CN112538557A - System and method for harmless and resource treatment of aluminum industry waste cathode carbon blocks - Google Patents
System and method for harmless and resource treatment of aluminum industry waste cathode carbon blocks Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 153
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 131
- 239000002699 waste material Substances 0.000 title claims abstract description 85
- 238000000034 method Methods 0.000 title claims abstract description 49
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 44
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000009628 steelmaking Methods 0.000 claims abstract description 81
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 50
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 44
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000003546 flue gas Substances 0.000 claims abstract description 30
- 239000002912 waste gas Substances 0.000 claims abstract description 29
- 229910052742 iron Inorganic materials 0.000 claims abstract description 25
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 23
- 239000010959 steel Substances 0.000 claims abstract description 23
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims abstract description 22
- 238000012216 screening Methods 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 16
- 239000002802 bituminous coal Substances 0.000 claims abstract description 14
- 239000010436 fluorite Substances 0.000 claims abstract description 14
- 238000004064 recycling Methods 0.000 claims abstract description 13
- 238000005453 pelletization Methods 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 239000008188 pellet Substances 0.000 claims abstract description 7
- 239000000428 dust Substances 0.000 claims description 82
- 239000007789 gas Substances 0.000 claims description 66
- 238000000746 purification Methods 0.000 claims description 26
- 238000007599 discharging Methods 0.000 claims description 25
- 239000000779 smoke Substances 0.000 claims description 24
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 19
- 238000003860 storage Methods 0.000 claims description 19
- 238000005406 washing Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
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- 239000011230 binding agent Substances 0.000 claims description 8
- 239000003034 coal gas Substances 0.000 claims description 8
- 235000019738 Limestone Nutrition 0.000 claims description 7
- 239000010459 dolomite Substances 0.000 claims description 7
- 229910000514 dolomite Inorganic materials 0.000 claims description 7
- 239000006028 limestone Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 claims description 3
- 239000007844 bleaching agent Substances 0.000 claims description 3
- 230000008569 process Effects 0.000 abstract description 13
- 239000002245 particle Substances 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000011161 development Methods 0.000 abstract description 2
- 238000009851 ferrous metallurgy Methods 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 239000002893 slag Substances 0.000 description 22
- 238000002844 melting Methods 0.000 description 21
- 230000008018 melting Effects 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 18
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 17
- 230000002829 reductive effect Effects 0.000 description 15
- 239000003792 electrolyte Substances 0.000 description 10
- 238000003723 Smelting Methods 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 8
- 229910001634 calcium fluoride Inorganic materials 0.000 description 8
- 150000002825 nitriles Chemical class 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 235000011941 Tilia x europaea Nutrition 0.000 description 7
- 239000010439 graphite Substances 0.000 description 7
- 229910002804 graphite Inorganic materials 0.000 description 7
- 239000004571 lime Substances 0.000 description 7
- 230000001590 oxidative effect Effects 0.000 description 7
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 6
- 239000011575 calcium Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
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- -1 thermal action Chemical compound 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminium flouride Chemical compound F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 4
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 229910001424 calcium ion Inorganic materials 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 4
- 229910052593 corundum Inorganic materials 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 150000002222 fluorine compounds Chemical class 0.000 description 4
- 238000005087 graphitization Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 4
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 description 3
- 239000003830 anthracite Substances 0.000 description 3
- 229910052918 calcium silicate Inorganic materials 0.000 description 3
- 239000000378 calcium silicate Substances 0.000 description 3
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 3
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 3
- 239000000571 coke Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000005188 flotation Methods 0.000 description 3
- 150000004673 fluoride salts Chemical class 0.000 description 3
- 239000002920 hazardous waste Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000010985 leather Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 238000004061 bleaching Methods 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 229910001567 cementite Inorganic materials 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 229910001610 cryolite Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 231100001261 hazardous Toxicity 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 229910001425 magnesium ion Inorganic materials 0.000 description 2
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- 238000012986 modification Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- MNWBNISUBARLIT-UHFFFAOYSA-N sodium cyanide Chemical compound [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
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- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910001021 Ferroalloy Inorganic materials 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- 239000004368 Modified starch Substances 0.000 description 1
- 208000001132 Osteoporosis Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
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- 230000002776 aggregation Effects 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 210000000078 claw Anatomy 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000008396 flotation agent Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 238000003895 groundwater pollution Methods 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
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- 230000036632 reaction speed Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011833 salt mixture Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000009270 solid waste treatment Methods 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
- C21C7/0025—Adding carbon material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/20—Agglomeration, binding or encapsulation of solid waste
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C5/00—Manufacture of carbon-steel, e.g. plain mild steel, medium carbon steel or cast steel or stainless steel
- C21C5/28—Manufacture of steel in the converter
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C5/00—Manufacture of carbon-steel, e.g. plain mild steel, medium carbon steel or cast steel or stainless steel
- C21C5/28—Manufacture of steel in the converter
- C21C5/36—Processes yielding slags of special composition
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
- C21C7/005—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00 using exothermic reaction compositions
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a system and a method for harmless and recycling treatment of aluminum industry waste cathode carbon blocks, which are used for treating the waste cathode carbon blocks and relate to the technical field of harmless and recycling treatment of the aluminum industry waste cathode carbon blocks, and the system comprises a crushing and screening unit, a mixing and ball making unit, a feeding unit, a steelmaking unit, a first waste gas treatment unit and a second waste gas treatment unit; the method comprises the steps of crushing and screening waste cathode carbon blocks, briquetting and pelletizing the waste cathode carbon powder within a small particle size range, replacing fluorite, iron oxide pellets, iron ore and bituminous coal in steelmaking auxiliary materials with the briquetting and pelletizing or the waste cathode carbon blocks within a large particle size range to carry out converter steelmaking production, and treating generated flue gas; the invention combines the characteristics of ferrous metallurgy process and the inherent characteristics of the waste cathode carbon block, realizes the safe, environment-friendly, economic and efficient comprehensive utilization of the waste cathode carbon block, eliminates the difficult problem to be solved urgently in the electrolytic aluminum industry, and promotes the win-win and synergistic high-quality development of two large plates in the domestic and foreign steel and aluminum industries.
Description
Technical Field
The invention relates to the technical field of harmless and recycling treatment of aluminum industry waste cathode carbon blocks, in particular to a system and a method for harmless and recycling treatment of aluminum industry waste cathode carbon blocks.
Background
The electrolytic aluminum cathode carbon block is prepared by using calcined coal, asphalt, petroleum coke and crushed graphite as main raw materials through the processes of kneading, agglomeration, roasting and the like, wherein according to the graphitization treatment temperature and the amount of contained graphite, the electrolytic aluminum cathode carbon block comprises semi-graphite carbon blocks and full-graphite carbon blocks, and in the aluminum electrolysis stage, the graphitization degree of the cathode carbon block is further improved through the processes of thermodynamics, crystallography and the like, and the crystal structure of the carbon is basically microcrystalline graphite with the crystal grain size of nano-grade to micron-grade.
The waste cathode carbon block for electrolyzing aluminum is a waste cathode conductive material dismantled in an industrial aluminum electrolysis cell. The cathode carbon block of the industrial aluminum electrolysis cell is directly contacted with the cryolite-alumina-fluoride salt mixture electrolyte melted at high temperature, and the electrolyte and the cathode carbon block are subjected to infiltration or generation of NaF and Na, such as thermal action, mechanical erosion action, molten salt reaction caused by electrolyte infiltration, electrochemical reaction and the like in the electrolysis process3AlF6And KF, LiF and the like, and meanwhile, the conductivity of the cathode carbon block is deteriorated, the body is damaged, and even the problem that the aluminum liquid in the electrolytic cell leaks from the crack opening occurs, so that the electrolytic cell is forced to stop for overhaul and the cathode carbon block is updated. The cathode carbon block of the common aluminum industry electrolytic cell needs to be replaced after being used for 3 to 5 years.
In the 2016 edition of the national records of hazardous wastes, the waste cathode carbon blocks are recorded as toxic hazardous wastes of HW48-321 series T class. The national latest standard GB5058.3-2007 Standard for identification of hazardous waste- -identification of Leaching toxicity requires fluoride (in the form of F)-Meter)<100mg/L of cyanide (as CN)-Meter)<5 mg/L. The leaching solution F of the waste cathode carbon block is common-The concentration can reach 3000-6000 mg/L and exceeds the national standard limit value; the standard for controlling the storage and pollution of dangerous wastes stipulates that the stacking time of the solid dangerous wastes cannot exceedOne year. CN of different processes in each enterprise-The monitored values differ greatly. The waste cathode carbon blocks are improperly stockpiled and disposed, which can cause the following harm to the environment, the ecological system and the organisms:
1. impact on groundwater: the waste cathode carbon blocks are influenced by rain or humid environment in the stacking process, and the existing soluble fluoride can be migrated to cause groundwater pollution.
2. Impact on the atmosphere: the surface of the waste cathode carbon block stored in the open air is pulverized in the environment of wind and sunshine, and the dust is easily raised and the atmosphere is polluted by adding the powder originally contained.
3. Impact on soil: if the waste cathode carbon blocks are improperly piled up, not only a large amount of land is occupied, but also soluble salts contained in the waste cathode carbon blocks can be slowly accumulated in the soil to cause soil salinization.
4. Adverse effects on ecosystem and living beings: soluble fluoride salts contained in the waste cathode carbon blocks disturb the normal physiological activities of plants. Over a certain dose can result in plant mutation or massive death, and excessive absorption by humans and animals can lead to reduced calcium in the bones, osteoporosis and osteopetrosis.
The electrolytic aluminum yield in China is kept first in the world for 19 years since 2001, the electrolytic aluminum yield reaches more than 3000 ten thousand tons per year at present, about 72-120 ten thousand tons of waste cathode carbon blocks are generated each year, the electrolytic aluminum industry develops rapidly, the problem of environmental pollution caused by the waste cathode carbon blocks is also highly concerned by the nation, the industry and the society, and the harmless recycling treatment of the aluminum industry hazardous wastes becomes one of the major problems to be solved urgently in the electrolytic aluminum industry.
Two aspects of work are mainly carried out on the disposal of the waste cathode carbon block in the industry, wherein the first is the conversion from soluble fluoride to insoluble fluoride to realize harmlessness; secondly, valuable substances such as high-quality carbon, fluoride salt and the like are separated and extracted for utilization, and recycling is realized. The current state of the art is mainly as follows:
1. a flotation method. The method is a way for treating the waste cathode carbon blocks by a wet method to realize harmlessness and recycling. The method is that the waste cathode carbon block is ground into powder, and the powder is mixed with water and flotation agent uniformlyAdding the mixture into a flotation tank, and performing repeated flotation to obtain the carbonaceous material and the electrolyte. The method comprises the following specific steps: the method comprises the steps of crushing and grinding waste cathode carbon blocks, grading materials, adding a solution containing a collecting agent into powder obtained by grading, enabling carbonaceous materials and electrolytes to be separated maximally, filtering to obtain filtrate and a solid phase, and further separating the solid phase to obtain two products mainly comprising the carbonaceous materials and the electrolytes. The carbonaceous material can be used for manufacturing a new cathode and can also be used for manufacturing a carbon electrode, and the electrolyte product can be continuously used as the electrolyte of the aluminum electrolytic cell. However, a large amount of fluorine-containing wastewater is generated in the method, secondary pollution is caused, the corrosivity of electrolyte in the waste cathode carbon blocks can corrode equipment, and SiO in the recovered electrolyte2The higher the effect of recycling.
2. Sulfuric acid acidolysis method. The method is another way for treating the waste cathode carbon blocks by a wet method to realize harmlessness and recycling, the method comprises the steps of crushing the waste cathode carbon blocks, putting the crushed waste cathode carbon blocks into a device filled with water and concentrated sulfuric acid for acidolysis, repeatedly leaching gas generated in the process by distilled water, and thus achieving the purpose of recovering hydrofluoric acid, wherein filter residues generated in the method can be used for producing graphite powder and industrial alumina.
3. And producing an anode protection ring by using the waste cathode carbon block. The waste cathode carbon blocks are crushed to be used as raw materials, the modified starch is used as a binder, the raw materials are uniformly mixed to form a protective material, the protective material is directly tamped and installed on an anode steel claw through a die, and finally, a quite firm protective ring can be formed by self-combustion.
4. A fire-process harmless technology adopts a graphitization furnace to directly charge waste cathode carbon blocks into the furnace, the waste cathode carbon blocks are roasted at a temperature lower than graphitization temperature but higher than the boiling point of salts to remove impurities from graphite, the salts enter furnace dust and are absorbed and precipitated by calcium-containing liquid such as lime water, the graphite after impurity removal can be used as a material for carbon enterprises, and the precipitated fluoride salt can be used as a raw material or a metallurgical flux of fluorine-containing product enterprises. The process still produces some salt-containing wastewater, but the amount is significantly reduced compared to wet treatment.
Through years of experimental research and full practical exploration by related experts at home and abroad, the treatment technology of the waste cathode carbon blocks is greatly improved, and the method for treating and utilizing the solid waste in the aluminum industry in the industry is mainly used for realizing resource recycling while being harmless, so that the method still has the following problems: the fire method or the wet method for treating the waste cathode carbon block needs a special and qualified solid waste treatment factory, and an aluminum industry unit needs to pay high treatment cost (800-.
Disclosure of Invention
In view of the above, the invention provides a system and a method for harmless and resource treatment of waste cathode carbon blocks in aluminum industry, which combine the characteristics of ferrous metallurgy process and the inherent characteristics of the waste cathode carbon blocks, realize the safe, environment-friendly, economic and efficient comprehensive utilization of the waste cathode carbon blocks, eliminate the difficult problems to be solved urgently in the electrolytic aluminum industry, and promote the win-win and synergistic high-quality development of two large plates in iron and steel and aluminum industry at home and abroad.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a system for harmless and resource treatment of aluminum industry waste cathode carbon blocks comprises a crushing and screening unit, a mixing and ball making unit, a feeding unit, a steelmaking unit, a first waste gas treatment unit and a second waste gas treatment unit;
the crushing and screening unit comprises a crusher and a double-layer vibrating screen arranged at a discharge port of the crusher;
the mixing and ball-making unit comprises a mixer, a ball press and a dryer, wherein a feed inlet of the mixer is arranged corresponding to a discharge outlet at the lower side of the double-layer vibrating screen, a discharge outlet of the mixer is arranged corresponding to a feed inlet of the ball press, and a discharge outlet of the ball press is arranged corresponding to a feed inlet of the dryer;
the feeding unit comprises a feeding bin, and a feeding port of the feeding bin corresponds to the positions of a discharge port at the upper side of the double-layer vibrating screen machine and a discharge port of the dryer;
the steelmaking unit comprises a steelmaking converter, and a feeding port of the steelmaking converter and a discharging port of the feeding bin are correspondingly arranged.
Carbon blocks or briquetted balls with the granularity range of 3mm-65mm are put into the steelmaking converter through a crushing and screening unit, under the action of high-temperature and strong oxidizing atmosphere at the temperature of more than 1500 ℃ in the steelmaking converter, carbon in the carbon blocks or briquetted balls with the granularity range of 3mm-65mm is fully combusted, heat is released, the temperature compensation effect is exerted, and the carbon blocks or briquetted balls can be used as a heating temperature compensation agent to replace expensive high-quality coke or anthracite;
the condition that lime is not easy to melt frequently occurs due to higher melting point of the lime in the smelting process, the chemical reaction speed and degree are influenced, fluoride in carbon blocks or briquetted balls with the granularity range of 3mm-65mm is firstly dissociated into ions in high-temperature liquid steel slag, and free fluoride ions react with calcium ions and magnesium ions to form calcium fluoride, magnesium fluoride and 3CaO. CaF with low melting point2.2SiO2And insoluble substances are added, so that the melting of lime is accelerated, the fluidity of slag is improved, the melting temperature and viscosity of the slag are reduced, particularly, fluoride ions and alkali metals in a molten state have the function of breaking silicon-oxygen tetrahedral chemical bonds of calcium silicate and silicon oxide, the melting effect of the slag is further promoted, the metallurgical reaction is promoted, the smelting time is reduced, the using amount of iron oxide leather balls, iron ore and other traditional slag melting agents is reduced, the steelmaking cost is reduced, and the related chemical reaction formula is as follows:
Na3AlF6→AlF3+3NaF；2NaF+(O2-)→Na2O+2F-；
2AlF3+3O2-→Al2O3+6F-；2AlF3+2NaF+4O2-→Na2O+Al2O3+8F-；
(2F-)+(2CaO·SiO2)+(CaO)→(3CaO·CaF2·2SiO2)；
most cyanides in carbon blocks or balls manufactured by pressing blocks with the particle size range of 3mm-65mm are decomposed and oxidized and destroyed under the conditions of high steel-making temperature and strong oxidizing atmosphere, the decomposition temperature of the cyanides is about 300 ℃, the cyanides can be completely decomposed at about 700 ℃, the temperature of steel smelting is more than 1500 ℃, the cyanides can be thoroughly decomposed and oxidized at the high temperature to realize harmless treatment, and the related chemical reaction formula is as follows:
3Fe(CN)2→Fe3C+2(CN)2↑+N2↑；2(NaCN)+5(FeO)→5Fe+2CO2↑+N2↑+Na2O；
2(KCN)+5(FeO)→5Fe+2CO2↑+N2↑+K2O；(CN)2+O2→CO2+NO↑；
2NO+O2→2NO2↑；NO2+H2O→HNO3+NO↑；
generation of NO2Enters the smoke outlet of the steelmaking converter 501 in a gas state, and finally NO is generated2With CaO particles and H in steelmaking dust2The O contact generates chemical reaction to generate Ca (NO)3)2Thereby avoiding the generation of HNO3Corrosion of equipment facilities;
other oxides such as alumina in carbon blocks or balls manufactured by pressing with the granularity ranging from 3mm to 65mm can also form composite oxides such as calcium aluminate and the like, can reduce the melting temperature and viscosity of the slag, and is beneficial to improving the phosphorus capacity of the slag.
Furthermore, the first waste gas treatment unit comprises a wet dust collector and a coal gas storage cabinet, an air inlet of the wet dust collector is arranged corresponding to an exhaust port of the steelmaking converter, and an air outlet of the wet dust collector is connected with an air inlet of the coal gas storage cabinet.
The flue gas discharged from the smoke outlet of the steel converter 501 is introduced into the wet dust collector 601 in the first waste gas treatment unit 600 for washing, and the flue gas discharged from the smoke outlet of the steel converter 501 contains a small amount of fluoride and gaseous NO due to high-temperature volatilization and the like2And trace cyanide, when the flue gas passes through the wet dust collector 601 in the first waste gas treatment unit 600, a small amount of fluoride reacts with CaO to form CaF in the environment of high water content, high alkalinity slurry and strong stirring2Precipitated, gaseous NO2Reacts with CaO to form Ca (NO)3)2ClO generated by dissolving and ionizing trace cyanide by bleaching powder-And oxidative conversion to CO2And N2. The chemical reaction involved therein is as follows:
2F-+Ca2+＝CaF2；2CN-+2OH-+5ClO-＝N2(g)+5Cl-+H2O+2CO3 2-；
through the process, the harmless treatment and resource utilization of the waste cathode carbon blocks in the steelmaking converter are realized.
Furthermore, the second waste gas treatment unit comprises a second bag-type dust collector, a gas purification processor and a smoke exhaust pipe, wherein the negative pressure of a gas inlet of the second bag-type dust collector is arranged above a furnace opening of the steelmaking converter, a gas outlet of the second bag-type dust collector and a gas inlet of the gas purification processor are connected, and a gas outlet of the gas purification processor and the smoke exhaust pipe are connected.
Further, the gas inlet of the gas purification processor is connected with the gas outlet of the wet dust collector.
Further, the feeding unit further comprises a first bag-type dust collector, and the negative pressure of the first bag-type dust collector is arranged at an air outlet of the feeding bin.
The technical scheme of the application also provides a method for harmless and resource treatment of the aluminum industry waste cathode carbon blocks, which comprises the following steps:
1) crushing and screening, namely conveying the waste cathode carbon blocks to a crushing and screening unit for crushing and screening to obtain carbon powder with the granularity range of 0-3mm and carbon blocks with the granularity range of 3-65 mm;
2) briquetting and pelletizing, namely conveying the 0mm-3mm carbon powder obtained in the step 1), limestone, dolomite and a binder to a mixing and pelletizing unit for briquetting and pelletizing, wherein the weight range ratio of the carbon powder, the limestone, the dolomite and the binder is 70-80: 15-10: 15-10: 2-4;
3) storing and utilizing, namely sending the carbon blocks of 3mm-65mm obtained in the step 1) and the balls pressed in the step 2) to a feeding bin in a feeding unit for storage, and adding the carbon blocks of 3mm-65mm or the balls pressed in the step to a steelmaking converter in a steelmaking unit instead of fluorite, iron oxide balls, iron ore and bituminous coal in steelmaking auxiliary materials;
4) waste gas washing, wherein flue gas discharged from a smoke outlet of a steelmaking converter in a steelmaking unit is introduced into a wet dust collector in a first waste gas treatment unit for washing; detecting the concentration of cyanide in leachate of the waste cathode carbon block, and when the concentration of the cyanide is more than 5mg/L, adding 4-6g of bleaching powder into circulating washing water according to the concentration of the cyanide per 1mg/L and per 1kg of carbon dust in flue gas;
5) recovering coal gas, and detecting CO and O in the gas washed by the wet dust collector on line2When the content of CO is higher than 20% and O2When the content is lower than 1.6%, the gas is qualified, the qualified gas is guided into a gas storage cabinet for storage, and the unqualified gas is guided into a gas purification processor for purification and then is discharged through a smoke discharge pipe;
6) and (3) discharging waste gas, namely introducing the flue gas scattered and escaped near the feed inlet of the steelmaking converter into a second bag-type dust remover for dust removal, introducing the flue gas subjected to dust removal by the second bag-type dust remover into a gas purification treater for purification, and then discharging the purified flue gas through a smoke discharge pipe.
Further, the diameter of the balls pressed and manufactured by the step 2) ranges from 25mm to 50 mm.
Further, introducing dust gas in an air outlet of the feeding bin in the feeding unit in the step 3) into the first bag-type dust remover for dust removal and then discharging.
Further, the temperature of the steel-making converter in the step 3) is controlled to be more than 1500 ℃.
Further, in the step 3), 3mm-65mm carbon blocks or briquetted balls are added into a steelmaking converter in a steelmaking unit instead of fluorite, iron oxide balls, iron ore and bituminous coal in steelmaking auxiliary materials, wherein when the 3mm-65mm carbon blocks are used for replacing fluorite, iron oxide balls, iron ore and bituminous coal, the adding amount of the carbon blocks is 5-10kg for every 1 ton of steel produced; when the briquetted pellets are used in place of fluorite, iron oxide pellets, iron ore and bituminous coal, the amount of the briquetted pellets added is in the range of 8 to 15kg per 1 ton of steel produced.
Based on the above explanation, compared with the prior art, the invention has the beneficial effects that:
1. realizes the low-cost harmless disposal of the waste cathode carbon block. The waste cathode carbon block is toxic and dangerous waste generated in non-ferrous metal metallurgy, contains a certain amount of fluoride and a trace amount of cyanide, and is prepared by the methodCaF, which can convert fluoride into calcium fluoride and magnesium fluoride and 3CaO with low melting point2.2SiO2Insoluble substances are beneficial to realizing harmless resource utilization; cyanide can be thoroughly decomposed and oxidized under the conditions of high temperature and strong oxidizing atmosphere in steel making, thereby realizing the harmless treatment of the waste cathode carbon block.
2. Realizes the resource utilization of the waste cathode carbon blocks and reduces the steel-making cost. By implementing the method, the resource utilization of the waste cathode carbon blocks is realized in the converter steelmaking process;
(1) the carbon in the waste cathode carbon block plays a role of temperature compensation and can be used as a heating temperature compensator to replace expensive high-quality coke or anthracite;
(2) fluoride in the waste cathode carbon blocks can partially replace fluorite, iron oxide balls, iron ore and bituminous coal, iron oxide leather balls and iron ore to promote slagging. The fluoride can form calcium fluoride, magnesium fluoride and 3CaO.CaF with low melting point2.2SiO2Insoluble substances accelerate the melting of lime, improve the fluidity of slag, and reduce the melting temperature and viscosity of the slag, particularly, fluoride ions and alkali metals in a molten state have the function of breaking silicon-oxygen tetrahedral chemical bonds of calcium silicate and silicon oxide, so that the melting function of the slag is promoted, the metallurgical reaction is promoted, the smelting time is reduced, the consumption of traditional slag melting agents such as iron oxide skin balls and iron ore is reduced, and the steelmaking cost is reduced;
(3) other oxides such as alumina also form composite oxides such as calcium aluminate and the like, can reduce the melting temperature and viscosity of the slag, and is beneficial to improving the phosphorus capacity of the slag and the like.
Drawings
FIG. 1 is a system connection diagram of the present invention;
FIG. 2 is a schematic diagram of the system apparatus connection according to the present invention.
Detailed Description
In order to make the technical solutions of the present invention better understood, those skilled in the art will now make further detailed descriptions of the present invention with reference to the accompanying drawings.
Referring to fig. 1 and 2, a system for harmless and recycling treatment of aluminum industry waste cathode carbon blocks comprises a crushing and screening unit 200, a mixing and ball-making unit 300, a feeding unit 400, a steel-making unit 500, a first waste gas treatment unit 600 and a second waste gas treatment unit 700;
the crushing and screening unit 200 comprises a crusher 201 and a double-layer vibrating screen 202 arranged at the discharge port of the crusher 201, wherein the crusher can use an impact crusher, a gyratory crusher or a cone crusher, and is preferably a gyratory crusher;
the mixing and ball-making unit 300 comprises a mixer 301, a ball press 302 and a dryer 303, wherein a feeding port of the mixer 301 and a lower discharging port of the double-layer vibrating screen 202 are correspondingly arranged, screen holes of a lower screen plate of the double-layer vibrating screen 202 are 3mm, screen holes of an upper screen plate are 65mm, the diameter of a material discharged from the lower discharging port is not more than 3mm, the diameter of the material discharged from the upper discharging port is not more than 65mm, a discharging port of the mixer 301 and a feeding port of the ball press 302 are correspondingly arranged, and a discharging port of the ball press 302 and a feeding port of the dryer 303 are correspondingly arranged;
the feeding unit 400 comprises a feeding bin 401, and a feeding port of the feeding bin 401 corresponds to the positions of a discharging port at the upper side of the double-layer vibrating screen 202 and a discharging port of the dryer 303;
the steelmaking unit 500 comprises a steelmaking converter 501, a feeding port of the steelmaking converter 501 and a discharging port of the charging bin 401 are correspondingly arranged, the steelmaking unit 500 utilizes the converter to make steel, takes molten iron, scrap steel and ferroalloy as main raw materials, does not need external energy, and completes the steelmaking process in the steelmaking converter by means of the physical heat of molten iron and the heat generated by the chemical reaction between molten iron components, and is a conventional steelmaking operation;
carbon blocks or briquetted balls with the granularity range of 3mm-65mm, which are made of the waste cathode carbon blocks 100, are put into the steelmaking converter 501, under the action of high-temperature and strong oxidizing atmosphere at the temperature of more than 1500 ℃ in the steelmaking converter 501, the carbon in the carbon blocks or briquetted balls with the granularity range of 3mm-65mm is fully combusted, the heat is released, the temperature compensation effect is exerted, and the carbon blocks or briquetted balls can be used as a heating temperature compensation agent to replace expensive high-quality coke or anthracite;
in the smelting process, due to the higher melting point of lime, the lime is not easy to meltUnder the condition of influencing the speed and the degree of chemical reaction, fluoride in carbon blocks or briquetted balls with the granularity ranging from 3mm to 65mm is firstly dissociated into ions in high-temperature liquid steel slag, and free fluoride ions react with calcium ions and magnesium ions to form calcium fluoride and magnesium fluoride and 3CaO. CaF with a low melting point2.2SiO2And insoluble substances are added, so that the melting of lime is accelerated, the fluidity of slag is improved, the melting temperature and viscosity of the slag are reduced, particularly, fluoride ions and alkali metals in a molten state have the function of breaking silicon-oxygen tetrahedral chemical bonds of calcium silicate and silicon oxide, the melting effect of the slag is further promoted, the metallurgical reaction is promoted, the smelting time is reduced, the using amount of iron oxide leather balls, iron ore and other traditional slag melting agents is reduced, the steelmaking cost is reduced, and the related chemical reaction formula is as follows:
Na3AlF6→AlF3+3NaF；2NaF+(O2-)→Na2O+2F-；
2AlF3+3O2-→Al2O3+6F-；2AlF3+2NaF+4O2-→Na2O+Al2O3+8F-；
(2F-)+(2CaO·SiO2)+(CaO)→(3CaO·CaF2·2SiO2)；
most cyanides in carbon blocks or balls manufactured by pressing blocks with the particle size range of 3mm-65mm are decomposed and oxidized and destroyed under the conditions of high steel-making temperature and strong oxidizing atmosphere, the decomposition temperature of the cyanides is about 300 ℃, the cyanides can be completely decomposed at about 700 ℃, the temperature of steel smelting is more than 1500 ℃, the cyanides can be thoroughly decomposed and oxidized at the high temperature to realize harmless treatment, and the related chemical reaction formula is as follows:
3Fe(CN)2→Fe3C+2(CN)2↑+N2↑；2(NaCN)+5(FeO)→5Fe+2CO2↑+N2↑+Na2O；
2(KCN)+5(FeO)→5Fe+2CO2↑+N2↑+K2O；(CN)2+O2→CO2+NO↑；
2NO+O2→2NO2↑；NO2+H2O→HNO3+NO↑；
generation of NO2Enters the smoke outlet of the steelmaking converter 501 in a gas state, and finally NO is generated2With CaO particles and H in steelmaking dust2The O contact generates chemical reaction to generate Ca (NO)3)2Thereby avoiding the generation of HNO3Corrosion of equipment facilities;
other oxides such as alumina in carbon blocks or balls manufactured by pressing with the granularity ranging from 3mm to 65mm can also form composite oxides such as calcium aluminate and the like, can reduce the melting temperature and viscosity of the slag, and is beneficial to improving the phosphorus capacity of the slag.
Referring to fig. 2, in the system, the first waste gas treatment unit 600 includes a wet dust collector 601 and a gas storage 602, an air inlet of the wet dust collector 601 is arranged corresponding to an air outlet of the steelmaking converter 501, and an air outlet of the wet dust collector 601 is connected to an air inlet of the gas storage 602.
The flue gas discharged from the smoke outlet of the steel converter 501 is introduced into the wet dust collector 601 in the first waste gas treatment unit 600 for washing, and the flue gas discharged from the smoke outlet of the steel converter 501 contains a small amount of fluoride and gaseous NO due to high-temperature volatilization and the like2And trace cyanide, when the flue gas passes through the wet dust collector 601 in the first waste gas treatment unit 600, a small amount of fluoride reacts with CaO to form CaF in the environment of high water content, high alkalinity slurry and strong stirring2Precipitated, gaseous NO2Reacts with CaO to form Ca (NO)3)2ClO generated by dissolving and ionizing trace cyanide by bleaching powder-And oxidative conversion to CO2And N2. The harmless treatment of the waste cathode carbon blocks in the steelmaking converter is realized through the processes, wherein the related chemical reaction formula is as follows:
2F-+Ca2+＝CaF2；2CN-+2OH-+5ClO-＝N2(g)+5Cl-+H2O+2CO3 2-；
referring to fig. 2, in the system, the second waste gas treatment unit 700 includes a second bag-type dust collector 701, a gas purification treatment device 702 and a smoke exhaust pipe 703, a negative pressure at a gas inlet of the second bag-type dust collector 701 is arranged above a furnace opening of the steel-making converter 501, a gas outlet of the second bag-type dust collector 701 and a gas inlet of the gas purification treatment device 702 are connected, a gas outlet of the gas purification treatment device 702 and the smoke exhaust pipe 703 are connected, and a gas inlet of the gas purification treatment device 702 and a gas outlet of the wet dust collector 601 are connected.
Referring to fig. 2, in the system, the charging unit 400 further includes a first bag-type dust collector 402, the first bag-type dust collector 402 is arranged at the air outlet of the charging bin 401 in a negative pressure manner, and a draught fan is added to realize negative pressure arrangement;
further, devices such as a lifting machine, a conveyor and a feeder and the like which are used for facilitating transportation can be added among the devices according to actual needs in the system.
Referring to fig. 1 and 2, a method for harmless and resource disposal of aluminum industry waste cathode carbon blocks comprises the following steps:
1) crushing and screening, namely conveying the waste cathode carbon blocks 100 to a crushing and screening unit 200 for crushing and screening to obtain carbon powder with the granularity range of 0-3mm and carbon blocks with the granularity range of 3-65 mm;
2) briquetting and pelletizing, namely conveying the carbon powder with the granularity range of 0mm-3mm, limestone, dolomite and a binder obtained in the step 1) to a mixing and pelletizing unit 300 for briquetting and pelletizing, wherein the weight range ratio of the carbon powder, the limestone, the dolomite and the binder is 70-80: 15-10: 15-10: 2-4; the diameter range of the balls manufactured by pressing is 25mm-50 mm;
3) storing and utilizing, namely, conveying the carbon blocks with the granularity range of 3mm-65mm obtained in the step 1) and the balls pressed in the step 2) to a feeding bin 401 in a feeding unit 400 for storage, introducing dust gas in an air outlet of the feeding bin 401 in the feeding unit 400 into a first bag-type dust collector 402 for dust removal and then discharging, so that dust removal of the feeding bin 401 is realized, and the safety of workers is protected; carbon blocks or briquetted balls with the granularity range of 3mm-65mm are added into the steelmaking converter 501 in the steelmaking unit 500 instead of fluorite, iron oxide balls, iron ore and bituminous coal in steelmaking auxiliary materials, and the temperature of the steelmaking converter 501 is controlled to be more than 1500 ℃, wherein when the carbon blocks with the granularity range of 3mm-65mm are used for replacing fluorite, iron oxide balls, iron ore and bituminous coal, the adding amount of the carbon blocks is 5-10kg for producing 1 ton of steel, and when the briquetted balls are used for replacing the fluorite, the iron oxide balls, the iron ore and the bituminous coal, the adding amount of the carbon blocks or briquetted balls is 8-15kg for producing 1 ton of steel;
4) waste gas washing, wherein flue gas discharged from a smoke outlet of a steelmaking converter 501 in a steelmaking unit 500 is introduced into a wet dust collector 601 in a first waste gas treatment unit 600 for washing, the cyanide concentration of the leachate of the waste cathode carbon blocks is detected, and when the cyanide concentration is more than 5mg/L, 4-6g of bleaching powder is added into circulating washing water according to the cyanide concentration of 1mg/L per 1kg of carbon dust powder in the flue gas per 1mg/L of cyanide concentration;
5) gas recovery, on-line detection of CO and O in the gas washed by the wet dust collector 6012When the content of CO is higher than 20% and O2When the content is lower than 1.6%, the gas is qualified, the qualified gas is guided into a gas storage cabinet for storage, and the unqualified gas is guided into a gas purification processor 702 for purification and then is discharged through a smoke discharge pipe 703;
6) and (3) discharging waste gas, namely introducing the flue gas scattered from the vicinity of the feed inlet of the steelmaking converter 501 into a second bag-type dust collector 701 for dust removal, introducing the flue gas subjected to dust removal by the second bag-type dust collector 701 into a gas purification processor 702 for purification, and then discharging the purified flue gas through a smoke discharge pipe 703.
The present invention will be described in further detail with reference to practical production examples.
In this example, the waste cathode carbon blocks generated by electrolytic aluminum of the Gansu Dongxing aluminum industry Co., Ltd were treated, and the harmless treatment and resource utilization of the waste cathode carbon blocks were carried out by using 120t steel-making converter of carbon steel sheet plant of the Gansu wine steel group Hongxing iron and steel Co., Ltd. The specific implementation steps are as follows:
1) crushing and screening the waste cathode carbon blocks, namely crushing the waste cathode carbon blocks 100 by using a crusher 201, conveying the crushed waste cathode carbon blocks 100 into a double-layer vibrating screen 202 for screening to obtain carbon blocks with the granularity range of 0-3mm and the granularity range of 3-65 mm and carbon powder with the granularity range of more than 65mm, and carbon powder with the granularity range of more than 65mmAnd putting the carbon powder into the crusher 201 again for crushing to finally obtain carbon powder with the granularity range of 0-3mm and carbon blocks with the granularity range of 3-65 mm. F recorded according to national standard GB5058.3-2007 identification standard requirement for leaching toxicity of hazardous waste-≤100mg/L，CN-Less than or equal to 5mg/L, and F in the waste cathode carbon block is obtained by determination-Leaching concentration of 3550mg/l, CN-The leaching concentration is 0.022mg/l, so that the main hazardous substance of the Dongxing aluminum industry waste cathode carbon block is soluble villiaumite, and the content of cyanide is low.
2) Briquetting and pelletizing, namely pressing the carbon powder with the granularity range of 0mm-3mm obtained in the step 1) and limestone: the weight range ratio of the dolomite to the external binder is 75: 13: 13: 4, adding the mixture into a mixer 301, putting the material mixed by the mixer 301 into a ball press 302, pressing the material into balls with the diameter of 40mm, and then drying the balls by a dryer 303.
3) Storing and utilizing, namely feeding the balls pressed in the step 2) and the carbon powder with the granularity range of 0mm-3mm obtained in the step 1) into a feeding bin 401 for storage and standby, introducing dust gas in an air outlet of the feeding bin 401 into a first bag-type dust collector 402 for dust collection and then discharging, conveying dust in the first bag-type dust collector 402 to a cement plant, and adding the balls pressed in the step 2) into a molten pool in a 120t steelmaking converter 501 instead of fluorite, iron oxide balls, iron ore and bituminous coal in steelmaking auxiliary materials according to the ratio of adding 10kg of balls into 1 ton of steel produced.
4) And (2) waste gas washing, wherein flue gas discharged from a smoke outlet of the steelmaking converter 501 is introduced into the wet dust collector 601 for washing, dust and mud generated by washing are concentrated and filtered to realize dehydration, a filter cake can be sintered and then reused as an iron material, and the dehydrated water can be recycled as washing water in the wet dust collector 601.
5) Gas recovery, on-line detection of CO and O in the gas washed by the wet dust collector 6012Content, measured CO content 23%, O2The content of (A) is 1.5%, and simultaneously the content of CO which meets the coal gas recovery standard is higher than 20%, and O2If the content of the coal gas is less than 1.6 percent, the qualified coal gas is guided into a coal gas storage cabinet for storage.
6) The method comprises the steps of discharging waste gas, wherein in the smelting process, the furnace mouth of the steelmaking converter 501 is in positive pressure, a small amount of flue gas overflows in a scattered mode, a draught fan is used for introducing the flue gas overflowing from the position near the feeding hole of the steelmaking converter 501 into the second bag-type dust collector 701 for dust removal, the flue gas dedusted by the second bag-type dust collector 701 is introduced into the gas purification processor 702 for purification, then the flue gas is discharged through the smoke exhaust pipe 703, and dust in the second bag-type dust collector 701 is conveyed to a cement plant.
The leached fluorides (as F) were measured on the slag in the steelmaking converter 501 and the metallurgical dust sludge cake in the wet precipitator 601 according to the measurement method in GB/T15555.11-1995 ion-selective electrode method for measuring fluorides of solid wastes-Measured) concentration, fluoride (as F) was measured for the flue gas in the flue gas exhaust pipe 703 in accordance with the measuring method in HJ/T67-2001 "ion selective electrode method for measuring fluoride in exhaust gas from atmospheric stationary pollution Source-Meter) concentration.
To obtain leached fluorides (as F) of the slag in the steelmaking converter 501-Calculated) concentration of 33.50mg/L, leached fluoride (in F) of metallurgical dust mud filter cake-Measured) the concentration is 35.50mg/L and is lower than the limit value of 100mg/L specified in GB 5058.3-2007; to obtain leached fluorides (as F) of the flue gas in the smoke exhaust pipe 703-Calculated) concentration of 1.91mg/m3Below the concentration limit of 11mg/m, as specified in GB16297-1996 Integrated emission Standard for atmospheric pollutants3Thereby realizing the low-cost harmless disposal of the waste cathode carbon block.
According to statistics, when 1kg of waste cathode carbon blocks are used in the steelmaking converter 501, the consumption of waste steel can be increased by 2.5kg, and the consumption of molten iron can be reduced by 2 kg; under the condition of not increasing the charging amount of the steel scrap of the steel-making converter 501, the temperature can be compensated by 4 ℃ when 1kg of carbon blocks are used, the steel-making cost is reduced, and the resource utilization of the waste cathode carbon blocks is realized.
The above is only a preferred embodiment of the present invention, and it should be noted that the above preferred embodiment should not be considered as limiting the present invention, and the protection scope of the present invention should be subject to the scope defined by the claims. It will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the spirit and scope of the invention, and these modifications and adaptations should be considered within the scope of the invention.
Claims (10)
1. A system for harmless and resource treatment of aluminum industry waste cathode carbon blocks is characterized by comprising a crushing and screening unit (200), a mixing and ball making unit (300), a feeding unit (400), a steelmaking unit (500), a first waste gas treatment unit (600) and a second waste gas treatment unit (700);
the crushing and screening unit (200) comprises a crusher (201) and a double-layer vibrating screen (202) arranged at a discharge hole of the crusher (201);
the mixing and ball-making unit (300) comprises a mixer (301), a ball pressing machine (302) and a dryer (303), wherein a feeding port of the mixer (301) is correspondingly arranged with a discharging port at the lower side of the double-layer vibrating screen (202), a discharging port of the mixer (301) is correspondingly arranged with a feeding port of the ball pressing machine (302), and a discharging port of the ball pressing machine (302) is correspondingly arranged with a feeding port of the dryer (303);
the feeding unit (400) comprises a feeding bin (401), and a feeding port of the feeding bin (401) corresponds to the positions of a discharging port on the upper side of the double-layer vibrating screen machine (202) and a discharging port of the dryer (303);
the steelmaking unit (500) comprises a steelmaking converter (501), and a feeding port of the steelmaking converter (501) and a discharging port of the charging bin (401) are correspondingly arranged.
2. The system for harmless and resource disposal of the aluminum industry waste cathode carbon blocks as claimed in claim 1, wherein the first waste gas treatment unit (600) comprises a wet dust collector (601) and a gas storage cabinet (602), an air inlet of the wet dust collector (601) is arranged corresponding to an air outlet of the steelmaking converter (501), and an air outlet of the wet dust collector (601) is connected with an air inlet of the gas storage cabinet (602).
3. The system for harmless and resource treatment of the aluminum industry waste cathode carbon blocks as claimed in claim 2, wherein the second waste gas treatment unit (700) comprises a second bag-type dust collector (701), a gas purification treatment device (702) and a smoke exhaust pipe (703), the negative pressure at the gas inlet of the second bag-type dust collector (701) is arranged above the furnace opening of the steelmaking converter (501), the gas outlet of the second bag-type dust collector (701) is connected with the gas inlet of the gas purification treatment device (702), and the gas outlet of the gas purification treatment device (702) is connected with the smoke exhaust pipe (703).
4. The system for the harmless and recycling treatment of the aluminum industry waste cathode carbon block as claimed in claim 3, wherein the gas inlet of the gas purification treater (702) is connected with the gas outlet of the wet dust collector (601).
5. The system for harmless and resource disposal of aluminum industry waste cathode carbon blocks as claimed in claim 1, wherein the charging unit (400) further comprises a first bag-type dust collector (402), and the first bag-type dust collector (402) is arranged at the air outlet of the charging bin (401) under negative pressure.
6. A method for harmless and resource treatment of aluminum industry waste cathode carbon blocks is characterized by comprising the following steps:
1) crushing and screening, namely conveying the waste cathode carbon blocks (100) to a crushing and screening unit (200) for crushing and screening to obtain carbon powder with the granularity range of 0-3mm and carbon blocks with the granularity range of 3-65 mm;
2) briquetting and pelletizing, namely conveying the 0mm-3mm carbon powder obtained in the step 1), limestone, dolomite and a binder to a mixing and pelletizing unit (300) for briquetting and pelletizing, wherein the weight range ratio of the carbon powder, the limestone, the dolomite and the binder is 70-80: 15-10: 15-10: 2-4;
3) storing and utilizing, namely feeding the carbon blocks of 3mm-65mm obtained in the step 1) and the balls pressed in the step 2) into a charging bin (401) in a charging unit (400) for storage, and adding the carbon blocks of 3mm-65mm or the balls pressed in the step to a steelmaking converter (501) in a steelmaking unit (500) instead of fluorite, iron oxide balls, iron ore and bituminous coal in steelmaking auxiliary materials;
4) waste gas washing, wherein flue gas discharged from a smoke outlet of a steelmaking converter (501) in a steelmaking unit (500) is introduced into a wet dust collector (601) in a first waste gas treatment unit (600) for washing, the cyanide concentration of leachate of waste cathode carbon blocks is detected, and when the cyanide concentration is more than 5mg/L, 4-6g of bleaching powder is added into circulating washing water according to the cyanide concentration of 1mg/L per 1kg of carbon dust in the flue gas per 1mg/L of cyanide concentration;
5) recovering coal gas, and detecting CO and O in the gas washed by the wet dust collector (601) on line2When the content of CO is higher than 20% and O2When the content is lower than 1.6%, the gas is qualified, the qualified gas is guided into a gas storage cabinet for storage, and the unqualified gas is guided into a gas purification processor (702) for purification and then is discharged through a smoke discharge pipe (703);
6) and (3) discharging waste gas, namely introducing the flue gas scattered from the vicinity of the feed inlet of the steelmaking converter (501) into a second bag-type dust remover (701) for dust removal, introducing the flue gas subjected to dust removal by the second bag-type dust remover (701) into a gas purification processor (702) for purification, and then discharging the purified flue gas through a smoke discharge pipe (703).
7. The method for the harmless and resource recycling of the aluminum industry waste cathode carbon block as claimed in claim 6, wherein the diameter of the balls manufactured by the pressing in the step 2) is in the range of 25mm-50 mm.
8. The method for harmlessly and resourcefully disposing the waste cathode carbon blocks in the aluminum industry according to claim 6, wherein the dust in the air outlet of the feeding bin (401) in the feeding unit (400) in the step 3) is introduced into the first bag-type dust collector (402) for dust removal and then discharged.
9. The method for the harmless and resource disposal of the aluminum industry waste cathode carbon blocks as claimed in claim 6, wherein the temperature of the steelmaking converter (501) in the step 3) is controlled to be more than 1500 ℃.
10. The method for harmless and resource disposal of the aluminum industry waste cathode carbon blocks as claimed in claim 6, wherein in the step 3), 3mm-65mm carbon blocks or briquetted balls are added into the steelmaking converter (501) in the steelmaking unit (500) instead of fluorite, iron oxide balls, iron ore and bituminous coal in steelmaking auxiliary materials, wherein when the 3mm-65mm carbon blocks are used for replacing the fluorite, the iron oxide balls, the iron ore and the bituminous coal, the addition amount is 5-10kg per 1 ton of produced steel; when the briquetted pellets are used in place of fluorite, iron oxide pellets, iron ore and bituminous coal, the amount of the briquetted pellets added is in the range of 8 to 15kg per 1 ton of steel produced.
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| CN113174463A (en) * | 2021-03-31 | 2021-07-27 | 甘肃酒钢集团宏兴钢铁股份有限公司 | Method for producing high-carbon steel by utilizing cathode carbon blocks in LF ladle furnace resource |
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| CN108558223A (en) * | 2018-06-07 | 2018-09-21 | 沈阳银海再生资源科技有限公司 | Aluminium electroloysis waste lining prepares the method and system of rock wool |
| CN111575430A (en) * | 2020-05-19 | 2020-08-25 | 西安热工研究院有限公司 | Method for treating waste cathode carbon block waste of electrolytic aluminum by using steelmaking converter |
| CN214270947U (en) * | 2020-11-11 | 2021-09-24 | 甘肃酒钢集团宏兴钢铁股份有限公司 | System for harmless, resourceful processing of aluminium industry waste cathode carbon piece |
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| CN108558223A (en) * | 2018-06-07 | 2018-09-21 | 沈阳银海再生资源科技有限公司 | Aluminium electroloysis waste lining prepares the method and system of rock wool |
| CN111575430A (en) * | 2020-05-19 | 2020-08-25 | 西安热工研究院有限公司 | Method for treating waste cathode carbon block waste of electrolytic aluminum by using steelmaking converter |
| CN214270947U (en) * | 2020-11-11 | 2021-09-24 | 甘肃酒钢集团宏兴钢铁股份有限公司 | System for harmless, resourceful processing of aluminium industry waste cathode carbon piece |
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