CN103726074A - Method for producing aluminum electrolyte by using aluminum electrolysis waste materials and recycling carbon - Google Patents
Method for producing aluminum electrolyte by using aluminum electrolysis waste materials and recycling carbon Download PDFInfo
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- CN103726074A CN103726074A CN201410034660.1A CN201410034660A CN103726074A CN 103726074 A CN103726074 A CN 103726074A CN 201410034660 A CN201410034660 A CN 201410034660A CN 103726074 A CN103726074 A CN 103726074A
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Abstract
The invention discloses a method for producing aluminum electrolyte by using aluminum electrolysis waste materials and recycling carbon. The method comprises the following steps: pretreating, floating and separating, preparing and post-treating. The method specifically comprises the following steps: crushing the aluminum electrolysis waste materials and magnetically selecting to remove scrap iron; separating the pre-treated aluminum electrolysis waste materials to obtain a bottom flow product and a foam product; carrying out filtering, carbon removing and crushing on the bottom flow product obtained by separating to obtain target electrolyte for the aluminum; carrying out filter pressing and drying on the foam product obtained by separating to obtain target carbon powder; and recycling smoke and wastewater generated in the preparation process and discharging after the standards are reached. The method takes wastes which need to be urgently treated as raw materials; all resources are recycled and utilized and waste gas is collected and purified; the produced aluminum electrolyte is low in water content and less in harmful impurities, and is an ideal raw material for aluminum electrolysis production; the floated carbon powder can be used as aluminum electrolysis cell bottom paste or can also be used as a dye for bottom carbon block production or metallurgy production.
Description
Technical field
The invention belongs to recovery and recycling of used resources technical field, be specifically related to a kind of method of recycling aluminum electrolysis waste material production aluminium ionogen and reclaiming carbon.
Background technology
The spent potlining piece carbon content 60%-80% of current domestic electrolysis of aluminum overhaul groove, because containing the fluorine-containing impurity of 20%-40%, belongs to Hazardous wastes, and its generation is along with electrolytic aluminum output increase face increases.Domestic aluminium manufacturer adopts treatment process to mainly contain landfill, makes the postcombustion of aluminum oxide and manufacture of cement, the fluorite in cupola furnace substitutes the methods such as articles for use and flotation process Separation and Recovery carbon and impurity.These methods have deficiency separately, as landfill method environmental risk is large, valuable element does not utilize, as fuel, do not utilized by supporting restriction and valuable element, and flotation process quality product is defective, and all end can be realized and be continued scale production.Therefore, developing a kind of waste materials that can effectively utilize electrolysis overhaul groove produces the method that ionogen reclaims carbon and is very important.
Summary of the invention
The object of the present invention is to provide that a kind of technique is simple, the recycling aluminum electrolysis waste material production aluminium ionogen of good product quality reclaim the method for carbon.
The object of the present invention is achieved like this, comprises pre-treatment, flotation separation, preparation, post-processing step, specifically comprises:
A, pre-treatment: by the fragmentation of waste and old electrolysis carbon material, iron filings are removed in magnetic separation;
B, flotation separation: waste and old premenstrual electrolysis after treatment carbon feed separation is obtained to underflow product and froth product;
C, preparation: the underflow product that separation is obtained after filtration, de-carbon, fragmentation obtain target compound aluminium ionogen, separates the froth product obtaining through press filtration, the dry target compound carbon dust that obtains;
D, aftertreatment: the flue gas producing in preparation process, waste water are reclaimed to qualified discharge processing.
The present invention is take refuse in need of immediate treatment as raw material, various resources are all recycled, the whole collection and purification processing of waste gas, and the aluminium of producing is low with ionogen water ratio, detrimental impurity content is few, be the desirable feedstock of Aluminium Electrolysis, the carbon dust flotating can be used as sticking with paste at the bottom of aluminium cell or bottom carbon block is produced or the dyestuff of metallurgical production.
Accompanying drawing explanation
Fig. 1 is process flow sheet of the present invention.
Embodiment
Below in conjunction with accompanying drawing, the present invention is further illustrated, but never in any form the present invention is limited, and any conversion or the replacement based on training centre of the present invention, done, all belong to protection scope of the present invention.
Recycling aluminum electrolysis waste material production aluminium of the present invention is with ionogen and reclaim the method for carbon, comprises pre-treatment, flotation separation, preparation, post-processing step, specifically comprises:
A, pre-treatment: by the fragmentation of waste and old electrolysis carbon material, iron filings are removed in magnetic separation;
B, flotation separation: waste and old premenstrual electrolysis after treatment carbon feed separation is obtained to underflow product and froth product;
C, preparation: the underflow product that separation is obtained after filtration, de-carbon, fragmentation obtain target compound aluminium ionogen, separates the froth product obtaining through press filtration, the dry target compound carbon dust that obtains;
D, aftertreatment: the flue gas producing in preparation process, waste water are reclaimed to qualified discharge processing.
Described waste materials is aluminum electrolysis waste cathode carbon piece and/or electrolytic aluminum breeze.
Particle size after cracking described in A step is 80 ~ 150 orders.
Separation described in B step is to use the one in flotation column, flotation machine to separate.
Described separation is to use the reverse-flow flotation column of microvesicle to separate.
Described in C step, be filtered into centrifuging, the press filtration one in filtering.
De-carbon described in C step is to use medium-frequency induction furnace to carry out de-carbon.
Described in D step the processing of flue gas be adopt secondary spraying absorption tower absorb, then after calcium salt primary treatment and polymer alumina secondary treatment qualified discharge.
Described in D step, the processing of waste water is to adopt one or more in Physical, chemical method or biological process to process.
Recycling aluminum electrolysis waste material cathode block of the present invention is produced aluminium ionogen and is reclaimed the method for carbon, that the bulk spent potlining piece input jaw crusher that aluminium cell overhaul is produced slightly breaks, the material obtaining enters ball mill again, wears into 80 order to 150 object powder.To after material powder, send into surge tank, then add salt acid for adjusting pH to 8-9, is 20% by amount of water control pulp density.The slip preparing enters microvesicle counter current contact formula flotation column, in 0.5Kg/ ton ratio, adds collecting agent, according to depth of foam, adjusts pore forming material add-on, according to bubble velocity, controls air supply well.Through triple cleaning and once purging selection, the froth product obtaining enters pressure filter, after washing, filtration, enter external-heat rotating drum dryer, after being dried at 400 ℃, the cooling carbon that is fixed is more than 85%, and ash content is below 10, block/gram above carbon dust of calorific value 7000, can be used as sticking with paste or bottom carbon block production at the bottom of aluminium cell.Water in flotation column can recycle, the wash water of froth product contains fluorine, collect and enter waste water disposal facility, processes together with intermediate frequency furnace flue gas, by adopting lime coagulation polyaddition aluminum chloride second-stage treatment to realize discharged wastewater met the national standard, processing the slag major ingredient producing is CaF
2, can be used as fluorite and use.
Floatation underflow slip enters centrifugal filter and washs, filter, after centrifuge dehydration, obtain moisture approximately 10% material, enter again intermediate frequency furnace, the whole meltings of material while being warming up to 1000 ℃ of left and right, now the impurity carbon granules in material is separated, float up to bath surface, can manually carbon slag be salvaged out, remaining melt be cooling after taking out, and fragmentation is qualified aluminium ionogen.The carbon slag of salvaging out returns to ball mill flotation again.The flue gas processing that intermediate frequency furnace produces is introduced into secondary spraying absorption tower and absorbs, and remaining gas adsorbs by activated alumina adsorption tower again, and expellant gas is qualified discharge after testing.The waste water reclaiming in absorption tower contains fluorine, also enters waste water disposal facility, processes together with froth product wash water.
Technique of the present invention is simple, and environmental benefit is obvious, and using raw material is refuse in need of immediate treatment, and various resources are all recycled, the whole collection and purification processing of gas.Aluminium that the present invention produces is moisture low with ionogen, and detrimental impurity is few, is the desirable feedstock of Aluminium Electrolysis, and the carbon dust flotating can be used as sticking with paste at the bottom of aluminium cell or bottom carbon block is produced or the fuel of metallurgical production.
Recycling aluminum electrolysis waste material electrolytic aluminum breeze of the present invention is produced aluminium ionogen and is reclaimed the method for carbon, first electrolytic aluminum breeze is carried out to sorting, fragmentation, and screening, obtains 100 to 150 object powder.Again powder is carried out to magnetic separation, the iron filings that in elimination shattering process, equipment and ironworker's tool are brought into, liquid-solid ratio is about 6:1, and ore pulp enters flotation machine, adds special flotation reagent, passes into pressurized air.The carbon dust obtaining at flotation machine overflow port, becomes fixed carbon more than 70%, ash content 20% below, block/gram above carbon dust of calorific value 6000 through washing, after dry, through forming machine extrusion molding, ground kilning roasts rear making electrolytic aluminium anode guard ring.The waste water that flotation, washing and off gas treatment produce all enters waste water disposal facility, processes rear discharge up to standard, processes the precipitation producing and can do fluorite use.
After mixture is dried, enter intermediate frequency furnace, add a small amount of aluminum metal, at impurity such as intermediate frequency furnace reduced iron, silicon, because its proportion conference sinks to furnace bottom, 10% left and right carbon can float over molten surface, and after salvaging, middle layer is industry and can uses ionogen.Intermediate frequency furnace adopts silicon carbide crucible, and according to fusing feature, its control parameter and part electric elements is adjusted, and major advantage is balanced for guaranteeing temperature control and heating, better controls furnace temperature, and crucible life is long, stable output power.Flue gas is processed and is adopted water dedusting to absorb, and the waste water of recovery contains fluorine, processes together with flotation waste water.
Feature of the present invention:
1, recycle the method that electrolytic aluminum breeze is produced aluminium ionogen and reclaimed carbon, comprise the steps:
Adopt sizing screen to carry out sorting to electrolysis breeze, by ironworker's tool, domestic refuse and scrap anode charcoal piece in breeze separately, after fragmentation, enter magnetic separation, floatation system, obtain common carbon dust and contain 90% electrolytical mixture, the iron filings that when fragmentation is removed in magnetic separation, equipment and ironworker's tool are brought into.
2, mixture enters intermediate frequency furnace after being dried, and adds a small amount of aluminum metal, and at impurity such as intermediate frequency furnace reduced iron, silicon, because its proportion conference sinks to furnace bottom, 10% left and right carbon can float over molten surface, and after salvaging, middle layer is industry and can uses ionogen.Intermediate frequency furnace adopts silicon carbide crucible, at crucible middle part, set up a graphite rod, and according to fusing feature, its control parameter and part electric elements are adjusted, major advantage is balanced for guaranteeing temperature control and heating, better controls furnace temperature, and crucible life is long, stable output power, temperature of reaction is 1100-1200 ℃, reaction times is that 18-25 divides, and flue gas adopts water dedusting to reclaim, and reclaims waste water and flotation waste water and handles together.
3, the common carbon dust forming machine extrusion molding separating, makes electrolytic aluminium anode guard ring after ground kilning roasting.
In abovementioned steps, operate except flotation needs flotation reagent without adding other any raw materials.
4, present method employing equipment is market common equipment, the short less investment of flow process, and low cost is fully recycled electrolysis breeze, and product separation all reaches electrolytic aluminium factory industrial application demand.
Embodiment 1
Raw material electrolysis spent potlining piece 100Kg is dropped into jaw crusher and carry out fragmentation, enter again broken 80 ~ 150 mesh sieves of crossing of ball mill, add diesel oil 2Kg coal floatation GF oil 0.6Kg to enter together the reverse-flow flotation column separation of microvesicle and obtain underflow product 30Kg and froth product 70Kg, underflow product is through centrifuging, use intermediate frequency furnace de-carbon, medium-frequency induction furnace power is controlled at 350KW, the carbon removal time is about 8-10 minute, through hammer crushing, obtain target compound aluminium ionogen 29Kg, separate the froth product obtaining through press filtration, the dry target compound carbon dust that obtains
?69.5Kg.The first secondary spraying of the flue gas absorption tower producing in preparation process absorbs, and then through the discharge of activated alumina adsorption tower, waste water is through precipitation recycle and reuse and qualified discharge, and processing the slag major ingredient producing is CaF
2, can be used as fluorite and use.
After testing, ionogen carbon content is 1.5%, and carbon dust fixed carbon content is 78%, and ash content is 4.5%, calorific value be 4970 cards/gram.
Embodiment 2
Raw material electrolysis spent potlining piece 100 Kg are dropped into jaw crusher and carry out fragmentation, enter again broken 80 ~ 150 mesh sieves of crossing of ball mill, add diesel oil 2.1Kg coal floatation GF oil 0.7Kg to enter together the reverse-flow flotation column separation of microvesicle and obtain underflow product 33Kg and froth product 67Kg, underflow product is through centrifuging, use intermediate frequency furnace de-carbon, medium-frequency induction furnace power is controlled at 350KW, the carbon removal time is about 8-10 minute, through hammer crushing, obtain target compound aluminium ionogen 32Kg, separate the froth product obtaining through press filtration, the dry target compound carbon dust 66.5Kg that obtains.The first secondary spraying of the flue gas absorption tower producing in preparation process absorbs, and then through the discharge of activated alumina adsorption tower, waste water is through precipitation recycle and reuse and qualified discharge, and processing the slag major ingredient producing is CaF
2, can be used as fluorite and use.
After testing, ionogen carbon content is 1.4%, and carbon dust fixed carbon content is 80%, and ash content is 5.4%, calorific value be 5045 cards/gram.
Embodiment 3
Raw material electrolysis spent potlining piece 100Kg is dropped into jaw crusher and carry out fragmentation, enter again broken 80 ~ 150 mesh sieves of crossing of ball mill, add diesel oil 2.2Kg coal floatation GF oil 0.8Kg to enter together the reverse-flow flotation column separation of microvesicle and obtain underflow product 32Kg and froth product 68Kg, underflow product is through centrifuging, use intermediate frequency furnace de-carbon, medium-frequency induction furnace power is controlled at 350KW, the carbon removal time is about 8-10 minute, through hammer crushing, obtain target compound aluminium ionogen 31Kg, separate the froth product obtaining through press filtration, the dry target compound carbon dust 67.5Kg that obtains.The first secondary spraying of the flue gas absorption tower producing in preparation process absorbs, and then through the discharge of activated alumina adsorption tower, waste water is through precipitation recycle and reuse and qualified discharge, and processing the slag major ingredient producing is CaF
2, can be used as fluorite and use.
After testing, ionogen carbon content is 1.5%, and carbon dust fixed carbon content is 79%, and ash content is 4.8%, calorific value be 5009 cards/gram.
Embodiment 4
Raw material electrolytic aluminum breeze 100Kg is dropped into jaw crusher and carry out fragmentation, enter again broken 100 ~ 150 mesh sieves of crossing of ball mill, magnetic separation is except scrap iron removing, add diesel oil 2.1Kg coal floatation GF oil 0.7Kg to enter together the reverse-flow flotation column separation of microvesicle and obtain underflow product 65Kg and froth product 35Kg, underflow product is through centrifuging, use intermediate frequency furnace de-carbon, medium-frequency induction furnace power is controlled at 350KW, the carbon removal time is about 8-10 minute, through hammer crushing, obtain target compound aluminium ionogen 63.5Kg, separate the froth product obtaining through press filtration, the dry target compound carbon dust 34Kg that obtains.The first secondary spraying of the flue gas absorption tower producing in preparation process absorbs, and then through the discharge of activated alumina adsorption tower, waste water is through precipitation recycle and reuse and qualified discharge, and processing the slag major ingredient producing is CaF
2, can be used as fluorite and use.
After testing, ionogen carbon content is 1.6%, and carbon dust fixed carbon content is 76%, and ash content is 4.3%, calorific value be 4579 cards/gram.
Embodiment 5
Raw material electrolytic aluminum breeze 100Kg is dropped into jaw crusher and carry out fragmentation, enter again broken 100 ~ 150 mesh sieves of crossing of ball mill, magnetic separation is except scrap iron removing, add diesel oil 2.2Kg coal floatation GF oil 0.8Kg to enter together the reverse-flow flotation column separation of microvesicle and obtain underflow product 62Kg and froth product 38Kg, underflow product is through centrifuging, use intermediate frequency furnace de-carbon, medium-frequency induction furnace power is controlled at 350KW, the carbon removal time is about 8-10 minute, through hammer crushing, obtain target compound aluminium ionogen 61Kg, separate the froth product obtaining through press filtration, the dry target compound carbon dust 37.5Kg that obtains.The first secondary spraying of the flue gas absorption tower producing in preparation process absorbs, and then through the discharge of activated alumina adsorption tower, waste water is through precipitation recycle and reuse and qualified discharge, and processing the slag major ingredient producing is CaF
2, can be used as fluorite and use.
After testing, ionogen carbon content is 1.4%, and carbon dust fixed carbon content is 75%, and ash content is 3.8%, calorific value be 4615 cards/gram.
Embodiment 6
Raw material electrolytic aluminum breeze 100Kg is dropped into jaw crusher and carry out fragmentation, enter again broken 100 ~ 150 mesh sieves of crossing of ball mill, magnetic separation is except scrap iron removing, add diesel oil 2.1Kg coal floatation GF oil 0.7Kg to enter together the reverse-flow flotation column separation of microvesicle and obtain underflow product 59Kg and froth product 41Kg, underflow product is through centrifuging, use intermediate frequency furnace de-carbon, medium-frequency induction furnace power is controlled at 350KW, the carbon removal time is about 8-10 minute, through hammer crushing, obtain target compound aluminium ionogen 58Kg, separate the froth product obtaining through press filtration, the dry target compound carbon dust 40Kg that obtains.The first secondary spraying of the flue gas absorption tower producing in preparation process absorbs, and then through the discharge of activated alumina adsorption tower, waste water is through precipitation recycle and reuse and qualified discharge, and processing the slag major ingredient producing is CaF
2, can be used as fluorite and use.
After testing, ionogen carbon content is 1.5%, and carbon dust fixed carbon content is 75%, and ash content is 4.6%, calorific value be 4586 cards/gram.
Claims (9)
1. recycle aluminum electrolysis waste material production aluminium ionogen and reclaim the method for carbon, it is characterized in that comprising pre-treatment, flotation separation, preparation, post-processing step, specifically comprise:
A, pre-treatment: by the fragmentation of electrolysis waste materials, iron filings are removed in magnetic separation;
B, flotation separation: premenstrual electrolysis waste materials after treatment is separated and obtains underflow product and froth product;
C, preparation: the underflow product that separation is obtained after filtration, de-carbon, fragmentation obtain target compound aluminium ionogen, separates the froth product obtaining through press filtration, the dry target compound carbon dust that obtains;
D, aftertreatment: the flue gas producing in preparation process, waste water are reclaimed to qualified discharge processing.
2. recycling aluminum electrolysis waste material production aluminium according to claim 1 with ionogen and reclaim the method for carbon, is characterized in that described waste materials is aluminum electrolysis waste cathode carbon piece and/or electrolytic aluminum breeze.
3. recycling aluminum electrolysis waste material production aluminium according to claim 1 is with ionogen and reclaim the method for carbon, it is characterized in that the particle size after cracking described in A step is 80 ~ 150 orders.
4. recycling aluminum electrolysis waste material production aluminium according to claim 1 is with ionogen and reclaim the method for carbon, it is characterized in that the separation described in B step is to use the one in flotation column, flotation machine to separate.
According to the recycling aluminum electrolysis waste material production aluminium described in claim 1 or 4 with ionogen and reclaim the method for carbon, it is characterized in that described separation is to use the reverse-flow flotation column of microvesicle to separate.
6. recycling aluminum electrolysis waste material production aluminium according to claim 1 is with ionogen and reclaim the method for carbon, it is characterized in that being filtered into centrifuging, the press filtration one in filtering described in C step.
7. recycling aluminum electrolysis waste material production aluminium according to claim 1 is with ionogen and reclaim the method for carbon, it is characterized in that the de-carbon described in C step is to use medium-frequency induction furnace to carry out de-carbon.
8. recycling aluminum electrolysis waste material production aluminium according to claim 1 is with ionogen and reclaim the method for carbon, it is characterized in that the processing of flue gas is to adopt secondary spraying absorption tower to absorb described in D step, then after calcium salt primary treatment and polymer alumina secondary treatment qualified discharge.
9. the recycling aluminum electrolysis waste material production aluminium of medicine with ionogen and reclaim the method for carbon, is characterized in that the processing of waste water described in D step is to adopt one or more in Physical, chemical method or biological process to process according to claim 1.
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| CN201410034660.1A CN103726074B (en) | 2014-01-25 | 2014-01-25 | Method for producing aluminum electrolyte by using aluminum electrolysis waste materials and recycling carbon |
| CN201410144571.2A CN103949459B (en) | 2014-01-25 | 2014-01-25 | A kind of electrolytic aluminium breeze of recycling produces aluminium electrolyte and the method reclaiming carbon |
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Cited By (6)
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| CN103949460A (en) * | 2014-04-17 | 2014-07-30 | 建水德福再生资源利用有限公司 | Device and method for producing regenerative electrolyte from aluminum-electrolysis carbon residues |
| CN105964659A (en) * | 2016-05-27 | 2016-09-28 | 中南大学 | Comprehensive resource recycling method for waste cathode carbon blocks of aluminum cells |
| CN106829912A (en) * | 2017-01-18 | 2017-06-13 | 清华大学 | A kind of method that crystalloid carbon is extracted from metal smelt waste residue and electronic waste burning waste |
| CN109136993A (en) * | 2018-09-25 | 2019-01-04 | 兰州中铝工业服务有限公司 | A kind of post-processing approach for the regeneration ice crystal that wet-treating electrolytic aluminium carbon slag obtains |
| CN109161930A (en) * | 2018-11-15 | 2019-01-08 | 洛阳豫港龙泉铝业有限公司 | A kind of separating technology of aluminium electrolyzing carbon slag and electrolyte |
| CN111893515A (en) * | 2020-08-04 | 2020-11-06 | 郑州经纬科技实业有限公司 | Heat treatment method for aluminum electrolysis carbon slag |
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| CN107604383A (en) * | 2017-09-08 | 2018-01-19 | 高毅 | A kind of method of electrolyte in smelting process extraction carbon slag |
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| CN109136993A (en) * | 2018-09-25 | 2019-01-04 | 兰州中铝工业服务有限公司 | A kind of post-processing approach for the regeneration ice crystal that wet-treating electrolytic aluminium carbon slag obtains |
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| CN111893515B (en) * | 2020-08-04 | 2021-07-27 | 郑州经纬科技实业有限公司 | Heat treatment method for aluminum electrolysis carbon slag |
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| CN103949459B (en) | 2016-01-27 |
| CN103726074B (en) | 2015-07-22 |
| CN103949459A (en) | 2014-07-30 |
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