CN102644093A - Method for producing metal aluminium by high-alumina fly ash chlorination electrolysis - Google Patents
Method for producing metal aluminium by high-alumina fly ash chlorination electrolysis Download PDFInfo
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Abstract
The invention discloses a method for producing metal aluminium by high-alumina fly ash chlorination electrolysis, which comprises the following process steps: firstly, magnetic separation of fly ash to remove iron; secondly, fluidizing chlorination, that is, mixing high-alumina fly ash and oil coke powder, adding the mixture into a fluidizing chlorination furnace, introducing chlorine into the furnace to allow the alumina in the fly ash to react completely so as to obtain aluminium chloride double molecular flue gas; thirdly, processing and purification of the aluminium chloride flue gas, that is, purifying the aluminium chloride flue gas by a filter, cooling the purified aluminium chloride flue gas in a condenser to condense other chloride impurities, discharging the impurities out of the flow in a form of ash, continuing cooling the flue gas in a trap to obtain raw anhydrous aluminum chloride crystals, performing impurity removal and sublimation purification of the raw anhydrous aluminum chloride crystals by an aluminium chloride sublimation purification furnace; fourthly, molten salt electrolysis, that is, adding the anhydrous aluminum chloride into an aluminium chloride electrolytic tank, performing electrolysis to obtain aluminium liquid, casting the obtained aluminium liquid to prepare aluminum ingots. The process of the invention is used for processing high-alumina fly ash to obtain aluminum ingots, and fly ash is utilized reasonably.
Description
Technical field
The present invention relates to a kind of aluminous fly-ash chlorination electrolytic process and produce the method for metallic aluminium.
Background technology
At present in the world aluminum electrolysis industry mainly to adopt aluminum oxide be raw material, aluminum oxide (Al
2O
3) and sodium aluminum fluoride (3NaFAlF
3) form the fused ionogen at more than 900 ℃ high temperature, form basic electrolyte ingredient, in electrolyzer, carry out electrolysis and obtain metallic aluminium.
Alumina producing mainly is raw material with bauxite, adopts the bayer's process production technique to make, and the purposes of aluminum oxide is a lot, but the overwhelming majority (more than 90%) is used to produce metallic aluminium as the raw material of electrolytic aluminium factory.
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, and ore type is main with unmanageable diaspore mainly, and complex manufacturing, energy consumption of unit product are high, production cost is also higher.
Because China's bauxite resource wretched insufficiency can only rely on Ore Imported to solve the raw material problem, about 3,000 ten thousand tons of year import bauxite accounts for about half of domestic bauxite usage quantity.The ore resource deficiency has restricted China's aluminium industrial development, seeks new alternative non-bauxite resource as the aluminum oxide industry raw material, and studies new electrolytic aluminium production process, and this has crucial meaning to China's aluminium industrial expansion.
Coal resources in China is very abundant, and coal production accounts for the first in the world, and more than 20 hundred million tons of coals of annual output will be discharged a large amount of flyash behind the coal burning, 3～400,000,000 tons of flyash of the annual discharging of China, and wherein aluminous fly-ash (refers to Al in the flyash
2O
3>=38%) more than 100,000,000 ton.Analyze after deliberation; Aluminous fly-ash mainly is made up of aluminum oxide, silicon oxide, and the content of 2 kinds of compositions accounts for 80%, in addition other compositions such as iron content, magnesium, titanium, calcium, gallium; Be the raw material that metallurgical-grade aluminum oxide and metallic aluminium are extracted in comprehensive utilization, have high industrial utilization and be worth.
Alumina content generally is higher than southern area in the flyash of north China; Like alumina content in the flyash of part mining area, ground outputs such as Shanxi, Shaanxi, Inner Mongol, Ningxia, Xinjiang usually about 40%; Belong to aluminous fly-ash, in the Erdos area flyash of the Inner Mongol there be alumina content up to 45～50%, and this is suitable with alumina content in the external bauxite trihydrate; From chemical composition analysis, can be used as the raw material that extracts metallurgical-grade aluminum oxide and metallic aluminium fully.
At present flyash thermal power plant's waste of discharging is normally stored up mainly as a kind of industrial residue, and this had both taken a large amount of soils, and severe contamination environment.The coastland is because populous, industry prosperity; Sometimes with flyash be used to build the road, 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 country still are in the experimental study stage to the total utilization of PCA problem, are seeking the approach that it rationally utilizes.
In recent years; Be rich in the present situation of aluminum oxide to China's bauxite resource wretched insufficiency and flyash; The many scientific research departments of China actively develop non-bauxite resource production metallurgy grade aluminum oxide research, and aluminous fly-ash comprehensive utilization production metallurgy grade aluminum oxide is one of emphasis research topic.Each research unit's basis achievement in research has separately proposed some and has handled the new process of aluminous fly-ashs, and main direction of studying is following:
(1) alkaline process: the main stream approach that is the aluminous fly-ash comprehensive utilizating research.It mainly uses for reference the existing sophisticated sintering process production technique of alumina industry; Utilize sintering process technology can processing low-grade, the characteristics of low alumina silica ratio ore; Aluminous fly-ash, Wingdale (or lime), alkali are pressed certain proportioning; Be prepared into charge pulp and carry out sintering, sintered clinker is through stripping, desiliconization, decomposition, roasting and obtain the metallurgical-grade aluminum oxide product.The advantage of this method is that Technology is ripe, can obtain qualified alumina product.But the shortcoming of this method is a lot, mainly is that the lime dosage is huge, red mud amount is big, concentration sodium aluminate solution is low, production energy consumption is high, its investment and cost height, its art recognized of this method but unreasonable economically.
(2) acid system: adopt hydrochloric acid or sulfuric acid and aluminous fly-ash to prepare burden in proportion; Aluminum oxide under certain temperature and pressure condition in the stripping flyash; Aluminum oxide is got in the solution; After evaporative crystallization, roasting obtain alumina product, its advantage is that flow process is simple, the quantity of slag is little, production cost is low to solution through the removal of impurities purification.Shortcoming be removing iron from solution and removal of impurities difficult, the corrosion resistance nature of equipment and material is required height, some technologies and problem of materials need further be researched and solved.
To China's bauxite resource and utilization of fly ash present situation, the present invention proposes a kind of aluminous fly-ash and produces the metallic aluminium process method, and is all different with traditional process method and thinking; Flyash and chlorine are reacted in the high-temp chlorination stove; Generate the aluminum chloride flue gas, and obtain Aluminum chloride anhydrous, obtain metallic aluminium by the anhydrous chlorides of rase electrolysis of aluminum through further handling; Can simplify flyash significantly and produce the technical process of 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; This method can thoroughly be improved existing aluminum oxide and electrolytic aluminium production process; Simplify flyash and produce the technical process of aluminium; Reduce construction investment and production cost; Make enterprise have favorable economic benefit, the lime dosage that prior art exists is huge, red mud amount big to overcome, the concentration of sodium aluminate solution is low, production energy consumption is high, perhaps removing iron from solution and removal of impurities difficult, the corrosion resistance nature of equipment and material is required high deficiency.
In order to solve described technical problem, the present invention takes following technical scheme: it comprises following process step:
The first, magnetically separating and removing ion from fly ash: adopt to contain Al
2O
3>=38% aluminous fly-ash contains the Fe about 2% usually in the ash
2O
3Impurity for eliminating the influence of red stone impurity to subsequent handling, adopts the mode of iron removal by magnetic separation, Fe in the flyash after the magnetic separation
2O
3Impurity≤1.0%.
The second, fluidizing chlorination: aluminous fly-ash, oil coke powder are mixed the back add boiling chloridizing furnace, and in stove, feed chlorine, under 750～900 ℃ of high temperature, the aluminum oxide in the 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 orders;
Time of chlorinating: 4-10 second;
750～900 ℃ of chlorination temperatures;
Aluminum oxide transformation efficiency >=80%;
Three, the aluminum chloride flue gas is handled and purified: the aluminum chloride flue gas is sent into after with filter cleaning and is cooled to 230～270 ℃ in the condensing surface; Make other chloride impurity condensation and discharge flow process with the form of ash; Flue gas gets into and cools to 70～90 ℃ in the trap, obtains Aluminum chloride anhydrous crystal just.
Just the iron(ic)chloride impurity in the Aluminum chloride anhydrous crystal about 1%, carries out removal of impurities with aluminum chloride distillation purification furnace to aluminum chloride usually again, and distillation purification furnace temperature is controlled at 200～250 ℃, promptly more than aluminum chloride literization temperature.
The be up to state standards salable product index of GB/T3959-2008 regulation of Aluminum chloride anhydrous intermediates after the purification, i.e. aluminum chloride>=98.5%, iron(ic)chloride≤0.08%.To guarantee that aluminium content reaches in the follow-up electrolytic aluminum product >=99.5% quality index requirement.
Four, fused salt electrolysis: Aluminum chloride anhydrous is joined the aluminum chloride electrolyzer, and Aluminum chloride anhydrous is dissolved in the fused ionogen, and ionogen is by NaCl+LiCl+AlCl
3+ MgCl
2+ KCl+CaCl
2Mixture is formed, because of AlCl
3Electroconductibility very poor, so select the NaCl+LiCl primary structure for use, can remedy AlCl
3Bad electroconductibility.Temperature is 670～700 ℃ in the electrolyzer, direct current consumption 10000～11000Kwh/T-aluminium.The aluminium liquid that electrolysis obtains send casting process, through purifying, clarify, the preparation aluminium ingot.
In the 4th step, the chlorine that anode electrolytic cell produces gets in the condensing surface, separate the electrolyte vapor of carrying secretly after, be sent to the front the fluidizing chlorination operation, make chlorine form closed cycle.
It is the raw material production metallic aluminium that the present invention adopts aluminous fly-ash; At high temperature be easy to take place chlorination reaction according to flyash and generate aluminum chloride with chlorine; Aluminum chloride anhydrous carries out the characteristic that electrolysis can obtain metallic aluminium under the NaCl+LiCl electrolyte system, proposed the new process that a kind of aluminous fly-ash is produced metallic aluminium.
Adopt art breading aluminous fly-ash of the present invention, can be met the aluminium ingot that national standard requires, flyash is rationally utilized; Solved also simultaneously that China's bauxite resource is not enough, flyash is to the pollution difficult problem of environment.
Description of drawings
Fig. 1: aluminous fly-ash chlorination electrolytic process is produced the metallic aluminium process flow diagram.
Embodiment
Embodiments of the invention: technological process of the present invention sees for details shown in the accompanying drawing 1.The present invention mainly contains following technological process:
Aluminous fly-ash alumina content 45%, iron oxide content 2%, iron oxide content is 0.9% in the ash behind iron removal by magnetic separation; With granularity is that 12 purpose oil coke powder mix back adding boiling chloridizing furnace; Feeding concentration is 40% chlorine in stove, and the chlorination temperature of boiling chloridizing furnace is 850 ℃, and the carbon in the oil coke powder of the aluminum oxide in the flyash is done under the situation of reductive agent; Fully react with the chlorine that feeds, obtain aluminum chloride bimolecular flue gas.The aluminum chloride flue gas is sent into after with filter cleaning and is cooled to 250 ℃ in the condensing surface, makes other chloride impurity condensation and discharges flow process with the form of ash, and flue gas gets into and cools to 80 ℃ in the trap and obtain Aluminum chloride anhydrous crystal just.Just anhydrous chlorides of rase gets into the distillation purification furnace to carrying out removal of impurities, and distillation purification furnace temperature is controlled at 200～250 ℃.The be up to state standards salable product index request of GB/T3959-2008 regulation of Aluminum chloride anhydrous intermediates after the purification.Aluminum chloride anhydrous obtains aluminium water through fused salt electrolysis, and aluminium water obtains metal aluminium ingot product through purifying casting.In the electrolytic process, the chlorine from anode produces gets in the condensing surface, separate the electrolyte vapor of carrying secretly after, be sent to the front the boiling operation, make chlorine form closed cycle.
Claims (6)
1. an aluminous fly-ash chlorination electrolytic process is produced the method for metallic aluminium, and it is characterized in that: it comprises following process step:
The first, magnetically separating and removing ion from fly ash;
The second, fluidizing chlorination; Be about to aluminous fly-ash, oil coke powder mixing back adding boiling chloridizing furnace, and in stove, feed chlorine, the aluminum oxide in the flyash is fully reacted, obtain aluminum chloride bimolecular flue gas;
Three, the aluminum chloride flue gas is handled and is purified; Be that the aluminum chloride flue gas is sent into after with filter cleaning and is cooled to 230～270 ℃ in the condensing surface, make other chloride impurity condensation and discharge flow process that flue gas gets into and continues in the trap to cool to 70～90 ℃, obtains Aluminum chloride anhydrous crystal just with the form of ash;
With aluminum chloride distillation purification furnace first Aluminum chloride anhydrous crystal is carried out removal of impurities, distillation purification furnace temperature is controlled at 200～250 ℃;
Aluminum chloride anhydrous intermediates after the purification reach the salable product index, i.e. aluminum chloride>=98.5%, iron(ic)chloride≤0.08%;
Four, fused salt electrolysis; Be about to Aluminum chloride anhydrous and join the aluminum chloride electrolyzer, Aluminum chloride anhydrous is dissolved in the fused ionogen, and temperature is 670～700 ℃ in the electrolyzer, and the aluminium liquid that electrolysis obtains send casting process, through purifying, clarify, the preparation aluminium ingot.
2. aluminous fly-ash chlorination electrolytic process according to claim 1 is produced the method for metallic aluminium, it is characterized in that: at first step, and Fe in the flyash behind the iron removal by magnetic separation
2O
3Impurity≤1.0%.
3. aluminous fly-ash chlorination electrolytic process according to claim 1 is produced the method for metallic aluminium, it is characterized in that: in second step, and fluidizing chlorination operation major technique condition:
Purity of chlorine gas feeding 30～50%;
Oil coke powder carbon content 75～85%, granularity 60～160 orders;
Time of chlorinating: 4-10 second;
750～900 ℃ of chlorination temperatures;
Aluminum oxide transformation efficiency >=80%.
4. aluminous fly-ash chlorination electrolytic process according to claim 1 is produced the method for metallic aluminium; It is characterized in that: at third step;: the aluminum chloride flue gas is sent into after with filter cleaning and is cooled to 250 ℃ in the condensing surface; Make other chloride impurity condensation and discharge flow process with the form of ash, flue gas gets into and cools to 80 ℃ in the trap.
5. aluminous fly-ash chlorination electrolytic process according to claim 1 is produced the method for metallic aluminium, and it is characterized in that: in the 4th step, ionogen is by NaCl+LiCl+AlCl
3+ MgCl
2+ KCl+CaCl
2Mixture is formed; Electrolyzer direct current consumption 10000～11000Kwh/T-aluminium.
6. aluminous fly-ash chlorination electrolytic process according to claim 1 is produced the method for metallic aluminium; It is characterized in that: in the 4th step; The chlorine that anode electrolytic cell produces gets in the condensing surface, separate the electrolyte vapor of carrying secretly after; Be sent to the front the fluidizing chlorination operation, make chlorine form closed cycle.
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Cited By (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 |
| CN103526234A (en) * | 2013-10-18 | 2014-01-22 | 东北大学 | Method for extracting metal from coal ash by fused salt electrolysis method |
| CN103572323A (en) * | 2013-11-08 | 2014-02-12 | 中国科学院过程工程研究所 | Method for preparing aluminum silicon alloy through mixed chlorination and low-temperature electrolysis of aluminum-containing mineral and fly ash |
| CN103911627A (en) * | 2012-12-31 | 2014-07-09 | 北京有色金属研究总院 | Molten salt electrolytic additive and method for preparing silicon composite material from the same |
| CN104313641A (en) * | 2014-09-22 | 2015-01-28 | 沈阳金博新技术产业有限公司 | Method for producing metal aluminum or aluminum magnesium alloy from low grade bauxite |
| CN106048226A (en) * | 2016-05-19 | 2016-10-26 | 东北大学 | Method for preparing metal aluminum through microwave chlorination of coal ash |
| CN107128957A (en) * | 2017-05-10 | 2017-09-05 | 东北大学 | A kind of fine coal lime balls chlorination electrolytic preparation aluminum oxide and the method for comprehensive utilization |
| CN110436502A (en) * | 2019-08-16 | 2019-11-12 | 东北大学 | A kind of flyash 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 |
| CN111661861A (en) * | 2019-03-08 | 2020-09-15 | 中国科学院过程工程研究所 | Method for producing high-purity anhydrous aluminum chloride from aluminum hydroxide |
| 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 |
| CN116282046A (en) * | 2023-02-23 | 2023-06-23 | 成都理工大学 | Purification device and method for silica fume |
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Cited By (19)
| 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 |
| CN103911627A (en) * | 2012-12-31 | 2014-07-09 | 北京有色金属研究总院 | Molten salt electrolytic additive and method for preparing silicon composite material from the same |
| CN103526234B (en) * | 2013-10-18 | 2016-06-22 | 东北大学 | Fused salt electrolysis process extracts the method for metal from flyash |
| CN103526234A (en) * | 2013-10-18 | 2014-01-22 | 东北大学 | Method for extracting metal from coal ash by fused salt electrolysis method |
| CN103572323A (en) * | 2013-11-08 | 2014-02-12 | 中国科学院过程工程研究所 | Method for preparing aluminum silicon alloy through mixed chlorination and low-temperature electrolysis of aluminum-containing mineral and fly ash |
| 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 |
| CN104313641A (en) * | 2014-09-22 | 2015-01-28 | 沈阳金博新技术产业有限公司 | Method for producing metal aluminum or aluminum magnesium alloy from low grade bauxite |
| CN106048226A (en) * | 2016-05-19 | 2016-10-26 | 东北大学 | Method for preparing metal aluminum through microwave chlorination of coal ash |
| 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 |
| CN107128957A (en) * | 2017-05-10 | 2017-09-05 | 东北大学 | A kind of fine coal lime balls chlorination electrolytic preparation aluminum oxide and the method for comprehensive utilization |
| CN111661861A (en) * | 2019-03-08 | 2020-09-15 | 中国科学院过程工程研究所 | Method for producing high-purity anhydrous aluminum chloride from aluminum hydroxide |
| 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 |
| CN110436502A (en) * | 2019-08-16 | 2019-11-12 | 东北大学 | A kind of flyash 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 |
| CN116282046A (en) * | 2023-02-23 | 2023-06-23 | 成都理工大学 | Purification device and method for silica fume |
| 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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