CN103086410A - Method for preparing alumina by mixing and roasting flyash and ammonium sulfate - Google Patents
Method for preparing alumina by mixing and roasting flyash and ammonium sulfate Download PDFInfo
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Abstract
The invention relates to a method for producing alumina by utilizing industrial solid wastes and in particular relates to a method for preparing alumina by mixing and roasting flyash and ammonium sulfate. The method comprises the steps of raw material preparation, grog firing, grog dissolution, high silicon residue separation and washing, primary iron removal of aluminium ammonium sulfate solution, secondary iron removal of aluminium ammonium sulfate solution, primary iron removal refining liquid reduction, aluminium ammonium sulfate refining liquid solution decomposition, coarse aluminium hydroxide separation and washing, coarse aluminium hydroxide desulfurization, aluminium hydroxide separation and washing and aluminium hydroxide roasting. The method has the advantages and effects that auxiliaries are not added; the flyash does not need to be roasted and activated at a high temperature; alumina in the flyash can be effectively extracted; and the extraction ratio of alumina can be over 85%.
Description
Technical field
The present invention relates to a kind of method of utilizing industrial solid castoff to produce aluminum oxide, relate in particular to a kind of baking mixed method for preparing aluminum oxide of flyash ammonium sulfate.
Background technology
Flyash is the solid waste that the coal-burning power plant discharges.China's flyash annual emissions in 2008 is up to 300,000,000 tons, and total volume of cargo in storage of China's flyash has five, sixties00000000 tons.A large amount of soils are are not only occupied in the discharging of a large amount of flyash, and serious environment pollution, have consisted of the dual destruction to ecosystem environment.Therefore the comprehensive utilization of carrying out flyash has Great significance and long-range strategic importance.Equally, China is the not rich country of a bauxite resource, and by rate of growth and the bauxite recovery rate of present aluminum oxide output, even consider prospective reserves, the time limit of the bauxite of China also is difficult to reach 30 years.So the method that solves this crisis of resource has two kinds: the one, rationally utilize existing bauxite resource; The 2nd, actively look for and utilize other to contain bauxite resource.And aluminum oxide is one of main component of flyash, and its massfraction is generally 15% ~ 40%, reaches as high as 58%.So, carry out from flyash the pollution that the research work of extracting aluminum oxide can solve flyash, turn waste into wealth.
At present, the method for extraction aluminum oxide mainly contains alkaline process, acid system and ammonia process from flyash.Comparative maturity limestone sintering method and soda-lime sintering process arranged, both are commonly referred to as alkaline process for this.In December, 2004, Inner Mongolia Autonomous Region Science and Technology Department held " flyash extracts the aluminum and coproducing cement industrialization technology " the project appraisal of scientific and technological achievements meeting of covering the research and development of western new and high technology Group Co.,Ltd, what adopt is exactly the limestone sintering method, and Datang international corporation adopts improved soda-lime sintering process treated coal ash to produce aluminum oxide.But in alkaline process extract powder coal ash, there are some problems in aluminum oxide, it is mainly the 1. calcium silicate slag that produces of sintering process, can only be used as cement raw material, the aluminum oxide that every production is 1 ton will produce the calcium silicate slag that is several times as much as flyash, and cement has its corresponding radius of selling, if local do not have large-scale Cement industry support will cause secondary pollution; 2. sintering process has only been extracted the aluminum oxide in flyash, and the utility value of its silicon-dioxide is low.3. the facility investment of sintering process treated coal ash is large, and energy consumption is high, and cost is high.
Because the alumina silica ratio of flyash is very low, generally all less than 1, so adopt acidic process flyash more reasonable in principle.The aluminium salt that aluminum oxide reaction in acid or acidic cpd and flyash generates enters solution after the dissolving of aluminium salt, and silicon does not react with acid or acidic cpd, stays fully in the solid phase slag.Acidic process flyash can overcome the deficiency of sintering process, can not produce the solid waste more than the raw material powder coal ash, and after extracting aluminum oxide, silicon-dioxide meeting enrichment, in slag, its content can reach 80 ~ 90%(by alumina extraction ratio 85%), so more be conducive to its utilization.In flyash, alumina extraction ratio refers to be dissolved in after roasting the ratio of aluminum oxide in aluminum oxide in solution and flyash.Acid system comprises sulfuric acid process and salt acid system, fluorine ammonia hydrotropy pickling process comparative maturity wherein, can obtain higher alumina extraction ratio, but owing to will adding fluorine ammonia, can produce ammonia and hydrogen fluoride toxic gas in the process of producing, surrounding environment and labor safety are brought disadvantageous effect, and because the acid system equipment corrosion is serious, the impact of the problems such as cost is high, not industrialization always.
Ammonia process is the baking mixed method of ammonium sulfate flyash, and the high white residue that 1. extracts after aluminum oxide that has the following advantages can be used as high silicon filler through processing, and also can be used for preparing the silicon series product such as white carbon black, because alkali-free can be directly used in production cement; Extract the high scum that produces in alumina process and can be used as iron-smelting raw material, the aluminium in flyash, silicon, iron have all obtained effective utilization; 2. reaction system is weak acid system, and equipment is easier to solve, and is beneficial to industrialization; 3. preparation process is the decrement process, and the quantity of slag is little.But the ammonia process that forms at present all comes with some shortcomings and problem: activate at 600 ~ 700 ℃ of roasting 1 ~ 2h such as mentioning adopting in patent CN100457628C " extraction aluminum oxide while co-producing white carbon black in flyash ", although can be that in flyash, alumina extraction ratio is higher like this, but the heat temperature raising of flyash and temperature-fall period energy consumption are high, and the aluminium hydroxide that is settled out of following adopted " alkali molten-carbon divide " art breading ammoniacal liquor or ammonia and the mixture of ironic hydroxide, aluminium hydroxide is dissolved in precipitation again, causes the long flow path cost high; All ignored in some present patents in the aluminium hydroxide solid phase that ammonia precipitation goes out and all contained sulfate radical, can not remove with hot wash, the existence meeting of sulfate radical produces harm to Aluminium hydroxide roasting.
Summary of the invention
For solving the problems of the technologies described above a kind of baking mixed method for preparing aluminum oxide of flyash ammonium sulfate that the invention provides, purpose is not add any auxiliary agent, cancels the calcination activation of highly energy-consuming, guarantees not reduce simultaneously alumina extraction ratio in flyash.
The baking mixed method for preparing aluminum oxide of a kind of flyash ammonium sulfate of the present invention, is characterized in that comprising the steps: for achieving the above object
The raw material preparation: flyash is mixed with ammonium sulfate, be prepared into raw material, wherein the weight ratio of the aluminum oxide in ammonium sulfate and flyash is 4.5～8:1;
Grog burns till: raw material are heated to 350 ~ 500 ℃, and firing time is controlled at 0.5 ~ 5h, makes grog and the ammonia of sulfur acid aluminium ammonium, and ammonia is for the preparation of ammoniacal liquor or pass into exsiccated ammonium alum refined liquid decomposition process;
The grog stripping: grog carries out stripping with hot water or washing lotion, dissolution time 0.1 ~ 5h, and aluminium enters solution with the form of exsiccated ammonium alum, and silicon is stayed and is formed high white residue in residue;
High white residue separating, washing: the slurries after stripping carry out solid-liquid separation and countercurrent washing, and solution is aluminum ammonium sulfate solution, and washing rear slag is high white residue;
A deironing of aluminum ammonium sulfate solution: adopt the goethite process add oxygenant to carry out a deironing to the aluminum ammonium sulfate solution of stripping, iron concentration is reduced to below 4g/L, after a deironing, solution carries out the secondary deironing or carries out a deironing refined liquid reduction, and an iron dross removing is high scum;
Aluminum ammonium sulfate solution secondary deironing: adopt logical oxygen iron purification mode to carry out the secondary deironing to a deironing refined liquid, iron concentration is down to below 30mg/L, get the exsiccated ammonium alum refined soln;
A deironing refined liquid reduction: add reductive agent in a deironing refined liquid, carry out the reduction of deironing refined liquid, make ferric ion wherein all be converted into ferrous ion;
Exsiccated ammonium alum refined liquid solution decomposes: exsiccated ammonium alum refined soln or deironing reduction after the secondary deironing are led to ammonia or the ammoniacal liquor that the grog firing process obtains in refined liquid afterwards, obtain thick aluminium hydroxide and ammoniumsulphate soln;
Thick aluminium hydroxide separating, washing: the slurries after exsiccated ammonium alum decomposes carry out solid-liquid separation and thick aluminium hydroxide washing, and liquid is the circulation fluid ammoniumsulphate soln, and solid is thick aluminium hydroxide;
Thick aluminium hydroxide desulfurization: the exsiccated ammonium alum refined liquid is decomposed the thick aluminium hydroxide that obtains and is adopted basic solution to carry out desulfurization, obtains sulfate radical-free aluminium hydroxide;
The aluminium hydroxide separating, washing: the slurries after desulfurization carry out solid-liquid separation and aluminium hydroxide washing, and solid is aluminium hydroxide;
Aluminium hydroxide roasting: aluminium hydroxide obtains the finished product aluminum oxide 900 ~ 1300 ℃ of lower roastings.
The preparation of described raw material is to adopt the mode of directly mixing or grinding mixing that flyash and ammonium sulfate are mixed.
Described grinding mixed employing wet-milling or dry grinding.
Described grog stripping is adopted the grinding machine stripping or is stirred a kind of in stripping.
A kind of in the stripping of one section mill or the stripping of two sections mills adopted in described grinding machine stripping.
Described stirring stripping is adopted to be interrupted and is stirred a kind of in stripping or continuously stirring stripping.
Described high white residue separating, washing adopts a kind of in vacuum separation, settlement separate or separation.
Described high white residue separating, washing adopts a kind of in one-level, secondary or multi-stage countercurrent washing.
In a deironing of described aluminum ammonium sulfate solution, oxygenant adopts a kind of in pressurized air, oxygen or hydrogen peroxide.
The neutralizing agent that in a deironing of described aluminum ammonium sulfate solution, goethite process adopts is a kind of in ammoniacal liquor, ammonia, lime or coal ash.
In the deironing of described aluminum ammonium sulfate solution secondary, oxygenant adopts a kind of in oxygen or hydrogen peroxide.
The neutralizing agent that adopts in the deironing of described aluminum ammonium sulfate solution secondary is a kind of in ammoniacal liquor, ammonia or aluminum hydroxide wash liquor.
In a deironing of described aluminum ammonium sulfate solution and the deironing of aluminum ammonium sulfate solution secondary, the separating, washing of high scum adopts a kind of in vacuum separation, settlement separate or separation.
The reductive agent that described deironing refined liquid reduction is adopted is a kind of in iron sulphide, elemental sulfur, sulphur trioxide, hydrogen sulfide or Iron sulfuret.
Described thick aluminium hydroxide separating, washing adopts a kind of in vacuum separation, settlement separate or separation.
A kind of as sweetening agent in sodium carbonate, sodium hydroxide, milk of lime or ammoniacal liquor adopted in described thick aluminium hydroxide desulfurization.
Described thick aluminium hydroxide separating, washing adopts a kind of in vacuum separation, settlement separate or separation.
Described Aluminium hydroxide roasting adopts a kind of in rotary kiln baking, fluosolids roasting or gas suspension calcination.
Described finished product aluminum oxide meets the metallurgical-grade aluminum oxide standard.
Described aluminium hydroxide separates the ammoniumsulphate soln that obtains and evaporates, the combination of one or more in employing falling film evaporation, pump circulation steaming or natural circulation evaporation.
The ammonia sulfate crystal that the evaporation of described ammoniumsulphate soln produces adopts a kind of in centrifugation, vacuum separation, settlement separate or separation.
Advantageous effect of the present invention: the present invention does not add any auxiliary agent, flyash does not need the high-temperature roasting activation, effective aluminum oxide in the extract powder coal ash, the extraction yield of aluminum oxide can reach more than 85%, adopt the dissolution fluid iron removal technology, simplification of flowsheet is cancelled follow-up alkali lye processing, adopts advanced aluminium hydroxide desulfurization technology, make the Aluminium hydroxide roasting process not produce sulphur trioxide, reduce flue gas intractability and the requirement of stoving oven material.Roasting grog product of the present invention is exsiccated ammonium alum, and product is that the exsiccated ammonium alum ammonium is compared and can be carried out stripping with less water.Realized the ammonium sulfate circulation in technical process of the present invention, by the circulation can be many batches of the extract powder coal ash in aluminum oxide, whole process does not have the discharge of waste gas, waste liquid, the high white residue main component that flyash extracts after aluminum oxide is silicon-dioxide, be easy to utilize, high scum can be used as iron-smelting raw material and supplies with iron industry.Reaction system of the present invention is weak acid system, and equipment easily solves, and is beneficial to industrialization.
Description of drawings
Fig. 1 is schema of the present invention.
Embodiment
The invention will be further described below in conjunction with accompanying drawing.
Embodiment 1
The raw material powder coal ash consists of: Al
2O
3: 41%, SiO
2: 48%, Fe
2O
3: 3.3%, CaO:3.3%, TiO
2: 1.3%, MgO:0.2%.The composition of raw material powder coal ash also can adopt other moiety, and this can not be used for limiting protection scope of the present invention.
Get the raw material powder coal ash of the above-mentioned composition of 1000g, flyash is obtained raw material with ammoniumsulphate soln mixing wet-milling, wherein the weight ratio of the aluminum oxide in ammonium sulfate and flyash is 5:1; Raw material are heated to 450 ℃, are incubated 1h, make grog and the ammonia of sulfur acid aluminium ammonium, ammonia adopts washing lotion to reclaim preparation ammoniacal liquor; With one section grinding machine stripping 0.5h, aluminium enters solution with the form of exsiccated ammonium alum to the grog that burns till in hot water, and silicon is stayed and formed high white residue in residue; The stripping rear slurry is through the countercurrent washing of separation one-level, and liquid is aluminum ammonium sulfate solution, and solid is high white residue; Aluminum ammonium sulfate solution carries out a deironing, adopts pressurized air as oxygenant, adopts lime as neutralizing agent, and iron ion in solution is reduced to 3.9g/L.The deironing rear slurry adopts the vacuum separation washing, solid is high scum, liquid carries out the secondary deironing, adopt oxygen as oxygenant, adopt ammoniacal liquor as neutralizing agent, in solution, iron ion is reduced to 29mg/L, the deironing rear slurry adopts the separation washing, solid returns to raw meal proportioning, the ammoniacal liquor that the Ammonia recovery that adds grog to burn till generation in aluminum ammonium sulfate solution after the deironing obtains decomposes solution and obtains thick aluminum hydroxide slurry, adopts vacuum separation and washing, solid is thick aluminium hydroxide, and liquid is ammoniumsulphate soln; Thick aluminium hydroxide adopts ammoniacal liquor to carry out desulfurization, obtains the desulfurization aluminum hydroxide slurry, adopts settlement separately to obtain without sulphur aluminium hydroxide with washing; After ammoniumsulphate soln adopts falling film evaporation, obtain ammonium sulfate through separation and return to the raw material preparation, recycle; Carry out roasting without sulphur aluminium hydroxide at 900 ℃ of employing rotary kilns, obtain aluminum oxide.In flyash, alumina extraction ratio is 86%.
Embodiment 2
Get the raw material powder coal ash that forms in 1000g embodiment 1, flyash is mixed dry grinding with ammonium sulfate and obtain raw material, wherein the weight ratio of the aluminum oxide in ammonium sulfate and flyash is 6:1; Raw material are heated to 500 ℃, are incubated 0.5h, make grog and the ammonia of sulfur acid aluminium ammonium, Ammonia recovery; With Secondary grinding mill stripping 3h, aluminium enters solution with the form of exsiccated ammonium alum to the grog that burns till in washing lotion, and silicon is stayed and formed high white residue in residue; The stripping rear slurry washs through settlement separate four-stage counter-current, and liquid is aluminum ammonium sulfate solution, and solid is high white residue; Aluminum ammonium sulfate solution carries out a deironing, adopts oxygen as oxygenant, adopts ammoniacal liquor as neutralizing agent, and iron ion in solution is reduced to 0.5g/L.The deironing rear slurry adopts the separation washing, solid is high scum, liquid carries out the secondary deironing, adopt hydrogen peroxide as oxygenant, adopt ammonia as neutralizing agent, in solution, iron ion is reduced to 20mg/L, the deironing rear slurry adopts the vacuum separation washing, solid returns to raw meal proportioning, the ammonia that the Ammonia recovery that adds grog to burn till generation in aluminum ammonium sulfate solution after the deironing obtains decomposes solution and obtains thick aluminum hydroxide slurry, adopts separation and washing, solid is thick aluminium hydroxide, and liquid is ammoniumsulphate soln; Thick aluminium hydroxide adopts sodium carbonate to carry out desulfurization, obtains the desulfurization aluminum hydroxide slurry, adopts settlement separately to obtain without sulphur aluminium hydroxide with washing; After ammoniumsulphate soln adopts forced circulation evaporation, obtain ammonium sulfate through centrifugation and return to the raw material preparation, recycle; Adopt gas suspension calcination without sulphur aluminium hydroxide at 1150 ℃, obtain aluminum oxide.In flyash, alumina extraction ratio is 87%.
Embodiment 3
Get the raw material powder coal ash that forms in 1000g embodiment 1, flyash is directly mixed with ammonium sulfate, wherein the weight ratio of the aluminum oxide in ammonium sulfate and flyash is 7:1; Raw material are heated to 350 ℃, are incubated 5h, make grog and the ammonia of sulfur acid aluminium ammonium, ammonia adopts water to reclaim preparation ammoniacal liquor; With continuously stirring stripping 5h, aluminium enters solution with the form of exsiccated ammonium alum to the grog that burns till in hot water, and silicon is stayed and formed high white residue in residue; The stripping rear slurry is through vacuum separation three stage countercurrent washings, and liquid is aluminum ammonium sulfate solution, and solid is high white residue; Aluminum ammonium sulfate solution carries out a deironing, adopts hydrogen peroxide as oxygenant, adopts coal ash as neutralizing agent, and iron ion in solution is reduced to 1g/L.The deironing rear slurry adopts settlement separate washing, solid is high scum, liquid carries out the secondary deironing, adopt hydrogen peroxide as oxygenant, adopt aluminum hydroxide wash liquor as neutralizing agent, in solution, iron ion is reduced to 10mg/L, the deironing rear slurry adopts settlement separate washing, solid returns to raw meal proportioning, the ammoniacal liquor that the Ammonia recovery that adds grog to burn till generation in aluminum ammonium sulfate solution after the deironing obtains decomposes solution and obtains thick aluminum hydroxide slurry, adopts settlement separate and washs, solid is thick aluminium hydroxide, and liquid is ammoniumsulphate soln; Thick aluminium hydroxide adopts sodium hydroxide to carry out desulfurization, obtains the desulfurization aluminum hydroxide slurry, adopts separation and washing to obtain without sulphur aluminium hydroxide; After ammoniumsulphate soln adopts the natural circulation evaporation, return to the raw material preparation through the settlement separate ammonium sulfate that obtains, recycle; Adopt fluosolids roasting without sulphur aluminium hydroxide at 1050 ℃, obtain aluminum oxide.In flyash, alumina extraction ratio is 85%.
Embodiment 4
Get the raw material powder coal ash that forms in 1000g embodiment 1, flyash is mixed dry grinding with ammonium sulfate and obtain raw material, wherein the weight ratio of the aluminum oxide in ammonium sulfate and flyash is 8:1; Raw material are heated to 450 ℃, are incubated 3h, make grog and the ammonia of sulfur acid aluminium ammonium, ammonia adopts washing lotion to reclaim preparation ammoniacal liquor; The grog that burns till stirs stripping 0.1h with being interrupted in washing lotion, aluminium enters solution with the form of exsiccated ammonium alum, and silicon is stayed and formed high white residue in residue; The stripping rear slurry is through the countercurrent washing of vacuum separation one-level, and liquid is aluminum ammonium sulfate solution, and solid is high white residue; Aluminum ammonium sulfate solution carries out a deironing, adopts pressurized air as oxygenant, adopts lime as neutralizing agent, and iron ion in solution is reduced to 2g/L.The deironing rear slurry adopts the vacuum separation washing, solid is high scum, liquid carries out the secondary deironing, adopt hydrogen peroxide as oxygenant, adopt ammonia as neutralizing agent, in solution, iron ion is reduced to 28mg/L, the deironing rear slurry adopts the vacuum separation washing, solid returns to raw meal proportioning, the ammoniacal liquor that the Ammonia recovery that adds grog to burn till generation in aluminum ammonium sulfate solution after the deironing obtains decomposes solution and obtains thick aluminum hydroxide slurry, adopts vacuum separation and washing, solid is thick aluminium hydroxide, and liquid is ammoniumsulphate soln; Thick aluminium hydroxide adopts milk of lime to carry out desulfurization, obtains the desulfurization aluminum hydroxide slurry, adopts vacuum separation and washing to obtain without sulphur aluminium hydroxide; Ammoniumsulphate soln adopts falling film evaporation and forced circulation evaporation combination, obtains ammonium sulfate through vacuum separation and returns to the raw material preparation, recycles; Adopt fluosolids roasting without sulphur aluminium hydroxide at 1200 ℃, obtain aluminum oxide.In flyash, alumina extraction ratio is 88%.
Embodiment 5
Get the raw material powder coal ash that forms in 1000g embodiment 1, flyash is obtained raw material with ammoniumsulphate soln mixing wet-milling, wherein the weight ratio of the aluminum oxide in ammonium sulfate and flyash is 4.5:1; Raw material are heated to 400 ℃, are incubated 1.5h, make grog and the ammonia of sulfur acid aluminium ammonium, ammonia adopts washing lotion to reclaim preparation ammoniacal liquor; The grog that burns till stirs stripping 1.5h with being interrupted in washing lotion, aluminium enters solution with the form of exsiccated ammonium alum, and silicon is stayed and formed high white residue in residue; The stripping rear slurry is through the countercurrent washing of vacuum separation secondary, and liquid is aluminum ammonium sulfate solution, and solid is high white residue; Aluminum ammonium sulfate solution carries out a deironing, adopts pressurized air as oxygenant, adopts lime as neutralizing agent, and iron ion in solution is reduced to 2.5g/L.The deironing rear slurry adopts the vacuum separation washing, solid is high scum, liquid carries out the secondary deironing, adopt hydrogen peroxide as oxygenant, adopt ammonia as neutralizing agent, in solution, iron ion is reduced to 25mg/L, the deironing rear slurry adopts the separation washing, solid returns to raw meal proportioning, the ammoniacal liquor that the Ammonia recovery that adds grog to burn till generation in aluminum ammonium sulfate solution after the deironing obtains decomposes solution and obtains thick aluminum hydroxide slurry, adopts vacuum separation and washing, solid is thick aluminium hydroxide, and liquid is ammoniumsulphate soln; Thick aluminium hydroxide adopts milk of lime to carry out desulfurization, obtains the desulfurization aluminum hydroxide slurry, adopts vacuum separation and washing to obtain without sulphur aluminium hydroxide; Ammoniumsulphate soln adopts falling film evaporation and forced circulation evaporation combination, obtains ammonium sulfate through vacuum separation and returns to the raw material preparation, recycles; Adopt fluosolids roasting without sulphur aluminium hydroxide at 1300 ℃, obtain aluminum oxide.In flyash, alumina extraction ratio is 85%.
Embodiment 6
Alum liquor secondary deironing step in embodiment 1 changes a deironing refined liquid reduction into, and the reductive agent that a deironing refined liquid reduction is adopted is iron sulphide, carries out alum liquor after a deironing refined liquid reduction and decomposes.The other the same as in Example 1 is identical.
Embodiment 7
Reductive agent in embodiment 6 is elemental sulfur, and other is identical with embodiment 6.
Embodiment 8
Reductive agent in embodiment 6 is sulphur trioxide, and other is identical with embodiment 6.
Embodiment 9
Reductive agent in embodiment 6 is Iron sulfuret, and other is identical with embodiment 6.
The main component of the high white residue in above-described embodiment is silicon-dioxide, for the preparation of white carbon black or other high silicon filler.The main component of high scum is ferric oxide, is used for ironmaking.
Above the embodiment of the present patent application is exemplarily described, but protection scope of the present invention is to be limited by following claims, and is not subjected to that in the present patent application, embodiment limits.
Claims (21)
1. the baking mixed method for preparing aluminum oxide of flyash ammonium sulfate, is characterized in that comprising the steps:
The raw material preparation: flyash is mixed with ammonium sulfate, be prepared into raw material, wherein the weight ratio of the aluminum oxide in ammonium sulfate and flyash is 4.5～8:1;
Grog burns till: raw material are heated to 350 ~ 500 ℃, and firing time is controlled at 0.5 ~ 5h, makes grog and the ammonia of sulfur acid aluminium ammonium, and ammonia is for the preparation of ammoniacal liquor or pass into exsiccated ammonium alum refined liquid decomposition process;
The grog stripping: grog carries out stripping with hot water or washing lotion, dissolution time 0.1 ~ 5h, and aluminium enters solution with the form of exsiccated ammonium alum, and silicon is stayed and is formed high white residue in residue;
High white residue separating, washing: the slurries after stripping carry out solid-liquid separation and countercurrent washing, and solution is aluminum ammonium sulfate solution, and washing rear slag is high white residue;
A deironing of aluminum ammonium sulfate solution: adopt the goethite process add oxygenant to carry out a deironing to the aluminum ammonium sulfate solution of stripping, iron concentration is reduced to below 4g/L, after a deironing, solution carries out the secondary deironing or carries out a deironing refined liquid reduction, and an iron dross removing is high scum;
Aluminum ammonium sulfate solution secondary deironing: adopt logical oxygen iron purification mode to carry out the secondary deironing to a deironing refined liquid, iron concentration is down to below 30mg/L, get the exsiccated ammonium alum refined soln;
A deironing refined liquid reduction: add reductive agent in a deironing refined liquid, carry out the reduction of deironing refined liquid, make ferric ion wherein all be converted into ferrous ion;
Exsiccated ammonium alum refined liquid solution decomposes: exsiccated ammonium alum refined soln or deironing reduction after the secondary deironing are led to ammonia or the ammoniacal liquor that the grog firing process obtains in refined liquid afterwards, obtain thick aluminium hydroxide and ammoniumsulphate soln;
Thick aluminium hydroxide separating, washing: the slurries after exsiccated ammonium alum decomposes carry out solid-liquid separation and thick aluminium hydroxide washing, and liquid is the circulation fluid ammoniumsulphate soln, and solid is thick aluminium hydroxide;
Thick aluminium hydroxide desulfurization: the exsiccated ammonium alum refined liquid is decomposed the thick aluminium hydroxide that obtains and is adopted basic solution to carry out desulfurization, obtains sulfate radical-free aluminium hydroxide;
The aluminium hydroxide separating, washing: the slurries after desulfurization carry out solid-liquid separation and aluminium hydroxide washing, and solid is aluminium hydroxide;
Aluminium hydroxide roasting: aluminium hydroxide obtains the finished product aluminum oxide 900 ~ 1300 ℃ of lower roastings.
2. the baking mixed method for preparing aluminum oxide of flyash ammonium sulfate according to claim 1 is characterized in that described raw material preparation is to adopt the mode of directly mixing or grinding mixing that flyash and ammonium sulfate are mixed.
3. the baking mixed method for preparing aluminum oxide of flyash ammonium sulfate according to claim 2, is characterized in that described grind mixing employing wet-milling or dry grinding.
4. the baking mixed method for preparing aluminum oxide of flyash ammonium sulfate according to claim 1 is characterized in that described grog stripping adopts the grinding machine stripping or stir a kind of in stripping.
5. the baking mixed method for preparing aluminum oxide of flyash ammonium sulfate according to claim 4 is characterized in that described grinding machine stripping adopts a kind of in the stripping of one section mill or the stripping of two sections mills.
6. the baking mixed method for preparing aluminum oxide of flyash ammonium sulfate according to claim 4 is characterized in that described stirring stripping is adopted to be interrupted to stir a kind of in stripping or continuously stirring stripping.
7. the baking mixed method for preparing aluminum oxide of flyash ammonium sulfate according to claim 1 is characterized in that described high white residue separating, washing adopts a kind of in vacuum separation, settlement separate or separation.
8. the baking mixed method for preparing aluminum oxide of flyash ammonium sulfate according to claim 1 is characterized in that described high white residue separating, washing adopts a kind of in one-level, secondary or multi-stage countercurrent washing.
9. the baking mixed method for preparing aluminum oxide of flyash ammonium sulfate according to claim 1 is characterized in that oxygenant in a deironing of described aluminum ammonium sulfate solution adopts a kind of in pressurized air, oxygen or hydrogen peroxide.
10. the baking mixed method for preparing aluminum oxide of flyash ammonium sulfate according to claim 1 is characterized in that neutralizing agent that in a deironing of described aluminum ammonium sulfate solution, goethite process adopts is a kind of in ammoniacal liquor, ammonia, lime or coal ash.
11. the baking mixed method for preparing aluminum oxide of flyash ammonium sulfate according to claim 1 is characterized in that oxygenant in the deironing of described aluminum ammonium sulfate solution secondary adopts a kind of in oxygen or hydrogen peroxide.
12. the baking mixed method for preparing aluminum oxide of flyash ammonium sulfate according to claim 1 is characterized in that the neutralizing agent that adopts in the deironing of described aluminum ammonium sulfate solution secondary is a kind of in ammoniacal liquor, ammonia or aluminum hydroxide wash liquor.
13. the baking mixed method for preparing aluminum oxide of flyash ammonium sulfate according to claim 1, the separating, washing that it is characterized in that high scum in a deironing of described aluminum ammonium sulfate solution and the deironing of aluminum ammonium sulfate solution secondary adopt a kind of in vacuum separation, settlement separate or separation.
14. the baking mixed method for preparing aluminum oxide of flyash ammonium sulfate according to claim 1 is characterized in that reductive agent that described deironing refined liquid reduction is adopted is a kind of in iron sulphide, elemental sulfur, sulphur trioxide, hydrogen sulfide or Iron sulfuret.
15. the baking mixed method for preparing aluminum oxide of flyash ammonium sulfate according to claim 1 is characterized in that described thick aluminium hydroxide separating, washing adopts a kind of in vacuum separation, settlement separate or separation.
16. the baking mixed method for preparing aluminum oxide of flyash ammonium sulfate according to claim 1 is characterized in that described thick aluminium hydroxide desulfurization adopts a kind of as sweetening agent in sodium carbonate, sodium hydroxide, milk of lime or ammoniacal liquor.
17. the baking mixed method for preparing aluminum oxide of flyash ammonium sulfate according to claim 1 is characterized in that described thick aluminium hydroxide separating, washing adopts a kind of in vacuum separation, settlement separate or separation.
18. the baking mixed method for preparing aluminum oxide of flyash ammonium sulfate according to claim 1 is characterized in that described Aluminium hydroxide roasting adopts a kind of in rotary kiln baking, fluosolids roasting or gas suspension calcination.
19. the baking mixed method for preparing aluminum oxide of flyash ammonium sulfate according to claim 1 is characterized in that described finished product aluminum oxide meets the metallurgical-grade aluminum oxide standard.
20. the baking mixed method for preparing aluminum oxide of flyash ammonium sulfate according to claim 1, it is characterized in that described aluminium hydroxide separates the ammoniumsulphate soln that obtains and evaporates, the combination of one or more in employing falling film evaporation, pump circulation steaming or natural circulation evaporation.
21. the baking mixed method for preparing aluminum oxide of flyash ammonium sulfate according to claim 20 is characterized in that ammonia sulfate crystal that the evaporation of described ammoniumsulphate soln produces adopts a kind of in centrifugation, vacuum separation, settlement separate or separation.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104030329A (en) * | 2013-07-04 | 2014-09-10 | 沈阳工业大学 | Method for comprehensively using aluminum-containing resource |
| CN106745124A (en) * | 2016-12-08 | 2017-05-31 | 湖南先导电子陶瓷科技产业园发展有限公司 | A kind of technique that aluminium hydroxide and concrete admixture are produced from Coaseries kaolin |
| CN107935006A (en) * | 2016-10-12 | 2018-04-20 | 北京矿冶研究总院 | Method for extracting aluminum oxide by mixing and roasting ammonium sulfate and fly ash in reducing atmosphere |
| CN109336140A (en) * | 2018-11-22 | 2019-02-15 | 谭春波 | A kind of technique that lepidolite addition LiFePO4 mentions lithium |
| CN110747347A (en) * | 2019-11-22 | 2020-02-04 | 东北大学 | Method for recovering iron by using fly ash and method for extracting aluminum by using fly ash |
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| CN104030329A (en) * | 2013-07-04 | 2014-09-10 | 沈阳工业大学 | Method for comprehensively using aluminum-containing resource |
| CN104030329B (en) * | 2013-07-04 | 2016-02-10 | 沈阳工业大学 | A kind of method containing bauxite resource comprehensive utilization |
| CN107935006A (en) * | 2016-10-12 | 2018-04-20 | 北京矿冶研究总院 | Method for extracting aluminum oxide by mixing and roasting ammonium sulfate and fly ash in reducing atmosphere |
| CN107935006B (en) * | 2016-10-12 | 2019-09-03 | 北京矿冶科技集团有限公司 | Ammonium sulfate and the baking mixed method for extracting aluminium oxide of flyash reducing atmosphere |
| CN106745124A (en) * | 2016-12-08 | 2017-05-31 | 湖南先导电子陶瓷科技产业园发展有限公司 | A kind of technique that aluminium hydroxide and concrete admixture are produced from Coaseries kaolin |
| CN106745124B (en) * | 2016-12-08 | 2018-07-03 | 湖南先导电子陶瓷科技产业园发展有限公司 | A kind of technique that aluminium hydroxide and concrete admixture are produced from Coaseries kaolin |
| CN109336140A (en) * | 2018-11-22 | 2019-02-15 | 谭春波 | A kind of technique that lepidolite addition LiFePO4 mentions lithium |
| CN109336140B (en) * | 2018-11-22 | 2022-09-30 | 湖南天泰天润新能源科技有限公司 | Process for extracting lithium by adding lithium iron phosphate into lepidolite |
| CN110747347A (en) * | 2019-11-22 | 2020-02-04 | 东北大学 | Method for recovering iron by using fly ash and method for extracting aluminum by using fly ash |
| CN111498882A (en) * | 2020-04-29 | 2020-08-07 | 沈阳工业大学 | Method for preparing coarse-particle aluminum hydroxide from aluminum ammonium sulfate solution |
| CN111498882B (en) * | 2020-04-29 | 2022-10-25 | 沈阳工业大学 | Method for preparing coarse-particle aluminum hydroxide from aluminum ammonium sulfate solution |
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