CN103145160A - Method for producing alumina by using high-alumina fly ash - Google Patents
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Abstract
The invention provides a method for producing alumina by using high-alumina fly ash. The method comprises adopting the high-alumina fly ash to be reacted with a sodium hydroxide solution to conduct desilicication in advance to obtain coal ash filter cakes and desilicication liquid firstly; and adding the desilicication coal ash filter cakes in slurry of the limestone and sodium carbonate to mix to form raw material slurry, then roasting the raw material slurry to form ripe materials, considering a liquid phase dissolved from the ripe materials as sodium aluminate coarse liquid, conducting carbon separation on the obtained sodium aluminate coarse liquid, and then conducting Bayer process dissolving, dilution desilicication, kind separation and roasting. Tedious desilicication processes of a first section and a second section are removed, equipment, such as high-pressure desilicication groove and deep desilicication groove which are difficult to operate is reduced, equipment cost and operation difficulties are reduced, and high-purity alumina products can be obtained simultaneously.
Description
Technical field
The present invention relates to the method for utilizing of flyash, relate in particular to a kind of method of being produced aluminum oxide by aluminous fly-ash.
Background technology
Aluminum oxide is the main raw material(s) of producing aluminium ingot.Aluminum oxide more than 95% is produced by bauxite in the world.China is alumina producing state the biggest in the world, and present annual aluminum oxide output is over 3,000 ten thousand tons.But China's bauxite resource is relatively deficient simultaneously, and the bauxite reserves only account for 7% left and right of world's total reserves, and mostly are unmanageable diaspore ore, and because bauxite resource is not enough, the bauxite of present 60% left and right depends on to external import.
And the regional rear aluminous fly-ash reserves that produce of coal generating such as China's Middle-west Inner Mongolia and North of Shanxi enrich, only the potential aluminous fly-ash resource standing stock in Inner Mongol Zhungeer coal field just reach 15,000,000,000 tons, be equivalent to more than 8 times of the present bauxite retained reserve of China, and in the part aluminous fly-ash, alumina content can reach 40%-50%.in recent years, each large universities and colleges of China and R﹠D institution have actively developed aluminous fly-ash and have extracted the research of aluminum oxide novel process, the main technique method is: pre-desiliconizing-soda-lime sintering process, one step acid pasting, ammonium sulfate sintering-Bayer process, limestone sintering-low temperature Bayer process etc., wherein acid system is because existing the equipment material seriously corroded, the product foreign matter content is more high-leveled and difficult is difficult to realize large-scale industrial production with problems such as production metallurgy grade aluminum oxides, the ammonium sulfate sintering process exists the slag phase flow rate large, the shortcomings such as Ammonia recovery utilization difficulty do not have the industrialization example yet, limestone sintering method and soda-lime stone sintering process are similar, but its quantity of slag is larger, energy consumption is higher, and the rate of recovery is slightly low than soda-lime stone sintering process, and pre-desiliconizing-soda-lime sintering process is present unique suitability for industrialized production and processing method of achieving success of realizing, patent CN201110117710 discloses the technical characterstic of this technique.
Yet CN201110117710 adopts a tediously long two-stage desilication technique, needs the equipment of the difficult operation such as high pressure desiliconization slot, deep desilication groove, the high and complicated operation of equipment cost.
How a kind of new process for making alumina is provided, does not adopt an above-mentioned two-stage desilication technique to become problems to be solved by the high efficiency extraction aluminum oxide from aluminous fly-ash.
Summary of the invention
The invention provides a kind of method of being produced aluminum oxide by aluminous fly-ash, avoided adopting a tediously long two-stage desilication technique, reduced equipment cost and operation easier, still can obtain the high alumina product of purity simultaneously.
A kind of method of being produced aluminum oxide by aluminous fly-ash provided by the invention comprises:
1) pre-desiliconizing with aluminous fly-ash and sodium hydroxide solution mixing post-heating, then imports and carries out the pre-desiliconizing reaction in pressure vessel, carries out solid-liquid separation after the pre-desiliconizing reaction and obtains flyash filter cake and desiliconization liquid;
2) charge pulp preparation joins described flyash filter cake in the slurries that sodium carbonate, Wingdale and/or unslaked lime is made into and obtains mixed serum, and described mixed serum is levigate and be deployed into charge pulp;
3) grog roasting is with described charge pulp roasting ripe material;
4) grog stripping mixes described grog and carries out stripping with adjustment liquid, carry out solid-liquid separation after stripping and obtain the thick slag of stripping and crude liquor of sodium aluminate, and described adjustment liquid composition comprises: the Na of 10～60g/l
2O
k, the Na of 10～60g/l
2O
c
5) carbonating is decomposed: pass in the described crude liquor of sodium aluminate that obtains to step 4) and contain CO
2Gas carry out the carbonating decomposition reaction, and to the reaction system solid-liquid separation, collect carbon mother liquid and aluminium hydroxide crude product;
6) the described aluminium hydroxide crude product that low temperature Bayer Process digestion: in step 5) obtains adds alkali lye A to carry out the low temperature Bayer Process digestion, solid-liquid separation obtains to separate filter cake and stripping slurries, wherein, during described low temperature Bayer Process digestion according to 1 gram aluminium hydroxide crude product: the weightmeasurement ratio of 2～5ml alkali lye adds alkali lye A, makes alkali concn in formed stripping system with Na
2O is expressed as 120g/L～180g/L, and controls 100 ℃～160 ℃ of stripping temperature, dissolution time 0.5h～2h;
7) dilution desiliconization: the stripping slurries that step 6) is obtained use alkali lye B to dilute desiliconization, solid-liquid separation obtains white residue and the thick liquid of desiliconization, white residue turns back to described charge pulp, the thick liquid of described desiliconization obtains the desiliconization seminal fluid by again filtering, wherein, volume ratio according to described stripping slurries and alkali lye B5～12:1 during described dilution desiliconization adds alkali lye B, makes alkali concn in formed dilution desiliconization system with Na
2O is expressed as 50g/L～110g/L;
8) plant minute: with step 7) the described desiliconization seminal fluid that obtains plant minute with aluminium hydroxide crystal seed, obtains aluminium hydroxide and kind is divided a decomposition nut liquid;
9) roasting: described Aluminium hydroxide roasting is obtained aluminum oxide.
In the solution of the present invention, Na
2O
k, Na
2O
cTechnology commonly used in aluminum oxide industry, wherein Na
2O
k(k is first phonetic alphabet severe in severe alkali.Sometimes the back does not add k, directly uses Na
2O represents, sometimes also directly represents with NK) be used for characterizing NaOH and NaAlO in sodium aluminate or other basic solution
2The content sum, namely in this class basic solution respectively with NaOH and NaAlO
2Content is all amounted to into Na
2O calculates, then will be both the value of addition gained be called severe alkali content in solution, use Na
2O
kRepresent.Described Na
2O
c(C is carbonate CO
3 2-Abbreviation, sometimes also directly represent with NC) be used for characterizing Na in sodium aluminate or other basic solution
2CO
3Content, with Na in solution
2CO
3Content amount to into Na
2O calculates.Above-mentioned method of calculation be this area know altogether general knowledge, those skilled in the art can be according to Na
2O
k, Na
2O
cMethod for expressing is the skimble-skamble calculation of correlation of carrying out directly.Can be referring to " alumina producing knowledge question " the 14th page.
In the solution of the present invention, solid-liquid separation can use conventional vacuum filtration equipment to carry out.The solid-liquid separation of the present invention program's step 5) also can be carried out in subsider.The aluminium hydroxide that obtains in step 8) is that the kind that contains higher degree aluminium hydroxide is divided product.
In the solution of the present invention, a part in the carbon mother liquid that obtains after step 5) carbon divides can (for example be carried out direct causticization, can use milk of lime to carry out causticization), gained causticization liquid is circulated to the pre-desiliconizing operation and uses as circulation alkali liquor, and the carbon mother liquid of rest part can join step 2) the middle preparation that participates in charge pulp.
Further, the mass concentration of the described sodium hydroxide solution that uses in the step 1) pre-desiliconizing is 10～30%, and the mass ratio of sodium hydroxide and aluminous fly-ash is 0.2～0.8:1, temperature of reaction: 70～135 ℃, and the reaction times: 0.5～3h.
Further, step 2) in the charge pulp preparation process, the calcium ratio of the described charge pulp of making is 1.95～2.01, and the alkali ratio is 0.95～1.05, and water ratio is 25～50wt%.The calcium ratio refers to CaO/SiO
2Mol ratio; The alkali ratio refers to Na
2O/(Al
2O
3+ Fe
2O
3) mol ratio.Above-mentioned condition can make the step 3) grog cure and obtain better effect.
Further, the maturing temperature of step 3) grog roasting is 1150～1300 ℃, roasting time 10～60 minutes.
Further, the particle diameter≤8mm of grog described in the stripping of described step 4) grog, the liquid-solid mass ratio of described adjustment liquid and grog is 2～8:1, and grog stripping temperature is 55～85 ℃, and the grog dissolution time is 5～30min.Above-mentioned particle diameter can be controlled by step 3) grog roasting process, can improve result of extraction and filtering separation effect.
Further, 4) Al in the described crude liquor of sodium aluminate of grog stripping acquisition
2O
3Be 60-120g/L, Na
2O
kBe 100-160g/L, Na
2O
cBe 20-80g/L.Further, Na in described crude liquor of sodium aluminate
2O and Al
2O
3Mol ratio can be 1.3-1.6.Described crude liquor of sodium aluminate can obtain by controlling the grog leaching condition.
What further, pass in step 5) contains CO
2Gas in CO
2Volumetric concentration is 30%～50%, and carbon minute temperature is 60-100 ℃, and it is 2h～4h that carbon divides the time, and carries out carbon and divide under agitation condition
Above-mentioned carbon minute condition can make carbon divide Al in rear described crude liquor of sodium aluminate
2O
3Rate of decomposition 〉=97%.
Further, the kind that obtains of step 8) divide decomposition nut liquid return step 6) as Bayer stripping do all or part of with alkali lye A.For example produce aluminum oxide by aluminous fly-ash first and can use sodium hydroxide solution; Can directly use step 8 in producing alumina process by the aluminous fly-ash serialization) kind that obtains divides decomposition nut liquid as alkali lye A, as long as low temperature Bayer Process digestion process has with Na
2The alkaline condition that O is expressed as 120g/L～180g/L gets final product, and certainly, is not enough to obtain above-mentioned alkaline condition if plant a minute decomposition nut liquid, can also replenish as required to add sodium hydroxide solution.
Further, the step 8) kind turns back to step 6 after dividing decomposition nut liquid to adopt 4～5 grades of flash vaporizers to evaporate) in.Low temperature Bayer Process digestion in the present invention program can carry out in tubular digester or pressure are boiled reactor.
Further, comprise that also the separation filter cake that step 6) is obtained carries out water washing, and the wash water after washing is as in step 7), the stripping slurries being diluted alkali lye B all or part of of desiliconization.For example produce aluminum oxide by aluminous fly-ash first and can use sodium hydroxide solution; Can directly use described wash water as alkali lye B in producing alumina process by the aluminous fly-ash serialization, have with Na as long as make at the dilution desiliconization process
2The alkaline condition that O is expressed as 50g/L～110g/L gets final product, and certainly, if wash water is not enough to obtain above-mentioned alkaline condition, can also replenishes as required and adds sodium hydroxide solution.Can make Al in described aluminium hydroxide crude product after above-mentioned dilution desiliconization
2O
3Solubility rate 〉=90%.
Further, can be with 80 ℃～90 ℃ water at rinse bath washing step 6) described separation filter cake 3～5 times, the add-on of water is 2～3 times of the separation filter cake that will wash.Wash water filtrate after the last washing is returned to rinse bath and is recycled, and remaining wash water turns back to step 7) and dilutes desiliconization.Moisture content≤the 40wt% of the separation filter cake after washing can return to the charge pulp preparation section and use as raw material.
Further, described step 7) again be filtered into the essence filter, control this essence filter and make seston content≤0.01g/L in described desiliconization seminal fluid.
Further, in described step 8) according to 1L desiliconization seminal fluid: the ratio of 400～800g aluminium hydroxide crystal seed adds aluminium hydroxide crystal seed, and plant minute through 8～12 seed precipitation tanks, planting minute time is 36h～48h, and the temperature when controlling first seed precipitation tank of process is 60 ℃～70 ℃, temperature during last seed precipitation tank of process is 48 ℃～59 ℃, and the every 4h of temperature that plants minute process reduces 1-2 ℃.Above-mentioned kind minute condition can make the aluminium hydroxide rate of decomposition in described desiliconization seminal fluid reach 43%～51%.
Further, in described step 9), aluminium hydroxide carries out fluidizing calcination to obtain aluminum oxide under 900～1100 conditions.
A kind of method of being produced aluminum oxide by aluminous fly-ash provided by the invention has the following advantages:
1, method provided by the invention is carried out carbon with the crude liquor of sodium aluminate that obtains after with the grog stripping and is divided, then carry out the low temperature Bayer Process digestion, overcome a tediously long two-stage desilication technique, reduced the equipment of the difficult operations such as high pressure desiliconization slot, deep desilication groove, reduce equipment cost and operation easier, still can obtain the high-purity alpha-alumina product simultaneously.
The carbon of 2, inciting somebody to action in method provided by the invention divides the aluminium hydroxide crude product of acquisition to adopt the low temperature stripping process by Bayer process to carry out stripping, mild condition, and energy consumption is lower, and apparatus adaptability is good, but has better industrialization amplification.
3, in producing the process of aluminum oxide by the aluminous fly-ash serialization, method provided by the invention is produced the process of aluminum oxide by the aluminous fly-ash serialization except the first round, the process by aluminous fly-ash serialization production aluminum oxide that other are continuous, the wash water that the described separation filter cake of washing can be obtained returns to step 7) and dilutes desiliconization as alkali lye B, also can directly return to plant a minute decomposition nut liquid to step 6) carry out the low temperature Bayer Process digestion as alkali lye A, make the carrying out that produces aluminum oxide energy continuous high-efficient, do not need the extra buck that replenishes new configuration yet, further saved production cost.
4, use the inventive method to be produced in the process of aluminum oxide by the aluminous fly-ash serialization, the carbon mother liquid that step 5) obtains is causticization partly, gained causticization liquid is capable of circulation to be used as alkali lye to the pre-desiliconizing step, the carbon mother liquid of rest part can join step 2) the middle preparation that participates in charge pulp, further improved the comprehensive utilization of resources degree.
Embodiment
Following examples only in order to technical scheme of the present invention to be described, are not intended to limit; Although with reference to previous embodiment, the present invention is had been described in detail, those of ordinary skill in the art is to be understood that: it still can be modified to the technical scheme that aforementioned each embodiment puts down in writing, and perhaps part technical characterictic wherein is equal to replacement; And these modifications or replacement do not make the essence of appropriate technical solution break away from the spirit and scope of various embodiments of the present invention technical scheme.
Embodiment 1:
1) pre-desiliconizing, be after mixing solutions that 20% sodium hydroxide solution (mass ratio of sodium hydroxide and aluminous fly-ash is 0.5:1) forms is heated to 110 ℃ with aluminous fly-ash and mass concentration, import in pressure vessel and carry out desilication reaction 2h, then carry out liquid-solid separation and obtain the desiliconization liquid of liquid phase and the flyash filter cake of solid phase, the aluminous fly-ash of the alumina silica ratio in the flyash filter cake before than desilication reaction is high; In aluminous fly-ash, quality of alumina content is higher than 40%;
2) charge pulp preparation joins the flyash filter cake in the slurries that Wingdale and sodium carbonate is made into and obtains mixed serum, and mixed serum is levigate and be deployed into charge pulp in ball mill; Need through levigate processing before unslaked lime and sodium carbonate mix, the calcium of charge pulp ratio is 2, and the alkali ratio is 1, and water ratio is 30wt%;
3) grog roasting, with charge pulp at 1200 ℃ of lower roasting 30min ripe materials;
4) grog stripping is carried out grog stripping after liquid mixes with grog with adjusting, and carries out solid-liquid separation acquisition crude liquor of sodium aluminate and the thick slag of stripping after stripping, and the liquid-solid mass ratio of described adjustment liquid and grog is 6:1, and the stripping temperature is 75 ℃, and dissolution time is 20min; Described adjustment liquid composition comprises: the Na of 30g/l
2O
k, the Na of 30g/l
2O
c
5) carbonating is decomposed:: get the crude liquor of sodium aluminate 2L(Al that step 4) obtains
2O
3Content is 101.5g/L, Na
2O
kContent is 128.2g/L, Na
2O
cContent is 58.3g/L, SiO
2Content is 2.24g/L) gas that passes into carbonated 38% volumetric concentration carries out the carbonating decomposition reaction within carbon divides groove, draft speed is 1L/min, carbon minute temperature is 60-100 ℃, after 3h to the reaction system solid-liquid separation, collect carbon mother liquid and aluminium hydroxide crude product, aluminium hydroxide crude product weight 297.1g detects carbon mother liquid and analyzes, wherein Al
2O
3The carbonating rate of decomposition is 97.2%, the aluminium hydroxide crude product is detected, wherein SiO
2Deposition rate is 96.0%;
6) low temperature Bayer Process digestion: get above-mentioned aluminium hydroxide crude product 100g and Na
2O
kFor the sodium hydroxide solution 288ml of 180g/L is mixed in the corrosion-resistant autoclave of 500ml, reaction 2h carries out the low temperature Bayer Process digestion under 160 ℃ of temperature, 0.6MPa pressure, obtain after solid-liquid separation to separate filter cake and stripping slurries, digesting efficiency of alumina is 92%;
7) dilution desiliconization: add the alkali lye B of 38ml in the stripping slurries with the step 6) acquisition, the alkali concn in control dilution desiliconization system is with Na
2O is expressed as 110g/L, stir 1h under the condition of 80 ℃ of stirrings of temperature, solid-liquid separation obtains white residue and the thick liquid of desiliconization, and white residue turns back to described charge pulp, the thick liquid of described desiliconization obtains the desiliconization seminal fluid by again filtering, and described desiliconization again makes that in the desiliconization seminal fluid that obtains, seston is 0.011g/L; Be 90% through dilution desiliconization rear oxidation aluminium solubility rate, in filtrate, the mass ratio of aluminum oxide and silicon oxide is 675;
8) plant minute: plant in the seed precipitation tank that the desiliconization seminal fluid that step 7) is obtained and aluminium hydroxide crystal seed are blended in heating in water bath minute, planting a minute rear solid-liquid separation obtains aluminium hydroxide and plants and divide a decomposition nut liquid, wherein the aluminium hydroxide crystal seed add-on is 800g/L, planting minute time is 48h, initial kind minute temperature is 60 ℃, planting at last minute temperature is 48 ℃, and 1 ℃ of every 4h reduction, and the rate of decomposition that finally makes the aluminium hydroxide in described desiliconization seminal fluid is 49.2%;
9) roasting: decompose gained aluminium hydroxide and calcine 1050 ℃ of temperature, obtain alumina content and be 98.6% alumina product.
Further, aforesaid method comprises that also the separation filter cake that step 6) is obtained carries out water washing, and the wash water after washing is as in step 7), the stripping slurries being diluted alkali lye B all or part of of desiliconization.Have with Na as long as make at the dilution desiliconization process
2The alkaline condition that O is expressed as 50g/L～110g/L gets final product, if wash water is not enough to obtain above-mentioned alkaline condition, can also replenishes as required and adds sodium hydroxide solution.For example: in producing alumina process by the aluminous fly-ash serialization, can be 80 ℃～90 ℃ with temperature, the water of 38ml be at rinse bath washing step 6) the described separation filter cake that obtains 3 times.Wash water filtrate after the last washing is returned to rinse bath and is recycled, and remaining wash water turns back to step 7) and dilutes desiliconization.Make by the aluminous fly-ash serialization and produce in the process of aluminum oxide, do not need extra a large amount of buck that replenishes new configuration, saved production cost.
After washing, the moisture content of gained separation filter cake≤40%, can return to the charge pulp preparation section and use as raw material, further improved the comprehensive utilization of resources degree.
Above-mentioned steps 5) carbon mother liquid that obtains can 200ml, and adding 140ml concentration is the Ca(OH of 180g/L)
2The ratio of solution, causticization 1h under 90 ℃ of conditions, filtering separation, causticizing efficiency can reach 95%, gained causticization liquid is circulated to the pre-desiliconizing operation of step 1) and uses as circulation alkali liquor, and the carbon mother liquid of rest part can join step 2) the middle preparation that participates in charge pulp.Make by the aluminous fly-ash serialization and produce in the process of aluminum oxide, do not need extra a large amount of buck that replenishes new configuration, saved production cost.
The present embodiment method is carried out carbon with the crude liquor of sodium aluminate that obtains after with the grog stripping and is divided, then carry out Bayer Process digestion, overcome a tediously long two-stage desilication technique, reduced the equipment of the difficult operations such as high pressure desiliconization slot, deep desilication groove, reduce equipment cost and operation easier, still can obtain the high-purity alpha-alumina product simultaneously.
Embodiment 2:
1) pre-desiliconizing, be after mixing solutions (mass ratio of sodium hydroxide solution and aluminous fly-ash is 0.6:1) that 10% sodium hydroxide solution forms is heated to 130 ℃ with aluminous fly-ash and mass ratio, import in the insulation remaining tank and carry out desilication reaction 2.5h, then carry out liquid-solid separation after the flash-pot step-down and obtain the desiliconization liquid of liquid phase and the desiliconization flyash filter cake of solid phase, the alumina silica ratio of its Central Plains flyash is 1.15, be elevated to 2.12 after desiliconization, SiO in desiliconization liquid
2Concentration is 62g/l;
2) charge pulp preparation joins the flyash filter cake in the slurries that Wingdale (unslaked lime) and sodium carbonate is made into and obtains mixed serum, and mixed serum is levigate and be deployed into charge pulp in ball mill; Need through levigate processing before Wingdale and sodium carbonate mix, wherein unslaked lime accounts for 25% of TC, and regulating the calcium ratio is 1.96, and the alkali ratio is 1.0, and the charge pulp water ratio is 35wt%;
3) grog roasting obtains grog with charge pulp after the revolution roasting in kilns 25min of 1220 ℃, grog is the coarse particles grog;
4) grog stripping, with grog with adjust liquid and mix after in cylindrical digester countercurrent flow carry out the grog stripping, carry out solid-liquid separation acquisition crude liquor of sodium aluminate and the thick slag of stripping after stripping, the liquid-solid mass ratio of described adjustment liquid and grog is 2.5:1, the stripping temperature is 70 ℃, and dissolution time is 10min; Described adjustment liquid composition comprises: the Na of 50g/l
2O
k, the Na of 30g/l
2O
c
5) carbon divides: get the crude liquor of sodium aluminate (Al that step 4) obtains
2O
3Content is 94.5g/L, Na
2O
kContent is 117.4g/L, Na
2O
cContent is 28.3g/L, SiO
2Content is 2.56g/L) gas that passes into carbonated 36.5% volumetric concentration carries out the carbonating decomposition reaction within continuous carbon divides groove, and carbon minute temperature is 60-100 ℃, to the reaction system solid-liquid separation, collects carbon mother liquid and aluminium hydroxide crude product after 4h.
Carbon mother liquid is detected analyze, wherein Al
2O
3The carbonating rate of decomposition is 97.0%, can be by the alumina content in the complexometric titration crude liquor of sodium aluminate, and carry out alumina content in complexometric titration aluminium hydroxide crude product after carbon being divided the aluminium hydroxide dissolving crude product of acquisition, thereby obtain Al
2O
3The carbonating rate of decomposition; The aluminium hydroxide crude product is detected, wherein SiO
2Deposition rate is 97.5%, SiO
2Content is measured by the method in GB/T6609.3-86.
6) low temperature Bayer Process digestion: with aluminium hydroxide crude product and Na
2O
kFor the sodium hydroxide solution of 180g/L with solid-to-liquid ratio 1:3(g:mL) be mixed into canalization-remaining tank device, 140 ℃ of temperature, 0.3MPa under pressure, reaction 2.5h carries out the low temperature Bayer Process digestion, obtains after solid-liquid separation to separate filter cake and stripping slurries, digesting efficiency of alumina is 92.3%; Can pass through the alumina content in complexometric titration stripping slurries, and will pass through alumina content in complexometric titration aluminium hydroxide crude product after the aluminium hydroxide dissolving crude product, thereby obtain digesting efficiency of alumina;
7) dilution desiliconization: the stripping slurries that step 6) is obtained use alkali lye B to dilute desiliconization, stir 1h under the condition of 80 ℃ of stirrings of temperature, solid-liquid separation obtains white residue and the thick liquid of desiliconization, white residue turns back to described charge pulp, the thick liquid of described desiliconization obtains the desiliconization seminal fluid by again filtering, and described desiliconization again makes that in the desiliconization seminal fluid that obtains, the filtrate seston is 0.013g/L; Dilute wherein that in the thick liquid of desiliconization after desiliconization, digesting efficiency of alumina is 90%, in filtrate, the mass ratio of aluminum oxide and silicon oxide is 720; Can pass through the alumina content in the thick liquid of complexometric titration desiliconization and stripping slurries, thereby obtain diluting desiliconization rear oxidation aluminium solubility rate;
8) plant minute: the desiliconization seminal fluid that step 7) is obtained mixes with aluminium hydroxide crystal seed plants in the continuous seed component groove of 15 single seed precipitation tanks compositions minute afterwards, planting a minute rear solid-liquid separation obtains aluminium hydroxide and plants and divide a decomposition nut liquid, wherein according to 1L desiliconization seminal fluid: the ratio of 800g aluminium hydroxide crystal seed adds aluminium hydroxide crystal seed, plant minute time and establish 46h, 65 ℃ of first seed precipitation tank temperature settings, 50 ℃ of last seed precipitation tank temperature settings, and every 4h reduces by 2 ℃, the rate of decomposition that finally makes the aluminium hydroxide in described desiliconization seminal fluid is 50%, can be by the aluminium hydroxide content in complexometric titration desiliconization seminal fluid, and by after the aluminium hydroxide dissolving that will obtain after planting minute by complexometric titration aluminium hydroxide content, thereby obtain the rate of decomposition of aluminium hydroxide,
9) roasting: decompose gained aluminium hydroxide through 1050 ℃ of temperature fluosolids roastings, obtain alumina content and be 98.4% alumina product.Alumina product content is 100%, and the amount of the aluminum oxide that wherein contains is the surplus that the alumina product total amount deducts the impurity summation.Impurity component comprises SiO
2, Fe
2O
3, Na
2These impurity of O are pressed GB8170 and are processed.Fe
2O
3Content is measured by the method in GB/T6609.4-86, Na
2O content is measured by the method in GB/T6609.5-86.
With above-mentioned steps 5) carbon mother liquid that obtains can be the Ca(OH of 180g/L with concentration)
2Solution is mixed in the causticizing reaction groove, causticization 1.5h under 90 ℃ of conditions, filtering separation, causticizing efficiency can reach 93.6%, gained causticization liquid is circulated to the pre-desiliconizing operation and uses as circulation alkali liquor, the carbon mother liquid of rest part can join step 2) the middle preparation that participates in charge pulp, further improved the comprehensive utilization of resources degree.
The present embodiment method is carried out carbon with the crude liquor of sodium aluminate that obtains after with the grog stripping and is divided, then carry out Bayer Process digestion, overcome a tediously long two-stage desilication technique, reduced the equipment of the difficult operations such as high pressure desiliconization slot, deep desilication groove, reduce equipment cost and operation easier, still can obtain the high-purity alpha-alumina product simultaneously.
Claims (11)
1. method of being produced aluminum oxide by aluminous fly-ash comprises:
1) pre-desiliconizing with aluminous fly-ash and sodium hydroxide solution mixing post-heating, then imports and carries out the pre-desiliconizing reaction in pressure vessel, carries out solid-liquid separation after the pre-desiliconizing reaction and obtains flyash filter cake and desiliconization liquid;
2) charge pulp preparation joins described flyash filter cake in the slurries that sodium carbonate, Wingdale and/or unslaked lime is made into and obtains mixed serum, and described mixed serum is levigate and be deployed into charge pulp;
3) grog roasting is with described charge pulp roasting ripe material;
4) grog stripping mixes described grog and carries out stripping with adjustment liquid, carry out solid-liquid separation after stripping and obtain the thick slag of stripping and crude liquor of sodium aluminate, and described adjustment liquid composition comprises: the Na of 10～60g/L
2O
k, the Na of 10～60g/L
2O
c
5) carbonating is decomposed: pass in the described crude liquor of sodium aluminate that obtains to step 4) and contain CO
2Gas carry out the carbonating decomposition reaction, and to the reaction system solid-liquid separation, collect carbon mother liquid and aluminium hydroxide crude product;
6) the described aluminium hydroxide crude product that low temperature Bayer Process digestion: in step 5) obtains adds alkali lye A to carry out the low temperature Bayer Process digestion, solid-liquid separation obtains to separate filter cake and stripping slurries, wherein, during described low temperature Bayer Process digestion according to 1 gram aluminium hydroxide crude product: the weightmeasurement ratio of 2～5ml alkali lye adds alkali lye A, makes alkali concn in formed stripping system with Na
2O is expressed as 120g/L～180g/L, and controls 100 ℃～160 ℃ of stripping temperature, dissolution time 0.5h～2h;
7) dilution desiliconization: the stripping slurries that step 6) is obtained use alkali lye B to dilute desiliconization, solid-liquid separation obtains white residue and the thick liquid of desiliconization, white residue turns back to described charge pulp, the thick liquid of described desiliconization obtains the desiliconization seminal fluid by again filtering, wherein, volume ratio according to described stripping slurries and alkali lye B5～12:1 during described dilution desiliconization adds alkali lye B, makes alkali concn in formed dilution desiliconization system with Na
2O is expressed as 50g/L～110g/L;
8) plant minute: with step 7) the described desiliconization seminal fluid that obtains plant minute with aluminium hydroxide crystal seed, obtains aluminium hydroxide and kind is divided a decomposition nut liquid;
9) roasting: described Aluminium hydroxide roasting is obtained aluminum oxide.
2. method according to claim 1, it is characterized in that, the mass concentration of the described sodium hydroxide solution that uses in the step 1) pre-desiliconizing is 10～30%, and the mass ratio of sodium hydroxide and aluminous fly-ash is 0.2～0.8:1, temperature of reaction: 70～135 ℃, the reaction times: 0.5～3h.
3. method according to claim 1, is characterized in that step 2) in the charge pulp preparation process, the calcium ratio of the described charge pulp of making is 1.95～2.01, and the alkali ratio is 0.95～1.05, and water ratio is 25～50wt%.
4. method according to claim 1, is characterized in that, the maturing temperature of step 3) grog roasting is 1150～1300 ℃, roasting time 10～60 minutes.
5. method according to claim 1, the particle diameter≤8mm of the described grog that uses in the stripping of described step 4) grog, the liquid-solid mass ratio of described adjustment liquid and grog is 2～8:1, and grog stripping temperature is 55～85 ℃, and the grog dissolution time is 5～30min.
6. method according to claim 1, Al in the described crude liquor of sodium aluminate that described step 4) grog stripping obtains
2O
3Be 60-120g/L, Na
2O
kBe 100-160g/L, Na
2O
cBe 20-80g/L.
7. according to claim 1,5 or 6 described methods, wherein, what pass in step 5) contains CO
2Gas in CO
2Volumetric concentration is 30%～50%, and carbon minute temperature is 60-100 ℃, and it is 2h～4h that carbon divides the time, and carries out carbon and divide under agitation condition.
8. method according to claim 1, the kind that step 8) obtains divide decomposition nut liquid return step 6) as Bayer stripping do all or part of with alkali lye A.
9. method according to claim 1 wherein, comprises that also the separation filter cake that step 6) is obtained carries out water washing, and the wash water after washing is as in step 7), the stripping slurries being diluted alkali lye B all or part of of desiliconization.
10. method according to claim 1, in described step 8) according to 1L desiliconization seminal fluid: the ratio of 400～800g aluminium hydroxide crystal seed adds aluminium hydroxide crystal seed, and plant minute through 8～12 seed precipitation tanks, planting minute time is 36h～48h, and the temperature when controlling first seed precipitation tank of process is 60 ℃～70 ℃, temperature during last seed precipitation tank of process is 48 ℃～59 ℃, and the every 4h of temperature that plants minute process reduces 1-2 ℃.
11. method according to claim 1, in described step 9), aluminium hydroxide carries out fluidizing calcination to obtain aluminum oxide under 900～1100 ℃ of conditions.
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| CN103771471A (en) * | 2014-01-26 | 2014-05-07 | 乌鲁木齐金石徽龙矿业有限公司 | Method for preparing aluminum oxide through coal ash |
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| CN103771471A (en) * | 2014-01-26 | 2014-05-07 | 乌鲁木齐金石徽龙矿业有限公司 | Method for preparing aluminum oxide through coal ash |
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| CN104030331B (en) * | 2014-06-27 | 2016-08-24 | 大唐国际发电股份有限公司高铝煤炭资源开发利用研发中心 | A kind of method utilizing aluminous fly-ash to produce aluminium oxide |
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| CN106276998A (en) * | 2016-08-25 | 2017-01-04 | 大唐国际发电股份有限公司高铝煤炭资源开发利用研发中心 | A kind of coal ash alkali lime sinter process extracts the raw slurry compound method of aluminium oxide |
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