CN103028592A - Recycle method of water recycled from overhaul slot slag of electrolytic cell - Google Patents
Recycle method of water recycled from overhaul slot slag of electrolytic cell Download PDFInfo
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- CN103028592A CN103028592A CN2012105119268A CN201210511926A CN103028592A CN 103028592 A CN103028592 A CN 103028592A CN 2012105119268 A CN2012105119268 A CN 2012105119268A CN 201210511926 A CN201210511926 A CN 201210511926A CN 103028592 A CN103028592 A CN 103028592A
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Abstract
The invention discloses a recycle method of water recycled from overhaul slot slag of an electrolytic cell. The recycle method is characterized by comprising the following steps of: carrying out water leaching on the overhaul slot slag of the electrolytic cell, so as to enable sodium fluoride in the overhaul slot slag of the electrolytic cell to be dissolved in water to remove fluorine in the overhaul slot slag of the electrolytic cell, recovering the water in the treatment by a reverse osmosis water treatment system, recycling separated clean water, and producing a metallurgical slag former by using obtained high-fluoride residue, so that the recycle of production water can be realized. According to the recycle method, fluoride salt which is hard to remove in the overhaul slot slag of the electrolytic cell can be separated, and the recycle value of the overhaul slot slag of the electrolytic cell can be improved, so that a waste material can be recycled, the overhaul slot slag of the electrolytic cell can be economically recycled without pollution, and the pollution hidden danger can be basically eliminated.
Description
Technical field
The present invention relates to the circulation utilization method that a kind of electrolytic cell overhaul groove slag reclaims water, belong to electrolytic cell overhaul groove slag processing technology field.
Background technology
Aluminium cell generally need carry out large repairs after using 4～5 years, and the average groove life of the most enterprises of China is about 1500 days, and the waste liner of removing during overhaul is the electrolytic cell overhaul slag, and this slag contains soluble fluoride.The overhaul slag mainly comprises waste cathode carbon block, useless refractory brick, pricks stick with paste, give up insulating brick, refractory powder, fire mortar and useless heat-insulating shield etc.Its generation is about the 30kg/tAl(relative number, becomes with groove length in age), present national electrolytic aluminium production capacity surpasses 9,000,000 t/a, and then overhaul slag generation is about 270,000 t/a.
Aluminium Electrolysis adopts fused salt electrolysis process.Namely take aluminium oxide as raw material, take fluoride salt (ice crystal, aluminum fluoride) as flux, in the electrolysis production process, a part of fluorine-containing electrolyte is absorbed by carbonaceous groove liner, is diffused in other furnace building material again.
According to " discriminating of hazardous waste judging standard corrosivity " (GB5085.1-1996) and " hazardous waste judging standard leaching characteristic identification " (GB5085.3-1996) with regard to promulgating in 1996 of country; The electrolytic cell overhaul slag belongs to hazardous solid waste because of Adsorption of fluoride compound and a small amount of cyanide, as effectively not fully utilizing with harmless treatment or storing mishandlingly, will have long-term potential pollution effect to soil and groundwater.
In the prior art, as follows to the processing method of aluminium cell overhaul groove slag:
1, add lime in waste cathode carbon block and make it to react with wherein electrolyte, obtain calcirm-fluoride, sodium fluoride and aluminum fluoride, make fluorine obtain solidifying to re-use, the charcoal of recovery is reused for the manufacturing cathode material, but disposal cost is too high.
2, utilize the cement kiln internal reaction temperature high, the charcoal piece conditions such as the time of staying is long on stream, make the harmful substance in the waste cathode carbon block decompose displacement in hot environment, and finally be solidificated in the clinker, the carbon in the waste cathode carbon block acts as a fuel and has reduced the consumption of coal simultaneously.But adopt the shortcoming of the method also very obvious: fluorine has infringement to refractory brick, and fluorine easily enters air with fume emission and causes atmosphere pollution; The content of sodium is high in the waste cathode carbon block, can be influential to the cement later strength.
3, Shandong Aluminum Plant just begins to utilize useless charcoal piece to add the use of alumina clinker calcining kiln replacement part anthracite as far back as nineteen eighty-two, although identify by country, obtains preferably effect, can not accomplish large argument, high value added utilization.
4, domestic and international research to the useless refractory brick treatment technology of useless SiC-Si3N4 is in blank substantially.
5, domestic and international recycling research to electrolytic aluminium fluorine-containing waste disposal industrial water is in blank substantially.
The method of above-mentioned processing electrolytic cell overhaul groove slag is all because of greatly argument, high value added utilization electrolytic cell overhaul groove slag, thus that realize commercial Application and few, cause most aluminium cell overhaul groove slags still to be thrown aside.
No matter the electrolytic cell overhaul slag is to store or landfill, all will drop into huge investment cost and operational and administrative expenses, and have long-term potentially contaminated hidden danger.Therefore the overhaul slag is carried out harmless treatment, it is turned waste into wealth, fundamentally pollution abatement hidden danger then is the best and final scheme.
Summary of the invention
The object of the invention is to, provide a kind of electrolytic cell overhaul groove slag to reclaim the circulation utilization method of water.After carbon, fluoride salt, electrolyte, insulation material, refractory material separate, purify in the overhaul groove slag, make it become the raw material that meets the commercial Application standard, be used for improving the comprehensive utilization of overhaul groove slag, the water in the recycling process can be recycling, do not have secondary pollution.
Technical scheme of the present invention.Electrolytic cell overhaul groove slag reclaims the circulation utilization method of water, electrolytic cell overhaul groove slag is carried out water logging, so that the sodium fluoride in the electrolytic cell overhaul groove slag is soluble in water, remove the fluorine in the electrolytic cell overhaul groove slag, water in the processing procedure reclaims by reverse osmosis water treatment system, separates the clear water that obtains and recycles, the high fluorine residue that obtains is made metallurgical slag former, realizes recycling of industrial water.
Above-mentioned electrolytic cell overhaul groove slag reclaims the circulation utilization method of water, comprises the steps:
A, electrolytic cell overhaul groove slag is carried out sorting, obtain respectively electrolyte block material, cathode bar, waste cathode carbon block, useless refractory brick, useless insulating brick, useless heat-insulating shield, and remaining mixing slag charge;
B, waste cathode carbon block is carried out water logging, obtain soaking the powder and the piece material that scatter, piece material is wherein selected, the piece material of selecting is by broken, again water logging is selected after the piece material drying wherein again as the aggregate of making cathode carbon pieces, and remaining powder carries out abrasive dust to be processed, again flotation obtains carbon dust;
C, useless refractory brick are alumina firebrick, alumina firebrick is carried out water logging, obtain soaking the powder and the piece material that scatter, the piece material is selected, and the piece material of selecting is by fragmentation, again water logging, select the piece material, reclaim as the aggregate of making refractory brick after dry, remaining powder carries out abrasive dust to be processed, and makes metallurgical slag former;
Useless refractory brick is silicon-carbide-silicon nitride refractory brick, silicon-carbide-silicon nitride refractory brick is carried out water logging, obtain soaking the powder and the piece material that scatter, piece material is wherein selected, the piece material of selecting is by broken, again water logging, again select wherein piece material as the aggregate of making refractory brick, remaining powder carries out abrasive dust and processes again flotation, obtain the refractory brick powder, refractory brick aggregate and the powder of gained after drying, carry out high-temperature calcination at 1700-1900 ℃, sodium fluoride gasification with wherein obtains highly purified refractory brick material;
D, useless insulating brick or useless heat-insulating shield are carried out respectively water logging, obtain soaking the powder and the piece material that scatter, the piece material is selected, the piece material of selecting is by broken, the piece material is selected in again water logging, reclaims as the aggregate of making insulating brick or heat-insulating shield respectively after the drying, remaining powder carries out abrasive dust to be processed, and makes metallurgical slag former;
E, carry out abrasive dust and process mixing slag charge, wherein carbon dust, refractory material powder are selected in then flotation, and remaining powder is made metallurgical slag former;
Water in described each step reclaims by reverse osmosis water treatment system, separates the clear water that obtains and recycles, and the high fluorine residue that obtains is made metallurgical slag former.
Above-mentioned electrolytic cell overhaul groove slag reclaims the circulation utilization method of water, and cathode carbon pieces aggregate and the carbon dust of described step b gained after drying, carry out high-temperature calcination at 1700-1900 ℃, and sodium fluoride, sulphur gasification with wherein obtain highly purified carbon materials
For electrolytic cell overhaul groove slag, take the 160KA pre-baking tank of certain electrolytic aluminium factory as example, all kinds of material composition situations see Table 1 in the overhaul slag.
Table 1 160KA pre-baking tank overhaul slag forms situation
Wherein, the main component that cathode carbon pieces, bundle are stuck with paste is carbon, and refractory brick is divided into again alumina firebrick and SiC-Si
3N
4The composite fireproof brick, also having into the insulating brick of piece and heat-insulating shield etc. can sort out.Simultaneously, electrolytic cell overhaul groove slag also has a small amount of electrolyte and cathode bar, is recoverable after sorting out.Method of the present invention first by preliminary sorting, obtains various blocks of material, and then by water logging, because fluoride salt can be soluble in water, and the high piece material of absorption fluoride salt (sodium fluoride is main) will soak and scatter.Remaining material absorption fluoride salt is low, after the again fragmentation of sorting rest block material, the immersion, can obtain highly purified block of material, such as cathode carbon pieces material, refractory brick blocks material, insulation fragment of brick material and adiabatic plate material etc., can be used as the aggregate of various products, improved economic worth.Water in the recycling process reclaims by reverse osmosis water treatment system, separates the clear water that obtains and recycles, and the high fluorine residue that obtains is made metallurgical slag former, realizes recycling of industrial water.For remaining powder, the powder of cathode carbon pieces after the flotation, can access carbon dust by ball milling, through the electric furnace high-temperature calcining, obtains high-purity carbon raw again, remains various fluorine-containing slag charges and can make alternative CaF
2Metallurgical slag former.Invention is carried out the harmless resource utilization advanced treating to electrolytic cell overhaul groove slag, adopt advanced technology and measure, the fluoride salt that is difficult to remove in the electrolytic cell overhaul groove slag is separated, the recycling that has improved electrolytic cell overhaul groove slag is worth, it is turned waste into wealth, electrolytic cell overhaul groove slag economy, pollution-free recovery have been realized, fundamentally pollution abatement hidden danger.Technology of the present invention can turn waste into wealth, and energy consumption is low, does not have the secondary pollution problem in the production process, has realized self cleaner production, is suitable for the large argument of electrolytic cell overhaul groove slag, the utilization of high added value.
The specific embodiment
Embodiments of the invention 1.Electrolytic cell overhaul groove slag reclaims the circulation utilization method of water, electrolytic cell overhaul groove slag is carried out water logging, so that the sodium fluoride in the electrolytic cell overhaul groove slag is soluble in water, remove the fluorine in the electrolytic cell overhaul groove slag, water in the processing procedure reclaims by reverse osmosis water treatment system, separates the clear water that obtains and recycles, the high fluorine residue that obtains is made metallurgical slag former, realizes recycling of industrial water.
Concrete grammar comprises the steps:
A, electrolytic cell overhaul groove slag is carried out sorting, obtain respectively electrolyte block material, cathode bar, waste cathode carbon block, useless refractory brick, useless insulating brick, useless heat-insulating shield, and remaining mixing slag charge.Wherein, the electrolyte block material mainly is aluminium, can directly be recovered to electrolytic aluminium factory, and cathode bar is iron staff, also can directly reclaim.
B, waste cathode carbon block is carried out water logging, fluoride salt is soluble in water, and the cathode carbon pieces that has adsorbed fluoride salt can scatter, obtain soaking the powder and the piece material that scatter, piece material is wherein selected, and the fluoride salt of the piece material absorption of selecting is few, passes through the piece material of selecting broken, again water logging, further remove fluoride salt, again select after the piece material drying wherein as the aggregate of making cathode carbon pieces, remaining powder carries out abrasive dust to be processed, again flotation obtains carbon dust.Cathode carbon pieces aggregate and the carbon dust of gained after drying, carry out high-temperature calcination at 1700-1900 ℃, and sodium fluoride, sulphur gasification with wherein obtain highly purified carbon materials
C, useless refractory brick are alumina firebrick, alumina firebrick is carried out water logging, obtain soaking the powder and the piece material that scatter, the piece material is selected, and the piece material of selecting is by fragmentation, again water logging, select the piece material, reclaim as the aggregate of making refractory brick after dry, remaining powder carries out abrasive dust to be processed, and makes metallurgical slag former;
Useless refractory brick is silicon-carbide-silicon nitride refractory brick, silicon-carbide-silicon nitride refractory brick is carried out water logging, obtain soaking the powder and the piece material that scatter, piece material is wherein selected, the piece material of selecting is by broken, again water logging, again select wherein piece material as the aggregate of making refractory brick, remaining powder carries out abrasive dust and processes again flotation, obtain the refractory brick powder, refractory brick aggregate and the powder of gained after drying, carry out high-temperature calcination at 1700-1900 ℃, sodium fluoride gasification with wherein obtains highly purified refractory brick material.
D, useless insulating brick or useless heat-insulating shield are carried out respectively water logging, obtain soaking the powder and the piece material that scatter, the piece material is selected, the piece material of selecting is by broken, the piece material is selected in again water logging, reclaims as the aggregate of making insulating brick or heat-insulating shield respectively after the drying, remaining powder carries out abrasive dust to be processed, and makes metallurgical slag former.
E, carry out abrasive dust and process mixing slag charge, wherein carbon dust, refractory material powder are selected in then flotation, and remaining powder is made metallurgical slag former.
Water in described each step reclaims by reverse osmosis water treatment system, separates the clear water that obtains and recycles, and the high fluorine residue that obtains is made metallurgical slag former.
Embodiments of the invention 2.Electrolytic cell overhaul groove slag reclaims the circulation utilization method of water, comprises the steps:
A, electrolytic cell overhaul groove slag is carried out sorting, obtain respectively electrolyte block material, cathode bar, waste cathode carbon block, useless refractory brick, useless insulating brick, useless heat-insulating shield, and remaining mixing slag charge.
B, waste cathode carbon block was carried out water logging 2-3 days, obtain soaking the powder and the piece material that scatter, particle diameter is selected greater than 1 centimetre piece material, the piece material of selecting is by being crushed to 0.5 centimetre of particle diameter, and again water logging is selected particle diameter greater than 0.3 centimetre piece material, the aggregate of cathode carbon pieces is made in conduct after dry, remaining powder carries out abrasive dust, and flotation obtains carbon dust.Cathode carbon pieces aggregate and the carbon dust of gained after drying, carry out high-temperature calcination at 1700-1900 ℃, and sodium fluoride, sulphur gasification with wherein obtain highly purified carbon materials.
C, useless refractory brick are useless alumina firebrick, the alumina firebrick that will give up carried out water logging 2-3 days, obtain soaking the powder and the piece material that scatter, particle diameter is selected greater than 1 centimetre piece material, and the piece material of selecting is by being crushed to 0.5 centimetre of particle diameter, again water logging, select particle diameter greater than 0.3 centimetre piece material, reclaim as the aggregate of making refractory brick after dry, remaining powder carries out abrasive dust to be processed, and makes metallurgical slag former.
When useless refractory brick is silicon-carbide-silicon nitride refractory brick, because it is higher that silicon-carbide-silicon nitride refractory brick is worth, can adopt the recovery technique of cathode blocks among the step b to process, specific as follows, silicon-carbide-silicon nitride refractory brick was carried out water logging 2-3 days, obtain soaking the powder and the piece material that scatter, particle diameter is selected greater than 1 centimetre piece material, the piece material of selecting is by being crushed to 0.5 centimetre of particle diameter, again water logging, again select particle diameter greater than 0.3 centimetre piece material drying after as the aggregate of making refractory brick, remaining powder carries out abrasive dust to be processed, again flotation obtains the refractory brick powder.Obtain the refractory brick powder, refractory brick aggregate and the powder of gained after drying, carry out high-temperature calcination at 1700-1900 ℃, and the sodium fluoride gasification with wherein obtains highly purified refractory brick material.
D, useless insulating brick or useless heat-insulating shield are carried out respectively water logging, obtain soaking the powder and the piece material that scatter, the piece material is selected, the piece material of selecting is by broken, the piece material is selected in again water logging, reclaims as the aggregate of making insulating brick or heat-insulating shield respectively after the drying, remaining powder carries out abrasive dust to be processed, and makes metallurgical slag former;
E, carry out abrasive dust and process mixing slag charge, then adopt existing floatation process, select wherein carbon dust, refractory material powder, remaining powder is made metallurgical slag former.
Water in the above steps reclaims by reverse osmosis water treatment system, separates the clear water that obtains and recycles, and the high fluorine residue that obtains is made metallurgical slag former with the powder that obtains before.
Embodiments of the invention 3.Electrolytic cell overhaul groove slag reclaims the circulation utilization method of water, comprises the steps:
A, electrolytic cell overhaul groove slag is carried out sorting, obtain respectively electrolyte block material, cathode bar, waste cathode carbon block, useless refractory brick, useless insulating brick, useless heat-insulating shield, and remaining mixing slag charge.
B, waste cathode carbon block was carried out water logging 2 days, obtain soaking the powder and the piece material that scatter, particle diameter is selected greater than 3 centimetres piece material, the piece material of selecting is by being crushed to 1 centimetre of particle diameter, and again water logging is selected particle diameter greater than 0.6 centimetre piece material, the aggregate of cathode carbon pieces is made in conduct after dry, remaining powder carries out abrasive dust, and flotation obtains carbon dust.Cathode carbon pieces aggregate and the carbon dust of gained after drying, carry out high-temperature calcination at 1700-1900 ℃, and sodium fluoride, sulphur gasification with wherein obtain highly purified carbon materials.
C, useless refractory brick are useless alumina firebrick, the alumina firebrick that will give up carried out water logging 2-3 days, obtain soaking the powder and the piece material that scatter, particle diameter is selected greater than 3 centimetres piece material, and the piece material of selecting is by being crushed to 1 centimetre of particle diameter, again water logging, select particle diameter greater than 0.6 centimetre piece material, reclaim as the aggregate of making refractory brick after dry, remaining powder carries out abrasive dust to be processed, and makes metallurgical slag former.
When useless refractory brick is silicon-carbide-silicon nitride refractory brick, because it is higher that silicon-carbide-silicon nitride refractory brick is worth, can adopt the recovery technique of cathode blocks among the step b to process, specific as follows, silicon-carbide-silicon nitride refractory brick was carried out water logging 2-3 days, obtain soaking the powder and the piece material that scatter, particle diameter is selected greater than 3 centimetres piece material, the piece material of selecting is by being crushed to 1 centimetre of particle diameter, again water logging, again select particle diameter greater than 0.6 centimetre piece material drying after as the aggregate of making refractory brick, remaining powder carries out abrasive dust to be processed, again flotation obtains the refractory brick powder.Obtain the refractory brick powder, refractory brick aggregate and the powder of gained after drying, carry out high-temperature calcination at 1700-1900 ℃, and the sodium fluoride gasification with wherein obtains highly purified refractory brick material.
D, useless insulating brick or useless heat-insulating shield are carried out respectively water logging, obtain soaking the powder and the piece material that scatter, the piece material is selected, the piece material of selecting is by broken, the piece material is selected in again water logging, reclaims as the aggregate of making insulating brick or heat-insulating shield respectively after the drying, remaining powder carries out abrasive dust to be processed, and makes metallurgical slag former;
E, carry out abrasive dust and process mixing slag charge, then adopt existing floatation process, select wherein carbon dust, refractory material powder, remaining powder is made metallurgical slag former.
Water in the above steps reclaims by reverse osmosis water treatment system, separates the clear water that obtains and recycles, and the high fluorine residue that obtains is made metallurgical slag former with the powder that obtains before.
Claims (3)
1. an electrolytic cell overhaul groove slag reclaims the circulation utilization method of water, it is characterized in that: electrolytic cell overhaul groove slag is carried out water logging, so that the sodium fluoride in the electrolytic cell overhaul groove slag is soluble in water, remove the fluorine in the electrolytic cell overhaul groove slag, water in the processing procedure reclaims by reverse osmosis water treatment system, separates the clear water that obtains and recycles, the high fluorine residue that obtains is made metallurgical slag former, realizes recycling of industrial water.
2. electrolytic cell overhaul groove slag according to claim 1 reclaims the circulation utilization method of water, it is characterized in that: comprise the steps:
A, electrolytic cell overhaul groove slag is carried out sorting, obtain respectively electrolyte block material, cathode bar, waste cathode carbon block, useless refractory brick, useless insulating brick, useless heat-insulating shield, and remaining mixing slag charge;
B, waste cathode carbon block is carried out water logging, obtain soaking the powder and the piece material that scatter, piece material is wherein selected, the piece material of selecting is by broken, again water logging is selected after the piece material drying wherein again as the aggregate of making cathode carbon pieces, and remaining powder carries out abrasive dust to be processed, again flotation obtains carbon dust;
C, useless refractory brick are alumina firebrick, alumina firebrick is carried out water logging, obtain soaking the powder and the piece material that scatter, the piece material is selected, and the piece material of selecting is by fragmentation, again water logging, select the piece material, reclaim as the aggregate of making refractory brick after dry, remaining powder carries out abrasive dust to be processed, and makes metallurgical slag former;
Useless refractory brick is silicon-carbide-silicon nitride refractory brick, silicon-carbide-silicon nitride refractory brick is carried out water logging, obtain soaking the powder and the piece material that scatter, piece material is wherein selected, the piece material of selecting is by broken, again water logging, again select wherein piece material as the aggregate of making refractory brick, remaining powder carries out abrasive dust and processes again flotation, obtain the refractory brick powder, refractory brick aggregate and the powder of gained after drying, carry out high-temperature calcination at 1700-1900 ℃, sodium fluoride gasification with wherein obtains highly purified refractory brick material;
D, useless insulating brick or useless heat-insulating shield are carried out respectively water logging, obtain soaking the powder and the piece material that scatter, the piece material is selected, the piece material of selecting is by broken, the piece material is selected in again water logging, reclaims as the aggregate of making insulating brick or heat-insulating shield respectively after the drying, remaining powder carries out abrasive dust to be processed, and makes metallurgical slag former;
E, carry out abrasive dust and process mixing slag charge, wherein carbon dust, refractory material powder are selected in then flotation, and remaining powder is made metallurgical slag former;
Water in described each step reclaims by reverse osmosis water treatment system, separates the clear water that obtains and recycles, and the high fluorine residue that obtains is made metallurgical slag former.
3. electrolytic cell overhaul groove slag according to claim 1 reclaims the circulation utilization method of water, it is characterized in that: cathode carbon pieces aggregate and the carbon dust of gained among the described step b, after drying, carry out high-temperature calcination at 1700-1900 ℃, sodium fluoride, sulphur gasification with wherein obtain highly purified carbon materials.
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| CN106565120A (en) * | 2016-11-07 | 2017-04-19 | 中国铝业股份有限公司 | Hazard-free treatment and utilization method for aluminium electrolysis waste slot liner |
| CN111495923A (en) * | 2020-03-17 | 2020-08-07 | 国家电投集团宁夏能源铝业科技工程有限公司 | Treatment method of electrolytic aluminum overhaul waste residue |
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