CN104445314A - Method for acid-base combined extraction of alumina from coal gangue or kaolinite minerals - Google Patents
Method for acid-base combined extraction of alumina from coal gangue or kaolinite minerals Download PDFInfo
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- CN104445314A CN104445314A CN201410602122.8A CN201410602122A CN104445314A CN 104445314 A CN104445314 A CN 104445314A CN 201410602122 A CN201410602122 A CN 201410602122A CN 104445314 A CN104445314 A CN 104445314A
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- coal gangue
- kaolinite
- sulfuric 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
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
Abstract
The invention discloses a method for extracting aluminum oxide from coal gangue or kaolinite minerals by acid-base combination. Mixing the crushed coal gangue or kaolinite mineral raw material with a proper amount of concentrated sulfuric acid, curing, then quickly reducing and desulfurizing at high temperature, realizing the regeneration and cyclic utilization of sulfuric acid by making acid from sulfur-containing flue gas, and producing alumina from reduced calcine by an alkaline leaching method. The method of the invention integrates the advantages of extracting alumina by the acid method and the alkaline method of the gangue or kaolinite mineral raw material, and effectively avoids the disadvantages of the gangue or kaolinite mineral raw material. The high-energy-consumption evaporative crystallization aluminum salt and aluminum salt crystallization water decomposition process in the conventional acid method process are not needed, so that a large amount of energy consumption is saved; compared with the conventional alkaline process, the method does not need a sintering process with high energy consumption, has low slag quantity and can be reused as a silicon raw material, has little waste output, and realizes real reduction green clean production; the alumina product has good quality, high recovery rate, low energy consumption, small equipment corrosion and easy realization of large-scale industrialization.
Description
Technical field
The invention belongs to the comprehensive utilization of coal gangue or kaolinite ore raw material, be specifically related to a kind of method extracting aluminum oxide from coal gangue or clay mineral raw material, especially adopt soda acid process integration to extract aluminum oxide.
Background technology
China is the country that enriches very much of kaolinite mineral resource in the world, and wherein Coal Gangue Resource is especially abundant, and in addition, the kaolinite class mineral wealth such as kaolin, dickite, nacrite are also very abundant.Coal gangue is the solid waste discharged in coal mining process and coal washing process, it is a kind of black gray expandable rock lower with a kind of carbon content of coal seam association in coalification course, general digging gangue accounts for about 10% of raw coal output, and coal separation spoil accounts for the 12%-18% of feed coal amount.Chinese raw coal output 36.8 hundred million tons in 2013, the coal gangue of exploitation course of processing discharge is one of maximum industrial solid castoff of current China quantity discharged, and coal gangue is stored up for a long time, takies a large amount of soil, causes spontaneous combustion simultaneously, atmosphere pollution and underground water.But it is again available resource, and its main component is Al
2o
3, SiO
2, micro-rare elements (gallium, vanadium etc.), wherein alumina content can up to 30%-40%, SiO
2content 50%-65%, extracts aluminum oxide and not only can extract supplementing of aluminum oxide as bauxite from coal gangue or other clay mineral raw material, and very important for the environmental problem solving process of coal mining coal measures solid waste.
Traditional alumina producing take bauxite as raw material, adopts alkali process to produce, and in bauxite into alumina, the silicon oxide in bauxite is the main harmful element during alkaline process is produced, and requires (the Al in ore of alumina silica ratio A/S in bauxite
2o
3with SiO
2mass values) be greater than 3.Alkaline process is divided into Bayer process, sintering process and integrated process, and wherein Bayer process is suitable for process containing Al
2o
3high, SiO
2low rich ore, general requirement Al
2o
3> 65%, A/S > 7, the aluminum oxide of more than 90% is produced by Bayer process in the world; It is the raw material of 3 ~ 5 that sintering process is applicable to process A/S; It is the raw material of 5 ~ 7 that integrated process is applicable to process A/S.And alumina silica ratio in coal gangue or other kaolinite ore raw material is very low, usual A/S≤1, and cannot beneficiation enrichment, the process for making alumina of conventional process bauxite is difficult to transplanting to process coal gangue or other kaolinite mineral, need research and development to be applicable to the Technology of coal gangue or other kaolinite mineral eka-aluminum resources characteristic, the coal gangue of research and development both at home and abroad at present or other kaolinite mineral extract aluminum oxide method and are roughly divided into alkaline process and the large class of acid system two.
Alkaline process comprises direct sintering and pre-desiliconizing-sintering process etc.A kind of method extracting aluminum and coproducing active calcium silicate from coal gangue disclosed in CN101941725B, its process mainly comprises: coal gangue pulverizes rear calcination activation; Coal gangue grog carries out the molten pre-desiliconizing of alkali, obtains desiliconization coal gangue and sodium silicate solution; Add Wingdale and sodium carbonate solution ball milling in desiliconization coal gangue to make charge pulp and sinter; Burn till grog with water-soluble go out, obtain crude liquor of sodium aluminate and calcium silicate slag, calcium silicate slag is after treatment as cement raw material; Crude liquor of sodium aluminate produces aluminum oxide through operations such as purification, carbon divides, calcinings; Active calcium silicate micro mist is produced by sodium silicate solution causticization.Adopt pre-desiliconizing technology by more than 50% silicon-dioxide Leaching Removal, thus the alumina silica ratio in coal gangue can be improved, but with high-silica diaspore ore ratio, still siliceous height, follow-up sintering amount is large, and energy consumption is high.Although can a large amount of active calcium silicate byproduct of output, because the cost of by-product active calcium silicate is high, output large, fully utilize for large-scale Coal Gangue Resource, the market sale of byproduct and competitive pressure be very large.
Acidic process coal gangue is not owing to 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.Acid system mainly comprises sulfuric acid process and hydrochloric acid method, normally by certain density sulfuric acid or hydrochloric acid and colliery powder in heating condition agitation leach, gained solution adds alkali reaction and generates aluminum hydroxide precipitation, filters to obtain aluminium hydroxide.Due to the poor activity of aluminum oxide in coal gangue, the alumina extraction ratio of general acidleach is lower, needs to adopt calcination activation, add the enhancements such as solubility promoter.Disclosed in CN101234774B, a kind of method being prepared aluminum oxide by coal series kaolin rock or coal gangue, then carry out activation treatment by roasting to coal gangue, adopts pulverizing, low temperature calcination, hydrochloric acid leaching, filtration, purification, the pyrogenically prepared aluminum oxide of substep.A kind of method utilizing coal gangue to produce aluminum oxide disclosed in CN103754912A, by the sulfuric acid reaction solidification of coal gangue and hydrofluoric acid, 50-90%, then aluminum oxide is extracted in water logging; The method of coal gangue eco-utilization coproduction aluminum oxide/white carbon black/low ash carbon disclosed in CN1903727A, then adopt coal gangue to mix with the sulfuric acid of 8-12mol/L, adopt fluorochemical to be that solubility promoter carries out sulfuric acid leaching aluminium simultaneously.Adopt solubility promoter acidleach, although calcination activation operation can be reduced, save the energy consumption of alumina extraction, fluorine-containing solubility promoter add the problem of environmental pollution that not only can cause water, gas, slag, and serious to equipment corrosion; Due to the leaching poor selectivity of acid system, the aluminium product salt directly obtaining meeting alumina impurities requirement is difficult to by crystallization, need periodic crystallisation to purify or adopt the method for extraction or ion-exchange to purify pickling liquor, or extract aluminum oxide through Bayer process again after the calcining of crude aluminum salt, complex process, cost is high; On the other hand, the energy consumption of aluminium salt condensing crystal, the pyrolysis of aluminium dehydration of salt is large.
Summary of the invention
The object of the invention is to overcome the deficiency extracting aluminum oxide technology in existing coal gangue or kaolinite mineral, a kind of method adopting using acid and alkali combination method to extract aluminum oxide from coal gangue or kaolinite mineral 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 coal gangue or kaolinite mineral raw material acid system treatment process, the defect such as simultaneously avoid coal gangue or kaolinite ore raw material alkaline process process sinter doses is large, energy consumption is high, the leaching quantity of slag is large.
For achieving the above object, the method for a kind of soda acid combined extracting aluminum oxide from coal gangue or kaolinite mineral of the present invention comprises the steps:
(1) sulfuric acid slaking: carry out slaking after mixing by a certain percentage with the vitriol oil after coal gangue or kaolinite mineral raw material pulverizing, obtains sulfuric acid slaking material;
(2) reducing roasting: sulfuric acid slaking material above-mentioned steps (1) obtained carries out reducing roasting desulfurization under reducing atmosphere, obtains calcining and sulfur-containing smoke gas, the rear relieving haperacidity of sulfur-containing smoke gas collection returns step (1) and recycles;
(3) calcining alkali leaching: the solution of calcining above-mentioned steps (2) obtained containing sodium hydroxide carries out alkali leaching, has leached rear solid-liquor separation and has obtained sodium aluminate solution and Silicon-rich slag.
(4) aluminum oxide is prepared: sodium aluminate solution above-mentioned steps (3) obtained is through to plant point or carbon divides and prepares aluminium hydroxide, then solid-liquid separation obtains aluminium hydroxide and mother liquor, mother liquor returns step (3) and recycles, and aluminium hydroxide produces aluminum oxide through calcining.
The method of a kind of soda acid combined extracting aluminum oxide from coal gangue or kaolinite mineral of the present invention, is characterized in that the grinding particle size of coal coal gangue or kaolinite ore raw material described in its step (1) is 100 ~ 200 orders.
The method of a kind of soda acid combined extracting aluminum oxide from coal gangue or kaolinite mineral of the present invention, it is characterized in that in its step (1), sulphuric acid is 1-2.5 times of described coal gangue or kaolinite mineral raw materials quality, preferred 1.1-1.5 times, concentration >=85% of sulfuric acid.
The method of a kind of soda acid combined extracting aluminum oxide from coal gangue or kaolinite mineral of the present invention, is characterized in that curing temperature 100-350 DEG C, preferred 150-250 DEG C, curing time 1-24h, preferred 1-4h in its step (1).
The method of a kind of soda acid combined extracting aluminum oxide from coal gangue or kaolinite mineral of the present invention, is characterized in that the reducing roasting described in its step (2), when process raw material is coal gangue, with the charcoal contained by coal gangue itself for reductive agent.
The method of a kind of soda acid combined extracting aluminum oxide from coal gangue or kaolinite mineral of the present invention, it is characterized in that the reducing roasting described in its step (2), when process raw material is other kaolinite class ore deposits such as kaolin, dickite, nacrite, allocate appropriate reductive agent into and carry out reducing roasting, reductive agent used is one or more the mixture in the low value carbonaceous fuels such as coal dust, coal gas, Sweet natural gas, sulphur or refinery coke, when using coal dust to make reductive agent, allocating into than the 1-30% for described sulfuric acid slaking material quality of coal dust.
The method of a kind of soda acid combined extracting aluminum oxide from coal gangue or kaolinite mineral of the present invention, it is characterized in that reducing roasting temperature 500-900 DEG C in its step (2), preferred 650-800 DEG C, reducing roasting time 0.1-60min, preferred 0.1-15min.
The method of a kind of soda acid combined extracting aluminum oxide from coal gangue or kaolinite mineral of the present invention, it is characterized in that the reducing roasting described in its step (2) is fast fluidization roasting, stoving oven is the one in cyclic fluid roaster, gaseous pollutant control or fluidised form flash roaster.
The method of a kind of soda acid combined extracting aluminum oxide from coal gangue or kaolinite mineral of the present invention, is characterized in that the alkali leaching described in its step (3) is the one in the leaching of normal pressure alkali, alkaline pressure of oxygen leaching or Bayer Process digestion.
The method of a kind of soda acid combined extracting aluminum oxide from coal gangue or kaolinite mineral of the present invention, it is characterized in that the alkali leaching described in its step (3), its alkali leaching condition is: leaching temperature 80-250 DEG C, alkali concn 30-220g/L, extraction time 20-80min, ingredients molecular ratio α
k0.8-2.0, lime-crushed stone pile 0-15%.
The method of a kind of soda acid combined extracting aluminum oxide from coal gangue or kaolinite mineral of the present invention, it is characterized in that described in its step (4) prepare aluminum oxide when adopt carbon divide prepare aluminum oxide time, mother liquor is through causticization process Posterior circle.
The method of a kind of soda acid combined extracting aluminum oxide from coal gangue or kaolinite mineral of the present invention, it is characterized in that the mother liquor described in its step (4), when containing gallium in mother liquor, regular extraction section mother liquor adopts carbonization precipitation, ion-exchange or solvent extration to reclaim gallium.
The method of a kind of soda acid combined extracting aluminum oxide from coal gangue or kaolinite mineral of the present invention, described sulfation slaking, utilize the pyroreaction of the vitriol oil active, react with the aluminum-containing mineral of coal gangue or kaolinite ore raw material, generate Tai-Ace S 150 thing phase, react as shown in the formula (1), thus destroy coal gangue or kaolinite ore raw material Minerals structure, 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)
The method of a kind of soda acid combined extracting aluminum oxide from coal gangue or kaolinite mineral of the present invention, described reducing roasting, that coal gangue or kaolinite mineral raw material sulphuric acid slaking material are carried out roasting, utilize charcoal contained in coal gangue as reductive agent thus realize reducing roasting desulfurization, the condensing crystal Tai-Ace S 150 and the crystalline sulfuric acid aluminium that avoid highly energy-consuming in acidic process coal gangue or kaolinite ore raw material dewater and Roasting Decomposition operation, simultaneously, because adopting the quick roasting of high temperature, ensureing that the leaching of aluminum oxide in calcining is simultaneously active, the stripping reducing silicon oxide is active, the reaction of coal reduction roasting is such as formula (2).In reducing roasting process, when process raw material is other kaolinite class ore deposits such as kaolin, dickite, nacrite, appropriate reductive agent of preparing burden carries out reducing roasting.
2Al
2(SO
4)
3+3C＝2Al
2O
3+6SO
2(g)+3CO
2(g)(2)
The method of a kind of soda acid combined extracting aluminum oxide from coal gangue or kaolinite mineral of the present invention, described calcining alkali leaching, because in the calcining that described reducing roasting obtains, alumina leaching activity is good, can leach under lesser temps and basicity condition, ensureing, under higher aluminium leaching yield prerequisite, the stripping of silicon to be reduced further.Calcining alkali leaching reaction is as shown in the formula (3).
Al
2O
3+3H
2O+2NaOH＝2NaAl(OH)
4(3)
The method of a kind of soda acid combined extracting aluminum oxide from coal gangue or kaolinite mineral of the present invention, vitriol oil pyroreaction is utilized to enhance the decomposition of silico-aluminate in coal gangue or kaolinite ore raw material, different from traditional acid system, directly do not carry out the leaching of Tai-Ace S 150, but the desulfurization utilizing reductive agent to realize sulfuric acid slaking material is decomposed, and ensureing the activity of aluminum oxide, the flue gas that desulfurization produces realizes the regeneration of main agents sulfuric acid by relieving haperacidity.In the calcining of desulfurization simultaneously, aluminum oxide has activity, can realize low-temperature low-alkali Bayer Process digestion, carry out the preparation of conventional alumina product.
Solve because leaching poor selectivity in traditional acidic process coal gangue or kaolinite ore raw material, a difficult problem for solution purification difficulty, without the need to highly energy-consuming processes such as the condensing crystal Tai-Ace S 150 in traditional sulfuric acid process, Tai-Ace S 150 dehydrations.Compared with traditional alkaline process process coal gangue or kaolinite mineral raw material process, avoid the sintering circuit of highly energy-consuming, without the need to adding the slag former such as limestone powder, lime, leaching the quantity of slag and significantly reducing.
Described coal gangue or kaolinite mineral raw material comprise coal gangue, clay, kaolin, andaluzite, sillimanite, dickite, nacrite etc.
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.
100 ~ 200 object coal gangues will be crushed to or other kaolinite ore raw material mixes by a certain percentage with sulfuric acid, sulphuric acid is 1-2.5 times of described coal gangue or kaolinite mineral raw materials quality, preferred 1.1-1.5 doubly, concentration >=85% of sulfuric acid, curing temperature 100-350 DEG C, curing time 1-24h.
Sulfuric acid slaking material is carried out reducing roasting desulfurization under reducing atmosphere, reducing roasting temperature 500-900 DEG C, roasting time 0.1-60min.The sulfur-containing smoke gas of reducing roasting output collects extracting sulfuric acid, realizes the recycling utilization of sulfuric acid.When process raw material is coal gangue, with the charcoal contained by coal gangue itself for reductive agent.When process raw material is other kaolinite class ore deposits such as kaolin, dickite, nacrite, allocate appropriate reductive agent into and carry out reducing roasting, reductive agent used is one or more the mixture in the low value carbonaceous fuels such as coal dust, coal gas, Sweet natural gas, sulphur or refinery coke, when using coal dust to make reductive agent, allocating into than the 1-30% for described sulfuric acid slaking material quality of coal dust
The solution of reduced calcine containing sodium hydroxide is leached, alkali leaching temperature 80-250 DEG C, alkali concn 30-220g/L, extraction time 20-80min, ingredients molecular ratio α
k0.8-2.0, lime-crushed stone pile 0-15%.After alkali leaching solid-liquid separation on ore pulp, the sodium aluminate solution that obtains is through to plant point or carbon divides and prepares aluminium hydroxide, and seed precipitation solution or carbon mother liquid causticization process Posterior circle use.The stripping slag of low-temperature low-alkali Bayer process can directly as the siliceous raw material of building product.
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 coal gangue or the kaolinite ore raw material of different chemical composition.
Embodiment 1
To be crushed to 200 order colliery powders to mix with sulfuric acid, sulphuric acid is 1.6 times of described colliery powder quality, and the sulfuric acid concentration of use is 90%, after mixing, and curing temperature 200 DEG C, obtains sulfuric acid slaking material under curing time 2h condition.The charcoal utilizing coal gangue itself contained is reductive agent, sulfuric acid slaking material 750 DEG C, carry out fast restore roasting, roasting time 5min under reducing atmosphere.
Carry out low-temperature low-alkali Bayer Process digestion to reduced calcine, leaching condition is: leaching temperature 100 DEG C, alkali concn 50g/L, ingredients molecular ratio α
k0.9, time 60min.Now, the actual solubility rate 87% of aluminium, carry out kind point to dissolution fluid, obtain aluminum hydroxide product, prepare metallurgical-grade aluminum oxide product after calcining, seed precipitation solution returns calcining stripping.
Embodiment 2
To be crushed to 200 object colliery powders to mix with sulfuric acid, sulphuric acid is 2 times of described colliery powder quality, and the sulfuric acid concentration of use is 93%, after mixing, and curing temperature 250 DEG C, obtains sulfuric acid slaking material under curing time 24h condition.The charcoal utilizing coal gangue itself contained is reductive agent, and sulfuric acid slaking material carries out fast restore roasting in 850 DEG C, roasting time 2min in fluidized roaster.
Carry out low-temperature low-alkali Bayer Process digestion to reduced calcine, leaching condition is: leaching temperature 120 DEG C, alkali concn 160g/L, ingredients molecular ratio α
k1.8, time 30min, lime-crushed stone pile 8%.Now, the actual solubility rate of aluminium, 90%, carries out kind point to dissolution fluid, obtains aluminum hydroxide product, prepare metallurgical-grade aluminum oxide product after calcining, and seed precipitation solution returns to the batching new ore deposit of stripping.
Embodiment 3
To be crushed to 200 object colliery powders to mix with sulfuric acid, sulphuric acid is 1.2 times of described colliery powder quality, and the sulfuric acid concentration of use is 90%, after mixing, and curing temperature 150 DEG C, obtains sulfuric acid slaking material under curing time 2h condition.The charcoal utilizing coal gangue itself contained is reductive agent, and sulfuric acid slaking material carries out fast restore roasting, roasting time 15min temperature 600 DEG C.
Carry out low-temperature low-alkali Bayer Process digestion to reduced calcine, leaching condition is: leaching temperature 100 DEG C, alkali concn 200g/L, ingredients molecular ratio α
k1.9, time 60min, lime-crushed stone pile 3%.Now, the actual solubility rate of aluminium, 77%, carries out kind point to dissolution fluid, obtains aluminum hydroxide product, prepare metallurgical-grade aluminum oxide product after calcining.
Embodiment 4
To be crushed to 200 object kaolin to mix with sulfuric acid, sulphuric acid is 2 times of described kaolinite soil property amount, and the sulfuric acid concentration of use is 93%, after mixing, and curing temperature 250 DEG C, obtains sulfuric acid slaking material under curing time 8h condition.Sulfuric acid slaking material mixes with coal dust than 15% by coal, carries out fast restore roasting, roasting time 10min temperature 800 DEG C.
Carry out low-temperature low-alkali Bayer Process digestion to reduced calcine, leaching condition is: leaching temperature 90 DEG C, alkali concn 70g/L, ingredients molecular ratio α
k1.2, time 40min, lime-crushed stone pile 2%.Now, the actual solubility rate of aluminium, 92%, carries out kind point to dissolution fluid, obtains aluminum hydroxide product, prepare metallurgical-grade aluminum oxide product after calcining, and seed precipitation solution returns to the batching new ore deposit of stripping.
Embodiment 5
To be crushed to 200 object dickite concentrate to mix with sulfuric acid, sulphuric acid is 1.8 times of described dickite concentrate quality, and the sulfuric acid concentration of use is 93%, after mixing, and curing temperature 350 DEG C, obtains sulfuric acid slaking material under curing time 4h condition.Sulfuric acid slaking material passes into coal gas in fluidized roaster, carries out fast restore roasting, roasting time 1min temperature 750 DEG C.
Carry out low-temperature low-alkali Bayer Process digestion to reduced calcine, leaching condition is: leaching temperature 150 DEG C, alkali concn 50g/L, ingredients molecular ratio α
k0.9, time 60min, lime-crushed stone pile 0%.Now, the actual solubility rate of aluminium, 90%, carries out kind point to dissolution fluid, obtains aluminum hydroxide product, prepare metallurgical-grade aluminum oxide product after calcining, and seed precipitation solution returns to the batching new ore deposit of stripping.
Embodiment 6
To be crushed to 200 object andalusite mines to mix with sulfuric acid, sulphuric acid is 1.8 times of described colliery powder quality, and the sulfuric acid concentration of use is 93%, after mixing, and curing temperature 320 DEG C, obtains sulfuric acid slaking material under curing time 4h condition.Sulfuric acid slaking material mixes with coal dust than 15% by coal, carries out fast restore roasting, roasting time 10min temperature 750 DEG C.
Carry out low-temperature low-alkali Bayer Process digestion to reduced calcine, leaching condition is: leaching temperature 95 DEG C, alkali concn 100g/L, ingredients molecular ratio α
k1.0, time 80min, lime-crushed stone pile 1%.Now, the actual solubility rate of aluminium is 89%.
Embodiment 7
To be crushed to 200 object colliery powders to mix with sulfuric acid, sulphuric acid is 1.8 times of described colliery powder quality, and the sulfuric acid concentration of use is 93%, after mixing, and curing temperature 230 DEG C, obtains sulfuric acid slaking material under curing time 12h condition.The charcoal utilizing coal gangue itself contained is reductive agent, and sulfuric acid slaking material carries out fast restore roasting, roasting time 7min temperature 650 DEG C.
Carry out low-temperature low-alkali Bayer Process digestion to reduced calcine, leaching condition is: leaching temperature 90 DEG C, alkali concn 50g/L, ingredients molecular ratio α
k1.4, time 120min, aluminium leaching yield is 92%.Carry out carbon to dissolution fluid to divide, obtain aluminum hydroxide product, after calcining, prepare metallurgical-grade aluminum oxide product, carbon mother liquid secondary carbonization precipitation enrichment gallium, gallium deposition rate 85%.
Embodiment 8
To be crushed to 200 object colliery powders to mix with sulfuric acid, sulphuric acid is 1.8 times of described colliery powder quality, and the sulfuric acid concentration of use is 93%, after mixing, and curing temperature 320 DEG C, obtains sulfuric acid slaking material under curing time 4h condition.The charcoal utilizing coal gangue itself contained is reductive agent, and sulfuric acid slaking material carries out fast restore roasting, roasting time 10min temperature 700 DEG C.
Carry out low-temperature low-alkali Bayer Process digestion to reduced calcine, leaching condition is: leaching temperature 95 DEG C, alkali concn 100g/L, ingredients molecular ratio α
k1.0, time 80min, lime-crushed stone pile 1%.Now, the actual solubility rate of aluminium, 93%, carries out kind point to dissolution fluid, obtains aluminum hydroxide product, prepare metallurgical-grade aluminum oxide product after calcining..Seed precipitation solution adopts acylamide-oxime resin absorption gallium, gallium adsorption rate 85%.
Claims (10)
1. the method for soda acid combined extracting aluminum oxide from coal gangue or kaolinite mineral, is characterized in that, comprise the following steps:
(1) sulfuric acid slaking: carry out slaking after mixing by a certain percentage with the vitriol oil after coal gangue or kaolinite mineral raw material pulverizing, obtains sulfuric acid slaking material;
(2) reducing roasting: sulfuric acid slaking material above-mentioned steps (1) obtained carries out reducing roasting desulfurization under reducing atmosphere, obtains calcining and sulfur-containing smoke gas, the rear relieving haperacidity of sulfur-containing smoke gas collection returns step (1) and recycles;
(3) calcining alkali leaching: the solution of calcining above-mentioned steps (2) obtained containing sodium hydroxide carries out alkali leaching, has leached rear solid-liquor separation and has obtained sodium aluminate solution and Silicon-rich slag.
(4) aluminum oxide is prepared: sodium aluminate solution above-mentioned steps (3) obtained is through to plant point or carbon divides and prepares aluminium hydroxide, then solid-liquid separation obtains aluminium hydroxide and mother liquor, mother liquor returns step (3) and recycles, and aluminium hydroxide produces aluminum oxide through calcining.
2. method according to claim 1, is characterized in that, described in its step (1), the grinding particle size of coal coal gangue or kaolinite ore raw material is 100 ~ 200 orders.
3. method according to claim 1, is characterized in that, its step (1) sulphuric acid is 1-2.5 times of described coal gangue or kaolinite mineral raw materials quality, preferred 1.1-1.5 times, concentration >=85% of sulfuric acid.
4. method according to claim 1, is characterized in that, curing temperature 100-350 DEG C, preferred 150-250 DEG C, curing time 1-24h, preferred 1-4h in its step (1).
5. method according to claim 1, is characterized in that, the reducing roasting described in its step (2), when process raw material is coal gangue, with the charcoal contained by coal gangue itself for reductive agent; When process raw material is other kaolinite class ore deposits such as kaolin, dickite, nacrite, allocate reductive agent into and carry out reducing roasting, reductive agent used is one or more the mixture in the low value carbonaceous fuels such as coal dust, coal gas, Sweet natural gas, sulphur or refinery coke, when using coal dust to make reductive agent, allocating into than the 1-30% for described sulfuric acid slaking material quality of coal dust.
6. method according to claim 1, is characterized in that, reducing roasting temperature 500-900 DEG C, preferred 650-800 DEG C in its step (2), reducing roasting time 0.1-60min, preferred 0.1-15min.
7. method according to claim 1, is characterized in that, the reducing roasting described in its step (2) is fast fluidization roasting, and stoving oven is the one in cyclic fluid roaster, gaseous pollutant control or fluidised form flash roaster.
8. method according to claim 1, is characterized in that, the alkali leaching described in its step (3), its alkali leaching condition is: leaching temperature 80-250 DEG C, alkali concn 30-220g/L, extraction time 20-80min, ingredients molecular ratio α k0.8-2.0, lime-crushed stone pile 0-15%.
9. method according to claim 1, is characterized in that, when containing gallium in the mother liquor described in its step (4), regular extraction section mother liquor adopts carbonization precipitation, ion-exchange or solvent extration to reclaim gallium.
10. method according to claim 1, is characterized in that, the coal gangue described in it or kaolinite mineral comprise one or more mixture of coal gangue, clay, kaolin, andaluzite, sillimanite, dickite, nacrite kind.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104787790A (en) * | 2015-04-17 | 2015-07-22 | 北京矿冶研究总院 | Method for extracting aluminum oxide and silicon oxide from coal-based solid waste |
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| CN111663046A (en) * | 2020-06-30 | 2020-09-15 | 东北大学 | System for recovering iron and aluminum by suspending and co-roasting red mud and coal gangue |
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