CN107363074B - A kind of aluminium cell carbonaceous materials recycling is the method for alternative fire coal - Google Patents
A kind of aluminium cell carbonaceous materials recycling is the method for alternative fire coal Download PDFInfo
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- CN107363074B CN107363074B CN201710600311.5A CN201710600311A CN107363074B CN 107363074 B CN107363074 B CN 107363074B CN 201710600311 A CN201710600311 A CN 201710600311A CN 107363074 B CN107363074 B CN 107363074B
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- aluminium cell
- coal
- waste material
- detoxification
- catalytic oxidant
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- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 149
- 239000004411 aluminium Substances 0.000 title claims abstract description 139
- 239000003245 coal Substances 0.000 title claims abstract description 137
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 238000000034 method Methods 0.000 title claims abstract description 69
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 21
- 238000004064 recycling Methods 0.000 title claims abstract description 21
- 239000002699 waste material Substances 0.000 claims abstract description 144
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 127
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 100
- 230000003197 catalytic effect Effects 0.000 claims abstract description 99
- 239000007800 oxidant agent Substances 0.000 claims abstract description 98
- 230000001590 oxidative effect Effects 0.000 claims abstract description 92
- 238000001784 detoxification Methods 0.000 claims abstract description 67
- 239000000463 material Substances 0.000 claims abstract description 46
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 41
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 33
- 230000003647 oxidation Effects 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 27
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims abstract description 16
- 235000011941 Tilia x europaea Nutrition 0.000 claims abstract description 16
- 239000004571 lime Substances 0.000 claims abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 16
- 230000004048 modification Effects 0.000 claims abstract description 14
- 238000012986 modification Methods 0.000 claims abstract description 14
- 238000001914 filtration Methods 0.000 claims abstract description 13
- 239000007921 spray Substances 0.000 claims abstract description 12
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 7
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 36
- 238000005469 granulation Methods 0.000 claims description 23
- 230000003179 granulation Effects 0.000 claims description 23
- 239000012047 saturated solution Substances 0.000 claims description 20
- 238000002386 leaching Methods 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 18
- 239000003610 charcoal Substances 0.000 claims description 17
- 239000003513 alkali Substances 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 238000007792 addition Methods 0.000 claims description 11
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 11
- 239000008187 granular material Substances 0.000 claims description 11
- 239000002893 slag Substances 0.000 claims description 11
- 239000002912 waste gas Substances 0.000 claims description 10
- 239000000292 calcium oxide Substances 0.000 claims description 9
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- 239000011280 coal tar Substances 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 6
- 229920002209 Crumb rubber Polymers 0.000 claims description 5
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 5
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 5
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 5
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 5
- 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 5
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 5
- 239000010903 husk Substances 0.000 claims description 4
- 238000005096 rolling process Methods 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 238000004090 dissolution Methods 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
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- UMPKMCDVBZFQOK-UHFFFAOYSA-N potassium;iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[K+].[Fe+3] UMPKMCDVBZFQOK-UHFFFAOYSA-N 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims 1
- 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 1
- 229910052804 chromium Inorganic materials 0.000 claims 1
- 239000011651 chromium Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 27
- 230000008569 process Effects 0.000 abstract description 18
- 238000012545 processing Methods 0.000 abstract description 13
- 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
- 230000003213 activating effect Effects 0.000 abstract description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 67
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 25
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 22
- 238000012360 testing method Methods 0.000 description 21
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 20
- 239000011737 fluorine Substances 0.000 description 20
- 229910052731 fluorine Inorganic materials 0.000 description 20
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 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
- 239000003546 flue gas Substances 0.000 description 17
- 238000006555 catalytic reaction Methods 0.000 description 16
- 239000004568 cement Substances 0.000 description 16
- 238000001514 detection method Methods 0.000 description 16
- 229910002651 NO3 Inorganic materials 0.000 description 15
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 15
- 238000005516 engineering process Methods 0.000 description 14
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 13
- 238000000227 grinding Methods 0.000 description 13
- 230000008859 change Effects 0.000 description 12
- 230000018109 developmental process Effects 0.000 description 12
- 230000007613 environmental effect Effects 0.000 description 12
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 12
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 12
- 238000002485 combustion reaction Methods 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
- 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
- 230000009467 reduction Effects 0.000 description 9
- 239000011449 brick Substances 0.000 description 8
- 235000012255 calcium oxide Nutrition 0.000 description 8
- 239000000446 fuel Substances 0.000 description 8
- 238000005868 electrolysis reaction Methods 0.000 description 7
- ALTWGIIQPLQAAM-UHFFFAOYSA-N metavanadate Chemical compound [O-][V](=O)=O ALTWGIIQPLQAAM-UHFFFAOYSA-N 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 229910001610 cryolite Inorganic materials 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 229910052744 lithium Inorganic materials 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
- 239000000126 substance Substances 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
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000002817 coal dust Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- -1 due to heat effect Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000005611 electricity 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
- 239000002245 particle Substances 0.000 description 5
- 239000002910 solid waste Substances 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 5
- 230000001360 synchronised effect Effects 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
- JOSWYUNQBRPBDN-UHFFFAOYSA-P ammonium dichromate Chemical compound [NH4+].[NH4+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O JOSWYUNQBRPBDN-UHFFFAOYSA-P 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-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
- 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 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000000047 product Substances 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
- 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 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
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 229910001576 calcium mineral Inorganic materials 0.000 description 3
- 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 description 3
- 230000006378 damage 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
- 229910017604 nitric acid 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
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- WBJXZTQXFVDYIZ-UHFFFAOYSA-N [Sb].[N+](=O)(O)[O-] Chemical compound [Sb].[N+](=O)(O)[O-] WBJXZTQXFVDYIZ-UHFFFAOYSA-N 0.000 description 2
- KKKAMDZVMJEEHQ-UHFFFAOYSA-N [Sn].[N+](=O)(O)[O-] Chemical compound [Sn].[N+](=O)(O)[O-] KKKAMDZVMJEEHQ-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 235000019504 cigarettes Nutrition 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000029087 digestion Effects 0.000 description 2
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 2
- 238000005485 electric heating Methods 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
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 229910000462 iron(III) oxide hydroxide Inorganic materials 0.000 description 2
- 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 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
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- 238000005192 partition Methods 0.000 description 2
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 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 description 2
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- 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 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
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- 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
- 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 description 1
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 1
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 description 1
- 239000004155 Chlorine dioxide Substances 0.000 description 1
- 229910021503 Cobalt(II) hydroxide Inorganic materials 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
- 241001465754 Metazoa Species 0.000 description 1
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- 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 description 1
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- 230000008901 benefit Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000002306 biochemical method Methods 0.000 description 1
- 239000002802 bituminous coal Substances 0.000 description 1
- 239000004566 building material Substances 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
- 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
- 235000019398 chlorine dioxide Nutrition 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011294 coal tar pitch Substances 0.000 description 1
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 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
- FGRVOLIFQGXPCT-UHFFFAOYSA-L dipotassium;dioxido-oxo-sulfanylidene-$l^{6}-sulfane Chemical compound [K+].[K+].[O-]S([O-])(=O)=S FGRVOLIFQGXPCT-UHFFFAOYSA-L 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000005008 domestic process Methods 0.000 description 1
- 229920001971 elastomer Polymers 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
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 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
- 238000007689 inspection Methods 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
- 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
- 229910052763 palladium Inorganic materials 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 230000000505 pernicious effect Effects 0.000 description 1
- 239000011295 pitch Substances 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 239000011591 potassium Substances 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
- 229910001950 potassium oxide Inorganic materials 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
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical group [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 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
- 239000004408 titanium dioxide Substances 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 the method for alternative fire coal, comprising the following steps: (1) is granulated detoxification: aluminium cell carbonaceous waste material being crushed, atomized spray detoxification agent solution must be granulated detoxification material；(2) it activating: catalytic oxidant is added, homogenizing is modified,；Or catalytic oxidant and lime is added, add water stirring or rolles over mixed, oxidation dealkalize, filtering or filtering washing, it is dry,；Or catalytic oxidant, lime, sodium hydroxide is added, add water stirring or rolles over mixed, oxidation dealuminzation dealkalize, filtering or filtering washing, it is dry,；Or molten processing is soaked using overcritical or liquid carbon dioxide, catalytic oxidant homogeneous modification is added in carbon dry mash,.The regenerated alternative fire coal of the present invention is suitable with semibituminous coal, anthracite calorific value, and average about 5000kcal/kg can be used as alternative fire coal；The method of the present invention simple process, low energy consumption, at low cost, is suitable for industrialized production.
Description
Technical field
The present invention relates to a kind of methods that materials recycling is alternative fire coal, and in particular to a kind of aluminium cell carbonaceous waste material
The method for being regenerated as alternative fire coal.
Background technique
Currently, the development of the electrolytic aluminium yield in China and the world is swift and violent.According to statistics, until in by the end of December, 2016, China's electrolytic aluminium
Aluminium smelter enterprise be completed production capacity up to 4369.8 ten thousand tons, run production capacity up to 3673.9 ten thousand tons.With the increasing of electrolytic aluminium yield
Add, the solid waste generated in electrolytic process, such as waste cathode carbon block, scrap anode carbon granule, useless refractory brick, useless insulating brick, useless guarantor
The yield of warm clinker also increases sharply, wherein the useless cathode that only China's aluminum electrolysis industry generates every year is up to 250,000 tons, in recent years still
There is more than 400 ten thousand tons of accumulative volume of cargo in storage to fill without suitable area, and the waste cathode carbon block actual amount of whole world stockpiling has reached ten million
Ton.
Aluminium cell carbonaceous waste material includes the waste cathode carbon block generated during electrolytic aluminium and scrap anode carbon granule etc., predominantly
Waste cathode carbon block.The main component of waste cathode of aluminum electrolytic cell carbon block is C, also contains Na3AlF6、CaF2、NaF、AlF3、α-Al2O3
Deng, wherein carbon content be 50~70%, electrolyte fluoride be 30~50%, cyanide is about 0.2%.Do not have in aluminium electrolysis process
The main component for participating in the anode carbon granule (also known as anode breeze) of electrolyte in electrolysis and Electolyte-absorptive is with Na3AlF6Based on
Sodium aluminium fluoride, α-Al2O3And C, remaining is electrolyte fluoride, wherein carbon content is 40~60%.
Electrolytic aluminium waste cathode carbon block belongs to the high artificial material of degree of graphitization, it is well known that electrolytic aluminium cathode is to forge
Anthracite, metallurgical coke, graphite of burning etc. are aggregate, and coal tar pitch etc. is made of binder shaping and roasting, are used for charcoal containing aluminium cell
The block class of matter liner or paste class carbon product have that hardness is big, coefficient of friction is small, no for graphitization or graphite carbon cellulosic material
The characteristics of easily broken, extremely difficult combustion (relative to fire coal).The electrolysis temperature of modern large-scale aluminium electrolysis pre-baking tank 950~970 DEG C it
Between, the electrolyte such as every production 1 ton of aluminium consumption about 50kg ice crystal, aluminum fluoride, magnesium fluoride, due to heat effect, chemical action, machinery
The reaction of fused salt caused by erosion effect, infiltration of electro ultrafiltration, sodium and electrolyte etc. chemically reacts, the cathode charcoal in aluminium cell
Using after a certain period of time can be damaged, generally 4~7 Nian Houxu's block of operation carry out large repairs, the mainly waste cathode carbon block that removes,
Waste refractory materials, useless thermal insulation material etc., while a certain amount of anode carbon granule is also generated in electrolytic process.
The processing technique of scrap anode carbon granule lesser for quantity, current research is concentrated mainly on is returned using floatation process
It receives charcoal and electrolyte and collecting agent is added after adding water to size mixing in scrap anode carbon granule grinding to certain particle size, keep charcoal abundant with electrolyte
Separation, so that obtaining take electrolyte as the two kinds of products advocated peace based on charcoal.Electrolyte therein can back within aluminium electroloysis
In slot, powdered carbon can be used for the raw material of Soderberg Anode In Aluminium Electrolysis Cells production anode mix, but processing cost is high and secondary pollution is big.
For waste cathode of aluminum electrolytic cell carbon block, at present both at home and abroad the technical method of processing waste cathode carbon block up to tens of kinds it
It is more, it may be summarized to be wet process, high temperature hydro-thermal method, superhigh temperature partition method, burning partition method, fuel process and safe landfill method etc..
(1) wet process: for the main direction of studying of current internal lining of aluminium electrolytic bath, basic working procedure is grinding, water logging/alkali leaching/acid
It washes, flotation, separation, drying etc..The external representative use aquation method released for M.M.Williams handles waste cathode carbon
Block (isolated thick carbon granule and fine grain electrolyte), and Lun Sihuofen aluminium manufacturer, Austria and Li Sita aluminium manufacturer, U.S. alkali
The molten leaching electrolyte therein of liquid (leachate is used for synthetic cryolite, and charcoal is used as the fuel of high temperature furnace collocation).Chalco stock
Part Co., Ltd, Beijing Mine and Metallurgy General Inst, Central South University etc. have also carried out a large amount of research and practice, as Lu Huimin et al. is used
Floatation recycles charcoal and electrolyte, obtains the powder of certain particle size after waste cathode carbon block is broken, classification, is added after adding water to size mixing
Collecting agent, to realize that carbon is separated with the maximum of electrolyte, so that obtaining take electrolyte as two kinds to advocate peace based on charcoal
Product.Electrolyte therein can back in aluminium cell, and graphited powdered carbon can return to cathode production system.But
It is that the toner value that method for wet separation obtains at present is not high, and resource utilization efficiency is low, and the processing power consumption such as grinding is high, place
Manage at high cost, and there are serious secondary pollutions.
(2) high temperature hydro-thermal method separation method: most representative to be used for J.E.Dentschman and J.S.Lobos etc.
1200 DEG C or more of hot water Hydrolyze method handles waste cathode carbon block, and the hydrogen fluoride for making fluoride react generation concentration 25% with steam is molten
Liquid, then aluminum fluoride is produced with synthetic method, and collect the fluorine ion in solution with gypsum.But this method investment is big, energy consumption is high,
Processing cost is high, and difficulty is administered in secondary pollution.
(3) superhigh temperature separation method: external representative " AUMSET " technique for the exploitation of Alcoa company, in powder
Flux, the blended stocks such as lime is added in broken waste lining carbon block to be heat-treated at 1300 DEG C of temperature in AUS-MELT furnace,
So that lime etc. is reacted with the electrolyte in waste cathode carbon block, obtain calcirm-fluoride, sodium fluoride and aluminum fluoride, recycles high-temperature flue gas
Middle HF gas generates aluminum fluoride, and fluorine is made to obtain solidifying to re-use, and final products are glassy state slag, and the charcoal of recycling is used again
In manufacture cathode material.The technique has carried out industrial application, handles waste lining year up to 12000t, but invests big, processing energy consumption
Height, processing cost are too high.It is domestic also to have research more, as CN105642649A discloses a kind of high-temperature treatment of electrolytic aluminium waste cathode
Method is that electrolytic aluminium waste cathode carbon block is crushed to 3~15mm, then, is roasted in 2600~2800 DEG C of superhigh temperature vacuum electric furnaces
Burning processing, volatilizing fluoride therein, decomposing cyanide therein is nitride, by the way of high-temperature flue gas is absorbed using water mist
Absorption handle using filtering drying etc., obtain can reuse fluoride, superhigh temperature roast after cathode carbon materials through being cooled to
Reach 97% carbon materials for fixed carbon content.But this method is significantly present of following problem: first is that electrolytic aluminium waste cathode carbon is broken
Toxic dust and toxic gas containing cyanide are generated in broken screening process；Second is that its is actual to 2600~2800 DEG C for electric heating
Power consumption is very high, maintains the power consumption of vacuum suction higher, the requirement of equipment and cost are also very high；Third is that 2600~2800 DEG C volatilization
Requirement of the fluoride gas using water mist absorption to equipment is too high, because 1200 DEG C of water vapour can be calcirm-fluoride etc. to be fluorinated
Object is converted into the hydrogen fluoride of the strong corrosive of severe toxicity；Fourth is that the carbon materials for being also easy to produce serious secondary pollution, and recycling
In still contain 3% or more fluoride, recycling can shorten overhaul life and uneconomical.CN106269787A discloses one kind
For disposing the high temperature continous way processing method of electrolytic aluminium waste cathode, teaches and a kind of be crushed to electrolytic aluminium waste cathode carbon block not
The compound particles of 3~100mm are made with kneadings such as pitches for particle greater than 3mm, then, compound particles are placed in superelevation
In warm vacuum electric furnace, the continous way calcination process in not less than 2000 DEG C (2300~2600 DEG C) superhigh temperature vacuum electric furnaces is obtained high
Warm electro-forge flue gas and electrolytic aluminium waste cathode carbon granules, then high temperature electro-forge flue gas is subjected to second-time burning, completely burned volatile matter flue gas
In carbon dust, carbon powder and ice crystal, decomposing cyanide therein is nitride, after cooling, dedusting, desulphurization denitration, obtains reuse
Fluoride and fixed carbon content reach 95% carbon materials.But this method is significantly present of following problem: first is that electrolytic aluminium waste is negative
Toxic dust and toxic gas containing cyanide are generated during the carbon crushing and screening of pole；Second is that electric heating to 2000~2600 DEG C its
Actual power consumption is very high, maintains the power consumption of vacuum suction higher, the requirement of equipment and cost are also very high；Third is that after second-time burning
Gas cleaning investment is high, is also easy to produce serious secondary pollution；Fourth is that still containing in the carbon of 2000~2600 DEG C of electric furnace calcination processing
A large amount of fluoride, because of 2497 DEG C of boils up till of calcirm-fluoride or more, fluorine-containing carbon materials recycling can shorten overhaul time
Limit and it is uneconomical.
(3) burn separation method: being using professional incinerator and fluid bed furnace technique etc., because of electrolytic aluminium waste cathode carbon difference
In fire coal, though calorific value is generally up to 4000~5500kcal/kg, activation energy needed for oxidation reaction is high, need to reach 1500 DEG C of height
It is warm could the efficient oxidation burning, therefore heating time is long, energy consumption is high and difficult needed for combustion method there are separating process cumbersome, after-flame
The problem of effectively to recycle wherein fluoride, and secondary pollution issue handling difficulty is also big.
(4) fuel process: because the main component of electrolytic aluminium waste cathode carbon block is charcoal, and the theoretical combustion heat of completely burned is typically up to
4000kcal/kg or more, high is equivalent to common anthracitic calorific value up to 5500kcal/kg, so, domestic and international a large amount of skill
Art worker has carried out unremitting effort, and effect pole is not so good as people's will so far.The domestic method as fuel has China YouSe metal
The identification for the Shandong Aluminum Co., Ltd. factory " recycling of waste cathode of aluminum electrolytic cell carbon block " that Industry Corporation organized on November 16th, 1988
Achievement.Specific method is: " Shandong Aluminum Plant in alumina producing, using waste and old cathode carbon block it is levigate after as desulfurizing agent and substitute
Part anthracite is added in alumina rotary kiln, produces alumina sintering block.Contained fluoride salt is converted in sinter leaching
Insoluble calcirm-fluoride enters red mud, and red mud replaces fluorescent mineralizer when preparing cement for manufacture of cement ingredient." still,
This method grinding energy is high, and the discharge amount of pernicious gas increases in flue gas.For the turning sludge into fuel benefit for further solving waste cathode carbon block
With problem, Shandong branch company, Chinese Aluminium Co., Ltd research institute poplar meeting guest waits the cement producing line in Shandong Aluminum Plant enterprising
It has gone in-depth study practice, the work of cement producing line is applied to the waste cathode carbon block of calorific value 21MJ/kg(5024kcal/kg)
Waste cathode carbon block, is specifically first crushed by industry test, and by the maximum ratio dosage of clinker 5kg waste cathode carbon block per ton, (conversion is
About the 3% or less of coal consumption), together grinding is incorporated in coal mill in grinding coal dust, and conclusion (of pressure testing) is clinker per ton by the useless yin of 5kg
Pole carbon block to clinker quality without visible influences (application study light metal of the waste cathode carbon block such as Yang Huibin in manufacture of cement,
2nd phase in 2008, P59-64.).Yang Huibin etc. is high using cement kiln internal reaction temperature, carbon block residence time on stream
The conditions such as long, make the harmful substance in waste cathode carbon block carry out decomposition displacement in the high temperature environment, and it is ripe to be finally solidificated in cement
In material, while attempt to using the carbon in waste cathode carbon block as the consumption of fuel reduction coal.But still have safety problem,
Additive amount problem and influence problem to production, after all, waste cathode carbon are not coal-fired, in waste cathode carbon block the extremely difficult combustions of charcoal.So
And real defect is not the problem that fluorine is exceeded in the erosion and flue gas of refractory material caused by fluoride, because of calcium aluminum fluoride
The production of cement also ensures that fluorine is not exceeded in the safety and flue gas of refractory material, after all normal cement kiln preheaters system visitor
Have in sight and realizes preheater of the Pyatyi with the exchange trapping of Alkaline high-strength powder；Nor the problem that alkali content is high, because often
Ton clinker consumes coal generally only 0.15~0.18t, and the electrolyte in a small amount of cathode carbon pieces is mainly aluminum fluoride, calcirm-fluoride, fluorine aluminium
Sour sodium, fluoaluminic acid magnesium, sodium fluoride only account on a small quantity, dosage hour it is limited with the total alkali content in cryolite and sodium fluoride, generally
Influence to cement later strength is limited.Therefore, Shandong Aluminum Plant so far still cannot be using cathode charcoal normal use as alternative combustion
The true cause of coal is: first influencing the mill efficiency of coal mill, is second that the graphitic carbon of low activity seriously reduces the whole of coal dust
Volumetric combustion performance, the serious normal combustion efficiency for affecting coal dust, the exothermic charcoal element that timely and effective cannot burn are fallen into
Clinker entrains into the strong reduction of generation in powder, affects kiln system operating condition, affects clinker quality.Obviously, the prior art is not still
It can be using electrolytic aluminium waste cathode carbon block as effective alternative fuel.
(5) safe landfill method: since existing processing method is there are high energy consumption, high cost and secondary pollution problems, because
This, the problem of environmental pollution of electrolytic aluminium waste cathode carbon block is never effectively solved, and most aluminium electrolytics are caused
Cathode carbon pieces are still thrown aside, and use high-cost safe landfill method at present or mainly.And currently generally use landfill, stockpiling
Method handles electrolytic aluminium solid waste method, can do great harm to the environment, even completely by the harmless of hazardous waste
Lasting contact scar will be generated by changing landfill, and cause vast resources waste.
In addition, electrolytic aluminium solid waste is due to containing a large amount of soluble fluoride and a small amount of cyanide (predominantly
Cymag and the sodium ferricyanide), belong to danger wastes, must be dealt carefully with.And under the conditions of the prior art, electrolytic aluminium factory is universal
Landfill, the stacked arrangement of use handle these solid waste, and contained soluble fluoride and cyanide can pass through wind, day
The effect transfer that shine, drenches with rain is volatized into atmosphere, or be mixed into rivers with rainwater, permeate the ground contaminated soil and underground water, right
Animals and plants and human body generate very big damage, destroy ecological environment, influence Agro-ecology balance, make crop production reduction, and harm will
It is long-term.Processing for cyanide in waste cathode carbon block, processing technique mainly have weak acid dissolution+polysulfide to be converted into sulphur
For the method for cyanate and metal thiophosphate object, manganese ion+ultraviolet catalytic oxidation method, ozone and sodium hypochlorite co-oxidation side
Method, high temperature chlorination processing method, high-temperature oxidation method, biochemical method handle cyanide technology.But at these existing cyanides
It is cumbersome, at high cost to manage technical method, and there are secondary pollutions.CN101811695A discloses a kind of from electrolytic aluminium waste cathode carbon block
The method of middle recycling graphite is that the processes such as acidleach remove fluoride therein again using grinding, water logging, flotation, separates and recovers it
In carbon materials drying to obtain refined graphite powder.But this method process is many and diverse, secondary pollution is big, energy consumption is high, the stone of recycling
Black fine powder impurity content is high.
To sum up, the outstanding problem as aluminum electrolysis industry general character, it is necessary to it is harmless to break through electrolytic aluminium solid waste as early as possible
Change industrialization technology problem.The characteristic of electrolytic aluminium solids waste material how is utilized to implement resource utilization, it is especially safe
, low energy consumption, low cost regeneration as alternative fire coal be the technical method problem for being worth researching and solving.
Summary of the invention
The technical problem to be solved by the present invention is to overcome drawbacks described above of the existing technology, provide a kind of regeneration institute
Alternative coal-fired safety and environmental protection, without secondary pollution, calorific value is high, regeneration technology is simple, low energy consumption, low cost, is suitable for industrialization
The aluminium cell carbonaceous materials recycling of production is the method for alternative fire coal.
The technical solution adopted by the present invention to solve the technical problems is as follows: a kind of aluminium cell carbonaceous materials recycling be for
For the method for property fire coal, comprising the following steps:
(1) it is granulated detoxification: aluminium cell carbonaceous waste material being crushed, while broken, atomized spray is equivalent to aluminium electroloysis
1~10%(of slot carbonaceous waste material quality preferably 3~8%) detoxification agent solution, and with catalytic oxidizer negative pressure extracting crushing system
Dust-removing waste gas must be granulated detoxification material；
(2) it activates: granulation detoxification material obtained by step (1) is placed in mixer, be added be equivalent to aluminium electricity under stiring
Solve 0.6~8.0%(of slot carbonaceous waste material quality preferably 2~6%) catalytic oxidant, homogenizing be modified, obtain alternative fire coal；
Or granulation detoxification material obtained by step (1) is placed in stirring or is rolled in the leaching slot or tank of mixing device, addition point
Be not equivalent to 1~8%(of aluminium cell carbonaceous waste material quality preferably 2~6%) catalytic oxidant and 2~20%(preferably 5~15%)
Lime, and the water stirring for being equivalent to 1~10 times of aluminium cell carbonaceous waste material quality (preferably 2~6 times) is added or rolles over mixed, oxidation
Dealkalize, filtering or filtering washing obtain dealkalize activated carbon slag, and dry to moisture≤15%, homogenizing is modified, and obtains alternative fire coal；
Or granulation detoxification material obtained by step (1) is placed in stirring or is rolled in the leaching slot or tank of mixing device, addition point
Be not equivalent to 1~8%(of aluminium cell carbonaceous waste material quality preferably 2~6%) catalytic oxidant, more preferable 5~15%) 2~20%(
Lime, more preferable 5~15%) 2~20%(sodium hydroxide, and be added be equivalent to 1~10 times of quality of aluminium cell carbonaceous waste material
The water of (more preferable 4~8 times) stirs or rolles over mixed, oxidation dealuminzation dealkalize, filtering or filtering washing, obtains the activated carbon slag of dealuminzation alkali,
Dry to moisture≤15%, homogenizing is modified, and obtains alternative fire coal；
Or granulation detoxification material leaching obtained by step (1) is dissolved in the overcritical or liquid of 0~80 DEG C (more preferable 10~50 DEG C)
It is processed in state carbon dioxide, then in separating obtained carbon dry mash, addition is equivalent to carbon dry mash quality 0.5~6%
(catalytic oxidant of more preferable 2~5%) carries out mixing homogeneous modification, obtains alternative fire coal.Using well known overcritical or liquid
The carbon-impregnated molten method of titanium dioxide processes granulation detoxification material.
Preferably, in step (1), the broken granularity≤25mm of waste material.
Preferably, in step (1), the crumbling method is that hammering, extruding or impact type are broken.The attrition crushing is preferred
Double roller squash type is broken.Electrolytic aluminium waste cathode carbon block has the characteristics that hardness is big, coefficient of friction is small, non-breakable, and aluminium electroloysis
There is the features at apparent interface for carbon-containing part and other ingredients in slot waste and old cathode carbonaceous material, using energy-efficient
First extruding/impact type crumbling method saves comminution energy conssumption and subsequent as possible grinding energy during fuel applications, and two
It is then the irregular granular material containing a large amount of cracks by waste cathode carbon block fragmentation, is seeped convenient for the absorption of cyanide detoxicant and depth
Enter reaction.
Preferably, in step (1), the main component of the aluminium cell carbonaceous waste material is waste cathode carbon block and/or useless sun
Pole carbon granule, wherein inanimate matter content 20~50%, carbon content 50~80%, 3800~6000kcal/kg of calorific value.
Preferably, in step (1), the detoxicant be can efficient digestion cyanide hypertoxicity substance, be ferrate
Detoxicant, bichromate detoxicant, thiosulfate detoxicant, perchlorate detoxicant, hydroxide detoxicant, hypochlorite
One or more of detoxicant or chlorine dioxide etc..For the main Toxic in electrolytic aluminium waste cathode carbon block be Cymag and
The sodium ferricyanide, main violent in toxicity be Cymag the characteristics of, during broken using efficient cyanide detoxicant progress and
When and efficiently remove toxicity processing, can efficient digestion cyanide hypertoxicity.
It is highly preferred that the ferrate detoxicant be one of potassium ferrate, ferrate-lithium or Na2Fe04 etc. or
Several, the bichromate detoxicant is one of potassium bichromate, sodium dichromate, dichromic acid cobalt or dichromic acid acid anhydride etc. or several
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 one or more of cobalt hydroxide, sodium hydroxide or potassium hydroxide etc., institute
Stating hypochlorite is sodium hypochlorite and/or calcium hypochlorite etc..
It is further preferred that the detoxicant is commercially available ZC-XJ1 type detoxification agent solution (i.e. ferrate detoxicant
The saturated solution prepared with hypochlorite detoxicant with mass ratio 1:1), (i.e. thiosulfate is gone ZC-XJ10 type detoxification agent solution
Toxic agent prepare saturated solution), (i.e. bichromate detoxicant and hypochlorite detoxicant is with quality for ZC-XJ3 type detoxification agent solution
Than 1:1 prepare saturated solution), (i.e. perchlorate detoxicant and hypochlorite detoxicant is with matter for ZC-XJ5 type detoxification agent solution
Measure the saturated solution prepared than 1:1) or ZC-XJ13 type detoxification agent solution (i.e. the saturated solution of hypochlorite detoxicant preparation).
Above-mentioned detoxification agent solution is purchased from Hunan Province little Yin Wuji environmental energy Science and Technology Development Co., Ltd..
The prepared solution of one or more of the detoxification agent solution, that is, detoxicant.
Preferably, in step (1), the detoxification agent solution is that sodium hypochlorite addition is first equivalent to its quality 1.5~5.5
The water dissolution of times (more preferable 1.8~3.0 times), then potassium ferrate and potassium hydroxide are dissolved in time by the mass ratio of 1:0.8~1.2
The saturated solution formed in sodium chlorate solution.
It, can be while dust suppression, so that detoxification agent solution penetrates into broken granular material by atomized spray in step (1)
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 safety of broken granulation detoxification process.
Preferably, in step (2), the catalytic oxidant is bichromate catalytic oxidant, metavanadate catalysis oxidation
One or more of agent, ferrate catalytic oxidant, perchlorate catalytic oxidant or nitrate catalytic oxidant.For
Electrolytic aluminium waste cathode carbon block is that graphitization or graphite carbon cellulosic material, carbon structure stablize extremely difficult combustion, must be effective up to 1500 DEG C of ability
The characteristics of oxidation, present invention use can destroy or activate the netted carbon structure of graphite, and can effectively facilitate charcoal element oxidation reaction
Catalytic oxidant is modified 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, allows to substitute 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 and/
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 of palladium or rhodium nitrate etc..
It is further preferred that the catalytic oxidant is that (i.e. perchlorate is catalyzed oxygen to ZC-7 type liquid catalytic oxidant
The saturated solution that agent and nitrate catalytic oxidant are prepared with the mixture of mass ratio 2:1), ZC-3 type powdery catalytic oxidant
(i.e. bichromate catalytic oxidant and nitrate catalytic oxidant is with the mixture of mass ratio 1:1), ZC-9 type catalytic oxidant
(i.e. metavanadate catalytic oxidant and nitrate catalytic oxidant is with the mixture of mass ratio 1:1) or ZC-11 type catalysis oxidation
Agent (i.e. ferrate catalytic oxidant and nitrate catalytic oxidant is with the mixture of mass ratio 1:1).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 in step (2), the catalytic oxidant be ammonium dichromate, metavanadic acid ammonia, lithium perchlorate, cerous nitrate,
The ratio of cobalt nitrate, nickel nitrate 2:0.8~1.2:0.8 in mass ratio~1.2:1.5~2.5:1.5~2.5:2.5~3.5 is dissolved in
Saturated solution made of water.
In step (2), other than catalytic oxidant, the raw material of other additions is auxiliary material.The lime includes hydroxide
Calcium and/or calcium oxide.When in auxiliary material contain lime when, under the conditions of strong oxidizing solution, calcium hydroxide with containing alkali sodium fluoride,
The reactions such as cryolite are converted into calcirm-fluoride and dealkalize, and oxidized activating carbon and catalysis oxidation element are attached to carbon materials
On；When containing lime and sodium hydroxide in auxiliary material, under strong oxidizing property solvent condition, calcium hydroxide and sodium hydroxide collaboration,
Reacted with sodium fluoride, cryolite, aluminium oxide etc. containing alkali 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, in step (2), water lotion be can be recycled for leaching, and filtrate containing alkali can be recycled concentrated base processed or mention aluminium concentrated base.
Preferably, in step (2), after catalytic oxidant is added or after dry, it is useless that addition is equivalent to aluminium cell carbonaceous
Expect more preferable 2~10 % of 1~20 %(of quality) calcium oxide and/or magnesia, and/or be equivalent to aluminium cell carbonaceous waste material matter
Measure more preferable 10~40 % of 1~50 %() hydrocarbon-containiproducts combustable organic object, then be homogenized modification；It is described to contain nytron
The combustable organic object of object is one or more of coal tar, useless molding powder, waste Crumb rubber or husk etc..
The present invention another to solve technical solution used by its technical problem as follows: a kind of aluminium cell carbonaceous waste material is again
Raw is the method for alternative fire coal, and after aluminium cell carbonaceous waste material is crushed to granularity≤25mm, addition is equivalent to its quality 0.8
The catalytic oxidant of more preferable 3~7%)~8.0%(and the organic of hydrocarbon-containiproducts of more preferable 20~40%) 1~50%(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 of catalytic oxidant, perchlorate catalytic oxidant or nitrate catalytic oxidant etc.；The bichromate
Catalytic oxidant is one or more of 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 of 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 object 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 half used with general industry kiln
Bituminous coal, anthracite calorific value are suitable, and average about 5000kcal/kg can be used as alternative fire coal；
(2) when being used for manufacture of cement, in the case where other controlling of production process parameter constants, test display: coal mill is produced
Quite, for kiln yield without visible change, kiln system operating condition is normal for amount, and without strongly reducing atmosphere in kiln, clinker is without strong reduction feature, clinker
Knot grain takes a turn for the better, the raising synchronous with later strength of the early stage of clinker, and online middle control data statistics coal consumption decline may be up to 7.5%, kiln tail
Fluorine content detection has no variation in discharge flue gas, and cyanide is not detected；It is used for fluidized bed furnace, rotary kiln, tunnel oven fire coal
When, coal mill yield is suitable, and for kiln yield without visible change, limekiln system condition is normal, without strongly reducing atmosphere, online middle control in kiln
Data statistics coal consumption is suitable, and fluorine content detection has no variation in kiln tail discharge flue gas, detects lime quality without visible change, does not examine
Measure cyanide；
(3) the alternative coal-fired safety and environmental protection of aluminium cell carbonaceous materials recycling of the present invention, it is without secondary pollution；
(4) the method for the present invention simple process, and there is ready-made equipment can be selected, low energy consumption, at low cost, and treating capacity is big, fits
Suitable industrialized production.
Specific embodiment
Below with reference to embodiment, the invention will be further described.
Raw material or chemical reagent used in the embodiment of the present invention are obtained by routine business approach unless otherwise specified
?.
Embodiment 1
Aluminium cell carbonaceous waste material used in the embodiment of the present invention is derived from the blocky carbonaceous waste material stored up in certain aluminium manufacturer library,
Detect aggregate sample inanimate matter content 28.49%, carbon content 71.51%, calorific value 5615kcal/kg；Detoxification used in the present embodiment
Agent is ZC-XJ1 type detoxification agent solution (the i.e. saturation prepared with mass ratio 1:1 of ferrate detoxicant and hypochlorite detoxicant
Solution), catalytic oxidant used in the present embodiment be ZC-7 type liquid catalytic oxidant (i.e. perchlorate catalytic oxidant and
The saturated solution that nitrate catalytic oxidant is prepared with the mixture of mass ratio 2:1), it is purchased from Hunan Province little Yin Wuji environment energy
Source Science and Technology Development Co., Ltd..
(1) it is granulated detoxification: block-like aluminium cell carbonaceous waste material is crushed to by partial size using double roller squash type crushing system
≤ 8mm, while broken, atomized spray is equivalent to the ZC-XJ1 type detoxification agent solution of aluminium cell carbonaceous waste material quality 8%,
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) it activates: granulation detoxification material obtained by step (1) is placed in mixer, be added be equivalent to aluminium electricity under stiring
The ZC-7 type liquid catalytic oxidant of slot carbonaceous waste material quality 6% is solved, homogenizing is modified, and obtains alternative fire coal.
Alternative fire coal obtained by the present embodiment is used on Mr. Yu Ф 3.5 × 54m new type nonaqueous cement production line (used in the factory
Raw coal is the semibituminous coal of volatile matter 16.7%, calorific value 5587kcal/kg, raw coal sulfur content 3.7%), it will be substituted obtained by the present embodiment
Property fire coal and raw coal 1:1 in mass ratio ratio supplying coal mill in grinding together.
In the case where other controlling of production process parameter constants, test display: coal mill yield is suitable, and kiln yield is without visible
Change, kiln system operating condition is normal, and without strongly reducing atmosphere in kiln, clinker takes a turn for the better without strong reduction feature, clinker knot grain, middle online to control number
Coal consumption decline 7.3% according to statistics, kiln tail discharge fluorine content detection in flue gas and have no variation, and cyanide is not detected.
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: being the fluorine sulphur mine brought into the cooperateed with generation of sulphur in raw coal by fluoride in alternative fire coal
Agent improves burn-ability, causes clinker knot graininess to take a turn for the better and declines with coal consumption, and since bringing into for fluorine generates suitable fluoaluminic acid
Calcium mineral cause the raising synchronous with later strength of the early stage of clinker.
This test display, the waste cathode carbon block material of activated modification have with the comparable combustibility of semibituminous coal, can make
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 stored up in certain aluminium manufacturer library
Waste material (contains anodic carbon residue), detects aggregate sample inanimate matter content 34.17%, carbon content 65.83%, calorific value 5169kcal/kg；This hair
Detoxification agent solution used in bright embodiment is: first sodium hypochlorite is added and is equivalent to the water of 2 times of its quality and dissolves, then by high-speed rail
Sour potassium and potassium hydroxide are dissolved in the saturated solution formed in liquor natrii hypochloritis by the mass ratio of 1:1；Used in the present embodiment
Catalytic oxidant is that (bichromate catalytic oxidant and nitrate catalytic oxidant are with mass ratio for ZC-3 type powdery catalytic oxidant
The mixture of 1:1), 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 useless molding powder.
(1) be granulated detoxification: using paddle type mill crushing system will mix blocky aluminium cell carbonaceous waste material be crushed to partial size≤
5mm, while broken, atomized spray is equivalent to the detoxification agent solution of aluminium cell carbonaceous waste material quality 6%, 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) it activates: granulation detoxification material obtained by step (1) is placed in mixer, be added be equivalent to aluminium electricity under stiring
It solves the ZC-3 type powdery catalytic oxidant of slot carbonaceous waste material quality 3.5% and is equivalent to the useless of aluminium cell carbonaceous waste material quality 15%
Molding powder, homogenizing are modified, and obtain alternative fire coal.
By alternative coal-fired (original used in the factory on Mr. Yu Ф 3 × 46m new type nonaqueous cement production line obtained by the present embodiment
Coal is the anthracite of volatile matter 8.3%, calorific value 5349kcal/kg, raw coal sulfur content 1.8%), by alternative combustion obtained by the present embodiment
The ratio of coal and raw coal 1:1 in mass ratio are incorporated in coal mill grinding together.
In the case where other controlling of production process parameter constants, test display: coal mill yield is suitable, and kiln yield is without visible
Change, kiln system operating condition is normal, and without strongly reducing atmosphere in kiln, clinker takes a turn for the better without strong reduction feature, clinker knot grain, middle online to control number
Coal consumption decline 5% according to statistics, kiln tail discharge fluorine content detection in flue gas and have no variation, and cyanide is not detected.
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: is improved by the fluorine sulphur mineralizer of fluoride in alternative fire coal brought into the cooperateed with generation of sulphur in raw coal
Burn-ability causes clinker knot graininess to take a turn for the better and coal consumption decline, and since bringing into for fluorine generates suitable calcium aluminum fluoride mineral and cause
Make the raising synchronous with later strength of the early stage of clinker.
This test display, the aluminium cell carbonaceous waste material of activated modification have with the comparable combustibility of 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 stored up in certain aluminium manufacturer library
Waste material (contains anodic carbon residue), detects inanimate matter content 34.17%, carbon content 65.83%, calorific value 5169kcal/kg；The present embodiment institute
The detoxicant used is ZC-XJ10 type detoxification agent solution (saturated solution that thiosulfate detoxicant is prepared), the present embodiment institute
The catalytic oxidant used be ZC-3 type powdery catalytic oxidant (bichromate catalytic oxidant and nitrate catalytic oxidant with
The mixture of mass ratio 1:1), it is purchased from Hunan Province little Yin Wuji environmental energy Science and Technology Development Co., Ltd.；The present embodiment is made
Auxiliary material is commercially available calcium hydroxide, calcium oxide and waste Crumb rubber.
(1) be granulated detoxification: using paddle type mill crushing system will mix blocky aluminium cell carbonaceous waste material be crushed to partial size≤
10mm, while broken, atomized spray is equivalent to the ZC-XJ10 type detoxification agent solution of aluminium cell carbonaceous waste material quality 5%,
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) activate: granulation detoxification material obtained by step (1) be placed in the leaching slot of band rolling mixing device, under stiring plus
Enter to be equivalent to 5% ZC-3 type powdery catalytic oxidant of aluminium cell carbonaceous waste material quality and 10.4% calcium hydroxide, phase is added
When the water in 4 times of quality of aluminium cell carbonaceous waste material rolles over mixed leaching oxidation dealkalize, filtering washing obtains dealkalize activated carbon slag, detects
Alkali removal efficiency 81.4%, filtrate containing alkali recycle concentrated base processed, and water lotion is recycled for leaching, and dry dealkalize activated carbon slag to moisture≤
10%, the scrap rubber for adding the calcium oxide for being equivalent to dealkalize activated carbon slag amount 5% and being equivalent to dealkalize activated carbon slag amount 20%
Powder mixture, homogenizing are modified, and obtain alternative fire coal.
Alternative fire coal obtained by the present embodiment is used on Mr. Yu Ф 3.5 × 54m new type nonaqueous cement production line (used in the factory
Raw coal is the anthracite of volatile matter 8.3%, calorific value 5349kcal/kg, raw coal sulfur content 3.1%), it will be alternative obtained by the present embodiment
Coal-fired and raw coal 1:1 in mass ratio ratio is incorporated in coal mill grinding together.
In the case where other controlling of production process parameter constants, test display: coal mill yield is suitable, and kiln yield is without visible
Change, kiln system operating condition is normal, and without strongly reducing atmosphere in kiln, clinker takes a turn for the better without strong reduction feature, clinker knot grain, middle online to control number
Coal consumption decline 7% according to statistics, kiln tail discharge fluorine content detection in flue gas and have no variation, and cyanide is not detected.
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: being the fluorine sulphur mine brought into the cooperateed with generation of sulphur in raw coal by fluoride in alternative fire coal
Agent improves burn-ability, causes clinker knot graininess to take a turn for the better and declines with coal consumption, and since bringing into for fluorine generates suitable fluoaluminic acid
Calcium mineral cause the raising synchronous with later strength of the early stage of clinker.
This test display, the waste cathode carbon block material of activated modification have with the comparable combustibility of anthracite, can make
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 stored up in certain aluminium manufacturer library
Waste material (contains anodic carbon residue), detects inanimate matter content 34.17%, carbon content 65.83%, calorific value 5169kcal/kg；The present invention is implemented
Detoxicant used in example is ZC-XJ10 type detoxification agent solution (saturated solution that thiosulfate detoxicant is prepared), this implementation
Catalytic oxidant used in example be ZC-9 type catalytic oxidant (metavanadate catalytic oxidant and nitrate catalytic oxidant with
The mixture of mass ratio 1:1), it is purchased from Hunan Province little Yin Wuji environmental energy Science and Technology Development Co., Ltd.；The present embodiment is made
Auxiliary material is commercially available calcium oxide and sodium hydroxide.
(1) be granulated detoxification: using paddle type mill crushing system will mix blocky aluminium cell carbonaceous waste material be crushed to partial size≤
5mm, while broken, atomized spray is equivalent to the ZC-XJ10 type detoxification agent solution of aluminium cell carbonaceous waste material quality 5%, and
Catalysis oxidation decomposition is implemented to body containing dicyanogen with the dust-removing waste gas of catalytic oxidizer negative pressure extracting crushing system, obtains granulation and removes poisonous substance
Material；
(2) activate: granulation detoxification material obtained by step (1) be placed in the leaching can of band rolling mixing device, under stiring plus
Enter to be equivalent to the ZC-9 type catalytic oxidant of aluminium cell carbonaceous waste material quality 4.6%, be equivalent to aluminium cell carbonaceous waste material quality
9.2% calcium oxide and the sodium hydroxide for being equivalent to aluminium cell carbonaceous waste material quality 8.6%, addition are equivalent to aluminium cell carbonaceous
The water that 5 times of waste material quality rolles over mixed leaching oxidation dealuminzation dealkalize, and filtering washing obtains the activated carbon slag of dealuminzation alkali, detects aluminium removal efficiency
74.9%, alkali removal efficiency 87.7%, the recycling of the filtrate of alkali containing aluminium mention aluminium concentrated base, and water lotion recycling is for leaching, the work of dry dealuminzation alkali
Change carbon slag to moisture≤15%, homogenizing is modified, and obtains alternative fire coal.
By alternative coal-fired (original used in the factory on Mr. Yu Ф 3 × 46m new type nonaqueous cement production line obtained by the present embodiment
Coal is the anthracite of volatile matter 8.3%, calorific value 5349kcal/kg, raw coal sulfur content 3.7%), by alternative combustion obtained by the present embodiment
The ratio of coal and raw coal 1:1 in mass ratio are incorporated in coal mill grinding together.
In the case where other controlling of production process parameter constants, test display: coal mill yield is suitable, and kiln yield is without visible
Change, kiln system operating condition is normal, and without strongly reducing atmosphere in kiln, clinker takes a turn for the better without strong reduction feature, clinker knot grain, middle online to control number
Coal consumption decline 7.5% according to statistics, kiln tail discharge fluorine content detection in flue gas and have no variation, and cyanide is not detected.
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: being the fluorine sulphur mine brought into the cooperateed with generation of sulphur in raw coal by fluoride in alternative fire coal
Agent improves burn-ability, causes clinker knot graininess to take a turn for the better and declines with coal consumption, and since bringing into for fluorine generates suitable fluoaluminic acid
Calcium mineral cause the raising synchronous with later strength of the early stage of clinker.
This test display, the waste cathode carbon block material of activated modification have with the comparable combustibility of anthracite, can make
For alternative fire coal.
Embodiment 5
Aluminium cell carbonaceous waste material used in the embodiment of the present invention is derived from the blocky carbonaceous waste material stored up in certain aluminium manufacturer library,
Detect inanimate matter content 28.49%, carbon content 71.51%, 5615 kcal/kg of calorific value；Detoxicant used in the embodiment of the present invention
For ZC-XJ1 type detoxification agent solution, (saturation that ferrate detoxicant and hypochlorite detoxicant are prepared with mass ratio 1:1 is molten
Liquid), catalytic oxidant used in the present embodiment is ZC-7 type liquid catalytic oxidant (perchlorate catalytic oxidant and nitric acid
The saturated solution that salt catalytic oxidant is prepared with the mixture of mass ratio 2:1), it is purchased from Hunan Province little Yin Wuji environmental energy section
Skill development corporation, Ltd.；The present embodiment selects commercially available liquid carbon dioxide as leaching solvent.
(1) be granulated detoxification: using double roller squash type crushing system by blocky aluminium cell carbonaceous waste material be crushed to partial size≤
8mm, while broken, atomized spray is equivalent to the ZC-XJ1 type detoxification agent solution of aluminium cell carbonaceous waste material quality 8%, and
Catalysis oxidation decomposition is implemented to body containing dicyanogen with the dust-removing waste gas of catalytic oxidizer negative pressure extracting crushing system, obtains granulation and removes poisonous substance
Material；
(2) it activates: granulation detoxification material obtained by step (1) being placed in the leaching fluid bowl with milling device, leaching is dissolved in 10 DEG C
Liquid carbon dioxide in process, separate, obtain carbon dry mash, resulting carbon dry mash be placed in mixer, is being stirred
Lower that the ZC-7 type liquid catalytic oxidant for being equivalent to carbon dry powder quality 3.1% is added, homogenizing is modified, and obtains alternative fire coal.
Alternative fire coal obtained by the present embodiment is used on Mr. Yu Ф 3.5 × 54m new type nonaqueous cement production line (used in the factory
Raw coal is the semibituminous coal of volatile matter 16.7%, calorific value 5587kcal/kg, raw coal sulfur content 3.7%), it will be substituted obtained by the present embodiment
Property fire coal and raw coal 1:1 in mass ratio ratio supplying coal mill in grinding together.
In the case where other controlling of production process parameter constants, test display: coal mill yield is suitable, and kiln yield is without visible
Change, kiln system operating condition is normal, and without strongly reducing atmosphere in kiln, clinker takes a turn for the better without strong reduction feature, clinker knot grain, middle online to control number
Coal consumption is suitable according to statistics, and fluorine content detection has no variation in kiln tail discharge flue gas, and cyanide is not detected.Detection gained clinker is solidifying
Tie the time it is normal, 3 days and 28 days compression strength it is suitable.
This test display, the waste cathode carbon block material of activated modification have with the comparable combustibility of semibituminous coal, can make
For alternative fire coal.
Embodiment 6
Aluminium cell carbonaceous waste material used in the embodiment of the present invention is derived from the blocky carbonaceous waste material stored up in certain aluminium manufacturer library
Mixture (carbon granules containing anode) detects inanimate matter content 41.14%, carbon content 58.86%, calorific value 4622kcal/kg；The present invention is real
Applying detoxicant used in example is that (bichromate detoxicant and hypochlorite detoxicant are with mass ratio for ZC-XJ3 type detoxification agent solution
The saturated solution that 1:1 is prepared), it is purchased from Hunan Province little Yin Wuji environmental energy Science and Technology Development Co., Ltd.；The present embodiment is used
Catalytic oxidant be commercially available ammonium dichromate, metavanadic acid ammonia, lithium perchlorate, cerous nitrate, cobalt nitrate, nickel nitrate in mass ratio 2:
The ratio of 1:1:2:2:3 is dissolved in saturated solution made of water.
(1) it is granulated detoxification: blocky aluminium cell carbonaceous waste material is crushed to by partial size≤25mm using paddle type mill crushing system,
While broken, atomized spray is equivalent to the ZC-XJ3 type detoxification agent solution of aluminium cell carbonaceous waste material quality 3.2%, 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) it activates: granulation detoxification material obtained by step (1) is placed in spreading formula mixer, be added under stiring suitable
In the catalysis oxidation agent solution of aluminium cell carbonaceous waste material quality 3.8%, homogenizing is modified, and obtains alternative fire coal.
Mr. Yu factory drying system is used to use on fluidized bed furnace as alternative coal-fired (factory alternative fire coal obtained by the present embodiment
Raw coal used in fluidized bed furnace be volatile matter 12.4% semibituminous coal, calorific value 4983kcal/kg, boil boiler ash sediment in carbon content 6.9%),
The alternative coal-fired raw coal of substitution completely obtained by the present embodiment is tested, test 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 boils, and drying system discharges in flue gas fluorine content detection not
See variation, cyanide is not detected.
This test display, combustibility phase of the aluminium cell carbonaceous waste material of activated modification with semibituminous coal in fluidized bed furnace
When can be used as alternative fire coal.
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 library, inspection
Survey inanimate 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 solution (saturated solution that perchlorate detoxicant and hypochlorite detoxicant are prepared with mass ratio 1:1),
Catalytic oxidant used in the present embodiment is that (metavanadate catalytic oxidant and nitrate are catalyzed oxygen to ZC-9 type catalytic oxidant
Agent is with the mixture of mass ratio 1:1), 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 partial size≤10mm using impact type crushing system, broken
While broken, atomized spray is equivalent to the ZC-XJ5 type detoxification agent solution of aluminium cell carbonaceous waste material quality 5%, 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) it activates: granulation detoxification material obtained by step (1) is placed in mixer, be added be equivalent to aluminium electricity under stiring
The ZC-9 type catalytic oxidant of slot carbonaceous waste material quality 2.9% is solved, homogenizing is modified, and obtains alternative fire coal.
By alternative coal-fired alternative coal-fired (burnt lime institute, factory for being used as certain factory revolution lime burning obtained by the present embodiment
It is the semibituminous coal of volatile matter 17.4%, calorific value 5523kcal/kg with raw coal), alternative fire coal obtained by the present embodiment is pressed with raw coal
The ratio supplying of mass ratio 1:1 is milled into coal dust.
In the case where other controlling of production process parameter constants, test display: coal mill yield is suitable, and kiln yield is without visible
Variation, limekiln system condition is normal, and without strongly reducing atmosphere in kiln, online middle control data statistics coal consumption is suitable, and kiln tail discharges cigarette
Fluorine content detection has no variation in gas, detects lime quality without visible change, cyanide is not detected.
This test display, combustibility phase of the waste cathode carbon block material of activated modification with semibituminous coal in rotary kiln
When can be used as alternative fire coal.
Embodiment 8
Aluminium cell carbonaceous waste material used in the embodiment of the present invention is derived from the blocky carbonaceous waste material stored up in certain aluminium manufacturer library,
Detect inanimate matter content 37.2%, carbon content 62.8%, 4931 kcal/kg of calorific value；Detoxicant used in the embodiment of the present invention is
ZC-XJ13 type detoxification agent solution (hypochlorite detoxicant prepare saturated solution), catalytic oxidant used in the present embodiment
For ZC-11 type catalytic oxidant (ferrate catalytic oxidant and nitrate catalytic oxidant are with the mixture of mass ratio 1:1),
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: blocky aluminium cell carbonaceous waste material is crushed to by partial size≤5mm using impact type crushing system,
While broken, atomized spray is equivalent to the ZC-XJ13 type detoxification agent solution of aluminium cell carbonaceous waste material quality 7%, 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) it activates: granulation detoxification material obtained by step (1) is placed in mixer, be added be equivalent to aluminium electricity under stiring
It solves the ZC-11 type catalytic oxidant of slot carbonaceous waste material quality 4.1% and is equivalent to the oxidation of aluminium cell carbonaceous waste material quality 5%
Calcium, homogenizing are modified, and obtain alternative fire coal.
Alternative fire coal obtained by the present embodiment is made into alternative fire coal with Mr. Yu Building Materials Factory tunnel oven shale brick firing system
(raw coal used in factory's tunnel oven shale brick firing system is the anthracite of volatile matter 7.6%, calorific value 5031kcal/kg), by this reality
It applies alternative coal-fired complete substitution raw coal obtained by example to be tested, test display, alternative fire coal obtained by the embodiment of the present invention exists
Combustibility is good in tunnel oven shale brick firing system, and tunnel oven operating condition is normal.Through detecting: using alternative coal-fired shale brick
Sintering quality is more preferable, and compression strength averagely improves 2.6MPa, and tunnel oven shale brick firing system discharges fluorine content detection in flue gas
It has no variation, cyanide is not detected.
This test display, the aluminium cell carbonaceous waste material and anthracite of activated modification are in tunnel oven shale brick firing system
In combustibility it is suitable, can be used as alternative fire coal.
Embodiment 9
Aluminium cell carbonaceous waste material used in the embodiment of the present invention is derived from the blocky carbonaceous waste material stored up in certain aluminium manufacturer library,
Detect aggregate sample inanimate matter content 28.49%, carbon content 71.51%, calorific value 5615kcal/kg；Catalysis used in the present embodiment
Oxidant is that (perchlorate catalytic oxidant and nitrate catalytic oxidant are with mass ratio 2:1 for ZC-7 type liquid catalytic oxidant
The saturated solution of preparation), 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 coal tar.
It after aluminium cell carbonaceous waste material is crushed to granularity≤15mm, is placed in mixer, is added is equivalent under stiring
The ZC-7 type liquid catalytic oxidant of aluminium cell carbonaceous waste material quality 6.5% and it is equivalent to aluminium cell carbonaceous waste material quality 30%
Coal tar, homogenizing be modified, obtain alternative fire coal.
By alternative coal-fired alternative coal-fired (burnt lime institute, factory for being used as certain factory revolution lime burning obtained by the present embodiment
It is the semibituminous coal of volatile matter 17.4%, calorific value 5523kcal/kg with raw coal), alternative fire coal obtained by the present embodiment is pressed with raw coal
The ratio supplying of mass ratio 1:1 is milled into coal dust.
In the case where other controlling of production process parameter constants, test display: coal mill yield is suitable, and kiln yield is without visible
Variation, limekiln system condition is normal, and without strongly reducing atmosphere in kiln, online middle control data statistics coal consumption is suitable, and kiln tail discharges cigarette
Fluorine content detection has no variation in gas, detects lime quality without visible change, cyanide is not detected.
This test display, combustibility phase of the waste cathode carbon block material of activated modification with semibituminous coal in rotary kiln
When can be used as alternative fire coal.
Claims (5)
1. a kind of method that aluminium cell carbonaceous materials recycling is alternative fire coal, which comprises the following steps:
(1) it is granulated detoxification: aluminium cell carbonaceous waste material being crushed, while broken, 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, it must be granulated
Detoxification material；The detoxification agent solution is the water dissolution that sodium hypochlorite addition is first equivalent to 1.5~5.5 times of its quality, then will
Potassium ferrate and potassium hydroxide are dissolved in the saturated solution formed in liquor natrii hypochloritis by the mass ratio of 1:0.8~1.2；
(2) it activates: granulation detoxification material obtained by step (1) being placed in mixer, is added is equivalent to aluminium cell under stiring
The catalytic oxidant of carbonaceous waste material quality 0.6~8.0%, homogenizing are modified, and obtain alternative fire coal；The catalytic oxidant is attached most importance to chromium
Sour ammonium, metavanadic acid ammonia, lithium perchlorate, cerous nitrate, cobalt nitrate, nickel nitrate 2:0.8~1.2:0.8 in mass ratio~1.2:1.5~
The ratio of 2.5:1.5~2.5:2.5~3.5 is dissolved in saturated solution made of water；
Or granulation detoxification material obtained by step (1) is placed in in the leaching slot or tank for stirring or rolling over mixing device, phase respectively is added
When in aluminium cell 1~8% catalytic oxidant of carbonaceous waste material quality and 2~20% lime, and it is added and is equivalent to aluminium cell
The water of 1~10 times of carbonaceous waste material quality stirs or rolles over mixed, oxidation dealkalize, filtering or filtering washing, obtains dealkalize activated carbon slag, dry
To moisture≤15%, homogenizing is modified, and obtains alternative fire coal；
Or granulation detoxification material obtained by step (1) is placed in in the leaching slot or tank for stirring or rolling over mixing device, phase respectively is added
When in 1~8% catalytic oxidant of aluminium cell carbonaceous waste material quality, 2~20% lime, 2~20% sodium hydroxide, and add
Enter to be equivalent to 1~10 times of quality of aluminium cell carbonaceous waste material of water stirring or roll over to mix, aoxidizes dealuminzation dealkalize, filter or cross drainage
It washes, obtains the activated carbon slag of dealuminzation alkali, dry to moisture≤15%, homogenizing is modified, and obtains alternative fire coal；
Or granulation detoxification material leaching obtained by step (1) is dissolved in 0~80 DEG C of overcritical or liquid carbon dioxide and is processed, then
In separating obtained carbon dry mash, the catalytic oxidant that addition is equivalent to carbon dry mash quality 0.5~6% mix
Matter is modified, obtains alternative fire coal.
2. aluminium cell carbonaceous materials recycling is the method for alternative fire coal according to claim 1, it is characterised in that: step
(1) in, the broken granularity≤25mm of waste material；The crumbling method is that hammering, extruding or impact type are broken.
3. the method that aluminium cell carbonaceous materials recycling according to claim 1 or claim 2 is alternative fire coal, it is characterised in that:
In step (1), the main component of the aluminium cell carbonaceous waste material is waste cathode carbon block and/or scrap anode carbon granule, wherein charcoal contains
Amount 50~80%, 3800~6000kcal/kg of calorific value.
4. the method that aluminium cell carbonaceous materials recycling according to claim 1 or claim 2 is alternative fire coal, it is characterised in that:
In step (2), after catalytic oxidant is added or after dry, addition is equivalent to 1~20 %'s of aluminium cell carbonaceous waste material quality
Calcium oxide and/or magnesia, and/or be equivalent to 1~50 % of aluminium cell carbonaceous waste material quality hydrocarbon-containiproducts it is organic
Combustible, then it is homogenized modification；The combustable organic object of the hydrocarbon-containiproducts is coal tar, useless molding powder, waste Crumb rubber or husk
One or more of.
5. aluminium cell carbonaceous materials recycling is the method for alternative fire coal according to claim 3, it is characterised in that: step
(2) in, after catalytic oxidant is added or after dry, the oxidation for being equivalent to 1~20 % of aluminium cell carbonaceous waste material quality is added
Calcium and/or magnesia, and/or it is equivalent to the combustable organic of the hydrocarbon-containiproducts of 1~50 % of aluminium cell carbonaceous waste material quality
Object, then it is homogenized modification；The combustable organic object of the hydrocarbon-containiproducts is coal tar, in useless molding powder, waste Crumb rubber or husk
It is one or more of.
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| CN113149476A (en) * | 2021-04-10 | 2021-07-23 | 浙江红狮环保股份有限公司 | Method for disposing electrolytic aluminum ash in cement clinker production |
| CN114749465B (en) * | 2022-05-02 | 2023-07-11 | 郑州大学 | Method for purifying aluminum electrolysis waste cathode carbon and preparing porous carbon adsorbent |
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