CN108906857B - Mechanochemical conversion and recovery method of sodium-containing and fluorine-containing compounds in waste refractory material of aluminum electrolytic cell - Google Patents
Mechanochemical conversion and recovery method of sodium-containing and fluorine-containing compounds in waste refractory material of aluminum electrolytic cell Download PDFInfo
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- CN108906857B CN108906857B CN201810867525.3A CN201810867525A CN108906857B CN 108906857 B CN108906857 B CN 108906857B CN 201810867525 A CN201810867525 A CN 201810867525A CN 108906857 B CN108906857 B CN 108906857B
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- conversion
- fluorine
- refractory material
- sodium
- containing compounds
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- 239000002699 waste material Substances 0.000 title claims abstract description 119
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 114
- 239000011819 refractory material Substances 0.000 title claims abstract description 95
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 85
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 74
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 239000011737 fluorine Substances 0.000 title claims abstract description 66
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 66
- 150000001875 compounds Chemical class 0.000 title claims abstract description 61
- 239000011734 sodium Substances 0.000 title claims abstract description 56
- 229910052708 sodium Inorganic materials 0.000 title claims abstract description 43
- 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 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 34
- 238000011084 recovery Methods 0.000 title claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 44
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 37
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 36
- 238000000227 grinding Methods 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 17
- 239000011707 mineral Substances 0.000 claims abstract description 17
- 239000000126 substance Substances 0.000 claims description 27
- 239000002002 slurry Substances 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 17
- 150000002500 ions Chemical class 0.000 claims description 15
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminium flouride Chemical compound F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 claims description 14
- 239000007790 solid phase Substances 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 11
- 238000000926 separation method Methods 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- 238000004458 analytical method Methods 0.000 claims description 9
- 239000011812 mixed powder Substances 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 239000002250 absorbent Substances 0.000 claims description 8
- 230000002745 absorbent Effects 0.000 claims description 8
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 8
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 8
- 239000000292 calcium oxide Substances 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 229910001610 cryolite Inorganic materials 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 238000005070 sampling Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- 229910001635 magnesium fluoride Inorganic materials 0.000 claims description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- 229910052593 corundum Inorganic materials 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- 239000012286 potassium permanganate Substances 0.000 claims description 3
- MNWBNISUBARLIT-UHFFFAOYSA-N sodium cyanide Chemical compound [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 claims description 3
- GTSHREYGKSITGK-UHFFFAOYSA-N sodium ferrocyanide Chemical compound [Na+].[Na+].[Na+].[Na+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] GTSHREYGKSITGK-UHFFFAOYSA-N 0.000 claims description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 229910002567 K2S2O8 Inorganic materials 0.000 claims description 2
- 229910004882 Na2S2O8 Inorganic materials 0.000 claims description 2
- 239000005642 Oleic acid Substances 0.000 claims description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 2
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- 229910000831 Steel Inorganic materials 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 claims description 2
- 150000001242 acetic acid derivatives Chemical class 0.000 claims description 2
- 230000032683 aging Effects 0.000 claims description 2
- -1 alcohol amine Chemical class 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 150000001860 citric acid derivatives Chemical class 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 239000010431 corundum Substances 0.000 claims description 2
- 150000004679 hydroxides Chemical class 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- 239000011344 liquid material Substances 0.000 claims description 2
- 150000002823 nitrates Chemical class 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 2
- 235000021313 oleic acid Nutrition 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 229920005862 polyol Polymers 0.000 claims description 2
- 150000003077 polyols Chemical class 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 2
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 2
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- 239000008117 stearic acid Substances 0.000 claims description 2
- 239000010959 steel Substances 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 2
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 2
- 230000009466 transformation Effects 0.000 claims description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 abstract description 18
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 abstract description 12
- 238000004519 manufacturing process Methods 0.000 abstract description 12
- 150000002222 fluorine compounds Chemical class 0.000 abstract description 6
- 238000004064 recycling Methods 0.000 abstract description 6
- 150000003388 sodium compounds Chemical class 0.000 abstract description 6
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract 1
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 17
- 239000000463 material Substances 0.000 description 16
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 14
- 239000000706 filtrate Substances 0.000 description 13
- 235000010755 mineral Nutrition 0.000 description 13
- 238000000967 suction filtration Methods 0.000 description 12
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 11
- 239000011449 brick Substances 0.000 description 9
- 239000003792 electrolyte Substances 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 239000006096 absorbing agent Substances 0.000 description 8
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 8
- 229910010271 silicon carbide Inorganic materials 0.000 description 8
- 238000002386 leaching Methods 0.000 description 7
- 239000002893 slag Substances 0.000 description 7
- 239000011775 sodium fluoride Substances 0.000 description 7
- 235000013024 sodium fluoride Nutrition 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 235000012255 calcium oxide Nutrition 0.000 description 6
- 239000012065 filter cake Substances 0.000 description 6
- 239000011575 calcium Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000007844 bleaching agent Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 3
- 229910052581 Si3N4 Inorganic materials 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000001110 calcium chloride Substances 0.000 description 3
- 229910001628 calcium chloride Inorganic materials 0.000 description 3
- 235000011148 calcium chloride Nutrition 0.000 description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000002910 solid waste Substances 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- 239000005708 Sodium hypochlorite Substances 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 235000011116 calcium hydroxide Nutrition 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000009614 chemical analysis method Methods 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 150000004673 fluoride salts Chemical class 0.000 description 2
- 239000010881 fly ash Substances 0.000 description 2
- 239000002920 hazardous waste Substances 0.000 description 2
- 229910001387 inorganic aluminate Inorganic materials 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- 235000011147 magnesium chloride Nutrition 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 1
- 229910016384 Al4C3 Inorganic materials 0.000 description 1
- 229910020187 CeF3 Inorganic materials 0.000 description 1
- 229910020186 CeF4 Inorganic materials 0.000 description 1
- 239000004155 Chlorine dioxide Substances 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 229910002319 LaF3 Inorganic materials 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- 229910001632 barium fluoride Inorganic materials 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910001622 calcium bromide Inorganic materials 0.000 description 1
- WGEFECGEFUFIQW-UHFFFAOYSA-L calcium dibromide Chemical compound [Ca+2].[Br-].[Br-] WGEFECGEFUFIQW-UHFFFAOYSA-L 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 235000019398 chlorine dioxide Nutrition 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007255 decyanation reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006115 defluorination reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910001506 inorganic fluoride Inorganic materials 0.000 description 1
- 229910052909 inorganic silicate Inorganic materials 0.000 description 1
- 229910052640 jadeite Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021527 natrosilite Inorganic materials 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical class [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229910001637 strontium fluoride Inorganic materials 0.000 description 1
- FVRNDBHWWSPNOM-UHFFFAOYSA-L strontium fluoride Chemical compound [F-].[F-].[Sr+2] FVRNDBHWWSPNOM-UHFFFAOYSA-L 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- BYMUNNMMXKDFEZ-UHFFFAOYSA-K trifluorolanthanum Chemical compound F[La](F)F BYMUNNMMXKDFEZ-UHFFFAOYSA-K 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/40—Destroying solid waste or transforming solid waste into something useful or harmless involving thermal treatment, e.g. evaporation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
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Abstract
The invention relates to a mechanochemical conversion and recovery method of sodium-containing and fluorine-containing compounds in waste refractory materials of an aluminum electrolytic cell. Book (I)The invention firstly crushes, grinds and homogenizes the waste refractory material to obtain waste refractory material powder, then adds the waste refractory material powder, sodium compound and fluorine compound conversion agent, cyanide conversion agent, grinding aid and water into the conversion mill, high-energy mechanical force synchronously acts on the mechanochemical conversion reaction of sodium-containing and fluorine-containing compounds to convert the sodium-containing compounds in the waste refractory material powder into soluble sodium compounds without fluorine, the fluorine-containing compounds into insoluble and harmless mineral fluorine compounds, and the cyanogen-containing compounds are converted into harmless N by oxidation2Or NH3And CO2Thereby thoroughly removing the harm of fluoride and cyanide in the waste refractory material for aluminum electrolysis and realizing the harmless and resource recycling of the waste refractory material for aluminum electrolysis. The invention has simple process, easy large-scale production, low production cost, no three-waste pollution and environmental protection.
Description
Technical Field
The invention relates to a mechanochemical conversion and recovery method of sodium-containing and fluorine-containing compounds in waste refractory materials of an aluminum electrolysis cell, belonging to the technical field of harmless and resource utilization of solid wastes in the electrolytic aluminum industry.
Background
The capacity of the electrolytic aluminum is about 4500 ten thousand tons in China by 2017, the actual yield exceeds 3600 ten thousand tons, and the capacity accounts for more than 50 percent of the global capacity of the electrolytic aluminum. The aluminum electrolysis cell generally needs to be stopped for overhaul after about 4 to 6 years of use, all waste cell lining materials (overhaul residues for short) are taken out, and the overhaul residues are solid wastes inevitable in the production process of the electrolytic aluminum. About 10-30 kg of overhaul residues are discharged when 1 ton of raw aluminum is produced in electrolytic aluminum production, the overhaul residues of electrolytic aluminum are specified as dangerous solid wastes (the category is HW48) in the national hazardous waste record, and waste tank liners are listed as HW32 inorganic fluoride wastes and HW33 inorganic cyanide wastes in the national hazardous waste record. The overhaul slag mainly comprises about 55 percent of waste cathode carbon blocks (including paste materials) and about 45 percent of waste refractory materials (including silicon carbide, silicon nitride, calcium silicate, ceramic fibers, insulating bricks, impermeable materials, castable, side blocks and the like). The carbon material in the overhaul residue accounts for 30-70 percent, and the rest is electrolyte, mainly Na3[AlF6]、NaF、CaF2、MgF2、LiF、AlF3、NaCN、Na4[Fe(CN)6]Etc., and also small amounts of Al and Al4C3AlN and Na, which are soluble and reactive with water to produce HF, HCN and H2、CH4、NH3And the harmful or flammable gases, fluorine-containing and cyanogen-containing compounds, which enter the environment, can cause great harm to the health and growth of human beings, animals and plants.
Both refractory materials and fluorine-containing electrolytes are valuable resources. Therefore, how to completely remove the harm of fluoride and cyanide in the waste refractory materials and realize the harmless and resource recycling of the waste refractory materials of the aluminum electrolytic cell is an industry difficult problem which needs to be overcome, and the expert and scholars in the industry and production front staff carry out years of continuous research and research aiming at the difficult problem.
Chinese invention CN107088570A provides a method for treating waste refractory material of aluminum electrolysis, which comprises the steps of grinding waste refractory material of aluminum electrolysis, stirring and mixing with water, adding bleaching powder and potassium permanganate to carry out decyanation reaction, adding phosphoric acid, sulfuric acid or mixed acid to adjust the pH value of the slurry to 6-8, filtering, adding calcium chloride, magnesium chloride and aluminum sulfate defluorination agent into filter residue to treat, adding concentrated phosphoric acid and concentrated sulfuric acid into the filtrate to convert fluorine into HF, and then carrying out evaporative crystallization treatment on the filtrate.
Chinese invention CN105327933A provides a method for treating waste cell lining of aluminum electrolysis cell based on chemical precipitation and oxidation reduction reaction, which comprises crushing and grinding the waste cell lining, adding sodium hypochlorite solution, controlling the pH value of alkalescence to 7.0-8.5, removing cyanide and sodium hypochlorite solution through oxidation reduction reaction, and reacting with lime water to generate insoluble CaF2。
Chinese invention CN106086938A provides a method for recycling electrolyte in aluminum electrolysis waste tank liner by ultrasonic-assisted pressure alkaline leaching, which comprises crushing and grinding the aluminum electrolysis waste tank liner, mixing with water to obtain slurry, pretreating with ultrasonic wave, pressure leaching the treated slurry with alkali liquor, filtering and separating; burying the filter residue, introducing CO into the filtrate2The separated electrolyte precipitate is recovered.
China invention CN107377592A provides a harmless treatment device and a treatment method for aluminum electrolysis waste cell liners, wherein the treatment device comprises a water adding reaction bin, a cyanogen removing agent or fluorine removing agent adding reaction bin, a fluorine removing agent or cyanogen removing agent adding reaction bin, a neutralizer adding reaction bin and a material collecting bin which are connected in sequence. Adding the milled aluminum electrolysis waste cell lining powder into a reaction bin, sequentially adding water, a fluorine removing agent (comprising quick lime, hydrated lime or calcium chloride) or a cyanogen removing agent (bleaching powder) and a neutralizing agent (mixed acid), and simultaneously performing feeding, reaction and discharging to form a continuous aluminum electrolysis waste cell lining harmless treatment process.
The invention CN105964660A of China proposes a method for harmlessly treating a waste cell lining of an aluminum electrolysis cell, which comprises the steps of crushing the waste cell lining of the aluminum electrolysis cell, heating and removing cyanogen in a muffle furnace at the constant temperature of 200 ℃ and 400 ℃ for a certain time, adding CaCl into the cyanogen-removing waste cell lining2、Ca3(NO3)2、CaBr2、Ca(ClO4)2Performing salt leaching treatment in the water solution, filtering after stirring and leaching, burying or storing filter residues, and recycling the filtrate as a salt leaching solution.
The invention CN105728440A in China provides an aluminum cell overhaul residue harmless treatment system and a treatment method, the system comprises a leaching bin and a reaction bin which is connected with the leaching bin and is used for carrying out cyanogen and fluorine removal treatment, the cyanogen removal agent is one or more of sodium chlorate, bleaching powder, hydrogen peroxide, bleaching powder essence and chlorine dioxide, and the fluorine removal agent is one or more of calcium chloride, aluminum chloride, magnesium chloride, calcium hydroxide and calcium oxide.
The invention CN102059736A of China proposes a method for producing insulating bricks by using aluminum electrolysis waste refractory materials, which comprises the steps of mixing, extruding, drying and firing the aluminum electrolysis waste refractory materials, fly ash or fly ash floating beads, a binder, an additive, a pore-forming agent and water to produce the insulating bricks, wherein flue gas is absorbed by alumina.
The invention CN106238439A of China proposes a method for removing fluorine from a waste cell lining of an aluminum electrolysis cell by vacuum distillation, the waste cell lining is crushed and placed into a crucible in a vacuum distillation furnace, a fluoride collector is arranged on the crucible, the pressure in the furnace is reduced to be less than 100Pa, the temperature is 500-1000 ℃, the temperature is kept for 1-3 h, and the fluoride obtained by the collector and the cyanide are decomposed at high temperature.
The invention CN107364880A of China proposes a method and a system for recovering fluorine from an electrolytic aluminum waste tank lining, which comprises an incinerator, a fluidized bed absorber and a conveying bed absorber. Rendering waste in high temperature environment of incineratorThe groove lining reacts with the auxiliary agent to generate HF adsorbed Al2O3Conversion to AlF3Separating with fume by cloth bag filter to recover AlF3。
China CN105499251A provides a glass curing and stabilizing method for treating aluminum electrolysis waste cell liners based on F-Si chemical bonds, the broken waste cell liners are placed into a metal curing tank and calcined at 750-850 ℃ for 2-3.5 h, then glass substances with the weight 0.8-2.0 times of that of the waste cell liners are added as curing agents and continuously calcined at 1050-1200 ℃ for 2-4 h, and the molten glassy state mixture flows into a receiving container and is annealed/quenched to obtain a glass cured body containing waste cell liner fluoride.
The Chinese invention CN106517209A provides a method for processing waste cathodes of aluminum cell liners, which comprises the steps of adding carbon materials and quartz sand into the waste cathodes of the aluminum cell liners, carrying out high-temperature carbothermic reduction to generate SiC, forming melt sinking by cryolite and carrying out solid-liquid separation on SiC, evaporating fluoride salt in furnace gas and carrying out gas-solid separation on the generated SiC to respectively prepare SiC, the cryolite melt and fluoride salt.
China CN107904622A provides a regeneration method of a silicon carbide material of a waste side lining of an aluminum electrolytic cell, the waste side lining material is crushed and placed in a high-temperature heat treatment furnace to be treated under the normal pressure (1200-1800 ℃) or the pressure of 0.001-0.5 atm (1000-1600 ℃), and fluoride and sodium salt volatilized from flue gas can be used for producing fluoride electrolyte through cooling crystallization.
The invention CN105503150A of China proposes a brick kiln co-processing method for harmlessly processing waste cell linings for aluminum electrolysis, and waste cell linings and CaSO are processed4And respectively crushing the coal, mixing the crushed coal with clay, adding water, fully mixing the crushed coal with the clay, extruding the mixture into a green brick through a vacuum extruder, a vacuum pump or a spiral reamer, drying and dehydrating the green brick under the condition of natural ventilation, sending the dried green brick into a roasting cellar, roasting the green brick for 1 to 3 hours at the temperature of 900 to 1050 ℃, and discharging tail gas in high altitude after the tail gas is purified and reaches the standard.
The Chinese invention CN102989744A provides a recycling method of mixed slag of overhaul groove slag of an electrolytic cell, which is used for sorting the overhaul groove slag of the electrolytic cell to respectively obtain an electrolyte lump material, a cathode bar, a waste cathode carbon block, a waste refractory brick, a waste heat-insulating plate, waste ramming paste and residual mixed slag; and (3) grinding the sorted mixed slag, then performing flotation to select carbon powder and refractory materials, and preparing the residual powder into a slagging agent. And drying the carbon powder, and then calcining at 1700-1900 ℃ to gasify sodium fluoride and sulfur in the carbon powder to obtain the high-purity carbon powder. And drying the refractory material, and then calcining at 1700-1900 ℃ to gasify sodium fluoride in the refractory material to obtain the high-purity refractory material.
The harmless and resource treatment and utilization of the waste refractory materials of the aluminum electrolytic cell can be divided into two categories of wet treatment of aqueous solution and pyrogenic treatment at high temperature. From the prior technical results, there are still many problems to be solved urgently in the wet treatment and the fire treatment of the waste refractory materials of the aluminum electrolysis cell.
The current wet processing technology has at least the following main problems: firstly, a large amount of generated salt-containing and fluorine-containing wastewater is not effectively treated, so that secondary pollution is caused; generated H2、CH4、NH3The gas is not controlled and utilized; the HF produced is not effectively pollution controlled or utilized. Secondly, the recovered electrolyte has too high content of impurities to be directly utilized, and a large amount of generated refractory waste residues still need to be further treated. Thirdly, the process route is complicated, the technology is complex and the treatment cost is too high. Fourthly, the production process is difficult to control due to the influence of factors such as fluctuation of components of the waste refractory material, high difficulty in powder refinement and the like.
The current fire treatment technology has at least the following main problems: first, the off-gas that generates large amounts of entrained HF and dust needs to be remediated. Second, the electrolyte salt is not completely recovered and remains in the spent refractory or slag requiring further treatment. And thirdly, the low-melting point electrolyte salt is melted and agglomerated in the furnace, so that the production working condition is deteriorated and the production stability is poor. Fourth, the reaction mass is difficult to achieve uniform mixing at the molecular level, resulting in incomplete conversion reactions. Fifthly, the equipment is seriously corroded and the energy consumption for treatment is high.
Disclosure of Invention
In order to solve the technical problems, the invention provides a mechanochemical conversion and recovery method of sodium-containing and fluorine-containing compounds in the waste refractory materials of the aluminum electrolytic cell. The invention has the characteristics of convenient control of the process, easy industrial stable production, low process cost, no three-waste pollution, no equipment corrosion and the like.
The invention is realized by the following technical scheme:
a mechanochemical conversion and recovery method for the sodium and fluorine-containing compounds in the waste refractory material of aluminium electrolyzer features that the waste refractory material powder, the conversion agent of sodium compound and fluorine compound, cyanide conversion agent, grinding aid and water are proportionally added to conversion mill where high-energy mechanical force synchronously acts on the mechanochemical conversion reaction of sodium and fluorine-containing compounds to transform the sodium-containing compound in waste refractory material powder to soluble sodium compound without fluorine, fluorine-containing compound to insoluble and harmless mineral fluorine compound and the cyanogen-containing compound to harmless N2Or NH3And CO2Thereby thoroughly removing the harm of fluoride and cyanide in the waste refractory material for aluminum electrolysis; the method specifically comprises the following steps (the sequence of the following steps is expressed for convenience and does not directly indicate the precedence relationship, and the included steps specifically include the parts subject to the literal logic description or logic relationship):
(1) crushing, grinding and homogenizing the waste refractory materials of the aluminum electrolytic cell to obtain waste refractory material powder with the particle size less than or equal to 200 mu m; analyzing and determining the mole number or mass of sodium and fluorine in the aluminum electrolysis waste refractory material powder per unit mass; analysis and determination of CN in unit mass of aluminum electrolysis waste refractory material powder-The number of moles or mass of ions;
adding the grinding body into the conversion mill, and then carrying out air evacuation or N on the conversion mill2Replacement, namely adding the measured waste refractory material powder into a conversion mill, controlling the mass ratio of the waste refractory material powder to a grinding body to be 1 (0.2-10), adding the measured water into the conversion mill, and controlling the solid-liquid mass ratio of the waste refractory material powder to the water to be 1 (1-10);
adding a conversion agent into a conversion mill according to the amount of 1-3 times of the stoichiometric ratio of the sodium-containing and fluorine-containing compounds in the waste refractory material powder to the corresponding products, or according to the amount of 5-80% of the mass of the waste refractory material powder;
adding a grinding aid into a conversion mill according to the mass of 0-1% of the waste refractory material powder;
(2) after the step (1) is finished, starting the conversion mill, and controlling the rotation speed of the conversion mill to be 10-1000 rpm and the conversion temperature to be 10-110 ℃; sampling and analyzing the slurry in batches in the conversion process until Na in the solid phase substance of the slurry+The ion content reaches the enterprise standard, and the soluble F-Stopping the conversion grinding when the ion content reaches the national emission standard;
(3) after the step (2) is finished, transferring the slurry into a stirring reactor (a reaction kettle, a reaction tank or a reaction tank) for gel breaking and aging treatment, wherein the temperature is controlled to be 60-150 ℃, and the treatment time is 0.5-5 h;
(4) carrying out solid-liquid separation on the slurry obtained in the step (3) by adopting a filtering or centrifugal separation mode, repeatedly carrying out dispersion washing and solid-liquid separation on a water-containing solid-phase substance in a conversion mill or a stirring reactor (a reaction kettle or a reaction tank) by taking water as a washing agent according to the solid-liquid mass ratio of 1 (1-10) for a plurality of times until the content of soluble ions in the solid-phase substance reaches the enterprise standard, combining separation liquids, and respectively obtaining a mixture of wet fluorine-containing mineral substances and refractory materials, namely a dilute solution of the water-containing solid-phase substance and the soluble mixture;
(5) drying or carrying out heat treatment on the aqueous solid phase obtained in the step (4) at the temperature of 80-300 ℃ for 1-10 h, and then crushing to obtain mixed powder of the fluorine-containing mineral and the refractory material, wherein the average particle size of the mixed powder material is less than or equal to 20 microns, and the mixed material can be sold as a commodity or further subjected to separation and purification to obtain a high-quality refractory material and a fluoride mineral raw material;
placing the mixed powder of the fluorine-containing mineral substance and the refractory material in an air atmosphere and a high-temperature furnace at the temperature of 700-1200 ℃ for calcining for 0.5-5 h, wherein the carbon component is completely oxidized and combusted, and the residue is a mixture of the fluorine-containing mineral substance and the refractory material;
(6) concentrating or crystallizing the dilute solution of the soluble mixture obtained in the step (4) to obtain a concentrated solution or a solid-phase mixture of the mixture, or further separating and purifying Na, K, Li, Al, Mg and Ca compounds in the mixture to obtain a sodium compound and other compound raw materials with higher quality and value;
(7) according to CN in the waste refractory powder-Conversion of ions to N2Or NH3And CO2In an amount of 1 to 5 times the stoichiometric ratio of the chemical reaction, or in an amount of 0.1 to 10% by mass of the waste refractory powder, a cyanide conversion agent is added to the step (2), or the step (3), or the step (6) to oxidize and convert the cyanide-containing compound into harmless N2Or NH3And CO2The analysis and check are carried out on the transformation system in batches and at regular time until CN in the system-Stopping the conversion reaction when the ion content reaches the national emission standard;
(8) NH generated in the step (2), the step (3) or the step (6)3、CO2、H2And converting and drying the O gas by an absorbent, and collecting the generated reducing gas or directly oxidizing and combusting the reducing gas.
Al and Al exist in the aluminum electrolysis waste refractory4C3AlN, Na, etc., and combustible gases (including H) generated by the reaction taking part in the conversion reaction2、CH4、NH3Etc.) is the reducing gas in the step (8).
In the conversion mill, high-energy mechanical force synchronously acts on the mechanochemical conversion reaction of the sodium-containing compound and the fluorine-containing compound, so that solid particles are continuously ground, ground and converted, reactants and products are continuously updated and stripped from the particles, and the conversion reaction is quickly and completely finished.
Further, in all the steps, the pH is controlled to be not less than 6, and no protonic acid substance is used; the sodium compound and fluorine compound conversion agent, cyanide conversion agent and grinding aid substance do not contain chlorine element.
Further, the waste refractory includes C as a main element (including graphite)Chemical C and non-graphitizing C), more than two of Na, F, Al, Ca, O, N, Li, Mg, Si, K and Fe; the sodium-containing compound comprises NaF and Na3AlF6、NaCN、Na4[Fe(CN)6]Two or more of (1); the fluorine-containing compound comprises NaF and Na3AlF6、AlF3、LiF、CaF2、MgF2And KF.
Further, the conversion agent of the sodium-containing compound and the fluorine-containing compound comprises one or more than two of oxides, hydroxides, sulfates, nitrates, carbonates, acetates and citrates corresponding to the elements of Ca, Al, Mg, Sr, Ba, La and Ce.
The conversion agent is used for converting sodium-containing compounds in the waste refractory materials into corresponding non-fluorine-containing soluble sodium-containing compounds including NaOH and Na2SO4、NaNO3、NaOAc、Na2CO3、Na3C6H5O7、Na2AlO4、Na[Al(OH)6]2(OH)3、NaAlSi2O6、Na2(H2SiO4)·7H2O、Na6Si8O19、Na2Al2SiO6、Na2Si2O5、Na2SiO3One or more than two of them.
The corresponding insoluble and harmless mineral fluorides including CaF from fluorine-containing compounds in the waste refractory materials after conversion with the conversion agent2、MgF2、AlF3、SrF2、BaF2、CaF2、LaF3、CeF3、CeF4One or more than two of them.
Further, the cyanide conversion agent comprises Na2CO3·1.5H2O2、K2CO3·1.5H2O2、Na2O2、K2O2、CaO2、SrO2、BaO2、H2O2、(NH4)2S2O8、Na2S2O8、K2S2O8、KMnO4、O2、O3One or more than two of them.
Further, the grinding aid comprises one or more of polymeric polyol, polymeric alcohol amine, triisopropanolamine, ethylene glycol, propylene glycol, glycerol, diethylene glycol, triethanolamine, amide, stearic acid, oleic acid, sodium hexametaphosphate and sodium stearate.
Further, the transforming agent and the grinding aid are added in a solid, aqueous solution or gas state in a one-time adding mode, or in a batch adding mode, or in a continuous adding mode.
Further, the conversion mill is a modified airtight ball mill, and a mill body is provided with a grinding body inlet and outlet, a powder inlet, a liquid material inlet, a gas outlet, a slurry outlet, a cleaning emptying port, a gas sampling port and a slurry sampling port; the grinding body is one or more than two of corundum balls, zirconia balls, ceramic balls, steel balls, stainless steel balls and alloy balls.
The invention has the beneficial effects that:
(1) the invention has the characteristics of convenient control of the process, easy industrial stable production, low production cost, no three-waste pollution, no equipment corrosion and the like.
(2) The invention solves the problems and the defects of the existing wet treatment and fire treatment production process. Provides an advanced and systematic solution for the harmlessness and resource recycling of the waste refractory materials for aluminum electrolysis.
Drawings
FIG. 1 is an SEM photograph of the waste refractory powder for an aluminum electrolytic cell used in example 1.
FIG. 2 is an X-ray diffraction chart of the used refractory powder for an aluminum electrolytic cell used in example 1.
FIG. 3 is an X-ray diffraction chart of a mixed powder material B of a fluorine-containing mineral and a refractory obtained in example 1.
FIG. 4 is an X-ray diffraction diagram of the soluble mixture A obtained in example 1.
Detailed Description
The following examples further illustrate the technical solutions of the present invention, but the present invention is not limited to the examples and is not intended to limit the scope of the present invention.
Example 1
(1) The waste refractory material of the aluminum electrolytic cell is crushed in a high-speed crusher, sieved by a 200-mesh sieve, and the waste refractory material powder of the undersize material is adopted to carry out mechanochemical conversion and recovery of compounds containing sodium and fluorine. Determining the mass content of sodium and fluorine elements in the unit mass of the waste refractory material powder by adopting a chemical analysis method, and determining CN in the unit mass of the waste refractory material powder by adopting the chemical analysis method-Mass content of ions.
(2) Adding 200g of stainless steel balls into a conversion mill, weighing 100g of waste refractory material powder, 20g of CaO and 0.5g of ethylene glycol, adding into the conversion mill, uniformly mixing, and adding N2Replacing air in the inversion mill, and adding 300gH into the inversion mill2And O. Starting the conversion mill, wherein the rotating speed is 500rpm, the temperature is 30 ℃, and the conversion reaction time is 3 h.
Transferring the slurry to a stirring reactor after the conversion reaction, wherein the stirring speed is 1000rpm, the temperature is 95 ℃, and Na with the mass percentage concentration of 5 percent is dropwise added into the system during the stirring reaction2CO3·1.5H2O240g of the solution was stirred at a constant temperature and reacted for 90 min.
Respectively passing the tail gas generated in the step (1) and the step (2) through an absorber using water as an absorbent and an absorber using CaO as an absorbent, wherein NH is3、CO2Is absorbed by H2、CH4And (4) carrying out combustion oxidation.
(3) Carrying out negative pressure suction filtration on the slurry after the stirring reaction, transferring a filter cake into a conversion mill after suction filtration, and adding 200gH2And O, performing conversion, grinding, dispersing, washing, performing suction filtration again, repeatedly washing, performing suction filtration and washing until the content of sodium ions in the final filtrate reaches the enterprise standard, and combining the filtrates.
The filtrate was evaporated under reduced pressure, concentrated and crystallized and dried in a vacuum oven at 100 ℃ for 10h to give a soluble mixture a.
(4) And drying the water-containing filter cake at 150 ℃ under normal pressure for 10h, and crushing the dried product to obtain a mixed powder material B of the fluorine-containing mineral substance and the refractory material.
As can be seen from FIG. 1, the particle size of the waste refractory powder used in example 1 was 45 μm or less, and the particles were in a random shape.
As can be seen from FIG. 2, the main phase components of the used refractory material for aluminum reduction cells used in example 1 were C, NaF and Na3AlF6、AlF3、LiF、MgF2、SiC、Si3N4。
As can be seen from FIG. 3, the main component of the fluorine-containing mineral and refractory B obtained by the treatment of example 1 was C, CaF2、SiC、Si3N4、Al2O3Description of NaF and Na in the waste refractory3AlF6、AlF3LiF, etc. have been converted into CaF2。
As can be seen from FIG. 4, the main components of the soluble mixture A obtained by the treatment of example 1 are NaOH and Na2CO3、LiOH、Na2AlO4Indicating that the elemental fluorine-containing component of the spent refractory material has been completely converted to the insoluble mineral CaF2。
From these test analysis data it can be seen that: example 1 realizes the complete conversion of sodium-containing and fluorine-containing compounds in the aluminum electrolysis cell waste refractory material, and thoroughly removes the harm of fluoride and cyanide in the aluminum electrolysis cell waste refractory material.
Example 2
(1) The waste refractory material of the aluminum electrolytic cell is crushed in a high-speed crusher, sieved by a 200-mesh sieve, and the waste refractory material powder of the undersize material is adopted to carry out mechanochemical conversion and recovery of compounds containing sodium and fluorine. Determining the mass content of sodium and fluorine elements in the unit mass of the waste refractory material powder by adopting a chemical analysis method, and determining CN in the unit mass of the waste refractory material powder by adopting the chemical analysis method-Mass content of ions.
(2) 200g of stainless steel balls are added into a conversion mill100g of waste refractory powder and 30g of CaSO were weighed4·H2Adding 0.8g of glycerol and O into a conversion mill, uniformly mixing, and adding N2Displacing air from the inversion mill and adding 500g H to the inversion mill2And O. Starting a conversion mill, wherein the rotating speed is 800rpm, the temperature is 50 ℃, and the conversion reaction time is 4 hours;
transferring the slurry to a stirring reactor after the conversion reaction, wherein the stirring speed is 1200rpm, the temperature is 110 ℃, and H with the mass percent concentration of 30 percent is dropwise added into the system during the stirring reaction2O2The solution (20 g) was stirred at a constant temperature for 100 min.
Respectively passing the tail gas generated in the step (1) and the step (2) through an absorber using water as an absorbent and an absorber using CaO as an absorbent, wherein NH is3、CO2Is absorbed by H2、CH4And (4) carrying out combustion oxidation.
(3) Carrying out negative pressure suction filtration on the slurry after the stirring reaction, transferring a filter cake into a conversion mill after suction filtration, and adding 300gH2And O, performing conversion, grinding, dispersing, washing, performing suction filtration again, repeatedly washing, performing suction filtration and washing until the content of sodium ions in the final filtrate reaches the enterprise standard, and combining the filtrates.
The filtrate was evaporated under reduced pressure, concentrated and crystallized and dried in a vacuum oven at 100 ℃ for 10h to give a soluble mixture a.
(4) And drying the water-containing filter cake at 150 ℃ under normal pressure for 10h, and crushing the dried product to obtain a mixed powder material B of the fluorine-containing mineral substance and the refractory material.
Experimental results show that the example 2 can realize the complete conversion of the sodium-containing and fluorine-containing compounds in the waste refractory materials of the aluminum electrolytic cell, and thoroughly remove the harm of fluoride and cyanide in the waste refractory materials of the aluminum electrolytic cell.
Example 3
(1) The waste refractory material of the aluminum electrolytic cell is crushed in a high-speed crusher, sieved by a 200-mesh sieve, and the waste refractory material powder of the undersize material is adopted to carry out mechanochemical conversion and recovery of compounds containing sodium and fluorine. Determining the mass content of sodium and fluorine elements in the unit mass of the waste refractory material powder by adopting a chemical analysis methodChemical analysis method for determining CN in unit mass of waste refractory material powder-Mass content of ions.
(2) 200g of stainless steel ball is added into a conversion mill, 100g of waste refractory powder and 25g of MgSO4Adding into a conversion mill, mixing, adding 400g H into the conversion mill2And O. Starting a conversion mill, wherein the rotating speed is 900rpm, the temperature is 40 ℃, and the conversion reaction time is 3.5 hours;
transferring the slurry to a stirring reactor after the conversion reaction, wherein the stirring speed is 800rpm, the temperature is 100 ℃, and (NH) with the mass percentage concentration of 10 percent is dropwise added into the system during the stirring reaction4)2S2O8The solution (50 g) was stirred at a constant temperature and the reaction was stopped for 110 min.
Respectively passing the tail gas generated in the step (1) and the step (2) through an absorber using water as an absorbent and an absorber using CaO as an absorbent, wherein NH is3、CO2Is absorbed by H2、CH4And (4) carrying out combustion oxidation.
(3) Carrying out negative pressure suction filtration on the slurry after the stirring reaction, transferring a filter cake into a conversion mill after suction filtration, and adding 400gH2O is subjected to conversion, grinding, dispersion, washing, suction filtration, repeated washing and suction filtration, and washing is carried out until the filtrate is finally treated with 2M BaCl2The solution was checked until no precipitate was produced and the filtrates were combined.
The filtrate was evaporated under reduced pressure, concentrated and crystallized and dried in a vacuum oven at 100 ℃ for 10h to give a soluble mixture a.
(4) And drying the water-containing filter cake at 150 ℃ under normal pressure for 10h, and crushing the dried product to obtain a mixed powder material B of the fluorine-containing mineral substance and the refractory material.
Experimental results show that the example 3 can realize the complete conversion of the sodium-containing and fluorine-containing compounds in the waste refractory materials of the aluminum electrolytic cell, and thoroughly remove the harm of fluoride and cyanide in the waste refractory materials of the aluminum electrolytic cell.
Claims (8)
1. A mechanochemical conversion and recovery method of sodium-containing compounds and fluorine-containing compounds in waste refractory materials of aluminum electrolysis cells is characterized by comprising the following steps:
(1) crushing, grinding and homogenizing the waste refractory materials of the aluminum electrolysis cell to obtain waste refractory material powder of the aluminum electrolysis cell with particles less than or equal to 200 mu m; analyzing and determining the mole number or mass of sodium and the mole number or mass of fluorine in the unit mass of the waste refractory material powder of the aluminum electrolytic cell; analysis and determination of CN in unit mass of waste refractory material powder of aluminum electrolysis cell-The number of moles or mass of ions;
adding the grinding body into the conversion mill, and then carrying out air evacuation or N on the conversion mill2Replacement, namely adding the measured waste refractory material powder of the aluminum electrolytic cell into a conversion mill, controlling the mass ratio of the waste refractory material powder of the aluminum electrolytic cell to a grinding body to be 1 (0.2-10), adding the measured water into the conversion mill, and controlling the solid-liquid mass ratio of the waste refractory material powder of the aluminum electrolytic cell to the water to be 1 (1-10);
adding a conversion agent of a sodium-containing compound and a fluorine-containing compound into a conversion mill according to the amount which is 1-3 times of the stoichiometric ratio of the chemical reaction of converting the sodium-containing compound and the fluorine-containing compound in the waste refractory material powder of the aluminum electrolytic cell into corresponding products, or according to the amount which is 5-80% of the mass of the waste refractory material powder of the aluminum electrolytic cell;
adding a grinding aid into a conversion mill according to the mass of 0-1% of the waste refractory material powder of the aluminum electrolytic cell;
(2) after the step (1) is finished, starting the conversion mill, and controlling the rotation speed of the conversion mill to be 10-1000 rpm and the conversion temperature to be 10-110 ℃; sampling and analyzing the slurry in batches in the conversion process until Na in the solid phase substance of the slurry+The ion content reaches the enterprise standard, and the soluble F-Stopping the conversion grinding when the ion content reaches the national emission standard;
(3) after the step (2) is completed, transferring the slurry into a stirring reactor for gel breaking and aging treatment, controlling the temperature to be 60-150 ℃ and the treatment time to be 0.5-5 h;
(4) carrying out solid-liquid separation on the slurry obtained in the step (3) by adopting a filtering or centrifugal separation mode, repeatedly carrying out dispersion washing and solid-liquid separation on the water-containing solid-phase substance in a conversion mill or a stirring reactor by taking water as a washing agent according to the solid-liquid mass ratio of 1 (1-10) until the content of soluble ions in the solid-phase substance reaches the enterprise standard, and combining separation solutions to respectively obtain dilute solutions of the water-containing solid-phase substance and a soluble mixture;
(5) drying or heat-treating the aqueous solid phase obtained in the step (4) at the temperature of 80-300 ℃ for 1-10 h, and then crushing to obtain mixed powder of the fluorine-containing mineral and the refractory material;
placing the mixed powder of the fluorine-containing mineral substance and the refractory material in an air atmosphere and a high-temperature furnace at the temperature of 700-1200 ℃ for calcining for 0.5-5 h, wherein the carbon component is completely oxidized and combusted, and the residue is a mixture of the fluorine-containing mineral substance and the refractory material;
(6) concentrating the dilute solution of the soluble mixture obtained in the step (4) to obtain a concentrated mixture solution or crystallizing to obtain a solid phase mixture, or further separating and purifying Na, K, Li, Al, Mg and Ca compounds in the solid phase mixture;
(7) according to CN in the waste refractory material powder of the aluminum electrolytic cell-Conversion of ions to N2And CO2Or NH3And CO2In an amount of 1 to 5 times of the stoichiometric ratio of the chemical reaction, or in an amount of 0.1 to 10 percent of the mass of the waste refractory material powder of the aluminum electrolysis cell, adding a cyanide conversion agent into the step (2), or the step (3), or the step (6) to oxidize and convert the cyanide-containing compound into harmless N2Or NH3And CO2The analysis and check are carried out on the transformation system in batches and at regular time until CN in the system-Stopping the conversion reaction when the ion content reaches the national emission standard;
(8) NH generated in the step (2), the step (3) or the step (6)3、CO2、H2And converting and drying the O gas by an absorbent, and collecting the generated reducing gas or directly oxidizing and combusting the reducing gas.
2. The method for mechanochemical conversion and recovery of sodium-containing compounds and fluorine-containing compounds contained in the spent refractory material for aluminum reduction cells according to claim 1, wherein in all the steps, the pH is controlled to not less than 6 and no protonic acid substance is used; the conversion agent of the sodium-containing compound and the fluorine-containing compound, the cyanide conversion agent and the grinding aid substance do not contain chlorine element.
3. The method for mechanochemical conversion and recovery of sodium-containing compounds and fluorine-containing compounds in the spent refractory material of an aluminum electrolysis cell according to claim 1, wherein the spent refractory material of an aluminum electrolysis cell comprises two or more of C, Na, F, Al, Ca, O, N, Li, Mg, Si, K, Fe as main elements; the sodium-containing compound comprises NaF and Na3AlF6、NaCN、Na4[Fe(CN)6]Two or more of (1); the fluorine-containing compound comprises NaF and Na3AlF6、AlF3、LiF、CaF2、MgF2And KF.
4. The method for mechanochemical conversion and recovery of sodium-containing compounds and fluorine-containing compounds in the spent refractory material of an aluminum electrolysis cell according to claim 1, wherein the conversion agent for the sodium-containing compounds and the fluorine-containing compounds comprises one or more of oxides, hydroxides, sulfates, nitrates, carbonates, acetates and citrates corresponding to each element of Ca, Al, Mg, Sr, Ba, La and Ce.
5. The method as claimed in claim 1, wherein the cyanide conversion agent comprises Na2CO3·1.5H2O2、K2CO3·1.5H2O2、Na2O2、K2O2、CaO2、SrO2、BaO2、H2O2、(NH4)2S2O8、Na2S2O8、K2S2O8、KMnO4、O2、O3One or more than two of them.
6. The method for mechanochemical conversion and recovery of sodium-containing and fluorine-containing compounds in the waste refractory material of an aluminum electrolysis cell according to claim 1, wherein the grinding aid comprises one or more of polymeric polyol, polymeric alcohol amine, triisopropanolamine, ethylene glycol, propylene glycol, glycerol, diethylene glycol, triethanolamine, amide, stearic acid, oleic acid, sodium hexametaphosphate and sodium stearate.
7. The method for mechanochemical conversion and recovery of sodium-containing compounds and fluorine-containing compounds in the waste refractory materials of aluminum electrolysis cells according to claim 1, wherein the conversion agent of sodium-containing compounds and fluorine-containing compounds, the cyanide conversion agent and the grinding aid are added in a solid, aqueous solution or gaseous state by a single addition, or by batch addition, or by continuous addition.
8. The mechanical chemical conversion and recovery method of sodium-containing compounds and fluorine-containing compounds in the waste refractory materials of the aluminum electrolytic cell according to claim 1, characterized in that the conversion mill is a modified airtight ball mill, and a mill body is provided with a mill body inlet and outlet, a powder inlet, a liquid material inlet, a gas outlet, a slurry outlet, a cleaning and exhausting port, a gas sampling port and a slurry sampling port; the grinding body is one or more than two of corundum balls, zirconia balls, ceramic balls, steel balls and alloy balls.
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