CN113149269A - Tantalum-niobium hydrometallurgy wastewater treatment method - Google Patents
Tantalum-niobium hydrometallurgy wastewater treatment method Download PDFInfo
- Publication number
- CN113149269A CN113149269A CN202110313622.XA CN202110313622A CN113149269A CN 113149269 A CN113149269 A CN 113149269A CN 202110313622 A CN202110313622 A CN 202110313622A CN 113149269 A CN113149269 A CN 113149269A
- Authority
- CN
- China
- Prior art keywords
- tantalum
- niobium
- acid
- wastewater
- filtering
- 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
- RHDUVDHGVHBHCL-UHFFFAOYSA-N niobium tantalum Chemical compound [Nb].[Ta] RHDUVDHGVHBHCL-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 238000009854 hydrometallurgy Methods 0.000 title claims abstract description 22
- 238000004065 wastewater treatment Methods 0.000 title description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 60
- 238000000605 extraction Methods 0.000 claims abstract description 49
- 239000002351 wastewater Substances 0.000 claims abstract description 46
- 239000000243 solution Substances 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 43
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- 239000000706 filtrate Substances 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000001914 filtration Methods 0.000 claims abstract description 32
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 30
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000012071 phase Substances 0.000 claims abstract description 26
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 claims abstract description 24
- 229910052776 Thorium Inorganic materials 0.000 claims abstract description 24
- 229910052770 Uranium Inorganic materials 0.000 claims abstract description 24
- 239000002253 acid Substances 0.000 claims abstract description 24
- 229910052705 radium Inorganic materials 0.000 claims abstract description 24
- HCWPIIXVSYCSAN-UHFFFAOYSA-N radium atom Chemical compound [Ra] HCWPIIXVSYCSAN-UHFFFAOYSA-N 0.000 claims abstract description 24
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000012074 organic phase Substances 0.000 claims abstract description 18
- 239000002244 precipitate Substances 0.000 claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- 238000010306 acid treatment Methods 0.000 claims abstract description 14
- 239000007787 solid Substances 0.000 claims abstract description 14
- 229910001626 barium chloride Inorganic materials 0.000 claims abstract description 11
- 239000012528 membrane Substances 0.000 claims abstract description 11
- 238000001556 precipitation Methods 0.000 claims abstract description 11
- 238000001728 nano-filtration Methods 0.000 claims abstract description 10
- 238000000926 separation method Methods 0.000 claims abstract description 10
- 239000012670 alkaline solution Substances 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 8
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 7
- 230000005496 eutectics Effects 0.000 claims abstract description 7
- 238000000638 solvent extraction Methods 0.000 claims abstract description 7
- 238000012216 screening Methods 0.000 claims abstract description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910000484 niobium oxide Inorganic materials 0.000 claims abstract description 4
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000011591 potassium Substances 0.000 claims abstract description 4
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 4
- 239000002736 nonionic surfactant Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 239000004094 surface-active agent Substances 0.000 claims description 10
- 229910052715 tantalum Inorganic materials 0.000 claims description 10
- 229910052758 niobium Inorganic materials 0.000 claims description 9
- 239000010955 niobium Substances 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- -1 carbon fatty alcohol Chemical class 0.000 claims description 8
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 7
- 239000003350 kerosene Substances 0.000 claims description 7
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 7
- 238000005345 coagulation Methods 0.000 claims description 6
- 230000015271 coagulation Effects 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 5
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 239000008346 aqueous phase Substances 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 2
- 238000010298 pulverizing process Methods 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 5
- 230000008569 process Effects 0.000 description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 230000002285 radioactive effect Effects 0.000 description 7
- 239000011737 fluorine Substances 0.000 description 6
- 229910052731 fluorine Inorganic materials 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000002893 slag Substances 0.000 description 5
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- 239000012141 concentrate Substances 0.000 description 4
- 229940051841 polyoxyethylene ether Drugs 0.000 description 4
- 229920000056 polyoxyethylene ether Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 235000011941 Tilia x europaea Nutrition 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000002563 ionic surfactant Substances 0.000 description 3
- 150000002500 ions Chemical group 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000004571 lime Substances 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- 239000002354 radioactive wastewater Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000000909 electrodialysis Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 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 2
- 239000007791 liquid phase Substances 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910001729 niobium mineral Inorganic materials 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical class [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 206010040880 Skin irritation Diseases 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910001080 W alloy Inorganic materials 0.000 description 1
- GFRMDONOCHESDE-UHFFFAOYSA-N [Th].[U] Chemical compound [Th].[U] GFRMDONOCHESDE-UHFFFAOYSA-N 0.000 description 1
- QSEKXEZFXPIFCJ-UHFFFAOYSA-N [W].[Mn].[Fe] Chemical compound [W].[Mn].[Fe] QSEKXEZFXPIFCJ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- XDFCIPNJCBUZJN-UHFFFAOYSA-N barium(2+) Chemical compound [Ba+2] XDFCIPNJCBUZJN-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical class [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000002288 cocrystallisation Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 235000003084 food emulsifier Nutrition 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- AYHSMYZXRJVASB-UHFFFAOYSA-D niobium(5+) tantalum(5+) decahydroxide Chemical compound [OH-].[Nb+5].[Ta+5].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-] AYHSMYZXRJVASB-UHFFFAOYSA-D 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- AOLPZAHRYHXPLR-UHFFFAOYSA-I pentafluoroniobium Chemical compound F[Nb](F)(F)(F)F AOLPZAHRYHXPLR-UHFFFAOYSA-I 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 230000036556 skin irritation Effects 0.000 description 1
- 231100000475 skin irritation Toxicity 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- MZQZQKZKTGRQCG-UHFFFAOYSA-J thorium tetrafluoride Chemical compound F[Th](F)(F)F MZQZQKZKTGRQCG-UHFFFAOYSA-J 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- SANRKQGLYCLAFE-UHFFFAOYSA-H uranium hexafluoride Chemical compound F[U](F)(F)(F)(F)F SANRKQGLYCLAFE-UHFFFAOYSA-H 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- 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
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
-
- 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
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/10—Hydrochloric acid, other halogenated acids or salts thereof
-
- 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
- C22B34/00—Obtaining refractory metals
- C22B34/20—Obtaining niobium, tantalum or vanadium
- C22B34/24—Obtaining niobium or tantalum
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/26—Treatment of water, waste water, or sewage by extraction
- C02F1/265—Desalination
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/006—Radioactive compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
- C02F2101/14—Fluorine or fluorine-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Environmental & Geological Engineering (AREA)
- Inorganic Chemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The application discloses a method for treating tantalum-niobium hydrometallurgy wastewater, which comprises the following steps: crushing the tantalum-niobium ore to 300 meshes, carrying out acid treatment at the temperature of 20-80 ℃, and reacting to obtain a solid and a reaction liquid; adding hydrofluoric acid and sulfuric acid into the solid for decomposition, and performing preparation processes of potassium fluotantalate and niobium oxide after decomposition; adjusting the reaction solution to acid by using water or an alkaline solution to enable the pH value of the reaction solution to be 1-1.5, and filtering to obtain a filtrate; passing the filtrate through a nanofiltration membrane system, and screening the filtrate; filtering the filtered liquidEntering an extraction separation tank, and extracting by adopting a solvent extraction method to obtain an organic phase containing uranium and thorium and a water phase containing radium; carrying out back extraction on the organic phase by using 5mol/L NaOH as a stripping agent; filtering the back-extracted solution to obtain a precipitate, and drying and storing the precipitate; putting the water phase into a reaction tank, and adding BaCl2Carrying out eutectic precipitation; filtering the water phase in the reaction tank, standing, and adding sodium hydroxide to adjust the pH value to 6-8.
Description
Technical Field
The application relates to the technical field of metallurgy, in particular to a method for treating tantalum-niobium hydrometallurgy wastewater.
Background
The production of tantalum, niobium fluoride salt and oxide mainly comprises four processes of ore decomposition, extraction separation, precipitation crystallization, drying and calcination. Firstly, grinding tantalum-niobium concentrate in a vibrating nodular graphite to a certain granularity; decomposing the ground concentrate in a decomposition tank with steam heating or water bath heating: firstly, adding hydrofluoric acid and sulfuric acid, then gradually concentrating, and simultaneously carrying out mechanical stirring, wherein the decomposition temperature is above 80 ℃; the purpose of adding sulfuric acid is to intensify decomposition reaction, reduce the degree of ore breakage, shorten reaction time, and partially replace expensive hydrofluoric acid, and the addition of sulfuric acid is very beneficial to tantalum-niobium purification and tantalum-niobium separation during later extraction.
The acid decomposition action, in addition to transferring Ta and Nb to the liquid phase, also consists in adjusting the pH of the solution to the acidity required for extraction. The process has the advantages that the ore decomposition reaction is complete by controlling the acidity, the residual quantity of Ta and Nb in slag is reduced, the metal recovery rate of the process is improved, and the economic benefit is improved. Meanwhile, by enhancing filtration, harmful impurities such as suspended solid particles or 'soluble' silicic acid and the like in a liquid phase are removed as much as possible, emulsification in the next extraction process is prevented, and smooth extraction is ensured. Separating the decomposed liquid from the residue by filtration. And adjusting the acidity of the filtrate and the concentration of tantalum and niobium, and then performing extraction separation.
In the acid decomposition process, the ratio of tantalum to niobium to H is respectively2TaF7、H2NbF7And H2NbOF5The form of the iron-manganese-tungsten alloy enters the solution, and simultaneously, a large amount of impurities such as iron, manganese, titanium, tungsten and the like enter the solution. Impurities such as rare earth, calcium, magnesium and the like enter the residue in the form of insoluble fluorides. During the decomposition process, the radioactive elements uranium and thorium in the ore enter the residue in the form of uranium fluoride and thorium fluoride in most part, and the other part is UO2 2+And Th4+And the complex ion form enters into decomposition liquid, which are sources of excessive radioactivity in the production wastewater.
At present, tantalum-niobium hydrometallurgy at home and abroad adopts chemical conditions of high-concentration hydrofluoric acid or high-concentration hydrofluoric acid-concentrated sulfuric acid to decompose ores. In the process of decomposing the tantalum-niobium concentrate with the concentrated hydrofluoric acid, not only the atmosphere environment is seriously polluted due to the volatilization of HF (hydrofluoric acid), but also a large amount of fluorine-containing wastewater is generated in the decomposition process, the wastewater is usually treated by a precipitation method, and a large amount of waste liquid generated in the treatment process generates huge pollution to water and soil. And the fluorine ion content in the wastewater is controlled to be less than 0.001g/L for multiple times of wastewater treatment before the wastewater is discharged. High treatment cost, low resource utilization, long process flow for treating wastewater, difficult one-time treatment qualification and poor effect.
Disclosure of Invention
The application provides a method for treating wastewater in tantalum-niobium hydrometallurgy, which aims to solve the problem that elements such as uranium, thorium and radium in wastewater can be precipitated into slag together to cause radioactive slag.
The application provides a method for treating tantalum-niobium hydrometallurgy wastewater, which comprises the following steps:
crushing the tantalum-niobium ore to 300 meshes, carrying out acid treatment at the temperature of 20-80 ℃, and reacting to obtain a solid and a reaction liquid; wherein the reaction liquid mainly contains soluble salts of iron, manganese and the like, and part of uranium thorium radium;
adding hydrofluoric acid and sulfuric acid into the solid for decomposition, and performing a preparation process of potassium fluotantalate and niobium oxide after decomposition;
adjusting the reaction solution to be acidic by using water or an alkaline solution to enable the pH value of the reaction solution to be 1-1.5, and filtering to obtain a filtrate;
passing the filtrate through a nanofiltration membrane system, and screening the filtrate;
feeding the screened filtrate into an extraction separation tank, and extracting by adopting a solvent extraction method to obtain an organic phase containing uranium and thorium and a water phase containing radium;
carrying out back extraction on the organic phase by using 5mol/L NaOH as a stripping agent; wherein, compared with 1:1, the back extraction stage number is 3 stages;
filtering the back-extracted solution to obtain a precipitate, and drying and storing the precipitate;
putting the water phase into a reaction tank, and adding BaCl2Carrying out eutectic precipitation;
filtering the water phase in the reaction tank, standing, adding sodium hydroxide to adjust the pH value to 6-8, and discharging.
Optionally, the step of crushing the tantalum-niobium ore to 300 meshes, performing acid treatment at 20-50 ℃, and obtaining a solid and a reaction solution after reaction comprises:
crushing the tantalum-niobium ore to 300 meshes, carrying out first acid treatment at the temperature of 20-50 ℃, and reacting for 24-48 h;
after reacting for 24-48h, filtering the acid liquor containing the tantalum-niobium ore to obtain supernatant, and performing secondary acid treatment on the filtered tantalum-niobium ore.
Optionally, the acid in the acid treatment is dilute sulfuric acid or dilute hydrochloric acid with the mass fraction of 10%, and the volume ratio of the tantalum niobium ore to the acid is 1 (2-4).
Optionally, the alkaline solution is an aqueous sodium hydroxide solution or an aqueous potassium hydroxide solution.
Optionally, the extractant comprises P204, TBP and kerosene, wherein the volume fractions of P204, TBP and kerosene are 20%, 15% and 65%, respectively; the extraction phase was 1: 2, the extraction stage number is 3; and a surfactant is also added in the extraction process, wherein the surfactant is a carbon fatty alcohol polyoxyalkylene ether or polyethylene glycol type nonionic surfactant.
Optionally, the aqueous phase is placed in a reaction tank and BaCl is added2The step of performing eutectic precipitation comprises:
putting the water phase into a reaction tank, and adding BaCl2Stirring and reacting for 4-8 h;
stirring for 4-8h, and adding coagulation agent Fe2(SO4)3Stirring for 1-2 h.
Optionally, the BaCl2The dosage of the Fe is 250-300 g/cubic meter of wastewater2(SO4)3The dosage is 250-350 g/cubic meter of wastewater.
According to the technical scheme, the application discloses a method for treating tantalum-niobium hydrometallurgy wastewater, which comprises the following steps: crushing the tantalum-niobium ore to 300 meshes, carrying out acid treatment at the temperature of 20-80 ℃, and reacting to obtain a solid and a reaction liquid; adding hydrofluoric acid and sulfuric acid into the solid for decomposition, and performing a preparation process of fluorotantalic acid and fluoroniobate acid after decomposition; adjusting the reaction solution to be acidic by using water or an alkaline solution to enable the pH value of the reaction solution to be 1-1.5, and filtering to obtain a filtrate; passing the filtrate through a nanofiltration membrane system, and screening the filtrate; feeding the screened filtrate into an extraction separation tank, and extracting by adopting a solvent extraction method to obtain an organic phase containing uranium and thorium and a water phase containing radium; carrying out back extraction on the organic phase by using 5mol/L NaOH as a stripping agent; wherein, compared with 1:1, the back extraction stage number is 3 stages; filtering the back-extracted solution to obtain a precipitate, and drying and storing the precipitate; putting the water phase into a reaction tank, and adding BaCl2Carrying out eutectic precipitation; filtering the water phase in the reaction tank, standing, and adding sodium hydroxide to adjust the pH value to 6-8. According to the method for treating wastewater in tantalum-niobium hydrometallurgy, elements such as uranium, thorium, radium and the like are separated from tantalum-niobium ore by predecomposition, and then the elements of uranium, thorium, radium can be extracted into an organic phase by an extraction method and can be back-extracted into a solution, so that the purpose of enriching the elements of uranium, thorium and radium is achieved. By adopting a coprecipitation method, radium elements in the wastewater are further removed, and byproducts such as sodium fluosilicate and the like are avoided. Can effectively remove radioactive elements and finally reach the discharge standard. The wastewater treatment process does not contain fluorinion, and the wastewater does not need to be treated for many times to control the fluorine in the wastewaterIon content. Low treatment cost, high resource utilization, qualified one-time treatment and good effect.
Drawings
In order to more clearly explain the technical solution of the present application, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious to those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a schematic flow chart of a method for treating tantalum-niobium hydrometallurgy wastewater provided by the application.
Detailed Description
Reference will now be made in detail to embodiments, examples of which are illustrated in the accompanying drawings. When the following description refers to the accompanying drawings, like numbers in different drawings represent the same or similar elements unless otherwise indicated. The embodiments described in the following examples do not represent all embodiments consistent with the present application. But merely as exemplifications of systems and methods consistent with certain aspects of the application, as recited in the claims.
Referring to fig. 1, the application provides a schematic flow chart of a method for treating tantalum-niobium hydrometallurgy wastewater.
The application provides a method for treating tantalum-niobium hydrometallurgy wastewater, which comprises the following steps:
crushing the tantalum-niobium ore to 300 meshes, carrying out first acid treatment at the temperature of 20-50 ℃, and reacting for 24-48 h.
After reacting for 24-48h, filtering the acid liquor containing the tantalum-niobium ore to obtain supernatant, and performing secondary acid treatment on the filtered tantalum-niobium ore to obtain a solid and a reaction liquid; the acid is dilute sulfuric acid or dilute hydrochloric acid with the mass fraction of 10%, and the volume ratio of the tantalum niobium ore to the acid is 1 (2-4).
In practical application, elements such as uranium, thorium, radium and the like are separated from tantalum-niobium ore by pre-decomposition, and diluted acid is used for carrying out multiple treatment, so that iron, manganese, aluminum and the like in the ore are changed into soluble sulfate. Radioactive elements such as uranium, thorium, radium and the like in the ore are also dissolved in the sulfuric acid solution. Has higher metal decomposition conversion rate. Hydrofluoric acid is traditionally used for decomposition, the decomposition rate of the hydrofluoric acid method is only about 85%, HF volatilization loss is 6-7% in the concentrate decomposition process, the average acid consumption for treating 1t of tantalum-niobium ore is about 4t, and the high toxicity and strong corrosivity of the hydrofluoric acid have high requirements on equipment materials and require a good ventilation device and a good recovery system. The diluted acid is used for multiple decomposition, and the method has the advantages of high conversion rate, safety, greenness and the like.
Adjusting the reaction solution to be acidic by using water or an alkaline solution to enable the pH value of the reaction solution to be 1-1.5, controlling the fluorine ions of the reaction solution to be less than or equal to 1g/L, and filtering to obtain a filtrate; wherein the alkaline solution is sodium hydroxide aqueous solution or potassium hydroxide aqueous solution.
In practical application, after filtering out residues, diluting the solution with water, hydrolyzing the sulfate of alkaline earth metal elements to generate precipitates, and after separating the precipitates, controlling different pH values to separate out pure tantalum-niobium hydroxide solutions through precipitation respectively.
In practical application, saturated lime water solution can be used for regulating acid, and the acidity value of the solution is regulated to 1-1.5 so as to precipitate most of residual fluorine ions in the wastewater solution, so that the fluorine ions are less than or equal to 1 g/L; wherein the consumption of lime is 400-500 kg/cubic meter of wastewater.
And (4) passing the filtrate through a nanofiltration membrane system, and screening the filtrate.
In practical applications, the filtrate is passed through the nanofiltration membrane system because the nanofiltration membrane system has monovalent ion selectivity. The nanofiltration membrane system comprises an electrodialysis subsystem and a reverse osmosis subsystem, ammonium sulfate in filtrate can be concentrated by using the nanofiltration membrane system, and ammonium fluoride remained in the ammonium sulfate can be further removed by a monovalent ion selective membrane in the electrodialysis subsystem.
Feeding the screened filtrate into an extraction separation tank, and extracting by adopting a solvent extraction method to obtain an organic phase containing uranium and thorium and a water phase containing radium; the extractant comprises P204, TBP and kerosene, wherein the volume fractions of the P204, the TBP and the kerosene are respectively 20%, 15% and 65%; the extraction phase was 1: 2, the extraction stage number is 3; and a surfactant is also added in the extraction process, wherein the surfactant is a carbon fatty alcohol polyoxyalkylene ether or polyethylene glycol type nonionic surfactant.
In practical application, a solvent extraction method is adopted to separate uranium and thorium in a solution. Respectively obtaining an organic phase containing uranium and thorium and a water phase containing radium. The extraction belongs to a synergistic extraction system, and the reaction mechanism is an addition reaction. The phase ratio using extraction was 1: 2, the extraction grade is 3 grades, so that the extraction rate of uranium and thorium can reach more than 99 percent.
The nonionic surfactant is used in practical applications because it has high surface activity, good solubilizing, washing, antistatic, lime soap dispersing and other properties, low irritation, and excellent wetting and washing functions. The pH value range of the surfactant can be wider than that of the common ionic surfactant, and the surfactant can also be used together with other ionic surfactants, and the surfactant of the system can be improved by adding a small amount of nonionic surfactant into the ionic surfactant.
The polyoxyethylene ether nonionic surfactants with strong functions and high cost performance in the market mainly comprise four types of primary alcohol polyoxyethylene ether (AEO), secondary alcohol polyoxyethylene ether (SEO), branched isomeric Guerbet alcohol ether (ISO-AEO) and Alkylphenol Polyoxyethylene Ether (APEO), and the four types of nonionic surfactants have advantages. Among them, AEO has the characteristics of low foamability, strong dispersing ability, and increased hydrophilicity with the increase of EO content, and has become the most rapidly developed nonionic surfactant, but its disadvantage is also obvious, i.e., the viscosity is high in aqueous solution, and a gel is easily generated, so that it is generally solved by adding sorbitol and ethylene glycol. Compared with AEO, the other three nonionic surfactants have less outstanding characteristics, but have less obvious defects and are also favored due to lower production cost. For example, SEO, ISO-AEO and APEO all have the characteristics of high fluidity, low viscosity, low pour point, narrow gel distribution, high permeability and the like, and the skin irritation of SEO, ISO-AEO and APEO is lower than that of AEO, and the SEO, ISO-AEO and APEO also are one of the advantages of the three types of nonionic surfactants.
The basic production principle of the polyol ester nonionic surfactant is that the polyol and fatty acid are directly subjected to esterification reaction, and the surfactant generally does not have a cleaning function, but has unique characteristics, so that the polyol ester nonionic surfactant is widely applied to some special production fields. Such as glycerides, are not substantially soluble in water due to their low HLB and are therefore often used in food emulsifiers and additives.
Carrying out back extraction on the organic phase by using 5mol/L NaOH as a stripping agent; wherein, compared with 1:1, the back extraction stage is 3 stages.
And filtering the back-extracted solution to obtain a precipitate, and drying and storing the precipitate.
In practical application, the precipitate obtained by filtering the strip liquor is dried and stored in a slag storage (containing radioactive elements uranium and thorium). The organic phase and the stripping solution can be recycled.
Putting the water phase into a reaction tank, and adding BaCl2Stirring and reacting for 4-8 h.
Stirring for 4-8h, and adding coagulation agent Fe2(SO4)3Stirring for 1-2 h; the BaCl2The dosage of the Fe is 250-300 g/cubic meter of wastewater2(SO4)3The dosage is 250-350 g/cubic meter of wastewater.
The chemical reaction formula is as follows: ra2++Ba2++SO4 2-＝Ba(Ra)SO4And ↓, ferric sulfate is used as coagulation agent to accelerate the coagulation effect of Ba (Ra) SO 4.
Because the waste water produced by smelting the tantalum-niobium mineral contains natural uranium, thorium and daughter 226Ra, 228Ra and 224Ra thereof, wherein 226Ra and 224Ra are alpha emitters,
228Ra is a beta emitter and many of these radium isotopes remain in solution after the lime milk neutralization precipitation and extraction process. The chemical properties of barium and radium are similar, so that barium sulfate radium co-crystallization co-precipitation can be formed. Through barium sulfate precipitation, the content of radium in the solution can be effectively reduced, so that the total alpha and beta radioactivity levels in the wastewater are obviously reduced.
Filtering the water phase in the reaction tank, standing, and adding sodium hydroxide to adjust the pH value to 6-8.
In practical application, the pH value of the wastewater in the reaction tank is adjusted to 6-8 to be neutral by using sodium hydroxide, and the wastewater can be discharged according with the national discharge standard.
And decomposing the pre-decomposed substances by using hydrofluoric acid, and entering a wet extraction system.
Examples
1. Predecomposition
Crushing tantalum-niobium ore to 300 meshes, mixing the ore with dilute sulfuric acid solution, wherein the acidity of the solution is 10%, and the weight ratio of the ore to the dilute sulfuric acid solution is 1: 2-1: 3, the decomposition temperature is below 80 ℃. The decomposition time is 24-48 hours. And finally filtering the acid liquor to obtain filter residue and filtrate. The filtrate was taken to the next step. The composition of the wastewater in the resulting solution was as follows:
the radioactive wastewater components are as follows (fluorine content 125 g/L)
The waste water produced by smelting the tantalum-niobium mineral contains natural uranium, thorium and daughter 226Ra, 228Ra and 224Ra thereof, wherein 226Ra and 224Ra are alpha emitters, and 228Ra is beta emitter.
2. Regulating acid
And (2) adding the filtrate obtained in the step (1) into a reaction tank, stirring and reacting 100 kg of prepared sodium hydroxide solution with the filtrate for 8-24 hours, filtering, and performing an extraction process on the filtrate, wherein the acidity pH of the filtrate is 1-1.5.
3. Extraction separation
And (3) extracting the filtrate obtained in the step (2) by using a prepared extracting agent (the extracting agent comprises 20% of P204+ 15% of TBP + 65% of kerosene), wherein the extracting ratio is 1: 2, extraction stage 3. The U in the extracted water phase is 0.082mg/L, the Th is 0.0004mg/L, which accords with the national discharge standard.
4. Back extraction
And (3) taking prepared 5mol/L NaOH as a stripping agent for the uranium-containing thorium organic phase in the step 3, and comparing the ratio of the prepared NaOH to the extraction agent in the step 1:1, the back extraction stage is 3 stages, and precipitates obtained by filtering back extraction liquid are dried and stored in a slag storage (containing radioactive elements uranium and thorium). Organic phase and filtered back extraction liquid circulationThe preparation is used. Drying and analyzing the precipitate obtained by filtering the stripping solution to obtain U3O8Is 0.060 percent,
5. putting the radium-containing water phase (raffinate) obtained in the step 3 into a reaction tank, and adding 900 g of BaCl2Dissolving in water, adding into a reaction tank, stirring for reaction for 4-8 hours, adding 1050 g of ferric sulfate as a coagulation agent, stirring for 1-2 hours, and standing for more than 24 hours.
6. Precision filtration
And 5, filtering the wastewater after standing in the step 5 by adopting a precision technology, and adjusting the pH value to 6-8 by using sodium hydroxide until the pH value is neutral and meets the national emission standard for discharge.
The components of the radioactive wastewater discharged after the treatment of the steps are shown in the following table
All indexes of the discharged radioactive wastewater treated by the steps meet the requirements of national discharge standards.
7. Acid decomposition of the ore is carried out, and substances in the product 1 are subjected to hydrofluoric acid decomposition. The potassium fluotantalate and the niobium oxide are obtained by tantalum-niobium hydrometallurgy.
According to the technical scheme, the application discloses a method for treating tantalum-niobium hydrometallurgy wastewater, which comprises the following steps: crushing the tantalum-niobium ore to 300 meshes, carrying out acid treatment at the temperature of 20-80 ℃, and reacting to obtain a solid and a reaction liquid; adding hydrofluoric acid and sulfuric acid into the solid for decomposition, and performing a preparation process of fluorotantalic acid and fluoroniobate acid after decomposition; adjusting the reaction solution to be acidic by using water or an alkaline solution to enable the pH value of the reaction solution to be 1-1.5, and filtering to obtain a filtrate; passing the filtrate through a nanofiltration membrane system, and screening the filtrate; feeding the screened filtrate into an extraction separation tank, and extracting by adopting a solvent extraction method to obtain an organic phase containing uranium and thorium and a water phase containing radium; carrying out back extraction on the organic phase by using 5mol/L NaOH as a stripping agent; wherein, compared with 1:1, the back extraction stage number is 3 stages; filtering the back-extracted solution to obtain a precipitate, and drying and storing the precipitate; placing the aqueous phase in a reaction tankInto BaCl2Carrying out eutectic precipitation; filtering the water phase in the reaction tank, standing, and adding sodium hydroxide to adjust the pH value to 6-8. According to the method for treating wastewater in tantalum-niobium hydrometallurgy, elements such as uranium, thorium, radium and the like are separated from tantalum-niobium ore by predecomposition, and then the elements of uranium, thorium, radium can be extracted into an organic phase by an extraction method and can be back-extracted into a solution, so that the purpose of enriching the elements of uranium, thorium and radium is achieved. By adopting a coprecipitation method, radium elements in the wastewater are further removed, and byproducts such as sodium fluosilicate and the like are avoided. Can effectively remove radioactive elements and finally reach the discharge standard. The wastewater treatment process does not contain fluorinion, and the fluorinion content in the wastewater is not required to be controlled by repeatedly treating the wastewater. Low treatment cost, high resource utilization, qualified one-time treatment and good effect.
The embodiments provided in the present application are only a few examples of the general concept of the present application, and do not limit the scope of the present application. Any other embodiments extended according to the scheme of the present application without inventive efforts will be within the scope of protection of the present application for a person skilled in the art.
Claims (7)
1. The method for treating the tantalum-niobium hydrometallurgy wastewater is characterized by comprising the following steps of:
crushing the tantalum-niobium ore to 300 meshes, carrying out acid treatment at the temperature of 20-80 ℃, and reacting to obtain a solid and a reaction liquid;
adding hydrofluoric acid and sulfuric acid into the solid for decomposition, and preparing potassium fluotantalate and niobium oxide after decomposition;
adjusting the reaction solution to be acidic by using water or an alkaline solution to enable the pH value of the reaction solution to be 1-1.5, and filtering to obtain a filtrate;
passing the filtrate through a nanofiltration membrane system, and screening the filtrate;
feeding the screened filtrate into an extraction separation tank, and extracting by adopting a solvent extraction method to obtain an organic phase containing uranium and thorium and a water phase containing radium;
carrying out back extraction on the organic phase by using 5mol/L NaOH as a stripping agent; wherein, compared with 1:1, the back extraction stage number is 3 stages;
filtering the back-extracted solution to obtain a precipitate, and drying and storing the precipitate;
putting the water phase into a reaction tank, and adding BaCl2Carrying out eutectic precipitation;
filtering the water phase in the reaction tank, standing, adding sodium hydroxide to adjust the pH value to 6-8, and discharging.
2. The method for treating wastewater from hydrometallurgy of tantalum and niobium in accordance with claim 1, wherein said steps of pulverizing tantalum-niobium ore to 300 mesh, acid treating at 20-50 ℃, reacting to obtain solid and reaction solution comprise:
crushing the tantalum-niobium ore to 300 meshes, carrying out first acid treatment at the temperature of 20-50 ℃, and reacting for 24-48 h;
after reacting for 24-48h, filtering the acid liquor containing the tantalum-niobium ore to obtain supernatant, and performing secondary acid treatment on the filtered tantalum-niobium ore.
3. The method for treating wastewater generated in hydrometallurgy of tantalum and niobium as claimed in claim 2, wherein acid in said acid treatment is dilute sulfuric acid or dilute hydrochloric acid with a mass fraction of 10%, and the volume ratio of tantalum and niobium ore to acid is 1 (2-4).
4. The method for treating wastewater from tantalum-niobium hydrometallurgy according to claim 1, wherein said alkaline solution is an aqueous solution of sodium hydroxide or potassium hydroxide.
5. The method for treating wastewater generated in hydrometallurgy of tantalum and niobium of claim 1, wherein the extractant comprises P204, TBP and kerosene, wherein the volume fractions of P204, TBP and kerosene are 20%, 15% and 65%, respectively; the extraction phase was 1: 2, the extraction stage number is 3; and a surfactant is also added in the extraction process, wherein the surfactant is a carbon fatty alcohol polyoxyalkylene ether or polyethylene glycol type nonionic surfactant.
6. The method for treating wastewater from tantalum-niobium hydrometallurgy according to claim 1, wherein the aqueous phase is placed in a reaction tank and BaCl is added2The step of performing eutectic precipitation comprises:
putting the water phase into a reaction tank, and adding BaCl2Stirring and reacting for 4-8 h;
stirring for 4-8h, and adding coagulation agent Fe2(SO4)3Stirring for 1-2 h.
7. The method for treating wastewater from hydrometallurgy of tantalum and niobium as claimed in claim 6, wherein said BaCl is added to said wastewater2The dosage of the Fe is 250-300 g/cubic meter of wastewater2(SO4)3The dosage is 250-350 g/cubic meter of wastewater.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110313622.XA CN113149269A (en) | 2021-03-24 | 2021-03-24 | Tantalum-niobium hydrometallurgy wastewater treatment method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110313622.XA CN113149269A (en) | 2021-03-24 | 2021-03-24 | Tantalum-niobium hydrometallurgy wastewater treatment method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113149269A true CN113149269A (en) | 2021-07-23 |
Family
ID=76888365
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110313622.XA Pending CN113149269A (en) | 2021-03-24 | 2021-03-24 | Tantalum-niobium hydrometallurgy wastewater treatment method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113149269A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115838872A (en) * | 2023-02-13 | 2023-03-24 | 锦益创典(天津)科技有限责任公司 | Filter pressing washing method for tantalum-niobium slurry decomposition liquid |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4446116A (en) * | 1981-04-02 | 1984-05-01 | Hermann C. Starck Bertin | Process for recovering niobium and/or tantalum compounds from such ores further containing complexes of uranium, thorium, titanium and/or rare earth metals |
| CN102491555A (en) * | 2011-12-01 | 2012-06-13 | 核工业北京化工冶金研究院 | Method for removing fluorine in acid uranium process wastewater |
| CN111020186A (en) * | 2019-12-10 | 2020-04-17 | 核工业北京化工冶金研究院 | Method for comprehensively recycling uranium, niobium and titanium from uranium-niobium-titanium ore |
| CN111087114A (en) * | 2019-12-27 | 2020-05-01 | 山东聚鑫新材料有限公司 | Treatment method of tantalum-niobium production wastewater |
| CN111876598A (en) * | 2019-12-10 | 2020-11-03 | 核工业北京化工冶金研究院 | Method for separating uranium and niobium through co-extraction |
-
2021
- 2021-03-24 CN CN202110313622.XA patent/CN113149269A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4446116A (en) * | 1981-04-02 | 1984-05-01 | Hermann C. Starck Bertin | Process for recovering niobium and/or tantalum compounds from such ores further containing complexes of uranium, thorium, titanium and/or rare earth metals |
| CN102491555A (en) * | 2011-12-01 | 2012-06-13 | 核工业北京化工冶金研究院 | Method for removing fluorine in acid uranium process wastewater |
| CN111020186A (en) * | 2019-12-10 | 2020-04-17 | 核工业北京化工冶金研究院 | Method for comprehensively recycling uranium, niobium and titanium from uranium-niobium-titanium ore |
| CN111876598A (en) * | 2019-12-10 | 2020-11-03 | 核工业北京化工冶金研究院 | Method for separating uranium and niobium through co-extraction |
| CN111087114A (en) * | 2019-12-27 | 2020-05-01 | 山东聚鑫新材料有限公司 | Treatment method of tantalum-niobium production wastewater |
Non-Patent Citations (2)
| Title |
|---|
| 汪加军等: "含钽铌废渣中钽铌资源的综合回收工艺研究", 《稀有金属》 * |
| 肖雄伟: "萃取法处理钽铌生产废水中铀钍的研究", 《稀有金属与硬质合金》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115838872A (en) * | 2023-02-13 | 2023-03-24 | 锦益创典(天津)科技有限责任公司 | Filter pressing washing method for tantalum-niobium slurry decomposition liquid |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103374652A (en) | Method for comprehensively recycling rare earth and fluorine in process of treating bastnaesite | |
| CN111876598B (en) | Method for separating uranium and niobium through co-extraction | |
| CN106676291A (en) | Method for comprehensively recovering uranium, niobium and tantalum from ore | |
| CN103305702A (en) | Process for recovering and purifying neptunium from waste liquor discharged from 2AW+2DW in Purex flow | |
| DE2448733A1 (en) | PROCESS FOR TREATMENT OF WASTE WATER FROM THE HYDROLYSIS OF UF TIEF 6 | |
| CN106636692A (en) | Uranium purification method for ammonium biuranate | |
| CN113149269A (en) | Tantalum-niobium hydrometallurgy wastewater treatment method | |
| CN100500568C (en) | Method for preparing superfine high-purity cerium oxide by using rear earth ore sulfuric acid calcination products | |
| CN106399685B (en) | A kind of uranium, iron, thorium, rare-earth extraction separating process | |
| CN105925797A (en) | Method and system for decomposing scheelite concentrate | |
| CN105668888A (en) | Low-grade mixed rare earth ore concentrate chemical dressing and chemical dressing waste water resource comprehensively recycling method | |
| DE10231308A1 (en) | Method and device for recycling stainless steel pickling baths | |
| CN106854706B (en) | A kind of HF-H2SO4System separation of U and Nb method | |
| CN109266838A (en) | The processing method of bastnaesite and the composite ore containing bastnaesite | |
| CN103602837A (en) | Method for collecting scandium oxide from anatase associated scandium mineral | |
| CN113699376B (en) | Method for separating calcium ions in rare earth transformation type calcium magnesium containing rare earth sulfate solution by extraction method | |
| CN115927884A (en) | Defluorination method for rare earth ore leaching solution | |
| CN111118313B (en) | Impurity removal and recovery method for rare earth extraction emulsified organic phase | |
| CN115893466A (en) | Preparation method of low-fluorine rare earth oxide | |
| CN106381406A (en) | Technology for extraction and separation of thorium and rare earth | |
| CN111057875B (en) | Method for separating vanadium and chromium from solution by using microemulsion | |
| CN110387474B (en) | Method for treating electrolytic slag generated in process of producing aluminum-scandium alloy by molten salt electrolysis method | |
| CN111087114A (en) | Treatment method of tantalum-niobium production wastewater | |
| CN105648225A (en) | Method for separating amphoteric metal in waste circuit boards | |
| CN111646546B (en) | Treatment method and application of mixed rare earth alkaline wastewater |
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 |
Application publication date: 20210723 |
|
| RJ01 | Rejection of invention patent application after publication |