CN102644093B - Aluminous fly-ash chlorination electrolytic process produces the method for metallic aluminium - Google Patents
Aluminous fly-ash chlorination electrolytic process produces the method for metallic aluminium Download PDFInfo
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- CN102644093B CN102644093B CN201110039081.2A CN201110039081A CN102644093B CN 102644093 B CN102644093 B CN 102644093B CN 201110039081 A CN201110039081 A CN 201110039081A CN 102644093 B CN102644093 B CN 102644093B
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Abstract
The invention discloses a kind of method that aluminous fly-ash chlorination electrolytic process produces metallic aluminium, it comprises following processing step: the first, magnetically separating and removing ion from fly ash; The second, fluidizing chlorination; Add boiling chloridizing furnace by after aluminous fly-ash, the mixing of oil coke powder, and pass into chlorine in stove, the aluminum oxide in flyash is fully reacted, obtains aluminum chloride bimolecular flue gas; Three, aluminum chloride fume treatment and purification; Namely send in condenser after aluminum chloride flue gas filter cleaning and lower the temperature, make other chloride impurity condensation and discharge flow process with the form of ash, flue gas enters in trap again and continues cooling, obtains just Aluminum chloride anhydrous crystal; With aluminum chloride sublimation purification furnace, removal of impurities, sublimation purification are carried out to first Aluminum chloride anhydrous crystal; Four, fused salt electrolysis; Join aluminum chloride electrolyzer by Aluminum chloride anhydrous, the aluminium liquid that electrolysis obtains send casting to prepare aluminium ingot.Adopt art breading aluminous fly-ash of the present invention to obtain aluminium ingot, make flyash obtain Appropriate application.
Description
Technical field
The present invention relates to a kind of method that aluminous fly-ash chlorination electrolytic process produces metallic aluminium.
Background technology
Aluminum electrolysis industry mainly adopts aluminum oxide to be raw material in the world at present, aluminum oxide (Al
2o
3) and sodium aluminum fluoride (3NaFAlF
3) form the ionogen of meltings at the high temperature of more than 900 DEG C, form basic electrolyte ingredient, in electrolyzer, carry out electrolysis obtain metallic aluminium.
Alumina producing is mainly raw material with bauxite, adopts bayer's process production technique to obtain, and the purposes of aluminum oxide is a lot, but the overwhelming majority (more than 90%) is as the raw material of electrolytic aluminium factory, for the production of metallic aluminium.
China is aluminum oxide, metallic aluminium largest production state in the world, aluminum oxide and electrolytic aluminum output account for about 40% of Gross World Product, but China's bauxite resource is poor, ore grade is lower, ore type is mainly based on unmanageable diaspore, and complex manufacturing, energy consumption of unit product are high, production cost is also higher.
Due to China's bauxite resource wretched insufficiency, Ore Imported can only be relied on to solve raw material problem, and about 3,000 ten thousand tons, year import bauxite, about accounting for the half of domestic bauxite usage quantity.Ore resource deficiency constrains China's aluminum i ndustry development, and find new alternative non-bauxitic resource as aluminum oxide industry raw material, and study new electrolytic aluminium production process, this is of great significance the development tool of China's aluminum i ndustry.
Coal resources in China is very abundant, and coal production accounts for the first in the world, and annual output more than 20 hundred million tons of coals, will discharge a large amount of flyash after coal burning, China discharges 3 ~ 400,000,000 tons of flyash every year, and wherein aluminous fly-ash (refers to Al in flyash
2o
3>=38%) more than 100,000,000 tons.Analyze after deliberation, aluminous fly-ash is primarily of aluminum oxide, silicon oxide composition, and the content of 2 kinds of compositions accounts for 80%, other compositions such as another iron content, magnesium, titanium, calcium, gallium, be the raw material of comprehensive utilization Extraction metallurgy grade aluminum oxide and metallic aluminium, there is high industrial utility value.
In the flyash of the northern area of China, alumina content is generally higher than southern area, if alumina content in the flyash of part mining area, the ground outputs such as Shanxi, Shaanxi, Inner Mongol, Ningxia, Xinjiang is usually about 40%, belong to aluminous fly-ash, Ordos, inner Mongolia area flyash in alumina content have up to 45 ~ 50%, alumina content in this and external bauxite trihydrate is suitable, chemically composition analysis, completely can as the raw material of Extraction metallurgy grade aluminum oxide and metallic aluminium.
Current flyash is thermal power plant's waste of discharging normally, and store up mainly as a kind of industrial residue, this had both occupied a large amount of soil, and severe contamination environment.Coastland is due to populous, industry prosperity, sometimes flyash is used for building the road, the material of construction such as brickmaking, this only belongs to low-grade, the low value-added application of flyash, and economically underdeveloped area or west area, flyash is still stored up mainly as industrial residue.On the whole, China and World Developed Countries are still in the experimental study stage to total utilization of PCA problem, are finding the approach of its Appropriate application.
In recent years, for China's bauxite resource wretched insufficiency and the rich salic present situation of flyash, many scientific research departments of China actively develop the research of non-bauxitic resource production metallurgy grade aluminum oxide, and aluminous fly-ash comprehensive utilization production metallurgy grade aluminum oxide is one of emphasis research topic.Each research unit is according to respective achievement in research, and propose the new process of some process aluminous fly-ashs, main direction of studying is as follows:
(1) alkaline process: the main stream approach being aluminous fly-ash comprehensive utilizating research.It mainly uses for reference the sintering process production technique of existing alumina industry maturation, utilize sintering process technique can process feature that is low-grade, low alumina-silica ratio ore, by aluminous fly-ash, Wingdale (or lime), alkali by certain proportioning, be prepared into charge pulp to sinter, sintered clinker is through stripping, desiliconization, decomposition, roasting and obtain metallurgical-grade aluminum oxide product.The advantage of this method is mature technology, can obtain qualified alumina product.But the shortcoming of this method is a lot, mainly lime dosage is huge, red mud amount large, the concentration of sodium aluminate solution is low, production energy consumption is high, its investment and cost high, it is technically feasible but unreasonable economically for this method.
(2) acid system: adopt hydrochloric acid or sulfuric acid and aluminous fly-ash to prepare burden in proportion, aluminum oxide at certain temperature and pressure condition in stripping flyash, aluminum oxide is made to enter in solution, solution obtains alumina product through evaporative crystallization, roasting after removal of impurities is purified, and its advantage is that flow process is simple, the quantity of slag is little, production cost is low.Shortcoming be removing iron from solution and removal of impurities more difficult, height is required to the corrosion resistance nature of equipment and material, some Design and material problems need be researched and solved further.
For China's bauxite resource and utilization of fly ash present situation, the present invention proposes a kind of aluminous fly-ash and produces metallic aluminium processing method, with traditional processing method and thinking all different, flyash and chlorine are reacted in high-temp chlorination stove, generate aluminum chloride flue gas, and obtain Aluminum chloride anhydrous through processing further, obtain metallic aluminium by anhydrous chlorides of rase electrolysis of aluminum, significantly can simplify the technical process that flyash produces aluminium, reduce investment and production cost.
Summary of the invention
The present invention will solve and reach technical problem and be: provide a kind of aluminous fly-ash chlorination electrolytic process to produce the method for metallic aluminium, the method can thoroughly improve existing aluminum oxide and electrolytic aluminium production process, simplify the technical process that flyash produces aluminium, reduce construction investment and production cost, enterprise is made to have good economic benefit, to overcome, huge, the red mud amount of the lime dosage concentration that is large, sodium aluminate solution that prior art exists is low, production energy consumption is high, or removing iron from solution and removal of impurities is more difficult, require high deficiency to the corrosion resistance nature of equipment and material.
In order to solve described technical problem, the present invention takes following technical scheme: it comprises following processing step:
The first, magnetically separating and removing ion from fly ash: adopt containing Al
2o
3the aluminous fly-ash of>=38%, the Fe usually containing about 2% in ash
2o
3impurity, for eliminating iron oxides impurities to the impact of subsequent handling, adopts the mode of iron removal by magnetic separation, Fe in the flyash after magnetic separation
2o
3impurity≤1.0%.
The second, fluidizing chlorination: add boiling chloridizing furnace by after aluminous fly-ash, the mixing of oil coke powder, and pass into chlorine in stove, under 750 ~ 900 DEG C of high temperature, the aluminum oxide in flyash is fully reacted, obtain aluminum chloride bimolecular flue gas.Fluidizing chlorination operation major technique condition:
Purity of chlorine gas feeding 30 ~ 50%;
Oil coke powder carbon content 75 ~ 85%, granularity 60 ~ 160 order;
Time of chlorinating: 4-10 second;
Chlorination temperature 750 ~ 900 DEG C;
Alumina conversion rate >=80%;
Three, aluminum chloride fume treatment and purification: send in condenser after aluminum chloride flue gas filter cleaning and be cooled to 230 ~ 270 DEG C, make other chloride impurity condensation and discharge flow process with the form of ash, flue gas enters in trap again and cools to 70 ~ 90 DEG C, obtains just Aluminum chloride anhydrous crystal.
Iron(ic) chloride impurity in first Aluminum chloride anhydrous crystal usually about 1%, then carries out removal of impurities with aluminum chloride sublimation purification furnace to aluminum chloride, and sublimation purification furnace temperature controls at 200 ~ 250 DEG C, namely more than aluminum chloride literization temperature.
Aluminum chloride anhydrous intermediates after purification are up to state standards the salable product index that GB/T3959-2008 specifies, i.e. aluminum chloride >=98.5%, iron(ic) chloride≤0.08%.Ensureing that in follow-up electrolytic aluminum product, aluminium content reaches >=the quality index requirement of 99.5%.
Four, fused salt electrolysis: Aluminum chloride anhydrous is joined aluminum chloride electrolyzer, Aluminum chloride anhydrous is dissolved in the ionogen of melting, and ionogen is by NaCl+LiCl+AlCl
3+ MgCl
2+ KCl+CaCl
2mixture forms, because of AlCl
3electroconductibility very poor, therefore select NaCl+LiCl primary structure, can AlCl be made up
3bad electroconductibility.Temperature 670 ~ 700 DEG C in electrolyzer, direct current consumption 10000 ~ 11000Kwh/T-aluminium.The aluminium liquid that electrolysis obtains send casting process, through purification, clarification, prepares aluminium ingot.
In the 4th step, anode electrolytic cell produce chlorine, enter in condenser, after separating the electrolyte vapor of carrying secretly, be sent to above fluidizing chlorination operation, make chlorine form closed cycle.
The present invention adopts aluminous fly-ash to be raw material production metallic aluminium, at high temperature be easy to chlorine that chlorination reaction occurs according to flyash and generate aluminum chloride, Aluminum chloride anhydrous carries out the characteristic that electrolysis can obtain metallic aluminium under NaCl+LiCl electrolyte system, proposes the new process that a kind of aluminous fly-ash produces metallic aluminium.
Adopt art breading aluminous fly-ash of the present invention, the aluminium ingot that national standard requires can be met, make flyash obtain Appropriate application; Also solve China's bauxite resource deficiency, flyash to a pollution difficult problem for environment simultaneously.
Accompanying drawing explanation
Fig. 1: aluminous fly-ash chlorination electrolytic process produces metallic aluminium process flow diagram.
Embodiment
Embodiments of the invention: technological process of the present invention refers to shown in accompanying drawing 1.The present invention is mainly containing following technological process:
Aluminous fly-ash alumina content 45%, iron oxide content 2%, after iron removal by magnetic separation, in ash, iron oxide content is 0.9%, be add boiling chloridizing furnace after 12 object oil coke powder mix with granularity, in stove, pass into the chlorine that concentration is 40%, the chlorination temperature of boiling chloridizing furnace is 850 DEG C, and the aluminum oxide in flyash is when in oil coke powder, carbon makes reductive agent, fully react with the chlorine passed into, obtain aluminum chloride bimolecular flue gas.Send in condenser after aluminum chloride flue gas filter cleaning and be cooled to 250 DEG C, make other chloride impurity condensation and discharge flow process with the form of ash, flue gas enters in trap again and cools to 80 DEG C and obtain just Aluminum chloride anhydrous crystal.First anhydrous chlorides of rase enters sublimation purification stove to carrying out removal of impurities, and sublimation purification furnace temperature controls at 200 ~ 250 DEG C.Aluminum chloride anhydrous intermediates after purification are up to state standards the salable product index request that GB/T3959-2008 specifies.Aluminum chloride anhydrous obtains aluminium water through fused salt electrolysis, and aluminium water obtains metal aluminium ingot product through purification casting.In electrolytic process, from anode produce chlorine, enter in condenser, after separating the electrolyte vapor of carrying secretly, be sent to above boiling operation, make chlorine form closed cycle.
Claims (5)
1. aluminous fly-ash chlorination electrolytic process produces a method for metallic aluminium, it is characterized in that: it comprises following processing step:
The first, magnetically separating and removing ion from fly ash;
The second, fluidizing chlorination; Add boiling chloridizing furnace by after aluminous fly-ash, the mixing of oil coke powder, and pass into chlorine in stove, the aluminum oxide in flyash is fully reacted, obtains aluminum chloride bimolecular flue gas;
Three, aluminum chloride fume treatment and purification; Namely send in condenser after aluminum chloride flue gas filter cleaning and be cooled to 230 ~ 270 DEG C, make other chloride impurity condensation and discharge flow process with the form of ash, flue gas enters in trap again and continues to cool to 70 ~ 90 DEG C, obtains just Aluminum chloride anhydrous crystal;
Carry out removal of impurities with aluminum chloride sublimation purification furnace to first Aluminum chloride anhydrous crystal, sublimation purification furnace temperature controls at 200 ~ 250 DEG C;
Aluminum chloride anhydrous intermediates after purification reach salable product index, i.e. aluminum chloride >=98.5%, iron(ic) chloride≤0.08%;
Four, fused salt electrolysis; Join aluminum chloride electrolyzer by Aluminum chloride anhydrous, Aluminum chloride anhydrous is dissolved in the ionogen of melting, temperature 670 ~ 700 DEG C in electrolyzer, and the aluminium liquid that electrolysis obtains send casting process, through purification, clarification, prepares aluminium ingot;
At second step, fluidizing chlorination operation major technique condition:
Purity of chlorine gas feeding 30 ~ 50%;
Oil coke powder carbon content 75 ~ 85%, granularity 60 ~ 160 order;
Time of chlorinating: 4-10 second;
Chlorination temperature 750 ~ 900 DEG C;
Alumina conversion rate >=80%.
2. aluminous fly-ash chlorination electrolytic process according to claim 1 produces the method for metallic aluminium, it is characterized in that: at first step, Fe in the flyash after iron removal by magnetic separation
2o
3impurity≤1.0%.
3. aluminous fly-ash chlorination electrolytic process according to claim 1 produces the method for metallic aluminium, it is characterized in that: at third step, send in condenser after aluminum chloride flue gas filter cleaning and be cooled to 250 DEG C, make other chloride impurity condensation and discharge flow process with the form of ash, flue gas enters in trap again and cools to 80 DEG C.
4. aluminous fly-ash chlorination electrolytic process according to claim 1 produces the method for metallic aluminium, it is characterized in that: in the 4th step, ionogen is by NaCl+LiCl+AlCl
3+ MgCl
2+ KCl+CaCl
2mixture forms; Electrolyzer direct current consumption 10000 ~ 11000Kwh/T-aluminium.
5. aluminous fly-ash chlorination electrolytic process according to claim 1 produces the method for metallic aluminium, it is characterized in that: in the 4th step, the chlorine that anode electrolytic cell produces, enter in condenser, after separating the electrolyte vapor of carrying secretly, be sent to above fluidizing chlorination operation, make chlorine form closed cycle.
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Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102923747A (en) * | 2012-11-28 | 2013-02-13 | 东北大学 | Method for producing aluminum chloride, silicon chloride and ferric chloride by utilizing coal gangue |
| CN103911627B (en) * | 2012-12-31 | 2017-03-01 | 国联汽车动力电池研究院有限责任公司 | A kind of molten-salt electrolysis additive and its be used for preparing silicon composite method |
| CN103526234B (en) * | 2013-10-18 | 2016-06-22 | 东北大学 | Fused salt electrolysis process extracts the method for metal from flyash |
| CN103572323B (en) * | 2013-11-08 | 2015-09-30 | 中国科学院过程工程研究所 | A kind of aluminum-containing mineral and the mixed chlorinated and low-temperature electrolytic of flyash prepare the method for aluminum silicon alloy |
| CN104313641B (en) * | 2014-09-22 | 2017-04-05 | 沈阳金博新技术产业有限公司 | A kind of method for producing metallic aluminium or almag with low-grade bauxite |
| CN106048226B (en) * | 2016-05-19 | 2018-10-23 | 东北大学 | A kind of method that the chlorination of flyash microwave prepares metallic aluminium |
| CN107128957B (en) * | 2017-05-10 | 2018-10-23 | 东北大学 | A kind of fine coal lime balls chlorination electrolytic preparation aluminium oxide and the method for comprehensive utilization |
| CN111661861B (en) * | 2019-03-08 | 2021-10-22 | 中国科学院过程工程研究所 | Method for producing high-purity anhydrous aluminum chloride from aluminum hydroxide |
| CN110436502B (en) * | 2019-08-16 | 2021-06-22 | 东北大学 | Fly ash decrement treatment method and device |
| CN111041193A (en) * | 2020-03-05 | 2020-04-21 | 吴君石 | Method for preparing aluminum from fly ash by using ionic liquid |
| CN115672931A (en) * | 2022-09-14 | 2023-02-03 | 江苏柏环环境科技有限公司 | Recycling method of aluminum-containing solid waste |
| CN116119727A (en) * | 2022-11-14 | 2023-05-16 | 中国科学院过程工程研究所 | Key technology for recycling coal ash chlorination product through fractional purification |
| CN116282046B (en) * | 2023-02-23 | 2024-06-04 | 成都理工大学 | Purification device and method for silica fume |
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