CN104556168A - Method of activated leaching alumina in fly ash - Google Patents
Method of activated leaching alumina in fly ash Download PDFInfo
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- CN104556168A CN104556168A CN201410806391.6A CN201410806391A CN104556168A CN 104556168 A CN104556168 A CN 104556168A CN 201410806391 A CN201410806391 A CN 201410806391A CN 104556168 A CN104556168 A CN 104556168A
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- flyash
- hydrosulfate
- oxide
- aluminum oxide
- alumina
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/68—Aluminium compounds containing sulfur
- C01F7/74—Sulfates
- C01F7/743—Preparation from silicoaluminious materials, e.g. clays or bauxite
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- Processing Of Solid Wastes (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention discloses a method of activated leaching alumina in fly ash and obtaining an aluminum sulfate solution and amorphous silica. The method comprises the following steps: after mixing the fly ash and bisulfate, calcining and decomposing a mixture in a sealed system, leaching a calcined product with water, and obtaining the aluminum sulfate solution and the amorphous silica by virtue of solid-liquid separation. According to the method disclosed by the invention, the extraction rate of the alumina in the fly ash is higher than 85 percent, the reaction condition is mild, and corrosion to equipment is small.
Description
Technical field
The present invention relates to a kind of solid waste and utilize technology, from flyash, especially extract the technology of aluminum oxide.
Background technology
The Main chemical component of flyash is silicon-dioxide, aluminum oxide.In China's some areas flyash, alumina content is more than 40%, can be used as bauxite resource and utilizes.At present, the method extracting aluminum oxide from flyash relates generally to alkaline process, soda-lime sintering process, acid system, using acid and alkali combination method and ammonium sulfate method.
Alkali ratio juris is under highly basic effect, and the aluminum oxide in flyash and alkali effect generate sodium aluminate, and sodium aluminate obtains sodium aluminate solution through water-soluble, and by the method preparing hydrogen aluminum oxide that kind is divided or carbon divides, finally calcining obtains aluminum oxide.
The principle of soda-lime sintering process is having under calcium oxide existence condition, use caustic digestion flyash, wherein most of silicon and calcium are reacted and generates insoluble silico-calcium compound, be separated under water-soluble condition with the sodium aluminate generated simultaneously, then prepare aluminum oxide by sodium aluminate solution.
Acid technological process is under strongly acidic conditions, by alumina leaching, realizes and being separated of siliceous oxide, then obtains alumina product through further removal of impurities.The hydrochloric acid acid pasting of representative is sulphate method and fluidized bed ash.
Using acid and alkali combination method is on acid-soluble basis, the acid aluminium salt obtained is obtained the alumina mixture of impure (iron etc.) through condensing crystal-thermolysis, more molten through alkali, is separated deironing, obtains wrought aluminum acid sodium solution, prepare aluminum oxide on this basis.
Divided by outside upper method, also there are the report and the patent that adopt ammonium sulfate method from flyash, extract aluminum oxide." method of co-producing white carbon black while of aluminum oxide in flyash, is extracted " as patent CN1868884 discloses one, by flyash abrasive dust, ammonium sulfate is added after activation, water is added again in reactant, filter, in filtrate, add ammonia, obtain aluminium hydroxide and ironic hydroxide mixed precipitation, divide obtain pure cerium hydroxide aluminium, the aluminum oxide finally fired by adding kind of carbon again after finally aluminum hydroxide precipitation being melted with sodium hydroxide solution.Adopt ammonium sulfate to be that circulatory mediator extracts aluminum oxide, both overcome harm and environmental protection problem that acid system (sulfuric acid, hydrochloric acid) technique brings equipment corrosion, and turn improved the extraction yield of aluminum oxide.Patent CN101117228 discloses " a kind of method extracting aluminum oxide from flyash ", relates to a kind ofly from flyash, extracting the processing method that residue after aluminum oxide is extracted in aluminum oxide and comprehensive utilization.It is characterized in that its method allocates ammonium sulfate into flyash to sinter, gained solid obtains the solution of sulfur acid aluminium ammonium after stripping, this solution obtains the exsiccated ammonium alum of solid by the method for crystallization, Solid aluminum sulfate ammonium and ammonia gas react obtain aluminium hydroxide and ammonium sulfate, pass through washing and filtering, obtain the aluminium hydroxide of solid, aluminium hydroxide can obtain alumina product after roasting; The ammonium sulfate entering liquid phase, after evaporation, continues to recycle.Patent CN101734698A discloses " a kind of method being prepared aluminum oxide by aluminiferous material ", the method of the products such as aluminum oxide is prepared by aluminiferous materials such as bauxite, high-iron bauxite, alunite, kaolin, bauxitic clay, flyash, coal gangue, aluminium ash, nepheline, clays, the method comprises the following steps: (1) is broken by aluminiferous material, after levigate and ammonium sulfate baking mixed; (2) product of roasting (grog) water-soluble, filter obtain aluminum ammonium sulfate solution and filter residue; (3) prepared by aluminum oxide to aluminum ammonium sulfate solution deironing, heavy aluminium or recrystallization, reclaim(ed) sulfuric acid ammonium simultaneously with ammonia; (4) filter residue prepares silica product, and recrement iron content, as iron-smelting raw material.
These three inventions all adopt Extraction of Alumina By The Method of Ammonium Sulfate-gas, produce a large amount of ammonia through Decomposition of ammonium sulfate, then experience liquid phase scrubbing and form the multi-step gas-liquid process implementation such as exsiccated ammonium alum, sulphate decomposition and sulfur trioxide absorption and circulate.
Above-mentioned various aluminum oxide method of extracting from flyash cuts both ways, and mostly adopts strong acid, highly basic that corrodibility is extremely strong, high to equipment requirements, and production operation is dangerous large, cumbersome.Existing ammonium sulfate method technique is more complicated, can produce a large amount of ammonia and sulphur trioxide.Current suitability for industrialized production is still based on traditional alkaline process.
Summary of the invention
The object of the invention is to for above-mentioned the deficiencies in the prior art, provide a kind of by aluminum oxide activating stripping in flyash, thus obtain the method for alum liquor and amorphous silicon di-oxide.
Method by aluminum oxide activating stripping in flyash provided by the present invention comprises the following steps:
(1) flyash mixes with hydrosulfate by the ratio being 1:0.5 ~ 1:3.0 according to flyash and hydrosulfate mass ratio, in airtight reaction vessel, within 1 ~ 4 hour, carry out material activating in 180 ~ 450 DEG C of roastings; Preferably, described hydrosulfate is sodium pyrosulfate or sal enixum;
(2) according to water and flyash liquid-solid ratio be the hot water that the ratio of 7 ~ 15L/kg adds 60 DEG C ~ 100 DEG C in the material after above-mentioned activation, soaking and stirring, carry out solid-liquid separation and washing at 60 ~ 95 DEG C, obtain the solution containing Tai-Ace S 150 and amorphous silicon di-oxide.
Raw material powder coal ash of the present invention is coal-powder boiler flyash or circulating fluid bed coal ash.When the raw material adopted is coal-powder boiler flyash, the activation temperature in step (1) in closed reaction vessel is 300 ~ 450 DEG C; When the raw material adopted is circulating fluid bed coal ash, the activation temperature in step (1) in closed reaction vessel is 180 ~ 350 DEG C.
Preferably, wherein step (1) is being carried out before by described flyash ball milling.
Preferably, 200 mesh sieves are crossed after wherein said flyash ball milling.
Preferably, wherein in step (1) by flyash and hydrosulfate mixed grinding.
Preferably, in step (2), add hot water before by activation after flyash be cooled to less than 100 DEG C.
Preferably, wherein the temperature of soaking and stirring described in step (2) is 55 DEG C to 95 DEG C; The time of described soaking and stirring is 0.5 ~ 1.0 hour.
Adopt present method to carry out the stripping of aluminum oxide in flyash, in coal-powder boiler flyash, the solubility rate of aluminum oxide is higher than 85%, and in circulating fluid bed coal ash, the solubility rate of aluminum oxide is higher than 90%.
Gained amorphous silicon di-oxide of the present invention has higher degree and sound response is active, can be used for product such as preparation White Carbon black, aerogel etc.
Beneficial effect: the present invention adopts alkali metal sulphuric acid hydrogen salt to activate decomposed powder coal ash, because alkali metal sulphuric acid hydrogen salt not easily decomposes generation volatile gases at low temperature, can react in confined conditions, ensure that carrying out smoothly of solid state reaction, thus improve the extraction yield of aluminum oxide.Reaction conditions of the present invention is gentle, and the acidity of hydrosulfate is little, little to equipment corrosion, not easily decomposes, operational safety, is easy to realize various Matter Transfer.
Embodiment
Below in conjunction with embodiment, the present invention is described, but the present invention is not limited to following examples.
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 composition is as shown in table 1.
Table 1 chemical composition of PCA (wt%): 1-circulating fluid bed coal ash, 2-coal-powder boiler flyash
| SiO 2 | Al 2O 3 | TiO 2 | CaO | MgO | TFe 2O 3 | FeO | K 2O | Na 2O | LOS | SO 3 | Summation | |
| 1 | 34.70 | 46.28 | 1.48 | 3.61 | 0.21 | 1.54 | 0.22 | 0.39 | 0.17 | 7.17 | 1.32 | 95.77 |
| 2 | 36.30 | 51.70 | 1.75 | 2.68 | 0.24 | 1.28 | 0.30 | 0.34 | 0.09 | 2.21 | 0.40 | 97.29 |
Embodiment 1
By coal-powder boiler flyash ball milling, cross 200 mesh sieves.Get above-mentioned flyash 1Kg, with 3Kg sodium pyrosulfate mixed grinding, be placed in airtight High Temperature Furnaces Heating Apparatus in 450 DEG C of roastings 1 hour.Come out of the stove and be cooled to 85 DEG C, add 80 DEG C of hot water 10L, stir 1 hour in 80 ± 5 DEG C, filtering separation, and with 80 DEG C of hot wash filter residues to sulfate radical-free ion, obtain alum liquor and amorphous silicon di-oxide.Replace the alumina content in complexometry mensuration alum liquor through fluorochemical, obtaining digesting efficiency of alumina in flyash is 87.3%.
Embodiment 2
By coal-powder boiler flyash ball milling, cross 200 mesh sieves.Get above-mentioned flyash 1Kg, with 1Kg sal enixum mixed grinding, be placed in airtight High Temperature Furnaces Heating Apparatus in 350 DEG C of roastings 2 hours.Come out of the stove and be cooled to 75 DEG C, add 70 DEG C of hot water 15L, stir 0.5 hour in 70 ± 5 DEG C, filtering separation, and with 70 DEG C of hot wash filter residues to sulfate radical-free ion, obtain alum liquor and amorphous silicon di-oxide.Replace complexometry through fluorochemical to measure, in flyash, digesting efficiency of alumina is 85.7%.
Embodiment 3
By circulating fluid bed coal ash ball milling, cross 200 mesh sieves.Get above-mentioned flyash 1Kg, with 2.5Kg sodium pyrosulfate mixed grinding, be placed in airtight High Temperature Furnaces Heating Apparatus in 180 DEG C of roastings 4 hours.Come out of the stove and be cooled to 95 DEG C, add 100 DEG C of hot water 7L, stir 1 hour in 90 ± 5 DEG C, filtering separation, and with 90 DEG C of hot wash filter residues to sulfate radical-free ion, obtain alum liquor and amorphous silicon di-oxide.Replace complexometry through fluorochemical to measure, in flyash, digesting efficiency of alumina is 90.4%.
Embodiment 4
By circulating fluid bed coal ash ball milling, cross 200 mesh sieves.Get above-mentioned flyash 1Kg, with 0.5Kg sal enixum mixed grinding, be placed in airtight High Temperature Furnaces Heating Apparatus in 350 DEG C of roastings 3 hours.Come out of the stove and be cooled to 65 DEG C, add 60 DEG C of hot water 8L, stir 1 hour in 60 ± 5 DEG C, filtering separation, and with 60 DEG C of hot wash filter residues to sulfate radical-free ion, obtain alum liquor and amorphous silicon di-oxide.Replace complexometry through fluorochemical to measure, in flyash, digesting efficiency of alumina is 92.1%.
Embodiment 5
By coal-powder boiler flyash ball milling, cross 200 mesh sieves.Get above-mentioned flyash 1Kg, with 1Kg sal enixum mixed grinding, be placed in airtight High Temperature Furnaces Heating Apparatus in 300 DEG C of roastings 3 hours.Come out of the stove and be cooled to 75 DEG C, add 70 DEG C of hot water 12L, stir 0.5 hour in 70 ± 5 DEG C, filtering separation, and with 70 DEG C of hot wash filter residues to sulfate radical-free ion, obtain alum liquor and amorphous silicon di-oxide.Replace complexometry through fluorochemical to measure, in flyash, digesting efficiency of alumina is 93.3%.
Claims (10)
1. aluminum oxide activating stripping in flyash is obtained the method for alum liquor and amorphous silicon di-oxide, it is characterized in that, described method comprises:
(1) flyash mixes with hydrosulfate by the ratio being 1:0.5 ~ 1:3.0 according to flyash and hydrosulfate mass ratio, in airtight reaction vessel, within 1 ~ 4 hour, carry out material activating in 180 ~ 450 DEG C of roastings;
(2) according to water and flyash liquid-solid ratio be the hot water that the ratio of 7 ~ 15L/kg adds 60 DEG C ~ 100 DEG C in the material after above-mentioned activation, soaking and stirring, carry out solid-liquid separation and washing at 60 DEG C ~ 95 DEG C, obtain alum liquor and amorphous silicon di-oxide.
2. method according to claim 1, wherein, when the flyash adopted is coal-powder boiler flyash, the maturing temperature in step (1) in closed reaction vessel is 300 ~ 450 DEG C.
3. method according to claim 1, wherein, when the flyash adopted is circulating fluid bed coal ash, the maturing temperature in step (1) in closed reaction vessel is 180 ~ 350 DEG C.
4. method according to claim 1, wherein, described hydrosulfate is sodium pyrosulfate or sal enixum.
5. method according to claim 1, wherein, by described flyash ball milling before carrying out step (1).
6. method according to claim 5, wherein, crosses 200 mesh sieves after described flyash ball milling.
7. method according to claim 1, wherein, by flyash and hydrosulfate mixed grinding in step (1).
8. method according to claim 1, wherein, by flyash activation after is cooled to less than 100 DEG C before adding hot water in step (2).
9. method according to claim 1, wherein, the temperature of soaking and stirring described in step (2) is 55 DEG C to 95 DEG C.
10. method according to claim 1, wherein, the time of soaking and stirring described in step (2) is 0.5 ~ 1.0 hour.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105923640A (en) * | 2016-04-20 | 2016-09-07 | 航天推进技术研究院 | Method for extracting aluminum oxide from fly ash through sulfuric acid activation impurity removal |
| 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 |
| CN112850793A (en) * | 2021-02-11 | 2021-05-28 | 贵州大学 | High-value utilization method of red mud |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0024131A1 (en) * | 1979-07-27 | 1981-02-25 | Maria Emilia Garcia Clavel | A method of obtaining alumina from clay and other alumino-silicates and alumina obtained by this method |
| CN102515221A (en) * | 2011-12-02 | 2012-06-27 | 吉林大学 | Method for extracting alumina and amorphous silica from fly ash or coal gangue |
| CN103880012A (en) * | 2014-01-27 | 2014-06-25 | 吉林大学 | Method for activating and decomposing silicon-aluminum material |
| CN103977846A (en) * | 2014-05-22 | 2014-08-13 | 中国神华能源股份有限公司 | Method for preparing zeolite phosphorus fixation agent from coal ash as well as product prepared by method |
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2014
- 2014-12-22 CN CN201410806391.6A patent/CN104556168B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0024131A1 (en) * | 1979-07-27 | 1981-02-25 | Maria Emilia Garcia Clavel | A method of obtaining alumina from clay and other alumino-silicates and alumina obtained by this method |
| CN102515221A (en) * | 2011-12-02 | 2012-06-27 | 吉林大学 | Method for extracting alumina and amorphous silica from fly ash or coal gangue |
| CN103880012A (en) * | 2014-01-27 | 2014-06-25 | 吉林大学 | Method for activating and decomposing silicon-aluminum material |
| CN103977846A (en) * | 2014-05-22 | 2014-08-13 | 中国神华能源股份有限公司 | Method for preparing zeolite phosphorus fixation agent from coal ash as well as product prepared by method |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105923640A (en) * | 2016-04-20 | 2016-09-07 | 航天推进技术研究院 | Method for extracting aluminum oxide from fly ash through sulfuric acid activation impurity removal |
| 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 |
| CN112850793A (en) * | 2021-02-11 | 2021-05-28 | 贵州大学 | High-value utilization method of red mud |
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Inventor after: Guo Zhaohua Inventor after: Jiang Yinshan Inventor after: Wei Cundi Inventor after: Xue Bing Inventor after: Zhang Xiaodong Inventor after: Luo Feng Inventor after: Guo Chunbin Inventor after: Zou Jingjing Inventor after: Bai Jian Inventor before: Guo Zhaohua |