CN101734698A - Method for preparing aluminum oxide from aluminiferous material - Google Patents

Method for preparing aluminum oxide from aluminiferous material Download PDF

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CN101734698A
CN101734698A CN 200910187282 CN200910187282A CN101734698A CN 101734698 A CN101734698 A CN 101734698A CN 200910187282 CN200910187282 CN 200910187282 CN 200910187282 A CN200910187282 A CN 200910187282A CN 101734698 A CN101734698 A CN 101734698A
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ammonium
aluminium
bauxite
solution
iron
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CN101734698B (en
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翟玉春
吴艳
牟文宁
王佳东
王伟
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Northeastern University China
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Abstract

The invention provides a method for preparing aluminum oxide and other products from aluminiferous materials such as bauxite, high iron bauxite, alunite, kaoline, alumina, fly ash, coal gangue, aluminum ash, nepheline, clay and the like. The method comprises the following steps: (1) crushing, grinding and mixing the aluminiferous materials with ammonium sulfate and then roasting; (2) dissolving the roasted product (clinker aggregate) in water, and filtering to obtain aluminum ammonium sulfate solution and filter residues; (3) carrying out deferrization, aluminum deposition or recrystallization on the aluminium ammonum sulfate solution with ammonia to prepare aluminum oxide, and meanwhile, recycling the ammonium sulfate; (4) preparing silicon dioxide from the filter residues, and taking the remaining residues containing ferrum as the raw material for ironmaking. The method is suitable for treating various aluminiferous materials, has the advantages of simple technical process, simple equipment, no emission of solid, liquid and gas wastes, and no secondary pollution, and realizes the high-added-value green complex utilization of the aluminiferous materials such as bauxite, high iron bauxite, alunite, kaoline, alumina, fly ash, coal gangue, aluminum ash, nepheline, clay and the like.

Description

A kind ofly prepare method of alumina by aluminiferous material
Technical field
The present invention relates to a kind of method of handling aluminiferous material, be specifically related to the method that aluminiferous materials such as bauxite, high-iron bauxite, alunite, kaolin, bauxitic clay, flyash, coal gangue, aluminium ash, nepheline, clay prepare exsiccated ammonium alum, aluminum oxide and silica product.
Background technology
Aluminiferous materials such as bauxite, high-iron bauxite, alunite, kaolin, bauxitic clay, nepheline, clay, flyash, coal gangue, aluminium ash are aluminum-containing mineral or aluminiferous solid waste, contain a large amount of silicon-dioxide and oxide compounds such as iron, calcium usually.Wherein, the main aluminum-containing mineral in bauxite, high-iron bauxite, the bauxitic clay is a diaspore and gibbsite; Main aluminum-containing mineral in kaolin, nepheline, clay, flyash, the coal gangue is an aluminosilicate; Main aluminum-containing mineral in the alunite is a potassium aluminium sulfate; Main aluminum-containing mineral in the aluminium ash is metallic aluminium and crystalline state aluminum oxide and non-crystalline state aluminum oxide.The chemical ingredients of these aluminiferous materials is not only because of becoming thereby different, and composition changes greatly, and physicochemical property also vary, and especially aluminium usually and silicon formation aluminosilicate and increased aluminium, the isolating cost of silicon and difficulty.Producing aluminum oxide with bauxite or other aluminum-containing raw material, is exactly in fact aluminum oxide and other impurity separating process that makes in the ore.The production method of alumina has alkaline process, acid system, electric heating process.
1 alkaline process is produced aluminum oxide
The ultimate principle of alkaline process is to make aluminum oxide and alkali in the ore generate water-soluble sodium aluminate under certain condition, separate with impurity such as ferric oxide with silicon-dioxide after the stripping, and then making purified sodium aluminate solution branch parse aluminium hydroxide, aluminium hydroxide makes the finished product aluminum oxide through high-temperature calcination.
Alkaline process is produced aluminum oxide can be divided into bayer's process, sintering process, integrated process etc. again.
1.1 Bayer process
Bayer's process is directly to handle bauxite with soda lye, makes aluminum oxide generation sodium aluminate in the ore, and the silicon-dioxide in the ore then becomes insoluble sludge--red mud, separates with sodium aluminate solution.Sodium aluminate solution after purifying is decomposed, filter and obtain aluminium hydroxide, after washing, be sintered into aluminum oxide.The caustic solution that decomposites aluminium hydroxide is called mother liquor, and mother liquor is used further to handle next batch ore, recycle through inspissation.
1.2 sintering process
Sintering process is with ore, soda ash, Wingdale mix, and high temperature sintering makes in the ore aluminum oxide generate solid sodium aluminate, ferric oxide generate can hydrolysis sodium ferrite, and silicon-dioxide and calcium oxide generate insoluble calcium orthosilicate 2CaOSiO 2Use sig water stripping agglomerate-grog again, make sodium aluminate enter solution and separate with red mud.
The solution that contains part silicon-dioxide obtains the sodium aluminate solution refined liquid after desiliconization, the feeding carbon dioxide makes it to decompose and obtains aluminium hydroxide and mother liquor.Mother liquor replenishes suitable soda ash and following batch ore and lime batching sintering after evaporating.Aluminium hydroxide after the washing obtains aluminum oxide through calcining.
In general, it is simple that bayer's process has flow process, invest less, quality product height, the advantage that production cost is lower.But it is relatively poor to handle its superiority of low grade ore, but also will consume expensive caustic alkali.
The advantage of sintering process is to handle the low ore of grade, and only consume low-cost yellow soda ash, compare with bayer's process, under same condition, handle low grade ore, the alkaline consumption of sintering process is lower, the aluminum oxide total yield is higher, but the flow process complexity, investment is big, product aluminum oxide quality is relatively poor, cost is higher.
Therefore siliceous very low high-quality bauxite just adopts bayer's process, and siliceous height, the aluminum ore that alumina silica ratio is lower generally adopt sintering process.
1.3 integrated process
In order to make full use of Mineral resources, the advantage of comprehensive two kinds of methods to improve the aluminum oxide total yield, is improved the quality of products, and reduces production costs, and two kinds of methods are joined together to use, and has so just produced integrated process.Integrated process is divided into series, parallel, mixed combining method again.
Multiple process is to handle high-grade ore with bayer's process, and sintering process is handled low grade ore; Sintering process is only handled Bayer process red mud in the series process; Bayer process red mud is joined the operation that some low grade ores can improve Dayao simultaneously, this will connect and the method that combines in parallel is called mixed combining method.
2. acid system is produced aluminum oxide
Acid system is with mineral acid treatment aluminum-containing raw materials such as nitric acid, hydrochloric acid, sulfuric acid and obtain the acidic aqueous solution of corresponding aluminium salt.These aluminium salt or hydrate crystal (passing through evaporative crystallization) or alkaline aluminium salt (hydrolysis crystallization) are separated out from solution, and also available bases these aluminum saline solutions that neutralize make aluminium become aluminium hydroxide and separate out.The hydrate of calcinations of aluminum hydroxide, various aluminium salt or alkaline aluminium salt just obtain aluminum oxide.
The high-silica diaspore ore production aluminum oxide that distributes very wide with acidic process is reasonably in theory, and sila matter content is few in the aluminium product of preparation.But need with expensive acid-resistant system, and employed acid recovery difficulty, so be difficult to carry out large-scale industrial production.In recent years, the research of acid system has obtained progress, but can't compete mutually with the alkaline process of handling high-quality bauxite economically.
3. electric heating process is produced aluminum oxide
Electric heating process is used for handling the high ferro aluminium ore, and ore deposit and charcoal reductive agent are made into furnace charge high temperature reduction melting in electric arc furnace.Silicon oxide and ferric oxide in the ore are reduced into ferro-silicon, and aluminum oxide then is the calcium aluminate slag come-up of molten state, the layering owing to the proportion difference.Gained aluminum oxide slag is handled with alkaline process again, therefrom extracts aluminum oxide, and the gained ferro-silicon is a finished product.The aluminum oxide of electric heating process production at present also is in conceptual phase.
4. blast furnace process is produced aluminum oxide
Blast furnace process is handled high-iron bauxite, and ore and coke are added blast furnace, and ferriferous oxide is reduced into iron, and aluminum oxide, silicon-dioxide and the lime of allocating into form slag, and silicon-dioxide and lime generate calcium orthosilicate.Slag filters and obtains sodium aluminate solution through the alkali stripping, divides or plant to divide through carbon to obtain aluminium hydroxide, and calcining obtains aluminum oxide.
Up to the present, proposed much to refine method of alumina from aluminum ore or other aluminum-containing raw material, but because technical and various reasons economically, what have is eliminated, what have belongs to experimental stage, industrially almost all adopts alkaline process production.
Summary of the invention
Present domestic high-quality alum clay ore reserves is fewer and feweri, and other contain bauxite resource and are not utilized effectively as yet, therefore, is badly in need of finding and a kind ofly can handles novel process and the new technology that all aluminum-containing minerals are produced aluminum oxide.The present invention is directed to these aluminiferous materials and fail the present situation rationally utilized, the method for aluminiferous materials such as a kind of high value-added greening comprehensive utilization bauxite, high-iron bauxite, alunite, kaolin, bauxitic clay, flyash, coal gangue, aluminium ash, nepheline, clay is provided.
Technology of the present invention comprises the two parts, the one, extract aluminum oxide; The 2nd, propose the processing of aluminium slag.
1. extraction aluminum oxide
1.1 contain the ore deposit that aluminium component is an oxide compound
With aluminiferous material fragmentations such as bauxite, high-iron bauxite, kaolin, bauxitic clay, flyash, coal gangue, aluminium ash, nepheline, clays, levigate to 80 μ m, aluminum oxide and ammonium sulfate in molar ratio 1 in the material: 4-1: 10, add the water for ball milling uniform mixing.Mixed material at drying and dehydrating below 200 ℃, 200-700 ℃ of roasting, is incubated 1-8h.The ammonia that produces in the reaction process absorbs preparation ammoniacal liquor through water, or adds and be pressed into liquefied ammonia.The roasting grog adds water-solublely to go out, and filters, and filtrate is aluminum ammonium sulfate solution; Filter residue is for carrying the aluminium slag, and main component is silicon-dioxide, ferric oxide etc.
The chemical reaction that relates to is:
xAl 2O 3·ySiO 2+(NH 4) 2SO 4→NH 4Al(SO 4) 2+SiO 2+NH 3↑+H 2O↑
Al 2O 3+4(NH 4) 2SO 4＝2NH 4Al(SO 4) 2+2SiO 2+6NH 3↑+3H 2O
NH 3+H 2O＝NH 3·H 2O
4FeSO 4+O 2+2H 2SO 4＝2Fe 2(SO 4) 3+2H 2O
Fe 2(SO 4) 3+6NH 3+6H 2O＝2Fe(OH) 3↓+3(NH 4) 2SO 4
For raw material is the aluminum ammonium sulfate solution that high-iron bauxite is prepared, and adds oxygenant oxidation ferrous ion, adopts the deironing of ammonium jarosite method; And then regulator solution pH value prepares aluminium hydroxide for 3.5-4.5.
4FeSO 4+O 2+2H 2SO 4＝2Fe 2(SO 4) 3+2H 2O
3Fe 2(SO 4) 3+2NH 3+12H 2O＝(NH 4) 2Fe 6(SO 4) 4(OH) 12+5H 2SO 4
NH 4Al(SO 4) 2+3NH 3+3H 2O＝Al(OH) 3↓+2(NH 4) 2SO 4
If the non-high-iron bauxite of raw material is then purified the filtrate-aluminum ammonium sulfate solution that obtains with recrystallization method, obtain the higher ammonium aluminum sulfate crystal of purity, four kinds of schemes below adopting are again handled:
Scheme one:
White sulfate of alumina ammonium crystal 200-400 ℃ of dehydration, is heated to 500-700 ℃ and decomposes 2-6h, obtain Tai-Ace S 150, be warming up to 800-1300 ℃ of calcining then, the preparation alumina product, byproduct sulphur trioxide and ammonia, water absorbs, the preparation ammoniumsulphate soln.The chemical reaction that relates to is:
NH 4Al(SO 4) 2·12H 2O＝NH 4Al(SO 4) 2+12H 2O
2NH 4Al(SO 4) 2＝Al 3(SO 4) 2+(NH 4) 2SO 4
Al 2(SO 4) 3＝Al 2O 3+3SO 3
(NH 4) 2SO 4＝2NH 3+SO 3+H 2O
2NH 3·H 2O+SO 3＝(NH 4) 2SO 4+2H 2O
Scheme two:
Purified ammonium aluminum sulfate crystal is water-soluble, in this solution, add ammonia again, at following two temperature sections, under 20 ℃-80 ℃, 40 ℃-60 ℃ [Al in the control solution down 3+] starting point concentration is at 0.05-0.2molL -1, the pH value is 3.4-4.5, preparation aluminium hydroxide.Wherein 40 ℃ of-60 ℃ of temperature effects are best.The solution that filters out behind the aluminium hydroxide is ammoniumsulphate soln, evaporation, returns burden process after concentrating.The chemical reaction that relates to is:
3NH 3+NH 4Al(SO 4) 2+3H 2O＝Al(OH) 3↓+2(NH 4) 2SO 4
2Al(OH) 3＝Al 2O 3+3H 2O↑
Scheme three: purified ammonium aluminum sulfate crystal is water-soluble, to wherein adding urea, control [Al in the solution down again at 50 ℃-100 ℃ 3+] concentration is at 0.05-0.2molL -1, [Al 3+]/[CO (NH 2) 2] molar ratio be 0.04-0.06, the preparation aluminium hydroxide.The solution that filters out behind the aluminium hydroxide is ammoniumsulphate soln, evaporation, returns burden process after concentrating; The ammonia that discharges with carbonic acid gas that discharges in the urea production aluminium hydroxide process and ammonium sulfate roasting reclaims preparation urea.Decompose the preparation of aluminium hydroxide aluminum oxide.The chemical reaction that relates to is:
CO(NH 2) 2+3H 2O＝CO 2↑+2NH 4OH
NH 4Al(SO 4) 2+3NH 4OH＝Al(OH) 3↓+2(NH 4) 2SO 4
2Al(OH) 3＝Al 2O 3+3H 2O↑
Scheme four: with the stripping of purified ammonium aluminum sulfate crystal water, be added to preparation aluminium carbonate ammonium precipitation in the ammonium bicarbonate soln, control [Al in the solution down at 20 ℃-60 ℃ 3+] starting point concentration is at 0.4molL -1More than, NH 4HCO 3Starting point concentration is at 1.5molL -1More than, the pH value is 8.0-10.0, preparation aluminium carbonate ammonium precipitation.The solution that filters out behind the aluminium carbonate ammonium is ammoniumsulphate soln, evaporation, returns burden process after concentrating.The aluminium carbonate ammonium is deposited in 800 ℃ of-1200 ℃ of following calcining and decomposing and prepares aluminum oxide, and the ammonia water that ammonia that calcining obtains and carbon dioxide gas mixture and ammonium sulfate roasting discharge absorbs, the preparation ammonium bicarbonate soln; Filtrate behind the filtration aluminium carbonate ammonium is ammoniumsulphate soln, returns compounding process after the evaporation concentration.The chemical reaction that relates to is:
NH 4Al(SO 4) 2+4NH 4HCO 3＝NH 4AlO(OH)HCO 3↓+CO 2↑+2(NH 4) 2SO 4+H 2O
2NH 4AlO(OH)HCO 3＝Al 2O 3+2NH 3↑+2CO 2↑+2H 2O↑
NH 3+CO 2+H 2O＝NH 4HCO 3
1.2 contain the ore deposit that aluminium component is a vitriol
Alunite is a kind of aluminium of natural output and the sulfate mineral of potassium, and chemical molecular formula can be write as: K 2SO 4Al 2(SO 4) 34Al (OH) 3Remove the alumstone ore beyond the region of objective existence in the alumstone ore, mainly contain a large amount of quartz and kaolinite etc.Therefore, prepare aluminum oxide with alumstone ore and be not only and separate with vitriolate of tartar bonded Tai-Ace S 150, and will will separate, in addition, also aluminium must be separated with silicon-dioxide in the mineral with vitriol bonded aluminum oxide.Therefore, scheme modifying is as follows:
At first to the alunite mineral at 500-750 ℃ of calcined dehydration, react and be:
K 2SO 4·Al 2(SO 4) 3·4Al(OH) 3＝K 2SO 4·Al 2(SO 4) 3+2Al 2O 3+6H 2O↑
Then with ammonium sulfate 400-550 ℃ baking mixed, react and be:
K 2SO 4·Al 2(SO 4) 3+2(NH 4) 2SO 4＝K 2SO 4+2NH 4Al(SO 4) 2+2NH 3↑
Al 2O 3+4(NH 4) 2SO 4＝2NH 4Al(SO 4) 2+6NH 3↑+3H 2O↑
xAl 2O 3·ySiO 2+(NH 4) 2SO 4→NH 4Al(SO 4) 2+SiO 2+NH 3↑+H 2O↑
Obtain filtrate and slag with the grog stripping of roasting, after filtering.Filtrate is the solution of sulfur acid aluminium, vitriolate of tartar, ammonium sulfate, regulates the pH value aluminum hydroxide precipitation is separated out, and surplus materials is vitriolate of tartar and ammonium sulfate in the solution, and evaporative crystallization promptly gets nitrogen potassium mixed fertilizer.Obtain slag for carrying the aluminium slag after the grog stripping of roasting, the filtration, mainly contain silicon-dioxide.
2. carrying the aluminium slag handles
This part is taked following two kinds of schemes according to the composition difference of carrying the aluminium slag:
2.1 high white residue
If it is few to carry impurity such as aluminium slag iron content, be mainly SiO 2, can comprise sulfuric acid leaching and sulfuric acid roasting method with proposing aluminium slag acid treatment removal of impurities.Sulfuric acid leaching is to be that (g: ml) 1: 3-1: 6 mix, and react 0.5-3h under temperature is 60-200 ℃ and stirring condition by mass volume ratio for the sulphuric acid soln of 20%-90% with putting forward aluminium slag and concentration.Sulfuric acid roasting method is to be that (g: ml) 1: 0.5-1: 2 mix, and react 0.5-3h under temperature is 200-300 ℃ and stirring condition by mass volume ratio for sulfuric acid more than 90% with putting forward aluminium slag and concentration.After acidleach or the sour roasting, system temperature is reduced to below 100 ℃, add the water dilution of 2-5 times of volume, continue to stir 20-40min, leach the vitriol that generates at 80-90 ℃.Filtering separation, filter cake washing, drying is mainly silicon-dioxide behind the 800-1300 ℃ of calcination dehydroxylation, and filtrate is iron content and other ionic sulphuric acid solns, can reclaim iron.The main chemical reactions that relates to is:
Fe 2O 3+3H 2SO 4＝Fe 2(SO 4) 3+3H 2O
2.2 high scum
If it is many to put forward aluminium slag iron content, then adopt alkaline purification to put forward the method for silicon, mainly divide lixiviation process and roasting method.Lixiviation process is to be that (g: ml) 1: 2-1: 6 mix by mass volume ratio for the sodium hydroxide of 20%-90% with putting forward aluminium slag and concentration, under being 60 ℃-280 ℃ and stirring condition, temperature reacts 0.5-3h, system temperature is brought down below 100 ℃, add the water dilution of 2-5 times of volume, continue stripping 20-40min at 80-90 ℃.Obtain sodium silicate solution and slag after the filtering separation.Sodium silicate solution both can be used as product, also can divide preparation silicon-dioxide by carbon.The slag that obtains mainly contains iron, can be as iron-smelting raw material.Roasting method will be carried aluminium slag and sodium hydroxide or yellow soda ash, and (g: ml) 1: 0.5-1: 8 mix by mass ratio, be to react 0.5-3h under the condition of 350 ℃-600 ℃ (sodium hydroxide) or 800 ℃-1200 ℃ (yellow soda ash) in temperature, the water that adds 2-5 times of volume then stirs stripping 20-40min at 80-90 ℃.Obtain sodium silicate solution and slag after the filtering separation.Sodium silicate solution both can be used as product, also can divide preparation silicon-dioxide by carbon.The slag that obtains mainly contains iron, can be as iron-smelting raw material.Main chemical reactions is:
SiO 2+2NaOH＝Na 2SiO 3+H 2O
Fe 2O 3+NaOH+3H 2O＝2Fe(OH) 3↓+NaOH
Na 2SiO 3+CO 2＝SiO 2↓+2Na 2CO 3
The inventive method technical process is simple, simple equipments, exsiccated ammonium alum, aluminum oxide, silica product have been prepared with lower cost, realized that flyash, bauxite etc. contain the high added value comprehensive utilization of aluminium, silicon mine resource, whole technological process forms closed cycle, can not cause secondary pollution, meet the requirement that greenization industry is produced environment.
Description of drawings
The process flow sheet for preparing exsiccated ammonium alum, aluminum oxide, silica product by aluminiferous materials such as bauxite, high-iron bauxite, alunite, kaolin, bauxitic clay, flyash, coal gangue, aluminium ash, nepheline, clays
Fig. 1 is a process flow sheet of taking scheme one to handle to the exsiccated ammonium alum refined liquid
Fig. 2 is a process flow sheet of taking scheme two to handle to the exsiccated ammonium alum refined liquid
Fig. 3 is a process flow sheet of taking scheme three to handle to the exsiccated ammonium alum refined liquid
Fig. 4 is a process flow sheet of taking scheme to manage everywhere to the exsiccated ammonium alum refined liquid
Fig. 5 is to carrying the process flow sheet that the aluminium slag takes scheme five and scheme six to handle
Embodiment
Embodiment 1
Used flyash mainly consists of: Al 2O 341.2%, SiO 248.5%, Fe 2O 33.4%, CaO 3.3%, TiO 21.3%, MgO 0.2%.
Will be behind fragmentation, levigate magnetically separating and removing ion from fly ash to 80 μ m, mix (wherein aluminum oxide and ammonium sulfate mol ratio are 1: 6) with ammonium sulfate and water at 1: 3.2: 5 by mass ratio, at 500 ℃ of roasting reaction 5h, the ammonia water that produces in the reaction process absorbs.Product of roasting cooling, add water-soluble go out after, carry out solid-liquid separation.Filtrate is aluminum ammonium sulfate solution, and filter residue is for carrying the aluminium slag.
Aluminum ammonium sulfate solution prepares purified ammonium aluminum sulfate crystal after adopting recrystallization method to purify impurity such as removing de-iron.Ammonium aluminum sulfate crystal is at 200 ℃ of dehydration 3h, and 550 ℃ are decomposed 3h, is warming up to 1200 ℃ of calcining 5h then, makes aluminum oxide.
(g: ml) mixing at 1: 4, is that stirring reaction 2h filters, and obtains the sulphuric acid soln and the slag of metal ions such as iron content under 120 ℃ the condition in temperature by mass volume ratio with to put forward aluminium slag and concentration be 50% sulphuric acid soln.Slag is a silicon powder behind washing, dry, 550 ℃ of calcination de-carbons.
Embodiment 2
Used bauxite consists of: Al 2O 365.3%, SiO 223.1%, Fe 2O 34.8%, CaO 1.6%, TiO 23.5%, K 2O0.5%.
Will be behind fragmentation, levigate bauxite iron removal by magnetic separation to 80 μ m, mix (wherein aluminum oxide and ammonium sulfate mol ratio are 1: 6) with ammonium sulfate and water at 1: 5: 7.2 by mass ratio, at 450 ℃ of roasting reaction 6h, the gas water of emitting in the reaction process absorbs.Product of roasting after being dissolved in water, carries out solid-liquid separation through cooling.Filtrate is aluminum ammonium sulfate solution, and filter residue is for carrying the aluminium slag.
Aluminum ammonium sulfate solution prepares purified ammonium aluminum sulfate crystal after adopting recrystallization method to purify impurity such as removing de-iron.With the stripping of white sulfate of alumina ammonium crystal water, add ammoniacal liquor and control [Al in the solution down for 50 ℃ in temperature 3+] starting point concentration is at 0.15molL -1, the pH value is 4.0, prepares aluminum hydroxide precipitation.The solution of preparing behind the aluminium hydroxide is ammoniumsulphate soln, evaporation, returns burden process after concentrating.Aluminium hydroxide is warming up to 1300 ℃ of calcining 4h, makes α-Al 2O 3
With putting forward aluminium slag and concentration is that 85% sulfuric acid is by mass volume ratio (g: ml) mix at 1: 5, under 180 ℃ and stirring condition, react 1h, stop heating then, be cooled to 80 ℃, the water dilution that adds 5 times of volumes, after 30min was leached in 85 ℃ of continuation, filtering separation obtained the sulphuric acid soln of metal ions such as iron content and mainly contains SiO 2Slag.Slag is SiO behind washing, dry, 1050 ℃ of calcination deshydroxies 2
Embodiment 3
Used high iron low grade bauxite mainly consists of: Al 2O 329.4%, SiO 28.9%, Fe 2O 343.5%, TiO 21.6%, MnO 1.1%, K 2O 0.78%.
To mix (wherein aluminum oxide and ammonium sulfate mol ratio are 1: 8) at 1: 3: 4.3 by mass ratio through broken, levigate high-iron bauxite to 80 μ m and ammonium sulfate and water, react 4h, carry out, the gas water absorption of emitting in the reaction process 500 ℃ of roastings.Product of roasting after being dissolved in water, carries out solid-liquid separation through cooling.Filtrate is aluminum ammonium sulfate solution, and filter residue is for carrying the aluminium slag.
To aluminum ammonium sulfate solution bubbling air iron protoxide ion, with the deironing of ammonium jarosite method.PH value to 4.5 is regulated in aluminum ammonium sulfate solution ammonification after deironing, is settled out aluminium hydroxide.Aluminium hydroxide is warming up to 1200 ℃ of calcining 3h, makes aluminum oxide.Filtrate is ammoniumsulphate soln, is used for the roasting reaction after concentrating.
Carry the oxide compound that the aluminium slag is mainly iron, its grade can reach more than 60%, can directly make iron-smelting raw material.
Embodiment 4
Used kaolin consists of: Al 2O 346.6%, SiO 250.9%, Fe 2O 30.41%, CaO 0.08%, TiO 20.35%, K 2O 0.36%.
To mix (wherein aluminum oxide and ammonium sulfate mol ratio are 1: 7) at 1: 4.2: 6 by mass ratio to the following kaolin of 80 μ m and ammonium sulfate and water through broken, levigate, react 4h 450 ℃ of roastings,, the gas water absorption of emitting in the reaction process.Product of roasting after being dissolved in water, carries out solid-liquid separation through cooling.Filtrate is aluminum ammonium sulfate solution, and filter residue is for carrying the aluminium slag.
Aluminum ammonium sulfate solution prepares purified ammonium aluminum sulfate crystal after adopting recrystallization method to purify impurity such as removing de-iron.With the stripping of ammonium aluminum sulfate crystal water, in aluminum ammonium sulfate solution, add urea again, control [Al in the solution down at 80 ℃ 3+] concentration is at 0.15molL -1, [Al 3+]/[CO (NH 2) 2] molar ratio be 0.05, the preparation aluminium hydroxide.The solution of preparing behind the aluminium hydroxide is ammoniumsulphate soln, evaporation, returns burden process after concentrating; The ammonia that carbonic acid gas that urea discharges in preparation aluminium hydroxide process and ammonium sulfate roasting discharge reclaims preparation urea.
(g: ml) mixing at 1: 6, is that stirring reaction 2.5h filters, and obtains the sulphuric acid soln and the slag of metal ions such as iron content under 100 ℃ the condition in temperature by mass volume ratio with to put forward aluminium slag and concentration be 40% sulphuric acid soln.Slag is a silicon-dioxide behind washing, dry, 1000 ℃ of calcination dehydroxylations.
Embodiment 5
Used bauxitic clay consists of: Al 2O 369.8%, SiO 225.7%, Fe 2O 31.71%, MgO 0.17%, TiO 22.44%, K 2O 0.12%, Na 2O 0.06%.
To the following bauxitic clay iron removal by magnetic separation of 80 μ m, mix (wherein aluminum oxide and ammonium sulfate mol ratio are 1: 5) at 1: 4.5: 6.5 by mass ratio through broken, levigate with ammonium sulfate and water, at 450 ℃ of insulation 3h, carry out the roasting reaction, the gas water of emitting in the reaction process absorbs.Product of roasting after being dissolved in water, carries out solid-liquid separation through cooling.Filtrate is aluminum ammonium sulfate solution, and filter residue is for carrying the aluminium slag.
Aluminum ammonium sulfate solution prepares purified ammonium aluminum sulfate crystal after adopting recrystallization method to purify impurity such as removing de-iron.With the stripping of ammonium aluminum sulfate crystal water, in aluminum ammonium sulfate solution, add ammonia again, control [Al in the solution down at 50 ℃ 3+] starting point concentration is at 0.2molL -1, the pH value is 4.5, preparation aluminium hydroxide.The solution of preparing behind the aluminium hydroxide is ammoniumsulphate soln, evaporation, returns burden process after concentrating.Aluminium hydroxide makes aluminum oxide at 1000 ℃ of calcining 5h.
(g: ml) mixing at 1: 5, is that stirring reaction 2.5h filters, and obtains the sulphuric acid soln and the slag of metal ions such as iron content under 100 ℃ the condition in temperature by mass volume ratio with to put forward aluminium slag and concentration be 30% sulphuric acid soln.Slag is a silicon-dioxide behind washing, dry, 1000 ℃ of calcination dehydroxylations.
Embodiment 6
Used aluminium ash consists of: Al 14%, Al 2O 370.5%, SiO 28.6%, Fe 2O 33.7%.
To mix (wherein aluminum oxide and ammonium sulfate mol ratio are 1: 4) with ammonium sulfate and water at 1: 5: 7.2 by mass ratio behind broken, levigate aluminium ash iron removal by magnetic separation to 80 μ m, at 450 ℃ of roasting reaction 5h, the gas water of emitting in the reaction process absorbs.Product of roasting after being dissolved in water, carries out solid-liquid separation through cooling.Filtrate is aluminum ammonium sulfate solution, and filter residue is for carrying the aluminium slag.
Aluminum ammonium sulfate solution prepares purified ammonium aluminum sulfate crystal after adopting recrystallization method to purify impurity such as removing de-iron.Ammonium aluminum sulfate crystal 300 ℃ of dehydrations, is heated to 700 ℃ and decomposes 5h, obtain Tai-Ace S 150, be warming up to 1200 ℃ of calcinings then, preparation alumina product, byproduct sulphur trioxide and ammonia water absorb preparation ammonium sulfate.
With putting forward aluminium slag and concentration is that 80% sulfuric acid is by mass volume ratio (g: ml) mix at 1: 5, under 180 ℃ and stirring condition behind the reaction 1h, be cooled to 80 ℃, the water dilution that adds 5 times of volumes, after 30min is leached in 85 ℃ of continuation, filtering separation obtains the sulphuric acid soln of metal ions such as iron content and mainly contains SiO 2Slag.Slag is SiO behind washing, dry, 1000 ℃ of calcination dehydroxylations 2
Embodiment 7
Used nepheline mainly consists of: Al 2O 323.21%, SiO 254.32%, Fe 2O 33.41%, FeO 1.91%, Na 2O 10.42%, K 2O 3.14%.
To mix (wherein aluminum oxide and ammonium sulfate mol ratio are 1: 5) at 1: 1.5: 2.2 by mass ratio through broken, levigate nepheline to 80 μ m and ammonium sulfate and water, react 2h, the gas water of emitting in reaction process absorption 500 ℃ of roastings.Product of roasting after being dissolved in water, carries out solid-liquid separation through cooling.Filtrate is aluminum ammonium sulfate solution, and filter residue is for carrying the aluminium slag.
Aluminum ammonium sulfate solution prepares purified ammonium aluminum sulfate crystal after adopting recrystallization method to purify impurity such as removing de-iron.At 350 ℃ of dehydration 3h, 550 ℃ are decomposed 3h with white sulfate of alumina ammonium crystal, are warming up to 1200 ℃ of calcining 5h then, make aluminum oxide.
(g: ml) mixing at 1: 4, is that stirring reaction 2h filters, and obtains the sulphuric acid soln and the slag of metal ions such as iron content under 270 ℃ the condition in temperature by mass volume ratio with to put forward aluminium slag and concentration be 98% sulphuric acid soln.Slag is a silicon-dioxide behind washing, dry, 1000 ℃ of calcination dehydroxylations.
Embodiment 8
Used clay mainly consists of: Al 2O 318.26%, SiO 261.99%, Fe 2O 34.5%, MgO 2.98%, and CaO 0.18%, Na 2O 3.24%, K 2O 3.46%, TiO 20.21%, MnO 0.04%, other impurity 5.14%.
Will be behind fragmentation, levigate clay iron removal by magnetic separation to 80 μ m, mix (wherein aluminum oxide and ammonium sulfate mol ratio are 1: 6) with ammonium sulfate and water at 1: 1.4: 2 by mass ratio, at 400 ℃ of insulation 5h, carry out the roasting reaction, the gas water of emitting in the reaction process absorbs.Product of roasting after being dissolved in water, carries out solid-liquid separation through cooling.Filtrate is aluminum ammonium sulfate solution, and filter residue is for carrying the aluminium slag.
Aluminum ammonium sulfate solution prepares purified ammonium aluminum sulfate crystal after purifying impurity such as removing de-iron with recrystallization method.Ammonium aluminum sulfate crystal is water-soluble, in aluminum ammonium sulfate solution, add ammonium bicarbonate soln again, control [Al in the solution down at 50 ℃ 3+] starting point concentration is at 0.4molL -1, NH 4HCO 3Starting point concentration is at 1.5molL -1, the pH value is 9.0, preparation aluminium carbonate ammonium precipitation.The solution of preparing behind the aluminium carbonate ammonium is ammoniumsulphate soln, evaporation, returns burden process after concentrating.The aluminium carbonate ammonium is deposited in 1200 ℃ of following calcining and decomposing and prepares aluminum oxide, and the ammonia water that ammonia that calcining obtains and carbon dioxide gas mixture and ammonium sulfate roasting discharge absorbs, the preparation ammonium bicarbonate soln; Filtrate behind the filtration aluminium carbonate ammonium is ammoniumsulphate soln, returns compounding process after the evaporation concentration.
(g: ml) mixing at 1: 4, is that stirring reaction 2h filters, and obtains isoionic sulphuric acid soln of iron content and slag under 120 ℃ the condition in temperature by mass volume ratio with to put forward aluminium slag and concentration be 50% sulphuric acid soln.Slag is a silicon-dioxide behind washing, dry, 1000 ℃ of calcination dehydroxylations.
Embodiment 9
Used alunite mainly consists of: Al 2O 354.78%, SiO 217.63%, Fe 2O 35.04%, SO 311.34%, CaO0.26%, Na 2O 0.19%, K 2O 3.26%, TiO 20.53%.
Will be behind fragmentation, levigate alunite iron removal by magnetic separation to 80 μ m, at 650 ℃ of calcined dehydration 4h, mix (wherein aluminum oxide and ammonium sulfate mol ratio are 1: 7) with ammonium sulfate and water at 1: 5: 7.2 by mass ratio then, at 450 ℃ of insulation 5h, carry out the roasting reaction, the gas water of emitting in the reaction process absorbs.Product of roasting after being dissolved in water, carries out solid-liquid separation through cooling.Filtrate is the vitriol mixing solutions, and leading ion is aluminum ion, ammonium radical ion, potassium ion, sulfate ion in the solution; Filter residue is for carrying the aluminium slag.
Aluminum ammonium sulfate solution prepares purified ammonium aluminum sulfate crystal after adopting recrystallization method to purify impurity such as removing de-iron.With the stripping of ammonium aluminum sulfate crystal water, in aluminum ammonium sulfate solution, add ammonia again, control [Al in the solution down at 40 ℃ 3+] starting point concentration is at 0.18molL -1, the pH value is 4.5, preparation aluminium hydroxide.Aluminium hydroxide makes aluminum oxide at 1000 ℃ of calcining 3h.After aluminum hydroxide precipitation comes out, be mainly ammonium sulfate and vitriolate of tartar in the solution, make nitrogen potassium mixed fertilizer behind evaporation concentration, the crystallisation by cooling.
(g: ml) mixing at 1: 4, is that stirring reaction 2h filters, and obtains isoionic sulphuric acid soln of iron content and slag under 120 ℃ the condition in temperature by mass volume ratio with to put forward aluminium slag and concentration be 50% sulphuric acid soln.Slag is a silicon-dioxide behind washing, dry, 1000 ℃ of calcination dehydroxylations.

Claims (9)

1. one kind prepares the method for exsiccated ammonium alum, aluminum oxide and silica product by aluminiferous materials such as bauxite, high-iron bauxite, alunite, kaolin, bauxitic clay, flyash, coal gangue, aluminium ash, nepheline, clays, it is characterized in that comprising the steps:
(1) with aluminiferous materials such as bauxite, high-iron bauxite, alunite, kaolin, bauxitic clay, flyash, coal gangue, aluminium ash, nepheline, clay through broken, be ground to below the 80 μ m as raw material the roasting of need dewatering of kaolin and alunite, clay;
(2) levigated aluminiferous material and ammonium sulfate are added the water mix, remove moisture in drying below 200 ℃, more dried siccative is heated to 200-700 ℃ and carries out roasting, insulation 1-8h, the ammonia water that reaction produces absorbs and obtains ammoniacal liquor, or adds and be pressed into liquefied ammonia; Maturing temperature can be divided into three scope: 200-700 ℃, 300-600 ℃, 350-550 ℃.Wherein, best 350-550 ℃ of temperature section roasting effect, secondly be 300-600 ℃.
(3) the solid roasting product water dissolution that will obtain by (2) is filtered, and obtains aluminum ammonium sulfate solution and carries the aluminium slag.The gas water that roasting produces absorbs, and makes ammoniacal liquor.If raw material is a high-iron bauxite, then direct oxidizer iron protoxide ion in solution is regulated the pH value with ammonia then and is settled out ironic hydroxide earlier, and redeposition goes out aluminium hydroxide, and post precipitation solution is ammoniumsulphate soln, returns batching after the inspissation; If the non-high-iron bauxite of raw material then adopts recrystallization method that aluminum ammonium sulfate solution is purified except that behind the impurity such as de-iron, prepare purified ammonium aluminum sulfate crystal.
(4) can adopt four kinds of schemes to handle to the white sulfate of alumina ammonium crystal that obtains:
Scheme one: with ammonium aluminum sulfate crystal drying, calcining, obtain aluminum oxide, the ammonia water that ammonia that calcining obtains and sulphur trioxide mixed gas and calcining process produce absorbs, and makes ammoniumsulphate soln, obtains concentrated ammonium sulfate solution through inspissation and returns batching;
Scheme two: ammonium aluminum sulfate crystal is water-soluble, this solution is regulated pH value precipitation preparation aluminium hydroxide with ammonia, filtering and obtaining filter residue is aluminium hydroxide, prepares aluminum oxide through calcining and decomposing, filtrate is ammoniumsulphate soln, returns compounding process after the inspissation;
Scheme three: ammonium aluminum sulfate crystal is water-soluble, this solution is regulated pH value precipitation preparation aluminium hydroxide with urea, it is aluminium hydroxide that filtration obtains filter residue, prepare aluminum oxide through calcining and decomposing, filtrate is ammoniumsulphate soln, return compounding process after the inspissation, the ammonia that carbonic acid gas that discharges in the urea production aluminium hydroxide process and calcining process produce prepares urea;
Scheme four: ammonium aluminum sulfate crystal is water-soluble, to wherein adding ammonium bicarbonate soln, obtain aluminium carbonate ammonium precipitation.Filtration obtains filter residue and is aluminium carbonate ammonium precipitation, filtrate is ammoniumsulphate soln, and aluminium carbonate ammonium calcining and decomposing prepares aluminum oxide, and the ammonia water that ammonia and carbon dioxide gas mixture and calcining process produce absorbs, mixing the back is volatile salt or ammonium bicarbonate soln, returns batching; Ammoniumsulphate soln returns compounding process after evaporation concentration.
(5) by (3) if obtain to put forward aluminium slag iron content less, then adopt acidleach or sour roasting, carrying out washing treatment, remove metallic impurity such as Fe, Ca in removing slag, Al, filter and obtain pickle solution and silicon-dioxide.Pickle solution returns acid treatment removal of impurities operation;
(6) by (3) if obtain to put forward aluminium slag iron content more, then adopt alkali to soak or the alkali calcination process, generate the water glass product, perhaps again water glass carbon is divided the preparation silica product.Extract and to put forward the main iron content of white residue behind the silicon-dioxide, can be used as iron-smelting raw material.
2. a kind of method for preparing exsiccated ammonium alum, aluminum oxide and silica product by aluminiferous materials such as bauxite, high-iron bauxite, alunite, kaolin, bauxitic clay, flyash, coal gangue, aluminium ash, nepheline, clays according to claim 1, it is characterized in that in step (2) the batch mixing process that the mol ratio of aluminum oxide and ammonium sulfate is 1 in the aluminiferous materials such as bauxite, high-iron bauxite, alunite, kaolin, bauxitic clay, flyash, coal gangue, aluminium ash, nepheline, clay: 4-1: 10, ammonium sulfate is 5 with the quality ratio in the ammoniumsulphate soln: 10-7: 10.
3. a kind of method for preparing exsiccated ammonium alum, aluminum oxide and silica product by aluminiferous materials such as bauxite, high-iron bauxite, alunite, kaolin, bauxitic clay, flyash, coal gangue, aluminium ash, nepheline, clays according to claim 1, it is characterized in that step (3) is the aluminum ammonium sulfate solution that high-iron bauxite is prepared for raw material, regulating the pH value with ammonium is that 1.7-3.5 prepares ironic hydroxide; And then regulator solution pH value prepares aluminium hydroxide for 3.5-4.5.
4. according to claim 1 a kind of by bauxite, high-iron bauxite, alunite, kaolin, bauxitic clay, flyash, coal gangue, the aluminium ash, nepheline, aluminiferous materials such as clay prepare exsiccated ammonium alum, the method of aluminum oxide and silica product, it is characterized in that scheme one adopts white sulfate of alumina ammonium crystal 200-400 ℃ of dehydration in step (4), be heated to 500-700 ℃ and decompose 2-6h, obtain Tai-Ace S 150, be warming up to 800-1300 ℃ of calcining then, the preparation alumina product, byproduct sulphur trioxide and ammonia water absorb, as the raw material of preparation ammoniumsulphate soln.
5. a kind of method for preparing exsiccated ammonium alum, aluminum oxide and silica product by aluminiferous materials such as bauxite, high-iron bauxite, alunite, kaolin, bauxitic clay, flyash, coal gangue, aluminium ash, nepheline, clays according to claim 1, it is characterized in that scheme two adopts white sulfate of alumina ammonium crystal is water-soluble in step (4), in the white sulfate of alumina ammonium solution, add ammonium again, at following two temperature sections, under 20 ℃-80 ℃, control [Al in the solution down for 40 ℃-60 ℃ 3+] starting point concentration is at 0.05-0.2molL -1, the pH value is 3.4-4.5, preparation aluminium hydroxide.Wherein effect is best under 40 ℃ of-60 ℃ of temperature sections.The solution of preparing behind the aluminium hydroxide is ammoniumsulphate soln, evaporation, returns burden process after concentrating.
6. a kind of method for preparing exsiccated ammonium alum, aluminum oxide and silica product by aluminiferous materials such as bauxite, high-iron bauxite, alunite, kaolin, bauxitic clay, flyash, coal gangue, aluminium ash, nepheline, clays according to claim 1, it is characterized in that scheme three adopts white sulfate of alumina ammonium crystal is water-soluble in step (4), in the white sulfate of alumina ammonium solution, add urea again, control [Al in the solution down at 50 ℃-100 ℃ 3+] concentration is at 0.05-0.2molL -1, [Al 3+]/[CO (NH 2) 2] molar ratio be 0.04-0.06, the preparation aluminium hydroxide.The solution of preparing behind the aluminium hydroxide is ammoniumsulphate soln, evaporation, returns burden process after concentrating; The ammonia that carbonic acid gas that discharges in the urea production aluminium hydroxide process and ammonium sulfate roasting discharge prepares urea.
7. a kind of method for preparing exsiccated ammonium alum, aluminum oxide and silica product by aluminiferous materials such as bauxite, high-iron bauxite, alunite, kaolin, bauxitic clay, flyash, coal gangue, aluminium ash, nepheline, clays according to claim 1, it is characterized in that scheme four adopts the stripping of white sulfate of alumina ammonium crystal water in step (4), be added in the ammonium bicarbonate soln, control [Al in the solution down at 20 ℃-60 ℃ 3+] starting point concentration is at 0.4molL -1More than, NH 4HCO 3Starting point concentration is at 1.5molL -1More than, the pH value is 8.0-10.0, preparation aluminium carbonate ammonium precipitation.The solution of preparing behind the aluminium carbonate ammonium is ammoniumsulphate soln, evaporation, returns burden process after concentrating.The aluminium carbonate ammonium is deposited in 800 ℃ of-1200 ℃ of following calcining and decomposing and prepares aluminum oxide, and the ammonia water that ammonia that calcining obtains and carbon dioxide gas mixture and calcining process are emitted absorbs, preparation bicarbonate of ammonia.
8. according to claim 1 a kind of by bauxite, high-iron bauxite, alunite, kaolin, bauxitic clay, flyash, coal gangue, the aluminium ash, nepheline, aluminiferous materials such as clay prepare ammonium sulfate, aluminum oxide, the method of silica product, what it is characterized in that step (5) proposes the acidleach of aluminium slag, washing impurity-removing is to be that (g: ml) 1: 3-1: 6 mix by mass volume ratio for the sulfuric acid of 20%-90% with putting forward aluminium slag and concentration, under being 60 ℃-200 ℃ and stirring condition, temperature reacts 0.5-3h, system temperature is brought down below 100 ℃, add the water dilution of 2-5 times of volume, continue to leach 20-40min at 80-90 ℃.The wash heat that obtains washs, be silicon-dioxide after dry, the calcination.Perhaps adopt and propose aluminium slag acid roasting, washing, removal of impurities, (g: ml) 1: 0.5-1: 2 mix by mass volume ratio to be about to put forward aluminium slag and concentration and to be sulfuric acid more than 90%, be to react 0.5-3h under 200 ℃-300 ℃ the condition in temperature, the water that adds 2-5 times of volume then stirs stripping 20-40min at 80-90 ℃.The wash heat that obtains washs, be silicon-dioxide after dry, the calcination.
9. a kind of method for preparing ammonium sulfate, aluminum oxide, silica product by aluminiferous materials such as bauxite, high-iron bauxite, alunite, kaolin, bauxitic clay, flyash, coal gangue, aluminium ash, nepheline, clays according to claim 1, the aluminium slag alkali of carrying that it is characterized in that step (6) soaks or the alkali roasting, promptly adopts sodium hydroxide leaching, sodium hydroxide roasting respectively, reaches three kinds of technologies of sodium carbonate roasting.It is to be that (g: ml) 1: 2-1: 6 mix by mass volume ratio for the sodium hydroxide of 20%-90% with putting forward aluminium slag and concentration that sodium hydroxide leaches, under being 60 ℃-280 ℃ and stirring condition, temperature reacts 0.5-3h, system temperature is brought down below 100 ℃, add the water dilution of 2-5 times of volume, continue stripping 20-40min at 80-90 ℃.Obtain sodium silicate solution and slag after the filtering separation.Sodium silicate solution both can be used as product, also can divide preparation silicon-dioxide by carbon.The slag that obtains mainly contains iron, can be as iron-smelting raw material.Propose sodium hydroxide roasting of aluminium slag or sodium carbonate roasting and be that (g: ml) 1: 0.5-1: 8 mix by mass ratio with carrying aluminium slag and sodium hydroxide or yellow soda ash, in temperature is that 350 ℃-600 ℃ (sodium hydroxide) or 800 ℃ react 0.5-3h under the condition of (yellow soda ash) more than-1200 ℃, and the water that adds 2-5 times of volume then stirs stripping 20-40min at 80-90 ℃.Obtain sodium silicate solution and slag after the filtering separation.Sodium silicate solution both can be used as product, also can divide preparation silicon-dioxide by carbon.The slag that obtains mainly contains iron, can be as iron-smelting raw material.
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