CN109127655A - A kind of aluminium electroloysis is given up in breeze containing sodium, the method for transformation of fluorochemical and system - Google Patents
A kind of aluminium electroloysis is given up in breeze containing sodium, the method for transformation of fluorochemical and system Download PDFInfo
- Publication number
- CN109127655A CN109127655A CN201810867522.XA CN201810867522A CN109127655A CN 109127655 A CN109127655 A CN 109127655A CN 201810867522 A CN201810867522 A CN 201810867522A CN 109127655 A CN109127655 A CN 109127655A
- Authority
- CN
- China
- Prior art keywords
- breeze
- conversion
- mill
- fluorochemical
- equipment
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 110
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 239000004411 aluminium Substances 0.000 title claims abstract description 87
- 239000011734 sodium Substances 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 54
- 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 42
- 230000009466 transformation Effects 0.000 title claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 86
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 33
- 239000011737 fluorine Substances 0.000 claims abstract description 33
- 239000007788 liquid Substances 0.000 claims abstract description 30
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 22
- 238000012545 processing Methods 0.000 claims abstract description 22
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 19
- 239000011707 mineral Substances 0.000 claims abstract description 19
- 230000001131 transforming effect Effects 0.000 claims abstract description 17
- JMANVNJQNLATNU-UHFFFAOYSA-N glycolonitrile Natural products N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 238000003801 milling Methods 0.000 claims abstract description 15
- 230000008569 process Effects 0.000 claims abstract description 15
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- -1 cyanogen compound Chemical class 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 91
- 229910052799 carbon Inorganic materials 0.000 claims description 78
- 239000002893 slag Substances 0.000 claims description 62
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 47
- 239000003610 charcoal Substances 0.000 claims description 36
- 239000000463 material Substances 0.000 claims description 35
- 239000007789 gas Substances 0.000 claims description 33
- 239000000203 mixture Substances 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 238000000926 separation method Methods 0.000 claims description 26
- 238000004458 analytical method Methods 0.000 claims description 21
- 239000002002 slurry Substances 0.000 claims description 20
- 238000003860 storage Methods 0.000 claims description 17
- 239000007787 solid Substances 0.000 claims description 15
- 230000003647 oxidation Effects 0.000 claims description 14
- 238000007254 oxidation reaction Methods 0.000 claims description 14
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminium flouride Chemical compound F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 claims description 12
- 239000011812 mixed powder Substances 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- 238000010521 absorption reaction Methods 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- 238000002425 crystallisation Methods 0.000 claims description 10
- 230000008025 crystallization Effects 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- 239000000292 calcium oxide 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
- 238000000227 grinding Methods 0.000 claims description 8
- 150000002500 ions Chemical class 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 7
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- 229910001610 cryolite Inorganic materials 0.000 claims description 6
- 238000001514 detection method Methods 0.000 claims description 6
- 125000001153 fluoro group Chemical group F* 0.000 claims description 6
- 230000008676 import Effects 0.000 claims description 6
- 229910001635 magnesium fluoride Inorganic materials 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 238000006073 displacement reaction Methods 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 4
- 229910052593 corundum Inorganic materials 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 230000008020 evaporation Effects 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000003292 glue Substances 0.000 claims description 4
- 238000000265 homogenisation Methods 0.000 claims description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 4
- 229910052760 oxygen 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
- 150000005846 sugar alcohols Polymers 0.000 claims description 4
- 229910002567 K2S2O8 Inorganic materials 0.000 claims description 3
- 229910004882 Na2S2O8 Inorganic materials 0.000 claims description 3
- 229910000831 Steel Inorganic materials 0.000 claims description 3
- 238000005275 alloying Methods 0.000 claims description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000012141 concentrate Substances 0.000 claims description 3
- 239000010431 corundum Substances 0.000 claims description 3
- 238000007689 inspection Methods 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 239000011344 liquid material Substances 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000008188 pellet Substances 0.000 claims description 3
- 229910052573 porcelain Inorganic materials 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000012286 potassium permanganate Substances 0.000 claims description 3
- 239000007790 solid phase Substances 0.000 claims description 3
- 238000001179 sorption measurement Methods 0.000 claims description 3
- 239000010959 steel Substances 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
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 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
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 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
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 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
- 150000001408 amides Chemical class 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 239000003599 detergent Substances 0.000 claims description 2
- 235000011187 glycerol Nutrition 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
- 239000011259 mixed solution Substances 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
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 230000005070 ripening Effects 0.000 claims description 2
- 238000005070 sampling Methods 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- MNWBNISUBARLIT-UHFFFAOYSA-N sodium cyanide Chemical compound [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 claims description 2
- 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 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
- 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
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims 3
- 239000002699 waste material Substances 0.000 abstract description 38
- 238000004519 manufacturing process Methods 0.000 abstract description 25
- 238000004064 recycling Methods 0.000 abstract description 13
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 abstract description 11
- 230000006378 damage Effects 0.000 abstract description 7
- 150000002222 fluorine compounds Chemical class 0.000 abstract description 4
- 150000003388 sodium compounds Chemical class 0.000 abstract description 2
- 239000003792 electrolyte Substances 0.000 description 37
- 239000000047 product Substances 0.000 description 20
- 238000005188 flotation Methods 0.000 description 16
- 238000005868 electrolysis reaction Methods 0.000 description 15
- 238000002386 leaching Methods 0.000 description 15
- 239000000428 dust Substances 0.000 description 14
- 235000010755 mineral Nutrition 0.000 description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 13
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 13
- 239000003575 carbonaceous material Substances 0.000 description 12
- 239000013078 crystal Substances 0.000 description 11
- 239000000706 filtrate Substances 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 9
- 150000004673 fluoride salts Chemical class 0.000 description 9
- 239000002250 absorbent Substances 0.000 description 8
- 230000002745 absorbent Effects 0.000 description 8
- 238000002485 combustion reaction Methods 0.000 description 8
- 235000012255 calcium oxide Nutrition 0.000 description 7
- 239000012065 filter cake Substances 0.000 description 7
- 238000003672 processing method Methods 0.000 description 7
- 239000006096 absorbing agent Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 230000001698 pyrogenic effect Effects 0.000 description 6
- 238000012216 screening Methods 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 5
- 230000005611 electricity Effects 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 238000005087 graphitization Methods 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000003546 flue gas Substances 0.000 description 3
- 230000008595 infiltration Effects 0.000 description 3
- 238000001764 infiltration Methods 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000002910 solid waste Substances 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical group [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- RQMIWLMVTCKXAQ-UHFFFAOYSA-N [AlH3].[C] Chemical compound [AlH3].[C] RQMIWLMVTCKXAQ-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000011449 brick Substances 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002001 electrolyte material Substances 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Chemical compound [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 238000007885 magnetic separation Methods 0.000 description 2
- 229910021527 natrosilite Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical group CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-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
- 229910020187 CeF3 Inorganic materials 0.000 description 1
- 229910020186 CeF4 Inorganic materials 0.000 description 1
- 239000004155 Chlorine dioxide Substances 0.000 description 1
- 206010010741 Conjunctivitis Diseases 0.000 description 1
- HTJDQJBWANPRPF-UHFFFAOYSA-N Cyclopropylamine Chemical group NC1CC1 HTJDQJBWANPRPF-UHFFFAOYSA-N 0.000 description 1
- 241001269238 Data Species 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 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
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000006004 Quartz sand Substances 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
- 229920002125 Sokalan® Polymers 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- PRPAGESBURMWTI-UHFFFAOYSA-N [C].[F] Chemical compound [C].[F] PRPAGESBURMWTI-UHFFFAOYSA-N 0.000 description 1
- ROMMVUMWISCVBE-UHFFFAOYSA-N [F].N#CC#N Chemical compound [F].N#CC#N ROMMVUMWISCVBE-UHFFFAOYSA-N 0.000 description 1
- 201000004484 acute conjunctivitis Diseases 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 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
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 229910052925 anhydrite Inorganic materials 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 description 1
- 239000003830 anthracite Substances 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910001632 barium fluoride Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 235000019398 chlorine dioxide Nutrition 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 229960001484 edetic acid Drugs 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 229910001672 fluorine mineral Inorganic materials 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 238000007499 fusion processing Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910001387 inorganic aluminate Inorganic materials 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
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- YACKEPLHDIMKIO-UHFFFAOYSA-N methylphosphonic acid Chemical compound CP(O)(O)=O YACKEPLHDIMKIO-UHFFFAOYSA-N 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000002006 petroleum coke Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000003381 stabilizer Substances 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
- 230000001360 synchronised effect Effects 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 description 1
- BYMUNNMMXKDFEZ-UHFFFAOYSA-K trifluorolanthanum Chemical compound F[La](F)F BYMUNNMMXKDFEZ-UHFFFAOYSA-K 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B5/00—Operations not covered by a single other subclass or by a single other group in this subclass
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B9/00—General methods of preparing halides
- C01B9/08—Fluorides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/20—Halides
- C01F11/22—Fluorides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B2101/00—Type of solid waste
- B09B2101/02—Gases or liquids enclosed in discarded articles, e.g. aerosol cans or cooling systems of refrigerators
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The present invention relates to a kind of aluminium electroloysis give up breeze in containing sodium, the method for transformation of fluorochemical and system.Method for transformation is given up the harm of fluoride and cyanide in breeze to thoroughly release aluminium electroloysis including the use of transforming agent, by the way that aluminium electroloysis gives up in the mechanochemistry conversion reaction in conversion mill, the compounds containing sodium in breeze is transformed into not fluorine-containing soluble sodium compound, fluorochemical is transformed into insoluble and harmless minerals fluorine compounds, is oxidized containing cyanogen compound and is transformed into innocuous gas.The sequentially connected useless breeze crushing plant of conversion system, milling equipment, conversion mill, stirred reactor and solid-liquid separating equipment, solid-liquid separating equipment is directly connected to concentration or crystallizer, drying or Equipment for Heating Processing again, and dry or Equipment for Heating Processing connects disintegrating apparatus.Present invention process is simple, be easy to be mass produced, production cost is low, three-waste free pollution, environmentally friendly, can be realized aluminium electroloysis give up breeze innoxious and recycling processing target.
Description
Technical field
The present invention relates to, containing sodium, the method for transformation of fluorochemical and system, belong to electrolysis in a kind of useless breeze of aluminium electroloysis
Aluminum i ndustry solid waste is innoxious with application technology as the second resource field.
Background technique
It is more than 36,000,000 tons, accounts for global electricity to built about 45,000,000 tons of the aluminium electroloysis production capacity of China in 2017, actual production
Solve 50% or more of aluminium production capacity.In Aluminum Electrolysis Production, various useless breezes can be generated, including anode give up breeze (breeze containing acute conjunctivitis,
Anode ash, anode slime, anode mix etc.), cathode give up breeze, electrolytic cell overhaul waste cathode carbon block, it is useless smash (bundles) paste, new electrolytic cell
The useless breeze etc. that prebake is formed when starting.It averagely produces 1 ton of electrolytic aluminium and needs 0.48 ton of carbon anode, the useless breeze of anode is electrolysis
Charcoal falls into fused electrolyte and swims in caused by its surface, most breeze from carbon anode peeling in aluminium production process
It can be in bath surface combustion oxidation at CO2Gas consumption, but still there is small part to swim in the unburned useless charcoal of bath surface
Particle forms the useless breeze of anode after being pulled out.During aluminum electrolysis, charcoal cathode due to fluorine-containing salts infiltration and expand,
The breakage for further causing electrolytic cell is scrapped；Aluminium cell generally just needed to stop groove overhaul using 4~6 years or so, took out all
Waste lining material (referred to as slag from delining), waste cathode carbon block accounts for about the 50% of slag from delining.Useless breeze is Aluminum Electrolysis Production process
In inevitable solid waste, 1 ton of electrolytic aluminium of every production about generates the useless breeze of 10~30kg.Electrolytic aluminium waste breeze exists
Dangerous solid waste (classification are as follows: HW48) is defined as in " National Hazard waste register ", waste lining has been put into " National Hazard
Waste register " HW32 inorganic fluoride waste, HW33 inorganic cyanide waste.Aluminium electroloysis give up breeze in fluorine-containing electrolyte, contain
Cyanogen compound has a soluble and reactivity, it is fluorine-containing, enter environment containing cyanogen compound can be to the health of the mankind and animals and plants
Greatly harm is constituted with growth.
Fluorine-containing electrolyte and carbon materials in the useless breeze of aluminium electroloysis are a kind of valuable resources.Therefore, how thoroughly to release
The harm of fluorine, cyanogen compound in the useless breeze of aluminium electroloysis, realizing that the innoxious and resource utilization of the useless breeze of aluminium electroloysis utilizes is urgently
The industry difficulty that need to be captured.
Chinese invention CN106745137A, CN106077038A, CN106077040A, CN106587122A,
CN101817521A, CN106086938A, CN105821445A are proposed using alkali leaching or ultrasonic wave secondary flotation alkaline pressure of oxygen leaching
Method process aluminum electrolytic waste and old cathode carbon or aluminium electroloysis waste material, by waste material it is broken after by flotation and magnetic separation obtain carbon powder A,
Lye is added in carbon powder A and dissolves fluoride, then CO is added into solution2Ice crystal is precipitated, secondary flotation is carried out to carbon powder A and is obtained
High-purity powdered carbon.
Chinese invention CN106077037A, CN106077036A, CN106180118A, CN101984984A are proposed using acid
The method process aluminum electrolytic waste and old cathode carbon or slag from delining of processing or the pressurization acid processing of ultrasonic wave secondary flotation.
Chinese invention CN107162061A is proposed using alkali leaching, Ore Leaching and the united method of flyash, to aluminium electricity
It solves slot waste and old cathode carbon and carries out harmless treatment and resource utilization.
Chinese invention CN106064813A, CN105964659A proposition keep the temperature waste and old cathode powdered carbon at 200~400 DEG C
Except cyanogen, except cyanogen material obtains breeze and electrolyte slag through FLOTATION SEPARATION, it is miscellaneous that electrolyte slag heats removing charcoal at 550~800 DEG C
Matter obtains electrolyte powder, and breeze goes soluble matter to obtain the powdered carbon of purity is high by alkali leaching, and alkali lixivium leads to CO2Ice crystal is precipitated
And alumag.
Aluminum cell waste cathode carbon powder is soaked in water in Chinese invention CN105772486A proposition, by soluble cyaniding
Object leaches, then hydrogen peroxide, stabilizer is added (selected from citric acid, tartaric acid, ethylenediamine tetra-acetic acid, amino trimethylene in leachate
Methylphosphonic acid, polyacrylic acid, maleic acid, borax, ammonium carbonate, ammonium hydrogen carbonate, ammonium acetate, in ammonium citrate), catalyst (is selected from
ZnO、CuO、Fe3O4、WO3In) after so that cyanide oxidation product is resolved into CO in 30~70 DEG C of reactions2、NH3Gas.
Chinese invention CN105728440A proposes a kind of aluminium cell slag from delining innocuity disposal system and processing method,
System includes leaching storehouse, be connected with leaching storehouse and being used to carry out the reaction warehouse except the processing of cyanogen fluorine removal, except cyanogen agent is sodium chlorate, bleaches
One of powder, hydrogen peroxide, bleaching powder, chlorine dioxide are several, and defluorinating agent is calcium chloride, aluminium chloride, magnesium chloride, hydroxide
One of calcium, calcium oxide are several.
Chinese invention CN106166560A proposes a kind of processing method of waste cathode carbon block, and electrolytic cell overhaul slag is carried out
Water logging go out, leached after cathode carbon pieces and leachate, leachate and quick lime, milk of lime, carbide slag or calcium chloride is anti-
Should after carry out solid-liquor separation, filtrate returns to the step of leaching and is recycled, and filter cake stack or as the original for preparing calcirm-fluoride
Material.
Chinese invention CN107313073A proposes a kind of aluminum cell waste cathode liner dump leaching processing method, by aluminium electricity
The insulating brick in waste and old cathode liner, castable, Impervious Materials, the carbon materials sub-elected in solution groove overhaul slot slag are crushed sieve respectively
Point, it is handled together after broken waste and old insulating brick, castable, Impervious Materials are mixed, carbon materials are individually handled；To broken material
It leached in advance, dump leaching, washing, remove filters pressing after cyanogen is handled using hydrogen peroxide；CO is passed through in pressing filtering liquid2Gas carry out carbon point with
Neutralisation treatment, concentrated crystallization recycling obtains fluorine-containing NaHCO again3, fluorine-containing Na2CO3, NaF mixture.
Chinese invention CN105645449A provides a kind of system and method for aluminium electrolytic carbon slag recycling ice crystal, place
Reason system includes leaching storehouse, flotation unit, equipment for separating liquid from solid, by the ice crystal flotation recovery in useless carbon slag.
Chinese invention CN103803620A provides the production technology that ice crystal is refined in a kind of electrolytic aluminum residue, by electrolytic slag
Ball is clayed into power, then carries out three-level flotation to powder, respectively obtains ice crystal and powdered carbon after FLOTATION SEPARATION.
Chinese invention CN103949459A provides a kind of recycling electrolytic aluminium breeze production aluminium electrolyte and recycles
The method of carbon, including pre-treatment, FLOTATION SEPARATION, preparation, post-processing step, will premenstrual treated the waste and old carbon feed separation of electrolysis
Obtain underflow product and froth pulp, underflow product is filtered, except carbon, it is broken obtain electrolyte, froth pulp is through filters pressing, dry
It is dry to obtain carbon dust.
Chinese invention CN104499000A provides a kind of ore dressing processing method of electrolytic aluminium carbon slag, and carbon slag is crushed powder
Mill, in carbon slag plus ore pulp is made in water, collecting agent and foaming agent, ore pulp material is subjected to flotation, flotation froth product be carbon dust,
The material for removing froth pulp is ice crystal product after filtering, drying and calcining.
Chinese invention CN103949460A provides carbon dross of aluminium electrolysis production regenerative electrolytes device and method, and breeze is broken
Broken, ball milling, flotation, drying, regenerative electrolytes refining, vent gas treatment production technology, realize the comprehensive utilization of carbon dross of aluminium electrolysis.
Chinese invention CN105239097A provides water quenching and the sorting processing method of a kind of aluminium electrolysis anode breeze, including
Hot breeze water quenching, Water Quenching Slag classification, breeze wet-milling and flotation step obtain rich carbon products respectively and are rich in electrolyte product.
Chinese invention CN106917110A provides carbon slag and electrolyte in a kind of separation and recovery electrolytic aluminium waste anode slag
Method, the method for taking high-temperature fusion and flotation to combine realize that the separation and recovery of carbon and electrolyte utilizes.
Chinese invention CN102992300A provides a kind of High temperature calcination method of electrolytic aluminum anode scrap residue, by electrolytic aluminium waste
Anode material residue is broken, ball milling by flotation isolates carbon dust, removes ferrous contaminants therein using magnetic separation, carbon dust is existed
Fluoride salt and sulphur in 1700~1900 DEG C of calcining removal carbon dusts, obtain high-purity carbon dust；Fluoride salt is separately recovered from gas phase
With sulphur product.
Chinese invention CN1253369C provides a kind of method for recycling fluoride salt from aluminium electrolyzing carbon slag, will be in carbon slag
It is incorporated aluminium oxide, by carbonaceous completely burned, tail gas is absorbed with aluminium oxide, is obtained containing aluminium oxide for roasting at 650 DEG C~930 DEG C
Fluoride salt.
Chinese invention CN101063215A provides a kind of method for extracting electrolyte in aluminium electrolyzing carbon slag, in anode
In carbon slag be added binder be uniformly mixed, briquet, at 650 DEG C~800 DEG C roasting by combustible completely burned, obtain
Electrolyte content is greater than 98% product of roasting and returns to aluminium cell use.
Chinese invention CN101255566A provides a kind of method for recycling electrolyte in carbon dross of aluminium electrolysis, in anodic carbon residue
Obtained electrolyte is returned to aluminium electroloysis by middle addition dispersing agent calcirm-fluoride and bunker coal, the calcination process at 650 DEG C~800 DEG C
Slot uses.
Chinese invention CN103831285A provides a kind of aluminium electroloysis and gives up breeze innocuity disposal system and its method, including
Heating furnace, heat cycles device, exhaust gas cleaner.Breeze handles 7~8h in 1250~1350 DEG C of heating furnace, in burner hearth
Electrolyte after decomposition is discharged via discharge port, and carbon dust is discharged via slag notch.
Chinese invention CN102011148A provides a kind of processing of aluminum electrolysis anode carbon slag harmlessness and electrolyte recycling
Anode breeze is carried out melting in 800~1500 DEG C of high temperature furnaces by method, and for carbonaceous material after completely burned, electrolyte is complete
Holotype is at electrolyte melt；The flue gas access electrolytic series flue gas purification system generated in fusion process, fluoride gas use
Aluminium oxide returns to electrolytic cell after absorbing, electrolyte melt is directly entered electrolytic cell use.
Chinese invention CN107285354A provide a kind of Aluminum carbonaceous dangerous waste watery fusion infiltration continuous separation method and
Products obtained therefrom, including carbonaceous dangerous waste are pre-processed by the broken iron that removes；To pretreated carbonaceous dangerous waste at 1050~1200 DEG C
It carries out low temperature electric to forge, so that fluoride salt is melt into liquid and be saturated separation；Remaining low fluorine carbon granules enters height after infiltration removal of impurities
Warm electricity forge furnace, obtains high-purity carbon product after high-temperature electric is forged.
Chinese invention CN106629606A provide it is a kind of separation carbon slag in Aluminium electrolysis in fluoride salt and carbon method, using
The vacuum distillation furnace that temperature is 800~1200 DEG C, vacuum degree is 1~100Pa carries out the separation of fluoride salt and carbon in carbon slag, separation
Fluoride salt afterwards returns to electrolytic cell, and carbon return is used.
Chinese invention CN105463506A provides electrolyte and carbon in a kind of separation and recovery aluminium electrolyte anodic carbon residue
Aluminium electrolyte anodic carbon residue is placed in smelting furnace by method, under the atmosphere of nitrogen or inert gas, at 700~1600 DEG C
Heating fusing obtains aluminium electrolyte anodic carbon residue melt, then by the way of blowing to melt, reaches separation aluminium electrolyte
The purpose of electrolyte and carbon in anodic carbon residue obtains the electrolyte and carbon products of high-quality.
Chinese invention CN107604383A provides a kind of method that smelting process extracts electrolyte in carbon slag, by carbon slag molten
1250~1300 DEG C, after the electrolyte in carbon slag is smelted into liquid are heated in furnace, carbon floats on electrolytic liquid surface, will
The carbon of floating releases electrolyte after clawing, and returns to Aluminum Electrolysis Production after cooling and uses.
Chinese invention CN106247340A provides a kind of processing method and processing device of electrolytic aluminium carbon slag, and processing unit includes
Firing chamber, combustion chamber, firing chamber are warming up to 1000~1100 DEG C, and the electrolyte in carbon slag and carbon slag are layered, and release agent, which is added, to be made
Electrolyte is separated with carbon slag；Carbon slag after separation enters combustion chamber burning-up, and electrolyte is recycled.
Chinese invention CN106517209A proposes a kind of processing method of useless cathode of aluminium electrolytic tank, by aluminium electroloysis
Slot waste lining give up cathode be added carbon material and quartz sand, carry out high temperature carbon thermal reduction generate SiC, ice crystal formed melt sink with
SiC is separated by solid-liquid separation, and fluoride salt enters the SiC gas solid separation of furnace gas evaporation and generation, and SiC, cryolite melts and fluorine are made respectively
Salt dissolving.
Chinese invention CN107904621A proposes a kind of regeneration treating method of waste cathode of aluminum electrolytic cell carbon block, main to locate
Science and engineering skill includes broken, screening, toxicity inhibition, ingredient, pressure control heat treatment.Waste cathode of aluminum electrolytic cell charcoal block of material is after crushing and screening
Afterwards, the toxic inhibitors such as hydrogen peroxide, potassium permanganate, hypochlorite are added, are then incorporated anthracite, after-smithing petroleum coke, scrap anode
The carbonaceous materials such as carbon block, anode scrap as feed stock for blast furnace, be placed in resistance furnace normal pressure (1200~1800 DEG C) or pressure control (1000~
1600 DEG C, 0.01~0.5atm) under the conditions of be heat-treated, the fluoride to volatilize in flue gas through cooling, crystallization recycle, clinker
Carbon content can be used in producing a variety of carbon products up to 99%.Chinese invention CN107904622A handles aluminium electricity in a similar manner
It solves the useless side of slot and serves as a contrast carbofrax material.
Chinese invention CN106147910A proposes a kind of anthracitic with electrolytic aluminium waste cathode carbon block production high graphite
System and method, system include crushing and screening unit, automatic charging unit, superhigh-temperature calcination unit, finished product cooling unit and packet
Fill unit.The method for being promoted degree of graphitization under 2300~3000 DEG C of superelevation temperature states using electrolytic aluminium waste cathode carbon block, is obtained
Finished product material degree of graphitization >=90% arrived, the volatile matter contained in raw material under superelevation temperature state can decompose completely.
From the point of view of existing technological achievement, to aluminium electroloysis give up breeze innoxious, recycling treatment using being divided into aqueous solution
Wet-treating and high temperature under two major class of pyrogenic attack.Wet-treating further relates to washing (leaching), alkaline process, acid system, acid-alkali
Combination method simultaneously cooperates floatation process, mainly for the purpose of recycling electrolyte and carbon materials, uses oxidant will in wet-treating
Cyanide resolves into harmless gaseous matter.Pyrogenic attack technology is mainly for the purpose of innoxious, or based on carbon in useless breeze
Cellulose content can effectively utilize its calorific value resource 50% or more；Or electrolyte melting permeability and separation is recycled；Or
HF, which is converted, by fluoride carries out sorption enhanced utilization again；Or to be converted into electrolyte harmless and not by adding converting additive
The fluorine minerals of dissolubility；Or take high-temperature vacuum technology that utilization is separately recovered in carbon materials and electrolyte.In pyrogenic attack
In, be oxidized at high temperature containing cyanogen compound and resolve into harmless gaseous matter.
From the point of view of existing technological achievement, the wet-treating and pyrogenic attack of the useless breeze of aluminium electroloysis still have many urgent
Problem to be solved.
At least there is following main problem in current wet processing technique: the first, generated a large amount of saliferous, fluoride waste
The problem of not being effectively addressed, causing secondary pollution；Generated H2、CH4、NH3Gas is not under control and utilizes,
Generated HF causes serious pollution.The second, the electrolysis and carbon materials impurity content recycled be excessively high, cannot direct benefit
With.Third, process route are cumbersome, technology is complicated, equipment seriously corroded, and processing cost is excessively high.4th, due to aluminum electrolytic tank capacity
With the influence of the factors such as the difference in slot age, the fluctuation of ingredient, powder granularity, cause process parameter control difficulty big.
At least there is following main problem in current pyrogenic attack technology: the first, generating a large amount of entrainment HF and dust
Tail gas needs to administer.The second, electrolytic salt recycling, which is not thorough to remain in carbon materials or clinker, needs to be further processed.The
Three, the electrolytic salt of low melting point occurs vitreous clinker in furnace, causes the incomplete residual quantity of Carbon Materials oxidizing fire larger, in furnace
Vitreous clinker causes production status to deteriorate, production stability is poor.4th, reaction mass is difficult to realize the uniform mixed of molecular level
It closes, conversion reaction is caused to be not thorough.5th, equipment seriously corroded, processing energy consumption are high.
Summary of the invention
In order to solve the above technical problem, the present invention provides turns containing sodium, fluorochemical in a kind of useless breeze of aluminium electroloysis
Change method and system.The present invention has production technology convenient for control, is easy to industrialize that steady production, process costs are low, no three wastes
The features such as pollution and equipment are corroded.
The invention is realized by the following technical scheme:
A kind of aluminium electroloysis is given up the method for transformation containing sodium, fluorochemical in breeze, using transforming agent, by conversion mill
Mechanochemistry conversion reaction the aluminium electroloysis compounds containing sodium in breeze that gives up is transformed into not fluorine-containing soluble sodium compound, contains
Fluorine compounds are transformed into insoluble and harmless minerals fluorine compounds, are oxidized containing cyanogen compound and are transformed into harmless N2Or NH3
And CO2, to thoroughly release the harm of fluoride and cyanide in the useless breeze of aluminium electroloysis；Conversion system includes broken, milling, sieve
Point and homogenization system, mechanochemistry conversion reaction and solid-liquid separation system, concentration and crystal system, dry and heat treatment system,
Exhaust collection and absorption system, analysis of test system, packaging and warehousing system.The present invention has simple process, is easy to extensive
Production, production cost is low, three-waste free pollution, it is environmental-friendly the features such as.The harmless of the useless breeze of aluminium electroloysis will be realized using the present invention
Change, recycling and whole polarized disposition target.
A kind of aluminium electroloysis is given up the method for transformation containing sodium, fluorochemical in breeze, including following some or all of step
(sequence of steps below is to express for convenience, does not indicate which part precedence relationship, contained step specifically include directly
It is subject to literal logical specification or logical relation):
(1) aluminium electroloysis being given up, breeze is broken, is milled, homogenizing, obtains the useless charcoal ground-slag of particle≤200 μm；Analysis determines single
The molal quantity or quality of sodium and fluorine in the useless charcoal ground-slag of position quality；It analyzes and determines CN in the useless charcoal ground-slag of unit mass-Ion rubs
That number or quality；
Abrasive body is added in conversion mill, then conversion is ground and carries out air emptying or N2Displacement, by the useless charcoal of metering
Ground-slag is added in conversion mill, and the mass ratio for controlling useless charcoal ground-slag and abrasive body is 1:(0.2~10), the water of metering is added to
In conversion mill, the solid-liquid mass ratio for controlling useless charcoal ground-slag and water is 1:(1~10)；
By in useless charcoal ground-slag containing sodium, fluorochemical be converted to corresponding product chemistry stoichiometry 1~3 times of amount,
Or transforming agent is added in conversion mill by the amount of useless breeze silty amount 5~80%；
Grinding aid is added in conversion mill by the amount of useless breeze silty amount 0~1%；
(2) it completes to open conversion mill after step (1), the revolving speed of control conversion mill is 10~1000rpm, conversion temperature is
10~110 DEG C；In the conversion process, timing in batches is to slurry sampling analysis inspection, until Na in slurry solid formation+Ion contains
Amount meets company standard, solubility F-Ion concentration stops conversion mill when meeting national emission standard；
(3) after completing step (2), slurry is transferred to stirred reactor (reaction kettle or reactive tank or reactor tank) and carries out brokenly glue
With ripening, 60~150 DEG C of temperature is controlled, the processing time is 0.5~5h；
(4) by slurry that step (3) obtains using filtering or centrifuge separation mode is separated by solid-liquid separation and by aqueous solid phase
Object in conversion mill or stirred reactor (reaction kettle or reactive tank or reactor tank), using water be detergent by 1:(1~10) consolidate
Liquid quality than repeated several times dispensing laundry and be separated by solid-liquid separation, wash into solid formation soluble ion content meet enterprise mark
Until standard, merges separating liquid, respectively obtain the i.e. aqueous solid formation of mixture and mixture of wet fluorine-containing minerals and carbon
Weak solution；
(5) the aqueous solid formation that step (4) obtains is dried or is heat-treated 1 at a temperature of 80~300 DEG C~
10h, crushed to obtain the mixed powder material of fluorine-containing minerals and carbon again, the average particle size of mixed powder material≤
20 μm, which can be used as merchandise sales or further progress separating-purifying obtains high-quality carbon materials and fluorine
Compound mineral raw material；
The high temperature mixed powder material of fluorine-containing minerals and carbon being placed at a temperature of air atmosphere and 700~1200 DEG C
0.5~5h, the mixture that carbon component complete oxidation therein burns, its residue is fluorine-containing minerals are calcined in furnace；
(6) by the Dilute mixed solutions that step (4) obtains carry out concentration or crystallization treatment obtain mixture concentrated solution or
Person's solid-phase mixture, or Na, K, Li, Al, Mg, Ca compound separating-purifying in mixture are further obtained into more Gao Pin
The series compound raw material of matter and value；
(7) by CN in useless charcoal ground-slag-Ion conversion is at N2Or NH3And CO2Chemical reaction metering ratio 1~5 times of amount,
Perhaps by the amount of useless breeze silty amount 0.1~10% by cyanide transforming agent be added to or step (2) or step (3),
Or the oxidation containing cyanogen compound is converted to harmless N in step (6)2Or NH3And CO2, timing carries out transformation system in batches
Analysis checks, until the CN in system-Ion concentration stops conversion reaction when meeting national emission standard；
(8) by generated NH in step (2) or step (3) or step (6)3、CO2、H2O gas carry out sorption enhanced and
Dry, generated reducibility gas is collected or direct oxidation burning.
Above-mentioned aluminium electroloysis give up breeze refer in Aluminum Electrolysis Production caused by the component containing carbon (including graphitization C and
Non-graphitized C) all solids waste.
There are Al, Al in the useless breeze of above-mentioned aluminium electroloysis4C3, the substances such as AlN, Na, reaction institute is participated in conversion reaction
Imflammable gas (including the H of generation2、CH4、NH3Deng) it is reducibility gas described in step (8).
In above-mentioned conversion mill, the synchronous effect of high energy mechanical power is anti-in the mechanochemistry conversion containing sodium and fluorochemical
Answer so that solid particle is constantly ground, is levigate with conversion, make reactant and product constantly update from charcoal particle and
Removing, realizes the quick of conversion reaction and is properly completed.
Further, in all steps, pH control does not use protonic acid material for not less than 6, used to contain sodium
The transforming agent of compound and fluorochemical, cyanide transforming agent are free of chlorine element in grinding aid substance.
Further, the essential element that the useless charcoal ground-slag includes is C (including graphitization C and non-graphitized C), Na,
F, two or more in Al, Ca, O, N, Li, Mg, Si, K, Fe.
Further, the compounds containing sodium includes NaF, Na3AlF6、NaCN、Na4[Fe(CN)6] in two kinds with
On.
Further, the fluorochemical includes NaF, Na3AlF6、AlF3、LiF、CaF2、MgF2, two kinds in KF
More than.
Further, the transforming agent of compounds containing sodium and fluorochemical includes Ca, Al, Mg, Sr, Ba, La, Ce each element
One or more of corresponding oxide, hydroxide, sulfate, nitrate, carbonate, acetate, citrate.
After being converted using transforming agent, corresponding not fluorine-containing soluble sodium chemical combination that the compounds containing sodium in useless breeze is transformed into
Object includes NaOH, Na2SO4、NaNO3、NaOAc、Na2CO3、Na3C6H5O7、Na2AlO4、Na[Al(OH)6]2(OH)3、
NaAlSi2O6、Na2(H2SiO4)·7H2O、Na6Si8O19、Na2Al2SiO6、Na2Si2O5、Na2SiO3One or both of with
On.
After being converted using transforming agent, corresponding insoluble and harmless minerals that the fluorochemical in useless breeze is transformed into
Fluoride includes CaF2、MgF2、AlF3、SrF2、BaF2、CaF2、LaF3、CeF3、CeF4One or more of.
Further, the cyanide transforming agent includes Na2CO3·1.5H2O2、K2CO3·1.5H2O2、Na2O2、K2O2、
CaO2、SrO2、BaO2、H2O2、(NH4)2S2O8、Na2S2O8、K2S2O8、KMnO4、O2、O3One or more of.
Further, the grinding aid includes polymerized polyalcohol, polyalcohol amine, triisopropanolamine, ethylene glycol, the third two
One of alcohol, glycerine, diethylene glycol, triethanolamine, amide, stearic acid, oleic acid, calgon, odium stearate or two
Kind or more.
Further, the transforming agent, grinding aid be with the addition of solid, aqueous solution or gaseous state, using it is primary be added,
Or the mode for being added or being continuously added in batches.
A kind of aluminium electroloysis is given up the conversion system containing sodium, fluorochemical in breeze, including sequentially connected useless breeze is broken
Equipment, milling equipment, conversion mill, stirred reactor and solid-liquid separating equipment, solid-liquid separating equipment again with concentration or crystallizer,
Dry or Equipment for Heating Processing is directly connected to, and dry or Equipment for Heating Processing connects disintegrating apparatus.
It further, further include condensing plant, condensing plant is connect with concentration or crystallizer.
It further, further include exhaust collection absorption equipment, exhaust collection absorption equipment grinds with milling equipment, conversion, stirs
Mix reactor, condensing plant is all connected with.
It further, further include storage facilities, storage facilities includes the dusty material storage arrangement connecting with disintegrating apparatus
And the storage arrangement of concentrate or crystalline product.
It further, further include analysis Instrument equipment, analysis Instrument equipment is anti-to milling equipment, conversion mill, stirring is derived from
The sample of device, concentration or crystallizer, drying or Equipment for Heating Processing, storage facilities is answered to carry out analysis detection.
Further, the useless breeze crushing plant include jaw crusher, cone crusher, pillar crusher,
Double-shaft crusher or impact disintegrating machine.
Further, the milling equipment include column mill, Raymond mill, vertical mill, air swept mill or roll squeezer and with
The matched equipment for selecting dressing sieve point and homogenization, to obtain uniform, particle≤200 μm the useless charcoal ground-slags of composition.
Further, concentration and crystallizer are multiple-effect evaporation concentration or crystallization apparatus, for being concentrated or crystallizing solid-liquid point
From obtained mixture solution, it is related to thermal energy and provides, evaporates the heat exchange and condensation, the recycling of condensed water, concentration of phase
Liquid or the transmission of crystal etc..
Above-mentioned exhaust collection absorption equipment is used for being crushed, being milled, sieving and being homogenized, and conversion reaction is broken glue and washed
Wash, be concentrated with crystallization etc. during generate tail gas be collected and absorption handle.Material composition in tail gas includes H2O、NH3、
CO2、H2、CH4、N2And micro dust；Gas phase H therein2O passes through condensation reuse, NH3、CO2, dust pass through absorbent absorb
It utilizes, fuel gas H2、CH4It is collected storage or enters combustion furnace as fuel utilization.
Above-mentioned analysis Instrument equipment is used for the material component detection of each link of production process, substance changing effect and contains
Control detection, product quality detection, the environmental emission standard monitoring of amount.
Further, the described conversion mill is the air-tightness ball mill by transformation, body be equipped with abrasive body inlet and outlet,
Powder import, liquid material import, gas vent, slurry outlet, clean-drain mouth, gas sample mouth, slurry sample tap；Abrasive body
For one or more of corundum ball, zirconia ball, porcelain ball, steel ball, stainless steel ball, alloying pellet.
The beneficial effects of the present invention are:
(1) present invention has technical process convenient for control, is easy to industrialize that steady production, production cost are low, no three wastes is dirty
The features such as dye and equipment are corroded.
(2) present invention solves the problems of existing wet-treating and pyrogenic attack production technology and deficiency.For
The useless charcoal slag harmlessness of aluminium electroloysis and resource utilization, which utilize, provides a kind of advanced, system solution.
Detailed description of the invention
Fig. 1 is the process flow diagram of method for transformation of the present invention.
Fig. 2 is the structural schematic diagram of system of the present invention.
Fig. 3 is the x-ray diffraction pattern of the useless breeze of aluminium electroloysis used by embodiment 1.
Fig. 4 is the x-ray diffraction pattern of the obtained mixed powder material B of embodiment 1.
Fig. 5 is the thermogram of the obtained mixed powder material B of embodiment 1.
Fig. 6 is the x-ray diffraction pattern of the obtained soluble mixture A of embodiment 1.
Specific embodiment
Below with specific embodiment further illustrate technical solution of the present invention, but the invention is not limited to embodiment,
It is not intended to limit the scope of the invention.
As shown in Fig. 2, system of the invention includes sequentially connected useless breeze crushing plant 1, milling equipment 2, conversion mill
3, stirred reactor 4 and solid-liquid separating equipment 5, solid-liquid separating equipment 5 are set with concentration or crystallizer 7, dry or heat treatment again
Standby 6 are directly connected to, and dry or Equipment for Heating Processing 6 connects disintegrating apparatus 8；It further include condensing plant 9, exhaust collection absorption equipment
10 and storage facilities, condensing plant 9 connect with concentration or crystallizer 7, exhaust collection absorption equipment 10 and milling equipment 2, turn
Change mill 3, stirred reactor 4, condensing plant 9 to be all connected with, storage facilities includes the dusty material storage dress connecting with disintegrating apparatus
Set the storage arrangement 12 of 11 and concentrate or crystalline product.
It further include analysis Instrument equipment, analysis Instrument equipment is to being derived from milling equipment, conversion mill, stirred reactor, concentration
Or the sample of crystallizer, drying or Equipment for Heating Processing, storage facilities carries out analysis detection.
The waste cathode carbon block crushing plant includes that jaw crusher, cone crusher, pillar crusher, twin shaft are broken
Broken machine or impact disintegrating machine.
The milling equipment includes column mill, Raymond mill, vertical mill, air swept mill or roll squeezer and matched choosing
Dressing sieve divides the homogenization equipment of powder, to obtain uniform, particle≤200 μm the useless charcoal ground-slags of composition.
Concentration or crystallizer be multiple-effect evaporation be concentrated or crystallization apparatus, for be concentrated or crystallize be separated by solid-liquid separation obtain can
The separating liquid of soluble mixture is related to thermal energy and provides, evaporates the heat exchange and condensation, the recycling of condensed water, concentration of phase
Liquid or the transmission of crystal etc..
Above-mentioned exhaust collection absorption equipment, for broken, milling and homogenizing, glue and washing, concentration to be broken in conversion reaction
With crystallization etc. during generate tail gas be collected and absorption handle.Material composition in tail gas includes H2O、NH3、CO2、H2、
CH4、N2And micro dust；Gas phase H therein2O passes through condensation reuse, NH3、CO2, dust be absorbed and utilized by absorbent, can
Combustion gas body H2、CH4It is collected storage or enters combustion furnace as fuel utilization.
The described conversion mill is the air-tightness ball mill by transformation, body be equipped with abrasive body inlet and outlet, powder import,
Liquid material import, gas vent, slurry outlet, clean-drain mouth, gas sample mouth, slurry sample tap；Abrasive body be corundum ball,
One or more of zirconia ball, porcelain ball, steel ball, stainless steel ball, alloying pellet.
Embodiment 1
(1) the aluminium electroloysis breeze that gives up is crushed in high speed disintegrator, is sieved with the sieve of 200 mesh, using screenings into
Mechanochemistry conversion of the row containing sodium, fluorochemical.Sodium in the useless charcoal ground-slag of unit mass aluminium electroloysis is determined using chemical analysis
With the mass content of fluorine element, CN in the useless charcoal ground-slag of unit mass aluminium electroloysis is determined using chemical analysis-The quality of ion contains
Amount.
(2) 200g stainless steel ball is added in conversion mill, weighs 100g useless charcoal ground-slag, 45g CaSO4·2H2O、2.5g
CaO、2g K2S2O8It is added in conversion mill and is uniformly mixed, use N2Air in displacement conversion mill, then be added into conversion mill
300g H2O.Unlatching conversion mill, revolving speed 100rpm, temperature are 25 DEG C, and the conversion reaction time is 2h.
Slurry is transferred to stirred reactor after conversion reaction, mixing speed 1000rpm, temperature are 95 DEG C, and constant temperature stirs
Reaction 90min is mixed to stop.
By tail gas caused by step (1), step (2) respectively by being with the absorber that water is absorbent and with CaO
The absorber of absorbent, dust therein, NH3、CO2It is absorbed, H2、CH4Carry out combustion oxidation.
(3) negative pressure leaching is carried out to the slurry after being stirred to react, filter cake is transferred in conversion mill after suction filtration, is added
200gH2O dispensing laundry in conversion mill filters again, wash repeatedly and filters, BaCl of the washing to last filtrate with 2mol/L2
Until solution is examined without precipitating, filtrate is merged.
Filtrate is evaporated under reduced pressure, be concentrated and is crystallized, 10h is dried in 100 DEG C of vacuum ovens, obtains soluble mix
Close object A.
(4) filter cake is dried to 20h under 120 DEG C of normal pressures, dried object is crushed to obtain the mixing of fluorine-containing minerals and carbon
Powder body material B.
Mixed powder material B is placed in the high temperature furnace at a temperature of air atmosphere and 900 DEG C and calcines 3h, carbon group therein
Divide complete oxidation burning, the mixture C that its residue is fluorine-containing minerals.
As seen from Figure 3, aluminium electroloysis used by embodiment 1 give up breeze main object coordinate be divided into C, NaF,
Na3AlF6、AlF3、LiF、MgF2、CaF2、AlN。
As seen from Figure 4, embodiment 1 obtained fluorine-containing minerals and carbon mixed powder material B main object
It coordinates and is divided into C, CaF2、MgF2、Al2O3、SiO2、CaO、CaSO4.Illustrate NaF, Na in useless breeze3AlF6、AlF3, the fluorine such as LiF
Compound component has been totally converted metallogenic material CaF2、MgF2。
Residual rate when temperature is 900 DEG C it can be seen from the heat analysis of Fig. 5 mixed powder material B is 43.8%, scaling loss
Rate is 56.2%.
It as seen from Figure 6, is Na by the main component that embodiment 1 handles obtained soluble mixture A2SO4、
K2SO4、Li2SO4、MgSO4、Al2(SO4)3、Na2Si2O5、SiO2, illustrate NaF, Na in useless breeze3AlF6、AlF3, the fluorine such as LiF
Compound component is totally converted.
From these testing and analysis datas: embodiment 1 realize aluminium electroloysis give up breeze in containing sodium, fluorochemical it is complete
Full conversion thoroughly relieves the harm of fluoride and cyanide in the useless breeze of aluminium electroloysis.
Embodiment 2
(1) the aluminium electroloysis breeze that gives up is crushed in high speed disintegrator, is sieved with the sieve of 200 mesh, using screenings into
Mechanochemistry conversion of the row containing sodium, fluorochemical.Sodium in the useless charcoal ground-slag of unit mass aluminium electroloysis is determined using chemical analysis
With the mass content of fluorine element, CN in the useless charcoal ground-slag of unit mass aluminium electroloysis is determined using chemical analysis-The quality of ion contains
Amount.
(2) 300g stainless steel ball is added in conversion mill, weighs 100g useless charcoal ground-slag, 40g MgSO4, 0.8g second two
Alcohol, 3g Na2S2O8It is added in conversion mill and is uniformly mixed, use N2Air in displacement conversion mill, then be added into conversion mill
400g H2O.Unlatching conversion mill, revolving speed 400rpm, temperature are 35 DEG C, and the conversion reaction time is 3h.
Slurry is transferred to stirred reactor after conversion reaction, mixing speed 800rpm, temperature are 100 DEG C, and constant temperature stirs
Reaction 100min is mixed to stop.
By tail gas caused by step (1), step (2) respectively by being with the absorber that water is absorbent and with CaO
The absorber of absorbent, dust therein, NH3、CO2It is absorbed, H2、CH4Carry out combustion oxidation.
(3) negative pressure leaching is carried out to the slurry after being stirred to react, filter cake is transferred in conversion mill after suction filtration, is added
300gH2O dispensing laundry in conversion mill filters again, wash repeatedly and filters, BaCl of the washing to last filtrate with 2mol/L2
Until solution is examined without precipitating, filtrate is merged.
Filtrate is evaporated under reduced pressure, be concentrated and is crystallized, 10h is dried in 100 DEG C of vacuum ovens, obtains soluble mix
Close object A.
(4) filter cake is dried to 20h under 120 DEG C of normal pressures, dried object is crushed to obtain the mixing of fluorine-containing minerals and carbon
Powder body material B.
Mixed powder material B is placed in the high temperature furnace at a temperature of air atmosphere and 1200 DEG C and calcines 2h, carbon therein
The burning of component complete oxidation, the mixture C that its residue is fluorine-containing minerals.
The experimental results showed that embodiment 2 realizes the complete conversion containing sodium, fluorochemical in the useless breeze of aluminium electroloysis, it is thorough
Bottom relieves the harm of fluoride and cyanide in the useless breeze of aluminium electroloysis.
Embodiment 3
(1) the aluminium electroloysis breeze that gives up is crushed in high speed disintegrator, is sieved with the sieve of 200 mesh, using screenings into
Mechanochemistry conversion of the row containing sodium, fluorochemical.Sodium in the useless charcoal ground-slag of unit mass aluminium electroloysis is determined using chemical analysis
With the mass content of fluorine element, CN in the useless charcoal ground-slag of unit mass aluminium electroloysis is determined using chemical analysis-The quality of ion contains
Amount.
(2) 400g stainless steel ball is added in conversion mill, weighs 100g useless charcoal ground-slag, 30g Ce2(SO4)3、2g(NH4)2S2O8It is added in conversion mill and is uniformly mixed, use N2Air in displacement conversion mill, then 350g H is added into conversion mill2O.It opens
Opening conversion mill, revolving speed 700rpm, temperature is 50 DEG C, and the conversion reaction time is 1.5h.
Slurry is transferred to stirred reactor after conversion reaction, mixing speed 500rpm, temperature are 110 DEG C, and constant temperature stirs
Reaction 110min is mixed to stop.
By tail gas caused by step (1), step (2) respectively by being with the absorber that water is absorbent and with CaO
The absorber of absorbent, dust therein, NH3、CO2It is absorbed, H2、CH4Carry out combustion oxidation.
(3) negative pressure leaching is carried out to the slurry after being stirred to react, filter cake is transferred in conversion mill after suction filtration, is added
350gH2O dispensing laundry in conversion mill filters again, wash repeatedly and filters, BaCl of the washing to last filtrate with 2mol/L2
Until solution is examined without precipitating, filtrate is merged.
Filtrate is evaporated under reduced pressure, be concentrated and is crystallized, 10h is dried in 100 DEG C of vacuum ovens, obtains soluble mix
Close object A.
(4) filter cake is dried to 20h under 120 DEG C of normal pressures, dried object is crushed to obtain the mixing of fluorine-containing minerals and carbon
Powder body material B.
Mixed powder material B is placed in the high temperature furnace at a temperature of air atmosphere and 1100 DEG C and calcines 2h, carbon therein
The burning of component complete oxidation, the mixture C that its residue is fluorine-containing minerals.
The experimental results showed that embodiment 3 realizes the complete conversion containing sodium, fluorochemical in the useless breeze of aluminium electroloysis, it is thorough
Bottom relieves the harm of fluoride and cyanide in the useless breeze of aluminium electroloysis.
Claims (10)
- The method for transformation containing sodium, fluorochemical in breeze 1. a kind of aluminium electroloysis is given up, which is characterized in that including following part or Overall Steps:(1) aluminium electroloysis being given up, breeze is broken, is milled, homogenizing, obtains the useless charcoal ground-slag of particle≤200 μm；It analyzes and determines unit matter Measure the molal quantity or quality of sodium and fluorine in useless charcoal ground-slag；It analyzes and determines CN in the useless charcoal ground-slag of unit mass-The molal quantity of ion Or quality；Abrasive body is added in conversion mill, then conversion is ground and carries out air emptying or N2Displacement, the useless charcoal ground-slag of metering is added Enter into conversion mill, the mass ratio for controlling useless charcoal ground-slag and abrasive body is 1:(0.2~10), the water of metering is added to conversion mill In, the solid-liquid mass ratio for controlling useless charcoal ground-slag and water is 1:(1~10)；By in useless charcoal ground-slag containing sodium, fluorochemical be converted to corresponding product chemistry stoichiometry 1~3 times of amount or Transforming agent is added in conversion mill by the amount of useless breeze silty amount 5~80%；Grinding aid is added in conversion mill by the amount of useless breeze silty amount 0~1%；(2) complete to open conversion mill after step (1), the revolving speed of control conversion mill is 10~1000rpm, conversion temperature be 10~ 110℃；In the conversion process, timing in batches is to slurry sampling analysis inspection, until Na in slurry solid formation+Ion concentration symbol Close company standard, solubility F-Ion concentration stops conversion mill when meeting national emission standard；(3) after completing step (2), slurry is transferred to stirred reactor and carries out brokenly glue and ripening, controls temperature 60~150 DEG C, the processing time be 0.5~5h；(4) slurry that step (3) obtains is separated by solid-liquid separation using filtering or centrifuge separation mode and aqueous solid formation is existed Be detergent by 1:(1~10 using water in conversion mill or stirred reactor) solid-liquid mass ratio repeated several times dispensing laundry simultaneously Be separated by solid-liquid separation, washing is until into solid formation, the content of soluble ion meets company standard, merge separating liquid, respectively obtain wet Fluorine-containing minerals and carbon mixture, that is, aqueous solid formation and mixture weak solution；(5) the aqueous solid formation that step (4) obtains is dried or is heat-treated 1~10h, again at a temperature of 80~300 DEG C It is crushed to obtain the mixed powder material of fluorine-containing minerals and carbon；The mixed powder material of fluorine-containing minerals and carbon is placed in the high temperature furnace at a temperature of air atmosphere and 700~1200 DEG C Calcine 0.5~5h, the mixture that carbon component complete oxidation therein burns, its residue is fluorine-containing minerals；(6) Dilute mixed solutions that step (4) obtains are subjected to concentration or crystallization treatment obtains mixture concentrated solution or solid Phase mixture；(7) by CN in useless charcoal ground-slag-Ion conversion is at N2Or NH3And CO2Chemical reaction metering ratio 1~5 times of amount or press Cyanide transforming agent is added to or step (2) or step (3) or step by the amount of useless breeze silty amount 0.1~10% Suddenly the oxidation containing cyanogen compound is converted to harmless N in (6)2Or NH3And CO2, timing carries out analysis inspection to transformation system in batches It looks into, until the CN in system-Ion concentration stops conversion reaction when meeting national emission standard；(8) by generated NH in step (2) or step (3) or step (6)3、CO2、H2O gas carries out sorption enhanced and drying, Generated reducibility gas is collected or direct oxidation burning.
- The method for transformation containing sodium, fluorochemical in breeze 2. aluminium electroloysis according to claim 1 is given up, which is characterized in that In all steps, pH control does not use protonic acid material for not less than 6, used to turn containing sodium and fluorochemical Agent, cyanide transforming agent are free of chlorine element in grinding aid substance.
- The method for transformation containing sodium, fluorochemical in breeze 3. aluminium electroloysis according to claim 1 is given up, which is characterized in that The essential element that the useless charcoal ground-slag includes is two or more in C, Na, F, Al, Ca, O, N, Li, Mg, Si, K, Fe；It is described Compounds containing sodium include NaF, Na3AlF6、NaCN、Na4[Fe(CN)6] in it is two or more；The fluorochemical includes NaF、Na3AlF6、AlF3、LiF、CaF2、MgF2, it is two or more in KF.
- The method for transformation containing sodium, fluorochemical in breeze 4. aluminium electroloysis according to claim 1 is given up, which is characterized in that Compounds containing sodium and the transforming agent of fluorochemical include the corresponding oxide of Ca, Al, Mg, Sr, Ba, La, Ce each element, hydrogen-oxygen One or more of compound, sulfate, nitrate, carbonate, acetate, citrate.
- The method for transformation containing sodium, fluorochemical in breeze 5. aluminium electroloysis according to claim 1 is given up, which is characterized in that The cyanide transforming agent includes Na2CO3·1.5H2O2、K2CO3·1.5H2O2、Na2O2、K2O2、CaO2、SrO2、BaO2、 H2O2、(NH4)2S2O8、Na2S2O8、K2S2O8、KMnO4、O2、O3One or more of.
- The method for transformation containing sodium, fluorochemical in breeze 6. aluminium electroloysis according to claim 1 is given up, which is characterized in that The grinding aid include polymerized polyalcohol, polyalcohol amine, triisopropanolamine, ethylene glycol, propylene glycol, glycerine, diethylene glycol, One or more of triethanolamine, amide, stearic acid, oleic acid, calgon, odium stearate.
- The method for transformation containing sodium, fluorochemical in breeze 7. aluminium electroloysis according to claim 1 is given up, which is characterized in that The transforming agent, grinding aid with the addition of solid, aqueous solution or gaseous state, using it is primary be added or be added in batches or The mode that person is continuously added to.
- The conversion system containing sodium, fluorochemical in breeze 8. a kind of aluminium electroloysis is given up, which is characterized in that including sequentially connected useless Breeze crushing plant, milling equipment, conversion mill, stirred reactor and solid-liquid separating equipment, solid-liquid separating equipment again with concentration or Crystallizer, drying or Equipment for Heating Processing are directly connected to, and dry or Equipment for Heating Processing connects disintegrating apparatus.
- The conversion system containing sodium, fluorochemical in breeze 9. aluminium electroloysis according to claim 8 is given up, which is characterized in that It further include condensing plant, exhaust collection absorption equipment, storage facilities and analysis Instrument equipment, condensing plant is set with concentration or crystallization Standby connection, exhaust collection absorption equipment are all connected with milling equipment, conversion mill, stirred reactor, condensing plant, storage facilities packet Include the storage arrangement of the dusty material storage arrangement and concentrate or crystalline product that connect with disintegrating apparatus, analysis Instrument equipment pair It is derived from the sample of milling equipment, conversion mill, stirred reactor, concentration or crystallizer, drying or Equipment for Heating Processing, storage facilities Carry out analysis detection.
- The conversion system containing sodium, fluorochemical in breeze 10. aluminium electroloysis according to claim 9 is given up, which is characterized in that The useless breeze crushing plant includes jaw crusher, cone crusher, pillar crusher, double-shaft crusher or impact type Fine crusher；The milling equipment includes column mill, Raymond mill, vertical mill, air swept mill or roll squeezer and matched choosing Dressing sieve divides the homogenization equipment of powder；The concentration or crystallizer is multiple-effect evaporation concentration or crystallization apparatus；Described turns Change mill as the air-tightness ball mill by transformation, body is equipped with abrasive body inlet and outlet, powder import, liquid material import, gas Outlet, slurry outlet, clean-drain mouth, gas sample mouth, slurry sample tap；Abrasive body be corundum ball, zirconia ball, porcelain ball, One or more of steel ball, stainless steel ball, alloying pellet.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810867522.XA CN109127655B (en) | 2018-08-01 | 2018-08-01 | Method and system for converting sodium-containing and fluorine-containing compounds in aluminum electrolysis waste carbon slag |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810867522.XA CN109127655B (en) | 2018-08-01 | 2018-08-01 | Method and system for converting sodium-containing and fluorine-containing compounds in aluminum electrolysis waste carbon slag |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109127655A true CN109127655A (en) | 2019-01-04 |
| CN109127655B CN109127655B (en) | 2021-05-07 |
Family
ID=64798806
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810867522.XA Active CN109127655B (en) | 2018-08-01 | 2018-08-01 | Method and system for converting sodium-containing and fluorine-containing compounds in aluminum electrolysis waste carbon slag |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109127655B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110117718A (en) * | 2019-05-15 | 2019-08-13 | 东北大学 | The method for producing ferro-silicon-aluminium as raw material electric arc furnace smelting using waste refractory materials |
| CN114890447A (en) * | 2022-05-09 | 2022-08-12 | 东北大学 | Method for directly preparing aluminum fluoride by taking aluminum electrolyte as raw material without roasting |
| CN115198111A (en) * | 2022-07-19 | 2022-10-18 | 中南大学 | Lithium extraction method for lithium-containing waste aluminum electrolyte |
| CN115475816A (en) * | 2022-09-27 | 2022-12-16 | 内蒙古霍煤鸿骏铝电有限责任公司 | Aluminum electrolysis fluorine waste treatment system |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2858198A (en) * | 1954-10-19 | 1958-10-28 | Aluminium Lab Ltd | Recovery of material from aluminum reduction cell lining |
| US20090095686A1 (en) * | 2007-05-11 | 2009-04-16 | Myriam Chartier | Process And System For Treating Waste From Aluminum Production Containing PAH And Fluoride Ions By Flotation And Stabilization |
| CN101829670A (en) * | 2010-04-02 | 2010-09-15 | 北京矿冶研究总院 | Method for recovering carbon from electrolytic aluminum waste cathode carbon block |
| CN105821445A (en) * | 2016-05-27 | 2016-08-03 | 中南大学 | Method for recycling carbon and electrolytes from waste cathode carbon block of aluminum electrolytic cell |
| CN107282598A (en) * | 2017-07-03 | 2017-10-24 | 李立安 | A kind of aluminium cell discards the recoverying and utilizing method of cathode carbon pieces |
| CN107662913A (en) * | 2017-09-30 | 2018-02-06 | 陈湘清 | A kind of aluminium electroloysis waste cathode carbon block processing and treating method |
-
2018
- 2018-08-01 CN CN201810867522.XA patent/CN109127655B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2858198A (en) * | 1954-10-19 | 1958-10-28 | Aluminium Lab Ltd | Recovery of material from aluminum reduction cell lining |
| US20090095686A1 (en) * | 2007-05-11 | 2009-04-16 | Myriam Chartier | Process And System For Treating Waste From Aluminum Production Containing PAH And Fluoride Ions By Flotation And Stabilization |
| CN101829670A (en) * | 2010-04-02 | 2010-09-15 | 北京矿冶研究总院 | Method for recovering carbon from electrolytic aluminum waste cathode carbon block |
| CN105821445A (en) * | 2016-05-27 | 2016-08-03 | 中南大学 | Method for recycling carbon and electrolytes from waste cathode carbon block of aluminum electrolytic cell |
| CN107282598A (en) * | 2017-07-03 | 2017-10-24 | 李立安 | A kind of aluminium cell discards the recoverying and utilizing method of cathode carbon pieces |
| CN107662913A (en) * | 2017-09-30 | 2018-02-06 | 陈湘清 | A kind of aluminium electroloysis waste cathode carbon block processing and treating method |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110117718A (en) * | 2019-05-15 | 2019-08-13 | 东北大学 | The method for producing ferro-silicon-aluminium as raw material electric arc furnace smelting using waste refractory materials |
| CN110117718B (en) * | 2019-05-15 | 2020-07-24 | 东北大学 | Method for smelting and preparing ferro-silicon-aluminum by using waste refractory material as raw material in electric arc furnace |
| CN114890447A (en) * | 2022-05-09 | 2022-08-12 | 东北大学 | Method for directly preparing aluminum fluoride by taking aluminum electrolyte as raw material without roasting |
| CN114890447B (en) * | 2022-05-09 | 2023-09-29 | 东北大学 | Method for directly preparing aluminum fluoride by taking aluminum electrolyte as raw material without roasting |
| CN115198111A (en) * | 2022-07-19 | 2022-10-18 | 中南大学 | Lithium extraction method for lithium-containing waste aluminum electrolyte |
| CN115198111B (en) * | 2022-07-19 | 2023-06-13 | 中南大学 | Lithium extraction method of lithium-containing waste aluminum electrolyte |
| CN115475816A (en) * | 2022-09-27 | 2022-12-16 | 内蒙古霍煤鸿骏铝电有限责任公司 | Aluminum electrolysis fluorine waste treatment system |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109127655B (en) | 2021-05-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109047285A (en) | Containing sodium, the method for transformation of fluorochemical and system in a kind of waste cathode of aluminum electrolytic cell carbon block | |
| CN108941167A (en) | Mechanochemistry conversion and recovery method in a kind of waste cathode of aluminum electrolytic cell carbon block containing sodium, fluorochemical | |
| KR102537727B1 (en) | Recovery of lithium from silicate minerals | |
| CN106694514B (en) | A kind of aluminium ash recycling processing method | |
| CN108787718A (en) | A kind of aluminium electroloysis is given up mechanochemistry conversion and recovery method in breeze containing sodium, fluorochemical | |
| CN109127655A (en) | A kind of aluminium electroloysis is given up in breeze containing sodium, the method for transformation of fluorochemical and system | |
| CN102515279B (en) | Comprehensive extraction method of ferro-silico-aluminum in gangue | |
| CN109108050A (en) | Containing sodium, the method for transformation of fluorochemical and system in a kind of aluminium electroloysis slag from delining | |
| CN109108049A (en) | Containing sodium, the method for transformation of fluorochemical and system in a kind of aluminium electroloysis dangerous waste slag | |
| CN104445311B (en) | Poly-generation clean preparation method of high-content silicon dioxide fly ash | |
| CN110284157B (en) | Method for recycling anode carbon slag and aluminum electrolyte | |
| CN101723713A (en) | Overall treatment method of steel works sintering dust | |
| CN113278808B (en) | Method for recovering various solid waste materials in aluminum smelting process in linkage manner | |
| CN108584994A (en) | A kind of method of lepidolite calcined by rotary kiln lithium carbonate | |
| US20220144658A1 (en) | Method for preparing aluminum fluoride and aluminum oxide by decarburization and sodium removal of aluminum electrolysis carbon residue | |
| CN109108048A (en) | Mechanochemistry conversion and recovery method in a kind of aluminium electrolysis anode breeze containing sodium, fluorochemical | |
| CN109127656A (en) | Mechanochemistry conversion and recovery method in a kind of aluminium electroloysis dangerous waste slag containing sodium, fluorochemical | |
| CN110937619A (en) | Carbon-hydrogen co-reduction hot molten salt method slag-free production process of barium slag | |
| CN115156238B (en) | Comprehensive recycling method for aluminum electrolysis waste cathode carbon blocks and application thereof | |
| CN109127657A (en) | Mechanochemistry conversion and recovery method in a kind of aluminium electroloysis slag from delining containing sodium, fluorochemical | |
| CN105883843A (en) | Method for efficiently manufacturing borax by treating boron-bearing tailings through alkaline hydrolysis | |
| RU2472865C1 (en) | Method of processing fluorine-containing wastes from electrolytic production of aluminium | |
| CN214270947U (en) | System for harmless, resourceful processing of aluminium industry waste cathode carbon piece | |
| CN106350680B (en) | A method of sodium roasting extracts valuable metal from oil burnning ash | |
| CN108063295A (en) | The method that lithium is extracted in the clinker generated from pyrogenic process recycling lithium battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |