CN104787788A - Method for producing alumina from high-alumina fly ash - Google Patents
Method for producing alumina from high-alumina fly ash Download PDFInfo
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- CN104787788A CN104787788A CN201510184772.XA CN201510184772A CN104787788A CN 104787788 A CN104787788 A CN 104787788A CN 201510184772 A CN201510184772 A CN 201510184772A CN 104787788 A CN104787788 A CN 104787788A
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- flyash
- roasting
- sulfuric acid
- calcine
- alumina
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- 239000010881 fly ash Substances 0.000 title claims abstract description 82
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 title description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 71
- 238000000034 method Methods 0.000 claims abstract description 67
- 238000002386 leaching Methods 0.000 claims abstract description 44
- 230000002829 reductive effect Effects 0.000 claims abstract description 39
- 238000001354 calcination Methods 0.000 claims abstract description 28
- 239000002253 acid Substances 0.000 claims abstract description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 20
- 238000001556 precipitation Methods 0.000 claims abstract description 11
- 239000002893 slag Substances 0.000 claims abstract description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 9
- 239000010703 silicon Substances 0.000 claims abstract description 9
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910001388 sodium aluminate Inorganic materials 0.000 claims abstract description 8
- 238000000926 separation method Methods 0.000 claims abstract description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 42
- 239000000203 mixture Substances 0.000 claims description 27
- 239000003921 oil Substances 0.000 claims description 14
- 230000019635 sulfation Effects 0.000 claims description 13
- 238000005670 sulfation reaction Methods 0.000 claims description 13
- 238000007711 solidification Methods 0.000 claims description 11
- 230000008023 solidification Effects 0.000 claims description 11
- 238000005987 sulfurization reaction Methods 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 239000002817 coal dust Substances 0.000 claims description 8
- 239000012530 fluid Substances 0.000 claims description 8
- 239000004615 ingredient Substances 0.000 claims description 8
- 239000004575 stone Substances 0.000 claims description 8
- 238000000605 extraction Methods 0.000 claims description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 239000000779 smoke Substances 0.000 claims description 4
- 239000011593 sulfur Substances 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000005864 Sulphur Substances 0.000 claims description 2
- 239000003034 coal gas Substances 0.000 claims description 2
- 239000000571 coke Substances 0.000 claims description 2
- 235000009508 confectionery Nutrition 0.000 claims description 2
- 125000004122 cyclic group Chemical group 0.000 claims description 2
- 239000003344 environmental pollutant Substances 0.000 claims description 2
- 238000005243 fluidization Methods 0.000 claims description 2
- 239000000446 fuel Substances 0.000 claims description 2
- 239000003345 natural gas Substances 0.000 claims description 2
- 231100000719 pollutant Toxicity 0.000 claims description 2
- 238000005265 energy consumption Methods 0.000 abstract description 12
- 230000009467 reduction Effects 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 3
- 239000003638 chemical reducing agent Substances 0.000 abstract 2
- 238000010438 heat treatment Methods 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 239000012452 mother liquor Substances 0.000 abstract 1
- 238000011112 process operation Methods 0.000 abstract 1
- 239000007787 solid Substances 0.000 abstract 1
- 238000003756 stirring Methods 0.000 abstract 1
- 230000001180 sulfating effect Effects 0.000 abstract 1
- 230000008569 process Effects 0.000 description 26
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 21
- 229910052782 aluminium Inorganic materials 0.000 description 21
- 239000004411 aluminium Substances 0.000 description 20
- 239000000047 product Substances 0.000 description 20
- 239000003513 alkali Substances 0.000 description 18
- 238000005245 sintering Methods 0.000 description 11
- 239000003245 coal Substances 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 239000013078 crystal Substances 0.000 description 8
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 235000019738 Limestone Nutrition 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 4
- 239000006028 limestone Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 3
- 229910001570 bauxite Inorganic materials 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000010456 wollastonite Substances 0.000 description 3
- 229910052882 wollastonite Inorganic materials 0.000 description 3
- 238000004131 Bayer process Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000000378 calcium silicate Substances 0.000 description 2
- 229910052918 calcium silicate Inorganic materials 0.000 description 2
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000006002 Pepper Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910001569 aluminium mineral Inorganic materials 0.000 description 1
- 159000000013 aluminium salts Chemical class 0.000 description 1
- PZZYQPZGQPZBDN-UHFFFAOYSA-N aluminium silicate Chemical group O=[Al]O[Si](=O)O[Al]=O PZZYQPZGQPZBDN-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000010883 coal ash Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000006253 efflorescence Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 206010037844 rash Diseases 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Abstract
Adding concentrated sulfuric acid into the fly ash in batches, uniformly mixing, adding acid each time, uniformly stirring, carrying out acidolysis at 100-200 ℃, curing, and then heating to 200-500 ℃ for sulfating roasting for 1-4 hours to obtain sulfated calcine; reducing and roasting the sulfated calcine and a reducing agent together at the temperature of 550-900 ℃, leaching the reduced calcine by using a solution containing sodium hydroxide, performing liquid-solid separation to obtain a sodium aluminate solution and silicon-rich slag, performing seed precipitation and calcination to produce alumina after the sodium aluminate solution is desilicated, and returning seed precipitation mother liquor to leach the reduced calcine. The method not only ensures the activity of the alumina in the reduction calcine, but also cancels the high energy consumption procedure in the traditional sulfuric acid method, and has simple flow, low energy consumption and good quality of alumina products; and the acid is added step by step in the sulfuric acid acidolysis step, so that the acid utilization rate is improved, the acidolysis process operation is facilitated, and the consumption of the reducing agent in the subsequent reduction roasting is reduced.
Description
Technical field
The invention belongs to the comprehensive utilization of flyash, specifically relate to the method that aluminous fly-ash produces aluminum oxide, especially adopt soda acid process integration to extract aluminum oxide.
Background technology
Coal burning process produces a large amount of flyash, and be used for cement building material raw materials for production except small part and obtain except part utilization, most of flyash is stored up, and not only takies a large amount of land resources, and environmental pollution is serious.China's flyash is rich in aluminium, aluminum oxide average content 27%, and the alumina content of East China, North China's flyash is generally more than 30%, and in the flyash of some areas, aluminium content is especially up to 40-60%, is a kind of very important potential bauxite making & breaking.
Because the alumina silica ratio in flyash is very low, traditional process for making alumina is difficult to adapt to treated coal ash, need research and development to be applicable to the Technology of flyash feature, the flyash of research both at home and abroad is at present produced aluminum oxide method and is roughly divided into alkaline process and the large class of acid system two.
Alkaline process comprises direct sintering and pre-desiliconizing-sintering process etc.Direct sintering is similar to Bauxite Sintering method and produces alumina technology, comprise sintering, grog is from efflorescence, leach, carbon divides, the master operations such as calcination, disclosed in CN1644506A, one utilizes flyash to produce aluminum oxide method, flyash is mixed dry sintering after ore grinding by a certain percentage with limestone powder, then aluminum oxide is extracted with alkali stripping grog, leached mud is for the production of cement, due to the siliceous height of flyash, direct sintering needs to allocate large quantities of lime stone flour into, flyash and limestone powder quality proportioning reach 30:70, sintering energy consumption is high, and the meeting after extraction aluminum oxide produces a large amount of calcium silicate slag, often process 1 ton of flyash and newly can produce 3-5 ton, even more calcium silicate slag, the newly-increased top of the slag of disposal of how dissolving faces larger difficulty.
Carry out the process of alkali leaching pre-desiliconizing to flyash and can reduce sinter doses, thus reduce sintering energy consumption and reduce the leaching quantity of slag, the siliceous solution that pre-desiliconizing obtains simultaneously can produce the high level such as white carbon black, wollastonite silicon product.A kind of method extracting aluminum oxide from aluminous fly-ash disclosed in CN101284668A, aluminous fly-ash and sodium hydroxide solution are carried out pressure leaching in autoclave, make the stripping of part silicon, siliceous leach liquor is for the production of white carbon black, sinter after flyash after pre-desiliconizing mixes with limestone powder, sodium carbonate solution, then leach aluminium.Adopt pre-desiliconizing technology can improve the alumina silica ratio of flyash, reduce sintering amount, thus reduce alumina producing energy consumption, and the silicon products such as by-product white carbon black, wollastonite, but for large-scale total utilization of PCA, the market sale that white carbon black, wollastonite product face and competitive pressure very large.
Flyash acid system produces aluminum oxide owing to not needing to add slag former, and the level of residue extracted after aluminum oxide is few, meets the requirement of minimizing comprehensive utilization Industrial Solid Waste, and can obtain higher alumina recovery rate.But because the leach liquor of acidic process output needs condensing crystal, and it is higher containing crystal water to obtain aluminium intermediate product, and follow-up dehydration energy is high, causes the total energy consumption of acid oxidation aluminium high.Simultaneously due to the leaching poor selectivity of acidic process, the a large amount of strippings of impurity such as iron, calcium, magnesium, titanium, the aluminium purity salt of condensing crystal output is not high, the further Bayer process process of follow-up need, although adopt the flyash pre-deferrization of former grey magnetic separation and pickling liquor chemical purification to improve product purity, cost is high.A kind of method extracting aluminum oxide from flyash disclosed in CN1792802A, its technological process to be ground to 200 ~ 400 object flyash, first calcination activation 1 ~ 1.5h at 300 ~ 760 DEG C, then at 160 ~ 300 DEG C with the sulfuric acid leaching of 60 ~ 98% concentration, the slurry filtration leached is to be separated spent acid, and spent acid returns and leaches circulation, then from filter residue, leaches aluminium with water, then through condensing crystal, drying and dehydrating, calcination, γ-Al is obtained
2o
3adopt the method, the leaching rate of recovery of aluminium can reach 85%, but the method complex process, not only needs preroasting to activate, and leaching is carried out under the condition of high temperature concentrated acid, energy consumption is high, a large amount of acid carries out inefficient cycle in system, and the material of leaching, filtration, material transfer equipment is difficult to resolve certainly, operational difficulty.A kind of method being produced aluminum oxide by flyash disclosed in CN1923695A, first by flyash fine grinding and in 200-760 DEG C of calcination activation, again with appropriate vitriol oil mix evenly after burn till at 200-400 DEG C, then aluminum oxide is extracted in water logging, can obtain higher aluminium leaching yield equally.CN101811711A discloses a kind of Leaching in Hydrochloric Acid that adopts by the method extracting aluminum oxide in flyash, its process at 140-160 DEG C, leaches aluminium by after flyash and mixed in hydrochloric acid, then solid-liquid separation, condensing crystal, aluminum chloride calcining obtain active just aluminum oxide, by first aluminum oxide through Bayer process process for producing aluminum oxide.
To sum up, although alkali process alumina product quality is good, and close with traditional bauxite into alumina technique, be easy to technique and realize, but there is the problems such as by-product silicon produce market risk is high, sintering energy consumption large, the newly-increased quantity of slag is large, seriously constrain the industrial application of alkaline process.Although acid technological process achieves minimizing and utilizes coal measures solid waste, the aluminium salt-pepper noise of traditional acid system and dehydration energy is high, aluminium poor product quality.
Summary of the invention
The object of the invention is the deficiency in order to overcome in existing flyash extraction aluminum oxide technology, a kind of method adopting using acid and alkali combination method to extract aluminum oxide from flyash is provided, object is by soda acid process integration, solve aluminium salt condensing crystal and the problem that pyrolysis energy consumption is high, alumina product purity is low in flyash acidic process technique, avoid the defects such as flyash alkaline process process sinter doses is large, energy consumption is high, the leaching quantity of slag is large simultaneously.
For achieving the above object, technical scheme of the present invention is as follows.
Aluminous fly-ash produces the method for aluminum oxide, comprises the steps:
(1) vitriol oil is joined mix in flyash in batches and evenly carry out sulfuric acid solution, each acid adding mix thoroughly after acidolysis at 100 ~ 200 DEG C, solidification, add the next batch vitriol oil again, then acidolysis at 100 ~ 200 DEG C, solidification, until the required vitriol oil adds;
(2) sulfuric acid solution is warmed up to sulfurization roasting 1 ~ 4h under 200 ~ 500 DEG C of conditions after completing, and preferred maturing temperature 250 ~ 350 DEG C, obtains sulfation calcining;
(3) by the reducing roasting under 550 ~ 900 DEG C of temperature condition together with reductive agent of sulfation calcining, obtain reduced calcine and sulfur-containing smoke gas, the rear relieving haperacidity of sulfur-containing smoke gas collection returns step (1) sulfuric acid solution and recycles;
(4) solution of reduced calcine containing sodium hydroxide leaches, and has leached rear solid-liquor separation and has obtained sodium aluminate solution and Silicon-rich slag;
(5) after sodium aluminate solution desilicification, kind is divided, is calcined and produce aluminum oxide, and seed precipitation solution returns step (4) and leaches reduced calcine.
Aluminous fly-ash of the present invention produces the method for aluminum oxide, and in step (1), the total add-on of the vitriol oil presses H
2sO
4with Al in flyash
2o
3mole ratio 3:1 ~ 5:1 adds, preferred 3.5:1 ~ 4.5:1, h 2 so 4 concentration>=85%.
Aluminous fly-ash of the present invention produces the method for aluminum oxide, and the middle vitriol oil of step (1) divides more than 2 times and adds in batches, and each add-on is 20 ~ 70% of the total add-on of required sulfuric acid.
Aluminous fly-ash of the present invention produces the method for aluminum oxide, in step (3), reductive agent is one or more the mixture in the low value carbonaceous fuels such as coal dust, colliery powder, coal gas, Sweet natural gas, sulphur or refinery coke, and the amount of allocating into of reductive agent regulates according to the alumina content in flyash and the carbon left in flyash.
Aluminous fly-ash of the present invention produces the method for aluminum oxide, reducing roasting described in step (3) is fast fluidization roasting, stoving oven is the one in cyclic fluid roaster, gaseous pollutant control or fluidised form flash roaster, maturing temperature 650 ~ 800 DEG C, roasting time 0.1 ~ 60min, roasting time is 0.1 ~ 15min preferably.
Aluminous fly-ash of the present invention produces the method for aluminum oxide, and the leaching condition of step (4) is: extraction temperature 80 ~ 280 DEG C, ingredients molecular ratio α
k(molecular ratio of sodium oxide and aluminum oxide) 0.8 ~ 2.0, naoh concentration 100 ~ 300g/L, extraction time 30 ~ 120min, lime-crushed stone pile 0 ~ 15%.
Aluminous fly-ash of the present invention produces the method for aluminum oxide, and described aluminous fly-ash is the flyash of salic >=35%.
Sulfuric acid solution described in the present invention, is utilize the vitriol oil to change into generation Tai-Ace S 150 by flyash with aluminum-containing mineral, reacts as shown in the formula (1), thus destroys the mineral structure in raw material, and aluminium mineral and silicon mine are dissociated.
Al
2O
3·nSiO
2+3H
2SO
4＝Al
2(SO
4)
3+nSiO
2+3H
2O (1)
In sulfuric acid solution process, sulfuric acid adds in batches, can avoid because of one time that acid adding amount is excessive, and after flyash mixes acid, mixed material be pulpous state and causes being difficult to operate, and also can improve sulfuric acid utilization ratio.
Flyash and the acidolysis of sulfuric acid mixed material, solidify after be warmed up to 200 ~ 500 DEG C of roasting 1 ~ 4h, both can strengthen sulfuric acid solution process, can residual sulfuric acid be removed again, reduce sequential reduction roasting time reductive agent consumption.
Reducing roasting described in the present invention, that sulfation calcining is directly carried out reducing roasting with reductive agent, the condensing crystal Tai-Ace S 150 and the crystalline sulfuric acid aluminium that avoid highly energy-consuming in acidic process aluminium oxide extraction process dewater and Roasting Decomposition operation, simultaneously, because adopting quick medium temperature roast, in calcining, the leaching activity of aluminum oxide is high, utilizes the reaction of coal reduction roasting such as formula (2).
Al
2(SO
4)
3+3/2C＝Al
2O
3+3SO
2(g)+3/2CO
2(g)(2)
The calcining sodium hydroxide solution that in the present invention, reducing roasting obtains leaches aluminium, and Leaching reaction is as shown in the formula (3).
Al
2O
3+3H
2O+2NaOH＝2NaAl(OH)
4(3)
Aluminous fly-ash of the present invention produces the method for aluminum oxide, vitriol oil pyroreaction is utilized to enhance the decomposition of aluminium silicate mineral in flyash, then aluminum oxide is produced through fast restore desulfurization with roasting technique, alkali leaching, both the activity of aluminum oxide had been ensured, eliminate again the high energy consumption operation such as Tai-Ace S 150 condensing crystal, drying and dehydrating, calcining in traditional sulfuric acid process, flow process is simple, and energy consumption is low, and alumina product quality is good.In sulfuric acid solution step, by substep acid adding, improve acid-utilising rate, and be convenient to hydrolysis procedure operation, carry out sulfurization roasting again after acidolysis, solidification to remove remaining acid, thus reduce the reductive agent consumption of sequential reduction roasting.
Accompanying drawing explanation
Accompanying drawing is the principle flow chart of method of the present invention.
Embodiment
Below in conjunction with accompanying drawing the present invention made and further illustrating.
The required vitriol oil is joined mix in flyash in batches and evenly carries out sulfuric acid solution, each acid adding mix thoroughly after acidolysis at 100 ~ 200 DEG C, after solidification, be then warmed up to sulfurization roasting 1 ~ 4h under 200 ~ 500 DEG C of conditions, obtain sulfation calcining; By the reducing roasting under 550 ~ 900 DEG C of temperature condition together with reductive agent of sulfation calcining, the solution of the reduced calcine obtained containing sodium hydroxide carries out alkali leaching, after leaching completes, solid-liquor separation obtains sodium aluminate solution and Silicon-rich slag, after sodium aluminate solution desilicification, kind is divided, is calcined and produce aluminum oxide, and seed precipitation solution returns leaching reduced calcine.
Be further described method of the present invention with nonlimiting examples below, to contribute to understanding content of the present invention and advantage thereof, and not as limiting the scope of the present invention, protection scope of the present invention is determined by claims.
The present invention is suitable for the flyash of the different chemical composition of alumina content >=35%.Following table is the flyash main component that the embodiment of the present invention adopts.
| Main component | Al 2O 3 | CaO | Fe 2O 3 | K 2O | MgO | Na 2O | SiO 2 |
| Content (%) | 48.15 | 3.9 | 1.79 | 0.36 | 0.24 | 0.11 | 32.64 |
Embodiment 1
Get 100g flyash, by Al in flyash
2o
3get the sulfuric acid of 95% concentration for 3.5 times of mole number, divide 3 times and flyash mix, each acid adding mix thoroughly after acidolysis at 150 DEG C, solidification after, after in the end a collection of sulfuric acid adds and mixes thoroughly, be warmed up to 320 DEG C of sulfurization roasting 2h, the sulfation calcining of gained is pressed coal mix with coal dust than 8%, then reducing roasting 7min under 750 DEG C of conditions, the reduced calcine obtained.
Carry out alkali leaching to reduced calcine, leaching condition is: leaching temperature 100 DEG C, alkali concn 50g/L, ingredients molecular ratio α
k0.9, time 60min, lime-crushed stone pile 0%.The leaching of gained aluminium goes out rate 85%, and carry out desiliconization to dissolution fluid, plant and divide, obtain aluminum hydroxide product, prepare metallurgical-grade aluminum oxide product after calcining, seed precipitation solution returns reduced calcine stripping.
Embodiment 2
Get 100g flyash, by Al in flyash
2o
3get the sulfuric acid of 93% concentration for 4 times of mole number, divide 2 times and flyash mix, each acid adding mix thoroughly after acidolysis at 200 DEG C, solidification after, after in the end a collection of sulfuric acid adds and mixes thoroughly, be warmed up to 320 DEG C of sulfurization roasting 2h, the sulfation calcining of gained is pressed coal mix with coal dust than 10%, then reducing roasting 7min under 750 DEG C of conditions, the reduced calcine obtained.
Carry out alkali leaching to reduced calcine, leaching condition is: leaching temperature 90 DEG C, alkali concn 100g/L, ingredients molecular ratio α
k1.2, time 60min, lime-crushed stone pile 2%.The leaching of gained aluminium goes out rate 89%, and carry out desiliconization to dissolution fluid, plant and divide, obtain aluminum hydroxide product, prepare metallurgical-grade aluminum oxide product after calcining, seed precipitation solution returns reduced calcine stripping.
Embodiment 3
Get 100g flyash, by Al in flyash
2o
3get the sulfuric acid of 93% concentration for 4.5 times of mole number, divide 3 times and flyash mix, each acid adding mix thoroughly after acidolysis at 200 DEG C, solidification after, after in the end a collection of sulfuric acid adds and mixes thoroughly, be warmed up to 350 DEG C of sulfurization roasting 2h, the sulfation calcining of gained is pressed coal mix with coal dust than 10%, then reducing roasting 7min under 750 DEG C of conditions, the reduced calcine obtained.
Carry out alkali leaching to reduced calcine, leaching condition is: leaching temperature 150 DEG C, alkali concn 100g/L, ingredients molecular ratio α
k1.2, time 60min, lime-crushed stone pile 2%.The leaching of gained aluminium goes out rate 90%, and carry out desiliconization to dissolution fluid, plant and divide, obtain aluminum hydroxide product, prepare metallurgical-grade aluminum oxide product after calcining, seed precipitation solution returns reduced calcine stripping.
Embodiment 4
Get 100g flyash, by Al in flyash
2o
3get the sulfuric acid of 93% concentration for 4.5 times of mole number, divide 3 times and flyash mix, each acid adding mix thoroughly after acidolysis at 200 DEG C, solidification after, after in the end a collection of sulfuric acid adds and mixes thoroughly, be warmed up to 350 DEG C of sulfurization roasting 2h, the sulfation calcining of gained is pressed coal mix with coal dust than 10%, then in fluidized roaster under 750 DEG C of conditions reducing roasting 2min, the reduced calcine obtained.
Carry out alkali leaching to reduced calcine, leaching condition is: leaching temperature 150 DEG C, alkali concn 160g/L, ingredients molecular ratio α
k1.8, time 30min, lime-crushed stone pile 5%.The leaching of gained aluminium goes out rate 91%, and carry out desiliconization to dissolution fluid, plant and divide, obtain aluminum hydroxide product, prepare metallurgical-grade aluminum oxide product after calcining, seed precipitation solution returns reduced calcine stripping.
Embodiment 5
Get 100g flyash, by Al in flyash
2o
3get the sulfuric acid of 93% concentration for 3 times of mole number, divide 2 times and flyash mix, each acid adding mix thoroughly after acidolysis at 200 DEG C, solidification after, after in the end a collection of sulfuric acid adds and mixes thoroughly, be warmed up to 350 DEG C of sulfurization roasting 2h, the sulfation calcining of gained is pressed coal mix with coal dust than 10%, then in fluidized roaster under 750 DEG C of conditions reducing roasting 2min, the reduced calcine obtained.
Carry out alkali leaching to reduced calcine, leaching condition is: leaching temperature 250 DEG C, alkali concn 160g/L, ingredients molecular ratio α
k1.8, time 30min, lime-crushed stone pile 5%.The leaching of gained aluminium goes out rate 80%, and carry out desiliconization to dissolution fluid, plant and divide, obtain aluminum hydroxide product, prepare metallurgical-grade aluminum oxide product after calcining, seed precipitation solution returns reduced calcine stripping.
Embodiment 6
Get 100g flyash, by Al in flyash
2o
3get the sulfuric acid of 95% concentration for 3.5 times of mole number, by sulfuric acid and the disposable mix of flyash evenly after acidolysis at 200 DEG C, solidify after, after in the end a collection of sulfuric acid adds and mixes thoroughly, be warmed up to 350 DEG C of sulfurization roasting 2h, the sulfation calcining of gained is pressed coal mix with coal dust than 8%, then reducing roasting 7min under 750 DEG C of conditions, the reduced calcine obtained.
Carry out alkali leaching to reduced calcine, leaching condition is: leaching temperature 90 DEG C, alkali concn 100g/L, ingredients molecular ratio α
k1.2, time 60min, lime-crushed stone pile 0%.The leaching of gained aluminium goes out rate 87%, and carry out desiliconization to dissolution fluid, plant and divide, obtain aluminum hydroxide product, prepare metallurgical-grade aluminum oxide product after calcining, seed precipitation solution returns reduced calcine stripping.
Claims (10)
1. aluminous fly-ash produces the method for aluminum oxide, it is characterized in that, comprises the following steps:
(1) vitriol oil is joined mix in flyash in batches and evenly carry out sulfuric acid solution, each acid adding mix thoroughly after acidolysis at 100 ~ 200 DEG C, solidification, add the next batch vitriol oil again, then acidolysis at 100 ~ 200 DEG C, solidification, until the required vitriol oil adds;
(2) sulfuric acid solution is warmed up to sulfurization roasting 1 ~ 4h under 200 ~ 500 DEG C of conditions after completing, and obtains sulfation calcining;
(3) by the reducing roasting under 550 ~ 900 DEG C of temperature condition together with reductive agent of sulfation calcining, obtain reduced calcine and sulfur-containing smoke gas, the rear relieving haperacidity of sulfur-containing smoke gas collection returns step (1) sulfuric acid solution and recycles;
(4) solution of reduced calcine containing sodium hydroxide leaches, and has leached rear solid-liquor separation and has obtained sodium aluminate solution and Silicon-rich slag;
(5) after sodium aluminate solution desilicification, kind is divided, is calcined and produce aluminum oxide, and seed precipitation solution returns step (4) and leaches reduced calcine.
2. method according to claim 1, is characterized in that, in step (1), the total add-on of the vitriol oil presses H
2sO
4with Al in flyash
2o
3mole ratio 3:1 ~ 5:1 adds, h 2 so 4 concentration>=85%.
3. method according to claim 1, is characterized in that, sulfurization roasting temperature 250 ~ 350 DEG C in step (2).
4. method according to claim 2, is characterized in that, H
2sO
4with Al in flyash
2o
3mole ratio 3.5:1 ~ 4.5:1.
5. method according to claim 1, is characterized in that, the middle vitriol oil of step (1) divides more than 2 times and adds in batches, and each add-on is 20 ~ 70% of the total add-on of required sulfuric acid.
6. method according to claim 1, it is characterized in that, in step (3), reductive agent is one or more the mixture in the low value carbonaceous fuels such as coal dust, colliery powder, coal gas, Sweet natural gas, sulphur or refinery coke, and the amount of allocating into of reductive agent regulates according to the alumina content in flyash and the carbon left in flyash.
7. method according to claim 1, it is characterized in that, reducing roasting described in step (3) is fast fluidization roasting, stoving oven is the one in cyclic fluid roaster, gaseous pollutant control or fluidised form flash roaster, maturing temperature 650 ~ 800 DEG C, roasting time 0.1 ~ 60min.
8. method according to claim 7, is characterized in that, roasting time 0.1 ~ 15min.
9. method according to claim 1, is characterized in that, the leaching condition of step (4) is: extraction temperature 80 ~ 280 DEG C, ingredients molecular ratio α
k0.8 ~ 2.0, naoh concentration 100 ~ 300g/L, extraction time 30 ~ 120min, lime-crushed stone pile 0 ~ 15%.
10. method according to claim 1, is characterized in that, described aluminous fly-ash is the flyash of salic >=35%.
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| CN106477606A (en) * | 2016-10-12 | 2017-03-08 | 北京矿冶研究总院 | Method for extracting aluminum oxide from fly ash based on sulfuric acid curing |
| CN107089673A (en) * | 2017-06-09 | 2017-08-25 | 北京矿冶研究总院 | Method for preparing lithium carbonate by two-stage conversion of lithium ore |
| CN107326182A (en) * | 2017-06-09 | 2017-11-07 | 北京矿冶研究总院 | High-value comprehensive utilization method for red mud |
| CN107930576A (en) * | 2017-11-27 | 2018-04-20 | 吉林大学 | A kind of preparation method of fly ash micro-sphere porous material and obtained porous material |
| CN110395755A (en) * | 2019-09-05 | 2019-11-01 | 东北大学 | A method of aluminium oxide is produced using flyash |
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