CN103726074B - 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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- CN103726074B CN103726074B CN201410034660.1A CN201410034660A CN103726074B CN 103726074 B CN103726074 B CN 103726074B CN 201410034660 A CN201410034660 A CN 201410034660A CN 103726074 B CN103726074 B CN 103726074B
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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 ofly recycle aluminum electrolysis waste material production aluminium ionogen and reclaim the method for carbon.
Background technology
The spent potlining block carbon content 60%-80% of current domestic electrolysis of aluminum overhaul groove, because of the fluorine-containing impurity containing 20%-40%, belongs to Hazardous wastes, and its generation increases along with electrolytic aluminum output increases face.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 articles for use and the method such as flotation process Separation and Recovery carbon and impurity.These methods have respective deficiency, and as large in landfill method environmental risk, valuable element does not utilize, as fuel by supporting restriction and valuable element do not utilize, flotation process quality product is defective, and all end can realize lasting scale production.Therefore, develop a kind of method that can effectively utilize the waste materials of electrolysis overhaul groove to produce ionogen recovery carbon to be 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 comprise:
A, pre-treatment: waste and old for electrolysis carbon material is broken, iron filings are removed in magnetic separation;
B, flotation separation: waste and old for the electrolysis after pre-treatment carbon feed separation is obtained underflow product and froth product;
C, preparation: by be separated the underflow product that obtains after filtration, de-carbon, fragmentation obtain target compound aluminium ionogen, be separated the froth product obtained and obtain target compound carbon dust through press filtration, drying;
D, aftertreatment: the flue gas produced in preparation process, waste water are carried out the process of recovery qualified discharge.
The present invention with refuse in need of immediate treatment for raw material, various resource is all recycled, the whole collection and purification process of waste gas, and the aluminium ionogen water ratio produced is low, detrimental impurity content is few, be the desirable feedstock of Aluminium Electrolysis, the carbon dust flotated can be used as 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 present invention process schema.
Embodiment
Below in conjunction with accompanying drawing, the present invention is further illustrated, but limited the present invention never in any form, and any conversion done based on training centre of the present invention or replacement, all belong to protection scope of the present invention.
Recycling aluminum electrolysis waste material production aluminium ionogen of the present invention also reclaims the method for carbon, comprises pre-treatment, flotation separation, preparation, post-processing step, specifically comprises:
A, pre-treatment: waste and old for electrolysis carbon material is broken, iron filings are removed in magnetic separation;
B, flotation separation: waste and old for the electrolysis after pre-treatment carbon feed separation is obtained underflow product and froth product;
C, preparation: by be separated the underflow product that obtains after filtration, de-carbon, fragmentation obtain target compound aluminium ionogen, be separated the froth product obtained and obtain target compound carbon dust through press filtration, drying;
D, aftertreatment: the flue gas produced in preparation process, waste water are carried out the process of recovery qualified discharge.
Described waste materials is aluminum electrolysis waste cathode carbon block and/or electrolytic aluminum breeze.
Particle size after cracking described in step A is 80 ~ 150 orders.
Separation described in step B uses the one in flotation column, flotation machine to be separated.
Described separation uses the reverse-flow flotation column of microvesicle to be separated.
The one be filtered in centrifuging, press filtration filtration described in step C.
De-carbon described in step C uses medium-frequency induction furnace to carry out de-carbon.
The process of flue gas described in D step be adopt secondary spraying absorption tower absorb, then after calcium salt primary treatment and polymer alumina secondary treatment qualified discharge.
The process of waste water described in D step is that one or more adopting in Physical, chemical method or biological process process.
Recycling aluminum electrolysis waste material cathode block of the present invention is produced aluminium ionogen and is reclaimed the method for carbon, that bulk spent potlining block input jaw crusher aluminium cell overhaul produced slightly breaks, the material obtained enters ball mill again, wears into 80 order to 150 object powder.Send after material powder into surge tank, then add salt acid for adjusting pH to 8-9, controlling pulp density by amount of water is 20%.The slip prepared enters microvesicle counter current contact formula flotation column, adds collecting agent in 0.5Kg/ ton ratio, according to depth of foam adjustment pore forming material add-on, controls air supply well according to bubble velocity.Through triple cleaning and once purging selection, the froth product obtained enters pressure filter, after washing, filtration, enter external-heat rotating drum dryer, carry out drying at 400 DEG C after, namely cooling is fixed carbon more than 85%, ash content less than 10, calorific value 7000 blocks/gram more than carbon dust, can be used as sticking with paste at the bottom of aluminium cell or bottom carbon block is produced.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, the slag major ingredient that process produces is CaF
2, can be used as fluorite and use.
Floatation underflow slip enters centrifugal filter and washs, filter, the moisture material of about 10% is obtained after centrifuge dehydration, enter intermediate frequency furnace again, material whole melting when being warming up to about 1000 DEG C, the impurity carbon granules now in material is separated, float up to bath surface, can manually salvage out by carbon slag, cooling after remaining melt takes out, fragmentation be qualified aluminium ionogen.The carbon slag salvaged out returns ball mill flotation again.The fume treatment that intermediate frequency furnace produces is introduced into secondary spraying absorption tower and absorbs, and remaining gas is again by activated alumina absorption tower adsorbs, and expellant gas is qualified discharge after testing.The waste water reclaimed in absorption tower contains fluorine, also enters waste water disposal facility, processes together with froth product wash water.
Present invention process is simple, and environmental benefit is obvious, and use raw material to be refuse in need of immediate treatment, various resource is all recycled, the whole collection and purification process of gas.The aluminium ionogen that the present invention produces is moisture low, and detrimental impurity is few, is the desirable feedstock of Aluminium Electrolysis, and the carbon dust flotated can be used as 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 sorting, fragmentation, and screening, obtains 100 to 150 object powder.Carry out magnetic separation to powder again, eliminate the iron filings that in 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.At the carbon dust that flotation machine overflow port obtains, through washing, become fixed carbon more than 70% after drying, ash content less than 20%, calorific value 6000 block/gram above carbon dust, through forming machine extrusion molding, making electrolytic aluminium anode guard ring after ground kilning roasting.The waste water that flotation, washing and off gas treatment produce all enters waste water disposal facility, processes rear discharge up to standard, and the precipitation that process produces can be made fluorite and use.
Mixture enters intermediate frequency furnace after carrying out drying, 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, about 10% 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 adjusts its controling parameters and part electric elements according to fusing feature, and major advantage controls and heating equilibrium for guaranteeing temperature, better controls furnace temperature, and crucible life is long, stable output power.Fume treatment adopts 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 electrolytic aluminum breeze and produce aluminium ionogen and the method reclaiming carbon, comprise the steps:
Sizing screen is adopted to carry out sorting to electrolysis breeze, by ironworker's tool, domestic refuse and scrap anode charcoal block in breeze separately, enter magnetic separation, floatation system after fragmentation, obtain common carbon dust and contain 90% electrolytical mixture, the iron filings that when magnetic separation is removed broken, equipment and ironworker's tool are brought into.
2, mixture enters intermediate frequency furnace after carrying out drying, 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, about 10% carbon can float over molten surface, and after salvaging, middle layer is industry and can uses ionogen.Intermediate frequency furnace adopts silicon carbide crucible, a graphite rod is set up in the middle part of crucible, and according to fusing feature, its controling parameters and part electric elements are adjusted, major advantage controls and heating equilibrium for guaranteeing temperature, better controls furnace temperature, and crucible life is long, stable output power, temperature of reaction is 1100-1200 DEG C, reaction times is that 18-25 divides, and flue gas adopts water dedusting to reclaim, and recovery waste water and flotation waste water are handled together.
3, the common carbon dust forming machine extrusion molding be separated, makes electrolytic aluminium anode guard ring after ground kilning roasting.
Operate in abovementioned steps except flotation needs flotation reagent without the need to adding other any raw materials.
4, present method adopts equipment to be market common equipment, the short less investment of flow process, and low cost fully recycles electrolysis breeze, and product separation all reaches electrolytic aluminium factory industrial application demand.
Embodiment 1
Raw material electrolysis spent potlining block 100Kg is dropped into jaw crusher and carries out fragmentation, enter ball mill fragmentation again and cross 80 ~ 150 mesh sieves, add diesel oil 2Kg coal floatation GF oil 0.6Kg to enter the reverse-flow flotation column of microvesicle together and be separated 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 controls at 350KW, the carbon removal time is about 8-10 minute, obtain target compound aluminium ionogen 29Kg through hammer crushing, be separated the froth product obtained and obtain target compound carbon dust through press filtration, drying
69.5Kg.The first secondary spraying absorption tower of the flue gas produced in preparation process absorbs, and then through the discharge of activated alumina adsorption tower, waste water is through precipitating recycle and reuse and qualified discharge, and the slag major ingredient that process produces 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 block 100 Kg is dropped into jaw crusher and carries out fragmentation, enter ball mill fragmentation again and cross 80 ~ 150 mesh sieves, add diesel oil 2.1Kg coal floatation GF oil 0.7Kg to enter the reverse-flow flotation column of microvesicle together and be separated 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 controls at 350KW, the carbon removal time is about 8-10 minute, obtain target compound aluminium ionogen 32Kg through hammer crushing, be separated the froth product obtained and obtain target compound carbon dust 66.5Kg through press filtration, drying.The first secondary spraying absorption tower of the flue gas produced in preparation process absorbs, and then through the discharge of activated alumina adsorption tower, waste water is through precipitating recycle and reuse and qualified discharge, and the slag major ingredient that process produces 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 block 100Kg is dropped into jaw crusher and carries out fragmentation, enter ball mill fragmentation again and cross 80 ~ 150 mesh sieves, add diesel oil 2.2Kg coal floatation GF oil 0.8Kg to enter the reverse-flow flotation column of microvesicle together and be separated 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 controls at 350KW, the carbon removal time is about 8-10 minute, obtain target compound aluminium ionogen 31Kg through hammer crushing, be separated the froth product obtained and obtain target compound carbon dust 67.5Kg through press filtration, drying.The first secondary spraying absorption tower of the flue gas produced in preparation process absorbs, and then through the discharge of activated alumina adsorption tower, waste water is through precipitating recycle and reuse and qualified discharge, and the slag major ingredient that process produces 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 carries out fragmentation, enter ball mill fragmentation again and cross 100 ~ 150 mesh sieves, magnetic separation is except scrap iron removing, add diesel oil 2.1Kg coal floatation GF oil 0.7Kg to enter the reverse-flow flotation column of microvesicle together and be separated 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 controls at 350KW, the carbon removal time is about 8-10 minute, obtain target compound aluminium ionogen 63.5Kg through hammer crushing, be separated the froth product obtained and obtain target compound carbon dust 34Kg through press filtration, drying.The first secondary spraying absorption tower of the flue gas produced in preparation process absorbs, and then through the discharge of activated alumina adsorption tower, waste water is through precipitating recycle and reuse and qualified discharge, and the slag major ingredient that process produces 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 carries out fragmentation, enter ball mill fragmentation again and cross 100 ~ 150 mesh sieves, magnetic separation is except scrap iron removing, add diesel oil 2.2Kg coal floatation GF oil 0.8Kg to enter the reverse-flow flotation column of microvesicle together and be separated 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 controls at 350KW, the carbon removal time is about 8-10 minute, obtain target compound aluminium ionogen 61Kg through hammer crushing, be separated the froth product obtained and obtain target compound carbon dust 37.5Kg through press filtration, drying.The first secondary spraying absorption tower of the flue gas produced in preparation process absorbs, and then through the discharge of activated alumina adsorption tower, waste water is through precipitating recycle and reuse and qualified discharge, and the slag major ingredient that process produces 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 carries out fragmentation, enter ball mill fragmentation again and cross 100 ~ 150 mesh sieves, magnetic separation is except scrap iron removing, add diesel oil 2.1Kg coal floatation GF oil 0.7Kg to enter the reverse-flow flotation column of microvesicle together and be separated 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 controls at 350KW, the carbon removal time is about 8-10 minute, obtain target compound aluminium ionogen 58Kg through hammer crushing, be separated the froth product obtained and obtain target compound carbon dust 40Kg through press filtration, drying.The first secondary spraying absorption tower of the flue gas produced in preparation process absorbs, and then through the discharge of activated alumina adsorption tower, waste water is through precipitating recycle and reuse and qualified discharge, and the slag major ingredient that process produces 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 (3)
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: be 80 ~ 150 orders by aluminum electrolysis waste cathode carbon block and/or electrolytic aluminum breeze particle size after cracking, iron filings are removed in magnetic separation;
B, flotation separation: the electrolysis spent potlining block after pre-treatment or electrolytic aluminum breeze are added diesel oil, coal floatation GF oil enters the reverse-flow flotation column of microvesicle together and is separated, obtain underflow product and froth product;
C, preparation: by be separated the underflow product that obtains after filtration, in the intermediate frequency furnace to control at 350KW at power de-carbon 8 ~ 10min, fragmentation obtain target compound aluminium ionogen, be separated the froth product obtained and obtain target compound carbon dust through press filtration, drying; Target compound enters intermediate frequency furnace after carrying out drying, adds a small amount of aluminum metal, in intermediate frequency furnace reduced iron, sila matter; Described intermediate frequency furnace adopts silicon carbide crucible, and in the middle part of crucible, set up a graphite rod, temperature of reaction is 1100 ~ 1200 DEG C, and the reaction times is 18 ~ 25min;
D, aftertreatment: the flue gas produced in preparation process, waste water are carried out the process of recovery qualified discharge, the process of described flue gas adopts secondary spraying absorption tower to absorb, then after calcium salt primary treatment and polymer alumina secondary treatment qualified discharge.
2. recycling aluminum electrolysis waste material production aluminium ionogen according to claim 1 reclaim the method for carbon, it is characterized in that described in step C be filtered into centrifuging, press filtration filter in one.
3. recycling aluminum electrolysis waste material production aluminium ionogen according to claim 1 reclaim the method for carbon, is characterized in that the process of waste water described in D step is that one or more adopting in Physical, chemical method or biological process process.
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| 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 |
| CN201410034660.1A CN103726074B (en) | 2014-01-25 | 2014-01-25 | Method for producing aluminum electrolyte by using aluminum electrolysis waste materials and recycling carbon |
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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 |
| CN105964659B (en) * | 2016-05-27 | 2018-02-23 | 中南大学 | A kind of aluminum cell waste cathode carbon block comprehensive recovering process |
| CN106829912B (en) * | 2017-01-18 | 2019-06-18 | 清华大学 | A method of extracting crystalloid carbon from metal smelt waste residue and electronic waste burning waste |
| CN107604383A (en) * | 2017-09-08 | 2018-01-19 | 高毅 | A kind of method of electrolyte in smelting process extraction carbon slag |
| CN109136993B (en) * | 2018-09-25 | 2020-06-23 | 中国铝业股份有限公司 | Post-treatment method of regenerated cryolite obtained by wet-method treatment of electrolytic aluminum carbon slag |
| 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 |
| 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 |
Citations (3)
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| CN101480658A (en) * | 2008-12-26 | 2009-07-15 | 东北大学 | Method for electrolyzing waste and old cathode carbon block by comprehensive utilization of aluminum |
| CN101829670A (en) * | 2010-04-02 | 2010-09-15 | 北京矿冶研究总院 | Method for recovering carbon from electrolytic aluminum waste cathode carbon block |
| CN102978659A (en) * | 2012-12-04 | 2013-03-20 | 贵州铝城铝业原材料研究发展有限公司 | Deep comprehensive resource utilization method for electrolytic cell overhaul slag |
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| CN1358581A (en) * | 2001-11-20 | 2002-07-17 | 舒大平 | Harmless treatment and comprehensive utilization method for aluminium electrolytic carbon slag and waste cathode material |
| CA2367544A1 (en) * | 2002-01-08 | 2003-07-08 | Boleslaw Ignasiak | Method for spent potliner processing, separating and recycling the products therefrom |
| CN101508568A (en) * | 2009-02-27 | 2009-08-19 | 多氟多化工股份有限公司 | Purification method for electrolytic aluminium containing waste slag of fluorine |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101480658A (en) * | 2008-12-26 | 2009-07-15 | 东北大学 | Method for electrolyzing waste and old cathode carbon block by comprehensive utilization of aluminum |
| CN101829670A (en) * | 2010-04-02 | 2010-09-15 | 北京矿冶研究总院 | Method for recovering carbon from electrolytic aluminum waste cathode carbon block |
| CN102978659A (en) * | 2012-12-04 | 2013-03-20 | 贵州铝城铝业原材料研究发展有限公司 | Deep comprehensive resource utilization method for electrolytic cell overhaul slag |
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