CN114702048A - Lithium slag solid waste recycling process - Google Patents
Lithium slag solid waste recycling process Download PDFInfo
- Publication number
- CN114702048A CN114702048A CN202210300540.6A CN202210300540A CN114702048A CN 114702048 A CN114702048 A CN 114702048A CN 202210300540 A CN202210300540 A CN 202210300540A CN 114702048 A CN114702048 A CN 114702048A
- Authority
- CN
- China
- Prior art keywords
- lithium
- salt solution
- lithium slag
- mixed salt
- carbonate
- 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.)
- Pending
Links
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 115
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 115
- 239000002893 slag Substances 0.000 title claims abstract description 101
- 238000000034 method Methods 0.000 title claims abstract description 29
- 239000002910 solid waste Substances 0.000 title claims abstract description 28
- 238000004064 recycling Methods 0.000 title claims abstract description 24
- 239000012266 salt solution Substances 0.000 claims abstract description 75
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 70
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 59
- 239000002253 acid Substances 0.000 claims abstract description 44
- 239000007787 solid Substances 0.000 claims abstract description 38
- 238000000926 separation method Methods 0.000 claims abstract description 37
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 36
- 229910052742 iron Inorganic materials 0.000 claims abstract description 34
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims abstract description 33
- 229910052939 potassium sulfate Inorganic materials 0.000 claims abstract description 33
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 30
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 30
- 235000011151 potassium sulphates Nutrition 0.000 claims abstract description 30
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 30
- 239000000126 substance Substances 0.000 claims abstract description 30
- 238000003756 stirring Methods 0.000 claims abstract description 29
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 28
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 27
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims abstract description 23
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 23
- 229910000024 caesium carbonate Inorganic materials 0.000 claims abstract description 22
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 22
- WPFGFHJALYCVMO-UHFFFAOYSA-L rubidium carbonate Chemical compound [Rb+].[Rb+].[O-]C([O-])=O WPFGFHJALYCVMO-UHFFFAOYSA-L 0.000 claims abstract description 22
- 229910000026 rubidium carbonate Inorganic materials 0.000 claims abstract description 22
- 150000003839 salts Chemical class 0.000 claims abstract description 18
- -1 aluminum ions Chemical class 0.000 claims abstract description 15
- 238000004090 dissolution Methods 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 239000002244 precipitate Substances 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 6
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 6
- 239000002131 composite material Substances 0.000 claims abstract description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 40
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 32
- 239000008139 complexing agent Substances 0.000 claims description 31
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 24
- 230000001376 precipitating effect Effects 0.000 claims description 22
- 229910052701 rubidium Inorganic materials 0.000 claims description 22
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 22
- 229910052792 caesium Inorganic materials 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 18
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 17
- 238000001704 evaporation Methods 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 13
- 229910052725 zinc Inorganic materials 0.000 claims description 13
- 239000011701 zinc Substances 0.000 claims description 13
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- QJNBIFRUSFIANU-UHFFFAOYSA-N 4-butan-2-yl-2-(1-phenylethyl)phenol Chemical compound CCC(C)C1=CC=C(O)C(C(C)C=2C=CC=CC=2)=C1 QJNBIFRUSFIANU-UHFFFAOYSA-N 0.000 claims description 11
- 239000003463 adsorbent Substances 0.000 claims description 10
- 239000012153 distilled water Substances 0.000 claims description 10
- 239000011777 magnesium Substances 0.000 claims description 10
- 229910052749 magnesium Inorganic materials 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- 229910052700 potassium Inorganic materials 0.000 claims description 9
- 239000011591 potassium Substances 0.000 claims description 9
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 8
- 238000002425 crystallisation Methods 0.000 claims description 8
- 230000008025 crystallization Effects 0.000 claims description 8
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 7
- 230000008020 evaporation Effects 0.000 claims description 7
- 229910001447 ferric ion Inorganic materials 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 6
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 6
- 239000002738 chelating agent Substances 0.000 claims description 6
- 229910021645 metal ion Inorganic materials 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 235000017550 sodium carbonate Nutrition 0.000 claims description 6
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 5
- 159000000007 calcium salts Chemical class 0.000 claims description 5
- 229910001448 ferrous ion Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 5
- 238000000746 purification Methods 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- 238000001179 sorption measurement Methods 0.000 claims description 3
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 238000011084 recovery Methods 0.000 abstract description 14
- 239000003513 alkali Substances 0.000 abstract description 4
- 230000003301 hydrolyzing effect Effects 0.000 abstract description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 20
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 19
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 13
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 13
- 229910052593 corundum Inorganic materials 0.000 description 13
- 229910001845 yogo sapphire Inorganic materials 0.000 description 13
- 239000011259 mixed solution Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 229910052681 coesite Inorganic materials 0.000 description 10
- 229910052906 cristobalite Inorganic materials 0.000 description 10
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 10
- 239000000377 silicon dioxide Substances 0.000 description 10
- 229910052682 stishovite Inorganic materials 0.000 description 10
- 229910052905 tridymite Inorganic materials 0.000 description 10
- 229910052925 anhydrite Inorganic materials 0.000 description 9
- 239000004566 building material Substances 0.000 description 9
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- FLJPGEWQYJVDPF-UHFFFAOYSA-L caesium sulfate Chemical compound [Cs+].[Cs+].[O-]S([O-])(=O)=O FLJPGEWQYJVDPF-UHFFFAOYSA-L 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 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 7
- 239000006227 byproduct Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000004568 cement Substances 0.000 description 6
- 239000003337 fertilizer Substances 0.000 description 6
- 229910003002 lithium salt Inorganic materials 0.000 description 6
- 159000000002 lithium salts Chemical class 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000002699 waste material Substances 0.000 description 6
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 5
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 5
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- 229910001294 Reinforcing steel Inorganic materials 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 4
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Chemical compound [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 4
- 239000004567 concrete Substances 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- MHJAJDCZWVHCPF-UHFFFAOYSA-L dimagnesium phosphate Chemical compound [Mg+2].OP([O-])([O-])=O MHJAJDCZWVHCPF-UHFFFAOYSA-L 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 235000010755 mineral Nutrition 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- CPRMKOQKXYSDML-UHFFFAOYSA-M rubidium hydroxide Chemical compound [OH-].[Rb+] CPRMKOQKXYSDML-UHFFFAOYSA-M 0.000 description 4
- 229910000344 rubidium sulfate Inorganic materials 0.000 description 4
- GANPIEKBSASAOC-UHFFFAOYSA-L rubidium(1+);sulfate Chemical compound [Rb+].[Rb+].[O-]S([O-])(=O)=O GANPIEKBSASAOC-UHFFFAOYSA-L 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 4
- 229960001763 zinc sulfate Drugs 0.000 description 4
- 229910000368 zinc sulfate Inorganic materials 0.000 description 4
- 239000007832 Na2SO4 Substances 0.000 description 3
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- KOPBYBDAPCDYFK-UHFFFAOYSA-N Cs2O Inorganic materials [O-2].[Cs+].[Cs+] KOPBYBDAPCDYFK-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 229910052755 nonmetal Inorganic materials 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 229910052903 pyrophyllite Inorganic materials 0.000 description 2
- 229910001953 rubidium(I) oxide Inorganic materials 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 1
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- LAZOHFXCELVBBV-UHFFFAOYSA-N [Mg].[Ca].[Si] Chemical compound [Mg].[Ca].[Si] LAZOHFXCELVBBV-UHFFFAOYSA-N 0.000 description 1
- 239000008476 aike Substances 0.000 description 1
- FJMNNXLGOUYVHO-UHFFFAOYSA-N aluminum zinc Chemical compound [Al].[Zn] FJMNNXLGOUYVHO-UHFFFAOYSA-N 0.000 description 1
- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- AKUNKIJLSDQFLS-UHFFFAOYSA-M dicesium;hydroxide Chemical compound [OH-].[Cs+].[Cs+] AKUNKIJLSDQFLS-UHFFFAOYSA-M 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910052629 lepidolite Inorganic materials 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000002843 nonmetals Chemical class 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 229910052642 spodumene Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/08—Carbonates; Bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D17/00—Rubidium, caesium or francium compounds
- C01D17/003—Compounds of alkali metals
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
- C01D5/16—Purification
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/005—Preliminary treatment of scrap
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/20—Obtaining zinc otherwise than by distilling
- C22B19/22—Obtaining zinc otherwise than by distilling with leaching with acids
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/30—Obtaining zinc or zinc oxide from metallic residues or scraps
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B21/00—Obtaining aluminium
- C22B21/0015—Obtaining aluminium by wet processes
- C22B21/0023—Obtaining aluminium by wet processes from waste materials
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/20—Obtaining alkaline earth metals or magnesium
- C22B26/22—Obtaining magnesium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Treatment Of Sludge (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention relates to the technical field of lithium slag solid waste recovery, and discloses a lithium slag solid waste recycling process, which comprises the following steps: s1, acid dissolution and separation: uniformly mixing the lithium slag with water to infiltrate the lithium slag, and adding strong acid or composite acid to dissolve metal oxides in the lithium slag to generate acid salt; hydrolyzing to precipitate insoluble matters, and separating and removing insoluble and insoluble solids; s2, removing iron elements: adding liquid alkali into the mixed salt solution, stirring, adjusting the pH to 3-3.5, and centrifugally rinsing the iron-containing precipitate to obtain iron mud; s3, removing aluminum elements: adding liquid alkali into the mixed salt solution, stirring, adjusting to 6-7 to completely precipitate aluminum ions, and separating the precipitate to obtain aluminum mud; s4, removing heavy metal elements: adding a heavy metal collecting agent into the mixed salt solution to enable heavy metals to form insoluble substances, precipitate, separate and remove; s5, targeted separation: and performing targeted separation on the residual salt solution to obtain potassium sulfate, sodium sulfate, lithium carbonate, cesium carbonate and rubidium carbonate.
Description
Technical Field
The invention relates to the technical field of lithium slag solid waste recovery, in particular to a lithium slag solid waste recycling process.
Background
The lithium slag is filter residue generated after lithium carbonate (acid method lithium slag) is produced by spodumene or lepidolite through a sulfuric acid method or lithium hydroxide (alkali method lithium slag) is produced by limestone.
The analytical data of the main components in the lithium slag are shown in the following table 1:
| serial number | Name (R) | Content/% | Serial number | Name (R) | Content/% |
| 1 | SiO2 | 35.45 | 11 | Mn0 | 0.35 |
| 2 | Ai203 | 21.84 | 12 | Cs20 | 0.3 |
| 3 | CaO | 11.3 | 13 | Na2O | 0.3 |
| 4 | SO3 | 9.4 | 14 | Ti02 | 0.16 |
| 5 | K20 | 7.43 | 15 | P205 | 0.14 |
| 6 | Fe203 | 2.69 | 16 | Y203 | 0.12 |
| 7 | F | 2.52 | 17 | Zn0 | 0.05 |
| 8 | Rb20 | 0.63 | 18 | Nb205 | 0.02 |
| 9 | Mg0 | 0.56 | 19 | Sn02 | 0.04 |
| 10 | Li20 | 0.38 | 20 | Burn and relieve | 6.32 |
From the chemical components contained in table 1, the lithium slag has a complex chemical composition, but still contains many resources such as lithium, iron, cesium, rubidium, aluminum, zinc, potassium, and the like. With the rapid development of lithium batteries, the lithium salt yield is greatly increased, and the increment of the lithium slag matched with the lithium salt is several times that of the lithium salt. As manufacturers for producing lithium only extract lithium salt, and other noble metals or substances associated with or mixed with lithium are remained in slag and are not fully extracted and utilized, the resource waste and the environmental pollution are greatly caused.
The existing lithium slag treatment technology is mainly used for further extracting a certain single component from the lithium slag or applying the lithium slag to preparation of building materials, and the recovery rate and the utilization value of the lithium slag are still low.
Based on the above problems, the present application intends to provide a technical solution for recovering and comprehensively utilizing other metals in the lithium slag.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the prior art has low recovery rate and utilization value of the lithium slag, and causes resource waste and environmental pollution.
In order to solve the technical problems, the invention aims to provide a lithium slag solid waste recycling process, which comprises the following steps:
s1, acid dissolution and separation: uniformly mixing the lithium slag with water to enable the lithium slag to be completely soaked by the water, and then adding strong acid or composite acid, wherein the using amount of the acid is 20% -40% of the solid content of the lithium slag, so that metal oxides such as lithium, sodium, potassium, rubidium, cesium, magnesium, iron, aluminum, zinc and the like in the lithium slag are completely dissolved to generate acid salt; specifically, the lithium slag undergoes a series of chemical reactions in a mixed solution of water and acid, and the reactions are typically as follows:
Na2O+H2SO4＝Na2SO4+H2O；
K2O+H2SO4＝K2SO4+H2O；
Al2O3+3H2SO4＝Al2(SO4)3+3H2O；
Fe2O3+3H2SO4＝Fe2(SO4)3+3H2O；
P2O5+3H2O+Fe2(SO4)3＝2FePO4↓+3H2SO4；
fluorine in the lithium slag exists in the lithium slag in the forms of aluminum fluoride, sodium fluoride, potassium fluoride, calcium fluoride and magnesium fluoride.
CaO+2HF＝CaF2↓+H2O
In an acid solution, fluoride with high solubility is dissociated to form fluoride ions and metal cations, the fluoride ions are combined with calcium ions after stirring and mixing to form calcium fluoride which is insoluble and stable in chemical property, and insoluble matters are precipitated in an acid dissolving and hydrolyzing mode to realize harmlessness.
After the harmlessness is realized by acid dissolution and hydrolysis in step S1, the mixed solution is mainly divided into two substances: insoluble solids and soluble mixed salts, the composition of the insoluble solids is shown in table 2:
TABLE 2
| Serial number | Name (R) | Content (wt.) |
| 1 | Al2O3 | 25.00％ |
| 2 | SiO2 | 42.15％ |
| 3 | TiO2 | 0.20％ |
| 4 | CaF2 | 6.52％ |
| 5 | CaSO4 | 23.22％ |
| 6 | MgHPO4 | 0.30％ |
| 7 | Others | 2.61％ |
From the chemical composition, the insoluble solid is mainly composed of Al2O3、SiO2、TiO2、CaF2、CaSO4、MgHPO4And the like, wherein the insoluble and insoluble solids are removed from the mixed solution containing the insoluble solids and the mixed salt through centrifugal separation and rinsing, and part of the insoluble solids do not contain chloride ions which are easy to cause the corrosion of reinforcing steel bars, so that the insoluble and insoluble solid can be used as building material materials to realize resource utilization, such as concrete mineral admixture, baking-free ecological cement and the like.
After separation of insoluble solids, the mixed salt solution is mainly: sodium sulfate, potassium sulfate, lithium sulfate, ferric sulfate, cesium sulfate, rubidium sulfate, aluminum sulfate, and zinc sulfate. Then adjusting the pH to respectively realize Fe3+、AL3+、Zn2+The heavy metals are precipitated and separated step by step, so that the resource utilization is realized. The remaining salt solution is subjected to targeted separation. Adsorbing, precipitating, evaporating, crystallizing, purifying and the like to obtain potassium sulfate, sodium sulfate, lithium carbonate, cesium carbonate, rubidium carbonate and other products. The method comprises the following specific steps:
s2, removing iron elements: adding liquid caustic soda into the mixed salt solution after the step S1, adjusting the pH value of the mixed salt solution to 3-3.5, stirring the mixed salt solution uniformly to form precipitates of ferrous ions or ferric ions, and then performing centrifugal rinsing on the precipitates containing iron through a centrifugal machine to obtain iron mud with high iron content so as to be sold as a raw material of an iron and steel plant;
s3, removing aluminum elements: and (4) adding liquid caustic soda into the mixed salt solution after the step S2 is completed, adjusting the pH value to 6-7, completely precipitating aluminum ions to enable the aluminum ions to form colloidal insoluble substances, separating and rinsing the colloidal insoluble substances through a centrifugal machine to obtain aluminum mud with high aluminum content, wherein the aluminum mud can be further sold to professional companies for resource utilization, and the value of solid waste of the lithium slag is further improved.
S4, removing heavy metal elements: and (4) adding a heavy metal collecting agent into the mixed salt solution after the step S3 is completed, forming insoluble matters or insoluble matters such as Zn, Mg, Ni and the like through the heavy metal collecting agent and metal ions, and removing the heavy metal in the mixed salt solution for export sale.
S5, targeted separation: and performing targeted separation on the residual salt solution, and preparing potassium sulfate, sodium sulfate, lithium carbonate, cesium carbonate and rubidium carbonate through the working procedures of adsorption, precipitation, evaporative crystallization, purification and the like. Since carbonate is easy to preserve and can be used as a raw material for the production of other salts, which is an intermediate product, the product is used for supply in the form of lithium carbonate, cesium carbonate, rubidium carbonate. The potassium sulfate meets the national potassium fertilizer standard GBT2040-2017, can be sold as a chemical fertilizer, and can also be used in other chemical fields. The sodium sulfate has low impurity content, meets the industrial salt standard GB/T5462-2015, and can be sold as a general industrial raw material.
Preferably, the aqueous solution obtained by solid-liquid separation, rinsing, evaporation, condensation and purification in the steps S1 to S5 is completely recycled and used for the countercurrent rinsing of the lithium slag in the step S1, so that zero discharge of wastewater is realized. In the production process, each stirring and mixing tank is covered, tail gas is collected and then is intensively sprayed and absorbed, and absorption liquid is mixed with reuse water for recycling, so that the influence on the environment is avoided.
Preferably, the strong acid used for acid dissolution in step S1 is sulfuric acid or hydrofluoric acid, or a complex acid composed of both, and the sulfuric acid and the hydrofluoric acid may be by-products, so as to reduce the recovery cost and improve the resource utilization rate.
Preferably, the liquid alkali in steps S2 and S3 is sodium carbonate or sodium bicarbonate or potassium bicarbonate or sodium hydroxide, or a mixture of several of them, so as to adjust the pH of the acid-containing mixed salt solution to a value suitable for precipitating the metal ions to be removed in this step.
Preferably, the heavy metal collector added in step S4 is a TMT organic sulfide chelating agent.
Preferably, the step S5 includes the steps of:
s501, extracting lithium carbonate: adding a lithium adsorbent into the mixed salt solution after the step S4, stirring, precipitating and centrifuging to obtain a lithium slag compound, and adding hydrofluoric acid into the lithium slag compound to generate HLiF2Then adding calcium salt to produce LiOH and CaF2And finally adding CO2Production of Li2CO3Then extracting to obtain lithium carbonate; the reaction formula of each step is as follows:
Li++HF→HLiF2
LiF+OH-→LiOH
LiOH+CO2→Li2CO3；
the lithium adsorbent is a first complexing agent, and the first complexing agent is one or a mixture of two of CH-95 and polyethylene isothiourea functional group resin.
S502, extracting rubidium carbonate: adding a rubidium collecting agent into the mixed salt solution after the step S501 is finished, stirring, precipitating and centrifuging, roasting and dissolving rubidium slag in water, and adding CO2Extracting rubidium carbonate; the reaction formula of each step is as follows:
Rb2O+H2O→RbOH
RbOH+CO2→Rb2CO3(ii) a The cesium collector is a second complexing agent, and the second complexing agent specifically refers to BAMBP (4-sec-butyl-2- (alpha-methylbenzyl) phenol, and the pH value is 7-8.
S503, extracting cesium carbonate: adding a cesium collecting agent into the mixed salt solution after the step S502 is completed, stirring, precipitating and centrifuging, roasting, dissolving cesium residues in water, and adding CO2Extracting cesium carbonate; the reaction in each step is as follows:
Cs2O+H2O→CsOH
CsOH+CO2→Cs2CO3(ii) a The cesium collecting agent is a third complexing agent, and the third complexing agent specifically refers to BAMBP (4-sec-butyl-2- (alpha-methylbenzyl) phenol and has a pH value of 8-9.
S504, extracting potassium sulfate and sodium sulfate: treating the mixed salt solution after the step S503 by a water source heat pump, crystallizing the mixed salt solution into potassium sulfate at a low temperature of 5-15 ℃, and returning distilled water generated during high-temperature evaporation crystallization into a clean water tank so as to recycle the distilled water; evaporating and crystallizing at the medium temperature of 60-70 ℃ to produce sodium sulfate, and obtaining sodium sulfate and potassium sulfate.
Compared with the prior art, the invention has the following advantages:
1. according to the lithium slag solid waste recycling process, lithium, sodium, potassium, cesium, rubidium, zinc, aluminum and iron produced by the separation technology have high market competitiveness, the recovery rate of the lithium slag is improved, contained metals and non-metals are effectively utilized, and the comprehensive utilization rate reaches 95%;
2. according to the lithium slag solid waste recycling process, the lithium slag value is improved from the previous use for preparing building materials to subdivision recycling after lithium salt is extracted, waste and pollution caused by other metals in the lithium slag are avoided, waste is changed into valuable, the environment is protected, the comprehensive utilization value of the lithium slag is improved, and economic and social values are generated.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings and the detailed description, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, not all of the embodiments.
The reagents/materials used in the following examples were either manufactured or sold: the first complexing agent is CH-95, polyethylene isothiourea functional group resin, Beijing Kehai Si company; heavy metal collector TMT organic sulfide chelating agent, santong aike corporation; BAMBP (4-sec-butyl-2- (α -methylbenzyl) phenol, Guizhou non-ferrous metals and Nuclear industries.
Example 1: the embodiment provides a lithium slag solid waste resource recovery process, which is carried out according to the following steps:
s1, acid dissolution and separation: uniformly mixing 1t of lithium slag with water to enable the lithium slag to be completely soaked by the water, and then adding sulfuric acid, wherein the dosage of the sulfuric acid is 25% of the solid content of the lithium slag, so that metal oxides such as lithium, sodium, potassium, rubidium, cesium, magnesium, iron, aluminum, zinc and the like in the lithium slag are completely dissolved to generate acid salt; in this embodiment, the sulfuric acid uses a by-product acid with a concentration of 50 wt%, and the by-product acid is more suitable for the price of reagent-grade sulfuric acid, so as to reduce the recovery cost and improve the resource utilization rate. Specifically, the lithium slag undergoes a series of chemical reactions in a mixed solution of water and sulfuric acid, and the reactions are typically as follows:
Na2O+H2SO4＝Na2SO4+H2O；
K2O+H2SO4＝K2SO4+H2O；
Al2O3+3H2SO4＝Al2(SO4)3+3H2O；
Fe2O3+3H2SO4＝Fe2(SO4)3+3H2O；
P2O5+3H2O+Fe2(SO4)3＝2FePO4↓+3H2SO4；
after the harmlessness is realized by acid dissolution and hydrolysis in step S1, the mixed solution is mainly divided into two substances: insoluble solids and soluble mixed salts, the composition of the insoluble solids is shown in table 3:
TABLE 3
| Serial number | Name (R) | Content (wt.) |
| 1 | Al2O3 | 25.00％ |
| 2 | SiO2 | 42.15％ |
| 3 | TiO2 | 0.20％ |
| 4 | CaF2 | 6.52％ |
| 5 | CaSO4 | 23.22％ |
| 6 | MgHPO4 | 0.30％ |
| 7 | Others (C) | 2.61％ |
From the chemical composition, the insoluble solid is mainly composed of Al2O3、SiO2、TiO2、CaF2、CaSO4、MgHPO4And the like, wherein the insoluble and insoluble solids are removed from the mixed solution containing the insoluble solids and the mixed salt through separation steps such as centrifugal separation, rinsing and the like, and part of the insoluble solids do not contain chloride ions which are easy to cause the corrosion of reinforcing steel bars, so that the insoluble and insoluble solid can be used as a material for building materials to realize resource utilization, such as concrete mineral admixture, baking-free ecological cement and the like.
After separation of insoluble solids, the mixed salt solution is mainly: sodium sulfate, potassium sulfate, lithium sulfate, ferric sulfate, cesium sulfate, rubidium sulfate, aluminum sulfate, and zinc sulfate. Then respectively realizing Fe by adjusting the pH3+、AL3+、Zn2+The heavy metals are precipitated and separated step by step, so that the resource utilization is realized. The remaining salt solution is subjected to targeted separation. Adsorbing, precipitating, evaporating, crystallizing, purifying and the like to obtain potassium sulfate, sodium sulfate, lithium carbonate, cesium carbonate, rubidium carbonate and other products.
S2, removing iron elements: adding sodium carbonate into the mixed salt solution after the step S1, adjusting the pH value of the mixed salt solution to 3.2, stirring the mixed salt solution uniformly to precipitate ferrous ions or ferric ions, and then carrying out centrifugal rinsing on the iron-containing precipitate through a centrifugal machine to obtain iron mud with high iron content so as to be sold as a raw material of an iron and steel plant;
s3, removing aluminum elements: and (4) adding sodium carbonate into the mixed salt solution obtained in the step S2 while stirring to adjust the pH value to 6.5, so that the aluminum ions are completely precipitated to form colloidal insoluble substances, separating and rinsing the colloidal insoluble substances through a centrifugal machine to obtain aluminum mud with high aluminum content, wherein the aluminum mud can be sold to professional companies for resource utilization, and the value of the lithium slag solid waste is further improved.
S4, removing heavy metal elements: and (4) adding a heavy metal collector TMT organic sulfide chelating agent into the mixed salt solution after the step S3 is completed, forming insoluble matters or insoluble matters of Zn, Mg, Ni and the like with metal ions through the heavy metal collector, and then removing the heavy metal in the mixed salt solution through precipitation, wherein the mixed salt solution is marketable.
S5, targeted separation: and performing targeted separation on the residual salt solution, and specifically comprising the following steps of:
s501, extracting lithium carbonate: adding a lithium adsorbent into the mixed salt solution after the step S4, stirring, precipitating and centrifuging to obtain a lithium slag compound, and adding hydrofluoric acid into the lithium slag compound to generate HLiF2Then adding calcium salt to produce LiOH and CaF2And finally adding CO2Production of Li2CO3Then extracting to obtain lithium carbonate, wherein the lithium adsorbent is a first complexing agent, and the first complexing agent is CH-95 specifically;
s502, extracting rubidium carbonate: adding a rubidium collecting agent into the mixed salt solution which is finished by the step S501, stirring, precipitating and centrifuging, roasting, dissolving water and adding CO into rubidium slag2Extracting rubidium carbonate, wherein the rubidium collecting agent is a second complexing agent, the second complexing agent is BAMBP (4-sec-butyl-2- (alpha-methylbenzyl) phenol), and the pH value is 7-8;
s503, extracting cesium carbonate: adding a cesium collecting agent into the mixed salt solution after the step S502 is completed, stirring, precipitating and centrifuging, roasting, dissolving cesium residues in water, and adding CO2Extracting cesium carbonate, wherein the cesium collector is a third complexing agent, and the third complexing agent is BAMBP (4-sec-butyl-2- (alpha-methylbenzyl) phenol with the pH value of 8-9;
s504, extracting potassium sulfate and sodium sulfate: treating the mixed salt solution after the step S503 by a water source heat pump, crystallizing the mixed salt solution into potassium sulfate at the low temperature of 8-10 ℃, and returning distilled water generated during high-temperature evaporation crystallization into a clean water tank so as to recycle the distilled water; evaporating and crystallizing at the medium temperature of 65 ℃ to produce sodium sulfate and potassium sulfate.
Example 2: the embodiment provides a lithium slag solid waste resource recovery process, which is carried out according to the following steps:
s1, acid dissolution and separation: uniformly mixing 1t of lithium slag with water to enable the lithium slag to be completely soaked by the water, and then adding sulfuric acid and hydrofluoric acid, wherein the molar ratio of the sulfuric acid to the hydrofluoric acid is 1: 1, the dosage of sulfuric acid and hydrofluoric acid is 25 percent of the solid content of the lithium slag, so that metal oxides such as lithium, sodium, potassium, rubidium, cesium, magnesium, iron, aluminum, zinc and the like in the lithium slag are completely dissolved to generate acid salt; in this embodiment, the sulfuric acid uses a by-product acid with a concentration of 50 wt%, and the by-product acid is more suitable for the price of reagent-grade sulfuric acid, so as to reduce the recovery cost and improve the resource utilization rate. Specifically, the lithium slag undergoes a series of chemical reactions in a mixed solution of water and sulfuric acid, and the reactions are typically as follows:
Na2O+H2SO4＝Na2SO4+H2O；
K2O+H2SO4＝K2SO4+H2O；
Al2O3+3H2SO4＝Al2(SO4)3+3H2O；
Fe2O3+3H2SO4＝Fe2(SO4)3+3H2O；
P2O5+3H2O+Fe2(SO4)3＝2FePO4↓+3H2SO4；
after the harmlessness is realized by acid dissolution and hydrolysis in step S1, the mixed solution is mainly divided into two substances: insoluble solids and soluble mixed salts, the composition of the insoluble solids is shown in table 4:
TABLE 4
| Serial number | Name (R) | Content (c) of |
| 1 | Al2O3 | 25.00％ |
| 2 | SiO2 | 42.15％ |
| 3 | TiO2 | 0.20％ |
| 4 | CaF2 | 6.52％ |
| 5 | CaSO4 | 23.22％ |
| 6 | MgHPO4 | 0.30％ |
| 7 | Others | 2.61％ |
From the chemical composition, the insoluble solid is mainly composed of Al2O3、SiO2、TiO2、CaF2、CaSO4、MgHPO4And the like, wherein the insoluble and insoluble solids are removed from the mixed solution containing the insoluble solids and the mixed salt through separation steps such as centrifugal separation, rinsing and the like, and part of the insoluble solids do not contain chloride ions which are easy to cause the corrosion of reinforcing steel bars, so that the insoluble and insoluble solid can be used as a material for building materials to realize resource utilization, such as concrete mineral admixture, baking-free ecological cement and the like.
After separation of insoluble solids, the mixed salt solution is mainly: sodium sulfate, potassium sulfate, lithium sulfate, ferric sulfate, cesium sulfate, rubidium sulfate, aluminum sulfate, and zinc sulfate. Then adjusting the pH to respectively realize Fe3+、AL3+、Zn2+The heavy metals are precipitated and separated step by step, so that the resource utilization is realized. The remaining salt solution is subjected to targeted separation. Adsorbing, precipitating, evaporating, crystallizing, purifying and the like to obtain potassium sulfate, sodium sulfate, lithium carbonate, cesium carbonate, rubidium carbonate and other products.
S2, removing iron elements: adding sodium bicarbonate into the mixed salt solution after the step S1, adjusting the pH value of the mixed salt solution to 3.2, stirring the mixed salt solution uniformly to precipitate ferrous ions or ferric ions, and then carrying out centrifugal rinsing on the ferrous precipitate through a centrifugal machine to obtain iron mud with high iron content so as to be sold as a raw material of an iron and steel plant;
s3, removing aluminum elements: and (4) adding sodium bicarbonate into the mixed salt solution after the step S2, stirring, adjusting the pH value to 6.5, completely precipitating aluminum ions to form colloidal insoluble substances, separating and rinsing the colloidal insoluble substances through a centrifugal machine to obtain aluminum mud with high aluminum content, wherein the aluminum mud can be sold to professional companies for resource utilization, and the value of the lithium slag solid waste is further improved.
S4, removing heavy metal elements: and (4) adding a heavy metal collecting agent TMT organic sulfide chelating agent into the mixed salt solution after the step S3 is completed, forming insoluble matters or insoluble matters of Zn, Mg, Ni and the like through the heavy metal collecting agent and metal ions, and removing the heavy metal in the mixed salt solution for sale.
S5, targeted separation: and (3) performing targeted separation on the residual salt solution, and specifically comprising the following steps:
s501, extracting lithium carbonate: adding a lithium adsorbent into the mixed salt solution after the step S4, stirring, precipitating and centrifuging to obtain a lithium slag compound, and adding hydrofluoric acid into the lithium slag compound to generate HLiF2Then adding calcium salt to produce LiOH and CaF2And finally adding CO2Production of Li2CO3Post-extractionObtaining lithium carbonate, wherein the lithium adsorbent is a first complexing agent, and the first complexing agent is specifically CH-95;
s502, extracting rubidium carbonate: adding a rubidium collecting agent into the mixed salt solution after the step S501 is finished, stirring, precipitating and centrifuging, roasting and dissolving rubidium slag in water, and adding CO2Extracting rubidium carbonate, wherein the rubidium collecting agent is a second complexing agent, the second complexing agent is BAMBP (4-sec-butyl-2- (alpha-methylbenzyl) phenol, and the pH value is 7-8;
s503, extracting cesium carbonate: adding a cesium collecting agent into the mixed salt solution obtained in the step S502, stirring, precipitating and centrifuging, roasting, dissolving in water and adding CO into the cesium slag2Extracting cesium carbonate, wherein the cesium collector is a third complexing agent, and the third complexing agent is BAMBP (4-sec-butyl-2- (alpha-methylbenzyl) phenol with the pH value of 8-9;
s504, extracting potassium sulfate and sodium sulfate: treating the mixed salt solution after the step S503 by a water source heat pump, crystallizing the mixed salt solution into potassium sulfate at the low temperature of 8-10 ℃, and returning distilled water generated during high-temperature evaporation crystallization into a clean water tank so as to recycle the distilled water; evaporating and crystallizing at the medium temperature of 65 ℃ to produce sodium sulfate and potassium sulfate.
Example 3: the embodiment provides a lithium slag solid waste resource recovery process, which is carried out according to the following steps:
s1, acid dissolution and separation: uniformly mixing 1t of lithium slag with water to completely infiltrate the lithium slag with the water, and then adding hydrofluoric acid, wherein the dosage of the hydrofluoric acid is 25% of the solid content of the lithium slag, so that metal oxides such as lithium, sodium, potassium, rubidium, cesium, magnesium, iron, aluminum, zinc and the like in the lithium slag are completely dissolved to generate acid salt; in this embodiment, the hydrofluoric acid is a byproduct acid having a concentration of 50 wt%, and the byproduct acid is more suitable in price than reagent grade hydrofluoric acid, so as to reduce the recovery cost and improve the resource utilization rate. Specifically, the lithium slag undergoes a series of chemical reactions in a mixed solution of water and sulfuric acid, and the reactions are typically as follows:
Na2O+2HF＝2NaF+H2O；
K2O+2HF＝2KF+H2O；
Al2O3+6HF＝2AlF3+3H2O；
Fe2O3+6HF＝2FeF3+3H2O；
after the harmlessness is realized by acid dissolution and hydrolysis in step S1, the mixed solution is mainly divided into two substances: insoluble solids and soluble mixed salts, the composition of the insoluble solids is shown in table 5:
TABLE 5
| Serial number | Name (R) | Content (wt.) |
| 1 | Al2O3 | 25.00％ |
| 2 | SiO2 | 42.15％ |
| 3 | TiO2 | 0.20％ |
| 4 | CaF2 | 6.52％ |
| 5 | CaSO4 | 23.22％ |
| 6 | MgHPO4 | 0.30％ |
| 7 | Others | 2.61％ |
From the chemical composition, the insoluble solid is mainly composed of Al2O3、SiO2、TiO2、CaF2、CaSO4、MgHPO4And the insoluble and insoluble solids are removed from the mixed solution containing the insoluble solids and the mixed salt through separation steps such as centrifugal separation, rinsing and the like, and part of the insoluble solids do not contain chloride ions which are easy to cause corrosion of reinforcing steel bars, so that the insoluble and insoluble solid can be used as materials for building materials to realize resource utilization, such as concrete mineral admixture, baking-free ecological cement and the like.
After separation of insoluble solids, the mixed salt solution is mainly: sodium sulfate, potassium sulfate, lithium sulfate, ferric sulfate, cesium sulfate, rubidium sulfate, aluminum sulfate, and zinc sulfate. Then respectively realizing Fe by adjusting the pH3+、AL3+、Zn2+The heavy metals are precipitated and separated step by step, so that the resource utilization is realized. The remaining salt solution is subjected to targeted separation. Adsorbing, precipitating, evaporating, crystallizing, purifying and the like to obtain potassium sulfate, sodium sulfate, lithium carbonate, cesium carbonate, rubidium carbonate and other products.
S2, removing iron elements: adding sodium carbonate into the mixed salt solution after the step S1, adjusting the pH value of the mixed salt solution to 3.2, stirring the mixed salt solution uniformly to precipitate ferrous ions or ferric ions, and then carrying out centrifugal rinsing on the iron-containing precipitate through a centrifugal machine to obtain iron mud with high iron content so as to be sold as a raw material of an iron and steel plant;
s3, removing aluminum elements: and (4) adding sodium carbonate into the mixed salt solution obtained in the step S2 while stirring to adjust the pH value to 6.5, so that the aluminum ions are completely precipitated to form colloidal insoluble substances, separating and rinsing the colloidal insoluble substances through a centrifugal machine to obtain aluminum mud with high aluminum content, wherein the aluminum mud can be sold to professional companies for resource utilization, and the value of the lithium slag solid waste is further improved.
S4, removing heavy metal elements: and (4) adding a heavy metal collector TMT organic sulfide chelating agent into the mixed salt solution after the step S3 is completed, and forming insoluble matters or insoluble matters of Zn, Mg, Ni and the like by the heavy metal collector and metal ions to remove the heavy metal in the mixed salt solution for sale.
S5, targeted separation: and performing targeted separation on the residual salt solution, and specifically comprising the following steps of:
s501, extracting lithium carbonate: adding a lithium adsorbent into the mixed salt solution after the step S4, stirring, precipitating and centrifuging to obtain a lithium slag compound, and adding hydrofluoric acid into the lithium slag compound to generate HLiF2Followed by addition of calcium salt to produce LiOH and CaF2And finally adding CO2Production of Li2CO3Then extracting to obtain lithium carbonate, wherein the lithium adsorbent is a first complexing agent, and the first complexing agent is CH-95 specifically;
s502, extracting rubidium carbonate: adding a rubidium collecting agent into the mixed salt solution after the step S501 is finished, stirring, precipitating and centrifuging, roasting and dissolving rubidium slag in water, and adding CO2Extracting rubidium carbonate, wherein the rubidium collecting agent is a second complexing agent, the second complexing agent is BAMBP (4-sec-butyl-2- (alpha-methylbenzyl) phenol, and the pH value is 7-8;
s503, extracting cesium carbonate: adding a cesium collecting agent into the mixed salt solution obtained in the step S502, stirring, precipitating and centrifuging, roasting, dissolving in water and adding CO into the cesium slag2Extracting cesium carbonate, wherein the cesium collector is a third complexing agent, and the third complexing agent is BAMBP (4-sec-butyl-2- (alpha-methylbenzyl) phenol with the pH value of 8-9;
s504, extracting potassium sulfate and sodium sulfate: treating the mixed salt solution after the step S503 by a water source heat pump, crystallizing the mixed salt solution into potassium sulfate at the low temperature of 8-10 ℃, and returning distilled water generated during high-temperature evaporation and crystallization into a clean water tank so as to recycle the distilled water; evaporating and crystallizing at the medium temperature of 65 ℃ to produce sodium sulfate and potassium sulfate.
In the recovery processes of examples 1 to 3, potassium sulfate, sodium sulfate, lithium carbonate, cesium carbonate, and rubidium carbonate were obtained through the steps of adsorption, precipitation, evaporative crystallization, purification, and the like. Since carbonate is easy to preserve and can be used as a raw material for the production of other salts, which is an intermediate product, the product is used for supply in the form of lithium carbonate, cesium carbonate, rubidium carbonate. The potassium sulfate meets the national potash fertilizer standard GBT2040-2017, can be sold as a chemical fertilizer, and can also be used in other chemical fields. The sodium sulfate has low impurity content, meets the industrial salt standard GB/T5462-2015, and can be sold as a general industrial raw material. The aqueous solution obtained by solid-liquid separation, rinsing, evaporation, condensation and purification in the steps S1 to S5 of the embodiment 1-3 is completely recycled and used for the lithium slag in the countercurrent rinsing step S1, so that zero discharge of wastewater is realized, and water resources are saved. In the production process, each stirring and mixing tank is covered, tail gas is collected and then is intensively sprayed and absorbed, and absorption liquid is mixed with reuse water for recycling, so that the influence on the environment is avoided.
The examples 1-3 of the lithium slag solid waste recycling process are compared with the examples 1-3 of the comparison document 1(CN108273826B) and the example 10 of the comparison document 2(CN108101077A) in terms of process cost, utilization rate and overall value, and the comparison data are shown in the following table 6:
TABLE 6 comparison table of lithium slag solid waste recycling process data
Wherein the market price of the cement admixture obtained in the comparison document 1 is about 50 yuan/ton, and the production cost of the obtained lithium pyrophyllite is 185-And the market price of the pyrophyllite micro powder for preparing the glass fiber is 620 yuan/ton, and the estimated potential value is 1000 yuan/ton. In the comparison document 2, the lithium salt is calculated by using the market value of industrial-grade lithium sulfate of 475400 yuan/ton, and the silicon-calcium-potassium-magnesium-lithium fertilizer is calculated by using the silicon-calcium-magnesium granular fertilizer of 720 yuan/ton as the basis for the reference value. The selling price of the several extracts of the invention is as follows: 50% industrial sulfuric acid 200 yuan/ton, hydrofluoric acid 10830 yuan/ton, Al2O3、SiO2、TiO2、CaF2、CaSO4、MgHPO4The selling price of the building material of the insoluble substances or the indissoluble substances of the substances is calculated by the market price of the cement admixture of the comparison document 1, the selling price of the iron mud with higher iron content is 800-unit/ton, the selling price of the aluminum-zinc mud is 1200-unit/ton and 1800-unit/ton, the selling price of the calcium fluoride is 1500-unit/ton and 200-unit/ton, the selling price of the lithium carbonate is 471352-unit/ton, the selling price of the rubidium carbonate is 150000-unit/ton, the selling price of the cesium carbonate is 350000-unit/ton, the selling price of the potassium sulfate is 5066-unit/ton, the selling price of the sodium sulfate is 580-unit/ton, the amount of the products is converted from the content of the lithium slag into the corresponding amount of the products, the selling price of the product is quoted from the business society and the Aliibaba 2022 year 3, month 21, the process cost part of the application is the cost of the strong acid or the composite acid in brackets, because other operations and costs are substantially consistent, the costs of manpower, energy and materials other than acid are uniformly calculated at 1000 yuan.
As can be seen from table 6, the lithium slag solid waste recycling process of the present application recovers lithium slag on the basis of a certain cost, not only can improve the utilization rate of lithium slag, but also improves the overall value of lithium slag from 50 yuan per ton, which is only used as a building material before recovery, to 4874.7203-7532.2203 yuan per ton, which is much higher than the maximum overall value of 1000 yuan per ton of document 1, and is still much higher than the overall value 1464.836 of document 2, thereby improving the overall utilization value of lithium slag.
In conclusion, the lithium slag solid waste recycling process improves the prior process of preparing building materials into fine recycling, lithium, sodium, potassium, cesium, rubidium, zinc, aluminum and iron produced by the separation technology have higher market competitiveness, the recycling rate of the lithium slag is improved, the contained metal and nonmetal are effectively utilized, and the comprehensive utilization rate reaches 95%; the waste and pollution of other metals in the lithium slag are avoided, the waste is changed into valuable, the environment is protected, the comprehensive utilization value of the lithium slag is improved, and economic and social values are generated.
The above embodiments are only preferred embodiments of the present invention, and the protection scope of the present invention is not limited thereby, and any insubstantial changes and substitutions made by those skilled in the art based on the present invention are within the protection scope of the present invention.
Claims (8)
1. The lithium slag solid waste recycling process is characterized by comprising the following steps:
s1, acid dissolution and separation: uniformly mixing the lithium slag with water to enable the lithium slag to be completely soaked by the water, then adding strong acid or composite acid, wherein the using amount of the acid is 20% -40% of the solid content of the lithium slag, and completely dissolving metal oxides such as lithium, sodium, potassium, rubidium, cesium, magnesium, iron, aluminum, zinc and the like in the lithium slag to generate acid salt;
s2, removing iron elements: adding liquid caustic soda into the mixed salt solution after the step S1, adjusting the pH value of the mixed salt solution to 3-3.5, stirring the mixed salt solution uniformly to form precipitates of ferrous ions or ferric ions, and then carrying out centrifugal rinsing on the precipitates through a centrifugal machine to obtain iron mud;
s3, removing aluminum elements: adding liquid caustic soda into the mixed salt solution after the step S2 is completed, stirring the mixed salt solution, adjusting the pH value to be 6-7, completely precipitating aluminum ions to enable the aluminum ions to form colloidal insoluble substances, and separating and rinsing the colloidal insoluble substances through a centrifugal machine to obtain aluminum mud;
s4, removing heavy metal elements: adding a heavy metal collecting agent into the mixed salt solution after the step S3 is completed, and removing heavy metals in the mixed salt solution by forming insoluble matters or insoluble matters such as Zn, Mg, Ni and the like through the heavy metal collecting agent and metal ions;
s5, targeted separation: and performing targeted separation on the residual salt solution, and performing the procedures of adsorption, precipitation, evaporative crystallization, purification and the like to respectively prepare potassium sulfate, sodium sulfate, lithium carbonate, cesium carbonate and rubidium carbonate.
2. The lithium slag solid waste recycling process according to claim 1, characterized in that: the strong acid used for acid dissolution in the step S1 is sulfuric acid or hydrofluoric acid, and the complex acid is a mixture of the two.
3. The lithium slag solid waste recycling process according to claim 1, characterized in that: the caustic soda liquid in the steps S2 and S3 is sodium carbonate or sodium bicarbonate or potassium bicarbonate.
4. The lithium slag solid waste recycling process according to claim 1, characterized in that: the heavy metal collector added in the step S4 is a TMT organic sulfide chelating agent.
5. The lithium slag solid waste recycling process of claim 1, wherein the step S5 comprises the following steps:
s501, extracting lithium carbonate: adding a lithium adsorbent into the mixed salt solution after the step S4, uniformly stirring to obtain a lithium slag compound, and adding hydrofluoric acid into the lithium slag to generate HLiF2Then adding calcium salt to produce LiOH and CaF2And finally adding CO2Production of Li2CO3Then extracting to obtain lithium carbonate;
s502, extracting rubidium carbonate: adding a rubidium collecting agent into the mixed salt solution after the step S501 is finished, stirring, precipitating and centrifuging, roasting and dissolving rubidium slag in water, and adding CO2Extracting rubidium carbonate;
s503, extracting cesium carbonate: adding a cesium collecting agent into the mixed salt solution after the step S502 is completed, stirring, precipitating and centrifuging, roasting, dissolving cesium residues in water, and adding CO2Extracting cesium carbonate;
s504, extracting potassium sulfate and sodium sulfate: treating the mixed salt solution after the step S503 by a water source heat pump, crystallizing the mixed salt solution into potassium sulfate at a low temperature of 5-15 ℃, and returning distilled water generated during high-temperature evaporation crystallization into a clean water tank so as to recycle the distilled water; evaporating and crystallizing at the medium temperature of 60-70 ℃ to produce sodium sulfate, and obtaining sodium sulfate and potassium sulfate.
6. The lithium slag solid waste recycling process according to claim 5, characterized in that: the lithium adsorbent is a first complexing agent, and the first complexing agent is one or a mixture of two of CH-95 and polyethylene isothiourea functional group resin.
7. The lithium slag solid waste recycling process according to claim 5, characterized in that: the rubidium collecting agent is a second complexing agent, the second complexing agent is BAMBP (4-sec-butyl-2- (alpha-methylbenzyl) phenol, and the pH value is 7-8.
8. The lithium slag solid waste recycling process according to claim 5, characterized in that: the cesium collector is a third complexing agent, and the third complexing agent is BAMBP (4-sec-butyl-2- (alpha-methylbenzyl) phenol and has the pH value of 8-9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210300540.6A CN114702048A (en) | 2022-03-25 | 2022-03-25 | Lithium slag solid waste recycling process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210300540.6A CN114702048A (en) | 2022-03-25 | 2022-03-25 | Lithium slag solid waste recycling process |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114702048A true CN114702048A (en) | 2022-07-05 |
Family
ID=82170718
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210300540.6A Pending CN114702048A (en) | 2022-03-25 | 2022-03-25 | Lithium slag solid waste recycling process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114702048A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115432723A (en) * | 2022-09-05 | 2022-12-06 | 南京工程学院 | Method for preparing battery-grade lithium carbonate by taking waste residues generated in production of n-butyllithium and sec-butyllithium as raw materials |
| CN115448318A (en) * | 2022-09-13 | 2022-12-09 | 湖南绿脉环保科技股份有限公司 | Comprehensive recycling method for extracting silicon and aluminum from lithium slag |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104495880A (en) * | 2014-12-29 | 2015-04-08 | 宜春市科远化工有限公司 | Method for preparing lithium chloride and byproducts of lithium chloride from lepidolite |
| CN105271317A (en) * | 2015-10-28 | 2016-01-27 | 四川天齐锂业股份有限公司 | Method for converting rubdium and cesium in spodumene lithium-extracted slag into soluble salt |
| CN110015855A (en) * | 2019-04-01 | 2019-07-16 | 中国地质科学院郑州矿产综合利用研究所 | Treatment method of lithium slag |
| CN110902699A (en) * | 2019-12-27 | 2020-03-24 | 宜春市科远化工有限公司 | Method for preparing high-purity potassium sulfate from waste residue raw material obtained after lithium is extracted from lepidolite |
| CN214488258U (en) * | 2021-01-15 | 2021-10-26 | 中冶长天国际工程有限责任公司 | Comprehensive recycling system for lithium slag |
-
2022
- 2022-03-25 CN CN202210300540.6A patent/CN114702048A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104495880A (en) * | 2014-12-29 | 2015-04-08 | 宜春市科远化工有限公司 | Method for preparing lithium chloride and byproducts of lithium chloride from lepidolite |
| CN105271317A (en) * | 2015-10-28 | 2016-01-27 | 四川天齐锂业股份有限公司 | Method for converting rubdium and cesium in spodumene lithium-extracted slag into soluble salt |
| CN110015855A (en) * | 2019-04-01 | 2019-07-16 | 中国地质科学院郑州矿产综合利用研究所 | Treatment method of lithium slag |
| CN110902699A (en) * | 2019-12-27 | 2020-03-24 | 宜春市科远化工有限公司 | Method for preparing high-purity potassium sulfate from waste residue raw material obtained after lithium is extracted from lepidolite |
| CN214488258U (en) * | 2021-01-15 | 2021-10-26 | 中冶长天国际工程有限责任公司 | Comprehensive recycling system for lithium slag |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115432723A (en) * | 2022-09-05 | 2022-12-06 | 南京工程学院 | Method for preparing battery-grade lithium carbonate by taking waste residues generated in production of n-butyllithium and sec-butyllithium as raw materials |
| CN115448318A (en) * | 2022-09-13 | 2022-12-09 | 湖南绿脉环保科技股份有限公司 | Comprehensive recycling method for extracting silicon and aluminum from lithium slag |
| CN115448318B (en) * | 2022-09-13 | 2024-01-26 | 湖南绿脉环保科技股份有限公司 | Comprehensive recycling method for extracting silicon aluminum from lithium slag |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108611494B (en) | Method for recycling arsenic alkali residue efficiently and comprehensively | |
| CN101812593B (en) | Method for depositing vanadium wastewater by utilizing vanadium-extraction tailings and acid ammonium salt | |
| CN114702048A (en) | Lithium slag solid waste recycling process | |
| CN109734115B (en) | Method for leaching and recovering fluorine in waste cathode of aluminum electrolytic cell | |
| CN107697884A (en) | The harmless treatment Application way of aluminium ash | |
| CN101723458B (en) | Method for cleanly extracting vanadium pentexide from vanadium containing material | |
| CN101880780A (en) | Method for separating and extracting tungsten-molybdenum from mixed solution of tungstate-molybdate | |
| CN107151746A (en) | The alkaline process handling process of lithium ore | |
| CN101392332B (en) | Cleaning production technique for directly transforming rare earth sulfate bake ore to extract rare earth | |
| CN102586612A (en) | Method for recovering vanadium and chromium from vanadium and chromium-containing slag | |
| CN109354071B (en) | Method for producing battery-grade manganese sulfate by using manganese tailings and waste sulfuric acid of titanium white | |
| CN101323914A (en) | Process for extracting vanadic anhydride by high calcium calcination | |
| CN85101989A (en) | Processing method with preparation of Li 2 CO 3 by treating lithium-loaded mica with K 2 SO 4 | |
| CN106636653B (en) | A kind of method of comprehensive utilization of spent acid, alkaline residue and dedusting ash | |
| CN101746822A (en) | Method for extracting sodium metavanadate from vanadium extraction leaching solution | |
| CN111792650A (en) | Full-element recycling process of coal ash or coal gangue by hot-melt salt method | |
| CN113651342A (en) | Method for producing lithium product by processing lepidolite through nitric acid atmospheric pressure method | |
| CN110775998A (en) | System and method for producing nano zinc oxide by industrially recycling zinc | |
| CN106978531A (en) | The method that soda acid joint decomposes mixed rare earth concentrate | |
| CN101824531A (en) | Liquid alkali low-temperature roasting decomposition process of caustic soda liquid of mixed rare earth concentrates | |
| CN108947012A (en) | A method of separating and recovering ammonia from ammonia nitrogen waste water | |
| CN102849782B (en) | Method for producing high-purity zinc oxide by steel mill smoke dust ash ammonia method decarburization | |
| CN110229964B (en) | Method for extracting rubidium from fly ash | |
| CN115466854B (en) | Comprehensive extraction method of lithium ore | |
| CN102863009B (en) | Method of using low-grade zinc oxide ore to produce high-purity zinc oxide |
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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20220705 |