CN107363074A - A kind of aluminium cell carbonaceous materials recycling is alternative coal-fired method - Google Patents
A kind of aluminium cell carbonaceous materials recycling is alternative coal-fired method Download PDFInfo
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- CN107363074A CN107363074A CN201710600311.5A CN201710600311A CN107363074A CN 107363074 A CN107363074 A CN 107363074A CN 201710600311 A CN201710600311 A CN 201710600311A CN 107363074 A CN107363074 A CN 107363074A
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- Prior art keywords
- nitrate
- coal
- catalytic oxidant
- aluminium cell
- alternative
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- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 152
- 239000004411 aluminium Substances 0.000 title claims abstract description 142
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 238000000034 method Methods 0.000 title claims abstract description 70
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 25
- 238000004064 recycling Methods 0.000 title claims abstract description 19
- 239000002699 waste material Substances 0.000 claims abstract description 143
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 129
- 239000003245 coal Substances 0.000 claims abstract description 128
- 239000007800 oxidant agent Substances 0.000 claims abstract description 118
- 230000003197 catalytic effect Effects 0.000 claims abstract description 115
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 102
- 230000001590 oxidative effect Effects 0.000 claims abstract description 96
- 238000001784 detoxification Methods 0.000 claims abstract description 66
- 239000000463 material Substances 0.000 claims abstract description 48
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 41
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 32
- 230000003647 oxidation Effects 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 27
- 239000007788 liquid Substances 0.000 claims abstract description 16
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims abstract description 14
- 235000011941 Tilia x europaea Nutrition 0.000 claims abstract description 14
- 238000001914 filtration Methods 0.000 claims abstract description 14
- 239000004571 lime Substances 0.000 claims abstract description 14
- 230000004913 activation Effects 0.000 claims abstract description 13
- 238000012986 modification Methods 0.000 claims abstract description 13
- 230000004048 modification Effects 0.000 claims abstract description 13
- 239000007921 spray Substances 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 10
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 7
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 34
- 230000008859 change Effects 0.000 claims description 30
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims description 26
- 238000005469 granulation Methods 0.000 claims description 23
- 230000003179 granulation Effects 0.000 claims description 23
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 claims description 21
- 239000012047 saturated solution Substances 0.000 claims description 21
- 229910002651 NO3 Inorganic materials 0.000 claims description 19
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 19
- 238000006555 catalytic reaction Methods 0.000 claims description 18
- 238000002386 leaching Methods 0.000 claims description 18
- 239000003610 charcoal Substances 0.000 claims description 17
- 239000000203 mixture 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
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 17
- 239000003513 alkali Substances 0.000 claims description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 13
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- 238000013019 agitation Methods 0.000 claims description 11
- 239000008187 granular material Substances 0.000 claims description 11
- 229910052744 lithium Inorganic materials 0.000 claims description 11
- ALTWGIIQPLQAAM-UHFFFAOYSA-N metavanadate Chemical compound [O-][V](=O)=O ALTWGIIQPLQAAM-UHFFFAOYSA-N 0.000 claims description 11
- 239000002893 slag Substances 0.000 claims description 11
- 239000000292 calcium oxide Substances 0.000 claims description 10
- 239000002912 waste gas Substances 0.000 claims description 10
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 9
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 8
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 8
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 8
- 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 7
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 7
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 7
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- 229920002209 Crumb rubber Polymers 0.000 claims description 6
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 6
- 239000011280 coal tar Substances 0.000 claims description 6
- 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 6
- -1 dichromic acid acid anhydride Chemical class 0.000 claims description 6
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 6
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 6
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 5
- 229910000462 iron(III) oxide hydroxide Inorganic materials 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 5
- UMPKMCDVBZFQOK-UHFFFAOYSA-N potassium;iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[K+].[Fe+3] UMPKMCDVBZFQOK-UHFFFAOYSA-N 0.000 claims description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- WBJXZTQXFVDYIZ-UHFFFAOYSA-N [Sb].[N+](=O)(O)[O-] Chemical compound [Sb].[N+](=O)(O)[O-] WBJXZTQXFVDYIZ-UHFFFAOYSA-N 0.000 claims description 4
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 4
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 4
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 4
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 claims description 4
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 claims description 4
- JLGUDDVSJCOLTN-UHFFFAOYSA-N strontium;oxido-(oxido(dioxo)chromio)oxy-dioxochromium Chemical compound [Sr+2].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O JLGUDDVSJCOLTN-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- KKKAMDZVMJEEHQ-UHFFFAOYSA-N [Sn].[N+](=O)(O)[O-] Chemical compound [Sn].[N+](=O)(O)[O-] KKKAMDZVMJEEHQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 239000010903 husk Substances 0.000 claims description 3
- XDBSEZHMWGHVIL-UHFFFAOYSA-M hydroxy(dioxo)vanadium Chemical compound O[V](=O)=O XDBSEZHMWGHVIL-UHFFFAOYSA-M 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 3
- 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 2
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004155 Chlorine dioxide Substances 0.000 claims description 2
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims description 2
- 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 2
- 235000019398 chlorine dioxide Nutrition 0.000 claims description 2
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical group [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 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
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- CMMUKUYEPRGBFB-UHFFFAOYSA-L dichromic acid Chemical group O[Cr](=O)(=O)O[Cr](O)(=O)=O CMMUKUYEPRGBFB-UHFFFAOYSA-L 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 238000005984 hydrogenation reaction Methods 0.000 claims 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims 1
- 229910001948 sodium oxide Inorganic materials 0.000 claims 1
- 229910052726 zirconium Inorganic materials 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 24
- 238000012545 processing Methods 0.000 abstract description 14
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 abstract description 12
- 239000003830 anthracite Substances 0.000 abstract description 12
- 238000005265 energy consumption Methods 0.000 abstract description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 62
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 25
- 238000001514 detection method Methods 0.000 description 25
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 19
- 238000002474 experimental method Methods 0.000 description 19
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 18
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 17
- 239000003792 electrolyte Substances 0.000 description 17
- 238000005516 engineering process Methods 0.000 description 17
- 239000003546 flue gas Substances 0.000 description 17
- 239000004568 cement Substances 0.000 description 16
- 230000007613 environmental effect Effects 0.000 description 13
- 238000000227 grinding Methods 0.000 description 13
- 239000002245 particle Substances 0.000 description 13
- 230000018109 developmental process Effects 0.000 description 11
- 230000002940 repellent Effects 0.000 description 11
- 239000005871 repellent Substances 0.000 description 11
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 10
- 238000002485 combustion reaction Methods 0.000 description 10
- 238000007906 compression Methods 0.000 description 10
- 230000006835 compression Effects 0.000 description 10
- 238000000354 decomposition reaction Methods 0.000 description 10
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminium flouride Chemical compound F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 9
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 9
- 235000012255 calcium oxide Nutrition 0.000 description 9
- 239000011737 fluorine Substances 0.000 description 9
- 229910052731 fluorine Inorganic materials 0.000 description 9
- 239000011449 brick Substances 0.000 description 8
- 239000000446 fuel Substances 0.000 description 8
- 230000009467 reduction Effects 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000005868 electrolysis reaction Methods 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 229910001610 cryolite Inorganic materials 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 239000011775 sodium fluoride Substances 0.000 description 6
- 235000013024 sodium fluoride Nutrition 0.000 description 6
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 5
- 239000005864 Sulphur Substances 0.000 description 5
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 5
- 239000002817 coal dust Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000010304 firing Methods 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000002910 solid waste Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 241000196324 Embryophyta Species 0.000 description 4
- 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 description 4
- XGCDHPDIERKJPT-UHFFFAOYSA-N [F].[S] Chemical compound [F].[S] XGCDHPDIERKJPT-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 239000000920 calcium hydroxide Substances 0.000 description 4
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 4
- ODPUKHWKHYKMRK-UHFFFAOYSA-N cerium;nitric acid Chemical group [Ce].O[N+]([O-])=O ODPUKHWKHYKMRK-UHFFFAOYSA-N 0.000 description 4
- 239000000428 dust Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 235000009854 Cucurbita moschata Nutrition 0.000 description 3
- 235000009852 Cucurbita pepo Nutrition 0.000 description 3
- 240000001980 Cucurbita pepo Species 0.000 description 3
- 238000007792 addition Methods 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910001576 calcium mineral Inorganic materials 0.000 description 3
- 229960004424 carbon dioxide Drugs 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000005087 graphitization Methods 0.000 description 3
- 239000006210 lotion Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 231100000614 poison Toxicity 0.000 description 3
- 230000007096 poisonous effect Effects 0.000 description 3
- 238000003672 processing method Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000011819 refractory material Substances 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- MNWBNISUBARLIT-UHFFFAOYSA-N sodium cyanide Chemical compound [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 description 3
- 235000020354 squash Nutrition 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 235000019504 cigarettes Nutrition 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000029087 digestion Effects 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 238000005188 flotation Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 238000005192 partition Methods 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 229910052594 sapphire Inorganic materials 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000002341 toxic gas Substances 0.000 description 2
- 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 2
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 241000219000 Populus Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000012237 artificial material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000003851 biochemical process Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011294 coal tar pitch Substances 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
- 238000012272 crop production Methods 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000005008 domestic process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation 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
- 239000012535 impurity Substances 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
- 230000001788 irregular Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- XQHAGELNRSUUGU-UHFFFAOYSA-M lithium chlorate Chemical compound [Li+].[O-]Cl(=O)=O XQHAGELNRSUUGU-UHFFFAOYSA-M 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
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 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
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 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
- 239000010802 sludge Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003860 storage Methods 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
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000000108 ultra-filtration Methods 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
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L5/00—Solid fuels
- C10L5/02—Solid fuels such as briquettes consisting mainly of carbonaceous materials of mineral or non-mineral origin
- C10L5/04—Raw material of mineral origin to be used; Pretreatment thereof
Landscapes
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
A kind of aluminium cell carbonaceous materials recycling is alternative coal-fired method, is comprised the following steps：（1）It is granulated detoxification：Aluminium cell carbonaceous waste material is crushed, atomized spray detoxification agent solution, detoxification material must be granulated；（2）Activation：Catalytic oxidant is added, homogenizing is modified,；Or catalytic oxidant and lime are added, add water stirring or roll over mixed, oxidation dealkalize, filtering or filtering washing, dry,；Or catalytic oxidant, lime, sodium hydroxide are added, add water stirring or roll over mixed, oxidation dealuminzation dealkalize, filtering or filtering washing, dry,；Or molten processing is soaked using overcritical or liquid carbon dioxide, catalytic oxidant homogeneous modification is added in carbon dry mash,.The alternative fire coal that the present invention regenerates is suitable with semibituminous coal, anthracite calorific value, average about 5000kcal/kg, can be used as alternative fire coal；The inventive method technique is simple, and energy consumption is low, cost is low, suitable industrialized production.
Description
Technical field
It is alternative coal-fired method the present invention relates to a kind of materials recycling, and in particular to a kind of aluminium cell carbonaceous waste material
It is regenerated as alternative coal-fired method.
Background technology
At present, the development of the electrolytic aluminium yield in China and the world is swift and violent.According to statistics, 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, caused solid waste 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 only the caused negative electrode that gives up is up to 250,000 tons every year for China's aluminum electrolysis industry, in recent years still
The accumulative volume of cargo in storage for having more than 400 ten thousand tons fills without suitable area, and the waste cathode carbon block actual amount of whole world stockpiling is up to ten million
Ton.
Aluminium cell carbonaceous waste material includes caused waste cathode carbon block and scrap anode carbon granule during electrolytic aluminium 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
Participate in the anode carbon granule of electrolyte in electrolysis and Electolyte-absorptive（Also known as anode breeze）Main component be 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 negative electrode is to forge
The anthracite of burning, metallurgical coke, graphite etc. are that aggregate, coal tar pitch etc. is made up of binding agent shaping and roasting, for charcoal containing aluminium cell
The block class or paste class carbon product of matter liner, are graphitization or graphite carbon cellulosic material, with hardness is big, coefficient of friction is small, no
Broken, extremely difficult combustion（Relative to fire coal）The characteristics of.The electrolysis temperature of modern large-scale aluminium electrolysis pre-baking tank 950~970 DEG C it
Between, the electrolyte such as 1 ton of aluminium consumption about 50kg ice crystals, aluminum fluoride, magnesium fluoride are often produced, due to heat effect, chemical action, machinery
Erosion effect, electro ultrafiltration, sodium and electrolyte infiltration etc. caused by fused salt reaction, chemical reaction, the negative electrode charcoal in aluminium cell
Block can be damaged after using certain time, needs to carry out large repairs after typically running 4~7 years, the mainly waste cathode carbon block that removes,
Waste refractory materials, useless insulation material etc., while a certain amount of anode carbon granule is also produced in electrolytic process.
For the treatment technology of the less scrap anode carbon granule of quantity, current research is concentrated mainly on is returned using floatation process
Charcoal and electrolyte are received, by scrap anode carbon granule grinding to certain particle size, adds water to add collecting agent after sizing mixing, makes charcoal abundant with electrolyte
Separation, so as to obtain using electrolyte as two kinds of products advocating peace based on charcoal.Electrolyte therein can back within aluminium electroloysis
In groove, powdered carbon can be used for the raw material that Soderberg Anode In Aluminium Electrolysis Cells make 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 method, high temperature hydro-thermal method, superhigh temperature partition method, burning partition method, fuel process and security landfill method etc..
（1）Wet method：For the main direction of studying of current internal lining of aluminium electrolytic bath, basic working procedure is grinding, water logging/alkali leaching/acid
Wash, 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 Austrian Lun Sihuofen aluminium manufacturers and Li Sita aluminium manufacturers of 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 substantial amounts of research and practice, as Lu Huimin et al. is used
Floatation reclaims charcoal and electrolyte, and waste cathode carbon block is crushed, obtains the powder of certain particle size after classification, adds water to be added after sizing mixing
Collecting agent, to realize farthest separating for carbon and electrolyte, so as to obtain using electrolyte as advocate peace based on charcoal two kinds
Product.Electrolyte therein can be backed within aluminium cell, and graphited powdered carbon can return to negative electrode 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
It is high to manage cost, and serious secondary pollution be present.
（2）High temperature hydro-thermal method separation method：It is most representational to be used for J.E.Dentschman and J.S.Lobos etc.
More than 1200 DEG C of hot water Hydrolyze method processing waste cathode carbon block, make fluoride and the hydrogen fluoride of steam reaction generation concentration 25% 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, high energy consumption,
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 companies, in powder
Adding the flux such as lime in broken waste lining carbon block, blended stock is heat-treated in AUS-MELT stoves at 1300 DEG C of temperature,
Lime etc. is reacted with the electrolyte in waste cathode carbon block, obtain calcirm-fluoride, sodium fluoride and aluminum fluoride, reclaim high-temperature flue gas
Middle HF gases generate aluminum fluoride, make fluorine obtain solidifying to re-use, final products are glassy state slag, and the charcoal of recovery is used again
In manufacture cathode material.The technique has carried out commercial 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, it 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, it be nitride to volatilize fluoride therein, decompose cyanide therein, and high-temperature flue gas is by the way of water smoke absorbs
Absorb again by the processing such as filtering drying, obtain can reuse fluoride, the negative electrode carbon materials after superhigh temperature roasting is through being cooled to
Reach 97% carbon materials for fixed carbon content.But this method is significantly present of following problem：First, electrolytic aluminium waste cathode carbon is broken
Toxic dust and toxic gas containing cyanide are produced in broken screening process；Second, it is actual to 2600~2800 DEG C for electrical heating
Power consumption is very high, maintain vacuum suction power consumption it is higher, the requirement of equipment and cost are also very high；Third, 2600~2800 DEG C volatilization
It is too high that fluoride gas using water smoke absorb requirement to equipment, because 1200 DEG C of water vapour can be so that calcirm-fluoride etc. to be fluorinated
Thing is converted into the hydrogen fluoride of the severe corrosive of severe toxicity；Fourth, serious secondary pollution is also easy to produce, and the carbon materials reclaimed
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, teach one kind and be crushed to electrolytic aluminium waste cathode carbon block not
Particle more than 3mm, 3~100mm compound particles are made with kneadings such as pitches, then, compound particles are placed in superelevation
In warm vacuum electric furnace, in not less than 2000 DEG C（2300~2600 DEG C）Continous way calcination process in superhigh temperature vacuum electric furnace, 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, it is nitride to decompose cyanide therein, 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, electrolytic aluminium waste is cloudy
Toxic dust and toxic gas containing cyanide are produced during the carbon crushing and screening of pole；Second, electrical heating to 2000~2600 DEG C its
Actual power consumption is very high, maintains that the power consumption of vacuum suction is higher, and the requirement of equipment and cost are also very high；Third, after second-time burning
Gas cleaning investment is high, is also easy to produce serious secondary pollution；Fourth, still contain in the carbon of 2000~2600 DEG C of electric furnace calcination processing
Substantial amounts of fluoride, because more than 2497 DEG C of the boils up till of calcirm-fluoride, fluorine-containing carbon materials, which recycles, can shorten overhaul time
Limit and it is uneconomical.
（3）Burn separation method：It is to use professional incinerator and fluid bed furnace technique etc., because electrolytic aluminium waste cathode carbon is different
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 combustion method is present that separating process is cumbersome, the heat time needed for after-flame is long, energy consumption is big and difficult
The problem of effectively to reclaim 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
More than 4000kcal/kg, high reaches 5500kcal/kg equivalent to conventional anthracitic calorific value, so, domestic and international substantial amounts 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 changes into sinter leaching
Insoluble calcirm-fluoride enters red mud, and red mud replaces fluorescent mineralizer for manufacture of cement dispensing when preparing cement." still,
This method grinding energy is high, the discharge capacity increase of pernicious gas in flue gas.Further to solve the turning sludge into fuel profit of waste cathode carbon block
With problem, research institute of Shandong branch company of Chinese Aluminium Co., Ltd poplar meeting guest waits the cement producing line in Shandong Aluminum Plant enterprising
In-depth study practice is gone, with calorific value 21MJ/kg（5024kcal/kg）Waste cathode carbon block be applied to cement producing line work
Industry is tested, and is specifically first crushed waste cathode carbon block, by the maximum ratio dosage of clinker 5kg waste cathode carbon blocks per ton（Convert and be
About less than the 3% 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 the moon of 5kg
Pole carbon block is to clinker quality without visible influences（Application study light metal of the waste cathode carbon blocks 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 condition such as long, makes the harmful substance in waste cathode carbon block carry out decomposition displacement in hot environment, and it is ripe to be finally solidificated in cement
In material, while attempt to reducing the consumption of coal by the use of the carbon in waste cathode carbon block as fuel.But its still have safety problem,
Addition problem and the influence problem to production, after all, waste cathode carbon are not coal-fired, the extremely difficult combustions of charcoal in waste cathode carbon block.So
And the defects of real is not the problem of fluorine is exceeded in the erosion of refractory material caused by fluoride and flue gas, because calcium aluminum fluoride
The production of cement also ensure that refractory material safety and flue gas in fluorine it is not exceeded, normal cement kiln preheaters system visitor after all
There is the preheater for realizing that Pyatyi exchanges trapping with Alkaline high-strength powder in sight；Nor the problem of alkali content is high, because often
Ton clinker consumption coal normally only 0.15~0.18t, 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, typically
Influence to cement later strength is limited.Therefore, Shandong Aluminum Plant so far still can not be using negative electrode charcoal normal use as alternative combustion
The true cause of coal is：First the mill efficiency of coal mill is influenceed, is second that the graphitic carbon of low activity seriously reduces the whole of coal dust
Body combustibility, the serious normal combustion efficiency that have impact on coal dust, it is impossible to which the timely and effective exothermic charcoal element of burning is fallen into
Clinker entrains into the strong reduction of generation in powder, have impact on kiln system operating mode, have impact on clinker quality.Obviously, prior art is not still
Can be using electrolytic aluminium waste cathode carbon block as effective alternative fuel.
（5）Security landfill method：Because high energy consumption, high cost and secondary pollution problems be present in existing processing method, because
This, the problem of environmental pollution of electrolytic aluminium waste cathode carbon block is never effectively solved, and causes most aluminium electrolytics
Cathode carbon pieces are still thrown aside, and use the security landfill method of high cost at present or mainly.And the current landfill generally used, stockpiling
Method handles electrolytic aluminium solid waste method, high risks can be caused to environment, even completely by the harmless of hazardous waste
Lasting contact scar will be produced by changing landfill, and cause ample resources waste.
In addition, electrolytic aluminium solid waste is due to containing substantial amounts 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 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 air, or be mixed into rivers with rainwater, permeate the ground contaminated soil and underground water, right
Animals and plants and human body produce very big infringement, destroy ecological environment, influence Agro-ecology balance, make crop production reduction, and it endangers will
It is long-term.Processing for cyanide in waste cathode carbon block, treatment technology mainly have weak acid dissolving+polysulfide to be converted into sulphur
For the method for cyanate and metal thiophosphate thing, manganese ion+ultraviolet catalytic oxidation method, ozone and sodium hypochlorite co-oxidation side
Method, high temperature chlorination processing method, high-temperature oxidation method, biochemical process processing cyanide technology.But at these existing cyanides
Reason technical method is cumbersome, cost is high, and secondary pollution be present.CN101811695A discloses a kind of from electrolytic aluminium waste cathode carbon block
The method of middle recovery graphite, it is that the process such as acidleach removes 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 numerous and diverse, secondary pollution is big, high energy consumption, the stone of recovery
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 recycling, it is especially safe
, low energy consumption, low cost regeneration as alternative fire coal be the technical method for being worth a researching and solving problem.
The content of the invention
The technical problems to be solved by the invention are to overcome drawbacks described above existing for prior art, there is provided one kind regeneration institute
It is high to obtain alternative coal-fired safety and environmental protection, non-secondary pollution, calorific value, regeneration technology is simple, low energy consumption, low cost, suitable industrialization
The aluminium cell carbonaceous materials recycling of production is alternative coal-fired method.
The technical solution adopted for the present invention to solve the technical problems is as follows：A kind of aluminium cell carbonaceous materials recycling be for
For the method that property is coal-fired, comprise the following steps：
（1）It is granulated detoxification：Aluminium cell carbonaceous waste material is crushed, broken while, atomized spray is equivalent to aluminium cell charcoal
Matter waste material quality 1~10%（It is preferred that 3~8%）Detoxification agent solution, and with the dedusting of catalytic oxidizer negative pressure extracting crushing system
Waste gas, detoxification material must be granulated；
（2）Activation：By step（1）Gained granulation detoxification material is placed in blender, is added under agitation equivalent to aluminium cell
Carbonaceous waste material quality 0.6~8.0%（It is preferred that 2~6%）Catalytic oxidant, homogenizing be modified, obtain alternative fire coal；
Or by step（1）Gained granulation detoxification material is placed in in the leaching groove or tank that stir or roll over mixing device, adds phase respectively
When in aluminium cell carbonaceous waste material quality 1~8%（It is preferred that 2~6%）Catalytic oxidant and 2~20%（It is preferred that 5~15%）Stone
Ash, and add equivalent to 1~10 times of aluminium cell carbonaceous waste material quality（It is preferred that 2~6 times）Water stirring or roll over mixed, oxidation is de-
Alkali, filtering or filtering washing, obtain dealkalize activated carbon slag, dry to moisture≤15%, homogenizing and are modified, obtain alternative fire coal；
Or by step（1）Gained granulation detoxification material is placed in in the leaching groove or tank that stir or roll over mixing device, adds phase respectively
When in aluminium cell carbonaceous waste material quality 1~8%（It is preferred that 2~6%）Catalytic oxidant, 2~20%（More preferably 5~15%）Stone
Ash, 2~20%（More preferably 5~15%）Sodium hydroxide, and add equivalent to 1~10 times of aluminium cell carbonaceous waste material quality（More
It is preferred that 4~8 times）Water stirring or roll over mixed, aoxidize dealuminzation dealkalize, filtering or filtering washing, obtain the activated carbon slag of dealuminzation alkali, dry
To moisture≤15%, homogenizing is modified, and obtains alternative fire coal；
Or by step（1）Gained granulation detoxification material leaching is dissolved in 0~80 DEG C（More preferably 10~50 DEG C）Overcritical or liquid two
Process in carbonoxide, then in separating obtained carbon dry mash, add equivalent to carbon dry mash quality 0.5~6%（It is more excellent
Select 2~5%）Catalytic oxidant carry out mixing homogeneous modification, obtain alternative fire coal.Using known overcritical or liquid dioxy
Change the molten method of carbon-impregnated to be processed granulation detoxification material.
Preferably, step（1）In, granularity≤25mm after waste material is broken.
Preferably, step（1）In, the crumbling method is hammering, extruding or impact type crush.The attrition crushing is preferred
Double roller squash type crushes.Electrolytic aluminium waste cathode carbon block has the characteristics of hardness is big, coefficient of friction is small, non-breakable, and aluminium electroloysis
Carbon-containing part and other compositions in groove waste and old cathode carbonaceous material is there is the feature at obvious interface, using energy-efficient
Extruding/impact type crumbling method, first save comminution energy conssumption and be subsequently used as possible grinding energy during fuel applications, two
It is then the irregular granular material containing a large amount of cracks by waste cathode carbon block fragmentation, the absorption and depth for being easy to cyanide detoxicant are oozed
Enter reaction.
Preferably, step（1）In, 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%, 3800~6000kcal/kg of calorific value.
Preferably, step（1）In, the detoxicant for can efficient digestion cyanide hypertoxicity material, be ferrate
Detoxicant, bichromate detoxicant, thiosulfate detoxicant, perchlorate detoxicant, hydroxide detoxicant, hypochlorite
One or more in detoxicant or chlorine dioxide etc..For the main Toxic in electrolytic aluminium waste cathode carbon block be Cymag and
The sodium ferricyanide, the characteristics of main violent in toxicity is Cymag, carried out during broken using efficient cyanide detoxicant and
When and efficiently remove toxicity processing, can efficient digestion cyanide hypertoxicity.
It is highly preferred that the ferrate detoxicant be one kind in potassium ferrate, ferrate-lithium or Na2Fe04 etc. or
Several, the bichromate detoxicant is one kind or several in potassium bichromate, sodium dichromate, dichromic acid cobalt or dichromic acid acid anhydride etc.
Kind, the thiosulfate detoxicant is sodium thiosulfate and/or potassium thiosulfate etc., and the perchlorate is lithium perchlorate
And/or cobaltous perchlorate etc., the hydroxide are the one or more in cobalt hydroxide, sodium hydroxide or potassium hydroxide etc., institute
Hypochlorite is stated as sodium hypochlorite and/or calcium hypochlorite etc..
It is further preferred that the detoxicant is commercially available ZC-XJ1 type detoxification agent solutions（That is ferrate detoxicant
With hypochlorite detoxicant with mass ratio 1:1 saturated solution prepared）, ZC-XJ10 type detoxification agent solutions（I.e. thiosulfate is gone
The saturated solution that toxic agent is prepared）, ZC-XJ3 type detoxification agent solutions（That is bichromate detoxicant and hypochlorite detoxicant is with quality
Than 1:1 saturated solution prepared）, ZC-XJ5 type detoxification agent solutions（That is perchlorate detoxicant and hypochlorite detoxicant is with matter
Measure ratio 1:1 saturated solution prepared）Or ZC-XJ13 type detoxification agent solutions（The saturated solution that i.e. hypochlorite detoxicant is prepared）.
Above-mentioned detoxification agent solution is purchased from Hunan Province little Yin Wuji environmental energy Science and Technology Development Co., Ltd..
The detoxification agent solution is the solution that the one or more in the detoxicant are prepared.
Preferably, step（1）In, the detoxification agent solution is first by sodium hypochlorite addition equivalent to its quality 1.5~5.5
Times（More preferably 1.8~3.0 times）Water dissolving, then potassium ferrate and potassium hydroxide are pressed 1:0.8~1.2 mass ratio is dissolved in secondary
The saturated solution formed in sodium chlorate solution.
Step（1）In, can be while dust suppression by atomized spray so that detoxification agent solution penetrates into broken granular material
In hole crack, the resolution of cyanide toxicity is realized；And catalytic oxidizer can implement catalysis oxidation decomposition to body containing dicyanogen, it is ensured that
The security of broken granulation detoxification process.
Preferably, step（2）In, the catalytic oxidant is bichromate catalytic oxidant, metavanadate catalysis oxidation
One or more in agent, ferrate catalytic oxidant, perchlorate catalytic oxidant or nitrate catalytic oxidant.For
Electrolytic aluminium waste cathode carbon block is graphitization or graphite carbon cellulosic material, and carbon structure stablizes extremely difficult combustion, must be effective up to 1500 DEG C of ability
The characteristics of oxidation, use of the present invention can destroy or activate the netted carbon structure of graphite, and can effectively facilitate charcoal element oxidation reaction
Catalytic oxidant is modified to it, first, the activation that charcoal element oxidizing fire reacts in electrolytic aluminium waste cathode carbon block is greatly reduced
Can, second implement dynamic multiphase catalytic oxidation combustion, it is substituted coal-fired application.
It is highly preferred that the bichromate catalytic oxidant is one in ammonium dichromate, strontium dichromate or lithium bichromate etc.
Kind or it is several, the metavanadate catalytic oxidant be ammonium metavanadate, the ferrate catalytic oxidant be ferric acid cobalt with/
Or ferrate-lithium etc., the perchlorate are lithium perchlorate and/or cobaltous perchlorate etc., the nitrate catalytic oxidant is nitric acid
Cerium, lanthanum nitrate, ferric nitrate, copper nitrate, lithium nitrate, nitric acid tin, nitric acid antimony, cobalt nitrate, zirconium nitrate, nickel nitrate, platinum nitrate, nitric acid
One or more in palladium or rhodium nitrate etc..
It is further preferred that the catalytic oxidant is ZC-7 type liquid catalytic oxidants（That is perchlorate catalysis oxygen
Agent and nitrate catalytic oxidant are with mass ratio 2:The saturated solution that 1 mixture is prepared）, ZC-3 type powdery catalytic oxidants
（That is bichromate catalytic oxidant and nitrate catalytic oxidant is with mass ratio 1:1 mixture）, ZC-9 type catalytic oxidants
（That is metavanadate catalytic oxidant and nitrate catalytic oxidant is with mass ratio 1:1 mixture）Or ZC-11 type catalysis oxidations
Agent（That is ferrate catalytic oxidant and nitrate catalytic oxidant is with mass ratio 1:1 mixture）.Above-mentioned catalytic oxidant
It is purchased from Hunan Province little Yin Wuji environmental energy Science and Technology Development Co., Ltd..
It is highly preferred that step（2）In, the catalytic oxidant be ammonium dichromate, metavanadic acid ammonia, lithium perchlorate, cerous nitrate,
Cobalt nitrate, nickel nitrate in mass ratio 2:0.8~1.2:0.8~1.2:1.5~2.5:1.5~2.5:2.5~3.5 ratio is dissolved in
Saturated solution made of water.
Step（2）In, in addition to catalytic oxidant, the raw material of other additions is auxiliary material.The lime includes hydroxide
Calcium and/or calcium oxide.When containing lime in auxiliary material, under the conditions of strong oxidizing solution, calcium hydroxide and the sodium fluoride containing alkali,
The reactions such as cryolite are converted into calcirm-fluoride and dealkalize, and oxidized activating carbon and catalysis oxidation element are attached into carbon materials
On；When containing lime and sodium hydroxide in auxiliary material, under strong oxidizing property solvent condition, calcium hydroxide and sodium hydroxide collaboration,
With the reactions such as the sodium fluoride containing alkali, cryolite, aluminum oxide be converted into calcirm-fluoride, water-soluble sodium metaaluminate, sodium hydroxide and take off
Aluminium dealkalize, and oxidized activating carbon materials and catalysis oxidation element is attached on carbon materials.
Preferably, step（2）In, water lotion is recyclable to be used to leach, and the recyclable concentrated base processed of filtrate containing alkali or carries aluminium concentrated base.
Preferably, step（2）In, after catalytic oxidant is added or after drying, add and given up equivalent to aluminium cell carbonaceous
Expect the % of quality 1~20（More preferably 2~10 %）Calcium oxide and/or magnesia, and/or equivalent to aluminium cell carbonaceous waste material matter
Measure 1~50 %（More preferably 10~40 %）Hydrocarbon-containiproducts combustable organic thing, then be homogenized modification；It is described to contain nytron
The combustable organic thing of thing is the one or more in coal tar, useless molding powder, waste Crumb rubber or husk etc..
Technical scheme is as follows used by of the invention another solves its technical problem：A kind of aluminium cell carbonaceous waste material is again
Life is alternative coal-fired method, after aluminium cell carbonaceous waste material is crushed into granularity≤25mm, is added equivalent to its quality 0.8
~8.0%（More preferably 3~7%）Catalytic oxidant and 1~50%（More preferably 20~40%）The organic of hydrocarbon-containiproducts can
Combustion things, homogenizing are modified, and obtain alternative fire coal.
Preferably, the catalytic oxidant is bichromate catalytic oxidant, metavanadate catalytic oxidant, ferrate
One or more in catalytic oxidant, perchlorate catalytic oxidant or nitrate catalytic oxidant etc.；The bichromate
Catalytic oxidant is the one or more in ammonium dichromate, strontium dichromate or lithium bichromate etc., the metavanadate catalysis oxidation
Agent is ammonium metavanadate, and the ferrate catalytic oxidant is ferric acid cobalt and/or ferrate-lithium etc., and the perchlorate is height
Lithium chlorate and/or cobaltous perchlorate etc., the nitrate catalytic oxidant are cerous nitrate, lanthanum nitrate, ferric nitrate, copper nitrate, nitric acid
One or more in lithium, nitric acid tin, nitric acid antimony, cobalt nitrate, zirconium nitrate, nickel nitrate, platinum nitrate, palladium nitrate or rhodium nitrate etc..
Preferably, the combustable organic thing of the hydrocarbon-containiproducts is in coal tar, useless molding powder, waste Crumb rubber or husk etc.
One or more.
Beneficial effects of the present invention are as follows：
（1）1 ton of aluminium cell carbonaceous waste material can be processed into 1 ton of alternative fire coal, and used with general industry kiln semibituminous coal,
Anthracite calorific value is suitable, average about 5000kcal/kg, can be used as alternative fire coal；
（2）During for manufacture of cement, in the case of other controlling of production process parameter constants, experiment display：Coal grinds yield phase
When kiln yield is without visible change, and kiln system operating mode is normal, and without strongly reducing atmosphere in kiln, clinker is without strong reduction feature, clinker knot grain
Take a turn for the better, the early stage of clinker and later strength are synchronously improved, and data statistics coal consumption is controlled in online and declines up to 7.5%, kiln tail discharge
Oil repellent detection has no change in flue gas, is not detected by cyanide；For fluidized bed furnace, rotary kiln, tunnel cave fire coal in use, coal
It is suitable to grind yield, for kiln yield without visible change, limekiln system condition is normal, and without strongly reducing atmosphere in kiln, data are controlled in online
It is suitable to count coal consumption, Oil repellent, which detects, in kiln tail discharge flue gas has no change, and detection lime quality is not detected by without visible change
Cyanide；
（3）The alternative coal-fired safety and environmental protection of aluminium cell carbonaceous materials recycling of the present invention, non-secondary pollution；
（4）The inventive method technique is simple, and has ready-made equipment can be selected, and energy consumption is low, cost is low, and treating capacity is big, suitable work
Industry metaplasia is produced.
Embodiment
With reference to embodiment, the invention will be further described.
Raw material used in the embodiment of the present invention or chemical reagent, unless otherwise specified, obtained by routine business approach
.
Embodiment 1
Aluminium cell carbonaceous waste material used in the embodiment of the present invention is derived from the block carbonaceous waste material stored up in certain aluminium manufacturer storehouse, detection
Aggregate sample inanimate matter content 28.49%, carbon content 71.51%, calorific value 5615kcal/kg；Detoxicant is used in the present embodiment
ZC-XJ1 type detoxification agent solutions（That is ferrate detoxicant and hypochlorite detoxicant is with mass ratio 1:1 saturation prepared is molten
Liquid）, catalytic oxidant used in the present embodiment is ZC-7 type liquid catalytic oxidants（That is perchlorate catalytic oxidant and nitre
Hydrochlorate catalytic oxidant is with mass ratio 2:The saturated solution that 1 mixture is prepared）, it is purchased from Hunan Province little Yin Wuji environmental energy
Science and Technology Development Co., Ltd..
（1）It is granulated detoxification：The aluminium cell carbonaceous waste material of bulk is crushed to by particle diameter using double roller squash type crushing system
≤ 8mm, broken while, atomized spray equivalent to aluminium cell carbonaceous waste material quality 8% ZC-XJ1 type detoxification agent solutions,
And catalysis oxidation decomposition is implemented to body containing dicyanogen with the dust-removing waste gas of catalytic oxidizer negative pressure extracting crushing system, obtain granulation detoxification
Material；
（2）Activation：By step（1）Gained granulation detoxification material is placed in blender, is added under agitation equivalent to aluminium cell
The ZC-7 type liquid catalytic oxidants of carbonaceous waste material quality 6%, homogenizing are modified, and obtain alternative fire coal.
Alternative fire coal obtained by the present embodiment is used for certain Ф 3.5 × 54m new type nonaqueous cement production line（Used in the factory
Raw coal be volatile matter 16.7% semibituminous coal, calorific value 5587kcal/kg, raw coal sulfur content 3.7%）, will be substituted obtained by the present embodiment
Property coal-fired and raw coal in mass ratio 1:1 ratio is incorporated in coal mill grinding together.
In the case of other controlling of production process parameter constants, experiment display：Coal mill yield is suitable, and kiln yield is without visible
Change, kiln system operating mode is normal, and kiln is interior to be taken a turn for the better without strongly reducing atmosphere, clinker without strong reduction feature, clinker knot grain, and number is controlled in online
Coal consumption declines 7.3% according to statistics, and kiln tail discharges Oil repellent detection in flue gas and has no change, is not detected by cyanide.
Detection gained clinker setting time is normal, and 3 days compression strength improves 3.3MPa, and compression strength improves within 28 days
3.9MPa.Through thinking：It is due to that bringing into for fluoride cooperates with caused fluorine sulphur ore deposit with sulphur in raw coal in alternative fire coal
Agent, burn-ability is improved, cause clinker knot graininess to take a turn for the better and decline with coal consumption, and because bringing into for fluorine generates appropriate fluoaluminic acid
Calcium mineral cause the early stage of clinker and later strength synchronously to improve.
This experiment shows that the waste cathode carbon block material of activated modification has the combustibility suitable with semibituminous coal, can made
For alternative fire coal.
Embodiment 2
Aluminium cell carbonaceous waste material used in the embodiment of the present invention is derived from the mixing bulk carbonaceous waste material stored up in certain aluminium manufacturer storehouse
（Containing anodic carbon residue）, detection aggregate sample inanimate matter content 34.17%, carbon content 65.83%, calorific value 5169kcal/kg；It is of the invention real
Applying detoxification agent solution used in example is：Sodium hypochlorite is first added to water of 2 times equivalent to its quality to dissolve, then by potassium ferrate
1 is pressed with potassium hydroxide:1 mass ratio is dissolved in the saturated solution formed in liquor natrii hypochloritis；It is catalyzed used in the present embodiment
Oxidant is ZC-3 type powdery catalytic oxidants（Bichromate catalytic oxidant and nitrate catalytic oxidant are with mass ratio 1:1
Mixture）, it is purchased from Hunan Province little Yin Wuji environmental energy Science and Technology Development Co., Ltd.；Auxiliary material used in the present embodiment is city
The useless molding powder sold.
（1）It is granulated detoxification：Using paddle type mill crushing system will mix block aluminium cell carbonaceous waste material be crushed to particle diameter≤
5mm, broken while, atomized spray equivalent to aluminium cell carbonaceous waste material quality 6% detoxification agent solution, and to be catalyzed oxygen
The dust-removing waste gas for changing device negative pressure extracting crushing system implements catalysis oxidation decomposition to body containing dicyanogen, must be granulated detoxification material；
（2）Activation：By step（1）Gained granulation detoxification material is placed in blender, is added under agitation equivalent to aluminium cell
The ZC-3 type powdery catalytic oxidants of carbonaceous waste material quality 3.5% and the useless modeling equivalent to aluminium cell carbonaceous waste material quality 15%
Powder, homogenizing are modified, and obtain alternative fire coal.
Alternative fire coal obtained by the present embodiment is used for certain Ф 3 × 46m new type nonaqueous cement production line（It is former used in the factory
Coal be volatile matter 8.3% anthracite, calorific value 5349kcal/kg, raw coal sulfur content 1.8%）, by alternative combustion obtained by the present embodiment
Coal and raw coal in mass ratio 1:1 ratio is incorporated in coal mill grinding together.
In the case of other controlling of production process parameter constants, experiment display：Coal mill yield is suitable, and kiln yield is without visible
Change, kiln system operating mode is normal, and kiln is interior to be taken a turn for the better without strongly reducing atmosphere, clinker without strong reduction feature, clinker knot grain, and number is controlled in online
Coal consumption declines 5% according to statistics, and kiln tail discharges Oil repellent detection in flue gas and has no change, is not detected by cyanide.
Detection clinker setting time is normal, and 3 days compression strength improves 2.9MPa, and compression strength improves 1.8MPa within 28 days.Through
Think：It is due to that bringing into for fluoride cooperates with caused fluorine sulphur mineralizer with sulphur in raw coal in alternative fire coal, improves
Burn-ability, causes that clinker knot graininess takes a turn for the better and coal consumption declines, and because bringing into for fluorine generates appropriate calcium aluminum fluoride mineral and caused
The early stage and later strength for making clinker synchronously improve.
This experiment shows that the aluminium cell carbonaceous waste material of activated modification has the combustibility suitable with anthracite, can
As alternative fire coal.
Embodiment 3
Aluminium cell carbonaceous waste material used in the embodiment of the present invention is derived from the mixing bulk carbonaceous waste material stored up in certain aluminium manufacturer storehouse
（Containing anodic carbon residue）, detection inanimate matter content 34.17%, carbon content 65.83%, calorific value 5169kcal/kg；The present embodiment is used
Detoxicant be ZC-XJ10 type detoxification agent solutions（The saturated solution that thiosulfate detoxicant is prepared）, the present embodiment used
Catalytic oxidant be ZC-3 type powdery catalytic oxidants（Bichromate catalytic oxidant and nitrate catalytic oxidant are with quality
Than 1:1 mixture）, it is purchased from Hunan Province little Yin Wuji environmental energy Science and Technology Development Co., Ltd.；Used in the present embodiment
Auxiliary material is commercially available calcium hydroxide, calcium oxide and waste Crumb rubber.
（1）It is granulated detoxification：Using paddle type mill crushing system will mix block aluminium cell carbonaceous waste material be crushed to particle diameter≤
10mm, broken while, atomized spray equivalent to aluminium cell carbonaceous waste material quality 5% ZC-XJ10 type detoxification agent solutions,
And catalysis oxidation decomposition is implemented to body containing dicyanogen with the dust-removing waste gas of catalytic oxidizer negative pressure extracting crushing system, obtain granulation detoxification
Material；
（2）Activation：By step（1）Gained granulation detoxification material is placed in in the leaching groove for rolling over mixing device, adds phase under agitation
When in the ZC-3 type powdery catalytic oxidants and 10.4% calcium hydroxide of aluminium cell carbonaceous waste material quality 5%, add equivalent to
The water of 4 times of aluminium cell carbonaceous waste material quality rolles over mixed leaching oxidation dealkalize, and filtering washing obtains dealkalize activated carbon slag, and detection alkali takes off
Except rate 81.4%, filtrate containing alkali reclaims concentrated base processed, and water lotion is reclaimed for leaching, dry dealkalize activated carbon slag to moisture≤10%,
Add equivalent to the calcium oxide of dealkalize activated carbon slag amount 5% and mixed equivalent to the waste Crumb rubber of dealkalize activated carbon slag amount 20%
Compound, homogenizing are modified, and obtain alternative fire coal.
Alternative fire coal obtained by the present embodiment is used for certain Ф 3.5 × 54m new type nonaqueous cement production line（Used in the factory
Raw coal be volatile matter 8.3% anthracite, calorific value 5349kcal/kg, raw coal sulfur content 3.1%）, will be alternative obtained by the present embodiment
Coal-fired and raw coal in mass ratio 1:1 ratio is incorporated in coal mill grinding together.
In the case of other controlling of production process parameter constants, experiment display：Coal mill yield is suitable, and kiln yield is without visible
Change, kiln system operating mode is normal, and kiln is interior to be taken a turn for the better without strongly reducing atmosphere, clinker without strong reduction feature, clinker knot grain, and number is controlled in online
Coal consumption declines 7% according to statistics, and kiln tail discharges Oil repellent detection in flue gas and has no change, is not detected by cyanide.
Detection gained clinker setting time is normal, and 3 days compression strength improves 3.2MPa, and compression strength improves within 28 days
2.7MPa.Through thinking：It is due to that bringing into for fluoride cooperates with caused fluorine sulphur ore deposit with sulphur in raw coal in alternative fire coal
Agent, burn-ability is improved, cause clinker knot graininess to take a turn for the better and decline with coal consumption, and because bringing into for fluorine generates appropriate fluoaluminic acid
Calcium mineral cause the early stage of clinker and later strength synchronously to improve.
This experiment shows that the waste cathode carbon block material of activated modification has the combustibility suitable with anthracite, can made
For alternative fire coal.
Embodiment 4
Aluminium cell carbonaceous waste material used in the embodiment of the present invention is derived from the mixing bulk carbonaceous waste material stored up in certain aluminium manufacturer storehouse
（Containing anodic carbon residue）, detection inanimate matter content 34.17%, carbon content 65.83%, calorific value 5169kcal/kg；Institute of the embodiment of the present invention
The detoxicant used is ZC-XJ10 type detoxification agent solutions（The saturated solution that thiosulfate detoxicant is prepared）, the present embodiment institute
The catalytic oxidant used is ZC-9 type catalytic oxidants（Metavanadate catalytic oxidant and nitrate catalytic oxidant are with quality
Than 1:1 mixture）, it is purchased from Hunan Province little Yin Wuji environmental energy Science and Technology Development Co., Ltd.；Used in the present embodiment
Auxiliary material is commercially available calcium oxide and sodium hydroxide.
（1）It is granulated detoxification：Using paddle type mill crushing system will mix block aluminium cell carbonaceous waste material be crushed to particle diameter≤
5mm, broken while, atomized spray equivalent to aluminium cell carbonaceous waste material quality 5% ZC-XJ10 type detoxification agent solutions, and
Catalysis oxidation decomposition is implemented to body containing dicyanogen with the dust-removing waste gas of catalytic oxidizer negative pressure extracting crushing system, granulation is obtained and removes poisonous substance
Material；
（2）Activation：By step（1）Gained granulation detoxification material is placed in in the leaching can for rolling over mixing device, adds phase under agitation
When the ZC-9 types catalytic oxidant in aluminium cell carbonaceous waste material quality 4.6%, equivalent to aluminium cell carbonaceous waste material quality 9.2%
Calcium oxide and the sodium hydroxide equivalent to aluminium cell carbonaceous waste material quality 8.6%, add equivalent to aluminium cell carbonaceous waste material
The water that 5 times of quality rolles over mixed leaching oxidation dealuminzation dealkalize, filtering washing, obtains the activated carbon slag of dealuminzation alkali, detects aluminium removal efficiency
74.9%th, alkali removal efficiency 87.7%, the recovery of the filtrate of alkali containing aluminium carry aluminium concentrated base, and water lotion is reclaimed for leaching, and dries the work of dealuminzation alkali
Change carbon slag to moisture≤15%, homogenizing to be modified, obtain alternative fire coal.
Alternative fire coal obtained by the present embodiment is used for certain Ф 3 × 46m new type nonaqueous cement production line（It is former used in the factory
Coal be volatile matter 8.3% anthracite, calorific value 5349kcal/kg, raw coal sulfur content 3.7%）, by alternative combustion obtained by the present embodiment
Coal and raw coal in mass ratio 1:1 ratio is incorporated in coal mill grinding together.
In the case of other controlling of production process parameter constants, experiment display：Coal mill yield is suitable, and kiln yield is without visible
Change, kiln system operating mode is normal, and kiln is interior to be taken a turn for the better without strongly reducing atmosphere, clinker without strong reduction feature, clinker knot grain, and number is controlled in online
Coal consumption declines 7.5% according to statistics, and kiln tail discharges Oil repellent detection in flue gas and has no change, is not detected by cyanide.
Detection gained clinker setting time is normal, and 3 days compression strength improves 3.0MPa, and compression strength improves within 28 days
2.1MPa.Through thinking：It is due to that bringing into for fluoride cooperates with caused fluorine sulphur ore deposit with sulphur in raw coal in alternative fire coal
Agent, burn-ability is improved, cause clinker knot graininess to take a turn for the better and decline with coal consumption, and because bringing into for fluorine generates appropriate fluoaluminic acid
Calcium mineral cause the early stage of clinker and later strength synchronously to improve.
This experiment shows that the waste cathode carbon block material of activated modification has the combustibility suitable with anthracite, can made
For alternative fire coal.
Embodiment 5
Aluminium cell carbonaceous waste material used in the embodiment of the present invention is derived from the block carbonaceous waste material stored up in certain aluminium manufacturer storehouse, detection
Inanimate matter content 28.49%, carbon content 71.51%, the kcal/kg of calorific value 5615；Detoxicant is used in the embodiment of the present invention
ZC-XJ1 type detoxification agent solutions（Ferrate detoxicant and hypochlorite detoxicant are with mass ratio 1:1 saturated solution prepared）,
Catalytic oxidant used in the present embodiment is ZC-7 type liquid catalytic oxidants（Perchlorate catalytic oxidant and nitrate are urged
Change oxidant with mass ratio 2:The saturated solution that 1 mixture is prepared）, it is purchased from Hunan Province little Yin Wuji environmental energy science and technology and opens
Send out Co., Ltd；The present embodiment is from commercially available liquid carbon dioxide as leaching solvent.
（1）It is granulated detoxification：Using double roller squash type crushing system by block aluminium cell carbonaceous waste material be crushed to particle diameter≤
8mm, broken while, atomized spray equivalent to aluminium cell carbonaceous waste material quality 8% ZC-XJ1 type detoxification agent solutions, and
Catalysis oxidation decomposition is implemented to body containing dicyanogen with the dust-removing waste gas of catalytic oxidizer negative pressure extracting crushing system, granulation is obtained and removes poisonous substance
Material；
（2）Activation：By step（1）Gained granulation detoxification material is placed in the leaching fluid bowl with milling device, and leaching is dissolved in 10 DEG C of liquid
Processed in state carbon dioxide, separate, obtain carbon dry mash, the carbon dry mash of gained is placed in blender, added under agitation
Enter the ZC-7 type liquid catalytic oxidants equivalent to carbon dry powder quality 3.1%, homogenizing is modified, and obtains alternative fire coal.
Alternative fire coal obtained by the present embodiment is used for certain Ф 3.5 × 54m new type nonaqueous cement production line（Used in the factory
Raw coal be volatile matter 16.7% semibituminous coal, calorific value 5587kcal/kg, raw coal sulfur content 3.7%）, will be substituted obtained by the present embodiment
Property coal-fired and raw coal in mass ratio 1:1 ratio is incorporated in coal mill grinding together.
In the case of other controlling of production process parameter constants, experiment display：Coal mill yield is suitable, and kiln yield is without visible
Change, kiln system operating mode is normal, and kiln is interior to be taken a turn for the better without strongly reducing atmosphere, clinker without strong reduction feature, clinker knot grain, and number is controlled in online
Coal consumption is suitable according to statistics, and Oil repellent, which detects, in kiln tail discharge flue gas has no change, is not detected by cyanide.Detection gained clinker coagulates
Tie the time it is normal, 3 days and 28 days compression strength it is suitable.
This experiment shows that the waste cathode carbon block material of activated modification has the combustibility suitable with semibituminous coal, can made
For alternative fire coal.
Embodiment 6
Aluminium cell carbonaceous waste material used in the embodiment of the present invention is derived from the block carbonaceous waste material mixing stored up in certain aluminium manufacturer storehouse
Thing（Carbon granules containing anode）, detection inanimate matter content 41.14%, carbon content 58.86%, calorific value 4622kcal/kg；The embodiment of the present invention
Used detoxicant is ZC-XJ3 type detoxification agent solutions（Bichromate detoxicant and hypochlorite detoxicant are with mass ratio 1:1
The saturated solution of preparation）, it is purchased from Hunan Province little Yin Wuji environmental energy Science and Technology Development Co., Ltd.；Urged used in the present embodiment
Change oxidant is commercially available ammonium dichromate, metavanadic acid ammonia, lithium perchlorate, cerous nitrate, cobalt nitrate, nickel nitrate in mass ratio 2:1:1:
2:2:3 ratio is dissolved in saturated solution made of water.
（1）It is granulated detoxification：Block aluminium cell carbonaceous waste material is crushed to by particle diameter≤25mm using paddle type mill crushing system,
Broken while, atomized spray equivalent to aluminium cell carbonaceous waste material quality 3.2% ZC-XJ3 type detoxification agent solutions, and with
The dust-removing waste gas of catalytic oxidizer negative pressure extracting crushing system implements catalysis oxidation decomposition to body containing dicyanogen, obtains granulation and removes poisonous substance
Material；
（2）Activation：By step（1）Gained granulation detoxification material is placed in spreading formula blender, is added under agitation equivalent to aluminium
The catalysis oxidation agent solution of electrolytic cell carbonaceous waste material quality 3.8%, homogenizing are modified, and obtain alternative fire coal.
Using alternative coal-fired certain factory's drying system that is used for obtained by the present embodiment by the use of being used as alternative fire coal on fluidized bed furnace（The factory
Raw coal used in fluidized bed furnace be volatile matter 12.4% semibituminous coal, calorific value 4983kcal/kg, seethe with excitement boiler ash sediment in carbon content 6.9%）,
The alternative coal-fired raw coal of substitution completely obtained by the present embodiment is tested, experiment display, alternative fire coal fires in fluidized bed furnace
Burn functional, furnace temperature is normal, and carbon content is down to 2.9% in the boiler ash sediment that seethes with excitement, and Oil repellent detection is not in drying system discharge flue gas
See change, be not detected by cyanide.
This experiment shows, the combustibility phase of the aluminium cell carbonaceous waste material of activated modification with semibituminous coal in fluidized bed furnace
When alternative fire coal can be used as.
Embodiment 7
Aluminium cell carbonaceous waste material used in the embodiment of the present invention is derived from the waste cathode carbon block stored up in certain aluminium manufacturer storehouse, detects nothing
Machine matter content 30.47%, carbon content 69.53%, calorific value 5460kcal/kg；Detoxicant used in the embodiment of the present invention is ZC-
XJ5 type detoxification agent solutions（Perchlorate detoxicant and hypochlorite detoxicant are with mass ratio 1:1 saturated solution prepared）, this reality
It is ZC-9 type catalytic oxidants to apply catalytic oxidant used in example（Metavanadate catalytic oxidant and nitrate catalytic oxidant
With mass ratio 1:1 mixture）, it is purchased from Hunan Province little Yin Wuji environmental energy Science and Technology Development Co., Ltd..
（1）It is granulated detoxification：Aluminium cell carbonaceous waste material is crushed to by particle diameter≤10mm using impact type crushing system, broken
While broken, atomized spray equivalent to aluminium cell carbonaceous waste material quality 5% ZC-XJ5 type detoxification agent solutions, and to be catalyzed oxygen
The dust-removing waste gas for changing device negative pressure extracting crushing system implements catalysis oxidation decomposition to body containing dicyanogen, must be granulated detoxification material；
（2）Activation：By step（1）Gained granulation detoxification material is placed in blender, is added under agitation equivalent to aluminium cell
The ZC-9 type catalytic oxidants of carbonaceous waste material quality 2.9%, homogenizing are modified, and obtain alternative fire coal.
By the alternative coal-fired alternative fire coal for being used as certain factory revolution lime burning obtained by the present embodiment（The burnt lime institute of factory
With the semibituminous coal that raw coal is volatile matter 17.4%, calorific value 5523kcal/kg）, alternative fire coal obtained by the present embodiment is pressed with raw coal
Mass ratio 1:1 ratio supplying is milled into coal dust.
In the case of other controlling of production process parameter constants, experiment display：Coal mill yield is suitable, and kiln yield is without visible
Change, limekiln system condition is normal, and without strongly reducing atmosphere in kiln, online middle control data statistics coal consumption is suitable, kiln tail discharge cigarette
Oil repellent detection has no change in gas, and detection lime quality is not detected by cyanide without visible change.
This experiment shows, the combustibility phase of the waste cathode carbon block material of activated modification with semibituminous coal in rotary kiln
When alternative fire coal can be used as.
Embodiment 8
Aluminium cell carbonaceous waste material used in the embodiment of the present invention is derived from the block carbonaceous waste material stored up in certain aluminium manufacturer storehouse, detection
Inanimate matter content 37.2%, carbon content 62.8%, the kcal/kg of calorific value 4931；Detoxicant used in the embodiment of the present invention is ZC-
XJ13 type detoxification agent solutions（The saturated solution that hypochlorite detoxicant is prepared）, catalytic oxidant used in the present embodiment is
ZC-11 type catalytic oxidants（Ferrate catalytic oxidant and nitrate catalytic oxidant are with mass ratio 1:1 mixture）,
It is purchased from Hunan Province little Yin Wuji environmental energy Science and Technology Development Co., Ltd.；Auxiliary material used in the present embodiment is commercially available oxidation
Calcium.
（1）It is granulated detoxification：Block aluminium cell carbonaceous waste material is crushed to by particle diameter≤5mm using impact type crushing system,
Broken while, atomized spray equivalent to aluminium cell carbonaceous waste material quality 7% ZC-XJ13 type detoxification agent solutions, and to urge
The dust-removing waste gas for changing oxidator negative pressure extracting crushing system implements catalysis oxidation decomposition to body containing dicyanogen, must be granulated detoxification material；
（2）Activation：By step（1）Gained granulation detoxification material is placed in blender, is added under agitation equivalent to aluminium cell
The ZC-11 types catalytic oxidant of carbonaceous waste material quality 4.1% and the calcium oxide equivalent to aluminium cell carbonaceous waste material quality 5%,
Change and be modified, obtain alternative fire coal.
Alternative fire coal obtained by the present embodiment is made into alternative fire coal for certain Building Materials Factory's tunnel cave shale brick firing system
（Raw coal used in factory's tunnel cave shale brick firing system be volatile matter 7.6% anthracite, calorific value 5031kcal/kg）, by this reality
Apply alternative coal-fired complete substitution raw coal obtained by example to be tested, experiment display, alternative fire coal obtained by the embodiment of the present invention exists
Combustibility is good in tunnel cave shale brick firing system, and tunnel cave operating mode is normal.After testing：Using alternative coal-fired shale brick
Sintering quality is more preferable, and compression strength averagely improves 2.6MPa, and Oil repellent detects in tunnel cave shale brick firing system discharge flue gas
Change is had no, is not detected by cyanide.
This experiment shows that the aluminium cell carbonaceous waste material and anthracite of activated modification are in tunnel cave shale brick firing system
In combustibility it is suitable, alternative fire coal can be used as.
Embodiment 9
Aluminium cell carbonaceous waste material used in the embodiment of the present invention is derived from the block carbonaceous waste material stored up in certain aluminium manufacturer storehouse, detection
Aggregate sample inanimate matter content 28.49%, carbon content 71.51%, calorific value 5615kcal/kg；Catalysis oxidation used in the present embodiment
Agent is ZC-7 type liquid catalytic oxidants（Perchlorate catalytic oxidant and nitrate catalytic oxidant are with mass ratio 2:1 prepares
Saturated solution）, it is purchased from Hunan Province little Yin Wuji environmental energy Science and Technology Development Co., Ltd.；Auxiliary material used in the present embodiment
For commercially available coal tar.
After aluminium cell carbonaceous waste material is crushed into granularity≤15mm, be placed in blender, add under agitation equivalent to
ZC-7 type liquid catalytic oxidants of aluminium cell carbonaceous waste material quality 6.5% and equivalent to aluminium cell carbonaceous waste material quality 30%
Coal tar, homogenizing be modified, obtain alternative fire coal.
By the alternative coal-fired alternative fire coal for being used as certain factory revolution lime burning obtained by the present embodiment（The burnt lime institute of factory
With the semibituminous coal that raw coal is volatile matter 17.4%, calorific value 5523kcal/kg）, alternative fire coal obtained by the present embodiment is pressed with raw coal
Mass ratio 1:1 ratio supplying is milled into coal dust.
In the case of other controlling of production process parameter constants, experiment display：Coal mill yield is suitable, and kiln yield is without visible
Change, limekiln system condition is normal, and without strongly reducing atmosphere in kiln, online middle control data statistics coal consumption is suitable, kiln tail discharge cigarette
Oil repellent detection has no change in gas, and detection lime quality is not detected by cyanide without visible change.
This experiment shows, the combustibility phase of the waste cathode carbon block material of activated modification with semibituminous coal in rotary kiln
When alternative fire coal can be used as.
Claims (9)
1. a kind of aluminium cell carbonaceous materials recycling is alternative coal-fired method, it is characterised in that is comprised the following steps：
（1）It is granulated detoxification：Aluminium cell carbonaceous waste material is crushed, broken while, atomized spray is equivalent to aluminium cell charcoal
The detoxification agent solution of matter waste material quality 1~10%, and with the dust-removing waste gas of catalytic oxidizer negative pressure extracting crushing system, must be granulated
Detoxification material；
（2）Activation：By step（1）Gained granulation detoxification material is placed in blender, is added under agitation equivalent to aluminium cell
The catalytic oxidant of carbonaceous waste material quality 0.6~8.0%, homogenizing are modified, and obtain alternative fire coal；
Or by step（1）Gained granulation detoxification material is placed in in the leaching groove or tank that stir or roll over mixing device, adds phase respectively
When in the catalytic oxidant and 2~20% lime of aluminium cell carbonaceous waste material quality 1~8%, and add equivalent to aluminium cell
Mixed, oxidation dealkalize, filtering or filtering washing are rolled in the water stirring of 1~10 times of carbonaceous waste material quality, are obtained dealkalize activated carbon slag, are dried
To moisture≤15%, homogenizing is modified, and obtains alternative fire coal；
Or by step（1）Gained granulation detoxification material is placed in in the leaching groove or tank that stir or roll over mixing device, adds phase respectively
When in the catalytic oxidant of aluminium cell carbonaceous waste material quality 1~8%, 2~20% lime, 2~20% sodium hydroxide, and add
Enter water stirring of 1~10 times equivalent to aluminium cell carbonaceous waste material quality or roll over mixed, oxidation dealuminzation dealkalize, filtering or filter water
Wash, obtain the activated carbon slag of dealuminzation alkali, dry to moisture≤15%, homogenizing and be modified, obtain alternative fire coal；
Or by step（1）Gained granulation detoxification material leaching, which is dissolved in 0~80 DEG C of overcritical or liquid carbon dioxide, processes, then
In separating obtained carbon dry mash, the catalytic oxidant added equivalent to carbon dry mash quality 0.5~6% mix
Matter is modified, and obtains alternative fire coal.
2. aluminium cell carbonaceous materials recycling is alternative coal-fired method according to claim 1, it is characterised in that：Step
（1）In, granularity≤25mm after waste material is broken；The crumbling method is hammering, extruding or impact type crush.
3. aluminium cell carbonaceous materials recycling according to claim 1 or claim 2 is alternative coal-fired method, it is characterised in that：
Step（1）In, the main component of the aluminium cell carbonaceous waste material is waste cathode carbon block and/or scrap anode carbon granule, wherein, it is inorganic
Matter content 20~50%, carbon content 50~80%, 3800~6000kcal/kg of calorific value.
4. being alternative coal-fired method according to one of claims 1 to 3 aluminium cell carbonaceous materials recycling, its feature exists
In：Step（1）In, the detoxicant is ferrate detoxicant, bichromate detoxicant, thiosulfate detoxicant, high chlorine
One or more in hydrochlorate detoxicant, hydroxide detoxicant, hypochlorite detoxicant or chlorine dioxide；The ferrate
Detoxicant is the one or more in potassium ferrate, ferrate-lithium or Na2Fe04, and the bichromate detoxicant is dichromic acid
One or more in potassium, sodium dichromate, dichromic acid cobalt or dichromic acid acid anhydride, the thiosulfate detoxicant are sodium thiosulfate
And/or potassium thiosulfate, the perchlorate are lithium perchlorate and/or cobaltous perchlorate, the hydroxide is cobalt hydroxide, hydrogen
One or more in sodium oxide molybdena or potassium hydroxide, the hypochlorite are sodium hypochlorite and/or calcium hypochlorite.
5. being alternative coal-fired method according to one of Claims 1 to 4 aluminium cell carbonaceous materials recycling, its feature exists
In：Step（2）In, the catalytic oxidant is bichromate catalytic oxidant, metavanadate catalytic oxidant, ferrate are urged
Change the one or more in oxidant, perchlorate catalytic oxidant or nitrate catalytic oxidant；The bichromate catalysis
Oxidant is the one or more in ammonium dichromate, strontium dichromate or lithium bichromate, and the metavanadate catalytic oxidant is inclined
Ammonium vanadate, the ferrate catalytic oxidant are ferric acid cobalt and/or ferrate-lithium, and the perchlorate is lithium perchlorate
And/or cobaltous perchlorate, the nitrate catalytic oxidant are cerous nitrate, lanthanum nitrate, ferric nitrate, copper nitrate, lithium nitrate, nitric acid
One or more in tin, nitric acid antimony, cobalt nitrate, zirconium nitrate, nickel nitrate, platinum nitrate, palladium nitrate or rhodium nitrate.
6. being alternative coal-fired method according to one of Claims 1 to 5 aluminium cell carbonaceous materials recycling, its feature exists
In：Step（1）In, the detoxification agent solution dissolves for sodium hypochlorite first to be added to water of 1.5~5.5 times equivalent to its quality,
Potassium ferrate and potassium hydroxide are pressed 1 again:0.8~1.2 mass ratio is dissolved in the saturated solution formed in liquor natrii hypochloritis；Step
Suddenly（2）In, the catalytic oxidant is ammonium dichromate, metavanadic acid ammonia, lithium perchlorate, cerous nitrate, cobalt nitrate, nickel nitrate press quality
Than 2:0.8~1.2:0.8~1.2:1.5~2.5:1.5~2.5:2.5~3.5 ratio is dissolved in saturated solution made of water.
7. being alternative coal-fired method according to one of claim 1~6 aluminium cell carbonaceous materials recycling, its feature exists
In：Step（2）In, after catalytic oxidant is added or after drying, add equivalent to the % of aluminium cell carbonaceous waste material quality 1~20
Calcium oxide and/or magnesia, and/or hydrocarbon-containiproducts equivalent to the % of aluminium cell carbonaceous waste material quality 1~50 have
Machine combustible, then it is homogenized modification；The combustable organic thing of the hydrocarbon-containiproducts is coal tar, useless molding powder, waste Crumb rubber or paddy
One or more in shell.
8. a kind of aluminium cell carbonaceous materials recycling is alternative coal-fired method, it is characterised in that：Aluminium cell carbonaceous is given up
After material is crushed to granularity≤25mm, the catalytic oxidant equivalent to its quality 0.8~8.0% and 1~50% carbon containing hydrogenation are added
The combustable organic thing of compound, homogenizing are modified, and obtain alternative fire coal.
9. aluminium cell carbonaceous materials recycling is alternative coal-fired method according to claim 8, it is characterised in that：It is described
Catalytic oxidant is bichromate catalytic oxidant, metavanadate catalytic oxidant, ferrate catalytic oxidant, perchlorate
One or more in catalytic oxidant or nitrate catalytic oxidant；The bichromate catalytic oxidant be ammonium dichromate,
One or more in strontium dichromate or lithium bichromate, the metavanadate catalytic oxidant are ammonium metavanadate, the ferric acid
Salt catalytic oxidant is ferric acid cobalt and/or ferrate-lithium, and the perchlorate is lithium perchlorate and/or cobaltous perchlorate, described
Nitrate catalytic oxidant is cerous nitrate, lanthanum nitrate, ferric nitrate, copper nitrate, lithium nitrate, nitric acid tin, nitric acid antimony, cobalt nitrate, nitre
One or more in sour zirconium, nickel nitrate, platinum nitrate, palladium nitrate or rhodium nitrate；The combustable organic thing of the hydrocarbon-containiproducts
For the one or more in coal tar, useless molding powder, waste Crumb rubber or husk.
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