CN107159688B - A kind of aluminium cell carbonaceous materials recycling is made a living the method for producing electricity stone raw material - Google Patents
A kind of aluminium cell carbonaceous materials recycling is made a living the method for producing electricity stone raw material Download PDFInfo
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- CN107159688B CN107159688B CN201710599991.3A CN201710599991A CN107159688B CN 107159688 B CN107159688 B CN 107159688B CN 201710599991 A CN201710599991 A CN 201710599991A CN 107159688 B CN107159688 B CN 107159688B
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- activator
- strong oxdiative
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- aluminium
- living
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- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 168
- 239000004411 aluminium Substances 0.000 title claims abstract description 157
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 99
- 239000002994 raw material Substances 0.000 title claims abstract description 73
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 238000004064 recycling Methods 0.000 title claims abstract description 41
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 39
- 239000004575 stone Substances 0.000 title claims abstract description 29
- 230000005611 electricity Effects 0.000 title claims abstract description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 181
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 122
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 107
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 93
- 239000005997 Calcium carbide Substances 0.000 claims abstract description 85
- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 claims abstract description 85
- 239000002699 waste material Substances 0.000 claims abstract description 79
- 238000000034 method Methods 0.000 claims abstract description 77
- 239000003513 alkali Substances 0.000 claims abstract description 54
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 49
- 238000002386 leaching Methods 0.000 claims abstract description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 41
- 235000011121 sodium hydroxide Nutrition 0.000 claims abstract description 36
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 33
- 239000000292 calcium oxide Substances 0.000 claims abstract description 28
- 235000012255 calcium oxide Nutrition 0.000 claims abstract description 28
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 27
- 239000007787 solid Substances 0.000 claims abstract description 25
- 230000003647 oxidation Effects 0.000 claims abstract description 24
- 239000002893 slag Substances 0.000 claims abstract description 24
- 239000011230 binding agent Substances 0.000 claims abstract description 18
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 16
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 16
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 238000011084 recovery Methods 0.000 claims abstract description 15
- 230000003213 activating effect Effects 0.000 claims abstract description 12
- 238000005096 rolling process Methods 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 239000012190 activator Substances 0.000 claims description 103
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims description 30
- 239000008187 granular material Substances 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 25
- 230000008569 process Effects 0.000 claims description 24
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 23
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 23
- 239000004571 lime Substances 0.000 claims description 23
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 20
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 18
- 239000011575 calcium Substances 0.000 claims description 17
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 17
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 16
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 16
- 229910052791 calcium Inorganic materials 0.000 claims description 16
- 229910052744 lithium Inorganic materials 0.000 claims description 16
- UMPKMCDVBZFQOK-UHFFFAOYSA-N potassium;iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[K+].[Fe+3] UMPKMCDVBZFQOK-UHFFFAOYSA-N 0.000 claims description 16
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 claims description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 13
- 230000004913 activation Effects 0.000 claims description 13
- 238000001784 detoxification Methods 0.000 claims description 13
- JHWIEAWILPSRMU-UHFFFAOYSA-N 2-methyl-3-pyrimidin-4-ylpropanoic acid Chemical compound OC(=O)C(C)CC1=CC=NC=N1 JHWIEAWILPSRMU-UHFFFAOYSA-N 0.000 claims description 12
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 claims description 12
- 239000011294 coal tar pitch Substances 0.000 claims description 12
- BSUSEPIPTZNHMN-UHFFFAOYSA-L cobalt(2+);diperchlorate Chemical compound [Co+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O BSUSEPIPTZNHMN-UHFFFAOYSA-L 0.000 claims description 12
- -1 dichromic acid acid anhydride Chemical class 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical group [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- 230000008859 change Effects 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 239000011236 particulate material Substances 0.000 claims description 9
- 239000010426 asphalt Substances 0.000 claims description 8
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 claims description 8
- 229940037003 alum Drugs 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 239000003208 petroleum Substances 0.000 claims description 7
- 239000011347 resin Substances 0.000 claims description 7
- 229920005989 resin Polymers 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
- VJPDDQWBXCUEKU-UHFFFAOYSA-L [Co].[Cr](=O)(=O)(O)O[Cr](=O)(=O)O Chemical compound [Co].[Cr](=O)(=O)(O)O[Cr](=O)(=O)O VJPDDQWBXCUEKU-UHFFFAOYSA-L 0.000 claims description 6
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 6
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 6
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 5
- 239000011591 potassium Substances 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical group CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 claims description 4
- WHQOKFZWSDOTQP-UHFFFAOYSA-N 2,3-dihydroxypropyl 4-aminobenzoate Chemical compound NC1=CC=C(C(=O)OCC(O)CO)C=C1 WHQOKFZWSDOTQP-UHFFFAOYSA-N 0.000 claims description 4
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- YALMXYPQBUJUME-UHFFFAOYSA-L calcium chlorate Chemical compound [Ca+2].[O-]Cl(=O)=O.[O-]Cl(=O)=O YALMXYPQBUJUME-UHFFFAOYSA-L 0.000 claims description 4
- RMISVBXFFXBNAD-UHFFFAOYSA-N calcium;oxido-(oxido(dioxo)chromio)oxy-dioxochromium Chemical group [Ca+2].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O RMISVBXFFXBNAD-UHFFFAOYSA-N 0.000 claims description 4
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims description 4
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 claims description 4
- 239000012286 potassium permanganate Substances 0.000 claims description 4
- 239000012047 saturated solution Substances 0.000 claims description 4
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical group [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 claims description 4
- JOSWYUNQBRPBDN-UHFFFAOYSA-P ammonium dichromate Chemical compound [NH4+].[NH4+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O JOSWYUNQBRPBDN-UHFFFAOYSA-P 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- 239000003595 mist Substances 0.000 claims description 3
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 claims description 3
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004155 Chlorine dioxide Substances 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005864 Sulphur Substances 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 235000019398 chlorine dioxide Nutrition 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- FGRVOLIFQGXPCT-UHFFFAOYSA-L dipotassium;dioxido-oxo-sulfanylidene-$l^{6}-sulfane Chemical compound [K+].[K+].[O-]S([O-])(=O)=S FGRVOLIFQGXPCT-UHFFFAOYSA-L 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 235000014413 iron hydroxide Nutrition 0.000 claims description 2
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 claims description 2
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 claims description 2
- ALTWGIIQPLQAAM-UHFFFAOYSA-N metavanadate Chemical compound [O-][V](=O)=O ALTWGIIQPLQAAM-UHFFFAOYSA-N 0.000 claims 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 239000010941 cobalt Substances 0.000 claims 1
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- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims 1
- BDRTVPCFKSUHCJ-UHFFFAOYSA-N molecular hydrogen;potassium Chemical compound [K].[H][H] BDRTVPCFKSUHCJ-UHFFFAOYSA-N 0.000 claims 1
- 229910052938 sodium sulfate Inorganic materials 0.000 claims 1
- PMZURENOXWZQFD-UHFFFAOYSA-L sodium sulphate Substances [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims 1
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- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000012272 crop production Methods 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005008 domestic process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 230000000505 pernicious effect Effects 0.000 description 1
- 239000011295 pitch Substances 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 231100000241 scar Toxicity 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- MNWBNISUBARLIT-UHFFFAOYSA-N sodium cyanide Chemical compound [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical group [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- RYYWUUFWQRZTIU-UHFFFAOYSA-K thiophosphate Chemical compound [O-]P([O-])([O-])=S RYYWUUFWQRZTIU-UHFFFAOYSA-K 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- DCXPBOFGQPCWJY-UHFFFAOYSA-N trisodium;iron(3+);hexacyanide Chemical compound [Na+].[Na+].[Na+].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCXPBOFGQPCWJY-UHFFFAOYSA-N 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- WQEVDHBJGNOKKO-UHFFFAOYSA-K vanadic acid Chemical compound O[V](O)(O)=O WQEVDHBJGNOKKO-UHFFFAOYSA-K 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- 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
- B09B5/00—Operations not covered by a single other subclass or by a single other group in this subclass
Landscapes
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
A kind of aluminium cell carbonaceous materials recycling is made a living the method for producing electricity stone raw material, includes the following steps: that aluminium cell carbonaceous waste material is crushed by (1)；(2) it is placed in leaching pond, stirring leaching device or spreading mixing leaching device, water is first added, add caustic soda or its solution, quick lime and Strong oxdiative activating agent, Oxidation Leaching, it is separated by filtration, obtains aluminium lye and solid filter residue, solid filter residue is through washing, it is dry, obtain the activated carbon slag containing carbon and calcirm-fluoride；(3) it is placed in the mixed machine of rolling, hydrocarbon class binder is added, or be additionally added quick lime, roll over mixed, molding, calcium carbide raw material must be produced.The carbon content of production calcium carbide raw material obtained by the method for the present invention is high, and impurity content is low, and aluminium, the removing rate of recovery of alkali are high；Gained production calcium carbide is used in calcium carbide production with raw material, output increased, the average current drain decline of ton calcium carbide, calcium carbide gas production improves, and cyanide-free detects；The method of the present invention is safe and simple, treating capacity is big, energy consumption, at low cost.
Description
Technical field
The present invention relates to a kind of methods of aluminium cell carbonaceous materials recycling, and in particular to a kind of aluminium cell carbonaceous waste material
The method for being regenerated as production calcium carbide raw material.
Background technique
Currently, the development of the electrolytic aluminium yield in China and the world is swift and violent.According to statistics, until in by the end of December, 2016, China's electrolytic aluminium
Aluminium smelter enterprise be completed production capacity up to 4369.8 ten thousand tons, run production capacity up to 3673.9 ten thousand tons.With the increasing of electrolytic aluminium yield
Add, the solid waste generated in electrolytic process, such as waste cathode carbon block, scrap anode carbon granule, useless refractory brick, useless insulating brick, useless guarantor
The yield of warm clinker also increases sharply, wherein the useless cathode that only China's aluminum electrolysis industry generates every year is up to 250,000 tons, in recent years still
There is more than 400 ten thousand tons of accumulative volume of cargo in storage to fill without suitable area, and the waste cathode carbon block actual amount of whole world stockpiling has reached ten million
Ton.
Aluminium cell carbonaceous waste material includes the waste cathode carbon block generated during electrolytic aluminium and scrap anode carbon granule etc., predominantly
Waste cathode carbon block.The main component of waste cathode of aluminum electrolytic cell carbon block is C, also contains Na3AlF6、CaF2、NaF、AlF3、α-Al2O3
Deng, wherein carbon content be 50~70%, electrolyte fluoride be 30~50%, cyanide is about 0.2%.Do not have in aluminium electrolysis process
The main component for participating in the anode carbon granule (also known as anode breeze) of electrolyte in electrolysis and Electolyte-absorptive is with Na3AlF6Based on
Sodium aluminium fluoride, α-Al2O3And C, remaining is electrolyte fluoride, wherein carbon content is 40~60%.
Electrolytic aluminium waste cathode carbon block belongs to the high artificial material of degree of graphitization, it is well known that electrolytic aluminium cathode is to forge
Anthracite, metallurgical coke, graphite of burning etc. are aggregate, and coal tar pitch etc. is made of binder shaping and roasting, are used for charcoal containing aluminium cell
The block class of matter liner or paste class carbon product have that hardness is big, coefficient of friction is small, no for graphitization or graphite-like carbon materials
The characteristics of easily broken, extremely difficult combustion (relative to fire coal).The electrolysis temperature of modern large-scale aluminium electrolysis pre-baking tank 950~970 DEG C it
Between, the electrolyte such as every production 1 ton of aluminium consumption about 50kg ice crystal, aluminum fluoride, magnesium fluoride, due to heat effect, chemical action, machinery
The reaction of fused salt caused by erosion effect, infiltration of electro ultrafiltration, sodium and electrolyte etc. chemically reacts, the cathode charcoal in aluminium cell
Using after a certain period of time can be damaged, generally 4~7 Nian Houxu's block of operation carry out large repairs, the mainly waste cathode carbon block that removes,
Waste refractory materials, useless thermal insulation material etc., while a certain amount of anode carbon granule is also generated in electrolytic process.
The processing technique of scrap anode carbon granule lesser for quantity, current research is concentrated mainly on is returned using floatation process
It receives charcoal and electrolyte and collecting agent is added after adding water to size mixing in scrap anode carbon granule grinding to certain particle size, keep charcoal abundant with electrolyte
Separation, so that obtaining take electrolyte as the two kinds of products advocated peace based on charcoal.Electrolyte therein can back within aluminium electroloysis
In slot, powdered carbon can be used for the raw material of Soderberg Anode In Aluminium Electrolysis Cells production anode mix, but processing cost is high and secondary pollution is big.
For waste cathode of aluminum electrolytic cell carbon block, at present both at home and abroad the technical method of processing waste cathode carbon block up to tens of kinds it
It is more, it may be summarized to be wet process, high temperature hydro-thermal method, superhigh temperature partition method, burning partition method, fuel process and safe landfill method etc..
(1) wet process: for the main direction of studying of current internal lining of aluminium electrolytic bath, basic working procedure is grinding, water logging/alkali leaching/acid
It washes, flotation, separation, drying etc..The external representative use aquation method released for M.M.Williams handles waste cathode carbon
Block (isolated thick carbon granule and fine grain electrolyte), and Lun Sihuofen aluminium manufacturer, Austria and Li Sita aluminium manufacturer, U.S. alkali
The molten leaching electrolyte therein of liquid (leachate is used for synthetic cryolite, and charcoal is used as the fuel of high temperature furnace collocation).Chalco stock
Part Co., Ltd, Beijing Mine and Metallurgy General Inst, Central South University etc. have also carried out a large amount of research and practice, as Lu Huimin et al. is used
Floatation recycles charcoal and electrolyte, obtains the powder of certain particle size after waste cathode carbon block is broken, classification, is added after adding water to size mixing
Collecting agent, to realize that carbon is separated with the maximum of electrolyte, so that obtaining take electrolyte as two kinds to advocate peace based on charcoal
Product.Electrolyte therein can back in aluminium cell, and graphited powdered carbon can return to cathode production system.But
It is that the toner value that method for wet separation obtains at present is not high, and resource utilization efficiency is low, and the processing power consumption such as grinding is high, place
Manage at high cost, and there are serious secondary pollutions.
(2) high temperature hydro-thermal method separation method: most representative to be used for J.E.Dentschman and J.S.Lobos etc.
1200 DEG C or more of hot water Hydrolyze method handles waste cathode carbon block, and the hydrogen fluoride for making fluoride react generation concentration 25% with steam is molten
Liquid, then aluminum fluoride is produced with synthetic method, and collect the fluorine ion in solution with gypsum.But this method investment is big, energy consumption is high,
Processing cost is high, and difficulty is administered in secondary pollution.
(3) superhigh temperature separation method: external representative " AUMSET " technique for the exploitation of Alcoa company, in powder
Flux, the blended stocks such as lime is added in broken waste lining carbon block to be heat-treated at 1300 DEG C of temperature in AUS-MELT furnace,
So that lime etc. is reacted with the electrolyte in waste cathode carbon block, obtain calcirm-fluoride, sodium fluoride and aluminum fluoride, recycles high-temperature flue gas
Middle HF gas generates aluminum fluoride, and fluorine is made to obtain solidifying to re-use, and final products are glassy state slag, and the charcoal of recycling is used again
In manufacture cathode material.The technique has carried out industrial application, handles waste lining year up to 12000t, but invests big, processing energy consumption
Height, processing cost are too high.It is domestic also to have research more, as CN105642649A discloses a kind of high-temperature treatment of electrolytic aluminium waste cathode
Method is that electrolytic aluminium waste cathode carbon block is crushed to 3~15mm, then, is roasted in 2600~2800 DEG C of superhigh temperature vacuum electric furnaces
Burning processing, volatilizing fluoride therein, decomposing cyanide therein is nitride, by the way of high-temperature flue gas is absorbed using water mist
Absorption handle using filtering drying etc., obtain can reuse fluoride, superhigh temperature roast after cathode carbon materials through being cooled to
Reach 97% carbon materials for fixed carbon content.But this method is significantly present of following problem: first is that electrolytic aluminium waste cathode carbon is broken
Toxic dust and toxic gas containing cyanide are generated in broken screening process；Second is that its is actual to 2600~2800 DEG C for electric heating
Power consumption is very high, maintains the power consumption of vacuum suction higher, the requirement of equipment and cost are also very high；Third is that 2600~2800 DEG C volatilization
Requirement of the fluoride gas using water mist absorption to equipment is too high, because 1200 DEG C of water vapour can be calcirm-fluoride etc. to be fluorinated
Object is converted into the hydrogen fluoride of the strong corrosive of severe toxicity；Fourth is that the carbon materials for being also easy to produce serious secondary pollution, and recycling
In still contain 3% or more fluoride, recycling can shorten overhaul life and uneconomical.CN106269787A discloses one kind
For disposing the high temperature continous way processing method of electrolytic aluminium waste cathode, teaches and a kind of be crushed to electrolytic aluminium waste cathode carbon block not
The compound particles of 3~100mm are made with kneadings such as pitches for particle greater than 3mm, then, compound particles are placed in superelevation
In warm vacuum electric furnace, the continous way calcination process in not less than 2000 DEG C (2300~2600 DEG C) superhigh temperature vacuum electric furnaces is obtained high
Warm electro-forge flue gas and electrolytic aluminium waste cathode carbon granules, then high temperature electro-forge flue gas is subjected to second-time burning, completely burned volatile matter flue gas
In carbon dust, carbon powder and ice crystal, decomposing cyanide therein is nitride, after cooling, dedusting, desulphurization denitration, obtains reuse
Fluoride and fixed carbon content reach 95% carbon materials.But this method is significantly present of following problem: first is that electrolytic aluminium waste is negative
Toxic dust and toxic gas containing cyanide are generated during the carbon crushing and screening of pole；Second is that electric heating to 2000~2600 DEG C its
Actual power consumption is very high, maintains the power consumption of vacuum suction higher, the requirement of equipment and cost are also very high；Third is that after second-time burning
Gas cleaning investment is high, is also easy to produce serious secondary pollution；Fourth is that still containing in the carbon of 2000~2600 DEG C of electric furnace calcination processing
A large amount of fluoride, because of 2497 DEG C of boils up till of calcirm-fluoride or more, fluorine-containing carbon materials recycling can shorten overhaul time
Limit and it is uneconomical.
(3) burn separation method: being using professional incinerator and fluid bed furnace technique etc., because of electrolytic aluminium waste cathode carbon difference
In fire coal, though calorific value is generally up to 4000~5500kcal/kg, activation energy needed for oxidation reaction is high, need to reach 1500 DEG C of height
It is warm could the efficient oxidation burning, therefore heating time is long, energy consumption is high and difficult needed for combustion method there are separating process cumbersome, after-flame
The problem of effectively to recycle wherein fluoride, and secondary pollution issue handling difficulty is also big.
(4) fuel process: because the main component of electrolytic aluminium waste cathode carbon block is charcoal, and the theoretical combustion heat of completely burned is typically up to
4000kcal/kg or more, high is equivalent to common anthracitic calorific value up to 5500kcal/kg, so, domestic and international a large amount of skill
Art worker has carried out unremitting effort, and effect pole is not so good as people's will so far.The domestic method as fuel has China YouSe metal
The identification for the Shandong Aluminum Co., Ltd. factory " recycling of waste cathode of aluminum electrolytic cell carbon block " that Industry Corporation organized on November 16th, 1988
Achievement.Specific method is: " Shandong Aluminum Plant in alumina producing, using waste and old cathode carbon block it is levigate after as desulfurizing agent and substitute
Part anthracite is added in alumina rotary kiln, produces alumina sintering block.Contained fluoride salt is converted in sinter leaching
Insoluble calcirm-fluoride enters red mud, and red mud replaces fluorescent mineralizer when preparing cement for manufacture of cement ingredient." still,
This method grinding energy is high, and the discharge amount of pernicious gas increases in flue gas.For the turning sludge into fuel benefit for further solving waste cathode carbon block
With problem, Shandong branch company, Chinese Aluminium Co., Ltd research institute poplar meeting guest waits the cement producing line in Shandong Aluminum Plant enterprising
It has gone in-depth study practice, the work of cement producing line is applied to the waste cathode carbon block of calorific value 21MJ/kg(5024kcal/kg)
Waste cathode carbon block, is specifically first crushed by industry test, and by the maximum ratio dosage of clinker 5kg waste cathode carbon block per ton, (conversion is
About the 3% or less of coal consumption), together grinding is incorporated in coal mill in grinding coal dust, and conclusion (of pressure testing) is clinker per ton by the useless yin of 5kg
Pole carbon block to clinker quality without visible influences (application study light metal of the waste cathode carbon block such as Yang Huibin in manufacture of cement,
2nd phase in 2008, P59-64.).Yang Huibin etc. is high using cement kiln internal reaction temperature, carbon block residence time on stream
The conditions such as long, make the harmful substance in waste cathode carbon block carry out decomposition displacement in the high temperature environment, and it is ripe to be finally solidificated in cement
In material, while attempt to using the carbon in waste cathode carbon block as the consumption of fuel reduction coal.But still have safety problem,
Additive amount problem and influence problem to production, after all, waste cathode carbon are not coal-fired, in waste cathode carbon block the extremely difficult combustions of charcoal.So
And real defect is not the problem that fluorine is exceeded in the erosion and flue gas of refractory material caused by fluoride, because of calcium aluminum fluoride
The production of cement also ensures that fluorine is not exceeded in the safety and flue gas of refractory material, after all normal cement kiln preheaters system visitor
Have in sight and realizes preheater of the Pyatyi with the exchange trapping of Alkaline high-strength powder；Nor the problem that alkali content is high, because often
Ton clinker consumes coal generally only 0.15~0.18t, and the electrolyte in a small amount of cathode carbon pieces is mainly aluminum fluoride, calcirm-fluoride, fluorine aluminium
Sour sodium, fluoaluminic acid magnesium, sodium fluoride only account on a small quantity, dosage hour it is limited with the total alkali content in cryolite and sodium fluoride, generally
Influence to cement later strength is limited.Therefore, Shandong Aluminum Plant so far still cannot be using cathode charcoal normal use as alternative combustion
The true cause of coal is: first influencing the mill efficiency of coal mill, is second that the graphitic carbon of low activity seriously reduces the whole of coal dust
Volumetric combustion performance, the serious normal combustion efficiency for affecting coal dust, the exothermic carbon that timely and effective cannot burn are fallen into
Clinker entrains into the strong reduction of generation in powder, affects kiln system operating condition, affects clinker quality.Obviously, the prior art is not still
It can be using electrolytic aluminium waste cathode carbon block as effective alternative fuel.
(5) safe landfill method: since existing processing method is there are high energy consumption, high cost and secondary pollution problems, because
This, the problem of environmental pollution of electrolytic aluminium waste cathode carbon block is never effectively solved, and most aluminium electrolytics are caused
Cathode carbon pieces are still thrown aside, and use high-cost safe landfill method at present or mainly.And currently generally use landfill, stockpiling
Method handles electrolytic aluminium solid waste method, can do great harm to the environment, even completely by the harmless of hazardous waste
Lasting contact scar will be generated by changing landfill, and cause vast resources waste.
In addition, electrolytic aluminium solid waste is due to containing a large amount of soluble fluoride and a small amount of cyanide (predominantly
Cymag and the sodium ferricyanide), belong to danger wastes, must be dealt carefully with.And under the conditions of the prior art, electrolytic aluminium factory is universal
Landfill, the stacked arrangement of use handle these solid waste, and contained soluble fluoride and cyanide can pass through wind, day
The effect transfer that shine, drenches with rain is volatized into atmosphere, or be mixed into rivers with rainwater, permeate the ground contaminated soil and underground water, right
Animals and plants and human body generate very big damage, destroy ecological environment, influence Agro-ecology balance, make crop production reduction, and harm will
It is long-term.Processing for cyanide in waste cathode carbon block, processing technique mainly have weak acid dissolution+polysulfide to be converted into sulphur
For the method for cyanate and metal thiophosphate object, manganese ion+ultraviolet catalytic oxidation method, ozone and sodium hypochlorite co-oxidation side
Method, high temperature chlorination processing method, high-temperature oxidation method, biochemical method handle cyanide technology.But at these existing cyanides
It is cumbersome, at high cost to manage technical method, and there are secondary pollutions.CN101811695A discloses a kind of from electrolytic aluminium waste cathode carbon block
The method of middle recycling graphite is that the processes such as acidleach remove fluoride therein again using grinding, water logging, flotation, separates and recovers it
In carbon materials drying to obtain refined graphite powder.But this method process is many and diverse, secondary pollution is big, energy consumption is high, the stone of recycling
Black fine powder impurity content is high.
To sum up, the outstanding problem as aluminum electrolysis industry general character, it is necessary to it is harmless to break through electrolytic aluminium solid waste as early as possible
Change industrialization technology problem.The characteristic of electrolytic aluminium solids waste material how is utilized to implement resource utilization, it is especially safe
, low energy consumption, inexpensive resource utilization be the technical method problem for being worth researching and solving.
Summary of the invention
The technical problem to be solved by the present invention is to overcome drawbacks described above of the existing technology, provide a kind of safety letter
List, treating capacity are big, and low energy consumption, at low cost and without secondary pollution, and the aluminium cell carbonaceous materials recycling of suitable industrialized production is
The method for producing calcium carbide raw material.
The technical solution adopted by the present invention to solve the technical problems is as follows: a kind of aluminium cell carbonaceous materials recycling is made a living
The method for producing electricity stone raw material, includes the following steps:
(1) it pre-processes: aluminium cell carbonaceous waste material is broken for partial size≤20mm bulk granular material；
(2) bulk granular material obtained by step (1) activation carbon and alkali alum recovery: is placed in leaching pond, stirring leaching device
Or in spreading mixing leaching device, water is first added, and add caustic soda or its solution, lime and Strong oxdiative activating agent, Oxidation Leaching,
It being separated by filtration, obtains aluminium lye and solid filter residue, solid filter residue is washed, and it is dry, obtain the activated carbon slag containing carbon and calcirm-fluoride；
(3) carbide raw material is processed: the activated carbon slag containing carbon and fluorite obtained by step (2) being placed in the mixed machine of rolling, is added
Hydrocarbon class binder, or it is additionally added quick lime, the particulate material for mixing, being shaped to 5~18mm is rolled over, calcium carbide raw material must be produced.
Preferably, in step (1), the main component of the aluminium cell carbonaceous waste material is waste cathode carbon block and/or useless sun
Pole carbon granule, wherein inanimate matter content 20~50%, carbon content 50~80%, each component gross mass percentage composition≤100%；Wherein,
In inanimate matter, aluminium content is 1~14%, and alkali content is 5~20%, cyanide content < 2.5%.
Preferably, in step (1), the broken crumbling method is that squash type or impact type are broken.Due to aluminium cell
Carbonaceous waste material has the characteristics that hardness is big, coefficient of friction is small, non-breakable grinding, and the charcoal material in aluminium cell carbonaceous waste material
Material and other ingredients are there is the feature of sharp interface, using energy-efficient squash type or impact type crumbling method by aluminium cell charcoal
Matter waste material is broken for the material that partial size is less than 20mm, and energy consumption is extremely low, and processing capacity is strong.
Preferably, in step (1), while broken, atomized spray be equivalent to aluminium cell carbonaceous waste material quality 0.5~
The detoxification agent solution of more preferable 3~5%) 6.0%(.Through atomized spray detoxification agent solution while broken, while dust suppression
It can penetrate into broken granular material hole crack and clear up the toxicity of cyanide, then is broken by catalytic oxidizer negative pressure extracting
The dust-removing waste gas of system can realize that catalysis oxidation is decomposed to body containing dicyanogen.
Preferably, the detoxicant be ferrate detoxicant, it is bichromate detoxicant, dichromic acid acid anhydride detoxicant, thio
One of sulfate detoxicant, perchlorate detoxicant, hydroxide detoxicant, hypochlorite detoxicant or chlorine dioxide etc.
Or it is several；The ferrate detoxicant is one or more of potassium ferrate, ferrate-lithium or Na2Fe04 etc., described heavy
Chromate detoxicant is one or more of potassium bichromate, sodium dichromate or dichromic acid cobalt etc., the thiosulfate detoxification
Agent is sodium thiosulfate and/or potassium thiosulfate etc., and the perchlorate is lithium perchlorate and/or cobaltous perchlorate etc., the hydrogen
Oxide is one or more of cobalt hydroxide, iron hydroxide or potassium hydroxide etc., the hypochlorite be sodium hypochlorite and/
Or calcium hypochlorite etc..Detoxification agent solution is the solution that the detoxicant is prepared.
It is further preferred that the detoxicant is ZC-XJ1 type detoxification agent solution (i.e. ferrate detoxicant and time chlorine
The saturated solution that hydrochlorate detoxicant is prepared with mass ratio 1:1).
Preferably, the detoxification agent solution is the water dilution that sodium hypochlorite addition is first equivalent to 2 times of its quality, then will be high
Potassium ferrite and potassium hydroxide are dissolved in the saturated solution formed in liquor natrii hypochloritis by the mass ratio of 1:1.
Preferably, in step (2), the dosage of the water is 1~10 times (more preferable 2~8 times) of bulk granular material quality,
The caustic soda or its solution, lime, Strong oxdiative activating agent and bulk granular material mass ratio be 3~30:1~30:0.5~5.0:
More preferable 5~the 20:5 of 100(~20:2.5~4.5:100).The caustic soda of addition can be used for dissolving removing carbonaceous waste material and dissipate shot-like particle
Solid alumina etc. in material；The alkali that the lime of addition can be used in causticization removing solid material, and fluorine is converted by fluoride
Change calcium.The lime is white lime (i.e. Ca (OH)2) and/or quick lime.
Preferably, in step (2), the caustic soda is the alkali recycled in sodium hydroxide or alumina producing or this step
Aluminium lye mentions the alkali recycled after aluminium.The resulting aluminium lye of step (2) can be recycled for mentioning aluminium and concentrated base, and resulting alkali can reuse
In this step.
Preferably, in step (2), the Strong oxdiative activator refers to the netted carbon structure that can destroy or activate graphite, mentions
High carbon materials activity can effectively facilitate the object of charcoal element and calcium oxide respond and energy efficient oxidation cyanide resolution toxicity
Matter is strong for chlorosulfonic acid Strong oxdiative activator, ferrate Strong oxdiative activator, bichromate Strong oxdiative activator, dichromic acid acid anhydride
Oxidation activator, perchlorate Strong oxdiative activator, chlorate Strong oxdiative activator, hypochlorite Strong oxdiative activator, vanadic acid
One or more of salt Strong oxdiative activator or permanganate Strong oxdiative activator etc.；The ferrate Strong oxdiative activator
For one or more of calcium ferrate, potassium ferrate, ferrate-lithium or Na2Fe04 etc., the bichromate Strong oxdiative activation
Agent is one or more of calcium bichromate, potassium bichromate, sodium dichromate, dichromic acid cobalt or ammonium dichromate etc., the perchloric acid
Salt Strong oxdiative activator is one of Calcium perchlorate, cobaltous perchlorate, lithium perchlorate, sodium perchlorate or potassium hyperchlorate etc. or several
Kind, the chlorate Strong oxdiative activator is one or more of calcium chlorate, sodium chlorate or potassium chlorate etc., the hypochlorite
Strong oxdiative activator is sodium hypochlorite and/or calcium hypochlorite etc., and the vanadate Strong oxdiative activator is for sodium metavanadate and/or partially
Lithium vanadate etc., the permanganate Strong oxdiative activator are potassium permanganate and/or acerdol etc..
It is further preferred that the Strong oxdiative activator is ZC-YO7 type Strong oxdiative activator (the i.e. strong oxygen of bichromate
Change activator and hypochlorite Strong oxdiative activator with the mixture of mass ratio 1:1), ZC-YO5 type Strong oxdiative activator it is (i.e. high
Ferrite Strong oxdiative activator and perchlorate Strong oxdiative activator are with the mixture of mass ratio 1:1), ZC-YO8 type Strong oxdiative it is living
Agent (i.e. perchlorate Strong oxdiative activator and permanganate Strong oxdiative activator is with the mixture of mass ratio 1:1), ZC-YO11
(i.e. bichromate Strong oxdiative activator and perchlorate Strong oxdiative activator is with the mixing of mass ratio 1:1 for type Strong oxdiative activator
Object).
Preferably, in step (2), the Strong oxdiative activator is potassium ferrate, sodium dichromate, cobaltous perchlorate, metavanadic acid
The oxidation activator that the ratio of lithium, calcium hypochlorite 3:1:2:1:2 in molar ratio are mixed.
Preferably, in step (2), the temperature of the Oxidation Leaching is room temperature~300 DEG C (more preferable 20~200 DEG C), when
Between be the more preferable 0.5~3.0h of 0.1~8.0h().In oxidative leaching process, by dissolution, displacement, oxidation reaction, it can remove solid
Cured aluminium, alkali in body material, and oxidized activating carbon and oxygenolysis cyanide.
In step (2), when reaction unit is leaching pond, caustic soda or its solution, lime and Strong oxdiative activating agent are added
After stirring into suspension in water, add in leaching pond；It is mixed in stirring after water is added when reaction unit is stirring leaching device
During conjunction, caustic soda or its solution, lime and Strong oxdiative activating agent is added；When reaction unit is spreading mixing leaching device,
After water is added, in rolling mixed process, caustic soda or its solution, lime and Strong oxdiative activating agent is added.
Preferably, in step (2), the drying to moisture content≤5%.
Preferably, in step (2), the water lotion after washing is recyclable as leaching water.
Preferably, in step (3), the matter of the activated carbon slag containing carbon and fluorite and hydrocarbon class binder, quick lime
Measure ratio are as follows: more preferable 100:15~38:50~150 100:5~40:0~160().
Preferably, in step (3), the hydrocarbon class binder be one of selected from coal tar pitch and petroleum asphalt or resin etc. or
It is several.
In step (3), the particulate material of 5~18mm is mixed, is shaped to by rolling over, can further improve the straight of carbon and calcium oxide
Reaction efficiency is connect, to effectively improve the production capacity of furnace of calcium carbide.
Production calcium carbide obtained by the method for the present invention i.e. energy saving flux type carbon raw of raw material or energy saving flux type carbide raw material,
It can be by normal calcium carbide controlling of production process method in calcium carbide production.
The technical thought of the method for the present invention is as follows: the main component for aluminium cell carbonaceous waste material is carbon, fluorine, aluminium, alkali
Four big ingredients, and aluminium metallurgical industry needs aluminium, alkali raw material, the production of Elementary Chemical Industry raw material calcium carbide needs carbon, lime and fluorination
Therefore calcium flux raw material can implement resource utilization to aluminium cell carbonaceous waste material.Due to calcium carbide (CaC2) production it is substantially former
Material is carbon raw (C) and quick lime (CaO), it is generally the case that in order to reduce power consumption, firm molten bath, reduction calcium carbide melt/
Eutectic viscosity obtains the calcium carbide of high yield and high quality to increase mobility or production, and electric furnace is enable to run under high furnace temperature, often needs
With fluorite (CaF2) make molten bath flux, the method for the present invention is by dealuminzation alkali isolation of purified containing the solid group based on carbon and calcirm-fluoride
The carbon raw produced for calcium carbide or energy saving flux type carbon raw are allocated as inherently to aluminium cell carbonaceous waste resource recovery
The breakthrough and innovation of Land use systems.
The technical principle of the method for the present invention is as follows: first aluminium cell carbonaceous waste material is crushed, synchronize impose alkali leaching, lime it is severe
Change and strong oxidizer aoxidizes.Under the conditions of strong oxidizing property, by the Na in carbonaceous waste material3AlF6、AlF3, NaF etc. be converted into CaF2For
It leads and removes solid alkali in solids, by Al2O3Equal aluminum-containing minerals are converted into water-soluble sodium metaaluminate and remove solid in solids
The aluminium of change, aluminium, alkali composition enter in solution, meanwhile, the toxicity of strong oxidizer oxygenolysis cyanide removal material therein, and
To the part graphite in aluminium cell carbonaceous waste material or the carbon materials that tendency is serious and reactivity is poor are graphitized, are implemented strong
Oxidized activating improves carbon materials activity, to obtain activated carbon raw material, by force to destroy or activate the netted carbon structure of graphite
Oxidant finally completely consumes in activation carbon structure；Finally obtain aluminium, lye to be simply separated by filtration, and containing carbon and
The big component of solid filter residue two based on calcirm-fluoride, aluminium lye can be recycled for aluminium producing.
The method of the present invention has the beneficial effect that:
(1) carbon content of production calcium carbide raw material obtained by the method for the present invention is high, and aluminium, alkali impurity content are lower, aluminium, alkali it is de-
Except the rate of recovery is up to 93.7%, 94.6% respectively, a kind of aluminium alkali raw material is developed for aluminium producing, be conducive to resources circulation and drops this increasing
Effect；
(2) production calcium carbide obtained by the method for the present invention is used for calcium carbide by normal calcium carbide controlling of production process method with raw material
In production, under conditions of substituting 25~35% block grain carbon raw, the tune furnace operation with fluorite and secondary lime can be cancelled,
Molten bath is stablized, and is discharged smooth, i.e., calcium carbide eutectic viscosity reduces, and output increased is up to 16.8%, under the average current drain of ton calcium carbide
Drop up to 10.7%, calcium carbide gas production averagely improves up to 8.6%, i.e., the calcium content that is carbonized in calcium carbide increases, and grade improves, and without cyanogen
Compound detection is fluorinated calcium source for a kind of effective alternative carbon raw of calcium carbide production development and molten bath flux, is conducive to electricity
Stone manufacturing enterprise it is energy-saving；
(3) the method for the present invention is safe and simple, treating capacity is big, and low energy consumption, at low cost and without secondary pollution, is suitable for industrialization
Production.
Specific embodiment
Below with reference to embodiment, the invention will be further described.
Raw material or chemical reagent used in the embodiment of the present invention are obtained by routine business approach unless otherwise specified
?.
Embodiment 1
Aluminium cell carbonaceous waste material used in the embodiment of the present invention is derived from the blocky carbonaceous waste material stored up in certain aluminium manufacturer library,
Detect aggregate sample inanimate matter content 32.67%(wherein, aluminium content 2.43%, alkali content 11.98%, cyanide content
0.17%), carbon content 67.16%；Strong oxdiative activator used in the present embodiment is ZC-YO7 type Strong oxdiative activator (i.e. heavy chromium
Hydrochlorate Strong oxdiative activator and hypochlorite Strong oxdiative activator are with the mixture of mass ratio 1:1) it is purchased from Hunan Province's little Yin Wuji
Environmental energy Science and Technology Development Co., Ltd..
(1) it pre-processes: 1t aluminium cell carbonaceous waste material impact type is broken for partial size≤12mm bulk granular material；
(2) activation carbon is with alkali alum recovery: 1t bulk granular material obtained by step (1) is placed in spreading mixing leaching device
In, 4t water is first added, in spreading mixed process, it is strong to add 95kg sodium hydroxide, 127kg calcium hydroxide and 38kgZC-YO7 type
Active oxide, at 20 DEG C, heating leaching 80min is separated by filtration, and obtains aluminium lye and solid filter residue, solid filter residue through washing,
Drying to moisture content is 1%, obtains activated carbon slag of the 992kg containing carbon and calcirm-fluoride；
(3) carbide raw material is processed: 992kg obtained by step (2) is placed in the mixed machine of rolling containing the activated carbon slag of carbon and fluorite,
234kg coal tar pitch is added, rolles over the particulate material for mixing, being shaped to 10mm, calcium carbide raw material must be produced.
Through detecting, the carbon content of production calcium carbide raw material obtained by the present embodiment is 69.63%, and aluminium content 0.31%, alkali contains
Amount be 0.81%, aluminium, alkali the removing rate of recovery be respectively 84.3%, 91.7%.
The graininess production calcium carbide of partial size 10mm obtained by the present embodiment is transferred to press at certain calcium carbide factory's production technology with raw material
Normal calcium carbide controlling of production process method is in calcium carbide production.
It feeds back at factory's production technology: using the graininess production calcium carbide raw material of partial size 10mm with carbometer, replacing
The block grain carbon raw in generation 25% can cancel the tune furnace operation with fluorite and secondary lime, and molten bath stablizes, discharges smooth, that is, be carbonized
Calcium eutectic viscosity reduces, output increased 8.4%, and the average current drain decline 7.9% of ton calcium carbide, calcium carbide gas production averagely improves
6.8%, i.e., the calcium content that is carbonized in calcium carbide increases, and grade improves, and cyanide-free detects.
By aluminium recycle of alkali liquor obtained by the present embodiment step (2) for mentioning aluminium and concentrated base, concentrated base can be back to step (2)；Institute
Water lotion recycling after stating washing is as leaching water.
Embodiment 2
Aluminium cell carbonaceous waste material used in the embodiment of the present invention is derived from the blocky carbonaceous waste material stored up in certain aluminium manufacturer library,
Detect aggregate sample inanimate matter content 30.68%(wherein, aluminium content 2.41%, alkali content 9.87%, cyanide content 0.16%),
Carbon content 69.16%；Strong oxdiative activator used in the present embodiment is potassium ferrate, sodium dichromate, cobaltous perchlorate, metavanadic acid
The oxidation activator that the ratio of lithium, calcium hypochlorite 3:1:2:1:2 in molar ratio are mixed.
(1) it pre-processes: 1t aluminium cell carbonaceous waste material impact type is broken for partial size≤10mm bulk granular material；
(2) activation carbon and alkali alum recovery: 1t bulk granular material obtained by step (1) is placed in stirring leaching device, first
5t water is added, during being stirred, add the sodium hydroxide solution of 117kg mass concentration 40%, 93kg calcium hydroxide and
43kg Strong oxdiative activator, at 70 DEG C, heating leaching 120min is separated by filtration, and obtains aluminium lye and solid filter residue, solid filter residue
It is washed, drying to moisture content is 1.5%, obtains activated carbon slag of the 990.8kg containing carbon and calcirm-fluoride；
(3) carbide raw material is processed: 990.8kg obtained by step (2) is placed in the mixed machine of rolling containing the activated carbon slag of carbon and fluorite
In, 162kg coal tar pitch is added, rolles over the particulate material for mixing, being shaped to 10mm, calcium carbide raw material must be produced.
Through detecting, the carbon content of production calcium carbide raw material obtained by the present embodiment is 72.04%, and aluminium content 0.32%, alkali contains
Amount be 0.71%, aluminium, alkali the removing rate of recovery be respectively 84.6%, 91.7%.
The graininess production calcium carbide of partial size 10mm obtained by the present embodiment is transferred to press at certain calcium carbide factory's production technology with raw material
Normal calcium carbide controlling of production process method is in calcium carbide production.
It feeds back at factory's production technology: using the graininess production calcium carbide raw material of partial size 10mm with carbometer, replacing
The block grain carbon raw in generation 30% can cancel the tune furnace operation with fluorite and secondary lime, and molten bath stablizes, discharges smooth, that is, be carbonized
Calcium eutectic viscosity reduces, output increased 9.3%, and the average current drain decline 8.7% of ton calcium carbide, calcium carbide gas production averagely improves 8%,
The calcium content that is carbonized i.e. in calcium carbide increases, and grade improves, and cyanide-free detects.
By aluminium recycle of alkali liquor obtained by the present embodiment step (2) for mentioning aluminium and concentrated base, concentrated base can be back to step (2)；Institute
Water lotion recycling after stating washing is as leaching water.
Embodiment 3
Aluminium cell carbonaceous waste material used in the embodiment of the present invention is derived from the blocky carbonaceous waste material stored up in certain aluminium manufacturer library,
Detect aggregate sample inanimate matter content 40.59%(wherein, aluminium content 4.93%, alkali content 13.76%, cyanide content
0.14%), carbon content 59.27%；Quick lime used in the present embodiment selects powdered lime (the calcium oxide quality under calcium carbide factory's sieve
91.6%) content is；Strong oxdiative activator used in the present embodiment is that (i.e. ferrate is strong for ZC-YO5 type Strong oxdiative activator
Oxidation activator and perchlorate Strong oxdiative activator are with the mixture of mass ratio 1:1), detoxicant used in the present embodiment is molten
Liquid is ZC-XJ1 type detoxification agent solution (the i.e. saturation prepared with mass ratio 1:1 of ferrate detoxicant and hypochlorite detoxicant
Solution), it is purchased from Hunan Province little Yin Wuji environmental energy Science and Technology Development Co., Ltd..
(1) it pre-processes: 1t aluminium cell carbonaceous waste material impact type is broken for partial size≤5mm bulk granular material；Broken
While broken, the detoxification agent solution of atomized spray 45kg；
(2) activation carbon and alkali alum recovery: 1t bulk granular material obtained by step (1) is placed in stirring leaching device, first
5t water is added, during being stirred, adds 105kg sodium hydroxide, 157kg calcium hydroxide and 28kgZC-YO5 type Strong oxdiative
Activating agent, at 150 DEG C, heating leaching 45min is separated by filtration, and obtains aluminium lye and solid filter residue, and solid filter residue is washed, and is done
It is dry to moisture content be 1.5%, obtain activated carbon slag of the 969kg containing carbon and calcirm-fluoride；
(3) carbide raw material is processed: 969kg obtained by step (2) is placed in the mixed machine of rolling containing the activated carbon slag of carbon and fluorite,
353kg coal tar pitch and 918kg quick lime is added, rolles over the particulate material for mixing, being shaped to 12mm, calcium carbide raw material must be produced.
Through detecting, the carbon content of production calcium carbide raw material obtained by the present embodiment is 40.1%, aluminium content 0.14%, alkali content
Be 0.35%, aluminium, alkali the removing rate of recovery be respectively 93.7%, 94.6%.
The graininess production calcium carbide of partial size 12mm obtained by the present embodiment is transferred to press at certain calcium carbide factory's production technology with raw material
Normal calcium carbide controlling of production process method is in calcium carbide production.
It is fed back at factory's production technology: replacing 35% simultaneously using the graininess production calcium carbide raw material of partial size 12mm
Block grain carbon and quick lime raw material can cancel the tune furnace operation with fluorite and secondary lime, and molten bath stablizes, discharges smooth, that is, be carbonized
Calcium eutectic viscosity reduces, output increased 16.8%, and the average current drain decline 10.7% of ton calcium carbide, calcium carbide gas production averagely improves
8.6%, i.e., the calcium content that is carbonized in calcium carbide increases, and grade improves, and the quick lime that display activated carbon slag fills up enough chemical reaction equivalents is rolled over
Molding particulate material is mixed, carbon can be significantly increased and calcium oxide reaction generates the speed of calcium carbide, and then greatly improve furnace of calcium carbide
Yield, and cyanide-free detect.
By aluminium recycle of alkali liquor obtained by the present embodiment step (2) for mentioning aluminium and concentrated base, concentrated base can be back to step (2)；Institute
Water lotion recycling after stating washing is as leaching water.
Embodiment 4
Aluminium cell carbonaceous waste material used in the embodiment of the present invention is derived from the blocky carbonaceous waste material stored up in certain aluminium manufacturer library,
Detect aggregate sample inanimate matter content 36.55%(wherein, aluminium content 2.39%, alkali content 10.98%, cyanide content
0.19%), carbon content 63.26%；Quick lime used in the present embodiment selects powdered lime (the calcium oxide quality under calcium carbide factory's sieve
91.6%) content is；Strong oxdiative activator used in the present embodiment is that (i.e. perchlorate is strong for ZC-YO8 type Strong oxdiative activator
Oxidation activator and permanganate Strong oxdiative activator are with the mixture of mass ratio 1:1) it is purchased from Hunan Province little Yin Wuji environment energy
Source Science and Technology Development Co., Ltd..
(1) it pre-processes: 1t aluminium cell carbonaceous waste material impact type is broken for partial size≤15mm bulk granular material；
(2) activation carbon is with alkali alum recovery: 1t bulk granular material obtained by step (1) is placed in spreading mixing leaching device
In, 4t water is first added, in spreading mixed process, it is strong to add 103kg sodium hydroxide, 114kg quick lime and 35kgZC-YO8 type
Active oxide, at 80 DEG C, heating leaching 80min is separated by filtration, and obtains aluminium lye and solid filter residue, solid filter residue through washing,
Drying to moisture content is 1 %, obtains activated carbon slag of the 976kg containing carbon and calcirm-fluoride；
(3) carbide raw material is processed: 976kg obtained by step (2) is placed in the mixed machine of rolling containing the activated carbon slag of carbon and fluorite,
155.2kg coal tar pitch is added, rolles over the particulate material for mixing, being shaped to 12mm, calcium carbide raw material must be produced.
Through detecting, the carbon content of production calcium carbide raw material obtained by the present embodiment is 66.8%, aluminium content 0.31%, alkali content
Be 0.69%, aluminium, alkali the removing rate of recovery be respectively 85.3%, 92.8%.
The graininess production calcium carbide of partial size 12mm obtained by the present embodiment is transferred to press at certain calcium carbide factory's production technology with raw material
Normal calcium carbide controlling of production process method is in calcium carbide production.
It feeds back at factory's production technology: using the graininess production calcium carbide raw material of partial size 12mm with carbometer, replacing
The block grain carbon raw in generation 25% can cancel the tune furnace operation with fluorite and secondary lime, and molten bath stablizes, discharges smooth, that is, be carbonized
Calcium eutectic viscosity reduces, output increased 9.5%, and the average current drain decline 8.1% of ton calcium carbide, calcium carbide gas production averagely improves
5.8%, i.e., the calcium content that is carbonized in calcium carbide increases, and grade improves, and cyanide-free detects.
By aluminium recycle of alkali liquor obtained by the present embodiment step (2) for mentioning aluminium and concentrated base, concentrated base can be back to step (2)；Institute
Water lotion recycling after stating washing is as leaching water.
Embodiment 5
Aluminium cell carbonaceous waste material used in the embodiment of the present invention is derived from the blocky carbonaceous waste material stored up in certain aluminium manufacturer library,
Detect aggregate sample inanimate matter content 28.81%(wherein, aluminium content 2.42%, alkali content 10.31%, cyanide content
0.13%), carbon content 71.06%；Quick lime used in the present embodiment selects powdered lime (the calcium oxide quality under calcium carbide factory's sieve
91.6%) content is；Strong oxdiative activator used in the present embodiment is that (i.e. bichromate is strong for ZC-YO11 type Strong oxdiative activator
Oxidation activator and perchlorate Strong oxdiative activator are with the mixture of mass ratio 1:1), it is purchased from Hunan Province little Yin Wuji environment energy
Source Science and Technology Development Co., Ltd.；Detoxification agent solution used in the present embodiment is that sodium hypochlorite addition is first equivalent to its quality 2
Times water dilution, then that potassium ferrate and potassium hydroxide are dissolved in the saturation formed in liquor natrii hypochloritis by the mass ratio of 1:1 is molten
Liquid.
(1) it pre-processes: 1t aluminium cell carbonaceous waste material squash type is broken for partial size≤5mm bulk granular material；Broken
While broken, the detoxification agent solution of atomized spray 50kg；
(2) activation carbon and alkali alum recovery: 1t bulk granular material obtained by step (1) is placed in leaching pond, by 56kg hydrogen
Sodium oxide molybdena, 84kg quick lime and 40kgZC-YO11 type Strong oxdiative activating agent are added in 7t water and stir into suspension, add leaching pond
In, at 20 DEG C, heating leaching 80min is separated by filtration, and obtains aluminium lye and solid filter residue, and solid filter residue is washed, dry to containing
Water rate is 1%, obtains activated carbon slag of the 987kg containing carbon and calcirm-fluoride；
(3) carbide raw material is processed: 987kg obtained by step (2) is placed in the mixed machine of rolling containing the activated carbon slag of carbon and fluorite,
170kg asphalt is added, rolles over the particulate material for mixing, being shaped to 10mm, calcium carbide raw material must be produced.
Through detecting, the carbon content of production calcium carbide raw material obtained by the present embodiment is 72.83%, and aluminium content 0.29%, alkali contains
Amount be 0.76%, aluminium, alkali the removing rate of recovery be respectively 86.1%, 91.47%.
The graininess production calcium carbide of partial size 10mm obtained by the present embodiment is transferred to press at certain calcium carbide factory's production technology with raw material
Normal calcium carbide controlling of production process method is in calcium carbide production.
It feeds back at factory's production technology: being substituted using the graininess production calcium carbide of partial size 10mm with raw material with carbometer
25% carbon raw can cancel the tune furnace operation with fluorite and secondary lime, and molten bath stablizes, discharges smooth, i.e. calcium carbide eutectic
Viscosity reduces, output increased 7.6%, and the average current drain decline 7.1% of ton calcium carbide, calcium carbide gas production averagely improves 4.5%, i.e. calcium carbide
Middle carbonization calcium content increases, and grade improves, and cyanide-free detects.
By aluminium recycle of alkali liquor obtained by the present embodiment step (2) for mentioning aluminium and concentrated base, concentrated base can be back to step (2)；Institute
Water lotion recycling after stating washing is as leaching water.
Claims (23)
- A kind of method for producing electricity stone raw material 1. aluminium cell carbonaceous materials recycling is made a living, which comprises the steps of:(1) it pre-processes: aluminium cell carbonaceous waste material is broken for partial size≤20mm bulk granular material；While broken, mist Change the detoxification agent solution that sprinkling is equivalent to aluminium cell carbonaceous waste material quality 0.5~6.0%；(2) bulk granular material obtained by step (1) activation carbon and alkali alum recovery: is placed in leaching pond, stirring leaching device or rolling In pressure mixing leaching device, water is first added, adds caustic soda or its solution, lime and Strong oxdiative activating agent, Oxidation Leaching, filtering Separation, obtains aluminium lye and solid filter residue, and solid filter residue is washed, dry, obtains the activated carbon slag containing carbon and calcirm-fluoride；The water Dosage be 1~10 times of bulk granular material quality, the caustic soda or its solution, lime, Strong oxdiative activating agent and scattered shot-like particle The mass ratio of material is 3~30:1~30:0.5~5.0:100；(3) carbide raw material is processed: the activated carbon slag containing carbon and calcirm-fluoride obtained by step (2) being placed in the mixed machine of rolling, carbon is added Hydrogen species binder, or it is additionally added quick lime, the particulate material for mixing, being shaped to 5~18mm is rolled over, calcium carbide raw material must be produced.
- 2. aluminium cell carbonaceous materials recycling is made a living the method for producing electricity stone raw material according to claim 1, it is characterised in that: In step (1), the main component of the aluminium cell carbonaceous waste material is waste cathode carbon block and/or scrap anode carbon granule, wherein inorganic Matter content 20~50%, carbon content 50~80%, each component gross mass percentage composition≤100%；Wherein, in inanimate matter, aluminium content is 1~14%, alkali content is 5~20%, cyanide content < 2.5%.
- The method for producing electricity stone raw material 3. aluminium cell carbonaceous materials recycling according to claim 1 or claim 2 is made a living, feature exist In: in step (1), the detoxicant is ferrate detoxicant, bichromate detoxicant, dichromic acid acid anhydride detoxicant, thio sulphur One of hydrochlorate detoxicant, perchlorate detoxicant, hydroxide detoxicant, hypochlorite detoxicant or chlorine dioxide are several Kind；The ferrate detoxicant is one or more of potassium ferrate, ferrate-lithium or Na2Fe04, the bichromate Detoxicant is one or more of potassium bichromate, sodium dichromate or dichromic acid cobalt, and the thiosulfate detoxicant is thio Sodium sulphate and/or potassium thiosulfate, the perchlorate are lithium perchlorate and/or cobaltous perchlorate, and the hydroxide is hydrogen-oxygen Change one or more of cobalt, iron hydroxide or potassium hydroxide, the hypochlorite is sodium hypochlorite and/or calcium hypochlorite.
- The method for producing electricity stone raw material 4. aluminium cell carbonaceous materials recycling according to claim 1 or claim 2 is made a living, feature exist It is that first sodium hypochlorite is added to be equivalent to the water of 2 times of its quality and dilute in: the detoxification agent solution, then by potassium ferrate and hydrogen-oxygen Change potassium and is dissolved in the saturated solution formed in liquor natrii hypochloritis by the mass ratio of 1:1.
- 5. aluminium cell carbonaceous materials recycling is made a living the method for producing electricity stone raw material according to claim 3, it is characterised in that: The detoxification agent solution is that first sodium hypochlorite is added to be equivalent to the water of 2 times of its quality and dilute, then by potassium ferrate and hydroxide Potassium is dissolved in the saturated solution formed in liquor natrii hypochloritis by the mass ratio of 1:1.
- The method for producing electricity stone raw material 6. aluminium cell carbonaceous materials recycling according to claim 1 or claim 2 is made a living, feature exist In: in step (2), the caustic soda is for sodium hydroxide or the alkali recycled in alumina producing or from this step Aluminium lye mentions the alkali recycled after aluminium；The Strong oxdiative activator is chlorosulfonic acid Strong oxdiative activator, the activation of ferrate Strong oxdiative Agent, bichromate Strong oxdiative activator, dichromic acid acid anhydride Strong oxdiative activator, perchlorate Strong oxdiative activator, the strong oxygen of chlorate Change one in activator, hypochlorite Strong oxdiative activator, vanadate Strong oxdiative activator or permanganate Strong oxdiative activator Kind is several；The ferrate Strong oxdiative activator is one in calcium ferrate, potassium ferrate, ferrate-lithium or Na2Fe04 Kind is several, and the bichromate Strong oxdiative activator is calcium bichromate, potassium bichromate, sodium dichromate, dichromic acid cobalt or weight chromium One or more of sour ammonium, the perchlorate Strong oxdiative activator are Calcium perchlorate, cobaltous perchlorate, lithium perchlorate, high chlorine One or more of sour sodium or potassium hyperchlorate, the chlorate Strong oxdiative activator are in calcium chlorate, sodium chlorate or potassium chlorate One or more, the hypochlorite Strong oxdiative activator be sodium hypochlorite and/or calcium hypochlorite, the vanadate Strong oxdiative Activator is sodium metavanadate and/or lithium metavanadate, and the permanganate Strong oxdiative activator is potassium permanganate and/or permanganic acid Calcium.
- 7. aluminium cell carbonaceous materials recycling is made a living the method for producing electricity stone raw material according to claim 3, it is characterised in that: In step (2), the caustic soda is for sodium hydroxide or the alkali recycled in alumina producing or from this step aluminium Lye mentions the alkali recycled after aluminium；The Strong oxdiative activator be chlorosulfonic acid Strong oxdiative activator, ferrate Strong oxdiative activator, Bichromate Strong oxdiative activator, dichromic acid acid anhydride Strong oxdiative activator, perchlorate Strong oxdiative activator, chlorate Strong oxdiative are living One of agent, hypochlorite Strong oxdiative activator, vanadate Strong oxdiative activator or permanganate Strong oxdiative activator or It is several；The ferrate Strong oxdiative activator be one of calcium ferrate, potassium ferrate, ferrate-lithium or Na2Fe04 or Several, the bichromate Strong oxdiative activator is calcium bichromate, potassium bichromate, sodium dichromate, dichromic acid cobalt or ammonium dichromate One or more of, the perchlorate Strong oxdiative activator is Calcium perchlorate, cobaltous perchlorate, lithium perchlorate, sodium perchlorate Or one or more of potassium hyperchlorate, the chlorate Strong oxdiative activator are one in calcium chlorate, sodium chlorate or potassium chlorate Kind is several, and the hypochlorite Strong oxdiative activator is sodium hypochlorite and/or calcium hypochlorite, the vanadate Strong oxdiative activation Agent is sodium metavanadate and/or lithium metavanadate, and the permanganate Strong oxdiative activator is potassium permanganate and/or acerdol.
- 8. aluminium cell carbonaceous materials recycling is made a living the method for producing electricity stone raw material according to claim 4, it is characterised in that: In step (2), the caustic soda is for sodium hydroxide or the alkali recycled in alumina producing or from this step aluminium Lye mentions the alkali recycled after aluminium；The Strong oxdiative activator be chlorosulfonic acid Strong oxdiative activator, ferrate Strong oxdiative activator, Bichromate Strong oxdiative activator, dichromic acid acid anhydride Strong oxdiative activator, perchlorate Strong oxdiative activator, chlorate Strong oxdiative are living One of agent, hypochlorite Strong oxdiative activator, vanadate Strong oxdiative activator or permanganate Strong oxdiative activator or It is several；The ferrate Strong oxdiative activator be one of calcium ferrate, potassium ferrate, ferrate-lithium or Na2Fe04 or Several, the bichromate Strong oxdiative activator is calcium bichromate, potassium bichromate, sodium dichromate, dichromic acid cobalt or ammonium dichromate One or more of, the perchlorate Strong oxdiative activator is Calcium perchlorate, cobaltous perchlorate, lithium perchlorate, sodium perchlorate Or one or more of potassium hyperchlorate, the chlorate Strong oxdiative activator are one in calcium chlorate, sodium chlorate or potassium chlorate Kind is several, and the hypochlorite Strong oxdiative activator is sodium hypochlorite and/or calcium hypochlorite, the vanadate Strong oxdiative activation Agent is sodium metavanadate and/or lithium metavanadate, and the permanganate Strong oxdiative activator is potassium permanganate and/or acerdol.
- The method for producing electricity stone raw material 9. aluminium cell carbonaceous materials recycling according to claim 1 or claim 2 is made a living, feature exist In: in step (2), the Strong oxdiative activator is potassium ferrate, sodium dichromate, cobaltous perchlorate, lithium metavanadate, calcium hypochlorite are pressed The oxidation activator that the ratio of molar ratio 3:1:2:1:2 is mixed.
- 10. aluminium cell carbonaceous materials recycling is made a living the method for producing electricity stone raw material according to claim 3, feature exists In: in step (2), the Strong oxdiative activator is potassium ferrate, sodium dichromate, cobaltous perchlorate, lithium metavanadate, calcium hypochlorite are pressed The oxidation activator that the ratio of molar ratio 3:1:2:1:2 is mixed.
- 11. aluminium cell carbonaceous materials recycling is made a living the method for producing electricity stone raw material according to claim 4, feature exists In: in step (2), the Strong oxdiative activator is potassium ferrate, sodium dichromate, cobaltous perchlorate, lithium metavanadate, calcium hypochlorite are pressed The oxidation activator that the ratio of molar ratio 3:1:2:1:2 is mixed.
- 12. aluminium cell carbonaceous materials recycling is made a living the method for producing electricity stone raw material according to claim 6, feature exists In: in step (2), the Strong oxdiative activator is potassium ferrate, sodium dichromate, cobaltous perchlorate, lithium metavanadate, calcium hypochlorite are pressed The oxidation activator that the ratio of molar ratio 3:1:2:1:2 is mixed.
- The method for producing electricity stone raw material 13. aluminium cell carbonaceous materials recycling according to claim 1 or claim 2 is made a living, feature Be: in step (2), the temperature of the Oxidation Leaching is 20~300 DEG C, and the time is 0.1~8.0h；The drying is to moisture content ≤5%。
- 14. aluminium cell carbonaceous materials recycling is made a living the method for producing electricity stone raw material according to claim 3, feature exists In: in step (2), the temperature of the Oxidation Leaching is 20~300 DEG C, and the time is 0.1~8.0h；The drying to moisture content≤ 5%。
- 15. aluminium cell carbonaceous materials recycling is made a living the method for producing electricity stone raw material according to claim 4, feature exists In: in step (2), the temperature of the Oxidation Leaching is 20~300 DEG C, and the time is 0.1~8.0h；The drying to moisture content≤ 5%。
- 16. aluminium cell carbonaceous materials recycling is made a living the method for producing electricity stone raw material according to claim 6, feature exists In: in step (2), the temperature of the Oxidation Leaching is 20~300 DEG C, and the time is 0.1~8.0h；The drying to moisture content≤ 5%。
- 17. aluminium cell carbonaceous materials recycling is made a living the method for producing electricity stone raw material according to claim 9, feature exists In: in step (2), the temperature of the Oxidation Leaching is 20~300 DEG C, and the time is 0.1~8.0h；The drying to moisture content≤ 5%。
- The method for producing electricity stone raw material 18. aluminium cell carbonaceous materials recycling according to claim 1 or claim 2 is made a living, feature It is: in step (3), the mass ratio of the activated carbon slag containing carbon and calcirm-fluoride and hydrocarbon class binder, quick lime are as follows: 100:5~40:0~160；The hydrocarbon class binder is one or more of selected from coal tar pitch and petroleum asphalt or resin.
- 19. aluminium cell carbonaceous materials recycling is made a living the method for producing electricity stone raw material according to claim 3, feature exists In: in step (3), the mass ratio of the activated carbon slag containing carbon and calcirm-fluoride and hydrocarbon class binder, quick lime are as follows: 100: 5~40:0~160；The hydrocarbon class binder is one or more of selected from coal tar pitch and petroleum asphalt or resin.
- 20. aluminium cell carbonaceous materials recycling is made a living the method for producing electricity stone raw material according to claim 4, feature exists In: in step (3), the mass ratio of the activated carbon slag containing carbon and calcirm-fluoride and hydrocarbon class binder, quick lime are as follows: 100: 5~40:0~160；The hydrocarbon class binder is one or more of selected from coal tar pitch and petroleum asphalt or resin.
- 21. aluminium cell carbonaceous materials recycling is made a living the method for producing electricity stone raw material according to claim 6, feature exists In: in step (3), the mass ratio of the activated carbon slag containing carbon and calcirm-fluoride and hydrocarbon class binder, quick lime are as follows: 100: 5~40:0~160；The hydrocarbon class binder is one or more of selected from coal tar pitch and petroleum asphalt or resin.
- 22. aluminium cell carbonaceous materials recycling is made a living the method for producing electricity stone raw material according to claim 9, feature exists In: in step (3), the mass ratio of the activated carbon slag containing carbon and calcirm-fluoride and hydrocarbon class binder, quick lime are as follows: 100: 5~40:0~160；The hydrocarbon class binder is one or more of selected from coal tar pitch and petroleum asphalt or resin.
- 23. the 3 aluminium cell carbonaceous materials recyclings are made a living the method for producing electricity stone raw material according to claim 1, feature exists In: in step (3), the mass ratio of the activated carbon slag containing carbon and calcirm-fluoride and hydrocarbon class binder, quick lime are as follows: 100: 5~40:0~160；The hydrocarbon class binder is one or more of selected from coal tar pitch and petroleum asphalt or resin.
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