CN116716493A - Method for secondarily recycling germanium from low-grade germanium-containing material - Google Patents
Method for secondarily recycling germanium from low-grade germanium-containing material Download PDFInfo
- Publication number
- CN116716493A CN116716493A CN202310481057.7A CN202310481057A CN116716493A CN 116716493 A CN116716493 A CN 116716493A CN 202310481057 A CN202310481057 A CN 202310481057A CN 116716493 A CN116716493 A CN 116716493A
- Authority
- CN
- China
- Prior art keywords
- germanium
- low
- grade
- leaching
- alkaline
- 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
- 229910052732 germanium Inorganic materials 0.000 title claims abstract description 308
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 title claims abstract description 300
- 238000000034 method Methods 0.000 title claims abstract description 67
- 239000000463 material Substances 0.000 title claims abstract description 63
- 238000004064 recycling Methods 0.000 title description 6
- 238000002386 leaching Methods 0.000 claims abstract description 164
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 61
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 61
- 239000002893 slag Substances 0.000 claims abstract description 58
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000011347 resin Substances 0.000 claims abstract description 47
- 229920005989 resin Polymers 0.000 claims abstract description 47
- 150000003839 salts Chemical class 0.000 claims abstract description 47
- 238000000605 extraction Methods 0.000 claims abstract description 21
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims abstract description 19
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 239000013522 chelant Substances 0.000 claims abstract description 7
- 239000012141 concentrate Substances 0.000 claims abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 51
- 239000003513 alkali Substances 0.000 claims description 41
- 238000006243 chemical reaction Methods 0.000 claims description 33
- 230000001276 controlling effect Effects 0.000 claims description 27
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 21
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 20
- 229910052760 oxygen Inorganic materials 0.000 claims description 20
- 239000001301 oxygen Substances 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- 239000004115 Sodium Silicate Substances 0.000 claims description 15
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 15
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 14
- 238000005342 ion exchange Methods 0.000 claims description 14
- 239000006184 cosolvent Substances 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 11
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 10
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- 235000012239 silicon dioxide Nutrition 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 230000001376 precipitating effect Effects 0.000 claims description 8
- 230000001105 regulatory effect Effects 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 6
- 229920001429 chelating resin Polymers 0.000 claims description 5
- 238000000151 deposition Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000004317 sodium nitrate Substances 0.000 claims description 5
- 235000010344 sodium nitrate Nutrition 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims description 4
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 4
- 238000001816 cooling Methods 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
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- 239000004323 potassium nitrate Substances 0.000 claims description 3
- 235000010333 potassium nitrate Nutrition 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 239000012752 auxiliary agent Substances 0.000 claims description 2
- 230000008021 deposition Effects 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 230000032683 aging Effects 0.000 claims 1
- 239000000243 solution Substances 0.000 abstract description 82
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 38
- 230000008569 process Effects 0.000 abstract description 22
- 229910052742 iron Inorganic materials 0.000 abstract description 19
- 238000001179 sorption measurement Methods 0.000 abstract description 10
- 239000012535 impurity Substances 0.000 abstract description 4
- 238000004090 dissolution Methods 0.000 abstract description 3
- 239000004566 building material Substances 0.000 abstract description 2
- 230000004907 flux Effects 0.000 abstract description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract 1
- 230000003213 activating effect Effects 0.000 abstract 1
- 239000012670 alkaline solution Substances 0.000 abstract 1
- 229910052791 calcium Inorganic materials 0.000 abstract 1
- 239000011575 calcium Substances 0.000 abstract 1
- 230000001172 regenerating effect Effects 0.000 abstract 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 24
- 239000011701 zinc Substances 0.000 description 24
- 229910052725 zinc Inorganic materials 0.000 description 23
- 238000011084 recovery Methods 0.000 description 13
- 239000000428 dust Substances 0.000 description 11
- 239000000779 smoke Substances 0.000 description 11
- 239000007787 solid Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000000126 substance Substances 0.000 description 10
- 239000011734 sodium Substances 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 238000001704 evaporation Methods 0.000 description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 230000004913 activation Effects 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000009854 hydrometallurgy Methods 0.000 description 6
- 238000006386 neutralization reaction Methods 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 239000007858 starting material Substances 0.000 description 6
- 230000009466 transformation Effects 0.000 description 6
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 description 5
- 239000001263 FEMA 3042 Substances 0.000 description 5
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 description 5
- 229910052785 arsenic Inorganic materials 0.000 description 5
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 5
- 230000008020 evaporation Effects 0.000 description 5
- 229940119177 germanium dioxide Drugs 0.000 description 5
- 239000003077 lignite Substances 0.000 description 5
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 description 5
- 229940033123 tannic acid Drugs 0.000 description 5
- 235000015523 tannic acid Nutrition 0.000 description 5
- 229920002258 tannic acid Polymers 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- 238000003723 Smelting Methods 0.000 description 4
- 239000003456 ion exchange resin Substances 0.000 description 4
- 229920003303 ion-exchange polymer Polymers 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910005793 GeO 2 Inorganic materials 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000004458 analytical method 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
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- VDNSGQQAZRMTCI-UHFFFAOYSA-N sulfanylidenegermanium Chemical compound [Ge]=S VDNSGQQAZRMTCI-UHFFFAOYSA-N 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- LEVVHYCKPQWKOP-UHFFFAOYSA-N [Si].[Ge] Chemical compound [Si].[Ge] LEVVHYCKPQWKOP-UHFFFAOYSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 230000001698 pyrogenic effect Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 229920001864 tannin Polymers 0.000 description 2
- 235000018553 tannin Nutrition 0.000 description 2
- 239000001648 tannin Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- DJHGAFSJWGLOIV-UHFFFAOYSA-K Arsenate3- Chemical class [O-][As]([O-])([O-])=O DJHGAFSJWGLOIV-UHFFFAOYSA-K 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- 229910000577 Silicon-germanium Inorganic materials 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- FNIHDXPFFIOGKL-UHFFFAOYSA-N disodium;dioxido(oxo)germane Chemical compound [Na+].[Na+].[O-][Ge]([O-])=O FNIHDXPFFIOGKL-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 229910052598 goethite Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 210000001503 joint Anatomy 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000009853 pyrometallurgy Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- PHIQPXBZDGYJOG-UHFFFAOYSA-N sodium silicate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-][Si]([O-])=O PHIQPXBZDGYJOG-UHFFFAOYSA-N 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- IEXRMSFAVATTJX-UHFFFAOYSA-N tetrachlorogermane Chemical compound Cl[Ge](Cl)(Cl)Cl IEXRMSFAVATTJX-UHFFFAOYSA-N 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C22B41/00—Obtaining germanium
-
- 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
-
- 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/12—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic alkaline solutions
-
- 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for secondarily recovering germanium from a low-grade germanium material. Specifically, leaching a low-grade germanium material by a sub-molten salt method to obtain germanium-containing alkaline leaching solution and alkaline leaching slag; determining whether an aluminum removal process is adopted according to the aluminum content in the alkaline leaching solution containing germanium, ensuring that the D403 resin is used for selectively adsorbing germanium after the aluminum content reaches the standard, concentrating and crystallizing the alkaline solution after germanium extraction, and then leaching by using a sub-molten salt method; resolving the D403 chelate resin for adsorbing germanium by using hydrochloric acid solution, activating and regenerating the resolved D403 chelate resin, and then re-adsorbing the germanium; the germanium-containing hydrochloric acid solution can be used for producing germanium oxide by adjusting the pH value or can be compatible with concentrated hydrochloric acid for distilling germanium concentrate. The invention realizes the efficient leaching of germanium in the low-grade germanium material, the enrichment ratio can reach more than 80 by resolving and re-precipitating germanium after the selective adsorption of the chelate resin, the germanium and other impurities in the low-grade germanium material are dissolved by a sub-molten salt method, and the content of iron or calcium in the alkaline leaching residue after the germanium dissolution is increased and can be used as a raw material of metallurgical flux, building materials or iron making.
Description
Technical Field
The invention relates to a method for secondarily recycling germanium from low-grade germanium materials, in particular to a method for preparing high-grade germanium concentrate from high-iron silicon-containing low-grade germanium materials such as neutralization slag, displacement slag, leaching slag, smoke dust and the like in a zinc hydrometallurgy process, and belongs to the technical field of chemical metallurgy.
Background
Germanium has an amphoteric character and is classified as rare dispersed metals (abbreviated as "dispersed metals") and exhibits different geochemical properties including lithophilic, iron-philic, copper-philic and organic-philic properties in different geochemical environments, so that the individual ores are relatively limited and are enriched in Fe-Ni phases (merle and pit), lead-zinc-silver-and copper-rich sulfides, iron oxide deposits (limonite, magnetite and goethite), germanium-rich sulfide oxide strips (hydroxides, oxides, hydroxysulfates and arsenates), coal and lignite (bonded with organics), with recovery of germanium from zinc sulfide concentrate and lignite being the major sources of germanium. It is counted that approximately 60% of germanium comes from various slag and byproducts of zinc smelting enterprises.
In the zinc smelting process, germanium enters leaching slag, smoke dust, neutralization slag, replacement slag, hard zinc, leftover zinc and the like along with the zinc refining process, and is enriched to different degrees relative to the original ore germanium. However, for low-grade germanium-containing materials with the germanium content of 0.1-2.0%, if the low-grade germanium-containing materials are directly used in a germanium smelting process, the germanium recovery rate is low, a large amount of hydrochloric acid is consumed by large other components in the low-grade germanium materials, waste hydrochloric acid and residues generated in the distillation process are often difficult to effectively utilize, and the environmental protection disposal difficulty is high.
For enriching and recovering germanium from low-grade germanium-containing materials, pyrometallurgy, hydrometallurgy and a combination thereof may be employed. The fire method generally adopts a Wilz rotary kiln, a fuming furnace, an electric arc furnace, an Osmehte furnace and other large-scale furnaces, and adopts a high-temperature carbon reduction or vulcanization volatilization process for treatment to produce the smoke dust containing germanium oxide or germanium sulfide. The pyrogenic volatilization method cannot completely destroy the connection between germanium and iron, silicon and sulfur. The recovery rate of germanium is low, the content of germanium in smoke dust is low, part of germanium enters kiln slag and is difficult to recover, and the low-concentration sulfur dioxide smoke produced in the volatilization process is difficult to treat. The wet process generally adopts sulfuric acid leaching, and also adopts different modes of oxygen pressure leaching, ultrasonic strengthening and adding leaching assisting agents such as ozone, hydrogen peroxide, manganese dioxide, sodium chlorate, sodium acetate, citric acid and the like to partially infuse insoluble materials, so that the germanium leaching rate can be improved to a certain extent, and after the germanium is dissolved in sulfuric acid solution, the germanium is precipitated by tannic acid or extracted by extracting agent to obtain high-grade germanium enriched matters. The tannin is used for precipitating germanium to directly obtain germanium slag, the germanium slag can be used as germanium concentrate for further extracting germanium after calcination, and the coarse germanium dioxide is obtained after washing and back extraction of germanium and then regulating the pH value by alkali liquor. In recent years, the price of tannic acid is high, the unit consumption of the tannic acid for depositing germanium is high, and the cost of adopting a tannic acid germanium depositing method is high; and the germanium extraction process flow is long, and fluorine in the back extraction agent enters the solution and is difficult to treat. In addition, for the two methods of tannin germanium precipitation and germanium extraction, tannic acid and an organic extractant can be dissolved into a solution to a certain extent, so that the subsequent process is affected.
Along with the increasing environmental protection requirements, enterprises have urgent demands for cost reduction and energy conservation, and it is necessary to develop a secondary recovery technology aiming at low-grade germanium materials, which has the advantages of high recovery rate, simple process, short flow, easy operation, recycling of auxiliary materials and low energy consumption, and prepare high-grade germanium concentrate.
Disclosure of Invention
The invention provides a method for secondarily recovering germanium from low-grade germanium materials, which adopts a sub-molten salt leaching-ion exchange adsorption process to recover germanium in the low-grade germanium materials in a coarse germanium dioxide form, and alkaline leaching residues can be recycled without waste water and waste residues.
The specific process steps for achieving the purpose of the invention are as follows:
step one
The low-grade germanium-containing material and a sub-molten salt medium are subjected to medium-temperature alkaline leaching and/or sub-molten salt leaching reaction in a reaction kettle at 70-250 ℃, wherein the sub-molten salt medium contains alkali metal hydroxide; filtering and washing after the reaction is finished to obtain alkaline leaching solution containing germanium and alkaline leaching slag;
step two
If the aluminum content of the alkaline leaching solution containing germanium is more than or equal to Amg/L, carrying out aluminum removal treatment on the alkaline leaching solution containing germanium to obtain aluminum slag and purifying solution containing germanium; the purified solution containing germanium passes through an ion exchange column filled with D403 chelate resin to obtain chelate resin adsorbed with germanium and alkali liquor after germanium extraction;
if the aluminum content of the germanium alkaline leaching solution is less than Amg/L, the germanium alkaline leaching solution passes through an ion exchange column filled with D403 chelating resin to obtain the chelating resin adsorbed with germanium and alkaline liquor after germanium extraction;
the value range of A is 20-50.
The invention applies the sub-molten salt leaching reaction to the treatment of low-grade germanium-containing materials for the first time, and realizes the low-temperature and high-efficiency recovery of germanium under the cooperation of corresponding condition parameters.
According to the invention, a low-grade germanium-containing material and a sub-molten salt medium are put into a reaction kettle to perform sub-molten salt leaching reaction, and under the condition of multi-factor coupling action, germanium in the germanium material reacts with alkali liquor to generate sodium germanate alkali leaching solution by regulating and controlling a plurality of technological parameters such as reaction temperature, oxygen partial pressure, concentration reduction, alkali-ore ratio, reaction time and the like, and amphoteric elements such as zinc, aluminum, silicon and arsenic in the germanium material are almost completely dissolved into the alkali leaching solution.
The content of germanium in the low-grade germanium material is 0.1-2.0wt%.
In industrial application, germanium in the low-grade germanium material mainly exists in the forms of germanium monoxide, germanium dioxide, germanium sulfide, germanate and germanium-silicon solid solution, and iron mainly exists in the forms of oxide and hydroxide. Of course, the method of the present invention is applicable to other forms of germanium that are present.
The invention provides a method for secondarily recovering germanium from low-grade germanium materials, which comprises the steps of firstly adding a cosolvent into a low-grade germanium material according to the proportion of 0-5% of the feeding amount by adopting alkali with the concentration of 50-90 wt% according to the alkali-ore ratio g: g=5-20:1, putting a sub-molten salt medium and the low-grade germanium material into a reaction kettle, closing a kettle cover, starting stirring, introducing oxygen-containing gas, controlling the oxygen partial pressure to be 0.05-2.00 MPa, controlling the reaction temperature to be 140-250 ℃, preferably 160-180 ℃, continuously reacting for 1-6 hours, closing an air inlet valve, cooling to 80-120 ℃, and preserving heat and filtering. When the cosolvent is required to be added, the adding proportion of the cosolvent can be 0.2-5%.
Of course, the scheme of the invention also comprises the following steps: mixing alkali with the concentration of 50-90 wt% and low-grade germanium material according to the alkali-ore ratio g being 5-20:1, filling alkali, cosolvent and medium-temperature alkali leaching slag into a reaction kettle, closing a kettle cover, starting stirring, introducing oxygen-containing gas, controlling the oxygen partial pressure to be 0.05-2.00 MPa, controlling the reaction temperature to be 140-250 ℃, preferably 160-180 ℃, continuously reacting for 1-6 h, closing an air inlet valve, cooling to 80-120 ℃, and preserving heat and filtering.
According to the invention, according to the alkali-ore ratio g, g=3-10:1, alkali liquor B is mixed with low-grade germanium materials, and the germanium-containing materials are leached by a sub-molten salt method alkali leaching solution under the condition of no boiling at 80-90 ℃ to obtain first alkali slag; then, carrying out second sub-molten salt leaching, wherein the second sub-molten salt leaching takes slag of the first step as a raw material;
the alkali liquor B is alkali liquor or alkali liquor with the concentration of 10-40% after leaching by sub-molten salt.
When the method is industrially applied, according to the alkali-ore ratio g, g=3-1:1, alkali-leaching liquid with the concentration of 100-150g/L after adsorbing germanium is mixed with low-grade germanium materials, and the mixture reacts at 80-90 ℃ under the condition of no boiling, so that about 50% of germanium can be leached, and the rest amphoteric impurities (aluminum, silicon, zinc and arsenic) are partially leached. And then carrying out second sub-molten salt leaching, wherein the second sub-molten salt leaching takes the intermediate-temperature alkaline leaching slag of the first sub-molten salt leaching as a raw material. The two-stage leaching adopting the combination of the medium-temperature alkaline leaching and the sub-molten salt leaching is particularly suitable for germanium materials containing amphoteric elements such as aluminum, silicon, arsenic, zinc and the like, and has the following advantages: 1. the germanium concentration in the alkaline leaching solution can be increased by about 50%, which is favorable for subsequent adsorption. 2. After the germanium-containing material is subjected to alkaline leaching in the first step, the reduction is quite large, the sub-molten salt working procedure in the second step is more efficient to treat, and the alkaline-solid ratio can be reduced. The second sub-molten salt leaching here is performed according to the process described above. Mixing alkali with concentration of 50-90 wt% and slag and/or low grade germanium material in the first step according to alkali-ore ratio g=5-20:1, loading alkali, cosolvent and low grade germanium material into a reaction kettle, closing a kettle cover, stirring, introducing oxygen-containing gas, controlling oxygen partial pressure to be 0.05-2.00 MPa, controlling rotating speed to be 300-900 r/min, controlling reaction temperature to be 140-250 ℃, preferably 160-180 ℃, continuously reacting for 1-6 h, closing an air inlet valve, cooling to 80-120 ℃, and preserving heat and filtering. 3. The sub-molten salt alkaline leaching solution is returned to the medium-temperature alkaline leaching solution, so that the heat of the sub-molten salt alkaline leaching solution can be fully utilized, and in addition, the medium-temperature alkaline leaching solution consumes part of the alkali in the sub-molten salt alkaline leaching solution, so that the service life of the resin is prolonged.
The invention adopts a two-stage leaching method combining medium-temperature alkaline leaching and sub-molten salt leaching for the first time, can obviously improve the germanium concentration of alkaline leaching liquid, can partially dissolve germanium, aluminum, arsenic, silicon, zinc and other components in low-grade germanium materials by the medium-temperature alkaline leaching, reduces the low-grade germanium materials by 30-50%, can effectively reduce the alkali-ore ratio of the sub-molten salt leaching, greatly improves the service efficiency of equipment, fully utilizes heat and prolongs the service life of resin.
The oxygen-containing gas in the present invention is industrial oxygen. Industrial oxygen is performed according to corresponding standards.
The alkali metal hydroxide is at least one selected from sodium hydroxide and potassium hydroxide; namely, the alkali metal hydroxide in the first step is at least one selected from sodium hydroxide and potassium hydroxide.
The sub-molten salt medium comprises an alkali metal hydroxide or comprises alkali metal hydroxide and a cosolvent; the cosolvent is selected from the group consisting of: at least one of nitrate, carbonate and chlorate, preferably at least one of sodium nitrate, potassium nitrate, sodium carbonate, potassium carbonate, sodium chlorate and potassium chlorate; no cosolvent may be added to the particular material that is soluble and contains the germanium oxide phase.
In the present invention, the alkali-ore ratio is the ratio of the material to the alkali metal oxide
In the invention, when the cosolvent is needed to be added, the feeding amount of sodium nitrate, for example, is 0.2-5% of the feeding amount according to the content of indissolvable germanium components in the material.
In the present invention, the alkali concentration means a weight ratio of alkali to alkali+water.
In the industrial application, the sub-molten salt medium is prepared from alkali and pure nitrate according to set components in the primary production, and then the solid alkali which is produced in the third step and subjected to evaporation concentration is adopted for extracting germanium and then leaching the alkali.
In the step 1, the rotating speed is controlled to be 300-900 rpm.
The first step is mainly to produce alkaline leaching solution containing germanium and residue after germanium extraction. The concentration of germanium in the alkaline leaching solution containing germanium is 100-2000 mg/L, the concentration of alkali is 10-250 g/L, and the content of germanium in the residue after germanium extraction is lower than 400-1000 g/t.
In the second step of the invention, when the aluminum content of the alkaline leaching solution containing germanium is larger than or equal to Amg/L, the alkaline leaching solution containing germanium adopts sodium silicate and silicon dioxide to combine an aluminum removing agent to precipitate and separate aluminum and the like, so as to obtain aluminum slag and the purifying solution containing germanium. The method specifically comprises the following steps: controlling the molar ratio of sodium silicate to aluminum in the alkaline leaching solution containing germanium to be 1.5-2.0, and reacting at 150-160 ℃ for 30-120 min to obtain filter residues with aluminum content of 5-30%, wherein the aluminum concentration of the purified solution of the alkaline leaching solution containing germanium is lower than Amg/L. The value range of A is 20-50.
As a further preference, the mass ratio of sodium silicate to silicon dioxide is 65-75:35-25. The sodium silicate is preferably sodium silicate nonahydrate.
In the second step of the invention, the alkaline leaching solution containing germanium with the aluminum content less than Amg/L passes through an ion exchange column filled with D403 resin according to the flow rate of 5-30 BV/h to obtain the resin with adsorbed germanium and alkaline liquor after germanium extraction, and the alkaline leaching solution after germanium extraction is evaporated and concentrated and then returns to the first step to be used as a sub-molten salt medium. The D403 resin is macroporous styrene chelating ion exchange resin and is milky opaque spherical particles.
In the second step of the present invention, the temperature is controlled to be 20 to 65℃and preferably 20 to 35℃when germanium is adsorbed by the ion exchange column of the D403 resin.
After the second step is completed, the obtained saturated resin for adsorbing germanium is subjected to saturation washing and rinsing, and is resolved by hydrochloric acid solution to obtain hydrochloric acid solution containing germanium and D403 resin which does not adsorb germanium. Industrially shouldWhen in use, the germanium adsorbed on the D403 resin is eluted by hydrochloric acid solution with the concentration of 0.2 to 4.0mol/L, the dosage of the hydrochloric acid solution is 2 to 4m 3 /m 3 R, the flow rate of the hydrochloric acid solution is 10-25 BV/h, and the operation temperature is 20-35 ℃.
The method adopts the D403 resin to adsorb the germanium under the alkaline condition for the first time, which provides a necessary condition for the efficient recovery of the germanium.
In the present invention, "m 3 /m 3 R "refers to how much cubic hydrochloric acid is needed per cubic resin.
In industrial applications, the resin adsorption can adsorb germanium in solution cleanly, but in practical operation, it is generally not done so from the standpoint of efficiency and cost, only a part of adsorption is needed, and the rest is left in solution for circulation, for example, 800mg/L is reduced to 300 mg/L.
In industrial application, D403 is transformed and activated and then returns to the second step for recycling. Methods of transformation activation include all existing methods.
Adding germanium deposition auxiliary agent into the obtained germanium-containing hydrochloric acid solution, regulating pH value to 8.0-10.0 with alkali under normal temperature environment to deposit germanium, filtering to obtain high-grade germanium concentrate with germanium content more than or equal to 20%, preferably more than or equal to 30%. The germanium precipitating agent can be ferric chloride or magnesium chloride alone or a mixture of ferric chloride and magnesium chloride. The base for pH adjustment is selected from at least one of sodium hydroxide, sodium carbonate and ammonia.
The invention takes low-grade germanium materials with the germanium content of 0.2-2.0% as raw materials, adopts a sub-molten salt method low-temperature leaching-ion exchange resin adsorption method to secondarily enrich germanium, and has higher germanium leaching rate compared with the methods of pyrogenic volatilization, acid method dissolution and single sodium hydroxide aqueous solution leaching, and the selected meglumine-polystyrene macroporous chelating resin has strong germanium adsorption selectivity and large saturation capacity. Based on the principle, the invention adopts the technical scheme that germanium is recovered from low-grade germanium materials by adopting a sub-molten salt method alkaline leaching-D403 resin adsorption method. According to the scheme, a low-grade germanium material and excessive sodium hydroxide or potassium hydroxide react in a sub-molten salt state, solid solutions of germanium dioxide, germanium sulfide and silicon germanium with stable structures are destroyed, germanium and hydroxyl are combined to generate germanate ions to enter a solution, after chemical aluminum removal, D403 macroporous resin can selectively adsorb germanium from the solution onto the resin, impurities such as silicon, arsenic and zinc are hardly adsorbed, after adsorption-analysis, the germanium enters a hydrochloric acid solution and can be directly used as ingredients of a germanium distillation process or added with alkali to adjust the pH value to generate crude germanium dioxide, so that the aim of efficiently recovering the germanium from the low-grade germanium-containing material is fulfilled, and a chemical reaction equation mainly related by the invention is as follows:
GeO 2 +2NaOH＝Na 2 GeO 3 +H 2 O
GeO+2NaOH＝Na 2 GeO 2 +H 2 O
GeO 2 ·SiO 2 +4NaOH＝Na 2 GeO 3 +Na 2 SiO 3 +2H 2 O
As 2 O 3 +6NaOH＝2Na 3 AsO 4 +H 2 O
Al 2 O 3 +2NaOH＝2NaAlO 2 +H 2 O
SiO 2 +2NaOH＝Na 2 SiO 3 +H 2 O
Zn 2 SiO 4 +6NaOH＝Na 2 SiO 3 +2Na 2 ZnO 2 +3H 2 O
ZnO+2NaOH＝Na 2 ZnO 2 +H 2 O
Na 2 SiO 3 +NaAlO 2 +H 2 O＝Na 2 Al 2 Si 2 O 8 +4NaOH
the invention has the beneficial effects that:
(1) And (5) efficiently recovering germanium. According to the invention, germanium and other amphoteric elements in the low-grade germanium material are dissolved by sub-molten salt state alkali and cosolvent for the first time, aluminum in alkaline leaching solution is removed by a chemical precipitation method, high-selectivity adsorption (the enrichment ratio can be more than 80) is realized by adopting ion exchange adsorption of D403 macroporous resin, after hydrochloric acid solution is resolved, the method can be directly used for producing high-purity germanium tetrachloride or precipitating germanium to prepare crude germanium dioxide, so that secondary recovery of germanium in the low-grade germanium material is realized, the germanium leaching rate of the sub-molten salt process can be more than 96%, and the total-process germanium recovery rate can be more than 94.5%.
(2) And (3) high-value utilization of iron. In the invention, iron is hardly dissolved into alkaline leaching slag in the middle-temperature alkaline leaching and sub-molten salt leaching processes, the slag rate of the alkaline leaching slag is 30-60% based on the dissolution of germanium and other amphoteric elements, iron is enriched in the form of oxides, the iron content in the alkaline leaching slag is 40-60%, the obtained alkaline leaching slag can be used as a metallurgical flux and a building material, and the alkaline leaching slag with the iron content of more than 50% can be used as an iron-making raw material, so that the high-value utilization of iron is realized.
(3) The smelting process is clean and efficient. The invention adopts a subtend alkaline leaching process or a medium-temperature alkaline leaching butt joint subtend alkaline leaching process, has low reaction temperature and low energy consumption, and can recycle the subtend molten salt medium alkali. After adsorption-analysis of the chelating ion exchange resin, the chelating ion exchange resin can be reused after simple activation transformation, and the resin is insoluble in a solution, so that an organic phase is not introduced, and the adsorption-analysis process can be carried out at normal temperature. The iron enrichment can be recycled in the alkaline leaching slag, and no wastewater and waste slag are discharged.
Drawings
FIG. 1 is a process flow diagram after optimization of the present invention.
Detailed Description
The invention is further described in detail by examples using low grade germanium slag from zinc hydrometallurgy as a raw material, but the scope of the invention is not limited to the above.
Example 1:
leaching residues in the zinc hydrometallurgy process are subjected to high-temperature volatilization of smoke dust containing zinc, germanium and lead in a fuming furnace, zinc calcine or zinc-containing smoke dust is added after the smoke dust is leached by sulfuric acid, the pH value of the smoke dust is adjusted to be 5.0, and the main chemical compositions of the germanium-containing neutralization residues after zinc separation are shown in a table 1.
TABLE 1 main chemical components (wt%) of the neutralization slag
(1) Controlling the alkali-solid ratio (g: g) of sodium hydroxide to the neutralized germanium slag to be 8, placing the neutralized germanium slag into a closed reaction kettle filled with 80wt% of sodium hydroxide, reacting for 2 hours at 170 ℃, performing hot filtration, and washing the slag with hot water at 80 ℃ to produce alkali leaching liquid and alkali leaching slag. The concentration of germanium in the alkaline leaching solution is 384mg/L, the concentration of iron is 5.78mg/L, the concentration of aluminum is 2.12g/L, and the alkaline leaching slag with the iron content of 41.46wt percent; the leaching rate of germanium is about 96.35% at this time through one step leaching.
(2) Adding an aluminum removing agent (the aluminum removing agent is prepared from sodium silicate and silicon dioxide according to the mass ratio, nine water and sodium silicate are respectively used for preparing silicon dioxide of 7:3), wherein the total molar weight ratio of the sodium silicate in the aluminum removing agent to the aluminum in the solution is 1.5:1, and then reacting at 160 ℃ for 90min to precipitate and separate the aluminum, so as to obtain germanium-containing alkaline leaching solution with the aluminum content of less than 20mg/L and aluminum slag with the aluminum content of 6.17 wt%;
(3) And (3) allowing the alkaline leaching solution containing germanium to pass through an ion exchange column carrying D403 resin at a flow rate of 18BV/h at normal temperature to obtain a low-germanium alkaline leaching solution with the germanium concentration of 1.26mg/L, adsorbing the germanium by resin particles, evaporating and concentrating the low-germanium alkaline leaching solution, and returning to the step (2).
(4) The resin particles absorbing germanium are washed by pure water for 2 times, the germanium is resolved by hydrochloric acid solution with the concentration of 2mol/L at the flow rate of 10BV/h, the resolved liquid can be recycled until the concentration of the germanium is enriched to be more than 2g/L, and the resolved resin is returned to the step (3) after activation transformation.
(5) The germanium-containing hydrochloric acid solution is directly transferred to the distilled germanium extraction process for proportioning or added with germanium precipitating agent, and the pH value is regulated to 10.0, so as to obtain the crude germanium oxide with the germanium content of 41.33 weight percent.
In this example, the germanium recovery was about 95.86%.
Example 2:
the main chemical compositions of the leaching solution obtained in the zinc hydrometallurgy oxygen pressure acid leaching process after flash evaporation adjustment and adding zinc calcine or zinc-containing smoke dust to adjust the pH value to 5.0 are shown in Table 2.
TABLE 2 main chemical components (wt%) of the neutralization slag
(1) Controlling the alkali-solid ratio (g: g) of sodium hydroxide to the neutralized germanium slag to be 6, placing the neutralized germanium slag into a closed reaction kettle filled with 80wt% of sodium hydroxide, controlling the oxygen partial pressure to be 0.5MPa, reacting for 3 hours at 160 ℃, performing hot filtration, and washing the slag with hot water at 80 ℃ to produce alkali leaching liquid and alkali leaching slag. The concentration of germanium in the alkaline leaching solution is 264mg/L, the concentration of iron is 6.17mg/L, the concentration of aluminum is 0.89g/L, and the alkaline leaching slag with the iron content of 55.68wt percent; the leaching rate of germanium is about 94.47% at this time through one leaching step.
(2) Adding an aluminum removing agent (the aluminum removing agent is prepared from sodium silicate and silicon dioxide according to the mass ratio, nine water and sodium silicate are respectively used for preparing silicon dioxide of 7:3), wherein the total molar weight ratio of the sodium silicate in the aluminum removing agent to the aluminum in the solution is 1.8:1, and then carrying out reaction at 150 ℃ for 60min to precipitate and separate the aluminum, so as to obtain germanium-containing alkaline leaching solution with the aluminum content of less than 20mg/L and aluminum slag with the aluminum content of 7.35 wt%;
(3) The alkaline leaching solution containing germanium passes through an ion exchange column loaded with D403 resin at the flow rate of 16BV/h at normal temperature to obtain low-germanium alkaline leaching solution with the germanium concentration of 1.11mg/L, the germanium is adsorbed by resin particles, and the low-germanium alkaline leaching solution returns to the step (2) after evaporation and concentration.
(4) Washing resin particles adsorbing germanium with pure water for 2 times, resolving germanium with 3mol/L hydrochloric acid solution at a flow rate of 10BV/h, and recycling resolving liquid until the germanium content is more than 2g/L, and returning the resolved resin to the step (3) after activation transformation.
(5) The germanium-containing hydrochloric acid solution is directly transferred to the distilled germanium extraction process for proportioning or added with germanium precipitating agent, and the pH value is regulated to 8.0 to obtain the crude germanium oxide with the germanium content of 39.54 weight percent.
In this example, the germanium recovery was about 93.98%.
Example 3:
the leaching solution in the wet zinc hydrometallurgy oxygen pressure acid leaching process is subjected to flash evaporation adjustment, zinc calcine is added to neutralize until the sulfuric acid content is 20g/L, zinc powder is added to replace and remove impurities, germanium, copper, cadmium and the like are replaced into replacement slag, and the main chemical compositions of the replacement slag after zinc and copper are separated are shown in table 3.
TABLE 3 replacement of the major chemical composition (wt%) of germanium slag
(1) Controlling the alkali-solid ratio (g: g) of sodium hydroxide to the replaced germanium slag to be 7, wherein the adding amount of sodium nitrate is 2wt% of the low-grade germanium material, placing the neutralized germanium slag into a closed reaction kettle with 80wt% concentration sodium hydroxide and 2wt% sodium nitrate, reacting for 4 hours at 180 ℃, performing hot filtration, and washing the slag with hot water at 80 ℃ to produce alkali leaching liquid and alkali leaching slag. The concentration of germanium in the alkaline leaching solution is 298mg/L, the concentration of iron is 2.05mg/L, the concentration of aluminum is lower than 1mg/L, and the content of iron in the alkaline leaching solution is 4.21wt percent; the leaching rate of germanium is about 95.21% at this time by one step leaching.
(2) The alkaline leaching solution containing germanium passes through an ion exchange column loaded with D403 resin at the flow rate of 15BV/h at normal temperature to obtain low-germanium alkaline leaching solution with the germanium concentration of 1.23mg/L, the germanium is adsorbed by resin particles, and the low-germanium alkaline leaching solution returns to the step (1) after evaporation and concentration.
(3) The resin particles absorbing germanium are washed by pure water for 2 times, the germanium is resolved by hydrochloric acid solution with the concentration of 3mol/L at the flow rate of 12BV/h, the resolved liquid can be recycled until the content of the germanium is more than 2g/L, and the resolved resin is returned to the step (2) after activation transformation.
(4) The germanium-containing hydrochloric acid solution is directly transferred to the distilled germanium extraction process for proportioning or added with germanium precipitating agent, and the pH value is regulated to 8.5 to obtain crude germanium oxide with the germanium content of 42.17 weight percent.
In this example, the germanium recovery was about 94.77%.
Example 4:
the main chemical compositions of the germanium-containing lignite dust obtained by burning and collecting the germanium-containing lignite through a vortex furnace are shown in table 4.
TABLE 4 main chemical components (wt%) of the neutralization residue
(1) And (2) reacting the germanium-containing lignite smoke dust with the returned alkaline leaching solution in a reaction tank according to the ratio of g to g of 10, controlling the reaction temperature to be 85 ℃, stirring for 500r/min, preserving heat, reacting for 3 hours, and filtering to obtain medium-temperature alkaline leaching residues and the germanium-containing alkaline leaching solution.
(2) Mixing the sub-molten salt medium from the step (4) with the medium-temperature alkaline leaching slag obtained in the step (1), adding part of potassium hydroxide to reach the proportion of 10 of alkali-solid ratio (g: g), reacting the mixture for 3.5 hours at 175 ℃ in a closed reaction kettle of potassium nitrate with the concentration of potassium hydroxide of 75% and the additional feeding amount of 3%, and thermally filtering to obtain alkaline leaching liquid and alkaline leaching slag. The concentration of germanium in alkaline leaching solution is 301mg/L, the concentration of iron is 9.30mg/L, the concentration of aluminum is 4.83g/L, and the concentration of iron in alkaline leaching slag is 43.88%; the leaching rate of germanium is about 93.80% at this time by one step leaching.
(3) Adding an aluminum removing agent (the aluminum removing agent is prepared from sodium silicate and silicon dioxide according to the mass ratio, nine water and sodium silicate are respectively used for preparing silicon dioxide of 7:3), wherein the total molar weight ratio of the sodium silicate in the aluminum removing agent to the aluminum in the solution is 2.0:1, and then reacting at 155 ℃ for 100min to precipitate and separate the aluminum, so as to obtain germanium-containing alkaline leaching solution with the aluminum content of less than 40mg/L and aluminum slag with the aluminum content of 25.58%;
(3) And (3) allowing the alkaline leaching solution containing germanium to pass through an ion exchange column carrying D403 resin at a flow rate of 17BV/h at normal temperature to obtain a low-germanium alkaline leaching solution with the germanium concentration of 1.57mg/L, adsorbing the germanium by resin particles, evaporating and concentrating the low-germanium alkaline leaching solution, and returning to the step (2).
(4) The resin particles absorbing germanium are washed by pure water for 2 times, the germanium is resolved by hydrochloric acid solution with the concentration of 2.5mol/L at the flow rate of 9.5BV/h, the resolved liquid can be recycled until the content of the germanium is more than 2g/L, and the resolved resin is returned to the step (3) after activation transformation.
(5) The germanium-containing hydrochloric acid solution is directly transferred to a distillation germanium extraction process for compatibility or a germanium precipitating agent is added, and the pH is regulated to 10.0, so as to obtain the crude germanium oxide with the germanium content of 43.45 percent.
In this example, the germanium recovery was about 92.49%.
Comparative example 1
The starting materials were identical to those used in example 1;
leaching with 500g/L sodium hydroxide aqueous solution, adding 20g of raw materials, controlling the reaction temperature to 90 ℃, controlling the liquid-solid ratio to 10:1, and reacting for 2 hours, wherein the leaching rate of germanium is 47.04 percent through one-step leaching.
Comparative example 2
The starting materials were identical to those used in example 1;
leaching with 500g/L sodium hydroxide aqueous solution, adding 20g of raw materials and 5g of sodium chlorate, controlling the reaction temperature to 90 ℃, controlling the liquid-solid ratio to be 10:1, and reacting for 2 hours, wherein the leaching rate of germanium is 42.25 percent through one-step leaching.
Comparative example 3
The starting materials were identical to those used in example 1;
leaching with 500g/L sodium hydroxide aqueous solution, adding 20g of raw materials, adding 5ml of hydrogen peroxide, controlling the reaction temperature to 80 ℃, controlling the liquid-solid ratio to 10:1, reacting for 2 hours, and leaching out the germanium by one step to obtain the leaching rate of 50.64 percent.
Comparative example 4
The starting materials were identical to those used in example 1;
leaching with 448g/L potassium hydroxide aqueous solution, adding 10g of raw materials, controlling the reaction temperature to 90 ℃, controlling the liquid-solid ratio to be 20:1, and reacting for 2 hours, wherein the leaching rate of germanium is 61.42 percent through one-step leaching.
Comparative example 5
The starting materials were identical to those used in example 1;
leaching with 240g/L sodium hydroxide aqueous solution, adding 10g of raw material, adding 2g of sodium sulfite, controlling the reaction temperature to 90 ℃, controlling the liquid-solid ratio to be 20:1, reacting for 2 hours, and leaching out the germanium by one step, wherein the leaching rate of germanium is 54.67%.
Comparative example 7
The starting materials were identical to those used in example 1;
oxygen pressure leaching: 118.2g of raw material, 240g/L of sodium hydroxide (1100 ml) is added, the reaction temperature is 180 ℃, the reaction time is 4.5h, the oxygen partial pressure is 0.45MPa, and the leaching rate of germanium is 53.02 percent through one-step leaching.
Claims (10)
1. A method for secondarily recovering germanium from a low-grade germanium material, which is characterized by comprising the steps of; comprising the following steps:
step one
The low-grade germanium-containing material and a sub-molten salt medium are subjected to medium-temperature alkaline leaching and/or sub-molten salt leaching reaction in a reaction kettle at 70-250 ℃, wherein the sub-molten salt medium contains alkali metal hydroxide; filtering and washing after the reaction is finished to obtain alkaline leaching solution containing germanium and alkaline leaching slag;
step two
If the aluminum content of the alkaline leaching solution containing germanium is more than or equal to A mg/L, carrying out aluminum removal treatment on the alkaline leaching solution containing germanium to obtain aluminum slag and purifying solution containing germanium; the purified solution containing germanium passes through an ion exchange column filled with D403 chelate resin to obtain chelate resin adsorbed with germanium and alkali liquor after germanium extraction;
if the aluminum content of the germanium alkaline leaching solution is less than Amg/L, the germanium alkaline leaching solution passes through an ion exchange column filled with D403 chelating resin to obtain the chelating resin adsorbed with germanium and alkaline liquor after germanium extraction;
the value range of A is 20-50.
2. The method for secondarily recovering germanium from a low-grade germanium material according to claim 1, wherein: the content of germanium in the low-grade germanium material is 0.1-2.0wt%.
3. The method for secondarily recovering germanium from a low-grade germanium material according to claim 1, wherein: in the first step, the first step is to perform,
according to the alkali-ore ratio g which is g=5-20:1, adding a cosolvent according to the proportion of 0.2-5% of the feeding amount and mixing with a low-grade germanium material, filling a sub-molten salt medium and the low-grade germanium material into a reaction kettle, closing a kettle cover, starting stirring, introducing oxygen-containing gas, controlling the oxygen partial pressure to be 0.05-2.00 MPa, controlling the reaction temperature to be 140-250 ℃, preferably 160-180 ℃, continuously reacting for 1-6 h, closing an air inlet valve, cooling to 80-120 ℃, and preserving heat and filtering.
4. The method for secondarily recovering germanium from a low-grade germanium material according to claim 1, wherein: in the step 1, the rotating speed is controlled to be 300-900 revolutions per minute.
5. The method for secondarily recovering germanium from a low-grade germanium material according to claim 1, wherein:
the oxygen-containing gas comprises industrial oxygen;
the alkali metal hydroxide is at least one selected from sodium hydroxide and potassium hydroxide.
6. The method for secondarily recovering germanium from a low-grade germanium material according to claim 1, wherein:
the sub-molten salt medium comprises an alkali metal hydroxide or comprises an alkali metal hydroxide and a co-solvent selected from the group consisting of: at least one of nitrate, carbonate and chlorate, preferably at least one of sodium nitrate, potassium nitrate, sodium carbonate, potassium carbonate, sodium chlorate and potassium chlorate; no cosolvent may be added to the fusible, specific material containing only the germanium oxide phase.
7. The method for secondarily recovering germanium from a low-grade germanium material according to claim 1, wherein:
according to the alkali-ore ratio g: g=3-10:1, mixing the alkaline liquor B with the low-grade germanium material, and leaching the germanium-containing material by using a sub-molten salt method alkaline leaching solution at 80-90 ℃ under the condition of no boiling to obtain first-stage intermediate-temperature alkaline leaching slag; then, carrying out second sub-molten salt leaching, wherein the second sub-molten salt leaching takes slag of the first step as a raw material;
the alkali liquor B is alkali liquor or alkali liquor with the concentration of 10-40% after leaching by sub-molten salt.
8. The method for secondarily recovering germanium from a low-grade germanium material according to claim 1, wherein:
the first step mainly comprises alkaline leaching solution containing germanium and residues after germanium extraction; the concentration of germanium in the alkaline leaching solution containing germanium is 100-2000 mg/L, the concentration of alkali is 150-250 g/L, and the content of germanium in the residue after germanium extraction is lower than 400-2000 g/t.
9. The method for secondarily recovering germanium from a low-grade germanium material according to claim 1, wherein:
in the second step, when the aluminum content of the alkaline leaching solution containing germanium is larger than or equal to Amg/L, precipitating and separating aluminum and the like by adopting a sodium silicate and silicon dioxide combined aluminum removing agent to obtain aluminum slag and a purifying solution containing germanium; the method specifically comprises the following steps: controlling the molar ratio of sodium silicate to aluminum in the alkaline leaching solution containing germanium to be 1.5-2.0, reacting for 30-120 min at 140-180 ℃, aging for 24h, and filtering to obtain filter residues with aluminum content of 5-30%, wherein the aluminum concentration is lower than the purifying liquid of the alkaline leaching solution containing germanium of Amg/L;
in the second step, the alkaline leaching solution containing germanium with the aluminum content less than Amg/L passes through an ion exchange column filled with D403 resin according to the flow rate of 5-30 BV/h to obtain resin which has adsorbed germanium and alkaline liquor after germanium extraction, and the alkaline leaching solution after germanium extraction is evaporated and concentrated and then returns to the first step to serve as a sub-molten salt medium;
in the second step, when the germanium is adsorbed by the ion exchange column of the D403 resin, the temperature is controlled to be 20-65 ℃.
10. The method for secondarily recovering germanium from a low-grade germanium material according to claim 1, wherein:
after the step two is completed, the obtained resin for adsorbing germanium is subjected to saturation washing and rinsing, and is resolved by hydrochloric acid solution to obtain hydrochloric acid solution containing germanium and resolved D403 resin; when the solution is used for resolving, the solution with the concentration of 0.2 to 4.0mol/L is used for eluting the germanium adsorbed on the D403 resin, and the dosage of the solution is 2 to 4m 3 /m 3 R, the flow rate of the hydrochloric acid solution is 10-25 BV/h, and the operation temperature is 20-35 ℃;
adding germanium deposition auxiliary agent into the obtained germanium-containing hydrochloric acid solution, regulating pH value to 8.0-10.0 with alkali at normal temperature, depositing germanium, filtering to obtain high-grade germanium concentrate with germanium content of more than or equal to 20%, preferably more than or equal to 30%.
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| CN117607080B (en) * | 2024-01-22 | 2024-03-29 | 昆明理工大学 | Analysis method of germanium chemical phase in germanium-containing complex minerals |
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