodium sulfate mixed crystal;
E, with Tai-Ace S 150, sodium sulfate mixed crystal 750 ℃ of calcinings 2 hours, take out and be cooled to below 100 ℃, decompose the sulfur trioxide gas that generates and absorb through metabisulfite solution;
F, in calcined product, add 80 milliliters of hot water, stir in 90 ℃ and soak the dissolving sodium sulphate, separate after filtration, wash and obtain aluminium oxide solid and metabisulfite solution;
G, metabisulfite solution are behind the sulphur trioxide that absorbs the calcining generation, and condensing crystal obtains the sodium pyrosulfate solid, turn back in the step 2 and use.
H, with the further drip washing of aluminum oxide solid, the drying that obtain in the step 6, through 1100 ℃ the calcining 2 hours, obtain alumina product.
Through measuring, alumina extraction ratio reaches 86.4%.The aluminum oxide that obtains satisfies in the People's Republic of China's non-ferrous metal industry standard " YS/T 274-1998 aluminum oxide " purity requirement to the metallurgical-grade aluminum oxide first grade.
Embodiment 2
A, with fluid bed powder coal ash ball milling, fineness is crossed 200 mesh sieves;
B, get above-mentioned flyash 10 grams and 23 gram sodium pyrosulfate mixed grindings, in the high alumina crucible of packing into, in High Temperature Furnaces Heating Apparatus, be heated to 320 ℃ from room temperature, roasting was taken out after 3 hours, was cooled to below 100 ℃;
C, in above-mentioned product of roasting, add 100 milliliters of hot water, under 85 ℃ of conditions, stir and soaked 30 minutes, carry out solid-liquid separation while hot, till drip washing residue to the sulfate radical-free ion, must contain the vitriol mixing solutions and the non-crystalline state SiO of aluminium, iron, sodium, potassium
2Non-crystalline state SiO
2, warp and yellow soda ash mixed sintering, water-soluble, filter, be used to prepare white carbon black to liquid acidifying, ageing, solid-liquid separation washing, after dry.
D, according to ferrous ion amount in the liquid, add excessive slightly potassium permanganate oxidant, be stirred to purple at 80 ℃ and disappear, add the manganous sulfate solid with the potassium permanganate equimolar amount, it is static to stir the back, carries out solid-liquid separation, obtains the POV salts solution.With this POV salts solution condensing crystal, obtain Tai-Ace S 150, sodium sulfate mixed crystal;
E, with Tai-Ace S 150, sodium sulfate mixed crystal 750 ℃ of calcinings 2 hours, take out and be cooled to below 100 ℃, decompose the sulfur trioxide gas that generates and absorb through metabisulfite solution;
F, in calcined product, add 80 milliliters of hot water, stir in 90 ℃ and soak the dissolving sodium sulphate, separate after filtration, wash and obtain aluminium oxide solid and metabisulfite solution;
G, metabisulfite solution are behind the sulphur trioxide that absorbs the calcining generation, and condensing crystal obtains the sodium pyrosulfate solid, turn back in the step 2 and use.
H, with the further drip washing of aluminum oxide solid, the drying that obtain in the step 6, through 1100 ℃ the calcining 2 hours, obtain alumina product.
Through measuring, alumina extraction ratio reaches 82.1%.The aluminum oxide that obtains satisfies in the People's Republic of China's non-ferrous metal industry standard " YS/T 274-1998 aluminum oxide " purity requirement to the metallurgical-grade aluminum oxide first grade.
Embodiment 3
A, with coal-powder boiler flyash ball milling, fineness is crossed 200 mesh sieves;
B, get above-mentioned flyash 10 grams and 28 gram sodium pyrosulfate mixed grindings, in the high alumina crucible of packing into, in High Temperature Furnaces Heating Apparatus, be heated to 420 ℃ from room temperature, roasting was taken out after 2 hours, was cooled to below 100 ℃;
C, in above-mentioned product of roasting, add 100 milliliters of hot water, under 85 ℃ of conditions, stir and soaked 30 minutes, carry out solid-liquid separation while hot, till drip washing residue to the sulfate radical-free ion, must contain the vitriol mixing solutions and the non-crystalline state SiO of aluminium, iron, sodium, potassium
2Non-crystalline state SiO
2, warp and yellow soda ash mixed sintering, water-soluble, filter, be used to prepare white carbon black to liquid acidifying, ageing, solid-liquid separation washing, after dry.
D, according to ferrous ion amount in the liquid, add excessive slightly potassium permanganate oxidant, be stirred to purple at 80 ℃ and disappear, add the manganous sulfate solid with the potassium permanganate equimolar amount, it is static to stir the back, carries out solid-liquid separation, obtains the POV salts solution.With this POV salts solution condensing crystal, obtain Tai-Ace S 150, sodium sulfate mixed crystal;
E, with Tai-Ace S 150, sodium sulfate mixed crystal 750 ℃ of calcinings 2 hours, take out and be cooled to below 100 ℃, decompose the sulfur trioxide gas that generates and absorb through metabisulfite solution;
F, in calcined product, add 80 milliliters of hot water, stir in 90 ℃ and soak the dissolving sodium sulphate, separate after filtration, wash and obtain aluminium oxide solid and metabisulfite solution;
G, metabisulfite solution are behind the sulphur trioxide that absorbs the calcining generation, and condensing crystal obtains the sodium pyrosulfate solid, turn back in the step 2 and use.
H, with the further drip washing of aluminum oxide solid, the drying that obtain in the step 6, through 1100 ℃ the calcining 2 hours, obtain alumina product.
Through measuring, alumina extraction ratio reaches 84.9%.The aluminum oxide that obtains satisfies in the People's Republic of China's non-ferrous metal industry standard " YS/T 274-1998 aluminum oxide " purity requirement to the metallurgical-grade aluminum oxide first grade.
Embodiment 4
A, with coal-powder boiler flyash ball milling, fineness is crossed 200 mesh sieves;
B, get above-mentioned flyash 10 grams and 38 gram sodium pyrosulfate mixed grindings, in the high alumina crucible of packing into, in High Temperature Furnaces Heating Apparatus, be heated to 310 ℃ from room temperature, roasting was taken out after 1 hour, was cooled to below 100 ℃;
C, in above-mentioned product of roasting, add 100 milliliters of hot water, under 85 ℃ of conditions, stir and soaked 30 minutes, carry out solid-liquid separation while hot, till drip washing residue to the sulfate radical-free ion, must contain the vitriol mixing solutions and the non-crystalline state SiO of aluminium, iron, sodium, potassium
2Non-crystalline state SiO
2, warp and yellow soda ash mixed sintering, water-soluble, filter, be used to prepare white carbon black to liquid acidifying, ageing, solid-liquid separation washing, after dry.
D, according to ferrous ion amount in the liquid, add excessive slightly potassium permanganate oxidant, be stirred to purple at 80 ℃ and disappear, add the manganous sulfate solid with the potassium permanganate equimolar amount, it is static to stir the back, carries out solid-liquid separation, obtains the POV salts solution.With this POV salts solution condensing crystal, obtain Tai-Ace S 150, sodium sulfate mixed crystal;
E, with Tai-Ace S 150, sodium sulfate mixed crystal 750 ℃ of calcinings 2 hours, take out and be cooled to below 100 ℃, decompose the sulfur trioxide gas that generates and absorb through metabisulfite solution;
F, in calcined product, add 80 milliliters of hot water, stir in 90 ℃ and soak the dissolving sodium sulphate, separate after filtration, wash and obtain aluminium oxide solid and metabisulfite solution;
G, metabisulfite solution are behind the sulphur trioxide that absorbs the calcining generation, and condensing crystal obtains the sodium pyrosulfate solid, turn back in the step 2 and use.
H, with the further drip washing of aluminum oxide solid, the drying that obtain in the step 6, through 1100 ℃ the calcining 2 hours, obtain alumina product.
Through measuring, alumina extraction ratio reaches 87.1%.The aluminum oxide that obtains satisfies in the People's Republic of China's non-ferrous metal industry standard " YS/T 274-1998 aluminum oxide " purity requirement to the metallurgical-grade aluminum oxide first grade.
Embodiment 5
A, with coal-powder boiler flyash ball milling, fineness is crossed 200 mesh sieves;
B, get above-mentioned flyash 10 grams and 28 gram sodium pyrosulfate mixed grindings, in the high alumina crucible of packing into, in High Temperature Furnaces Heating Apparatus, be heated to 400 ℃ from room temperature, roasting was taken out after 1 hour, was cooled to below 100 ℃;
C, in above-mentioned product of roasting, add 100 milliliters of hot water, under 80 ℃ of conditions, stir and soak, till solid-liquid separation, drip washing residue to the sulfate radical-free ion, obtain vitriol mixing solutions and amorphous silicon di-oxide; Non-crystalline state SiO
2, warp and yellow soda ash mixed sintering, water-soluble, filter, be used to prepare white carbon black to liquid acidifying, ageing, solid-liquid separation washing, after dry.
D, according to ferrous ion amount in the liquid, add excessive slightly potassium permanganate oxidant, be stirred to purple at 80 ℃ and disappear, add the manganous sulfate solid with the potassium permanganate equimolar amount, it is static to stir the back, carries out solid-liquid separation, obtains the POV salts solution.With this POV salts solution condensing crystal, obtain Tai-Ace S 150, sodium sulfate mixed crystal.
E, with Tai-Ace S 150, sodium sulfate mixed crystal 800 ℃ of calcinings 2 hours, take out and be cooled to below 100 ℃, decompose the sulfur trioxide gas that generates and absorb through metabisulfite solution;
F, in calcinate, add 100 milliliters of hot water, stir in 80 ℃ and soak the dissolving sodium sulfate, obtain aluminum oxide solid and metabisulfite solution through solid-liquid separation, washing;
G, metabisulfite solution are behind the sulphur trioxide that absorbs the calcining generation, and condensing crystal obtains the sodium pyrosulfate solid, turn back in the step 2 and use.
H, with the further drip washing of aluminum oxide solid, the drying that obtain in the step 6, through 1200 ℃ the calcining 2 hours, obtain alumina product.
Through measuring, alumina extraction ratio reaches 85.4%.The aluminum oxide that obtains satisfies in the People's Republic of China's non-ferrous metal industry standard " YS/T 274-1998 aluminum oxide " purity requirement to the metallurgical-grade aluminum oxide first grade.
Embodiment 6
A, with coal-powder boiler flyash ball milling, cross 200 mesh sieves, through the wet method deironing, make iron oxide content reduce to 0.9wt%;
B, get 1 kilogram in the flyash of the preparatory deironing of above-mentioned warp,, with 2.6 kilograms of POTASSIUM PYROSULPHATE mixed grindings, place rotary kiln in 380 ℃ of heating 4 hours, be cooled to below 100 ℃;
C, in above-mentioned product of roasting, add 10 liters of hot water, 95 ℃ of stirring, soak reaction product, wash, obtain vitriol mixing solutions and amorphous silicon di-oxide with the press filtration of plate basket pressure filter; Non-crystalline state SiO
2, warp and yellow soda ash mixed sintering, water-soluble, filter, be used to prepare white carbon black to liquid acidifying, ageing, solid-liquid separation washing, after dry.
D, according to ferrous ion amount in the liquid; Add excessive slightly potassium permanganate oxidant, be stirred to purple at 80 ℃ and disappear, add manganous sulfate solid with the potassium permanganate equimolar amount; It is static to stir the back; Vacuum filtration, washing obtain refined liquid, obtain Tai-Ace S 150, vitriolate of tartar mixed crystal behind the condensing crystal
E, with mixed crystal 730 ℃ of calcinings 4 hours, take out, be cooled to below 100 ℃, the sulfur trioxide gas that decompose to generate absorbs through metabisulfite solution;
F, in calcinate, add 50 liters of hot water, in 85 ℃ of dissolving vitriolate of tartar, vacuum filtration, washing obtain aluminum oxide solid and potassium sulfate solution;
G, potassium sulfate solution are behind the sulphur trioxide that absorbs the calcining generation, and condensing crystal obtains the sal enixum solid, turn back in the step 2 and use.
H, with the further drip washing of aluminum oxide solid, the drying that obtain in the step 6, in 1200 ℃ the calcining 3 hours, obtain alumina product.
Through measuring, alumina extraction ratio reaches 83.4%.The aluminum oxide that obtains satisfies in the People's Republic of China's non-ferrous metal industry standard " YS/T 274-1998 aluminum oxide " purity requirement to the metallurgical-grade aluminum oxide first grade.
Embodiment 7
A, with fluid bed powder coal ash ball milling, cross 200 mesh sieves, through the wet method deironing, make iron oxide content reduce to 0.9wt%;
B, get 1 kilogram in the flyash of the preparatory deironing of above-mentioned warp,, with 2 kilo sulfuric acid hydrogen potassium mixed grindings, place rotary kiln in 420 ℃ of heating 3 hours, be cooled to below 100 ℃;
C, in above-mentioned product of roasting, add 12 liters of hot water, 80 ℃ of stirring, soak reaction product, wash, obtain vitriol mixing solutions and amorphous silicon di-oxide with the press filtration of plate basket pressure filter; Non-crystalline state SiO
2, warp and yellow soda ash mixed sintering, water-soluble, filter, be used to prepare white carbon black to liquid acidifying, ageing, solid-liquid separation washing, after dry.
D, according to ferrous ion amount in the liquid, add excessive slightly potassium permanganate oxidant, be stirred to purple at 70 ℃ and disappear, add the manganous sulfate solid with the potassium permanganate equimolar amount, it is static to stir the back, vacuum filtration, washing obtain refined liquid.Obtain Tai-Ace S 150, vitriolate of tartar mixed crystal behind the condensing crystal;
E, with mixed crystal 780 ℃ of calcinings 2 hours, take out, be cooled to below 100 ℃, the sulfur trioxide gas that decompose to generate absorbs through metabisulfite solution;
F, in calcinate, add 60 liters of hot water, in 60 ℃ of dissolving vitriolate of tartar, vacuum filtration, washing obtain aluminum oxide solid and potassium sulfate solution;
G, potassium sulfate solution are behind the sulphur trioxide that absorbs the calcining generation, and condensing crystal obtains the sal enixum solid, turn back in the step 2 and use.
H, with the further drip washing of aluminum oxide solid, the drying that obtain in the step 6, in 1100 ℃ the calcining 4 hours, obtain alumina product.
With amorphous silicon di-oxide in the step 3 and yellow soda ash mixed sintering; Sintered product with water dissolution, filtration, is obtained sodium silicate solution, make the liquid acidifying to wherein adding Hydrogen chloride; After ageing, solid-liquid separation washing, obtain silica gel, make the WHITE CARBON BLACK product after the spraying drying.
Through measuring, alumina extraction ratio reaches aluminum oxide that 84.1%. obtains and satisfies in the People's Republic of China's non-ferrous metal industry standard " YS/T 274-1998 aluminum oxide " purity requirement to the metallurgical-grade aluminum oxide first grade.The WHITE CARBON BLACK that makes satisfies the requirement of white carbon black HB/T3061.
Embodiment 8
A, get coal gangue, its alumina content is 33.1%, dioxide-containing silica 29.2%, and fixed carbon 34%, surplus is other impurity.Coal gangue was calcined mistake 200 mesh sieves behind the crushing and grinding 2 hours in 850 ℃ in stoving oven;
B, get 1 kilogram of lime-ash behind the above-mentioned calcined coal gangue, behind 2.5 kilograms of sodium pyrosulfate mixed grindings, place rotary kiln, be cooled to below 100 ℃ in 450 ℃ of calcinings 2 hours;
C, in above-mentioned calcinate, add 15 liters of hot water, 90 ℃ of stirring, soak reaction product, wash, obtain vitriol mixing solutions and amorphous silicon di-oxide with the press filtration of plate basket pressure filter; Non-crystalline state SiO
2, warp and yellow soda ash mixed sintering, water-soluble, filter, be used to prepare white carbon black to liquid acidifying, ageing, solid-liquid separation washing, after dry.
D, according to ferrous ion amount in the liquid, add excessive slightly potassium permanganate oxidant, be stirred to purple at 80 ℃ and disappear, add the manganous sulfate solid with the potassium permanganate equimolar amount, it is static to stir the back, vacuum filtration, washing obtain refined liquid.Obtain Tai-Ace S 150, sodium sulfate mixed crystal behind the condensing crystal;
E, with this mixed crystal 760 ℃ of calcinings 3 hours, take out, be cooled to below 100 ℃,, the sulfur trioxide gas that decompose to generate absorbs through metabisulfite solution;
F, in calcinate, add 70 liters of hot water, in 70 ℃ of dissolving sodium sulfate, vacuum filtration, washing obtain aluminum oxide solid and metabisulfite solution;
G, metabisulfite solution are behind the sulphur trioxide that absorbs the calcining generation, and condensing crystal obtains the sal enixum solid, turn back in the step 2 and use.
H, with the further drip washing of aluminum oxide solid, the drying that obtain in the step 6, in 1200 ℃ the calcining 2 hours, obtain alumina product.
Through measuring, alumina extraction ratio reaches 83.3%.The aluminum oxide that obtains satisfies in the People's Republic of China's non-ferrous metal industry standard " YS/T 274-1998 aluminum oxide " purity requirement to the metallurgical-grade aluminum oxide first grade.
Claims (3)
1. a method of from flyash or coal gangue, extracting aluminum oxide and amorphous silicon di-oxide is characterized in that, comprises following order and step:
A, be broken to less than 200 orders with flyash or through the colliery powder of 700-1600 ℃ of calcining after 0.5-3.0 hour;
B, calculate the amount of required alkali metal sulfates according to alumina content in flyash or the coal gangue; According in contained sulphur trioxide and flyash or the coal gangue in the alkali metal sulfates salic mol ratio be 1.0～6.0 to carry out proportioning; Through mixing, roasting is 1～6 hour under 300～450 ℃ of conditions;
C, in the material that above-mentioned reaction generates, add entry, liquid-solid ratio is 5～20L/kg, soaking and stirring more than 60 ℃ 20～90 minutes, carries out solid-liquid separation while hot, must contain the vitriol mixing solutions and the non-crystalline state SiO of aluminium, iron, sodium, potassium
2Non-crystalline state SiO
2, warp and yellow soda ash mixed sintering, water-soluble, filter, be used to prepare white carbon black to liquid acidifying, ageing, solid-liquid separation washing, after dry;
D, the vitriol mixing solutions that contains aluminium, iron, sodium, potassium is carried out deironing, POV aluminium, sodium, potassium salt soln, obtain blended Tai-Ace S 150, sodium, sylvite crystal through evaporation concentration;
E, with blended Tai-Ace S 150, sodium, sylvite crystal 700～800 ℃ of calcinings 1-6 hour, decompose the sulfur trioxide gas that generates and absorb through sodium sulfate or potassium sulfate solution;
F, aluminum oxide+sodium sulfate that calcining is obtained or vitriolate of tartar are with 50～100 ℃ hot water dissolving, and liquid-solid ratio is 10～20L/Kg, obtains aluminum oxide solid and sodium sulfate or potassium sulfate solution through solid-liquid separation, washing;
After g, sodium sulfate or potassium sulfate solution absorb the sulphur trioxide of calcining generation,, obtain sodium pyrosulfate or sal enixum solid, turn back to the circulation that step b realizes oxysulfide through condensing crystal;
H, to step f, the aluminum oxide that obtains through further drip washing, drying, 1100～1200 ℃ of calcining temperature 1～4 hour, obtain the metallurgical-grade aluminum oxide product.
2. according to the described method of from flyash or coal gangue, extracting aluminum oxide and amorphous silicon di-oxide of claim 1, it is characterized in that described alkali metal sulfates is selected from any of sodium pyrosulfate, POTASSIUM PYROSULPHATE, sodium pyrosulfate, sal enixum.
3. according to the described method of from flyash or coal gangue, extracting aluminum oxide and amorphous silicon di-oxide of claim 1, it is characterized in that gained non-crystalline state SiO among the step c
2, warp and yellow soda ash mixed sintering, water-soluble, filter, be used to prepare white carbon black to liquid acidifying, ageing, solid-liquid separation washing, after dry.
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| CN103880012A (en) * | 2014-01-27 | 2014-06-25 | 吉林大学 | Method for activating and decomposing silicon-aluminum material |
| CN104556168A (en) * | 2014-12-22 | 2015-04-29 | 中国神华能源股份有限公司 | Method of activated leaching alumina in fly ash |
| CN104773739A (en) * | 2015-01-14 | 2015-07-15 | 南阳东方应用化工研究所 | Fly ash decomposition method |
| CN106698490A (en) * | 2017-01-24 | 2017-05-24 | 东华理工大学 | Methods for preparing aluminum precursor from fly ash and preparing nano alumina |
| CN112299721A (en) * | 2020-10-30 | 2021-02-02 | 神华准能资源综合开发有限公司 | Method for preparing alumina and co-producing microcrystalline glass based on pulverized coal furnace fly ash and product |
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